WO2004026921A1 - Polymer production at supercritical conditions - Google Patents

Polymer production at supercritical conditions Download PDF

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Publication number
WO2004026921A1
WO2004026921A1 PCT/US2003/029480 US0329480W WO2004026921A1 WO 2004026921 A1 WO2004026921 A1 WO 2004026921A1 US 0329480 W US0329480 W US 0329480W WO 2004026921 A1 WO2004026921 A1 WO 2004026921A1
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WIPO (PCT)
Prior art keywords
indenyl
butyl
iso
bis
dimethyl
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PCT/US2003/029480
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French (fr)
Inventor
Patrick Brant
Gerhard Franz Luft
John Richard Shutt
Lawrence Carl Smith
Douglas J. Mclain
Terry J. Burkhardt
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Exxonmobil Chemical Patents Inc.
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Priority to EP03752492A priority Critical patent/EP1539841B1/en
Priority to JP2004568943A priority patent/JP4664080B2/en
Priority to ES03752492T priority patent/ES2391766T3/en
Priority to AU2003270780A priority patent/AU2003270780A1/en
Publication of WO2004026921A1 publication Critical patent/WO2004026921A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/04—Monomers containing three or four carbon atoms
    • C08F110/06—Propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F10/04—Monomers containing three or four carbon atoms
    • C08F10/06—Propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/04—Monomers containing three or four carbon atoms
    • C08F210/06—Propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65916—Component covered by group C08F4/64 containing a transition metal-carbon bond supported on a carrier, e.g. silica, MgCl2, polymer
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S526/00—Synthetic resins or natural rubbers -- part of the class 520 series
    • Y10S526/943—Polymerization with metallocene catalysts

Definitions

  • This invention relates to polymerization of olefin monomers having three or more carbon atoms under supercritical conditions.
  • metallocene catalysts have been used in high- pressure reactors—mainly for producing ethylene-backbone polymers including ethylene copolymers with monomers of one or more of propylene, butene, and hexene, along with other specialty monomers such as 4-methyl-l,5-hexadiene.
  • US 5,756,608, granted to Langhausen et al. reports a process for polymerizing C 2 to C 10 1-alkenes using bridged metallocene catalysts.
  • Polypropylene production in high pressure conditions has, however, been seen as impractical and unworkable at temperatures much above the propylene critical point.
  • a process to produce commercially useful polypropylene in a high pressure system would provide advantages, such as increased reactivity, or increased catalyst productivity, or higher throughput, or shorter residence times, etc.
  • new polypropylene polymers are also in constant need for the preparation of new and improved products.
  • US 5,969,062 granted to Mole et al. describes a process for preparing ethylene copolymers with ⁇ -olefins in which polymerization is carried out at a pressure between 100-350 MPa and at a temperature from 200-280 °C.
  • the catalyst is based on a tetramethylcyclopentadienyl titanium complex.
  • US 5,408,017 describes an olefm polymerization catalyst for use at polymerization temperatures of 140°C-160°C, or greater. Mainly, temperatures exceeding the melting point temperature and approaching the polymer decomposition temperature are said to yield high productivity.
  • WO 93/11171 discloses a polyolef ⁇ n production process that comprises continuously feeding olefin monomer and a metallocene catalyst system into a reactor.
  • the monomer is continuously polymerized to provide a monomer-polymer mixture.
  • Reaction conditions keep this mixture at a pressure below the system's cloud-point pressure. These conditions create a polymer-rich and a monomer-rich phase and maintain the mixture's temperature above the polymer's melting point.
  • US 6,355,741 discloses a process for producing poly olefins having a bimodal molecular weight distribution.
  • the process comprises producing a first polyolef ⁇ n fraction in a first loop reactor.
  • the process couples this first loop reactor to a second loop reactor that prepares a second polyolefin fraction. At least one ofthe loops uses supercritical conditions.
  • WO 92/14766 describes a process comprising the steps of (a) continuously feeding olefinic monomer and a catalyst system, with a metallocene component and a cocatalyst component, to the reactor; (b) continuously polymerizing that monomer in a polymerization zone reactor under elevated pressure; (c) continuously removing the polymer/monomer mixture from the reactor; (d) continuously separating monomer from molten polymer; (e) reducing pressure to form a monomer-rich and a polymer-rich phase; and (f) separating monomer from the reactor.
  • US 5,326,835 describes bimodal polyethylene production.
  • This invention's first reactor stage is a loop reactor in which polymerization occurs in an inert, low-boiling hydrocarbon. After the loop reactor, the reaction medium transits into a gas-phase reactor where gas-phase ethylene polymerization occurs. The polymer produced appears to have a bimodal molecular weight distribution.
  • CA 2,118,711 (equivalent to DE 4,130,299) describes propylene polymerization at 149°C and 1510 bar using
  • This invention relates to a process to polymerize olefins comprising contacting, in a polymerization system, olefin monomers having three or more carbon atoms with a catalyst compound, an activator, optionally comonomer, and optionally diluent or solvent, at a temperature above the cloud point temperature ofthe polymerization system and a pressure no lower than lOMPa below the cloud point pressure ofthe polymerization system and less than 150 MPa, where the polymerization system comprises the monomers, any comonomer present, any diluent or solvent present, the polymer product, and where the olefin monomers having three or more carbon atoms are present at 40 weight % or more.
  • This invention also relates to polymers produced herein including a propylene polymer having a 1,3 regio defect population of greater than 5 per 10,000 monomer units, a melting point of 145°C or more, an g' of 0.97 or less and an Mw greater than 20,000.
  • This invention also relates to polymers produced herein including a propylene polymer having a 1,3 regio defect population of greater than 5 per 10,000 monomer units, a melting point of 145°C or more, an g' of 0.97 or more and an Mw greater than 20,000.
  • Figure 1 Shows that conversion increases with increasing catalyst concentration and with increasing pressure.
  • Figure 3 Shows cloud point isotherms for Polymer PP 45379 dissolved in bulk propylene.
  • Figure 4 Shows cloud point isotherms for Polymer PP 4062 dissolved in bulk propylene.
  • Figure 6 Shows cloud point isopleths for Polymer PP 45379 dissolved in bulk propylene.
  • Figure 7 Shows cloud point isopleths for Polymer PP 4062 dissolved in bulk propylene.
  • Figure 8 Shows a comparison of isopleths for PP 45379
  • Figures 9, 10 and 11 Show a comparison with literature data as described in J. Nladimir Oliveira, C. Dariva and J. C. Pinto, Ind. Eng, Chem. Res.
  • Figure 12 is a plot of G' versus Log Mw for PP 1 and PP-9.
  • a catalyst system is defined to be the combination of a catalyst compound and an activator.
  • the cloud point is the pressure below which, at a given temperature, the polymerization system becomes turbid as described in J. Nladimir Oliveira, C. Dariva and J. C. Pinto, Ind. Eng, Chem. Res. 29, 2000, 4627.
  • the cloud point is measured by shining a helium laser through the selected polymerization system in a cloud point cell onto a photocell and recording the pressure at the onset of light scattering for a given temperature.
  • a higher ⁇ -olefin is defined to be an olefin having 4 or more carbon atoms.
  • polymerization encompasses any polymerization reaction such as homopolymerization and copolymerization.
  • a copolymerization encompasses any polymerization reaction of two or more monomers.
  • the olefin present in the polymer is the polymerized form ofthe olefin.
  • An oligomer is defined to be compositions having 2-75 mer units.
  • a polymer is defined to be compositions having 76 or more mer units.
  • Me is methyl
  • Ph is phenyl
  • Et is ethyl
  • Pr is propyl
  • iPr is isopropyl
  • n-Pr is normal propyl
  • Bu is butyl
  • iBu is isobutyl
  • tBu is tertiary butyl
  • p-tBu is para-tertiary butyl
  • TMS is trimethylsilyl
  • TIBA is trisobutylaluminum
  • MAO is methylalumoxane
  • pMe is para-methyl
  • flu fluorenyl
  • cp is cyclopentadienyl.
  • slurry polymerization means a polymerization process that involves at least two phases, e.g., in which particulate, solid polymer (e.g., granular) is formed in a liquid, supercritical, or vapor polymerization medium, or in a liquid/vapor polymerization medium.
  • bulk polymerization means a polymerization process in which the polymerization medium is predominantly monomer and contains less than 50 wt % of solvent or diluent.
  • This invention relates to a process to polymerize olefins comprising contacting, in a polymerization system, olefin monomers having three or more carbon atoms with a metallocene catalyst compound, a bisamide catalyst compound or a bisimide catalyst compound, an activator, optionally comonomer, and optionally diluent or solvent, at a temperature above the cloud point temperature ofthe polymerization system and a pressure no lower than lOMPa below the cloud point pressure ofthe polymerization system and less than 150 MPa, where the polymerization system comprises the monomers, any comonomer present, any diluent or solvent present, the polymer product, and where the olefin monomers are present in the polymerization system at 40 weight % or more.
  • cloud point curves are shown in figures 2-10 for three different polypropylene samples having different molecular weights and crystallinities dissolved in propylene (at 18 weight %).
  • (Achieve 1635 PP is a commercially available metallocene catalyzed isotactic polypropylene having an Melt Flow Index (I 10 /I 2 -ASTM 1238, 190 °C, 2.16kg) of 32 dg/min available from ExxonMobil Chemical Company, Houston, Texas.
  • ESCORENE PP 4062 is a commercially available isotactic polypropylene having an MFI of 3.7 dg/min, available from ExxonMobil Chemical Company, Houston, Texas.
  • PP 45379 is an isotactic polypropylene having an MFI of 300 dg/min produced using a supported metallocene in a slurry polymerization process.
  • polymerization system is defined to be monomer(s) plus comonomers plus solvent/diluent plus polymer.
  • the polymerization system comprises less than 20 wt % aromatic hydrocarbons. Preferably less than 20 wt % toluene.
  • the temperature ofthe polymerization system is 3°C or more above the cloud point temperature for the polymerization system, alternately 5°C or more, alternately 10°C or more, alternately 15°C or more, alternately 20°C or more, alternately 25°C or more, alternately 30°C or more. Even more preferably the temperature is between 140 and 220°C, preferably 145 and 200°C, preferably 150 and 190°C, preferably 150 to 180°C, preferably 140 to 170°C.
  • the pressure ofthe polymerization system is no lower than 10 MPa below the cloud point pressure ofthe polymerization system, preferably no lower than 5 MPa below the cloud point pressure, preferably above the cloud point pressure, preferably 5 MPa or more above the cloud point pressure, preferably 50MPa or more, preferably 100 MPa.
  • the pressure is 5MPa or more, preferably lOMPa or more, more preferably up to 350MPa. Even more preferably the pressure is between 15 and 200 MPa, preferably 20 and 150 MPa, preferably 25 and 100 MPa, preferably 30 and 75 MPa, most preferably between 25 and 50 MPa.
  • solvent and or diluent is present in the polymerization system at 0 to 50 wt %, preferably 0 to 25 wt %, preferably 0 to 20, preferably 0 to 15 preferably 0 to 10 preferably 0 to 5, preferably, 0 to 4, preferably 0 to 3, preferably 0 to 2, preferably 0 to 1 wt %.
  • the olefin monomers are present in the polymerization system at 45 wt % or more, preferably 50 wt % or more, preferably at 55 wt % or more, preferably 60 wt % or more, preferably at 65 wt % or more, preferably 70 wt % or more, preferably at 75 wt % or more, preferably 80 wt % or more, preferably at 85 wt % or more.
  • propylene is present in the polymerization system at 45 wt % or more, preferably 50 wt % or more, preferably at 55 wt % or more, preferably 60 wt % or more, preferably at 65 wt % or more, preferably 70 wt % or more, preferably at 75 wt % or more, preferably 80 wt % or more, preferably at 85 wt % or more.
  • propylene and up to 30 mol % of one or more comonomers are present in the polymerization system at 45 wt % or more, preferably 50 wt % or more, preferably at 55 wt % or more, preferably 60 wt % or more, preferably at 65 wt % or more, preferably 70 wt % or more, preferably at 75 wt % or more, preferably 80 wt % or more, preferably at 85 wt % or more.
  • the temperature ofthe polymerization system is between 140 and 170°C and the pressure ofthe polymerization system is between 15 and 60 MPa.
  • the temperature ofthe polymerization system is between 140 and 170°C and the pressure ofthe polymerization system is between 20 and 60 MPa. In further particularly preferred embodiments the temperature ofthe polymerization system is between 140 and 170°C and the pressure is ofthe polymerization system between 25 and 60 MPa. In further particularly preferred embodiments the temperature ofthe polymerization system is between 140 and 170°C and the pressure ofthe polymerization system is between 30 and 60 MPa.
  • the processes of this invention occur in a supercritical polymerization medium, preferably above the cloud point ofthe medium. A supercritical state exists for a substance when the substance's temperature and pressure are above its critical point. When the pressure or temperature exceeds the critical state, the fluid is in its supercritical state.
  • the critical pressure and critical temperature of a fluid may be altered by combining it with another fluid, such as a diluent or anther monomer.
  • a supercritical polymerization medium is the state where the polymerization medium is present at a temperature above the critical temperature and critical pressure ofthe medium.
  • Tc critical temperatures
  • Pc critical pressures
  • the combined volume of monomer(s) and solvent/diluent comprises at least 50 wt % of neat monomer, preferably at least 60 vol% neat monomer, more preferably at least 70 vol%, more preferably at least 80 vol%, more preferably at least 90 vol%, more preferably at least 95 vol%.
  • optional comonomer, diluents or other fluids are present in the polymerization medium along with the monomer. Diluents, comonomers and other fluids each modify the media's critical point; and hence, alter the pressure-temperature regime within which a particular medium is in a supercritical state.
  • Diluents, comonomers and other fluids each also modify the phase behavior ofthe polymerization medium; and hence, alter the pressure- temperature regime within which a particular medium is single phased. Consequently, a two component reaction medium can have two phases above its critical point.
  • two-phase polymerization system or “two-phase polymerization medium” mean a system having two and, preferably, only two phases.
  • the two phases are referenced as a “first phase” and a “second phase.”
  • the first phase is or includes a "monomer phase,” which includes monomers and may also include solvent and some or all ofthe product of polymerization.
  • the monomer phase does not include the polymer product.
  • the monomer phase can be referred to as the "propylene phase.”
  • the second phase is or includes a solid phase, which may include products of polymerization, e.g., macromers and polymer product, but not monomers, e.g., propylene. None ofthe parts ofthe catalyst system are considered to be part ofthe polymerization system, although certain parts ofthe catalyst system can obviously be solid, e.g., supported catalysts. Furthermore, it is contemplated that parts ofthe catalyst system may be liquid or vapor or part ofthe vapor/liquid phase that exists in certain embodiments ofthe process.
  • Some embodiments select the temperature and pressure so that the polymer produced in the reaction and the reaction medium that solvates it remain single phased, i.e. above the reaction medium's cloud point with that polymer.
  • Other embodiments select the temperature and pressure so that the reaction medium remains supercritical, but at a pressure below the polymer's cloud point in the particular reaction medium. This results in a two phase reaction medium: a polymer rich phase and a polymer lean phase.
  • Some embodiments that are below the polymer's cloud point nonetheless operate above the polymer's crystallization temperature.
  • Preferred diluents for use in the present invention include one or more of C r C 24 alkanes, such as ethane, propane, n-butane, i-butane, n-pentane, i- pentane, n-hexane, toluene, cyclohexane, xylene, mixed hexanes and cyclopentane.
  • C r C 24 alkanes such as ethane, propane, n-butane, i-butane, n-pentane, i- pentane, n-hexane, toluene, cyclohexane, xylene, mixed hexanes and cyclopentane.
  • Some embodiments select a diluent from hydrocarbon diluents.
  • the diluent comprises one or more of ethane, propane, and isobutane.
  • Preferred diluents also include C 6 to C, 50 isoparaffins, preferably C 6 to C 100 isoparaffins, preferably C 6 to C 25 isoparaffins, more preferably C 8 to C 20 isoparaffins.
  • isoparaffm is meant that the paraffin chains possess C x to C 10 alkyl branching along at least a portion of each paraffin chain.
  • the isoparaffins are saturated aliphatic hydrocarbons whose molecules have at least one carbon atom bonded to at least three other carbon atoms or at least one side chain (i.e., a molecule having one or more tertiary or quaternary carbon atoms), and preferably wherein the total number of carbon atoms per molecule is in the range between 6 to 50, and between 10 and 24 in another embodiment, and from 10 to 15 in yet another embodiment. Narious isomers of each carbon number will typically be present.
  • the isoparaffins may also include cycloparaffins with branched side chains, generally as a minor component ofthe isoparaffin.
  • the density (ASTM 4052, 15.6/15.6°C) of these isoparaffins ranges from 0.70 to 0.83 g/cm 3 ; the pour point is -40°C or less, preferably -50°C or less, the viscosity (ASTM 445, 25°C) is from 0.5 to 20 cSt at 25°C; and the average molecular weights in the range of 100 to 300 g/mol.
  • Suitable isoparaffins are commercially available under the tradename ISOPAR (ExxonMobil Chemical Company, Houston TX), and are described in, for example, US 6,197,285, 3,818,105 and 3,439,088, and sold commercially as ISOPAR series of isoparaffins.
  • preferred diluents include C 5 to C 25 n- paraffins, preferably C 5 to C 20 n-paraffins, preferably C 5 to C, 5 n-paraffins having less than 0.1%, preferably less than 0.01% aromatics.
  • Suitable n-paraffins are commercially available under the tradename ⁇ ORPAR (ExxonMobil Chemical Company, Houston TX), and are sold commercially as ⁇ ORPAR series of n- paraffins.
  • preferred diluents include dearomaticized aliphatic hydrocarbon comprising a mixture of normal paraffins, isoparaffins and cycloparaffins.
  • C 4 to C 25 normal paraffins, isoparaffins and cycloparaffins preferably C 5 to C 18 , preferably C 5 to C 12 .
  • They contain very low levels of aromatic hydrocarbons, preferably less than 0.1, preferably less than 0.01 aromatics.
  • Suitable dearomatized aliphatic hydrocarbons are commercially available under the tradename EXXSOL (ExxonMobil Chemical Company, Houston TX), and are sold commercially as EXXSOL series of dearomaticized aliphatic hydrocarbons.
  • the diluent comprises up to 20 weight % of oligomers of C 6 to C 14 olefins and/or oligomers of linear olefins having 6 to 14 carbon atoms, more preferably 8 to 12 carbon atoms, more preferably 10 carbon atoms having a Kinematic viscosity of 10 or more (as measured by ASTM D 445) ; and preferably having a viscosity index ("NI"), as determined by ASTM D-2270 of 100 or more.
  • NI viscosity index
  • the diluent comprises up to 20 weight % of oligomers of C 20 to C 1500 paraffins, preferably C 4o to C 1000 paraffins, preferably C 50 to C 750 paraffins, preferably C 50 to C 500 paraffins.
  • the diluent comprises up to 20 weight % of oligomers of 1-pentene, 1-hexene, 1- heptene, 1-octene, 1-nonene, 1-decene, 1-undecene and 1-dodecene.
  • Such oligomers are commercially available as SHF and SuperSyn PAO's (ExxonMobil Chemical Company, Houston TX).
  • oligomers include those sold under the tradenames SynfluidTM available from ChevronPhillips Chemical Co. in Pasedena Texas, DurasynTM available from BP Amoco Chemicals in London England, ⁇ exbaseTM available from Fortum Oil and Gas in Finland, SyntonTM available from Crompton Corporation in Middlebury C ⁇ , USA, EMERYTM available from Cognis Corporation in Ohio, USA.
  • preferred monomers and diluents are those that are soluble in and inert to propylene and any other polymerization components at the polymerization temperatures and pressures.
  • This characteristic provides a lower pressure and temperature limit ⁇ the critical temperature and pressure ofthe reaction medium. Temperature and pressure are also constrained on tlie upper end.
  • the upper temperature range is the decomposition or ceiling temperature of polypropylene.
  • the following temperatures, in °C, are useful lower temperature limits for all invention processes: 130, 140, 150, 160, and 170.
  • the following temperatures, in °C, are useful upper temperature limits for all invention processes: 190, 210, 220, 230, 240, and 250.
  • the polymerization temperature is from 92 to 330°C, preferably 95 to 250°C, more preferably 100 to 200°C, more preferably 105 to 150°C, more preferably 120 to 160°C more preferably 120 to 140°C, more preferably 140 to 160°C.
  • pressure can go as high as can be commercially contained. More practically, pressure is limited by the desired properties ofthe resulting polypropylene.
  • the following pressures, in MPa are useful lower pressure limits for all invention processes: 4.62, 5, 10, 15, 30, 50, 60, 80, 100, 120, 140, 150, 160, 180, 200, 250, 260, 300, 330, 350, 400, 440, 500, and 600.
  • the following pressures, in MPa are useful upper pressure limits for all invention processes: 10, 15, 30, 50, 60, 80, 100, 120, 140, 150, 160, 180, 200, 250, 260, 300, 330, 350, 400, 440, 500, 600, and 1000 MPa.
  • the polymerization pressure is from 4.6 to 1000 MPa, preferably 15 to 500 MPa, more preferably 15 to 400 MPa, more preferably 15 to 300 MPa, more preferably 15 to 250 MPa, more preferably 15 to 200 MPa, more preferably 15 to 400 MPa, more preferably 15 to 190 MPa, more preferably 154.6 to 180 MPa, more preferably 15 to 170 MPa.
  • the lower limit in all ofthe above ranges is 20 MPa, rather than 15 MPa.
  • the lower limit in all ofthe above ranges is 25 MPa, rather than 15 MPa.
  • the lower limit in all ofthe above ranges is 30 MPa, rather than 15 MPa.
  • the lower limit in all ofthe above ranges is 40 MPa, rather than 15 MPa. In another embodiment the lower limit in all ofthe above ranges is 50 MPa, rather than 15 MPa. [0060] It is expected that any temperature range can be combined with any pressure range, provided that the chosen temperature and pressure are such that the reaction medium is above its cloud point ( or within 10 MPa ofthe cloud point). [0061] Temperatures above 140 °C and pressures between 100-150 MPa are particularly useful.
  • the process described herein can be used to polymerize any monomer having three or more carbon atoms.
  • Preferred monomers include propylene, butene, hexene, decene and octene.
  • the processes of this invention are used to polymerize any unsaturated monomer or monomers.
  • Preferred monomers include C 3 to C 100 olefins, preferably C 3 to C 60 olefins, preferably C 3 to C 40 olefins preferably C 3 to C 20 olefins, preferably C 3 to C 12 olefins.
  • preferred monomers include linear, branched or cyclic alpha-olefins, preferably C 3 to C 100 alpha-olefins, preferably C 3 to C 60 alpha-olefins, preferably C 3 to C 40 alpha- olefins preferably C 3 to C 20 alpha-olefins, preferably C 3 to C 12 alpha-olefins.
  • Preferred olefin monomers may be one or more of propylene, bute ⁇ e, pentene, hexene, heptene, octene, nonene, decene, dodecene, 4-methyl-pentene-l, 3 -methyl pentene-1, 3,5,5-trimethyl hexene 1, and 5-ethyl-l-nonene.
  • the polymer produced herein is a copolymer of one or more linear or branched C 3 to C 30 prochiral alpha-olefins or C 5 to C 30 ring containing olefins or combinations thereof capable of being polymerized by either stereospecific and non-stereospecific catalysts.
  • Prochiral refers to monomers that favor the formation of isotactic or syndiotactic polymer when polymerized using stereospecific catalyst(s).
  • Preferred monomers may also include aromatic-group-containing monomers containing up to 30 carbon atoms.
  • Suitable aromatic-group-containing monomers comprise at least one aromatic structure, preferably from one to three, more preferably a phenyl, indenyl, fluorenyl, or naphthyl moiety.
  • the aromatic- group-containing monomer further comprises at least one polymerizable double bond such that after polymerization, the aromatic structure will be pendant from the polymer backbone.
  • the aromatic-group containing monomer may further be substituted with one or more hydrocarbyl groups including but not limited to C, to C 10 alkyl groups. Additionally two adjacent substitutions may be joined to form a ring structure.
  • Preferred aromatic-group-containing monomers contain at least one aromatic structure appended to a polymerizable olefinic moiety. Particularly preferred aromatic monomers include styrene, alpha-methylstyrene, para- alkylstyrenes, vinyltoluenes, vinylnaphthalene, allyl benzene, and indene, especially styrene, paramethyl styrene, 4-phenyl-l-butene and allyl benzene. [0066] Non aromatic cyclic group containing monomers are also preferred.
  • Suitable non-aromatic cyclic group containing monomers preferably have at least one polymerizable olefinic group that is either pendant on the cyclic structure or is part ofthe cyclic structure.
  • the cyclic structure may also be further substituted by one or more hydrocarbyl groups such as, but not limited to, C j to C 10 alkyl groups.
  • Preferred non-aromatic cyclic group containing monomers include vinylcyclohexane, vinylcyclohexene, vinylnorbornene, ethylidene norbornene, cyclopentadiene, cyclopentene, cyclohexene, cyclobutene, vinyladamantane, norbornene, and the like.
  • Preferred diolefin monomers useful in this invention include any hydrocarbon structure, preferably C 4 to C 30 , having at least two unsaturated bonds, wherein at least two ofthe unsaturated bonds are readily incorporated into a polymer by either a stereospecific or a non-stereospecific catalyst(s).
  • the diolefin monomers be selected from alpha, omega-diene monomers (i.e. di-vinyl monomers). More preferably, the diolefin monomers are linear di-vinyl monomers, most preferably those containing from 4 to 30 carbon atoms.
  • Examples of preferred dienes include butadiene, pentadiene, hexadiene, heptadiene, octadiene, nonadiene, decadiene, undecadiene, dodecadiene, tridecadiene, tetradecadiene, pentadecadiene, hexadecadiene, heptadecadiene, octadecadiene, nonadecadiene, icosadiene, heneicosadiene, docosadiene, tricosadiene, tetracosadiene, pentacosadiene, hexacosadiene, heptacosadiene, octacosadiene, nonacosadiene, triacontadiene, particularly preferred dienes include 1,6-heptadiene, 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene
  • Preferred cyclic dienes include cyclopentadiene, vinylnorbomene, norbomadiene, ethylidene norbornene, divinylbenzene, dicyclopentadiene or higher ring containing diolefins with or without substituents at various ring positions.
  • Non-limiting examples of preferred polar unsaturated monomers include 6-nitro-l -hexene, N-methylallylamine, N-allylcyclopentylamine, N-allyl- hexylamine, methyl vinyl ketone, ethyl vinyl ketone, 5-hexen-2-one, 2-acetyl-5- norbornene, 7-syn methoxymethyl-5-norbomen-2-one, acrolein, 2,2-dimethyl-4- pentenal, undecylenic aldehyde, 2,4-dimethyl-2-6-heptadienal, acrylic acid, vinylacetic acid, 4-pentenoic acid, 2,2-dimethyl-4-pentenoic acid, 6-heptenoic acid, trans-2,4-pentadienoic acid, 2,6-heptadienoic acid, nona-fluoro-1 -hexene, allyl alcohol, 7-octene-l,2-diol, 2-
  • the processes described herein may be used to produce homopolymers or copolymers.
  • a copolymer may comprise two, three, four or more different monomer units.
  • Preferred polymers produced herein include homopolymers or copolymers of any ofthe above monomers.
  • the polymer is a homopolymer of any C 3 to C 12 alpha-olefin.
  • the polymer is a homopolymer of propylene.
  • the polymer is a copolymer comprising propylene and ethylene, preferably the copolymer comprises less than 40 weight % ethylene, more preferably less than 30 weight % ethylene, preferably the copolymer comprises less than 20 weight % ethylene, more preferably less than 10 weight % ethylene.
  • the polymer is a copolymer comprising propylene and one or more of any ofthe monomers listed above.
  • the copolymers comprises one or more diolefin comonomers, preferably one or more C 2 to C 40 diolefins.
  • the polymer produced herein is a copolymer of propylene and one or more C 2 or C 4 to C 20 linear, branched or cyclic monomers, preferably one or more C 2 or C 4 to C 12 linear, branched or cyclic alpha- olefins.
  • the polymer produced herein is a copolymer of propylene and one or more of ethylene, butene, pentene, hexene, heptene, octene, nonene, decene, dodecene, 4-methyl-pentene-l, 3-methyl pentene-1, and 3,5,5-trimethyl hexene 1.
  • the copolymers described herein comprise at least 50 mole% of a first monomer and up to 50 mole% of other monomers.
  • the polymer comprises: a first monomer present at from 40 to 95 mole %, preferably 50 to 90 mole %, preferably 60 to 80 mole %, and a comonomer present at from 5 to 40 mole %, preferably 10 to 60 mole %, more preferably 20 to 40 mole %,and a termonomer present at from 0 to 10 mole%, more preferably from 0.5 to 5 mole%, more preferably 1 to 3 mole %.
  • the first monomer comprises one or more of any C 3 to C 8 linear branched or cyclic alpha -olefins, including propylene, butene, (and all isomers thereof), pentene (and all isomers thereof), hexene (and all isomers thereof), heptene (and all isomers thereof), and octene (and all isomers thereof).
  • Preferred monomers include propylene, 1 -butene, 1 -hexene, 1 -octene, cyclohexene, cyclooctene, hexadiene, cyclohexadiene and the like.
  • the comonomer comprises one or more of any C 2 to C 40 linear, branched or cyclic alpha-olefins (provided ethylene, if present, is present at 5 mole% or less), including ethylene, propylene, butene, pentene, hexene, heptene, and octene, nonene, decene, undecene, dodecene, hexadecene, butadiene, hexadiene, heptadiene, pentadiene, octadiene, nonadiene, decadiene, dodecadiene, styrene, 3,5,5- trimethylhexene-1, 3-methylpentene-l, 4- methylpentene-1, cyclopentadiene, and cyclohexene.
  • C 2 to C 40 linear, branched or cyclic alpha-olefins provided ethylene, if present, is present at
  • the termonomer comprises one or more of any C 2 to C 40 linear, branched or cyclic alpha-olefins, (provided ethylene, if present, is present at 5 mole% or less), including ethylene, propylene, butene, pentene, hexene, heptene, and octene, nonene, decene, un-decene, do-decene, hexadecene, butadiene, hexadiene, heptadiene, pentadiene, octadiene, nonadiene, decadiene, dodecadiene, styrene, 3,5,5-trimethyl hexene-1, 3-methylpentene-l, 4- methylpentene-1, cyclopentadiene, and cyclohexene.
  • the polymers described above further comprise one or more dienes at up to 10 weight %, preferably at 0.00001 to 1.0 weight %, preferably 0.002 to 0.5 weight %, even more preferably 0.003 to 0.2 weight %, based upon the total weight ofthe composition.
  • 500 ppm or less of diene is added to the polymerization, preferably 400 ppm or less, preferably or 300 ppm or less.
  • at least 50 ppm of diene is added to the polymerization, or 100 ppm or more, or 150 ppm or more.
  • the processes describe herein are used to produce propylene copolymers with other monomer units, such as ethylene, other ⁇ -olefin, ⁇ -olefinic diolefin, or non-conjugated diolefin monomers, for example C 4 -C 20 olefins, C 4 -C 20 diolefins, C 4 -C 20 cyclic olefins, C 8 -C 20 styrenic olefins.
  • other monomer units such as ethylene, other ⁇ -olefin, ⁇ -olefinic diolefin, or non-conjugated diolefin monomers, for example C 4 -C 20 olefins, C 4 -C 20 diolefins, C 4 -C 20 cyclic olefins, C 8 -C 20 styrenic olefins.
  • Some invention embodiments limit the copolymerization of ⁇ -olefinic macromonomers to macromonomers with 2000 or less mer units.
  • United States Patent No. 6,300,451 discloses many useful comonomers. That disclosure refers to comonomers as "a second monomer”.
  • the following monomers can be copolymerized with propylene: ethylene, but-1- ene, hex- 1 -ene, 4-methylpent-l-ene, dicyclopentadiene, norbornene, C 4 -C 2000 , C 4 - C 20 o ; or C 4 -C 40 linear or branched, ⁇ , ⁇ -dienes; C 4 -C 2000 , C 4 -C 200j or C 4 -C 40 cyclic olefins; and C 4 -C 2000 , C 4 -C 200> or C 4 -C 40 linear or branched ⁇ -olefins.
  • reaction media that contain greater than 50 wt% of but-1-ene, pent-1-ene, or 3-methyl-but-l-ene.
  • these compounds can be freely mixed with each other and with propylene as monomer, bulk reaction media, or both.
  • a catalyst system comprising a single site type catalyst compounds in combination with an activator.
  • a catalyst system is defined to be the combination of at least one catalyst compound and at least one activator.
  • Catalyst compounds that may be used in the processes of this invention include any catalyst compound that can polymerize monomers under supercritical polymerization conditions. Such catalyst compounds typically do not decompose at polymerization temperatures.
  • the processes described herein can use any olefin polymerization catalyst capable of polymerizing propylene if that catalyst is sufficiently active under invention polymerization conditions.
  • ⁇ Group-3-10 transition metals can form suitable polymerization catalysts.
  • a suitable olefin polymerization catalyst will be able to coordinate to, or otherwise associate with, an alkenyl unsaturation.
  • Cp is a substituted or unsubstituted cyclopentadienyl ring, a substituted or unsubstituted indenyl ring or a substituted or unsubstituted fluorenyl ring;
  • Q is a heteroatom containing group; z is 0 or 1 ;
  • L is a bridging group connecting Cp to Q
  • X is a halogen or a substituted or unsubstituted hydrocarbyl group, a substituted or unsubstituted hydrocarboxy group, or a substituted or unsubstituted heteroatom containing group; and n is m minus 2.
  • RqSi- where each R is, independently, a substituted or unsubstituted C x to C 20 hydrocarbyl group and q is 1, 2, 3 or 4; and Q is a nitrogen containing group, preferably a hydrocarbyl group substituted with nitrogen.
  • the metallocene catalyst compound is represented by the formula II: L z (Cp) 2 M m X_ where: each Cp is independently a substituted or unsubstituted cyclopentadienyl ring, a substituted or unsubstituted indenyl ring or a substituted or unsubstituted fluorenyl ring; z is 0 or 1 ;
  • L is a bridging group connecting Cp to Cp
  • X is a halogen or a substituted or unsubstituted hydrocarbyl group, a substituted or unsubstituted hydrocarboxy group, or a substituted or unsubstituted heteroatom containing group; and n is m minus 2.
  • hydrocarbyl radical is sometimes used interchangeably with “hydrocarbyl” throughout this document.
  • hydrocarbyl radical encompasses C ⁇ -C 50 radicals. These radicals can be linear, branched, or cyclic including polycyclic. These radicals can be saturated, partially unsaturated or fully unsaturated, and when cyclic, may be aromatic or non- aromatic.
  • Substituted hydrocarbyl radicals are radicals in which at least one hydrogen atom has been replaced with a heteroatom or with at least one functional group such as NR" 2 , OR", PR" 2 , SR", BR" 2 , SiR" 3 , GeR” 3 and the like or where at least one non-hydrocarbon atom or group has been inserted within the hydrocarbyl radical, such as O, S, NR", PR", BR", SiR" 2 , GeR" 2 , and the like, where R" is independently a hydrocarbyl or halocarbyl radical.
  • the functional group can be an organometalloid radical.
  • Halocarbyl radicals are radicals in which one or more hydrocarbyl hydrogen atoms have been substituted with at least one halogen or halogen- containing group (e.g. F, Cl, Br, I).
  • Substituted halocarbyl radicals are radicals in which at least one hydrocarbyl hydrogen or halogen atom has been substituted with at least one functional group such as NR" 2 , OR", PR" 2 , SR", BR" 2 , SiR" 3 , GeR" 3 and the like or where at least one non-carbon atom or group has been inserted within the halocarbyl radical such as O, S, NR", PR", BR", SiR" 2 , GeR" 2 , and the like where R" is independently a hydrocarbyl or halocarbyl radical provided that at least one halogen atom remains on the original halocarbyl radical.
  • the functional group can be an organometalloid radical.
  • the hydrocarbyl radical is independently selected from methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl, triacontyl, ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, dec
  • Alkyl, alkenyl and alkynyl radicals listed include all isomers including where appropriate cyclic isomers, for example, butyl includes n-butyl, 2-methylpropyl, 1-methylpropyl, tert-butyl, and cyclobutyl (and analogous substituted cyclopropyls); pentyl includes n-pentyl, cyclopentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1- ethylpropyl, and neopentyl (and analogous substituted cyclobutyls and cyclopropyls); butenyl includes E and Z forms of 1-butenyl, 2-butenyl, 3-butenyl, 1 -methyl- 1-propenyl, l-methyl-2-pro ⁇ enyl, 2-methyl-
  • Cyclic compound having substitutions include all isomer forms, for example, methylphenyl would include ortho-methylphenyl, meta-methylphenyl and para-methylphenyl; dimethylphenyl would include 2,3-dimethylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6- diphenylmethyl, 3,4-dimethylphenyl , and 3,5-dimethylphenyl.
  • Preferred metallocene compounds include a group of suitable catalysts based on mono- or bis-cyclopentadiene. Useful compounds include transition metal compounds comprising extractable ligands described in U.S. Patent 5,198,401 and WO 92/00333. Syntheses of these compounds are well known from the published literature.
  • metallocene compounds with, or that can be alkylated to contain, at least one ligand abstractable to form catalytically active transition-metal cations appear in the patent literature, (e.g., EP-A-0 129 368, US patents 4,871,705, 4,937,299, 5,324,800, 5,470,993, 5,491,246, 5,512,693, EP-A- 0 418 044, EP-A-0 591 756, WO-A-92/00333, WO-A-94/01471 and WO 97/22635.) Such metallocenes can be described as mono- or biscyclopentadienyl-substituted Group-3, -4, -5, or -6 transition metals.
  • the transition metal ligands may themselves be substituted with one or more groups, and the ligands may bridge to each other or bridge through a heteroatom to the transition metal.
  • the cyclopentadienyl rings including substituted, cyclopentadienyl-based, fused-ring systems, such as indenyl, fluorenyl, azulenyl, or their substituted analogs
  • when bridged to each other are lower-alkyl substituted (C r C 6 ) in the 2 position (with or without a similar 4- position substituent in the fused ring) are useful.
  • the cyclopentadienyl rings may additionally comprise alkyl, cycloalkyl, aryl, alkylaryl, and arylalkyl substituents, the latter as linear, branched, or cyclic structures including multi-ring structures, for example, those of U.S. Patents 5,278,264 and 5,304,614.
  • substituents should each have essentially hydrocarbyl characteristics and will typically contain up to 30 carbon atoms, and may contain heteroatoms, such as 1 to 5 non-hydrogen or non-carbon atoms, e.g., N, S, O, P, Ge, B and Si.
  • a chemical entity is referred to as being substituted when at least one of its hydrogen atom has been replaced with a functional group or when at least one non-hydrocarbon atom or group has been inserted within it.
  • the following describe useful catalyst systems in invention processes US06365763, US06365764, US06369254, US06384144, US06388118, US06391989, US06391991, US06399533, US06403737, and US06410661.
  • Preferred metallocene catalyst compounds useful in this invention are represented by the formula:
  • L A L B L ci MDE where M is a Group-3-10 metal; L A is a substituted or unsubstituted, cyclopentadienyl or heterocyclopentadienyl ligand connected to M; and L B is a ligand as defined for LA, or is a heteroatom ligand connected to M. L A and L B may connect to each other through a Group-13-16-element-containing bridge.
  • L Ci is an optional, neutral, non-oxidizing ligand connected to M (i equals 0 to 3); and D and E are the same or different labile ligands, optionally bridged to each other, L A , or L B . Each of D and E are connected to M.
  • M select M to be a member ofthe Group-3-6 transition metals. Other embodiments select M to be a Group-4 transition metal. Some embodiments select M to be Ti, Zr, or Hf. L A and L B are sometimes called ancillary ligands because they are believed to help the metal center retain the correct electronic and geometric structure for olefin polymerizations.
  • Function typically constrains D and E in at least two ways: (1) upon activation, either the D-M or E-M connection breaks; and (2) monomer inserts between whichever of D-M or E-M remains. D and E are typically chosen to maximize these functions.
  • Cyclopentadienyl also encompasses fused-ring systems including but not limited to indenyl and fluorenyl radicals. Also, the use of heteroatom-containing rings or fused rings, where a non-carbon, Group- 13- 16 atom replaces a ring carbon is within the term "cyclopentadienyl" for this specification. See, for example, the background and illustrations of WO 98/37106, having priority with U.S. Ser. No. 08/999,214, filed 12/29/97, and WO 98/41530, having priority with U.S. Ser. No. 09/042,378, filed 3/13/98.
  • Substituted cyclopentadienyl structures can have one or more hydrogen atoms replaced by a hydrocarbyl, hydrocarbylsilyl, or similar heteroatom-containing structure.
  • Hydrocarbyl structures specifically include C,-C 30 linear, branched, and cyclic alkyl, and aromatic fused and pendant rings. These rings may also be substituted with ring structures.
  • Preferred metallocene catalyst compounds also include the mono- and biscyclopentadienyl compounds such as those listed and described in U.S. Patents 5,017,714, 5,324,800, and WO 92/00333 and EP-A-0 591 756.
  • Additional exemplary metallocene-type catalysts include those metallocene compounds represented by the formula:
  • M is selected from titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, or tungsten.
  • R and R are identical or different and are selected from hydrogen atoms, C,-C 10 alkyl groups, C,-C 10 alkoxy groups, C 6 -C 10 aryl groups, C 6 -C 10 aryloxy groups, C 2 - C 10 alkenyl groups, C 2 -C 40 alkenyl groups, C 7 -C 40 arylalkyl groups, C 7 -C 40 alkylaryl groups, C 8 -C 40 arylalkenyl groups, OH groups or halogen atoms; or conjugated dienes that are optionally substituted with one or more hydrocarbyl, tri(hydrocarbyl)silyl groups or hydrocarbyl, tri(hydrocarbyl)silylhydrocarbyl groups.
  • the conjugated diene can contain up to 30 atoms not counting hydrogen.
  • R 3 -R 12 are the same or different and are selected from hydrogen atoms, halogen atoms, Cj- o halogenated or unhalogenated alkyl groups, C 6 -C 10 halogenated or unhalogenated aryl groups, C 2 -C 10 halogenated or unhalogenated alkenyl groups, C 7 -C 40 halogenated or unhalogenated arylalkyl groups, C 7 -C 40 halogenated or unhalogenated alkylaryl groups, C 8 -C 40 halogenated or unhalogenated arylalkenyl groups, -NR' 2 , -SR', -OR , -OSiR' 3 or -PR' 2 radicals in which R' is one of a halogen atom, a C r C 10 alkyl group, or a C 6 -C 10 aryl group; or two or more adjacent
  • R 13 is selected from
  • R 14 , R 15 and R 16 are each independently selected from hydrogen, halogen, C,-C 20 alkyl groups, C 6 -C 30 aryl groups, C r C 20 alkoxy groups, C 2 -C 20 alkenyl groups, C 7 -C 40 arylalkyl groups, C 8 - C 40 arylalkenyl groups and C 7 -C 40 alkylaryl groups, or R 14 and R 15 , together with the atom(s) connecting them, form a ring; and M 3 is selected from carbon, silicon, germanium and tin.
  • R is represented by the formula:
  • R to R including R and R , together with the atoms connecting them form one or more rings;
  • M is carbon, silicon, germam ' um, or tin.
  • R , R ' R R and R can be identical or different and have the meanings stated for R 3 to R 7 .
  • dimethylsilyl(tetramethylcyclopentadienyl)(dodecylamido)titanium dichloride is used as a polymerization catalyst.
  • Mono-cyclopentadienyl-substituted metallocene catalyst compounds with excess MAO as the activator form a preferred catalyst system.
  • Some polymers produced by these systems may have different tacticities than those produced at lower temperatures and pressures.
  • Preferred catalyst compounds useful in this invention include: dimethylsiladiyl(2-methyl, 4-[3',5'-di-tbutylphenyl]indenyl) 2 zirconium dichloride; dimethylsiladiyl(2-ethyl, 4-[3',5'-di-tbutylphenyl]indenyl) 2 zirconium dichloride; dimethylsiladiyl(2-n-propyl, 4-[3',5'-di-tbutylphenyl]indenyl) 2 zirconium dichloride; dimethylsiladiyl(2-iso-propyl, 4-[3',5'-di-tbutylphenyl]indenyl) 2 zirconium dichloride; dimethylsiladiyl(2-n-butyl, 4-[3',5'-di-tbutylphenyl]indenyl) 2 zirconium dichlor
  • 1,3-butadiene dimethylsiladiyl(2-n-butyl, 4-[3',5'-di-tbutylphenyl]indenyl) 2 ⁇ 4 -l,4-diphenyl-l,3- butadiene; dimethylsiladiyl(2-iso-butyl, 4-[3',5'-di-tbutylphenyl]indenyl) 2 ⁇ 4 -l ,4-diphenyl-
  • scandium catalyst complexes may also be used in the processes of this invention with or without an activator, see
  • non-metallocene catalyst compounds such as bisamide catalyst compounds
  • Bisamide catalyst compounds are defined to be bidentate bisamide catalyst compounds, pyridine bisamide catalyst compounds, and amine bisamide catalyst compounds.
  • Bidentate bisamide catalyst compounds are those represented by the following formula:
  • M is Ti, Zr, or Hf.
  • R are the same or different alkyl, aryl, substituted alkyl, or substituted aryl radicals.
  • X are the same or different alkyl, aryl, or halide radicals. Substituted alkyls and aryls can be alkyl-, aryl-, and halo-substituted.
  • the bisamide catalyst compound is typically first chemically modified to transform X into an abstractable ligand. This can be done by alkylation, for example.
  • Pyridine bisamide catalyst compounds are those compounds that have the following formula:
  • M is Ti, Zr, or Hf.
  • R are the same or different alkyl, aryl, substituted alkyl, or substituted aryl radicals.
  • X are the same or different alkyl, aryl, or halide radicals. Substituted alkyls and aryls can be alkyl-, aryl-, and halo-substituted.
  • X is a halide
  • the pyridine bisamide catalyst compound is typically first chemically modified to transform X into an abstractable ligand. This can be done by alkylation, for example.
  • Amine bisamide catalyst compounds are also useful herein.
  • Amine bisamide catalyst compounds are those represented by the following formula:
  • M is Ti, Zr, or Hf.
  • R and R are the same or different alkyl, aryl, substituted alkyl, or substituted aryl radicals.
  • X are the same or different alkyl, aryl, or halide radicals. Substituted alkyl and aryls can be alkyl-, aryl-, and halo-substituted.
  • X is a halide
  • the amine bisamide catalyst compound must first be chemically modified to transform X into an abstractable ligand. This can be done by alkylation, for example.
  • Additional compounds are suitable as olefin polymerization catalysts for use in this invention.
  • Group-3-10 compounds that can be converted by ligand abstraction or bond scission into a cationic catalyst and stabilized in that state by a noncoordinating or weakly coordinating anion. That anion should be sufficiently labile to be displaced by an unsaturated monomer such as propylene.
  • Additional catalyst compounds that may be used herein include bisimide catalyst compounds represented by the formula:
  • M is a group 8,9,10, metal, preferably a group 10 metal, preferably Pd, Pt orNi;
  • n is the oxidation state of M and may be 2, 3, or 4;
  • each X is independently a halogen or a substituted or unsubstituted hydrocarbyl group, a substituted or unsubstituted hydrocarboxy group, or a substituted or unsubstituted heteroatom containing group;
  • y is 0 or 1 ;
  • R 1 is a heteroatom, a substituted C, to C 50 hydrocarbyl group or an unsubstituted
  • R 2 is a heteroatom, a substituted C x to C 50 hydrocarbyl group or an unsubstituted
  • R 3 is a heteroatom, a substituted Cj to C 50 hydrocarbyl group or an unsubstituted Cj to C 50 hydrocarbyl group, preferably a phenyl group;
  • R 4 is a heteroatom, a substituted Cj to C 50 hydrocarbyl group or an unsubstituted C j to C 50 hydrocarbyl group, preferably a phenyl group, where any adjacent R groups may form fused ring systems.
  • Exemplary compounds include those described in the patent literature. International patent publications WO 96/23010, WO 97/48735 and Gibson, et al., Chem. Comm., pp.
  • U.S. Patent 5,318,935 describes bridged and unbridged, bisamido catalyst compounds of Group-4 metals capable of ⁇ -olefins polymerization.
  • Bridged bis(arylamido)Group-4 compounds for olefin polymerization are described by D. H. McConville, et al., in Organometallics 1995, 14, 5478-5480. This reference presents synthetic methods and compound characterizations. Further work appearing in D. H. McConville, et al, Macromolecules 1996, 29, 5241-5243, describes bridged bis(arylamido)Group-4 compounds that are polymerization catalysts for 1 -hexene. Additional invention-suitable transition metal compounds include those described in WO 96/40805.
  • Cationic Group-3- or Lanthanide-metal olefin polymerization complexes are disclosed in copending U.S. Application Ser. No. 09/408,050, filed 29 September 1999.
  • a monoanionic bidentate ligand and two monoanionic ligands stabilize those catalyst compounds, which can be used herein.
  • the literature describes many additional suitable catalyst compound that can be used in this invention. See, for instance, N. C. Gibson, et al; "The Search for New-Generation Olefin Polymerization Catalysts: Life Beyond Metallocenes", Angew. Chem. Int. Ed, 38, 428-447 (1999).
  • the processes of this invention may be used with two or more catalyst compounds at the same time or in series.
  • two different catalyst compounds can be activated with the same or different activators and introduced into the polymerization system at the same or different times.
  • invention process can employ mixtures of catalyst compounds to select the properties that are desired from the polymer.
  • Mixed catalyst systems can be employed in invention processes to alter or select desired physical or molecular properties.
  • mixed catalyst systems can control the molecular weight distribution of isotactic polypropylene when used with the invention processes or for the invention polymers.
  • Mixed-catalyst systems can be used with the invention polymerization processes to tailor the composition distribution of copolymers with high catalyst productivity. These systems can also, optionally, be used with diene incorporation to facilitate long chain branching using mixed catalyst systems and high levels of vinyl terminated polymers.
  • two or more ofthe above catalysts compounds can be used together.
  • preferred catalyst combinations include any two or more of: ⁇ -dimethyl silylbis(-2-methyl, 4-phenylindenyl) zirconium dichloride, ⁇ -dimethyl silylbis(-2-methyl, 4-phenylindenyl) zirconium dimethyl,
  • 9-fluorenyl)hafhium dichloride 1 , 1 '-bis(4-triethylsilylphenyl)methylene-(cyclopentadienyl)(2,7-di-tertiary-butyl- 9-fluorenyl)hafhium dimethyl, dimethylsilyl(tetramethylcyclopentadienyl)(dodecylamido)titanium dimethyl, dimethylsilyl(tetramethylcyclopentadienyl)(dodecylamido)titanium dichloride, 1 , 1 '-bis(4-triethylsilylphenyl)methylene-(cyclopentadienyl)(2,7-di-tertiary-butyl- 9-fluorenyl)hafnium dichloride,
  • a particularly preferred combination includes dimethylsilyl(tetramethylcyclopentadienyl)(dodecylamido)titanium dichloride and ⁇ -dimethyl silylbis(-2-methyl, 4-phenylindenyl) zirconium dichloride.
  • Another particularly preferred combination includes dimethylsilyl(tetramethylcyclopentadienyl)(dodecylamido)titanium methyl and ⁇ - dimethyl silylbis(-2-methyl, 4-phenylindenyl) zirconium dimethyl.
  • Another particularly preferred combination includes 1, l'-bis(4- triethylsilylphenyl)methylene-(cyclopentadienyl)(2,7-di-tertiary-butyl-9- fluorenyl)hafhium dichloride and ⁇ -dimethyl silylbis(-2-methyl, 4-phenylindenyl) zirconium dichloride.
  • Another particularly preferred combination includes 1, 1'- bis(4-triethylsilylphenyl)methylene-(cyclopentadienyl)(2,7-di-tertiary-butyl-9- fluorenyl)hafhium dimethyl and ⁇ -dimethyl silylbis(-2-methyl, 4-phenylindenyl) zirconium dimethyl.
  • the catalyst compound is not dimethylmethenyl(flourenyl)(cyclopentadienyl)zirconium dichloride [Me 2 C(flu)(cp)ZrCl 2 ].
  • An activator is defined as any combination of reagents that increases the rate at which a metal complex polymerizes unsaturated monomers, such as olefins.
  • An activator may also affect the molecular weight, degree of branching, comonomer content, or other properties ofthe polymer.
  • one or more alumoxanes are utilized as an activator in the processes ofthe invention.
  • Alumoxanes sometimes called aluminoxanes in the art, are generally oligomeric compounds containing -A1(R)- O- subunits, where R is an alkyl group.
  • Examples of alumoxanes include methylalumoxane (MAO), modified methylalumoxane (MMAO), ethylalumoxane and isobutylalumoxane.
  • Alkylalumoxanes and modified alkylalumoxanes are suitable as catalyst activators, particularly when the abstractable ligand is a halide.
  • the activator is an alumoxane (modified or unmodified)
  • some embodiments select the maximum amount of activator at a 5000-fold molar excess Al/M over the catalyst compound (per metal catalytic site).
  • the minimum activator-to-catalyst-compound is typically a 1:1 molar ratio.
  • Alumoxanes may be produced by the hydrolysis ofthe respective trialkylaluminum compound.
  • MMAO may be produced by the hydrolysis of trimethylaluminum and a higher trialkylaluminum such as triisobutylaluminum. MMAO's are generally more soluble in aliphatic solvents and more stable during storage.
  • a visually clear methylalumoxane it may be preferable to use a visually clear methylalumoxane.
  • a cloudy or gelled alumoxane can be filtered to produce a clear solution or clear alumoxane can be decanted from the cloudy solution.
  • Another preferred alumoxane is a modified methyl alumoxane (MMAO) cocatalyst type 3 A (commercially available from Akzo Chemicals, Inc. under the trade name Modified Methylalumoxane type 3 A, covered under patent number US 5,041,584).
  • MMAO modified methyl alumoxane
  • Aluminum alkyl or organoaluminum compounds which may be utilized as activators (or scavengers) include trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n- octylaluminum and the like.
  • activators or scavengers
  • an ionizing or stoichiometric activator such as fri (n-butyl) ammonium tetrakis (pentafluorophenyl) boron, a trisperfluorophenyl boron metalloid precursor or a trisperfluoronaphtyl boron metalloid precursor, polyhalogenated heteroborane anions (WO 98/43983), boric acid (U.S. Patent No. 5,942,459) or combination thereof as an activator in the processes of this invention.
  • an ionizing or stoichiometric activator such as fri (n-butyl) ammonium tetrakis (pentafluorophenyl) boron, a trisperfluorophenyl boron metalloid precursor or a trisperfluoronaphtyl boron metalloid precursor, polyhalogenated heteroborane anions (WO 98/43983), boric acid (U.S. Patent No. 5,942,
  • neutral or ionic activators alone or in combination with alumoxane or modified alumoxane activators.
  • Examples of neutral stoichiometric activators include tri- substituted boron, tellurium, aluminum, gallium and indium or mixtures thereof.
  • the three substituent groups are each independently selected from alkyls, alkenyls, halogen, substituted alkyls, aryls, arylhalides, alkoxy and halides.
  • the three groups are independently selected from halogen, mono or multicyclic (including halosubstituted) aryls, alkyls, and alkenyl compounds and mixtures thereof, preferred are alkenyl groups having 1 to 20 carbon atoms, alkyl groups having 1 to 20 carbon atoms, alkoxy groups having 1 to 20 carbon atoms and aryl groups having 3 to 20 carbon atoms (including substituted aryls). More preferably, the three groups are alkyls having 1 to 4 carbon groups, phenyl, napthyl or mixtures thereof. Even more preferably, the three groups are halogenated, preferably fluorinated, aryl groups.
  • the neutral stoichiometric activator is trisperfluorophenyl boron or frisperfluoronapthyl boron.
  • Ionic stoichiometric activator compounds may contain an active proton, or some other cation associated with, but not coordinated to, or only loosely coordinated to, the remaining ion ofthe ionizing compound. Such compounds and the like are described in European publications EP-A-0 570 982, EP-A-0 520 732, EP-A-0 495 375, EP-B1-0 500 944, EP-A-0 277 003 and EP-A- 0 277 004, and U.S. Patent Nos. 5,153,157, 5,198,401, 5,066,741, 5,206,197, 5,241,025, 5,384,299 and 5,502,124 and U.S. Patent Application Serial No.
  • Preferred activators include a cation and an anion component, and may be represented by the following formula:
  • Wf + is a cation component having the charge f+
  • NCA " is a non-coordinating anion having the charge h- f is an integer from 1 to 3.
  • h is an integer from 1 to 3.
  • the cation component, (W ⁇ + ) may include Bronsted acids such as protons or protonated Lewis bases or reducible Lewis acids capable of protonating or abstracting a moiety, such as an akyl or aryl, from an analogous metallocene or Group 15 containing transition metal catalyst compound, resulting in a cationic transition metal species.
  • the activators include a cation and an anion component, and may be represented by the following formula:
  • LB is a neutral Lewis base
  • H is hydrogen
  • NCA is a non-coordinating anion having the charge h- f is an integer from 1 to 3
  • h is an integer from 1 to 3
  • ) may be a Bronsted acid, (LB-H f+ ), capable of donating a proton to the transition metal catalyst compound resulting in a transition metal cation, including ammoniums, oxoniums, phosphoniums, silyliums and mixtures thereof, preferably ammoniums of methylamine, aniline, dimethylamine, diethylamine, N-methylaniline, diphenylamine, trimethylamine, triethylamine, N,N-dimethylaniline, methyldiphenylamine, pyridine, p-bromo N,N-dimethylaniline, p-nitro-N,N-dimethylaniline, phosphoniums from triethylphosphine, triphenylphosphine, and diphenylphosphine, oxoniums from ethers such as dimethyl ether diethyl ether, tetrahydrofuran and dioxane, sulfoniums
  • the activating cation (W ⁇ + ) may also be an abstracting moiety such as silver, carboniums, tropylium, carbeniums, ferroceniums and mixtures, preferably carboniums and ferroceniums. Most preferably (W* + ) is triphenyl carbonium or N, N-dimethylanilinium.
  • the anion component includes those having the formula
  • each Q is a fluorinated hydrocarbyl group having 1 to 20 carbon atoms, more preferably each Q is a fluorinated aryl group, and most preferably each Q is a pentafluoryl aryl group.
  • NCA ⁇ also include diboron compounds as disclosed in U.S. Pat. No. 5,447,895, which is fully incorporated herein by reference.
  • Additional suitable anions are known in the art and will be suitable for use with the catalysts ofthe invention. See in particular, U.S. patent 5,278,119 and the review articles by S. H. Strauss, "The Search for Larger and More Weakly Coordinating Anions", Chem. Rev., 93, 921-942 (1993) and C. A. Reed, "Carboranes: A New Class of Weakly Coordinating Anions for Strong Elecfrophiles, Oxidants and Superacids", Ace. Chem. Res., 31, 133 -139 (1998).
  • the ionic stoichiometric activatoris N,N-dimethylanilinium tetra(perfluorophenyl)borate and/or triphenylcarbenium tetra(perfluorophenyl)borate.
  • an activation method using ionizing ionic compounds not containing an active proton but capable of producing an analogous metallocene catalyst cation and their non-coordinating anion are also contemplated, and are described in EP-A- 0 426 637, EP-A- 0 573 403 and U.S. Patent No. 5,387,568, which are all herein incorporated by reference.
  • NCA non-coordinating anion means an anion which either does not coordinate to said cation or which is only weakly coordinated to said cation thereby remaining sufficiently labile to be displaced by a neutral Lewis base.
  • Non-coordinating anions are those which are not degraded to neutrality when the initially formed complex decomposes.
  • Non-coordinating anions useful in accordance with this invention are those that are compatible, stabilize the metal cation in the sense of balancing its ionic charge, yet retain sufficient lability to permit displacement by an ethylenically or acetylenically unsaturated monomer during polymerization.
  • These types of cocatalysts sometimes use tri-isobutyl aluminum or tri-octyl aluminum as a scavenger.
  • invention process also can employ cocatalyst compounds or activator compounds that are initially neutral Lewis acids but form a cationic metal complex and a noncoordinating anion, or a zwitterionic complex upon reaction with the invention compounds.
  • tris(pentafluorophenyl) boron or aluminum act to abstract a hydrocarbyl or hydride ligand to yield an invention cationic metal complex and stabilizing noncoordinating anion, see EP- A-0 427 697 and EP-A-0 520 732 for illustrations of analogous Group-4 metallocene compounds.
  • EP-A-0 495 375 See the methods and compounds of EP-A-0 495 375.
  • Additional neutral Lewis-acids are known in the art and are suitable for abstracting formal anionic ligands. See in particular the review article by E. Y.-X. Chen and T.J. Marks, "Cocatalysts for Metal-Catalyzed Olefin ⁇
  • the catalyst compound does not contain at least one hydride or hydrocarbyl ligand but does contain at least one functional group ligand, such as chloride, amido or alkoxy ligands, and the functional group ligands are not capable of discrete ionizing abstraction with the ionizing, anion pre-cursor compounds, these functional group ligands can be converted via known alkylation reactions with organometallic compounds such as lithium or aluminum hydrides or alkyls, alkylalumoxanes, Grignard reagents, etc.
  • organometallic compounds such as lithium or aluminum hydrides or alkyls, alkylalumoxanes, Grignard reagents, etc.
  • EP-A-0 500 944, EP-Al-0 570 982 and EP-Al-0 612 768 for analogous processes describing the reaction of alkyl aluminum compounds with analogous dihalide substituted metallocene compounds prior to or with the addition of activating noncoordinating anion precursor compounds.
  • the catalyst-compound-to- activator molar ratio may be any ratio.
  • Combinations ofthe described activator compounds may also be used for activation. For example, tris(perfluorophenyl) boron can be used with methylalumoxane.
  • Activators are typically strong Lewis-acids which may play either the role of ionizing or non-ionizing activator. Activators previously described as ionizing activators may also be used as non-ionizing activators.
  • Abstraction of formal neutral ligands may be achieved with Lewis acids that display an affinity for the formal neutral ligands. These Lewis acids are typically unsaturated or weakly coordinated.
  • non-ionizing activators include R 10 (R ⁇ ) 3 , where R 10 is a group 13 element and R 11 is a hydrogen, a hydrocarbyl, a substituted hydrocarbyl, or a functional group. Typically, R 11 is an arene or a perfluorinated arene.
  • Non-ionizing activators also include weakly coordinated transition metal compounds such as low valent olefin complexes.
  • Non-limiting examples of non-ionizing activators include BMe 3 ,
  • Preferred non-ionizing activators include R 10 (R n ) 3 , where R 10 is a group 13 element and R 11 is a hydrogen, a hydrocarbyl, a substituted hydrocarbyl, or a functional group. Typically, R 11 is an arene or a perfluorinated arene.
  • More preferred non-ionizing activators include B(R 12 ) 3 , where R 12 is a an arene or a perfluorinated arene.
  • Even more preferred non-ionizing activators include B(C 6 H 5 ) 3 and B(C 6 F 5 ) 3 .
  • a particularly preferred non-ionizing activator is B(C 6 F 5 ) 3 .
  • More preferred activators are ionizing and non-ionizing activators based on perfluoroaryl borane and perfluoroaryl borates such as PhNMe 2 H + B(C 6 F 5 ) 4 ⁇ (C 6 H 5 ) 3 C + B(C 6 F 5 ) 4 " , and B(C 6 F 5 ) 3 .
  • Additional preferred activators that may be used with the catalysts compounds disclosed herein include those described in WO 03/064433 Al, which is incorporated by reference herein.
  • the catalyst compound(s) and the activator are combined in ratios of about 1000:1 to about 0.5:1.
  • the catalyst compounds and the activator are combined in a ratio of about 300:1 to about 1:1, preferably about 150:1 to about 1:1, for boranes, borates, aluminates, etc. the ratio is preferably about 1 :1 to about 10:1 and for alkyl aluminum compounds (such as diethylaluminum chloride combined with water) the ratio is preferably about 0.5:1 to about 10:1.
  • the ratio ofthe first catalyst to the second or additional catalyst is 5:95 to 95:5, preferably 25:75 to 75:25, even more preferably 40:60 to 60:40.
  • the combined catalyst compounds and the activator are combined in ratios of about 1 : 10,000 to about 1 : 1
  • the combined catalyst compounds and the activator are combined in ratios of 1 :1 to 100:1.
  • the combined catalyst compound-to-activator molar ratio is from 1:5000 to 10:1, alternatively from 1:1000 to 10:1; alternatively, 1:500 to 2:1; or 1 :300 to 1:1.
  • the combined catalyst compound-to-activator molar ratio is from 10:1 to 1:10; 5:1 to 1:5; 2:1 to 1:2; or 1.2:1 to 1:1.
  • Multiple activators may be used, including using mixtures of alumoxanes or aluminum alkyls with ionizing activators.
  • the catalyst compositions of this invention include a support material or carrier.
  • the one or more catalyst components and/or one or more activators may be deposited on, contacted with, vaporized with, bonded to, or incorporated within, adsorbed or absorbed in, or on, one or more supports or carriers.
  • the support material is any ofthe conventional support materials.
  • the supported material is a porous support material, for example, talc, inorganic oxides and inorganic chlorides.
  • Other support materials include resinous support materials such as polystyrene, functionalized or crosslinked organic supports, such as polystyrene divinyl benzene polyolefins or polymeric compounds, zeolites, clays, or any other organic or inorganic support material and the like, or mixtures thereof.
  • the preferred support materials are inorganic oxides that include those Group 2, 3, 4, 5, 13 or 14 metal oxides.
  • the preferred supports include silica, which may or may not be dehydrated, fumed silica, alumina (WO 99/60033), silica-alumina and mixtures thereof.
  • Other useful supports include magnesia, titania, zirconia, magnesium chloride (U.S. Patent No. 5,965,477), montmorillonite (European Patent EP-B1 0 511 665), phyllosilicate, zeolites, talc, clays (U.S. Patent No. 6,034,187) and the like.
  • support materials may be used, for example, silica-chromium, silica-alumina, silica-titania and the like.
  • Additional support materials may include those porous acrylic polymers described in EP 0 767 184 BI, which is incorporated herein by reference.
  • Other support materials include nanocomposites as described in PCT WO 99/47598, aerogels as described in WO 99/48605, spherulites as described in U.S. Patent No. 5,972,510 and polymeric beads as described in WO 99/50311, which are all herein incorporated by reference.
  • the support material most preferably an inorganic oxide, has a surface area in the range of from about 10 to about 700 m ⁇ /g, pore volume in the range of from about 0 to about 4.0 cc/g and average particle size in the range of from about 0.02 to about 50 ⁇ m. More preferably, the surface area ofthe support material is in the range of from about 50 to about 500 n_2/g, pore volume of from about 0 to about 3.5 cc/g and average particle size of from about 0.02 to about 20 ⁇ m. Most preferably the surface area ofthe support material is in the range is from about 100 to about 400 m ⁇ /g, pore volume from about 0 to about 3.0 cc/g and average particle size is from about 0.02 to about 10 ⁇ m.
  • Non-porous supports may also be used as supports in the processes described herein.
  • the nonporous, fumed silica supports described in US 6590055 can be used in the practice of this invention.
  • Additional useful activators for use in the processes of this invention include clays that have been treated with acids (such as H 2 SO 4 ) and then combined with metal alkyls (such as triethylaluminum) as described in US 6,531,552 and EP 1 160 261 Al, which is incorporated by reference herein.
  • Preferred activators include that may also be supports include ion- exchange layered silicate having an acid site of at most -8.2 pKa, the amount ofthe acid site is equivalent to at least 0.05 mmol/g of 2,6-dimethylpyridine consumed for neutralization.
  • Preferred examples include chemically treated smectite group silicates, acid-treated smectite group silicates.
  • ion-exchange layered silicates having a 1:1 type structure or a 2:1 type structure as described in "Clay Minerals (Nendo Kobutsu Gaku)" written by Haruo Shiramizu (published by Asakura Shoten in 1995).
  • Examples of an ion-exchange layered silicate comprising the 1 : 1 layer as the main constituting layer include kaolin group silicates such as dickite, nacrite, kaolinite, metahalloysite, halloysite or the like, and serpentine group silicates such as chrysotile, lizaldite, antigorite or the like.
  • ion-exchange layered silicates comprising the 2:2 layer as the main constituting layer
  • ion- exchange layered silicates comprising the 2:2 layer as the main constituting layer
  • smectite group silicates such as montmorillonite, beidellite, nontronite, saponite, hectorite, stephensite or the like
  • vermiculite group silicates such as vermiculite or the like
  • mica group silicates such as mica, illite, sericite, glauconite or the like
  • attapulgite sepiolite, palygorskite, bentonite, pyrophyllite, talc, chlorites and the like.
  • the clays are contacted with an acid, a salt, an alkali, an oxidizing agent, a reducing agent or a treating agent containing a compound intercalatable between layers of an ion-exchange layered silicate.
  • the intercalation means to introduce other material between layers of a layered material, and the material to be introduced is called as a guest compound.
  • acid treatment or salt treatment is particularly preferable.
  • the treated clay may then be contacted with an activator compound, such as TEAL, and the catalyst compound to polymerize olefins.
  • the polymerization system comprises less than 5 weight % polar species, preferably less than 4 weight %, more preferably less than 3 weight %, more preferably less than 2 weight %, more preferably less than 1 weight %, more preferably less than 1000 ppm, more preferably less than 750 ppm, more preferably less than 500 ppm, more preferably less than 250 ppm, more preferably less than 100 ppm, more preferably less than 50 ppm, more preferably less than 10 ppm.
  • Polar species include oxygen containing compounds (except for alumoxanes) such as alcohols, oxygen, ketones, aldehydes, acids, esters and ethers.
  • the polymerization system comprises less than 5 weight % trimethylaluminum and/or triethylaluminum, preferably less than 4 weight %, more preferably less than 3 weight %, more preferably less than 2 weight %, more preferably less than 1 weight %, more preferably less than 1000 ppm, more preferably less than 750 ppm, more preferably less than 500 ppm, more preferably less than 250 ppm, more preferably less than 100 ppm, more preferably less than 50 ppm, more preferably less than 10 ppm.
  • the polymerization system comprises methylalumoxane and less than 5 weight % trimethylaluminum and or triethylaluminum, preferably less than 4 weight %, more preferably less than 3 weight %, more preferably less than 2 weight %, more preferably less than 1 weight %, more preferably less than 1000 ppm, more preferably less than 750 ppm, more preferably less than 500 ppm, more preferably less than 250 ppm, more preferably less than 100 ppm, more preferably less than 50 ppm, more preferably less than 10 ppm.
  • Preferred invention processes can use finely divided, supported catalysts to prepare propylene/1 -hexene copolymers with greater than 1.0 mole % hex- 1 -ene.
  • invention processes can use fumed silica supports in which the support particle diameter can range from 200 angstroms to 1500 angstroms, small enough to form a colloid with reaction media.
  • This invention relates to processes to polymerize olefins comprising contacting one or more olefins having at least three carbon atoms with a catalyst compound and an activator at in a supercritical polymerization medium in a reactor.
  • a catalyst compound and an activator may be delivered as a solution or slurry, either separately to the reactor, activated in-line just prior to the reactor, or preactivated and pumped as an activated solution or slurry to the reactor.
  • a preferred operation is two solutions activated in-line.
  • Polymerizations are carried out in either single reactor operation, in which monomer, comonomers, catalyst/activator, scavenger, and optional modifiers are added continuously to a single reactor or in series reactor operation, in which the above components are added to each of two or more reactors connected in series.
  • the catalyst components can be added to the first reactor in the series.
  • the catalyst component may also be added to both reactors, with one component being added to first reaction and another component to other reactors.
  • invention methods also cover polymerization of propylene in high- pressure reactors where, preferably, the reactor is substantially unreactive with the polymerization reaction components and is able to withstand the high pressures and temperatures that occur during the polymerization reaction.
  • reactors are known as high-pressure reactors for purposes of this disclosure. Withstanding these high pressures and temperatures will allow the reactor to maintain the propylene under supercritical conditions.
  • Suitable reaction vessels include those known in the art to maintain supercritical or other high-pressure ethylene polymerization reactions. Suitable reactors are selected from autoclave, tubular, and autoclave/tubular reactors, among others.
  • autoclave reactors typically have length-to- diameter ratios of 1 : 1 to 20: 1 and are fitted with a high-speed (up to 1500 RPM) multiblade stirrer.
  • Autoclave pressures are typically greater than 6 MPa with a maximum of typically less than 260 MPa.
  • the autoclave has a low length- to-diameter ratio (such as less than 4) propylene and other monomers are typically injected at only one position. But injection at two or more positions in the autoclave is also possible. For instance, in reactors where the length-to-diameter ratio is around 4-20, the reactor can contain up to six different injection positions.
  • one or more lateral fixing devices support the high-speed stirrer. These fixing devices can also divide the autoclave into two or more zones. Mixing blades on the stirrer can differ from zone to zone to allow for plug flow or back mixing, largely independently, in the separate zones. Two or more autoclaves with one or more zones can connect in series to tailor polymer structure.
  • Tubular reactors are also well suited for use in this invention, preferably tubular reactors capable of operating up to about 350MPa.
  • Preferred tubular reactors are fitted with external cooling and one or more injection points along the (tubular) reaction zone. As in autoclaves, these injection points serve as entry points for monomers (such as propylene), one or more comonomer, catalyst, or mixtures of these.
  • external cooling allows for increased monomer conversion relative to an autoclave, where the low surface-to-volume ratio hinders any significant heat removal.
  • Tubular reactors have a special outlet valve that can send a pressure Shockwave backward along the tube. The Shockwave helps dislodge any polymer residue that has formed on reactor walls during operation. Another way of addressing wall deposits is to fabricate the tube with smooth, unpolished internal surfaces.
  • Preferred tubular reactors can operate at pressures up to 360 MPa and preferably have lengths of 100-2000 meters and internal diameters usually less than 10 cm.
  • Reactor trains that pair autoclaves with tubular reactors can also serve in invention processes.
  • the autoclave typically precedes the tubular reactor.
  • Such systems may have injection of additional catalyst and/or feed components at several points in the autoclave and more particularly along the tube length.
  • feeds are preferably room temperature or below to provide maximum polymer production within the limits of maximum operating temperature.
  • a preheater operates at startup, but not after the reaction reaches steady state if the first mixing zone has some back-mixing characteristics.
  • tubular reactors the first section of double-jacketed tubing is heated rather than cooled and is operated continuously since a tubular reactor is by nature plug flow.
  • catalyst can not only be injected at the inlet, but also optionally at one or more points along the reactor. The catalyst feeds injected at the inlet and other injection points can be the same or different in terms of content, density, concentration, etc.
  • the downstream vessel contains a polymer-rich phase and a polymer-lean phase. Typically, conditions in this vessel remain supercritical and temperature remains above the polymer product's crystallization temperature.
  • HPS high pressure separator
  • polymerizations based on propylene alternative choices are open to the design relative to classic high pressure polyethylene process technology.
  • the temperature in this vessel will be maintained above the polymer product's crystallization point but the pressure may be below the critical point.
  • the pressure need only be high enough that the propylene can be condensed against standard cooling water.
  • the liquid recycle stream can then be recycled to the reactor with a liquid pumping system instead ofthe hyper-compressors required for polyethylene units.
  • the relatively low pressure in this separator will reduce the monomer concentration in the liquid polymer phase which will result in a much lower polymerization rate.
  • This polymerization rate may be low enough to operate this system without adding a catalyst poison or "killer". If a catalyst killer is required (e.g., to prevent reactions in the high pressure recycle) then provision must be made to remove any potential catalyst poisons from the recycled propylene rich monomer stream e.g. by the use of fixed bed adsorbents or by scavenging with an aluminum alkyl.
  • the HPS may be operated over propylene's critical pressure but within the propylene/polypropylene two phase region. This is the economically preferred method if polypropylene is to be produced with a revamped HPPE plant.
  • the recycled HPS overhead is cooled and dewaxed before being returned to the suction ofthe secondary compressor, which is typical of HPPE plant operation.
  • the polymer from this intermediate or high pressure vessel will then go through another pressure reduction step to a low pressure separator.
  • the temperature of this vessel will be maintained above the polymer melting point so that the polymer from this vessel can be fed as a liquid directly to an extruder or static mixer.
  • the pressure in this vessel will be kept low by using a compressor to recover the unreacted monomers, etc to the condenser and pumping system referenced above.
  • loop-type reactors are useful in this invention.
  • monomer enters and polymer exits continuously at different points along the loop, while an in-line pump continuously circulates the contents (reaction liquid).
  • the feed/product takeoff rates control total average residence time.
  • a cooling jacket removes reaction heat from the loop.
  • United States Patent No. 6,355,741 discusses a reactor with at least two loops that is useful in the practice of this invention provided that one or both operate at the supercritical conditions.
  • United States Patent No. 5,326,835 describes a process said to produce polymer in a bimodal fashion.
  • This process's first reactor stage is a loop reactor in which polymerization occurs in an inert, low-boiling hydrocarbon. After the loop reactor, the reaction medium transits into a gas-phase reactor where gas-phase polymerization occurs. Since two very different environments create the polymer, it shows a bimodal molecular weight distribution.
  • This two stage procedure can be modified to work with the procedure ofthe instant application. For instance, a first stage loop reactor can use propylene as the monomer and a propylene-based reaction medium as the inert low-boiling hydrocarbon.
  • PCT publication WO 19/14766 describes a process comprising the steps of (a) continuously feeding olefinic monomer and a catalyst system, with a metallocene component and a cocatalyst component, to the reactor; (b) continuously polymerizing that monomer in a polymerization zone reactor under elevated pressure; (c) continuously removing the polymer/monomer mixture from the reactor; (d) continuously separating monomer from molten polymer; (e) reducing pressure to form a monomer-rich and a polymer-rich phase; and (f) separating monomer from the reactor.
  • the polymerization zoning technique described in the above process can be practiced using the instant invention's process conditions. That is, the above process is suitable for use with this invention provided at least one polymerization zone makes the propylene or the reaction media containing propylene supercritical.
  • feed inlet temperatures are generally at or below room temperature to provide cooling to the exothermic reaction in the reactor operating above the crystallization temperature ofthe polymer product.
  • the reactor temperature will be above 145°C.
  • the processes described herein may have residence times as short as 0.5 seconds and as long as several hours.
  • the residence times are from 1 second to 30 minutes, preferably 5 seconds to 10 minutes, more preferably from 10 seconds to 5 minutes, more preferably from 10 seconds to 3 minutes.
  • the residence time can be selected from 10, 30, 45, 50, 60, 120, and 150 seconds.
  • Maximum residence times can be selected from 200, 300, 400, 500, or 600 seconds.
  • invention processes choose residence times of from 30-600 seconds; more particularly 45-400 or 60- 300 seconds.
  • invention processes choose residence times of from 30 sec to 1 hour; more particularly 30 sec to 30 minutes; 45-400, or 60-300 sec.
  • the polymerization of propylene the residence times are up to 5 minutes.
  • invention processes produce polymer at a rate of 560-10000 LB/w-Ft 2 . More particularly, production rates can range from 560-2000 or 600-1500.
  • Catalyst productivities range from 828 to 5940 kg PP/kg catalyst * hr. These high levels of catalyst productivity may result in low residual solids in the polymer product. Residual solid amount of less than 0.5 wt%, particularly less than 0.3 wt%, or more particularly less than 0.1 wt% total solids residue are preferred.
  • the reactor effluent is depressurized to an intermediate pressure significantly below the cloud point pressure but nevertheless supercritical for that composition. This allows separation of a polymer rich phase for further purification and a propylene rich phase for recycle compression back to the reactor.
  • This separation is carried out in a vessel known as a high pressure separator (HPS). Since this vessel also has a significant residence time, the catalyst activity is killed by addition of a polar species such as water, alcohol or sodium/calcium stearate.
  • a polar species such as water, alcohol or sodium/calcium stearate.
  • the choice and quantity of killing agent will depend on the requirements for clean up ofthe recycle propylene and comonomers as well as the product properties, if the killing agent has low volatility.
  • the intermediate separation can be done at pressures well below the critical point so that the monomer concentration and therefore reactivity in the high pressure separator is relatively low.
  • the relatively small amount of continued polymerization in this vessel may not be a problem so addition of catalyst deactivating compounds as is done in PE processes may be avoided presuming that no undesired reactions occur in the high or intermediate pressure recycle system. If no killing compounds are added then the killer removal step can be eliminated.
  • Propylene is available commercially at two levels of purity - polymer grade at 99.5% and chemical grade at about 93 to 95%.
  • the choice of feed will set the level of purge required from the recycle to avoid over dilution of the feed by inert propane.
  • propane in the reactor and HPS will raise the pressure ofthe cloud point curve for a given temperature but will decrease the polymerization efficiency due to a decrease in propylene (and other olefin) concentrations in the reactor.
  • the elevation of cloud point pressure due to propane will widen the operating window ofthe HPS.
  • copolymerizations of propylene with limited amounts of ethylene a similar effect in raising the cloud point pressure will be noted due to the presence of low levels of ethylene in the HPS.
  • the LPS rurining at just above atmospheric pressure is just a simple sub critical flash of light components, reactants and oligomers thereof, for the sole purpose of producing a low volatile containing polymer melt entering the finishing extmder or static mixer.
  • This invention also relates to a propylene polymer having a 1 ,3 regio defect population of greater than 5 per 10,000 monomer units, a melting point of 145°C or more, and a g' of 0.97 or less and an Mw greater than 20,000.
  • This invention also relates to a propylene polymer having a 1 ,3 regio defect population of greater than 5 per 10,000 monomer units, a melting point of 70°C or more (preferably 145°C or more), and a g' of 0.97 or more and an
  • This invention also relates to copolymer comprising propylene an a comonomer having a 1,3 regio defect population of greater than 5 per 10,000 monomer units, a melting point of 70°C or more (preferably 145°C or more), and a g' of 0.97 or less and an Mw greater than 10,000.
  • the polymers produced by invention processes may be in any structures including block, linear, radial, star, branched, and combinations of these.
  • Some invention embodiments produce polypropylene and copolymers of polypropylene with a unique microstructure.
  • the process ofthe invention can be practiced such that novel isotactic and syndiotactic compositions are made.
  • the invention processes make crystalline polymers.
  • the processes ofthe invention produce propylene polymers with a melting point of 70 to 165°C, and a weight-average molecular weight of 2,000 to
  • the process of this invention produce polymers having an Hf of up to 110 J/g, preferably 50 to 110
  • the processes described herein can produce polymers having little or no ash or residue from catalyst or supports.
  • the polymers produced herein comprise less than 1 weight % silica, preferably less than 0.1 weight % silica, preferably less than 100 ppm silica, preferably less than
  • Dienes can be used as a comonomer to increase the molecular weight ofthe resulting polymer and to create long chain branching.
  • Vinyl chloride can be used as a comonomer to increase the degree of vinyl termination in the polymer.
  • invention processes can produce long-chain-branched polypropylene. Long-chain branching is achievable using invention process regardless of whether additional , ⁇ -diene or other diene such as vinylnorbomene are used. In a preferred embodiment, less than 0.5 wt% diene is used.
  • the present invention involves using as a comonomer an ⁇ , ⁇ -diene and the olefin/ ⁇ , ⁇ -diene copolymers resulting from that use. Additionally, the present invention involves a copolymerization reaction of olefin monomers, wherein the reaction includes propylene and ethylene copolymerization with an ⁇ , ⁇ -diene and the copolymers that are made. These copolymers may be employed in a variety of articles including, for example, films, fibers, such as spunbonded and melt blown fibers, fabrics, such as nonwoven fabrics, and molded articles.
  • these articles include, for example, cast films, oriented filnis, injection molded articles, blow molded articles, foamed articles, foam laminates and thermoformed articles.
  • linear ⁇ , ⁇ -dienes are preferred, other dienes can also be employed to make polymers of this invention. These would include branched, substituted ⁇ , ⁇ -dienes, such as 2-methyl-l,9-decadiene; cyclic dienes, such as vinylnorbomene; or aromatic types, such as divinyl benzene.
  • Embodiments ofthe present invention include copolymers having from 98 to 99.999 weight percent olefin units, and from 0.001 to 2.000 weight percent ⁇ , ⁇ -diene units.
  • Copolymer embodiments may have a weight-average molecular weight from 50,000 to 2,000,000, crystallization temperatures from 50 °C to 140 °C and a melt flow rate (MFR) from 0.1 dg/min to 1500 dg/min. Note that the these embodiments display high crystallization temperatures intrinsically; there is no need for externally added nucleating agents.
  • the copolymer includes from 90 to 99.999 weight percent of propylene units, from 0.000 to 8 weight percent of olefin units other than propylene units and from 0.001 to 2 weight percent ⁇ , ⁇ -diene units.
  • Copolymer embodiments may have weight-average molecular weights from 20,000 to 2,000,000, crystallization temperatures (without the addition of external nucleating agents) from 115 °C to 135 °C and MFRs from 0.1 dg/min to 100 dg/min.
  • the accompanying olefin may be any of C 2 -C 20 ⁇ -olefins, diolefins (with one internal olefin) and their mixtures thereof.
  • olefins include ethylene, butene- 1, pentene- 1, hexene- 1, heptene- 1, 4-methyl-l -pentene, 3- methyl- 1 -pentene, 4-methy 1-1 -hexene, 5-methyl-l -hexene, 1 -octene, 1 -decene, 1- undecene, and 1 -dodecene.
  • Copolymers of isotactic polypropylene made under supercritical conditions include ethylene and C 4 -C 12 comonomers such as but- 1 -ene, 3- methylpent-1-ene, hex- 1 -ene, 4-methylpent-l-ene, and oct- 1 -ene. Invention process can prepare these copolymers without the use of solvent or in an environment with low solvent concentration.
  • the polymers have a residual solid amount of less than 0.5 wt%, particularly less than 0.3 wt%, or more particularly less than 0.1 wt% total solids residue are preferred.
  • Preferred propylene polymers produced typically comprise 0 to 50 weight % of a comonomer, preferably 1 to 40 weight %, preferably 2 to 30 weight
  • % preferably 4 to 20 weight %, preferably 5 to 15 weight %, preferably 5 to 10 weight %, and have one or more of:
  • a heat of fusion of 30 J/g or more preferably 50 J/g or more, preferably 60 or more, preferably 70 or more, preferably 80 or more, preferably 90 or more, preferably 95 or more, preferably 100 or more, preferably 105 or more OR an Hf of 30 J/g or less, more preferably 20 J/g or less preferably 0;
  • a weight average molecular weight (as measured by GPC DRI) of 20,000 or more, preferably 50,000 to 2,000,000, preferably 100,000 to 1,000,000, preferably 150,000 to 900,000, preferably 200,000 to 800,000;
  • melt flow rate of 0.5 dg/min or more, preferably 0.7 dg/min or more, preferably 1.0 dg/min or more, preferably between 0.1 and 1500 dg/min;
  • %X percent crystallinity
  • the polymers produced herein have a melt viscosity of less than 10,000 centipoises at 180 °C as measured on a Brookfield viscometer, preferably between 1000 to 3000 cps for some embodiments (such as packaging and adhesives) and preferably between 5000 and 10,000 for other applications.
  • the polymer produced by this invention may be blended with one or more other polymers, including but not limited to, thermoplastic polymer(s) and/or elastomer(s).
  • thermoplastic polymer(s) is a polymer that can be melted by heat and then cooled with out appreciable change in properties.
  • Thermoplastic polymers typically include, but are not limited to, polyolefins, polyamides, polyesters, polycarbonates, polysulfones, polyacetals, polylactones, acrylonitrile- butadiene-styrene resins, polyphenylene oxide, polyphenylene sulfide, styrene- acrylonitrile resins, styrene maleic anhydride, polyimides, aromatic polyketones, or mixtures of two or more ofthe above.
  • Preferred polyolefins include, but are not limited to, polymers comprising one or more linear, branched or cyclic C 2 to C 40 olefins, preferably polymers comprising propylene copolymerized with one or more C 2 or C 4 to C 40 olefins, preferably a C 3 to C 20 alpha olefin, more preferably C 3 to C 10 ⁇ -olefins. More preferred polyolefins include, but are not limited to, polymers comprising ethylene including but not limited to ethylene copolymerized with a C 3 to C 40 olefin, preferably a C 3 to C 20 alpha olefin, more preferably propylene and or butene.
  • Elastomers encompass all natural and synthetic rubbers, including those defined in ASTM D1566).
  • the polymer produced by this invention is combined with one or more of isotactic polypropylene, highly isotactic polypropylene, syndiotactic polypropylene, random copolymer of propylene and ethylene and/or butene and/or hexene, polybutene, ethylene vinyl acetate, low density polyethylene (density 0.915 to less than 0.935 g/cm 3 ) linear low density polyethylene, ultra low density polyethylene (density 0.86 to less than 0.90 g/cm 3 ), very low density polyethylene (density 0.90 to less than 0.915 g/cm 3 ), medium density polyethylene (density 0.935 to less than 0.945 g/cm 3 ), high density polyethylene (density 0.945 to 0.98 g/cm 3 ), ethylene vinyl acetate, ethylene methyl acrylate, copolymers of acrylic acid, polymethylmethacrylate or any other polymers
  • elastomers are blended with the polymer produced by this invention to form rubber toughened compositions.
  • the rabber toughened composition is a two (or more) phase system where the elastomer is a discontinuous phase and the polymer produced by this invention is a continuous phase.
  • This blend may be combined with tackifiers and/or other additives as described herein.
  • the polymer produced by this invention may be blended with elastomers or other soft polymers to form impact copolymers.
  • the blend is a two (or more) phase system where the elastomer or soft polymer is a discontinuous phase and the polymer produced by this invention is a continuous phase.
  • This blend may be combined with tackifiers and/or other additives as described herein.
  • the polymers ofthe invention described above are combined with metallocene polyethylenes (mPEs) or metallocene polypropylenes (mPPs).
  • mPEs metallocene polyethylenes
  • mPPs metallocene polypropylenes
  • the mPE and mPP homopolymers or copolymers are typically produced using mono- or bis-cyclopentadienyl transition metal catalysts in combination with an activator of alumoxane and/or a non-coordinating anion in solution, slurry, high pressure or gas phase.
  • the catalyst and activator may be supported or unsupported and the cyclopentadienyl rings by may substituted or unsubstituted.
  • the polymer of this invention is present in the above blends, at from 10 to 99 weight %, based upon the weight ofthe polymers in the blend, preferably 20 to 95 weight %, even more preferably at least 30 to 90 weight %, even more preferably at least 40 to 90 weight %, even more preferably at least 50 to 90 weight %, even more preferably at least 60 to 90 weight %, even more preferably at least 70 to 90 weight %.
  • the blends described above may be produced by (a) mixing the polymers ofthe invention with one or more polymers (as described above), by (b) connecting reactors together in series to make in situ reactor blends or by (c) using more than one catalyst in the same reactor to produce multiple species of polymers.
  • the polymers can be mixed together prior to being put into the extruder or may be mixed in an extruder.
  • any ofthe above polymers may be functionalized.
  • Functionalized means that the polymer has been contacted with an unsaturated acid or anhydride.
  • Preferred unsaturated acids or anhydrides include any unsaturated organic compound containing at least one double bond and at least one carbonyl group.
  • Representative acids include carboxylic acids, anhydrides, esters and their salts, both metallic and non-metallic.
  • the unsaturated acid or anhydride is preferably present at about 0.1 weight % to about 5 weight %, preferably at about 0.5 weight % to about 4 weight %, even more preferably at about 1 to about 3 weight %, based upon the weight ofthe hydrocarbon resin and the unsaturated acid or anhydride.
  • Tackifiers may be blended with the polymers of this invention and/or with blends ofthe polymer produced by this inventions (as described above).
  • useful tackifiers include, but are not limited to, aliphatic hydrocarbon resins, aromatic modified aliphatic hydrocarbon resins, hydrogenated polycyclopentadiene resins, polycyclopentadiene resins, gum rosins, gum rosin esters, wood rosins, wood rosin esters, tall oil rosins, tall oil rosin esters, polyterpenes, aromatic modified polyterpenes, terpene phenolics, aromatic modified hydrogenated polycyclopentadiene resins, hydrogenated aliphatic resin, hydrogenated aliphatic aromatic resins, hydrogenated terpenes and modified terpenes, and hydrogenated rosin esters.
  • the tackifier is hydrogenated. In other embodiments the tackifier is non-polar. (Non-polar tackifiers are substantially free of monomers having polar groups. Preferably the polar groups are not present; however, if present, they are preferably not present at more that 5 weight %, preferably not more that 2 weight %, even more preferably no more than 0.5 weight %.) In some embodiments the tackifier has a sof ening point (Ring and Ball, as measured by ASTM E-28) of 80 °C to 140 °C, preferably 100 °C to 130 °C. In some embodiments the tackifier is functionalized.
  • unsaturated acids or anhydrides include any unsaturated organic compound containing at least one double bond and at least one carbonyl group.
  • Representative acids include carboxylic acids, anhydrides, esters and their salts, both metallic and non-metallic.
  • the unsaturated acid or anhydride is preferably present at about 0.1 weight % to about 10 weight %, preferably at about 0.5 weight % to about 7 weight %, even more preferably at about 1 to about 4 weight %, based upon the weight ofthe hydrocarbon resin and the unsaturated acid or anhydride.
  • the tackifier if present, is typically present at about 1 weight % to about 50 weight %, based upon the weight ofthe blend, more preferably 10 weight % to 40 weight %, even more preferably 20 weight % to 40 weight %. Preferably however, tackifier is not present, or if present, is present at less than 10 weight %, preferably less than 5 weight %, more preferably at less than 1 weight %.
  • the polymers of this invention, and/or blends thereof further comprise a crosslinking agent.
  • Preferred crosslinking agents include those having functional groups that can react with the acid or anhydride group.
  • crosslinking agents include alcohols, multiols, amines, diamines and/or triamines.
  • crosslinking agents useful in this invention include polyamines such as ethylenediamine, diethylenetriamine, hexamethylenediamine, diethylaminopropylamine, and/or menthanediamine.
  • the polymers of this invention, and/or blends thereof further comprise typical additives known in the art such as fillers, cavitating agents, antioxidants, surfactants, adjuvants, plasticizers, block, antiblock, color masterbatches, pigments, dyes, processing aids, UN stabilizers, neutralizers, lubricants, waxes, and/or nucleating agents.
  • the additives may be present in the typically effective amounts well known in the art, such as 0.001 weight % to 10 weight %.
  • Preferred fillers, cavitating agents and/or nucleating agents include titanium dioxide, calcium carbonate, barium sulfate, silica, silicon dioxide, carbon black, sand, glass beads, mineral aggregates, talc, clay and the like.
  • Preferred antioxidants include phenolic antioxidants, such as
  • oils include paraffinic or naphthenic oils such as Primol 352, or Primol 876 available from ExxonMobil Chemical France, S.A. in Paris, France. [00223] More preferred oils include aliphatic naphthenic oils, white oils or the like.
  • Preferred plasticizers and/or adjuvants include mineral oils, polybutenes, phthalates and the like.
  • Particularly preferred plasticizers include phthalates such as diisoundecyl phthalate (DIUP), diisononylphthalate (DI ⁇ P), dioctylphthalates (DOP) and polybutenes, such as Parapol 950 and Parapol 1300 available from ExxonMobil Chemical Company in Houston Texas.
  • Additional Preferred plasticizers include those disclosed in WO0118109 A 1 and USS ⁇ 10/640,435, which are incorporated by reference herein.
  • Preferred processing aids, lubricants, waxes, and/or oils include low molecular weight products such as wax, oil or low Mn polymer, (low meaning below Mn of 5000, preferably below 4000, more preferably below 3000, even more preferably below 2500).
  • Preferred waxes include polar or non-polar waxes, functionalized waxes, polypropylene waxes, polyethylene waxes, and wax modifiers.
  • Preferred waxes include ESCOMERTM 101.
  • Preferred functionalized waxes include those modified with an alcohol, an acid, or a ketone. Functionalized means that the polymer has been contacted with an unsaturated acid or anhydride.
  • Preferred unsaturated acids or anhydrides include any unsaturated organic compound containing at least one double bond and at least one carbonyl group.
  • Representative acids include carboxylic acids, anhydrides, esters and their salts, both metallic and non-metallic.
  • Examples include maleic, fumaric, acrylic, methacrylic, itaconic, crotonic, alpha-methyl crotonic, and cinnamic acids as well as their anhydrides, esters and salt derivatives.
  • Maleic anhydride is particularly preferred.
  • the unsaturated acid or anhydride is preferably present at about 0.1 weight % to about 10 weight %, preferably at about 0.5 weight % to about 7 weight %, even more preferably at about 1 to about 4 weight %, based upon the weight ofthe hydrocarbon resin and the unsaturated acid or anhydride.
  • Preferred examples include waxes modified by methyl ketone, maleic anhydride or maleic acid.
  • Preferred low Mn polymers include polymers of lower alpha olefins such as propylene, butene, pentene, hexene and the like.
  • a particularly preferred polymer includes polybutene having an Mn of less than 1000.
  • PARAPOLT 950 is an liquid polybutene polymer having an Mn of 950 and a kinematic viscosity of 220cSt at 100 °C, as measured by ASTM D 445.
  • Preferred UN stabilizers and or antioxidants include Irganox 1010 and the like.
  • polymers of this invention (and blends thereof as described above) whether formed in situ or by physical blending are preferably used in any known thermoplastic or elastomer application. Examples include uses in molded parts, films, tapes, sheets, tubing, hose, sheeting, wire and cable coating, adhesives, shoesoles, bumpers, gaskets, bellows, films, fibers, elastic fibers, nonwovens, spunbonds, sealants, surgical gowns and medical devices.
  • the polymers of this invention or blends thereof can be used as adhesives, either alone or combined with tackifiers.
  • the tackifier is typically present at about 1 weight % to about 50 weight %, based upon the weight ofthe , blend, more preferably 10 weight % to 40 weight %, even more preferably 20 weight % to 40 weight %.
  • Other additives, as described above, may be added also.
  • the adhesives of this invention can be used in any adhesive application, including but not limited to, disposables, packaging, laminates, pressure sensitive adhesives, tapes labels, wood binding, paper binding, nonwovens, road marking, reflective coatings, and the like.
  • the adhesives of this invention can be used for disposable diaper and napkin chassis constmction, elastic attachment in disposable goods converting, packaging, labeling, bookbinding, woodworking, and other assembly applications.
  • Particularly preferred applications include: baby diaper leg elastic, diaper frontal tape, diaper standing leg cuff, diaper chassis construction, diaper core stabilization, diaper liquid transfer layer, diaper outer cover lamination, diaper elastic cuff lamination, feminine napkin core stabilization, feminine napkin adhesive strip, industrial filtration bonding, industrial filter material lamination, filter mask lamination, surgical gown lamination, surgical drape lamination, and perishable products packaging.
  • Preferred substrates include wood, paper, cardboard, plastic, thermoplastic, rabber, metal, metal foil (such as aluminum foil and tin foil), metallized surfaces, cloth, non-wovens (particularly polypropylene spun bonded fibers or non- wovens), spunbonded fibers, cardboard, stone, plaster, glass (including silicon oxide (SiO x )coatings applied by evaporating silicon oxide onto a film surface), foam, rock, ceramics, films, polymer foams (such as polyurethane foam), substrates coated with inks, dyes, pigments, PNDC and the like or combinations thereof.
  • metal foil such as aluminum foil and tin foil
  • metallized surfaces cloth, non-wovens (particularly polypropylene spun bonded fibers or non- wovens), spunbonded fibers, cardboard, stone, plaster, glass (including silicon oxide (SiO x )coatings applied by evaporating silicon oxide onto a film surface), foam, rock, ceramics, films, polymer foams (such as polyurethan
  • Additional preferred substrates include polyethylene, polypropylene, poly acrylates, acrylics, polyethylene terephthalate, or any ofthe polymers listed above as suitable for blends.
  • Corona treatment, electron beam irradiation, gamma irradiation, microwave or silanization may modify any ofthe above substrates.
  • the polymer produced by this invention described above and the blends thereof may be formed into monolayer or multilayer films.
  • These films may be formed by any ofthe conventional techniques known in the art including extrasion, co-extrusion, extrusion coating, lamination, blowing, tenter frame, and casting.
  • the film may be obtained by the flat film or tubular process, which may be followed by orientation in an uniaxial direction, or in two mutually perpendicular directions in the plane ofthe film.
  • One or more ofthe layers ofthe film may be oriented in the transverse and/or longitudinal directions to the same or different extents. This orientation may occur before or after the individual layers are brought together.
  • a polyethylene layer can be extrasion coated or laminated onto an oriented polypropylene layer or the polyethylene and polypropylene can be coextruded together into a film then oriented.
  • oriented polypropylene could be laminated to oriented polyethylene or oriented polyethylene could be coated onto polypropylene then optionally the combination could be oriented even further.
  • the films are oriented in the Machine Direction (MD) at a ratio of up to 15, preferably between 5 and 7, and in the Transverse Direction (TD) at a ratio of up to 15 preferably 7 to 9.
  • MD Machine Direction
  • TD Transverse Direction
  • the film is oriented to the same extent in both the MD and TD directions.
  • the layer comprising the polymer composition of this invention may be combined with one or more other layers.
  • the other layer(s) may be any layer typically included in multilayer film structures.
  • the other layer or layers may be: 1 • Polyolefins.
  • Preferred polyolefins include homopolymers or copolymers of C 2 to C 40 olefins, preferably C 2 to C 20 olefins, preferably a copolymer of an ⁇ -olefin and another olefin or . ⁇ -olefin (ethylene is defined to be an ⁇ - olefin for purposes of this invention).
  • homopolyethylene, homopolypropylene, propylene copolymerized with ethylene and or butene, ethylene copolymerized with one or more of propylene, butene or hexene, and optional dienes Preferred examples include thermoplastic polymers such as ultra low density polyethylene, very low density polyethylene, linear low density polyethylene, low density polyethylene, medium density polyethylene, high density polyethylene, polypropylene, isotactic polypropylene, highly isotactic polypropylene, syndiotactic polypropylene, random copolymer of propylene and ethylene and/or butene and/or hexene, elastomers such as ethylene propylene rabber, ethylene propylene diene monomer rabber, neoprene, and blends of thermoplastic polymers and elastomers, such as for example, thermoplastic elastomers and rabber toughened plastics.
  • thermoplastic polymers such as ultra low density polyethylene
  • Polar polymers include homopolymers and copolymers of esters, amides, acrylates, anhydrides, copolymers of a C 2 to C 20 olefin, such as ethylene and/or propylene and/or butene with one or more polar monomers such as acetates, anhydrides, esters, alcohol, and or acrylics.
  • Preferred examples include polyesters, polyamides, ethylene vinyl acetate copolymers, and polyvinyl chloride.
  • Cationic polymers include polymers or copolymers of geminally disubstituted olefins, alpha-heteroatom olefins and/or styrenic monomers.
  • Preferred geminally disubstituted olefins include isobutylene, isopentene, isoheptene, isohexane, isooctene, isodecene, and isododecene.
  • Preferred ⁇ -heteroatom olefins include vinyl ether and vinyl carbazole
  • preferred styrenic monomers include styrene, alkyl styrene, para-alkyl styrene, alpha-methyl styrene, chloro-styrene, and brorno-para-methyl styrene.
  • Preferred examples of cationic polymers include butyl rabber, isobutylene copolymerized with para methyl styrene, polystyrene, and poly- ⁇ -methyl styrene. 4. Miscellaneous.
  • Other preferred layers can be paper, wood, cardboard, metal, metal foils (such as aluminum foil and tin foil), metallized surfaces, glass (including silicon oxide (SiO.x)coatings applied by evaporating silicon oxide onto a film surface), fabric, spunbonded fibers, and non- wovens (particularly polypropylene spun bonded fibers or non- wovens), and substrates coated with inks, dyes, pigments, PNDC and the like.
  • the films may vary in thickness depending on the intended application, however films of a thickness from 1 to 250 ⁇ m are usually suitable. Films intended for packaging are usually from 10 to 60 ⁇ m thick. The thickness ofthe sealing layer is typically 0.2 to 50 ⁇ m.
  • Additives such as block, antiblock, antioxidants, pigments, fillers, processing aids, UN stabilizers, neutralizers, lubricants, surfactants and/or nucleating agents may also be present in one or more than one layer in the films.
  • Preferred additives include silicon dioxide, titanium dioxide, polydimethylsiloxane, talc, dyes, wax, calcium stearate, carbon black, low molecular weight resins and glass beads.
  • one or more layers may be modified by corona treatment, electron beam irradiation, gamma irradiation, or microwave.
  • the films described herein may also comprise from 5 to 60 weight %, based upon the weight ofthe polymer and the resin, of a hydrocarbon resin.
  • the resin may be combined with the polymer ofthe seal layer(s) or may be combined with the polymer in the core layer(s).
  • the resin preferably has a softening point above 100°C, even more preferably from 130 to 180°C.
  • Preferred hydrocarbon resins include those described above.
  • the films comprising a hydrocarbon resin may be oriented in uniaxial or biaxial directions to the same or different degrees. [00233]
  • the films described above may be used as stretch and/or cling films.
  • Stretch/cling films are used in various bundling, packaging and palletizing operations.
  • tackifying additives include polybutenes, terpene resins, alkali metal stearates and hydrogenated rosins and rosin esters.
  • the well-known physical process referred to as corona discharge can also modify the cling properties of a film.
  • Some polymers (such as ethylene methyl acrylate copolymers) do not need cling additives and can be used as cling layers without tackifiers.
  • Stretch/clings films may comprise a slip layer comprising any suitable polyolefin or combination of polyolefins such as polyethylene, polypropylene, copolymers of ethylene and propylene, and polymers obtained from ethylene and/or propylene copolymerized with minor amounts of other olefins, particularly C 4 -C 12 olefins.
  • suitable polypropylene is normally solid and isotactic, i.e., greater than 90% hot heptane insolubles, having wide ranging melt flow rates of from about 0.1 to about 300 g/10 min.
  • the slip layer may include one or more anti-cling (slip and/or antiblock) additives, which may be added during the production ofthe polyolefin or subsequently blended in to improve the slip properties of this layer.
  • anti-cling additives are well-known in the art and include, for example, silicas, silicates, diatomaceous earths, talcs and various lubricants. These additives are preferably utilized in amounts ranging from about 100 ppm to about 20,000 ppm, more preferably between about 500 ppm to about 10,000 ppm, by weight based upon the weight ofthe slip layer.
  • the slip layer may, if desired, also include one or more other additives as described above [00234] Polymers produced herein can be used for nonwovens, sealing layers, oriented polypropylene, and high-clarity thermoforming.
  • Polymer made under supercritical conditions herein are useful for melt blown and spun bond fabrics.
  • Invention processes can be used for making PP for spun bonded (SB) and melt blown (MB) fibers.
  • Typical invention polymers have ash levels below 1000, 900, 700, 500, 400, 300, 200, 100, 50, 10, 1, 0.5, or 0.1 ppm. Some embodiments have ash levels of 1-500 ppb. All these characteristics combine to reduce polymer build-up on the die exits. These products can have high MFRs from 300-5000 useful for fiber applications.
  • polypropylene waxes from invention polymers and processes.
  • Some invention embodiments are isotactic polypropylene waxes. As such these materials are well suited for viscosity modification in adhesives, as carriers for inks, and other applications.
  • Some polypropylene waxes embodiments select melt viscosities of from 3-2000 cP at 180 °C.
  • Some invention embodiments produce syndiotactic polypropylene waxes.
  • Invention process can prepare long chain branched isotactic- polypropylene at high monomer conversion (35+% and especially 45+%) conditions. Some embodiments use higher amounts of diluent to promote long chain branching.
  • Laminates comprising invention polymers can be used as a thermoformable sheet where the substrate is either sprayed or injection molded to couple it with the ionomer/tie-layer laminate sheet.
  • the composite is formed into the desired shape to make the article, or composite article.
  • Narious types of substrate materials form highly desirable articles.
  • the laminate can be used with plastic substrates such as homopolymers, copolymers, foams, impact copolymers, random copolymers, and other applications.
  • plastic substrates such as homopolymers, copolymers, foams, impact copolymers, random copolymers, and other applications.
  • some articles in which the present invention can be incorporated are the following: vehicle parts, especially exterior parts such as bumpers and grills, rocker panels, fenders, doors, hoods, trim, and other parts can be made from the laminates , composites and methods ofthe invention.
  • the polypropylene copolymers described herein are suitable for applications such as molded articles, including injection and blow molded bottles and molded items used in automotive articles, such as automotive interior and exterior trims. Examples of other methods and applications for making polypropylene polymers and for which polypropylene polymers may be useful are described in the Encyclopedia of Chemical Technology, by Kirk-Otbmer, Fourth Edition, vol. 17, at pages 748-819, which are incorporated by reference herein. In those instances where the application is for molded articles, the molded articles may include a variety of molded parts, particularly molded parts related to and used in the automotive industry such as, for example, bumpers, side panels, floor mats, dashboards and instrument panels.
  • Foamed articles are another application and examples where foamed plastics, such as foamed polypropylene, are useful may be found in Encyclopedia of Chemical Technology, by Kirk-Otbmer, Fourth Edition, vol. 11, at pages 730-783, which are incorporated by reference herein. Foamed articles are particularly useful for constmction and automotive applications. Examples of constmction applications include heat and sound insulation, industrial and home appliances, and packaging. Examples of automotive applications include interior and exterior automotive parts, such as bumper guards, dashboards and interior liners.
  • the poly olefinic compositions ofthe present invention are suitable for such articles as automotive components, wire and cable jacketing, pipes, agricultural films, geomembranes, toys, sporting equipment, medical devices, casting and blowing of packaging films, extrasion of tubing, pipes and profiles, sporting equipment, outdoor furniture (e.g., garden furniture) and playground equipment, boat and water craft components, and other such articles.
  • the compositions are suitable for automotive components such as bumpers, grills, trim parts, dashboards and instrument panels, exterior door and hood components, spoiler, wind screen, hub caps, mirror housing, body panel, protective side molding, and other interior and external components associated with automobiles, tracks, boats, and other vehicles.
  • Other useful articles and goods may be formed economically by the practice of our invention including: crates, containers, packaging, labware, such as roller bottles for culture growth and media bottles, office floor mats, instrumentation sample holders and sample windows; liquid storage containers such as bags, pouches, and bottles for storage and IN infusion of blood or solutions; packaging material including those for any medical device or drags including unit-dose or other blister or bubble pack as well as for wrapping or containing food preserved by irradiation.
  • Other useful items include medical tubing and valves for any medical device including infusion kits, catheters, and respiratory therapy, as well as packaging materials for medical devices or food which is irradiated including trays, as well as stored liquid, particularly water, milk, or juice, containers including unit servings and bulk storage containers as well as transfer means such as tubing, pipes, and such.
  • the polymers described above may also be used to prepare the molded products of this invention in any molding process, including but not limited to, injection molding, gas-assisted injection molding, extrasion blow molding, injection blow molding, injection stretch blow molding, compression molding, rotational molding, foam molding, thermoforming, sheet extrasion, and profile extrasion.
  • the molding processes are well known to those of ordinary skill in the art.
  • the compositions described herein may be shaped into desirable end use articles by any suitable means known in the art.
  • Thermoforming, vacuum forming, blow molding, rotational molding, slush molding, transfer molding, wet lay-up or contact molding, cast molding, cold forming matched-die molding, injection molding, spray techniques, profile co-extrusion, or combinations thereof are typically used methods.
  • Thermoforming is a process of forming at least one pliable plastic sheet into a desired shape.
  • An embodiment of a thermoforming sequence is described, however this should not be constmed as limiting the thermoforming methods useful with the compositions of this invention.
  • First, an extradate film of the composition of this invention (and any other layers or materials) is placed on a shuttle rack to hold it during heating.
  • the shuttle rack indexes into the oven which pre-heats the film before forming. Once the film is heated, the shuttle rack indexes back to the forming tool.
  • the film is then vacuumed onto the forming tool to hold it in place and the forming tool is closed.
  • the forming tool can be either "male” or "female” type tools.
  • thermoforming is accomplished by vacuum, positive air pressure, plug-assisted vacuum forming, or combinations and variations of these, once the sheet of material reaches thermoforming temperatures, typically of from 140°C to 185°C or higher.
  • thermoforming temperatures typically of from 140°C to 185°C or higher.
  • a pre-stretched bubble step is used, especially on large parts, to improve material distribution.
  • an articulating rack lifts the heated laminate towards a male forming tool, assisted by the application of a vacuum from orifices in the male forming tool. Once the laminate is firmly formed about the male forming tool, the thermoformed shaped laminate is then cooled, typically by blowers.
  • Plug-assisted forming is generally used for small, deep drawn parts. Plug material, design, and timing can be critical to optimization ofthe process. Plugs made from insulating foam avoid premature quenching of the plastic.
  • the plug shape is usually similar to the mold cavity, but smaller and without part detail. A round plug bottom will usually promote even material distribution and uniform side-wall thickness. For a semicrystalline polymer such as polypropylene, fast plug speeds generally provide the best material distribution in the part.
  • the shaped laminate is then cooled in the mold. Sufficient cooling to maintain a mold temperature of 30°C to 65°C is desirable. The part is below 90 °C to 100 °C before ejection in one embodiment. For the good behavior in thermoforming, the lowest melt flow rate polymers are desirable. The shaped laminate is then trimmed of excess laminate material.
  • Blow molding is another suitable forming means, which includes injection blow molding, multi-layer blow molding, extrasion blow molding, and stretch blow molding, and is especially suitable for substantially closed or hollow objects, such as, for example, gas tanks and other fluid containers.
  • Blow molding is described in more detail in, for example, CONCISE ENCYCLOPEDIA OF POLYMER SCIENCE AND ENGINEERING 90-92 (Jacqueline I. Kroschwitz, ed., John Wiley & Sons 1990).
  • profile co-extmsion can be used.
  • the profile co-extrusion process parameters are as above for the blow molding process, except the die temperatures (dual zone top and bottom) range from 150°C - 235°C, the feed blocks are from 90°C - 250°C, and the water cooling tank temperatures are from 10°C - 40°C.
  • One embodiment of an injection molding process is described as follows. The shaped laminate is placed into the injection molding tool. The mold is closed and the substrate material is injected into the mold. The substrate material has a melt temperature between 200°C and 300°C in one embodiment, and from 215°C and 250 °C and is injected into the mold at an injection speed of between 2 and 10 seconds.
  • molded articles may be fabricated by injecting molten polymer into a mold that shapes and solidifies the molten polymer into desirable geometry and thickness of molded articles.
  • Sheet may be made either by extruding a substantially flat profile from a die, onto a chill roll, or alternatively by calendaring. Sheet will generally be considered to have a thickness of from 10 mils to 100 mils (254 ⁇ m to 2540 ⁇ m), although sheet may be substantially thicker.
  • Tubing or pipe may be obtained by profile extrasion for uses in medical, potable water, land drainage applications or the like. The profile extrasion process involves the extrusion of molten polymer through a die. The extruded tubing or pipe is then solidified by chill water or cooling air into a continuous extruded articles.
  • the tubing will generally be in the range of from 0.31 cm to 2.54 cm in outside diameter, and have a wall thickness of in the range of from 254 ⁇ m to 0.5 cm.
  • the pipe will generally be in the range of from 2.54 cm to 254 cm in outside diameter, and have a wall thickness of in the range of from 0.5 cm to 15 cm.
  • Sheet made from the products of an embodiment of a version ofthe present invention may be used to form containers. Such containers may be formed by thermoforming, solid phase pressure forming, stamping and other shaping techniques. Sheets may also be formed to cover floors or walls or other surfaces.
  • the oven temperature is between 160°C and 195°C, the time in the oven between 10 and 20 seconds, and the die temperature, typically a male die, between 10°C and 71°C.
  • the final thickness ofthe cooled (room temperature), shaped laminate is from 10 ⁇ m to 6000 ⁇ m in one embodiment, from 200 ⁇ m to 6000 ⁇ m in another embodiment, and from 250 ⁇ m to 3000 ⁇ m in yet another embodiment, and from 500 ⁇ m to 1550 ⁇ m in yet another embodiment, a desirable range being any combination of any upper thickness limit with any lower thickness limit.
  • the melt temperature ofthe substrate material is between 230°C and 255°C in one embodiment, and between 235°C and 250°C in another embodiment, the fill time from 2 to 10 seconds in one embodiment, from 2 to 8 seconds in another embodiment, and a tool temperature of from 25°C to 65°C in one embodiment, and from 27°C and 60°C in another embodiment.
  • the substrate material is at a temperature that is hot enough to melt any tie-layer material or backing layer to achieve adhesion between the layers.
  • the compositions of this invention may be secured to a substrate material using a blow molding operation.
  • Blow molding is particularly useful in such applications as for making closed articles such as fuel tanks and other fluid containers, playground equipment, outdoor furniture and small enclosed structures.
  • Compositions of this invention are extmded through a multi-layer head, followed by placement ofthe uncooled laminate into a parison in the mold.
  • the mold with either male or female patterns inside, is then closed and air is blown into the mold to form the part.
  • the polymers described above may also be used to prepare the nonwoven fabrics and fibers of this invention in any nonwoven fabric and fiber making process, including but not limited to, melt blowing, spunbonding, film aperturing, and staple fiber carding.
  • a continuous filament process may also be used.
  • a spunbonding process is used.
  • the spunbonding process is well known in the art. Generally it involves the extrasion of fibers through a spinneret. These fibers are then drawn using high velocity air and laid on an endless belt. A calender roll is generally then used to heat the web and bond the fibers to one another although other techniques may be used such as sonic bonding and adhesive bonding.
  • the fabric may be prepared with mixed metallocene polypropylene alone, physically blended with other mixed metallocene polypropylene or physically blended with single metallocene polypropylene.
  • the fabrics of this invention may be prepared with mixed metallocene polypropylene physically blended with conventional Ziegler-Natta produced polymer. If blended, the fabric of this invention is preferably comprised of at least 50% mixed metallocene polypropylene. With these nonwoven fabrics, manufacturers can maintain the desirable properties of fabrics prepared with metallocene produced polypropylene while increasing fabric strength and potentially increased line speed compared to fabrics made using conventional polymers.
  • Solvent for the SEC experiment was prepared by dissolving 6 grams of butylated hydroxy toluene as an antioxidant in 4 liters of Aldrich reagent grade 1,2,4 frichlorobenzene (TCB). The TCB mixture was then filtered through a 0.7 ⁇ m glass pre-filter and subsequently through a 0.1 ⁇ m Teflon filter. The TCB was then degassed with an online degasser before entering the SEC.
  • Polymer solutions were prepared by placing dry polymer in a glass container, adding the desired amount of TCB, then heating the mixture at 160 °C with continuous agitation for about 2 hours. All quantities were measured gravimetrically.
  • the TCB densities used to express the polymer concentration in mass/volume units are 1.463 g/ml at room temperature and 1.324 g/ml at 135 °C.
  • the injection concentration ranged from 1.0 to 2.0 mg/ml, with lower concentrations being used for higher molecular weight samples.
  • the DRI detector and the injector Prior to running each sample the DRI detector and the injector were purged.
  • Flow rate in the apparatus was then increased to 0.5 ml/minute, and the DRI was allowed to stabilize for 8-9 hours before injecting the first sample.
  • the LS laser was turned on 1 to 1.5 hours before running samples by mnning the laser in idle mode for 20-30 minutes and then switching to full power in light regulation mode.
  • the light scattering detector used is either a Wyatt Technology
  • ⁇ R( ⁇ ,c) is the excess Rayleigh scattering intensity at scattering angle ⁇
  • c is the polymer concenfration
  • a 2 is the second virial coefficient ofthe solution
  • P( ⁇ ) is the form factor
  • K 0 is the optical constant for the system:
  • N A is Avogadro's number
  • dn/dc is the refractive index increment for the system.
  • concentrations used in the analyses are the values obtained from the DRI output.
  • the refractive index n for TCB at 135 C for a 690 nm wavelength is 1.500.
  • a 2 0.0006 for propylene polymers and 0.0015 for butene polymers
  • (dn/dc) 0.104 for propylene polymers and 0.098 for butene polymers.
  • the viscometer used was a Niscotek Corporation high temperature viscometer which has four capillaries arranged in a Wheatstone bridge configuration with two pressure transducers. One transducer measures the total pressure drop across the detector, and the other, positioned between the two sides ofthe bridge, measures a differential pressure.
  • the specific viscosity, ⁇ s for the solution flowing through the viscometer is calculated from their outputs.
  • the branching index (g') is calculated using the output of the SEC-
  • the branching index g' is defined as:
  • M v is the viscosity-average molecular weight based on molecular weights determined by LS analysis.
  • T m Melting point
  • ⁇ H f heat of fusion
  • ⁇ H f heat of fusion
  • ⁇ H f multiple melting peak
  • any measurements related to detection of crystalline melting or crystallization are measured by Differential Scanning Calorimetry (DSC).
  • DSC Differential Scanning Calorimetry
  • a typical procedure used was as follows - Preferably, about 5 mg to about 9 mg of polymer that has aged at room temperature for at least 24 hours, is placed in a Differential Scanning Calorimeter. The sample is heated at about 10°C/minute to attain a final temperature of about 200°C. Subsequently, the sample is cooled to room temperature at about 10°C/min, during which the thermal output records the heat of crystallization.
  • the crystallization temperature (T cmax ) is recorded as the temperature at the peak ofthe crystallization exotherm.
  • the sample is then heated back to 200°C.
  • the thermal output is recorded as the area under the melting peak, or peaks, of the sample which is typically at a maximum peak at about 160°C.
  • the melting point is recorded as the temperature of the greatest heat abso ⁇ tion within the range of melting of the sample. In some cases, following the heating cycle the sample was cooled below room temperature prior to the second heating cycle.
  • the reaction temperature was from 150°C ⁇ 3°C up to 190°C ⁇ 3°C
  • the propylene had a density of 1.91 kg/m 3 (0°C, 1013 mbar), an Mw of 42.08 g/mol, a melting temperature of -185.25°C, a melting enthalpy of 69.9 kJ/kg, a boiling point at 1013 mbar of -47.75°C, a critical temperature of 91.85°C, a critical pressure of 46.2 bar (4.62MPa), and other CnHm of less than 1000 ppm.
  • Methylalumoxane (Mw 58.01, density 0.93 g/ml at 20 ° C, 30 weight % in toluene, 13.0 to 14.5 % aluminum ) was obtained from Crompton GmbH.
  • Tri-isobutyl aluminum (TIBAL) (Mw 198.33, density 0.789, g/ml at 20 ° C, 13.0 to 13.4 % aluminum ) was obtained from Crompton GmbH, Bergkamen. 95% pure hexane was obtained from Sigma- Aldrich, Deisenhofen. The hexane was purified by refluxing over a sodium-potassium alloy for 3 hours, followed by distillation under an inert atmosphere.
  • the hexane had an Mw of 86.18 g/mol, a melting temperature of -95.53°C, a melting enthalpy of 147.8 kJ/kg, a boiling point at 1013 mbar of 68.75°C, a critical temperature of 234.25 ° C, a critical pressure of 29.7 bar (2.97MPa), an enthalpy of evaporation of 3335 kJ/kg, a non-volatiles level of less than 0.0015%, less than 0.02% water and less than 0.001% acids (CH 3 COOH).
  • Sample concentrations were approximately 10 wt% (wt/ vol) in perdeutero tetrachloroethane. 10-mm NMR tubes contained these samples. Acquisition conditions were a 90-degree pulse, ungated broadband decoupling, approximately 15 seconds between successive data acquisitions, a sweep width of 8000 Hz, digital resolution Of ⁇ 0.2 Hz with the final spectrum composed of at least 1000 time-averaged data acquisitions.
  • Sample concentrations were approximately 1.5 wt% (wt/vol) in perdeutero tetrachloroethane. 5-mm NMR tubes contained these samples. Acquisition conditions were ⁇ 45-degree pulse, approximately 8 seconds between successive data acquisitions, and a sweep width of at least 10 ppm with the final spectrum composed of at least 120 time-averaged data acquisitions.
  • the core ofthe unit was a polymerization autoclave (volume 100 mL), designed for a maximum pressure of 200 MPa (2000 Bar) and a maximum temperature of 300°C and containing a stirrer, magnetic drive, an electric heater (controlled by the thermocouple TIC-504), and a rapture disc. Pressure was measured with a pressure transducer (PIRC) and manometer. A thermocouple measured the temperature inside the autoclave.
  • the autoclave was connected to the monomer and catalyst metering system and to the sampling device. Propylene was prepared in two tanks having a volume of 6 L each. It was fed by a membrane pump through the axis ofthe stirrer into the autoclave.
  • the pressure in the propylene feed line was measured and indicated by a manometer. Hexane was metered through a feed line from a tank having a volume of 3 L using a second membrane pump. Thirty mL of catalyst solution was placed in a syringe type pump. As the catalyst solution was dispensed from the syringe, it was diluted with hexane before entering the reactor. The pressure in the catalyst feed line was measured with a manometer. [00273] After the autoclave, the pressure was released to ambient by an automatically operated outlet valve. The polymer samples were collected in receptacles below the outlet valve. Each receptacle was joined to the outlet valve one after the other. Unreacted propylene was released to a flare. The polymer that formed before steady state was reached was collected in a separate receptacle.
  • TIB A tri-iso- butylaluminum
  • TIB A tri-iso- butylaluminum
  • a mixture of hexane and TIB A was metered into a tank.
  • propylene was taken from a bomb and condensed into the tank.
  • the propylene was evaporated into a second tank and condensed.
  • the metallocene catalyst was dissolved in a mixture of toluene and methyl alumoxane (MAO). This solution was stored under 2.5 MPa nitrogen. For each test 10 ml ofthe solution were placed in a syringe-type pump to be metered continuously into the autoclave.
  • the catalyst feed was further diluted with hexane. Before treatment, the hexane itself was also treated with TIB A under 2.5 MPa nitrogen. The mixture of catalyst, hexane and a negligible quantity of TIB A was fed by pump to adjust a ratio of 90 mol propylene to 10 mol hexane and a pre-set catalyst concentration in the feed. The conversion was determined from the total quantity of polymer that was collected during the 600 seconds and the amount of propylene added to the reaction. The typical feed temperature at start-up was 150-158° C. Once polymerization was commenced, the autoclave temperature rose to a stable polymerization temperature of from 150 to 190° C.
  • Table A reports conditions for the homopolymerizations using ( ⁇ -dimethylsilyl)bis(2-methy-4- phenylindenyl)zirconium dichloride (MW 628.82 g/mol)... Table A. Polymerization conditions for propylene homopolymerization
  • Table B Property data for PP1 to PP10.
  • Table D Repeat unit and end group structures - 13 C NMR.
  • PH-1 was evaluated for mechanical properties. Modulus was
  • Peak Stress was 1043+121 psi
  • Strain at break was 508+55%
  • Toughness was 2634+298 in-lb/in 3 .
  • Wax-producing polymerizations were conducted in the autoclave described above. In each of these experiments, the polymerization temperature was 190°C and the residence time was 4 minutes.
  • the catalyst for these polymerization reactions was ( ⁇ -dimethylsilyl)bis(2-methy-4- phenylindenyl)zirconium dichloride (MW 628.82 g/mol). The reactions used methylalumoxane as the activator.

Abstract

This invention relates to a process to polymerize olefins comprising contacting, in a polymerization system, olefins having three or more carbon atoms with a catalyst compound, activator, optionally comonomer, and optionally diluent or solvent, at a temperature above the cloud point temperature of the polymerization system and a pressure no lower than 10MPa below the cloud point pressure of the polymerization system, where the polymerization system comprises any comonomer present, any diluent or solvent present, the polymer product, where the olefins having three or more carbon atoms are present at 40 weight % or more. This invention also relates to polymers produced herein including a propylene polymer having a 1,3 regio defect population of greater than 5 per 10,000 monomer units, a melting point of 70°C or more, a g' of 0.97 or more and an Mw greater than 10,000.

Description

POLYMER PRODUCTION AT SUPERCRITICAL CONDITIONS
Inventors: Pat Brant, Gerhart Luft, Richard Shutt, Larry Smith, Doug McClain, and Terry Burkhardt
PRIORITY CLAIMS
[0001] This application claims priority to USSN 60/412,541, filed
September 20, 2002 and to USSN 60/431,077, filed December 5, 2002.
FIELD OF THE INVENTION
[0002] This invention relates to polymerization of olefin monomers having three or more carbon atoms under supercritical conditions.
BACKGROUND
[0003] Since the mid-1980s metallocene catalysts have been used in high- pressure reactors—mainly for producing ethylene-backbone polymers including ethylene copolymers with monomers of one or more of propylene, butene, and hexene, along with other specialty monomers such as 4-methyl-l,5-hexadiene. For example US 5,756,608, granted to Langhausen et al., reports a process for polymerizing C2 to C10 1-alkenes using bridged metallocene catalysts. Polypropylene production in high pressure conditions has, however, been seen as impractical and unworkable at temperatures much above the propylene critical point. A process to produce commercially useful polypropylene in a high pressure system would provide advantages, such as increased reactivity, or increased catalyst productivity, or higher throughput, or shorter residence times, etc. Likewise new polypropylene polymers are also in constant need for the preparation of new and improved products. Thus there is a need in the art to develop new processes capable of greater efficiency and manufacture of new polypropylene polymers.
[0004] In addition there is also a need for polymerization processes that are flexible enough to be used with other monomers. For example a high pressure process to make polybutene or polyhexene is also desirable. [0005] US 6,084,041, granted to Andtsjδ et al., discloses supercritical propylene polymerization under relatively mild conditions (90-100 °C and less than 6.89 MPa pressure) using supported Ziegler-Natta and metallocene catalysts. This patent does not relate to propylene copolymerization at temperatures or pressures much higher than described above. It also does not specifically disclose bulk propylene polymerization using soluble, unsupported metallocene catalysts. [0006] US 5,969,062 granted to Mole et al., describes a process for preparing ethylene copolymers with α-olefins in which polymerization is carried out at a pressure between 100-350 MPa and at a temperature from 200-280 °C. The catalyst is based on a tetramethylcyclopentadienyl titanium complex. [0007] US 5,408,017 describes an olefm polymerization catalyst for use at polymerization temperatures of 140°C-160°C, or greater. Mainly, temperatures exceeding the melting point temperature and approaching the polymer decomposition temperature are said to yield high productivity. [0008] WO 93/11171 discloses a polyolefϊn production process that comprises continuously feeding olefin monomer and a metallocene catalyst system into a reactor. The monomer is continuously polymerized to provide a monomer-polymer mixture. Reaction conditions keep this mixture at a pressure below the system's cloud-point pressure. These conditions create a polymer-rich and a monomer-rich phase and maintain the mixture's temperature above the polymer's melting point.
[0009] US 6,355,741 discloses a process for producing poly olefins having a bimodal molecular weight distribution. The process comprises producing a first polyolefϊn fraction in a first loop reactor. The process couples this first loop reactor to a second loop reactor that prepares a second polyolefin fraction. At least one ofthe loops uses supercritical conditions.
[0010] WO 92/14766 describes a process comprising the steps of (a) continuously feeding olefinic monomer and a catalyst system, with a metallocene component and a cocatalyst component, to the reactor; (b) continuously polymerizing that monomer in a polymerization zone reactor under elevated pressure; (c) continuously removing the polymer/monomer mixture from the reactor; (d) continuously separating monomer from molten polymer; (e) reducing pressure to form a monomer-rich and a polymer-rich phase; and (f) separating monomer from the reactor.
[0011] US 5,326,835 describes bimodal polyethylene production. This invention's first reactor stage is a loop reactor in which polymerization occurs in an inert, low-boiling hydrocarbon. After the loop reactor, the reaction medium transits into a gas-phase reactor where gas-phase ethylene polymerization occurs. The polymer produced appears to have a bimodal molecular weight distribution. [0012] CA 2,118,711 (equivalent to DE 4,130,299) describes propylene polymerization at 149°C and 1510 bar using
(CH3)2C(fluorenyl)(cyclopentadienyl)zirconium dichloride complex, methylalumoxane and trimethylaluminum. Catalyst activity is reported to be 8380 gPP/g Ic' h. The Mw is reported to be 2,000. CA 2,118,711 also describes propylene polymerization with ethylene at 190°C and 1508 bar using (CH3)2C(fluorenyl)(cyclopentadienyl)zirconium dichloride complex, methylalumoxane and trimethylaluminum. Catalyst activity is reported to be 24358g Polymer/glc' hr. The Mw is reported to be 10,000. [0013] Other references of interest include:
[0014] Olefin Polymerization Using Highly Congested grø -Metallocenes under High Pressure: Formation of Superhigh Molecular Weight Polyolefins, Suzuki, et al., Macromolecules, 2000, 33, 754-759, EP 1 123 226, WO 00 12572, WO 00 37514, EP 1 195 391, US 6,355,741, and Ethylene Bis(Indenyl) Zirconocenes..., Schaverien, C.J. et al., Organometallics, ACS, Columbus Ohio, vol 20, no. 16, August 2001, pg 3436-3452, WO 96/34023, WO 97/11098, US 5,084,534, US 2,852,501, WO 93/ 05082, EP 129 368 BI, WO 97/45434, JP 96-
208535 199660807, US 5,096,867, WO 96/12744, US 5,408,017, US 5, 084,534,
US 6,225,432, WO 02/090399, EP 1 195 391, WO 02/50145, US 2002 013440,
WO 01/46273, EP 1 008 607, JP- 1998- 110003 A, US 6,562,914, and JP-1998-
341202B2.
[0015] Another item of interest is an abstract obtained from the Borealis website that states:
Bar bo Loefgren, E. Kokko, L. Huhtanen, MLahelin, Petri Lehmus, Udo Stehling. "Metallocene-PP produced under supercritical conditions. " IstBluesky Conference on Catalytic Olefin Polymerization, 17.-20.6.2002, Sorrrento, Italy., Q, 2002. "mPP produced in bulk conditions (100% propylene), especially at elevated temperature and under supercritical conditions, shows rheological behaviour indicative for small amounts ofLCB in the polymer. This is a feature that can be utilized to produce mPP with enhanced melt strength under industrially meaningful conditions. "
SUMMARY
[0016] This invention relates to a process to polymerize olefins comprising contacting, in a polymerization system, olefin monomers having three or more carbon atoms with a catalyst compound, an activator, optionally comonomer, and optionally diluent or solvent, at a temperature above the cloud point temperature ofthe polymerization system and a pressure no lower than lOMPa below the cloud point pressure ofthe polymerization system and less than 150 MPa, where the polymerization system comprises the monomers, any comonomer present, any diluent or solvent present, the polymer product, and where the olefin monomers having three or more carbon atoms are present at 40 weight % or more. [0017] This invention also relates to polymers produced herein including a propylene polymer having a 1,3 regio defect population of greater than 5 per 10,000 monomer units, a melting point of 145°C or more, an g' of 0.97 or less and an Mw greater than 20,000. [0018] This invention also relates to polymers produced herein including a propylene polymer having a 1,3 regio defect population of greater than 5 per 10,000 monomer units, a melting point of 145°C or more, an g' of 0.97 or more and an Mw greater than 20,000.
FIGURE DESCRIPTION
[0019] Figure 1 Shows that conversion increases with increasing catalyst concentration and with increasing pressure.
[0020] Figure 2 Shows cloud point isotherms for Polymer Achieve™
1635.
[0021] Figure 3 Shows cloud point isotherms for Polymer PP 45379 dissolved in bulk propylene.
[0022] Figure 4 Shows cloud point isotherms for Polymer PP 4062 dissolved in bulk propylene.
[0023] Figure 5 Shows cloud point isopleths for Polymer Achieve™
1635 dissolved in bulk propylene.
[0024] Figure 6 Shows cloud point isopleths for Polymer PP 45379 dissolved in bulk propylene.
[0025] Figure 7 Shows cloud point isopleths for Polymer PP 4062 dissolved in bulk propylene.
[0026] Figure 8 Shows a comparison of isopleths for PP 45379,
Achieve™ 1635, and PP 4062 dissolved in bulk propylene.
[0027] Figures 9, 10 and 11 Show a comparison with literature data as described in J. Nladimir Oliveira, C. Dariva and J. C. Pinto, Ind. Eng, Chem. Res.
29, 2000, 4627.
[0028] Figure 12 is a plot of G' versus Log Mw for PP 1 and PP-9.
DEFINITIONS
[0029] For purposes of this invention and the claims thereto: 1. A catalyst system is defined to be the combination of a catalyst compound and an activator.
2. The cloud point is the pressure below which, at a given temperature, the polymerization system becomes turbid as described in J. Nladimir Oliveira, C. Dariva and J. C. Pinto, Ind. Eng, Chem. Res. 29, 2000, 4627. For purposes of this invention and the claims thereto, the cloud point is measured by shining a helium laser through the selected polymerization system in a cloud point cell onto a photocell and recording the pressure at the onset of light scattering for a given temperature.
3. A higher α-olefin is defined to be an olefin having 4 or more carbon atoms.
4. Use ofthe term "polymerization" encompasses any polymerization reaction such as homopolymerization and copolymerization.
5. A copolymerization encompasses any polymerization reaction of two or more monomers.
6. The new numbering scheme for the Periodic Table Groups is used as published in CHEMICAL AND ENGINEERING NEWS, 63(5), 27 (1985).
7. When a polymer is referred to as comprising an olefin, the olefin present in the polymer is the polymerized form ofthe olefin.
8. An oligomer is defined to be compositions having 2-75 mer units.
9. A polymer is defined to be compositions having 76 or more mer units.
10. The following abbreviations are used: Me is methyl, Ph is phenyl, Et is ethyl, Pr is propyl, iPr is isopropyl, n-Pr is normal propyl, Bu is butyl, iBu is isobutyl, tBu is tertiary butyl, p-tBu is para-tertiary butyl, TMS is trimethylsilyl, TIBA is trisobutylaluminum, MAO is methylalumoxane, pMe is para-methyl, flu is fluorenyl, cp is cyclopentadienyl.
[0030] As used herein, the term "slurry polymerization" means a polymerization process that involves at least two phases, e.g., in which particulate, solid polymer (e.g., granular) is formed in a liquid, supercritical, or vapor polymerization medium, or in a liquid/vapor polymerization medium. [0031] As used herein, the term "bulk polymerization" means a polymerization process in which the polymerization medium is predominantly monomer and contains less than 50 wt % of solvent or diluent.
Detailed Description
[0032] This invention relates to a process to polymerize olefins comprising contacting, in a polymerization system, olefin monomers having three or more carbon atoms with a metallocene catalyst compound, a bisamide catalyst compound or a bisimide catalyst compound, an activator, optionally comonomer, and optionally diluent or solvent, at a temperature above the cloud point temperature ofthe polymerization system and a pressure no lower than lOMPa below the cloud point pressure ofthe polymerization system and less than 150 MPa, where the polymerization system comprises the monomers, any comonomer present, any diluent or solvent present, the polymer product, and where the olefin monomers are present in the polymerization system at 40 weight % or more. [0033] For illustration, cloud point curves are shown in figures 2-10 for three different polypropylene samples having different molecular weights and crystallinities dissolved in propylene (at 18 weight %). (Achieve 1635 PP is a commercially available metallocene catalyzed isotactic polypropylene having an Melt Flow Index (I10/I2-ASTM 1238, 190 °C, 2.16kg) of 32 dg/min available from ExxonMobil Chemical Company, Houston, Texas. ESCORENE PP 4062 is a commercially available isotactic polypropylene having an MFI of 3.7 dg/min, available from ExxonMobil Chemical Company, Houston, Texas. PP 45379 is an isotactic polypropylene having an MFI of 300 dg/min produced using a supported metallocene in a slurry polymerization process. [0034] For purposes of this invention and the claims thereto polymerization system is defined to be monomer(s) plus comonomers plus solvent/diluent plus polymer.
[0035] In a preferred embodiment, the polymerization system comprises less than 20 wt % aromatic hydrocarbons. Preferably less than 20 wt % toluene. [0036] Preferably, the temperature ofthe polymerization system is 3°C or more above the cloud point temperature for the polymerization system, alternately 5°C or more, alternately 10°C or more, alternately 15°C or more, alternately 20°C or more, alternately 25°C or more, alternately 30°C or more. Even more preferably the temperature is between 140 and 220°C, preferably 145 and 200°C, preferably 150 and 190°C, preferably 150 to 180°C, preferably 140 to 170°C. [0037] Preferably the pressure ofthe polymerization system is no lower than 10 MPa below the cloud point pressure ofthe polymerization system, preferably no lower than 5 MPa below the cloud point pressure, preferably above the cloud point pressure, preferably 5 MPa or more above the cloud point pressure, preferably 50MPa or more, preferably 100 MPa. Preferably the pressure is 5MPa or more, preferably lOMPa or more, more preferably up to 350MPa. Even more preferably the pressure is between 15 and 200 MPa, preferably 20 and 150 MPa, preferably 25 and 100 MPa, preferably 30 and 75 MPa, most preferably between 25 and 50 MPa.
[0038] Preferably solvent and or diluent is present in the polymerization system at 0 to 50 wt %, preferably 0 to 25 wt %, preferably 0 to 20, preferably 0 to 15 preferably 0 to 10 preferably 0 to 5, preferably, 0 to 4, preferably 0 to 3, preferably 0 to 2, preferably 0 to 1 wt %.
[0039] In a preferred embodiment the olefin monomers are present in the polymerization system at 45 wt % or more, preferably 50 wt % or more, preferably at 55 wt % or more, preferably 60 wt % or more, preferably at 65 wt % or more, preferably 70 wt % or more, preferably at 75 wt % or more, preferably 80 wt % or more, preferably at 85 wt % or more. [0040] In a preferred embodiment propylene is present in the polymerization system at 45 wt % or more, preferably 50 wt % or more, preferably at 55 wt % or more, preferably 60 wt % or more, preferably at 65 wt % or more, preferably 70 wt % or more, preferably at 75 wt % or more, preferably 80 wt % or more, preferably at 85 wt % or more. [0041] In a preferred embodiment propylene and up to 30 mol % of one or more comonomers are present in the polymerization system at 45 wt % or more, preferably 50 wt % or more, preferably at 55 wt % or more, preferably 60 wt % or more, preferably at 65 wt % or more, preferably 70 wt % or more, preferably at 75 wt % or more, preferably 80 wt % or more, preferably at 85 wt % or more. [0042] In particularly preferred embodiments the temperature ofthe polymerization system is between 140 and 170°C and the pressure ofthe polymerization system is between 15 and 60 MPa. In further particularly preferred embodiments the temperature ofthe polymerization system is between 140 and 170°C and the pressure ofthe polymerization system is between 20 and 60 MPa. In further particularly preferred embodiments the temperature ofthe polymerization system is between 140 and 170°C and the pressure is ofthe polymerization system between 25 and 60 MPa. In further particularly preferred embodiments the temperature ofthe polymerization system is between 140 and 170°C and the pressure ofthe polymerization system is between 30 and 60 MPa. [0043] The processes of this invention occur in a supercritical polymerization medium, preferably above the cloud point ofthe medium. A supercritical state exists for a substance when the substance's temperature and pressure are above its critical point. When the pressure or temperature exceeds the critical state, the fluid is in its supercritical state. The critical pressure and critical temperature of a fluid may be altered by combining it with another fluid, such as a diluent or anther monomer. Thus, for the purposes of this invention and the claims thereto a supercritical polymerization medium is the state where the polymerization medium is present at a temperature above the critical temperature and critical pressure ofthe medium.
[0044] For purposes of this invention and the claims thereto, the critical temperatures (Tc) and critical pressures (Pc) are found in the Handbook of Chemistry and Physics, David R. Lide, Editor-in-Chief, 82nd edition 2001-2002, CRC Press, LLC. New York, 2001. In particular the Tc and Pc of various molecules are defined to be:
Figure imgf000011_0001
273.2K = 0 °C.
[0045] In a preferred embodiment, the combined volume of monomer(s) and solvent/diluent comprises at least 50 wt % of neat monomer, preferably at least 60 vol% neat monomer, more preferably at least 70 vol%, more preferably at least 80 vol%, more preferably at least 90 vol%, more preferably at least 95 vol%. [0046] In some embodiments, optional comonomer, diluents or other fluids are present in the polymerization medium along with the monomer. Diluents, comonomers and other fluids each modify the media's critical point; and hence, alter the pressure-temperature regime within which a particular medium is in a supercritical state. Diluents, comonomers and other fluids each also modify the phase behavior ofthe polymerization medium; and hence, alter the pressure- temperature regime within which a particular medium is single phased. Consequently, a two component reaction medium can have two phases above its critical point.
[0047] While this disclosure speaks of two phases for neat propylene with dissolved polypropylene converting to a single phase above the reaction mixture's cloud point, the reality is that the phase behavior is more complicated, especially when the reaction medium is more complicated than neat propylene. This added complication can show up anytime the reaction medium contains an additional component, such as a diluent.
[0048] The terms "two-phase polymerization system" or "two-phase polymerization medium" mean a system having two and, preferably, only two phases. In certain embodiments, the two phases are referenced as a "first phase" and a "second phase." In certain embodiments, the first phase is or includes a "monomer phase," which includes monomers and may also include solvent and some or all ofthe product of polymerization. Preferably, however, the monomer phase does not include the polymer product. That is, for example in a propylene polymerization, the monomer phase can be referred to as the "propylene phase." In certain embodiments, the second phase is or includes a solid phase, which may include products of polymerization, e.g., macromers and polymer product, but not monomers, e.g., propylene. None ofthe parts ofthe catalyst system are considered to be part ofthe polymerization system, although certain parts ofthe catalyst system can obviously be solid, e.g., supported catalysts. Furthermore, it is contemplated that parts ofthe catalyst system may be liquid or vapor or part ofthe vapor/liquid phase that exists in certain embodiments ofthe process. [0049] Some embodiments select the temperature and pressure so that the polymer produced in the reaction and the reaction medium that solvates it remain single phased, i.e. above the reaction medium's cloud point with that polymer. Other embodiments select the temperature and pressure so that the reaction medium remains supercritical, but at a pressure below the polymer's cloud point in the particular reaction medium. This results in a two phase reaction medium: a polymer rich phase and a polymer lean phase. Some embodiments that are below the polymer's cloud point nonetheless operate above the polymer's crystallization temperature.
[0050] Preferred diluents for use in the present invention include one or more of CrC24 alkanes, such as ethane, propane, n-butane, i-butane, n-pentane, i- pentane, n-hexane, toluene, cyclohexane, xylene, mixed hexanes and cyclopentane. Some embodiments select a diluent from hydrocarbon diluents. In some preferred embodiments the diluent comprises one or more of ethane, propane, and isobutane. In some preferred embodiments the diluent is recyclable. [0051] Preferred diluents also include C6 to C,50 isoparaffins, preferably C6 to C100 isoparaffins, preferably C6 to C25 isoparaffins, more preferably C8 to C20 isoparaffins. By isoparaffm is meant that the paraffin chains possess Cx to C10 alkyl branching along at least a portion of each paraffin chain. More particularly, the isoparaffins are saturated aliphatic hydrocarbons whose molecules have at least one carbon atom bonded to at least three other carbon atoms or at least one side chain (i.e., a molecule having one or more tertiary or quaternary carbon atoms), and preferably wherein the total number of carbon atoms per molecule is in the range between 6 to 50, and between 10 and 24 in another embodiment, and from 10 to 15 in yet another embodiment. Narious isomers of each carbon number will typically be present. The isoparaffins may also include cycloparaffins with branched side chains, generally as a minor component ofthe isoparaffin. Preferably the density (ASTM 4052, 15.6/15.6°C) of these isoparaffins ranges from 0.70 to 0.83 g/cm3; the pour point is -40°C or less, preferably -50°C or less, the viscosity (ASTM 445, 25°C) is from 0.5 to 20 cSt at 25°C; and the average molecular weights in the range of 100 to 300 g/mol. Suitable isoparaffins are commercially available under the tradename ISOPAR (ExxonMobil Chemical Company, Houston TX), and are described in, for example, US 6,197,285, 3,818,105 and 3,439,088, and sold commercially as ISOPAR series of isoparaffins. Other suitable isoparaffins are also commercial available under the trade names SHELLSOL (by Shell), SOLTROL (by Chevron Phillips) and SASOL (by Sasol Limited). SHELLSOL is a product ofthe Royal Dutch/Shell Group of Companies, for example Shellsol TM (boiling point = 215- 260°C). SOLTROL is a product of Chevron Phillips Chemical Co. LP, for example SOLTROL 220 (boiling point = 233-280°C). SASOL is a product of Sasol Limited (Johannesburg, South Africa), for example SASOL LPA-210, SASOL-47 (boiling point = 238-274°C).
[0052] In another embodiment, preferred diluents include C5 to C25 n- paraffins, preferably C5 to C20 n-paraffins, preferably C5 to C,5 n-paraffins having less than 0.1%, preferably less than 0.01% aromatics. Suitable n-paraffins are commercially available under the tradename ΝORPAR (ExxonMobil Chemical Company, Houston TX), and are sold commercially as ΝORPAR series of n- paraffins. In another embodiment preferred diluents include dearomaticized aliphatic hydrocarbon comprising a mixture of normal paraffins, isoparaffins and cycloparaffins. Typically they are a mixture of C4 to C25 normal paraffins, isoparaffins and cycloparaffins, preferably C5 to C18, preferably C5 to C12. They contain very low levels of aromatic hydrocarbons, preferably less than 0.1, preferably less than 0.01 aromatics. Suitable dearomatized aliphatic hydrocarbons are commercially available under the tradename EXXSOL (ExxonMobil Chemical Company, Houston TX), and are sold commercially as EXXSOL series of dearomaticized aliphatic hydrocarbons.
[0053] In another embodiment the diluent comprises up to 20 weight % of oligomers of C6 to C14 olefins and/or oligomers of linear olefins having 6 to 14 carbon atoms, more preferably 8 to 12 carbon atoms, more preferably 10 carbon atoms having a Kinematic viscosity of 10 or more (as measured by ASTM D 445) ; and preferably having a viscosity index ("NI"), as determined by ASTM D-2270 of 100 or more.
[0054] In another embodiment the diluent comprises up to 20 weight % of oligomers of C20 to C1500 paraffins, preferably C4o to C1000 paraffins, preferably C50 to C750 paraffins, preferably C50 to C500 paraffins. In another embodiment the diluent comprises up to 20 weight % of oligomers of 1-pentene, 1-hexene, 1- heptene, 1-octene, 1-nonene, 1-decene, 1-undecene and 1-dodecene. Such oligomers are commercially available as SHF and SuperSyn PAO's (ExxonMobil Chemical Company, Houston TX). Other useful oligomers include those sold under the tradenames Synfluid™ available from ChevronPhillips Chemical Co. in Pasedena Texas, Durasyn™ available from BP Amoco Chemicals in London England, Νexbase™ available from Fortum Oil and Gas in Finland, Synton™ available from Crompton Corporation in Middlebury CΝ, USA, EMERY™ available from Cognis Corporation in Ohio, USA. [0055] With regard to propylene polymerization media, preferred monomers and diluents are those that are soluble in and inert to propylene and any other polymerization components at the polymerization temperatures and pressures. [0056] As mentioned above, the polymerization processes described herein are run under supercritical conditions. This characteristic provides a lower pressure and temperature limit ~ the critical temperature and pressure ofthe reaction medium. Temperature and pressure are also constrained on tlie upper end. The upper temperature range is the decomposition or ceiling temperature of polypropylene. The following temperatures, in °C, are useful lower temperature limits for all invention processes: 130, 140, 150, 160, and 170. The following temperatures, in °C, are useful upper temperature limits for all invention processes: 190, 210, 220, 230, 240, and 250.
[0057] In another preferred embodiment the polymerization temperature is from 92 to 330°C, preferably 95 to 250°C, more preferably 100 to 200°C, more preferably 105 to 150°C, more preferably 120 to 160°C more preferably 120 to 140°C, more preferably 140 to 160°C.
[0058] Theoretically, pressure can go as high as can be commercially contained. More practically, pressure is limited by the desired properties ofthe resulting polypropylene. The following pressures, in MPa, are useful lower pressure limits for all invention processes: 4.62, 5, 10, 15, 30, 50, 60, 80, 100, 120, 140, 150, 160, 180, 200, 250, 260, 300, 330, 350, 400, 440, 500, and 600. The following pressures, in MPa, are useful upper pressure limits for all invention processes: 10, 15, 30, 50, 60, 80, 100, 120, 140, 150, 160, 180, 200, 250, 260, 300, 330, 350, 400, 440, 500, 600, and 1000 MPa.
[0059] In a preferred embodiment the polymerization pressure is from 4.6 to 1000 MPa, preferably 15 to 500 MPa, more preferably 15 to 400 MPa, more preferably 15 to 300 MPa, more preferably 15 to 250 MPa, more preferably 15 to 200 MPa, more preferably 15 to 400 MPa, more preferably 15 to 190 MPa, more preferably 154.6 to 180 MPa, more preferably 15 to 170 MPa. In another embodiment the lower limit in all ofthe above ranges is 20 MPa, rather than 15 MPa. In another embodiment the lower limit in all ofthe above ranges is 25 MPa, rather than 15 MPa. In another embodiment the lower limit in all ofthe above ranges is 30 MPa, rather than 15 MPa. In another embodiment the lower limit in all ofthe above ranges is 40 MPa, rather than 15 MPa. In another embodiment the lower limit in all ofthe above ranges is 50 MPa, rather than 15 MPa. [0060] It is expected that any temperature range can be combined with any pressure range, provided that the chosen temperature and pressure are such that the reaction medium is above its cloud point ( or within 10 MPa ofthe cloud point). [0061] Temperatures above 140 °C and pressures between 100-150 MPa are particularly useful.
Monomers
[0062] The process described herein can be used to polymerize any monomer having three or more carbon atoms. Preferred monomers include propylene, butene, hexene, decene and octene.
[0063] In a preferred embodiment the processes of this invention are used to polymerize any unsaturated monomer or monomers. Preferred monomers include C3 to C100 olefins, preferably C3 to C60 olefins, preferably C3 to C40 olefins preferably C3 to C20 olefins, preferably C3 to C12 olefins. In some embodiments preferred monomers include linear, branched or cyclic alpha-olefins, preferably C3 to C100 alpha-olefins, preferably C3 to C60 alpha-olefins, preferably C3 to C40 alpha- olefins preferably C3 to C20 alpha-olefins, preferably C3 to C12 alpha-olefins. Preferred olefin monomers may be one or more of propylene, buteήe, pentene, hexene, heptene, octene, nonene, decene, dodecene, 4-methyl-pentene-l, 3 -methyl pentene-1, 3,5,5-trimethyl hexene 1, and 5-ethyl-l-nonene. [0064] In another embodiment the polymer produced herein is a copolymer of one or more linear or branched C3 to C30 prochiral alpha-olefins or C5 to C30 ring containing olefins or combinations thereof capable of being polymerized by either stereospecific and non-stereospecific catalysts. Prochiral, as used herein, refers to monomers that favor the formation of isotactic or syndiotactic polymer when polymerized using stereospecific catalyst(s). [0065] Preferred monomers may also include aromatic-group-containing monomers containing up to 30 carbon atoms. Suitable aromatic-group-containing monomers comprise at least one aromatic structure, preferably from one to three, more preferably a phenyl, indenyl, fluorenyl, or naphthyl moiety. The aromatic- group-containing monomer further comprises at least one polymerizable double bond such that after polymerization, the aromatic structure will be pendant from the polymer backbone. The aromatic-group containing monomer may further be substituted with one or more hydrocarbyl groups including but not limited to C, to C10 alkyl groups. Additionally two adjacent substitutions may be joined to form a ring structure. Preferred aromatic-group-containing monomers contain at least one aromatic structure appended to a polymerizable olefinic moiety. Particularly preferred aromatic monomers include styrene, alpha-methylstyrene, para- alkylstyrenes, vinyltoluenes, vinylnaphthalene, allyl benzene, and indene, especially styrene, paramethyl styrene, 4-phenyl-l-butene and allyl benzene. [0066] Non aromatic cyclic group containing monomers are also preferred.
These monomers can contain up to 30 carbon atoms. Suitable non-aromatic cyclic group containing monomers preferably have at least one polymerizable olefinic group that is either pendant on the cyclic structure or is part ofthe cyclic structure. The cyclic structure may also be further substituted by one or more hydrocarbyl groups such as, but not limited to, Cj to C10 alkyl groups. Preferred non-aromatic cyclic group containing monomers include vinylcyclohexane, vinylcyclohexene, vinylnorbornene, ethylidene norbornene, cyclopentadiene, cyclopentene, cyclohexene, cyclobutene, vinyladamantane, norbornene, and the like. [0067] Preferred diolefin monomers useful in this invention include any hydrocarbon structure, preferably C4 to C30, having at least two unsaturated bonds, wherein at least two ofthe unsaturated bonds are readily incorporated into a polymer by either a stereospecific or a non-stereospecific catalyst(s). It is further preferred that the diolefin monomers be selected from alpha, omega-diene monomers (i.e. di-vinyl monomers). More preferably, the diolefin monomers are linear di-vinyl monomers, most preferably those containing from 4 to 30 carbon atoms. Examples of preferred dienes include butadiene, pentadiene, hexadiene, heptadiene, octadiene, nonadiene, decadiene, undecadiene, dodecadiene, tridecadiene, tetradecadiene, pentadecadiene, hexadecadiene, heptadecadiene, octadecadiene, nonadecadiene, icosadiene, heneicosadiene, docosadiene, tricosadiene, tetracosadiene, pentacosadiene, hexacosadiene, heptacosadiene, octacosadiene, nonacosadiene, triacontadiene, particularly preferred dienes include 1,6-heptadiene, 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene, 1,10-undecadiene, 1,11 -dodecadiene, 1,12-tridecadiene, 1,13 -tetradecadiene, and low molecular weight polybutadienes (Mw less than 1000 g/mol). Preferred cyclic dienes include cyclopentadiene, vinylnorbomene, norbomadiene, ethylidene norbornene, divinylbenzene, dicyclopentadiene or higher ring containing diolefins with or without substituents at various ring positions.
[0068] Non-limiting examples of preferred polar unsaturated monomers include 6-nitro-l -hexene, N-methylallylamine, N-allylcyclopentylamine, N-allyl- hexylamine, methyl vinyl ketone, ethyl vinyl ketone, 5-hexen-2-one, 2-acetyl-5- norbornene, 7-syn methoxymethyl-5-norbomen-2-one, acrolein, 2,2-dimethyl-4- pentenal, undecylenic aldehyde, 2,4-dimethyl-2-6-heptadienal, acrylic acid, vinylacetic acid, 4-pentenoic acid, 2,2-dimethyl-4-pentenoic acid, 6-heptenoic acid, trans-2,4-pentadienoic acid, 2,6-heptadienoic acid, nona-fluoro-1 -hexene, allyl alcohol, 7-octene-l,2-diol, 2-methyl-3-buten-l-ol, 5-norbornene-2- carbonitrile, 5-norbomene-2-carboxaldehyde, 5-norbomene-2-carboxylic acid, cis- 5-norbomene-endo-2,3-dicarboxylic acid, 5-norbomene-2,2,-dimethanol, cis-5- norbomene-endo-2,3-dicarboxylic anhydride, 5-norbornene-2-endo-3-endo- dimethanol, 5-norbomene-2-endo-3-exo-dimethanol, 5-norbomene-2-methanol, 5- norbomene-2-ol, 5-norbomene-2-yl acetate, l-[2-(5-norbornene-2-y_)ethyl]- 3,5,7,9, 11 , 13, 15-heptacyclopentylpentacyclo[9.5.1. I3'9.15'15.17,13]octasiloxane, 2- benzoyl-5- norbornene, allyl 1,1,2,2,-tetrafluoroethyl ether, acrolein dimethyl acetal, butadiene monoxide, l,2-epoxy-7-octene, l,2-epoxy-9-decene, 1,2-epoxy- 5-hexene, 2-methyl-2-vinyloxirane, allyl glycidyl ether, 2,5-dihydrofuran, 2- cyclopenten-1-one ethylene ketal, allyl disulfide, ethyl acrylate, methyl acrylate. [0069] In a preferred embodiment the processes described herein may be used to produce homopolymers or copolymers. (For the purposes of this invention and the claims thereto a copolymer may comprise two, three, four or more different monomer units.) Preferred polymers produced herein include homopolymers or copolymers of any ofthe above monomers. In a preferred embodiment the polymer is a homopolymer of any C3 to C12 alpha-olefin. Preferably the polymer is a homopolymer of propylene. In another embodiment the polymer is a copolymer comprising propylene and ethylene, preferably the copolymer comprises less than 40 weight % ethylene, more preferably less than 30 weight % ethylene, preferably the copolymer comprises less than 20 weight % ethylene, more preferably less than 10 weight % ethylene. In another embodiment the polymer is a copolymer comprising propylene and one or more of any ofthe monomers listed above. In another preferred embodiment the copolymers comprises one or more diolefin comonomers, preferably one or more C2 to C40 diolefins.
[0070] In another preferred embodiment the polymer produced herein is a copolymer of propylene and one or more C2 or C4 to C20 linear, branched or cyclic monomers, preferably one or more C2 or C4 to C12 linear, branched or cyclic alpha- olefins. Preferably the polymer produced herein is a copolymer of propylene and one or more of ethylene, butene, pentene, hexene, heptene, octene, nonene, decene, dodecene, 4-methyl-pentene-l, 3-methyl pentene-1, and 3,5,5-trimethyl hexene 1.
[0071] In a preferred embodiment the copolymers described herein comprise at least 50 mole% of a first monomer and up to 50 mole% of other monomers.
[0072] In another embodiment, the polymer comprises: a first monomer present at from 40 to 95 mole %, preferably 50 to 90 mole %, preferably 60 to 80 mole %, and a comonomer present at from 5 to 40 mole %, preferably 10 to 60 mole %, more preferably 20 to 40 mole %,and a termonomer present at from 0 to 10 mole%, more preferably from 0.5 to 5 mole%, more preferably 1 to 3 mole %.
[0073] In a preferred embodiment the first monomer comprises one or more of any C3 to C8 linear branched or cyclic alpha -olefins, including propylene, butene, (and all isomers thereof), pentene (and all isomers thereof), hexene (and all isomers thereof), heptene (and all isomers thereof), and octene (and all isomers thereof). Preferred monomers include propylene, 1 -butene, 1 -hexene, 1 -octene, cyclohexene, cyclooctene, hexadiene, cyclohexadiene and the like. [0074] In a preferred embodiment the comonomer comprises one or more of any C2 to C40 linear, branched or cyclic alpha-olefins (provided ethylene, if present, is present at 5 mole% or less), including ethylene, propylene, butene, pentene, hexene, heptene, and octene, nonene, decene, undecene, dodecene, hexadecene, butadiene, hexadiene, heptadiene, pentadiene, octadiene, nonadiene, decadiene, dodecadiene, styrene, 3,5,5- trimethylhexene-1, 3-methylpentene-l, 4- methylpentene-1, cyclopentadiene, and cyclohexene.
[0075] In a preferred embodiment the termonomer comprises one or more of any C2 to C40 linear, branched or cyclic alpha-olefins, (provided ethylene, if present, is present at 5 mole% or less), including ethylene, propylene, butene, pentene, hexene, heptene, and octene, nonene, decene, un-decene, do-decene, hexadecene, butadiene, hexadiene, heptadiene, pentadiene, octadiene, nonadiene, decadiene, dodecadiene, styrene, 3,5,5-trimethyl hexene-1, 3-methylpentene-l, 4- methylpentene-1, cyclopentadiene, and cyclohexene.
[0076] In a preferred embodiment the polymers described above further comprise one or more dienes at up to 10 weight %, preferably at 0.00001 to 1.0 weight %, preferably 0.002 to 0.5 weight %, even more preferably 0.003 to 0.2 weight %, based upon the total weight ofthe composition. In some embodiments 500 ppm or less of diene is added to the polymerization, preferably 400 ppm or less, preferably or 300 ppm or less. In other embodiments at least 50 ppm of diene is added to the polymerization, or 100 ppm or more, or 150 ppm or more. [0077] In another embodiment the processes describe herein are used to produce propylene copolymers with other monomer units, such as ethylene, other α-olefin, α-olefinic diolefin, or non-conjugated diolefin monomers, for example C4-C20 olefins, C4-C20 diolefins, C4-C20 cyclic olefins, C8-C20 styrenic olefins. Other unsaturated monomers besides those specifically described above may be copolymerized using the invention processes, for example, styrene, alkyl- substituted styrene, ethylidene norbornene, norbomadiene, dicyclopentadiene, vinylcyclohexane, vinylcyclohexene, acrylates, and other olefinically-unsaturated monomers, including other cyclic olefins, such as cyclopentene, norbornene, and alkyl-substituted norbornenes. Copolymerization can also incorporate α-olefmic macromonomers produced in-situ or added from another source. Some invention embodiments limit the copolymerization of α-olefinic macromonomers to macromonomers with 2000 or less mer units. United States Patent No. 6,300,451 discloses many useful comonomers. That disclosure refers to comonomers as "a second monomer".
[0078] In another embodiment, when propylene copolymers are desired, the following monomers can be copolymerized with propylene: ethylene, but-1- ene, hex- 1 -ene, 4-methylpent-l-ene, dicyclopentadiene, norbornene, C4-C2000, C4- C20o; or C4-C40 linear or branched, α,ω-dienes; C4-C2000, C4-C200j or C4-C40 cyclic olefins; and C4-C2000, C4-C200> or C4-C40 linear or branched α-olefins.
Other Primary Monomer
[0079] Some invention processes polymerize but-1-ene (Tc=146.5 °C;
Pc=3.56 MPa), pent-1-ene (T =191.8; Pc=3.56 MPa), hex-1-ene (Tc=230.8; Pc=3.21 MPa), and 3-methyl-but-l-ene (Tc=179.7; Pc=3.53 MPa) using these monomers or mixtures comprising the monomers at supercritical conditions as the reaction medium or solvent. These processes can employ at least one of but- 1- ene, pent- 1 -ene, or 3-methyl-but-l-ene as monomer. These processes can also employ reaction media that comprise but- 1 -ene, pent- 1 -ene, or 3-methyl-but-l- ene. These processes can employ reaction media that contain greater than 50 wt% of but-1-ene, pent-1-ene, or 3-methyl-but-l-ene. Of course, these compounds can be freely mixed with each other and with propylene as monomer, bulk reaction media, or both.
Catalyst Systems
[0080] The processes described herein are preferably used with a catalyst system comprising a single site type catalyst compounds in combination with an activator. A catalyst system is defined to be the combination of at least one catalyst compound and at least one activator.
Catalyst Compounds
[0081] Catalyst compounds that may be used in the processes of this invention include any catalyst compound that can polymerize monomers under supercritical polymerization conditions. Such catalyst compounds typically do not decompose at polymerization temperatures.
[0082] In a preferred embodiment, the processes described herein can use any olefin polymerization catalyst capable of polymerizing propylene if that catalyst is sufficiently active under invention polymerization conditions. Thus,
\ Group-3-10 transition metals can form suitable polymerization catalysts. A suitable olefin polymerization catalyst will be able to coordinate to, or otherwise associate with, an alkenyl unsaturation.
[0083] Particularly useful catalyst compounds that may be used in the practice of this invention include metallocene catalyst compounds represented by formulae I and II.
[0084] Formula I: L2(Cp)(Q)MmX_ where:
Cp is a substituted or unsubstituted cyclopentadienyl ring, a substituted or unsubstituted indenyl ring or a substituted or unsubstituted fluorenyl ring;
Q is a heteroatom containing group; z is 0 or 1 ;
L is a bridging group connecting Cp to Q,
M is a Group 4, 5, or 6 transition metal; m is 3, 4, 5 or 6;
X is a halogen or a substituted or unsubstituted hydrocarbyl group, a substituted or unsubstituted hydrocarboxy group, or a substituted or unsubstituted heteroatom containing group; and n is m minus 2.
[0085] In a preferred embodiment, z is 1, L is represented by the formula:
RqSi- where each R is, independently, a substituted or unsubstituted Cx to C20 hydrocarbyl group and q is 1, 2, 3 or 4; and Q is a nitrogen containing group, preferably a hydrocarbyl group substituted with nitrogen.
[0086] In a preferred embodiment, the metallocene catalyst compound is represented by the formula II: Lz(Cp)2MmX_ where: each Cp is independently a substituted or unsubstituted cyclopentadienyl ring, a substituted or unsubstituted indenyl ring or a substituted or unsubstituted fluorenyl ring; z is 0 or 1 ;
L is a bridging group connecting Cp to Cp,
M is a Group 4, 5, or 6 transition metal; m is 3, 4, 5 or 6;
X is a halogen or a substituted or unsubstituted hydrocarbyl group, a substituted or unsubstituted hydrocarboxy group, or a substituted or unsubstituted heteroatom containing group; and n is m minus 2.
[0087] In a preferred embodiment, z is 1, L is represented by the formula:
RqSi- where each R is, independently, a substituted or unsubstituted C, to C20 hydrocarbyl group and q is 1, 2, 3 or 4; and both Cp groups are indenyl rings substituted at the 2 and 4 positions. For purposes of this invention and the claims thereto: The term "hydrocarbyl radical" is sometimes used interchangeably with "hydrocarbyl" throughout this document. For purposes of this disclosure, "hydrocarbyl radical" encompasses Cι-C50 radicals. These radicals can be linear, branched, or cyclic including polycyclic. These radicals can be saturated, partially unsaturated or fully unsaturated, and when cyclic, may be aromatic or non- aromatic.
[0088] Substituted hydrocarbyl radicals are radicals in which at least one hydrogen atom has been replaced with a heteroatom or with at least one functional group such as NR"2, OR", PR"2, SR", BR"2, SiR"3, GeR"3 and the like or where at least one non-hydrocarbon atom or group has been inserted within the hydrocarbyl radical, such as O, S, NR", PR", BR", SiR"2, GeR"2, and the like, where R" is independently a hydrocarbyl or halocarbyl radical. The functional group can be an organometalloid radical.
[0089] Halocarbyl radicals are radicals in which one or more hydrocarbyl hydrogen atoms have been substituted with at least one halogen or halogen- containing group (e.g. F, Cl, Br, I).
[0090] Substituted halocarbyl radicals are radicals in which at least one hydrocarbyl hydrogen or halogen atom has been substituted with at least one functional group such as NR"2, OR", PR"2, SR", BR"2, SiR"3, GeR"3 and the like or where at least one non-carbon atom or group has been inserted within the halocarbyl radical such as O, S, NR", PR", BR", SiR"2, GeR"2, and the like where R" is independently a hydrocarbyl or halocarbyl radical provided that at least one halogen atom remains on the original halocarbyl radical. The functional group can be an organometalloid radical.
[0091] In some embodiments, the hydrocarbyl radical is independently selected from methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl, triacontyl, ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, nonadecenyl, eicosenyl, heneicosenyl, docosenyl, tricosenyl, tetracosenyl, pentacosenyl, hexacosenyl, heptacosenyl, octacosenyl, nonacosenyl, triacontenyl, propynyl, butynyl, pentynyl, hexynyl, heptynyl, octynyl, nonynyl, decynyl, undecynyl, dodecynyl, tridecynyl, tetradecynyl, pentadecynyl, hexadecynyl, heptadecynyl, octadecynyl, nonadecynyl, eicosynyl, heneicosynyl, docosynyl, tricosynyl, tetracosynyl, pentacosynyl, hexacosynyl, heptacosynyl, octacosynyl, nonacosynyl, or triacontynyl isomers. For this disclosure, when a radical is listed it indicates that radical type and all other radicals formed when that radical type is subjected to the substitutions defined above. Alkyl, alkenyl and alkynyl radicals listed include all isomers including where appropriate cyclic isomers, for example, butyl includes n-butyl, 2-methylpropyl, 1-methylpropyl, tert-butyl, and cyclobutyl (and analogous substituted cyclopropyls); pentyl includes n-pentyl, cyclopentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1- ethylpropyl, and neopentyl (and analogous substituted cyclobutyls and cyclopropyls); butenyl includes E and Z forms of 1-butenyl, 2-butenyl, 3-butenyl, 1 -methyl- 1-propenyl, l-methyl-2-proρenyl, 2-methyl-l-propenyl and 2-methyl-2- propenyl (and cyclobutenyls and cyclopropenyls). Cyclic compound having substitutions include all isomer forms, for example, methylphenyl would include ortho-methylphenyl, meta-methylphenyl and para-methylphenyl; dimethylphenyl would include 2,3-dimethylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6- diphenylmethyl, 3,4-dimethylphenyl , and 3,5-dimethylphenyl. [0092] Preferred metallocene compounds include a group of suitable catalysts based on mono- or bis-cyclopentadiene. Useful compounds include transition metal compounds comprising extractable ligands described in U.S. Patent 5,198,401 and WO 92/00333. Syntheses of these compounds are well known from the published literature.
[0093] Additional descriptions of metallocene compounds with, or that can be alkylated to contain, at least one ligand abstractable to form catalytically active transition-metal cations appear in the patent literature, (e.g., EP-A-0 129 368, US patents 4,871,705, 4,937,299, 5,324,800, 5,470,993, 5,491,246, 5,512,693, EP-A- 0 418 044, EP-A-0 591 756, WO-A-92/00333, WO-A-94/01471 and WO 97/22635.) Such metallocenes can be described as mono- or biscyclopentadienyl-substituted Group-3, -4, -5, or -6 transition metals. The transition metal ligands may themselves be substituted with one or more groups, and the ligands may bridge to each other or bridge through a heteroatom to the transition metal. Embodiments in which the cyclopentadienyl rings (including substituted, cyclopentadienyl-based, fused-ring systems, such as indenyl, fluorenyl, azulenyl, or their substituted analogs), when bridged to each other, are lower-alkyl substituted (CrC6) in the 2 position (with or without a similar 4- position substituent in the fused ring) are useful. The cyclopentadienyl rings may additionally comprise alkyl, cycloalkyl, aryl, alkylaryl, and arylalkyl substituents, the latter as linear, branched, or cyclic structures including multi-ring structures, for example, those of U.S. Patents 5,278,264 and 5,304,614. In some embodiments, such substituents should each have essentially hydrocarbyl characteristics and will typically contain up to 30 carbon atoms, and may contain heteroatoms, such as 1 to 5 non-hydrogen or non-carbon atoms, e.g., N, S, O, P, Ge, B and Si. A chemical entity is referred to as being substituted when at least one of its hydrogen atom has been replaced with a functional group or when at least one non-hydrocarbon atom or group has been inserted within it. [0094] The following describe useful catalyst systems in invention processes: US06365763, US06365764, US06369254, US06384144, US06388118, US06391989, US06391991, US06399533, US06403737, and US06410661. [0095] Preferred metallocene catalyst compounds useful in this invention are represented by the formula:
LA LB Lci MDE where M is a Group-3-10 metal; LA is a substituted or unsubstituted, cyclopentadienyl or heterocyclopentadienyl ligand connected to M; and LB is a ligand as defined for LA, or is a heteroatom ligand connected to M. LA and LB may connect to each other through a Group-13-16-element-containing bridge. LCi is an optional, neutral, non-oxidizing ligand connected to M (i equals 0 to 3); and D and E are the same or different labile ligands, optionally bridged to each other, LA, or LB. Each of D and E are connected to M. Some embodiments select M to be a member ofthe Group-3-6 transition metals. Other embodiments select M to be a Group-4 transition metal. Some embodiments select M to be Ti, Zr, or Hf. LA and LB are sometimes called ancillary ligands because they are believed to help the metal center retain the correct electronic and geometric structure for olefin polymerizations.
[0096] Function typically constrains D and E in at least two ways: (1) upon activation, either the D-M or E-M connection breaks; and (2) monomer inserts between whichever of D-M or E-M remains. D and E are typically chosen to maximize these functions.
[0097] Cyclopentadienyl also encompasses fused-ring systems including but not limited to indenyl and fluorenyl radicals. Also, the use of heteroatom-containing rings or fused rings, where a non-carbon, Group- 13- 16 atom replaces a ring carbon is within the term "cyclopentadienyl" for this specification. See, for example, the background and illustrations of WO 98/37106, having priority with U.S. Ser. No. 08/999,214, filed 12/29/97, and WO 98/41530, having priority with U.S. Ser. No. 09/042,378, filed 3/13/98. Substituted cyclopentadienyl structures can have one or more hydrogen atoms replaced by a hydrocarbyl, hydrocarbylsilyl, or similar heteroatom-containing structure. Hydrocarbyl structures specifically include C,-C30 linear, branched, and cyclic alkyl, and aromatic fused and pendant rings. These rings may also be substituted with ring structures.
[0098] Preferred metallocene catalyst compounds also include the mono- and biscyclopentadienyl compounds such as those listed and described in U.S. Patents 5,017,714, 5,324,800, and WO 92/00333 and EP-A-0 591 756. [0099] Additional exemplary metallocene-type catalysts include those metallocene compounds represented by the formula:
Figure imgf000028_0001
In the above structure, M is selected from titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, or tungsten.
1 2
R and R are identical or different and are selected from hydrogen atoms, C,-C10 alkyl groups, C,-C10 alkoxy groups, C6-C10 aryl groups, C6-C10 aryloxy groups, C2- C10 alkenyl groups, C2-C40 alkenyl groups, C7-C40 arylalkyl groups, C7-C40 alkylaryl groups, C8-C40 arylalkenyl groups, OH groups or halogen atoms; or conjugated dienes that are optionally substituted with one or more hydrocarbyl, tri(hydrocarbyl)silyl groups or hydrocarbyl, tri(hydrocarbyl)silylhydrocarbyl groups. The conjugated diene can contain up to 30 atoms not counting hydrogen. R3-R12 are the same or different and are selected from hydrogen atoms, halogen atoms, Cj- o halogenated or unhalogenated alkyl groups, C6-C10 halogenated or unhalogenated aryl groups, C2-C10 halogenated or unhalogenated alkenyl groups, C7-C40 halogenated or unhalogenated arylalkyl groups, C7-C40 halogenated or unhalogenated alkylaryl groups, C8-C40 halogenated or unhalogenated arylalkenyl groups, -NR'2, -SR', -OR , -OSiR'3 or -PR'2 radicals in which R' is one of a halogen atom, a CrC10 alkyl group, or a C6-C10 aryl group; or two or more adjacent
5 7 radicals R to R together with the atoms connecting them can form one or more rings.
R13 is selected from
Figure imgf000029_0001
I I I
-M3- -M3- M3- -0-M3-0-
Figure imgf000029_0002
Figure imgf000029_0003
I I I I I I
-M3- C - -O-M3- - C — C — C —
R I 15 RI16 R I 15 R I 15 RI15 RI 15
-B(R14)-, -A1(R14)-, -Ge-, -Sn-, -O-, -S-, -SO-, -SO2-, -N(R14)-, -CO-, -P(R14)- -
P(O)(R14)-, -B(NR14R15)- and -B[N(SiRl4R15R16)2]-. R14, R15 and R16 are each independently selected from hydrogen, halogen, C,-C20 alkyl groups, C6-C30 aryl groups, CrC20 alkoxy groups, C2-C20 alkenyl groups, C7-C40 arylalkyl groups, C8- C40 arylalkenyl groups and C7-C40 alkylaryl groups, or R14 and R15, together with the atom(s) connecting them, form a ring; and M3 is selected from carbon, silicon, germanium and tin. ι_ Alternatively, R is represented by the formula:
Figure imgf000029_0004
17 2. 1 2 wherein R to R are as defined for R and R , or two or more adjacent radicals
17 2. 20 21
R to R , including R and R , together with the atoms connecting them form one or more rings; M is carbon, silicon, germam'um, or tin.
R , R ' R R and R can be identical or different and have the meanings stated for R3to R7.
[00100] In a preferred embodiment dimethylsilyl(tetramethylcyclopentadienyl)(dodecylamido)titanium dichloride is used as a polymerization catalyst. Mono-cyclopentadienyl-substituted metallocene catalyst compounds with excess MAO as the activator form a preferred catalyst system. Some polymers produced by these systems may have different tacticities than those produced at lower temperatures and pressures. [00101] Preferred catalyst compounds useful in this invention include: dimethylsiladiyl(2-methyl, 4-[3',5'-di-tbutylphenyl]indenyl)2zirconium dichloride; dimethylsiladiyl(2-ethyl, 4-[3',5'-di-tbutylphenyl]indenyl)2zirconium dichloride; dimethylsiladiyl(2-n-propyl, 4-[3',5'-di-tbutylphenyl]indenyl)2zirconium dichloride; dimethylsiladiyl(2-iso-propyl, 4-[3',5'-di-tbutylphenyl]indenyl)2zirconium dichloride; dimethylsiladiyl(2-n-butyl, 4-[3',5'-di-tbutylphenyl]indenyl)2zirconium dichloride; dimethylsiladiyl(2-iso-butyl, 4-[3',5'-di-tbutylphenyl]indenyl)2zirconium dichloride; dimethylsiladiyl(2-sec-butyl, 4-[3',5'-di-tbutylphenyl]indenyl)2zirconium dichloride; dimethylsiladiyl(2-tert-butyl, 4-[3',5'-di-tbutylphenyl]indenyl)2zirconium dichloride; dimethylsiladiyl(2-methyl, 4-[3',5'-di-tbutylphenyl]indenyl)2hafhium dichloride; dimethylsiladiyl(2-ethyl, 4-[3',5'-di-tbutylphenyl]indenyl)2hafhium dichloride; dimethylsiladiyl(2-n-propyl, 4-[3',5'-di-tbutylphenyl]indenyl)2hafnium dimethylsiladiyl(2-iso-propyl, 4-[3',5'-di-tbutylphenyl]indenyl)2hafiιium dichloride; dimethylsiladiyl(2-butyl, 4-[3',5'-di-tbutylphenyl]indenyl) 2hafnium dichloride; \ 9-silafluorendiyl(2-methyl, 4-[3',5'-di-tbutylphenyl]indenyl)2zirconium dichloride; 9-silafluorendiyl(2 -ethyl, 4-[3',5'-di-tbutylphenyl]indenyl)2zirconium dichloride; 9-silafluorendiyl(2-n-propyl, 4-[3',5'-di-tbutylphenyl]indenyl)2zirconium dichloride;
9-silafluorendiyl(2-iso-propyl, 4-[3',5'-di-tbutylphenyl]indenyl)2zirconium dichloride;
9-silafluorendiyl(2-n-butyl, 4-[3 ',5'-di-tbutylρhenyl]indenyl)2zirconium dichloride; 9-silafluorendiyl(2-iso-butyl, 4-[3',5'-di-tbutylphenyl]indenyl)2zirconium dichloride;
9-silafluorendiyl(2-sec-butyl, 4-[3l,5'-di-tbutylphenyl]indenyl)2zirconium dichloride;
9-silafluorendiyl(2-tert-butyl, 4-[3',5'-di-tbutylphenyl]indenyl)2zirconium dichloride;
9-silaf_uorendiyl(2-methyl, 4-[3',5'-di-tbutylphenyl]indenyl) 2haf_ιium dichloride; 9-silafluorendiyl(2-ethyl, 4-[3',5'-di-tbutylphenyl]indenyl) 2hafnium dichloride; 9-silafluorendiyl(2-n-propyl, 4-[3',5'-di-tbutylphenyl]indenyl) 2hafhium dichloride; 9-silafluorendiyl(2-iso-propyl, 4-[3',5'-di-tbutylphenyl]indenyl)2hafhium dichloride;
9-silafluorendiyl(2-n-butyl, 4-[3',5'-di-tbutylphenyl]indenyl)2hafnium dichloride; 9-silafluorendiyl(2-iso-butyl, 4-[3',5'-di-tbutylphenyl]indenyl)2hafnium dichloride; 9-silafluorendiyl(2-sec-butyl, 4-[3',5'-di-tbutylphenyl]indenyl)2hafnium dichloride; 9-silaf_uorendiyl(2-tert-butyl, 4- [3 'jS'-di-tbutylphenylJindenyl^hafiiium dichloride; dimethylsiladiyl(2-methyl, 4-[3',5'-di-tbutylphenyl]indenyl)2zirconium dimethyl; dimethylsiladiyl(2-ethyl, 4-[3',5'-di-tbutylphenyl]indenyl)2zirconium dimethyl; dimethylsiladiyl(2-n-propyl, 4-[3',5'-di-tbutylρhenyl]indenyl)2zirconium dimethyl; dimethylsiladiyl(2-iso-propyl, 4-[3',5'-di-tbutylphenyl]indenyl)2zirconium dimethyl; dimethylsiladiyl(2-n-butyl, 4-[3',5'-di-tbutylphenyl]indenyl)2zirconium dimethyl; d_metl_ylsiladiyl(2-iso-butyl, 4-[3 ',5'-di-tbutylphenyl]indenyl)2zirconium dimethyl; dimethylsiladiyl(2-sec-butyl, 4-[3',5'-di-tbutylphenyl]indenyl)2zirconium dimethyl; dimethylsiladiyl(2-tert-butyl, 4-[3',5'-di-tbutylphenyl]indenyl)2zirconium dimethyl; dimethylsiladiyl(2-metl yl, 4-[3',5'-di-tbutylphenyl]indenyl)2hafnium dimethyl; dimethylsiladiyl(2-ethyl, 4-[3',5'-di-tbutylphenyl]indenyl)2hafhium dimethyl; dimemylsiladiyl(2-n-propyl, 4-[3',5'-di-tbutylphenyl]indenyl)2hafnium dimethyl dimethylsiladiyl(2-iso-propyl, 4-[3',5'-di-tbutylphenyl]indenyl)2hafi_ium dimethyl; dimethylsiladiyl(2-n-butyl, 4-[3',5'-di-tbutylphenyl]indenyl) 2hafnium dimethyl; dimethylsiladiyl(2-iso-butyl, 4-[3',5'-di-tbutylphenyl]indenyl) 2hafnium dimethyl; dimethylsiladiyl(2-sec-butyl, 4-[3',5'-di-tbutylphenyl]indenyl) 2hafnium dimethyl; dimethylsiladiyl(2-tert-butyl, 4-[3',5'-di-tbutylphenyl]indenyl) 2hafnium dimethyl;
9-silafluorendiyl(2-methyl, 4-[3',5'-di-tbutylphenyl]indenyl)2zirconium dimethyl;
9-silafluorendiyl(2-ethyl, 4-[3',5'-di-tbutylphenyl]indenyl)2zirconium dimethyl;
9-silafluorendiyl(2-n-propyl, 4-[3',5'-di-tbutylphenyl]indenyl)2zirconium dimethyl;
9-silafluorendiyl(2-iso-propyl, 4-[3',5'-di-tbutylphenyl]indenyl)2zirconium dimethyl;
9-silafluorendiyl(2-n-butyl, 4-[3',5'-di-tbutylphenyl]indenyl)2zirconium dimethyl;
9-silafluorendiyl(2-iso-butyl, 4-[3',5'-di-tbutylphenyl]indenyl)2zirconium dimethyl;
9-silafluorendiyl(2-sec-butyl, 4-[3',5'-di-tbutylphenyl]indenyl)2zirconium dimethyl;
9-silafluorendiyl(2-tert-butyl, 4-[3',5'-di-tbutylphenyl]indenyl)2zirconium dimethyl;
9-silafluorendiyl(2-methyl, 4-[3',5'-di-tbutylphenyl]indenyl) 2hafhium dimethyl;
9-silafluorendiyl(2-ethyl, 4-[3',5'-di-tbutylphenyl]indenyl) 2hafnium dimethyl;
9-silafluorendiyl(2-n-propyl, 4-[3',5'-di-tbutylphenyl]indenyl) 2hafnium dimethyl;
9-silafluorendiyl(2-iso-propyl, 4-[3',5'-di-tbutylphenyl]indenyl)2hafhium dimethyl;
9-silafluorendiyl(2-n-butyl, 4-[3 ',5'-di-tbuty_phenyl]indenyl)2hafnium dimethyl; 9-silafluorendiyl(2-iso-butyl, 4-[3',5'-di-tbutylphenyl]indenyl)2ha__tιium dimethyl
9-silafluorendiyl(2-sec-butyl, 4- [3 ',5'-di-tbutylphenyl]indenyl)2hafhium dimethyl
9-silafluorendiyl(2-tert-butyl, 4-[3',5'-di-tbutylphenyl]indenyl)2hafnium dimethyl dimethylsiladiyl(2-methyl, 4-[3',5'-bis-trifluoromethylphenyl]indenyl)2zirconium dichloride; dimethylsiladiyl(2-ethyl, 4-[3',5'-bis-trifluoromethylphenyl]indenyl)2zirconium dichloride; dimethylsiladiyl(2-n-propyl, 4-[3',5'-bis-trifluoromethylphenyl]indenyl)2zirconium dichloride; dimet__ylsiladiyl(2-iso-propyl, 4-[3',5'-bis- trifluoromethylphenyl]indenyl)2zirconium dichloride; dimethylsiladiyl(2-n-butyl, 4-[3',5'-bis-trifluoromethylphenyl]indenyl)2zirconium dichloride; dimethylsiladiyl(2-iso-butyl, 4-[3',5'-bis- trifluoromethylphenyl]indenyl)2zirconium dichloride; dimethylsiladiyl(2-sec-butyl, 4-[3',5'-bis- trifluoromethylphenyl]indenyl)2zirconium dichloride; dimethylsiladiyl(2-tert-butyl, 4-[3',5'-bis- trifluoromethylphenyl]indenyl)2zirconium dichloride; dimethylsiladiyl(2-methyl, 4-[3',5'-bis-trifluoromethylphenyl]indenyl)2hafnium dichloride; dimethylsiladiyl(2-ethyl, 4-[3',5'-bis-trifluoromethylphenyl]indenyl)2hafhium dichloride; dimethylsiladiyl(2-n-propyl, 4-[3',5'-bis- trifluoromethylphenyl]indenyl)2hafnium dichloride; dimethylsiladiyl(2-iso-propyl, 4-[3',5'-bis- trifluoromethylphenyl]indenyl)2hafhium dichloride; dimethylsiladiyl(2-n-butyl, 4-[3',5'-bis- trifluoromethylphenyl]indenyl)2hafhium dichloride; dimethylsiladiyl(2-iso-butyl, 4-[3',5'-bis- frifluoromethylphenyl]indenyl)2hafhium dichloride; dimethylsiladiyl(2-sec-butyl, 4-[3',5l-bis- trifluoromethylphenyl]indenyl)2hafnium dichloride; dimethylsiladiyl(2-tert-butyl, 4-[3',5'-bis- trifluoromethylphenyl]indenyl)2hafhium dichloride;
9-silafluorendiyl(2-methyl, 4-[3',5'-bis-trifluoromethylphenyl]indenyl)2zirconium dichloride; dimethylsiladiyl(2-ethyl, 4-[3',5'-bis- trifluoromethylphenyl]indenyl)2hafnium dichloride;
9-silafluorendiyl(2-n-propyl, 4-[3',5'-bis- trifluoromethylphenyl]indenyl)2zirconium dichloride;
9-silafluorendiyl(2-iso-propyl, 4- [3 ', 5 '-bis- trifluoromethylphenyl]indenyl)2zirconium dichloride;
9-silafluorendiyl(2-n-butyl, 4-[3',5'-bis- trifluoromethylphenyl]indenyl)2zirconium dichloride;
9-silafluorendiyl(2-iso-butyl, 4- [3 ', 5 '-bis- trifluoromethylphenyl]indenyl)2zirconium dichloride;
9-silafluorendiyl(2-sec-butyl, 4-[3',5'-bis- trifluoromethylphenyl]indenyl)2zirconium dichloride;
9-silafluorendiyl(2-tert-butyl, 4-[3',5'-bis- trifluoromethylphenyl]indenyl)2zirconium dichloride;
9-silafluorendiyl(2-methyl, 4-[3',5'-bis-trifluoromethylphenyl]indenyl)2hafnium dichloride;
9-silafluorendiyl(2-ethyl, 4-[3',5'-bis-trifluoromethylphenyl]indenyl)2hafnium dichloride;
9-silafluorendiyl(2-n-propyl, 4-[3',5'-bis- trifluoromethylphenyl]indenyl)2 hafnium dichloride;
9-silafluorendiyl(2-iso-propyl, 4-[3',5'-bis- trifluoromethylphenyl]indenyl)2 hafnium dichloride; 9-silafluorendiyl(2-n-butyl, 4-[3',5'-bis-frifluoromethylphenyl]mdenyl)2hafi_ium dichloride;
9-silafluorendiyl(2-iso-butyl, 4-[3',5'-bis-trifluoromethylphenyl]indenyl)2hafnium dichloride;
9-silaf_uorendiyl(2-sec-butyl, 4-[3',5'-bis-trifluoromethylρhenyl]indenyl)2hafnium dichloride;
9-silafluorendiyl(2-tert-butyl, 4- [3 ',5'-bis-trifluoromethylphenyl]indenyl)2haιhium dichloride; dimethylsiladiyl(2-methyl, 4-[3',5'-bis-trifluoromethylphenyl]indenyl)2zirconium dimethyl; dimethylsiladiyl(2-ethyl, 4-[3',5'-bis-trifluoromethylphenyl]indenyl)2zirconium dimethyl; dimethylsiladiyl(2-n-propyl, 4-[3',5'-bis-trifluoromethylphenyl]indenyl)2zirconium dimethyl; dimethylsiladiyl(2-iso-propyl, 4-[3',5'-bis- trifluoromethylphenyl]indenyI)2zirconium dimethyl; dimethylsiladiyl(2-n-butyl, 4-[3',5'-bis-frifluoromemylphenyl]indenyl)2zirconium dimethyl; dimethylsiladiyl(2-iso-butyl, 4-[3',5'-bis- trifluoromethylphenyl] indenyl)2zirconium dimethyl; dimethylsiladiyl(2-sec-butyl, 4- [3 ',5'-bis- trifluoromethylphenyl]indenyl)2zirconium dimethyl; dimethylsiladiyl(2-tert-butyl, 4- [3 ',5'-bis- trifluoromethylphenyl]indenyl)2zirconium dimethyl; dimethylsiladiyl(2-methyl, 4- [3 ',5'-bis-trifluoromethylphenyl]indenyl) 2hafhium dimethyl; dimethylsiladiyl(2-ethyl, 4-[3',5'-bis-ttifluoromethylphenyl]indenyl)2hafhium dimethyl; dimethylsiladiyl(2-n-propyl, 4-[3',5'-bis- trifluoromethylphenyl]indenyl)2hafhium dimethyl; dimethylsiladiyl(2-iso-propyl, 4-[3',5'-bis- frifluoromethylphenyl]indenyl)2hafnium dimethyl; dimethylsiladiyl(2-n-butyl, 4-[3',5'-bis- trifluorome ylphenyl]indenyl)2hafhium dimethyl; dimethylsiladiyl(2-iso-butyl, 4-[3l,5'-bis- trifluoromethylphenyl]indenyl)2hafnium dimethyl; dimethylsiladiyl(2-sec-butyl, 4-[3',5'-bis- frifluoromethylphenyl]indenyl)2hafnium dimethyl; dimethylsiladiyl(2-tert-butyl, 4-[3',5'-bis- trifluoromethylphenyl]indenyl)2hafnium dimethyl;
9-silafluorendiyl(2-methyl, 4-[3',5'-bis-trifluoromethylphenyl]indenyl)2zirconium dimethyl; dimethylsiladiyl(2-ethyl, 4-[3',5'-bis- trifluoromethylphenyl]indenyl)2hafhium dimethyl;
9-silafluorendiyl(2-n-propyl, 4-[3',5'-bis- trifluoromethylphenyl]indenyl)2zirconium dimethyl;
9-silafluorendiyl(2-iso-propyl, 4-[3',5'-bis- trifluoromethylphenyl]indenyl)2zirconium dimethyl;
9-silafluorendiyl(2-n-butyl, 4-[3',5'-bis- trifluoromethylphenyl]indenyl)2zirconium dimethyl;
9-silafluorendiyl(2-iso-butyl, 4-[3',5'-bis- trifluoromethylphenyl]indenyl)2zirconium dimethyl;
9-silafluorendiyl(2-sec-butyl, 4-[3',5'-bis- trifluoromethylphenyl]indenyl)2zirconium dimethyl;
9-silafluorendiyl(2-tert-butyl, 4-[3',5'-bis- trifluoromethylphenyl]indenyl)2zirconium dimethyl;
9-silafluorendiyl(2-methyl, 4-[3',5'-bis-trifluoromethylphenyl]indenyl)2hafnium dimethyl;
9-silafluorendiyl(2-ethyl, 4-[3',5'-bis-trifluoromethylphenyl]indenyl)2hafhium dimethyl; 9-silafluorendiyl(2-n-propyl, 4-[3',5'-bis- trifluoromethylphenyl]indenyl)2 hafiiium dimethyl;
9-silafluorendiyl(2-iso-propyl, 4-[3',5'-bis- trifluoromethylphenyl]indenyl)2 hafiiium dimethyl;
9-silafluorendiyl(2-n-butyl, 4-[3l,5'-bis-trifluoromethylphenyl]indenyl)2hafnium dimethyl;
9-silafluorendiyl(2-iso-butyl, 4-[3l,5'-bis-trifluoromethylphenyl]indenyl)2hafhium dimethyl;
9-silafluorendiyl(2-sec-butyl, 4-[3',5'-bis-trifluoromethylphenyl]indenyl)2hafnium dimethyl;
9-silafluorendiyl(2-tert-butyl, 4-[3',5'-bis-trifluoromethylphenyl]indenyl)2hafhium dimethyl; dimethylsiladiyl(2-ethyl, 4-[3',5'-di-iso-propylphenyl]indenyl)2zirconium dichloride; dimethylsiladiyl(2-n-propyl, 4-[3',5'-di-iso-propylphenyl]indenyl)2zirconium dichloride dimethylsiladiyl(2-iso-propyl, 4-[3',5'-di-iso-propylphenyl]indenyl)2zirconium dichloride; dimethylsiladiyl(2-n-butyl, 4-[3',5'-di-iso-propylphenyl]indenyl)2zirconium dichloride; dimethylsiladiyl(2-iso-butyl, 4-[3',5'-di-iso-propylphenyl]indenyl)2zirconium dichloride; dimethylsiladiyl(2-sec-butyl, 4-[3',5'-di-iso-propylphenyl]indenyl)2zirconium dichloride; dimethylsiladiyl(2-tert-butyl, 4-[3',5'-di-iso-propylphenyl]indenyl)2zirconium dichloride; dimethylsiladiyl(2-ethyl, 4-[3',5'-di-iso-propylphenyl]indenyl)2hafhium dichloride; dimethylsiladiyl(2-n-propyl, 4-[3',5'-di-iso-propylphenyl]indenyl)2hafiιium dichloride; dimethylsiladiyl(2-iso-propyl, 4-[3',5'-di- iso-propylphenyl]indenyl) 2hafhium dichloride; dimethylsiladiyl(2-n-butyl, 4-[3',5'-di- iso-propylphenyl]indenyl) 2hafnium dichloride; dimethylsiladiyl(2-iso-butyl, 4-[3',5'-di- iso-propylphenyl]indenyl) 2hafhium dichloride; dimethylsiladiyl(2-sec-butyl, 4-[3',5'-di- iso-propylphenyl]indenyl) 2hafhium dichloride; dimethylsiladiyl(2-tert-butyl, 4-[3',5'-di- iso-propylphenyl]indenyl) 2hafhium dichloride;
9-silafluorendiyl(2-ethyl, 4-[3',5'-di-iso-propylphenyl]indenyl)2zirconium dichloride;
9-silafluorendiyl(2-n-propyl, 4-[3',5'-di-iso-propylphenyl]indenyl)2zirconium dichloride;
9-silafluorendiyl(2-iso-propyl, 4-[3',5'-di-iso-propylphenyl]indenyl)2zirconium dichloride;
9-silafluorendiyl(2-n-butyl, 4-[3',5'-di-iso-propylphenyl]indenyl)2zirconium dichloride;
9-silafluorendiyl(2-iso-butyl, 4-[3',5'-di-iso-propylphenyl]indenyl)2zirconium dichloride;
9-silafluorendiyl(2-sec-butyl, 4-[3',5'-di-iso-propylphenyl]indenyl)2zirconium dichloride;
9-silafluorendiyl(2-tert-butyl, 4-[3',5'-di-iso-propylphenyl]indenyl)2zirconium dichloride;
9-silaf_uorendiyl(2-ethyl, 4-[3',5'-di-iso-propylphenyl]indenyl)2hafnium dichloride;
9-silafluorendiyl(2-n-propyl, 4-[3',5'-di-iso-propylphenyl]indenyl)2hafhium dichloride;
9-silafluorendiyl(2-iso-propyl, 4-[3',5'-di-iso-propylphenyl]indenyl)2hafhium dichloride; 9-silafluorendiyl(2-n-butyl, 4-[3',5'-di-iso-propylphenyl]indenyl)2hafhium dichloride;
9-silafluorendiyl(2-iso-butyl, 4-[3',5'-di-iso-propylphenyl]indenyl)2hafhium dichloride;
9-silafluorendiyl(2-sec-butyl, 4-[3',5'-di-iso-propylphenyl]indenyl)2hafnium dichloride;
9-silafluorendiyl(2-tert-butyl, 4-[3',5'-di-iso-propylphenyl]indenyl)2hafnium dichloride; dimethylsiladiyl(2-ethyl, 4-[3',5'-di-iso-propylphenyl]indenyl)2zirconium dimethyl; dimethylsiladiyl(2-n-propyl, 4-[3',5'-di-iso-propylphenyl]indenyl)2zirconium dimethyl dimethylsiladiyl(2-iso-propyl, 4-[3',5'-di-iso-propylphenyl]indenyl)2zirconium dimethyl; dimethylsiladiyl(2-n-butyl, 4-[3',5'-di-iso-propylphenyl]indenyl)2zirconium dimethyl; dimethylsiladiyl(2-isobutyl, 4-[3',5'-di-iso-propylphenyl]indenyl)2zirconium dimethyl; dimethylsiladiyl(2-sec-butyl, 4-[3',5'-di-iso-propylphenyl]indenyl)2zirconium dimethyl; dimethylsiladiyl(2-tert-butyl, 4-[3',5'-di-iso-propylphenyl]indenyl)2zirconium dimethyl; dimethylsiladiyl(2-ethyl, 4-[3',5'-di-iso-propylphenyl]indenyl) 2hafiιium dimethyl; dimethylsiladiyl(2-n-propyl, 4-[3',5'-di- iso-propylphenyl]indenyl) 2hafnium dimethyl; dimethylsiladiyl(2-iso-propyl, 4-[3',5'-di- iso-propylphenyl]indenyl) 2hafnium dimethyl; dimethylsiladiyl(2-n-butyl, 4-[3',5'-di- iso-propylphenyl]indenyl) 2hafnium dimethyl; dimet_ιylsiladiyl(2-iso-butyl, 4-[3',5'-di-iso-propylphenyl]indenyl)2zirconium dimethyl; dimethylsiladiyl(2-sec-butyl, 4-[3',5'-di-iso-propylphenyl]indenyl)2zirconium dimethyl; dimethylsiladiyl(2-tert-butyl, 4-[3',5'-di-iso-propylphenyl]indenyl)2zirconium dimethyl;
9-silafluorendiyl(2-ethyl, 4- [3 ',5'-di-iso-propylphenyl]indenyl)2zirconium dimethyl;
9-silafluorendiyl(2-n-propyl, 4-[3',5'-di-iso-propylphenyl]indenyl)2zirconium dimethyl;
9-silafluorendiyl(2-iso-propyl, 4-[3',5'-di-iso-propylphenyl]indenyl)2zirconium dimethyl;
9-silafluorendiyl(2-n-butyl, 4-[3',5'-di-iso-propylphenyl]indenyl)2zirconium dimethyl;
9-silaf_uorendiyl(2-iso-butyl, 4-[3',5'-di-iso-propylphenyl]indenyl)2zirconium dimethyl;
9-silafluorendiyl(2-sec-butyl, 4-[3 ', 5 '-di-iso-propylphenyl] indenyl)2zirconium dimethyl;
9-silafluorendiyl(2 -tert-butyl, 4-[3',5'-di-iso-propylphenyl]indenyl)2zirconium dimethyl;
9-silafluorendiyl(2-ethyl, 4-[3',5'-di-iso-propylphenyl]indenyl)2hafhium dimethyl;
9-silafluorendiyl(2-n-propyl, 4-[3',5'-di-iso-propylphenyl]indenyl)2hafhium dimethyl;
9-silafluorendiyl(2-iso-propyl, 4-[3',5'-di-iso-propylphenyl]mdenyl)2hafhium dimethyl;
9-silafluorendiyl(2-n-butyl, 4-[3',5'-di-iso-propylphenyl]indenyl)2hafhium dimethyl;
9-silafluorendiyl(2-iso-butyl, 4- [3 ', 5 '-di-iso-propylphenyl]indenyl)2hafnium dimethyl; 9-silafluorendiyl(2-sec-butyl, 4-[3',5'-di-iso-propylphenyl]indenyl)2hafnium dimethyl;
9-silafluorendiyl(2-tert-butyl, 4-[3',5'-di-iso-propylphenyl]indenyl)2hafhium dimethyl; dimethylsiladiyl(2-methyl, 4-[3',5'-di-phenylphenyl]indenyl)2zirconium dichloride; dimethylsiladiyl(2-ethyl, 4-[3',5'-di-phenylphenyl]indenyl)2zirconium dichloride; dimethylsiladiyl(2-n-propyl, 4-[3',5'-di-phenylphenyl]indenyl)2zirconium dichloride; dimethylsiladiyl(2-iso-propyl, 4-[3',5'-di-phenylphenyl]indenyl)2zirconium dichloride; dimethylsiladiyl(2-n-butyl, 4-[3',5'-di-phenylphenyl]indenyl)2zirconium dichloride; dimethylsiladiyl(2-iso-butyl, 4-[3',5'-di-phenylphenyl]indenyl)2zirconium dichloride; dimethylsiladiyl(2-sec-butyl, 4-[3',5'-di-phenylphenyl]indenyl)2zirconium dichloride; dimethylsiladiyl(2-tert-butyl, 4-[3',5'-di-phenylphenyl]indenyl)2zirconium dichloride; dimethylsiladiyl(2-methyl, 4-[3',5'-di-phenylphenyl]indenyl)2hafhium dichloride; dimethylsiladiyl(2-ethyl, 4-[3',5'-di-phenylphenyl]indenyl)2hafhium dichloride; dimethylsiladiyl(2-n-propyl, 4-[3',5'-di-phenylphenyl]indenyl)2hafnium dichloride; dimethylsiladiyl(2-iso-propyl, 4-[3',5'-di-phenylphenyl]indenyl)2hafiιium dichloride; dimethylsiladiyl(2-n-butyl, 4-[3',5'-di-phenylphenyl]indenyl)2hafnium dichloride; dimethylsiladiyl(2-iso-butyl, 4-[3',5'-di-phenylphenyl]indenyl)2hafnium dichloride; dimethylsiladiyl(2-sec-butyl, 4-[3',5'-di-phenylphenyl]indenyl)2hafhium dichloride; dimethylsiladiyl(2-tert-butyl, 4-[3',5'-di-phenylphenyl]indenyl)2hafnium dichloride;
9-silafluorendiyl(2-methyl, 4-[3',5'-di-phenylphenyl]indenyl)2zirconium dichloride;
9-silafluorendiyl(2-ethyl, 4-[3',5'-di-phenylphenyl]indenyl)2zirconium dichloride;
9-silafluorendiyl(2-n-propyl, 4-[3',5'-di-phenylphenyl]indenyl)2zirconium dichloride;
9-silafluorendiyl(2-iso-propyl, 4-[3',5'-di-phenylphenyl]indenyl)2zirconium dichloride;
9-silafTuorendiyl(2-n-butyl, 4- [3 ',5 '-di-phenylpheny 1] indenyl)2zirconium dichloride;
9-silafluorendiyl(2-iso-butyl, 4-[3',5'-di-phenylphenyl]indenyl)2zirconium dichloride;
9-silafluorendiyl(2-sec-butyl, 4-[3',5'-di-phenylphenyl]indenyl)2zirconium dichloride;
9-silafluorendiyl(2-tert-butyl, 4-[3',5'-di-phenylphenyl]indenyl)2zirconium dichloride;
9-silafluorendiyl(2-methyl, 4-[3',5'-di-phenylphenyl]indenyl)2hafnium dichloride;
9-silafluorendiyl(2-ethyl, 4-[3',5'-di-phenylphenyl]indenyl)2hafhium dichloride;
9-silafluorendiyl(2-n-propyl, 4-[3',5'-di-phenylphenyl]indenyl)2hafhium dichloride;
9-silafluorendiy l(2-iso-propyl, 4- [3 ', 5 '-di-phenylpheny 1] indenyl)2hafnium dichloride;
9-silafluorendiyl(2-n-butyl, 4-[3',5'-di-phenylphenyl]indenyl)2hafnium dichloride;
9-silafluorendiyl(2-iso-butyl, 4-[3',5'-di-phenylphenyl]indenyl)2hafnium dichloride;
9-silafluorendiyl(2-sec-butyl, 4-[3',5'-di-phenylphenyl]indenyl)2hafhium dichloride;
9-silafluorendiyl(2-tert-butyl, 4-[3',5'-di-phenylphenyl]indenyl)2hafhium dichloride; dimemylsiladiyl(2-methyl, 4-[3',5'-di-phenylphenyl]indenyl)2zirconium dimethyl; dimethylsiladiyl(2-ethyl, 4-[3',5'-di-phenylphenyl]indenyl)2zirconium dimethyl; dimethylsiladiyl(2-n-propyl, 4-[3',5'-di-phenylphenyl]indenyl)2zirconium dimethyl; dimethylsiladiyl(2-iso-propyl, 4-[3',5'-di-phenylphenyl]indenyl)2zirconium dimethyl; dimethylsiladiyl(2-n-butyl, 4- [3 ',5'-di-pheny_phenyl]indenyι)2zirconium dimethyl; dimethylsiladiyl(2-iso-butyl, 4-[3',5'-di-phenylphenyl]indenyl)2zirconium dimethyl; dimethylsiladiyl(2 -sec-butyl, 4-[3',5'-di-phenylphenyl]indenyl)2zirconium dimethyl; dimethylsiladiyl(2-tert-butyl, 4-[3',5'-di-phenylphenyl]indenyl)2zirconium dimethyl; dimethylsiladiyl(2-methyl, 4-[3',5'-di-phenylphenyl]indenyl)2hafnium dimethyl; dimethylsiladiyl(2-ethyl, 4-[3',5'-di-phenylphenyl]indenyl)2hafiιium dimethyl; dimethylsiladiyl(2-n-propyl, 4-[3',5'-di-phenylphenyl]indenyl)2hafhium dimethyl; dimethylsiladiyl(2-iso-propyl, 4-[3',5'-di-phenylphenyl]indenyl)2hafnium dimethyl; dimethylsiladiyl(2-n-butyl, 4-[3',5'-di-phenylphenyl]indenyl)2hafnium dimethyl; dimethylsiladiyl(2-iso-butyl, 4-[3',5'-di-phenylphenyl]indenyl)2hafhium dimethyl; dimethylsiladiyl(2-sec-butyl, 4-[3',5'-di-phenylphenyl]indenyl)2hafiιium dimethyl; dimethylsiladiyl(2-tert-butyl, 4-[3',5'-di-phenylphenyl]indenyl)2hafnium dimethyl;
9-silafluorendiyl(2-methyl, 4-[3',5'-di-phenylphenyl]mdenyl)2zirconium dimethyl;
9-silafluorendiyl(2-ethyl, 4-[3',5'-di-phenylphenyl]indenyl)2zirconium dimethyl;
9-silafluorendiyl(2-n-ρropyl, 4-[3',5'-di-phenylphenyl]indenyl)2zirconium dimethyl;
9-silafluorendiyl(2-iso-propyl, 4-[3',5'-di-phenylphenyl]indenyl)2zirconium dimethyl;
9-silafluorendiyl(2-n-butyl, 4-[3',5'-di-phenylphenyl]indenyl)2zirconium dimethyl; 9-silafluorendiyl(2-iso-butyl, 4-[3',5'-di-phenylphenyl]indenyl)2zirconium dimethyl;
9-silafluorendiyl(2-sec-butyl, 4-[3',5'-di-phenylphenyl]indenyl)2zirconium dimethyl;
9-silafluorendiyl(2-tert-butyl, 4-[3',5'-di-phenylphenyl]indenyl)2zirconium dimethyl;
9-silafluorendiyl(2-methyl, 4-[3',5'-di-phenylphenyl]indenyl)2hafnium dimethyl;
9-silafluorendiyl(2-ethyl, 4- [3 ', 5 '-di-phenylpheny 1] indeny l)2hafnium dichloride;
9-silafluorendiyl(2-n-propyl, 4-[3',5'-di-phenylphenyl]indenyl)2hafnium dimethyl;
9-silaf_uorendiyl(2-iso-propyl, 4-[3',5'-di-phenylphenyl]indenyl)2hafnium dimethyl;
9-silafluorendiyl(2-n-butyl, 4-[3',5'-di-phenylphenyl]indenyl)2hafhium dimethyl;
9-silafluorendiyl(2-iso-butyl, 4-[3',5'-di-phenylphenyl]indenyl)2hafnium dimethyl;
9-silafluorendiyl(2-sec-butyl, 4-[3',5'-di-phenylphenyl]indenyl)2hafnium dimethyl;
9-silafluorendiyl(2-tert-butyl, 4-[3',5'-di-phenylphenyl]indenyl)2hafnium dimethyl; dimethylsiladiyl(2-methyl, 4-[3',5'-di-tbutylphenyl]indenyl)2 η -l ,4-dipheny 1-1,3 - butadiene; dimethylsiladiyl(2-ethyl, 4-[3',5'-di-tbutylphenyl]indenyl)2η4-l,4-diphenyl-l,3- butadiene; dimethylsiladiyl(2-n-propyl, 4-[3',5'-di-tbutylphenyl]indenyl)2η4-l,4-diphenyl-
1,3-butadiene; dimethylsiladiyl(2-iso-propyl, 4-[3',5'-di-tbutylphenyl]indenyl)2 η4- 1 ,4-diphenyl-
1,3-butadiene; dimethylsiladiyl(2-n-butyl, 4-[3',5'-di-tbutylphenyl]indenyl)2η4-l,4-diphenyl-l,3- butadiene; dimethylsiladiyl(2-iso-butyl, 4-[3',5'-di-tbutylphenyl]indenyl)2 η4-l ,4-diphenyl-
1,3 -butadiene; dimethylsiladiyl(2-sec-butyl, 4-[3',5'-di-tbutylphenyl]indenyl)2 η4-l ,4-diphenyl-
1,3-butadiene; dimethylsiladiyl(2-tert-butyl, 4-[3',5'-di-tbutylphenyl]indenyl)2η4-l,4-diphenyl- 1,3 -butadiene; dimethylsiladiyl(2-ethyl, 4- [3 ',5'-bis-trifluoromethylphenyl]indenyl)2 η4- 1 ,4- diphenyl-1 ,3-butadiene; dimethylsiladiyl(2-n-propyl, 4-[3',5'-bis-trifluoromethylphenyl]indenyl)2 η4-l ,4- diphenyl- 1 ,3-butadiene; dimethylsiladiyl(2-iso-propyl, 4-[3',5'-bis- trifluoromethylphenyl]indenyl)2 η4-l,4- diphenyl- 1 ,3 -butadiene; dmιethylsiladiyl(2-n-butyl, 4-[3',5'-bis-trifluoromethylphenyl]indenyl)2 η4-l ,4- diphenyl-l,3-butadiene; dimethylsiladiyl(2-iso-butyl, 4- [3 ',5'-bis-trifluoromethylphenyl]indenyl)2 η4- 1 ,4- diphenyl-1 ,3-butadiene; dimethylsiladiyl(2-sec-butyl, 4-[3',5'-bis-trifluoromethylphenyl]indenyl)2 η -l ,4- diphenyl- 1 ,3-butadiene; dimethylsiladiyl(2-tert-butyl, 4-[3',5'-bis-trifluoromethylphenyl]indenyl)2 η4-l ,4- diphenyl- 1 ,3-butadiene; dimethylsiladiyl(2-ethyl, 4-[3',5'-di-iso-propylphenyl]indenyl)2 η4-l ,4-diphenyl- 1,3-butadiene; dimethylsiladiyI(2-n-propyl, 4-[3',5'-di-iso-propylpheny_]_ndenyl)2 η4-l,4- diphenyl- 1 ,3 -butadiene; dimethylsiladiyl(2-iso-propyl, 4-[3',5'-di-iso-propylphenyl]indenyl) η4-l ,4- diphenyl- 1 ,3-butadiene; dimethylsiladiyl(2-n-butyl, 4-[3',5'-di-iso-propylphenyl]indenyl)2 η4-l ,4-diphenyl- 1,3-butadiene; dimethylsiladiyl(2-iso-butyl, 4-[3',5'-di-iso-propylphenyl]indenyl)2η4-l,4- diphenyl-l,3-butadiene; dimethylsiladiyl(2-sec-butyl, 4-[3',5'-di-iso-propylphenyl]indenyl)2η4-l,4- diphenyl- 1 ,3 -butadiene; dimethylsiladiyl(2-tert-butyl, 4-[3',5'-di-iso-ρropy_phenylJ_ndenyl)2 η4-l ,4- diphenyl-l,3-butadiene; dimethylsiladiyl(2-methyl, 4-[3',5'-di-phenylphenyl]indenyl)2η4-l,4-diphenyl-l,3- butadiene; dimethylsiladiyl(2-ethyl, 4-[3',5'-di-phenylphenyl]indenyl)2η4-l,4-diphenyl-l,3- butadiene; dimethylsiladiyl(2-n-propyl, 4-[3',5'-di-phenylphenyl]indenyl)2 η4-l ,4-diphenyl- 1,3 -butadiene; dimethylsiladiyl(2-iso-propyl, 4-[3',5'-di-phenylphenyl]indenyl)2 η4-l ,4-diphenyl- 1,3-butadiene; dimethylsiladiyl(2-n-butyl, 4-[3 ',5'-di-phenylphenyl]indenyl)2 η4- 1 ,4-diphenyl- 1 ,3 - butadiene; dimethylsiladiyl(2-iso-butyl, 4-[3',5'-di-phenylphenyl]indenyl)2 η4-l ,4-diphenyl- 1,3 -butadiene; dimethylsiladiyl(2-sec-butyl, 4-[3',5'-di-phenylphenyl]indenyl)2 η4-l ,4-diphenyl- 1,3 -butadiene; dimethylsiladiyl(2-tert-butyl, 4-[3',5'-di-ρhenylphenyl]indenyl)2 η4-l ,4-diphenyl- 1,3-butadiene;
9-silafluorendiyl(2-methyl, 4-[3',5'-di-tbutylphenyl]indenyl)2 η4-l ,4-diphenyl- 1 ,3- butadiene;
9-silafluorendiyl(2-ethyl, 4- [3 ',5'-di-tbutylphenyl]indenyl)2 η4- 1 ,4-diphenyl- 1 ,3 - butadiene;
9-silafluorendiyl(2-n-propyl, 4-[3*,5'-di-tbutylphenyl]indenyl)2η4-l,4-diphenyl-
1,3-butadiene;
9-silafluorendiyl(2-iso-propyl, 4-[3',5'-di-tbutylphenyl]indenyl)2 η4-l ,4-diphenyl-
1,3-butadiene;
9-silafluorendiyl(2-n-butyl, 4-[3 ,,5'-di-tbutylphenyl]indenyl)2 η4- 1 ,4-diphenyl- 1 ,3- butadiene; 9-silafluorendiyl(2-iso-butyl, 4-[3',5'-di-tbutylphenyl]indenyl)2η4-l,4-diphenyl- 1,3-butadiene;
9-silafluorendiyl(2-sec-butyl, 4-[3',5'-di-tbutylphenyl]indenyl)2η4-l,4-diphenyl- 1,3 -butadiene;
9-silafluorendiyl(2-tert-butyl, 4-[3',5'-di-tbutylphenyl]indenyl)2 η4-l ,4-diphenyl- 1,3-butadiene;
9-silafluorendiyl(2-ethyl, 4-[3',5'-bis-trifluoromethylphenyl]indenyl)2 η4-l ,4- diphenyl- 1 ,3-butadiene;
9-silafluorendiyl(2-n-propyl, 4-[3',5'-bis-trifluoromethylphenyl]indenyl)2 η4-l ,4- diphenyl-1 ,3-butadiene;
9-silafluorendiyl(2-iso-propyl, 4-[3',5'-bis- trifluoromethylphenyl]indenyl)2 η4-l ,4- diphenyl- 1 ,3-butadiene;
9-silafluorendiyl(2-n-butyl, 4-[3',5'-bis-trifluoromethylphenyl]indenyl)2 η4-l ,4- diphenyl-1 ,3-butadiene;
9-silafluorendiyl(2-iso-butyl, 4-[3',5'-bis-trifluoromethylphenyl]indenyl)2 η4- 1 ,4- diphenyl-1 ,3-butadiene;
9-silafluorendiyl(2-sec-butyl, 4-[3',5'-bis-trifluoromethylphenyl]indenyl)2 η4- 1 ,4- diphenyl-1 ,3-butadiene;
9-silafluorendiyl(2-tert-butyl, 4-[3,,5'-bis-trifluoromethylphenyl]indenyl)2 η4-l ,4- diphenyl- 1 ,3-butadiene;
9-silafluorendiyl(2-ethyl, 4-[3',5'-di-iso-propylphenyl]indenyl)2 η4-l ,4-diphenyl- 1,3 -butadiene;
9-silafluorendiyl(2-n-propyl, 4-[3',5'-di-iso-propylphenyl]indenyl) 2 η4-l,4- diphenyl-l,3-butadiene;
9-silafluorendiyl(2-iso-propyl, 4-[3',5'-di-iso-propylphenyl]indenyl) η4-l,4- diphenyl- 1 ,3-butadiene;
9-silafluorendiyl(2-n-butyl, 4-[3',5'-di-iso-propylphenyl]indenyl)2 η4-l ,4-diphenyl- 1,3-butadiene; 9-silafluorendiyl(2-iso-butyl, 4-[3',5'-di-iso-propylphenyl]indenyl)2η4-l,4- diphenyl- 1 ,3-butadiene;
9-silafluorendiyl(2-sec-butyl, 4-[3',5'-di-iso-propylphenyl]indenyl)2η4-l,4- diphenyl-l,3-butadiene;
9-silafluorendiyl(2-tert-butyl, 4-[3',5'-di-iso-propylphenyl]indenyl)2η4-l,4- diphenyl-1 ,3-butadiene;
9-silafluorendiyl(2-methyl, 4-[3',5'-di-phenylphenyl]indenyl)2 η4-l ,4-diphenyl-l ,3- butadiene;
9-silafluorendiyl(2-ethyl, 4-[3',5'-di-phenylphenyl]indenyl)2η4-l,4-diphenyl-l,3- butadiene;
9-silafluorendiyl(2-n-propyl, 4-[3',5'-di-phenylphenyl]indenyl)2 η4-l ,4-diphenyl- 1,3-butadiene;
9-silafluorendiyl(2-iso-propyl, 4-[3',5'-di-phenylphenyl]indenyl)2η4-l,4-diphenyl- 1,3 -butadiene;
9-silafluorendiyl(2-n-butyl, 4-[3',5'-di-phenylphenyl]indenyl)2 η4-l ,4-diphenyl- 1,3 -butadiene;
9-silafluorendiyl(2-iso-butyl, 4-[3',5'-di-phenylphenyl]indenyl)2 η4-l ,4-diphenyl- 1,3-butadiene;
9-silafluorendiyl(2-sec-butyl, 4-[3',5'-di-phenylphenyl]indenyl)2 η4-l ,4-diphenyl- 1,3 -butadiene;
9-silafluorendiyl(2-tert-butyl, 4-[3',5'-di-phenylphenyl]indenyl)2 η4-l ,4-diphenyl- 1,3 -butadiene; dimethylamidoborane(2-methyl, 4-[3',5'-di-tbutylphenyl]indenyl)2zirconium dichloride; dimethylamidoborane(2-ethyl, 4-[3',5'-di-tbutylphenyl]indenyl)2zirconium dichloride; dimethylamidoborane(2-n-propyl, 4-[3',5'-di-tbutylphenyl]indenyl)2zirconium dichloride; dimethylamidoborane(2-iso-propyl, 4-[3',5'-di-tbutylphenyl]indenyl)2zirconium dichloride; dimethylamidoborane(2-n-butyl, 4- [3 ',5'-di-tbutylphenyl]indenyl)2zirconium dichloride; dimethylamidoborane(2-iso-butyl, 4-[3',5'-di-tbutylphenyl]indenyl)2zirconium dichloride; dimethylamidoborane(2-sec-butyl, 4-[3',5'-di-tbutylphenyl]indenyl)2zirconium dichloride; dimethylamidoborane(2-tert-butyl, 4-[3',5'-di-tbutylphenyl]indenyl)2zirconium dichloride; dimethylamidoborane(2-ethyl, 4-[3',5'-bis- trifluoromethylphenyl]indenyl)2zirconium dichloride; dimethylamidoborane(2-n-propyl, 4-[3',5'-bis- trifluoromethylphenyl]indenyl)2zirconium dichloride; dimethylamidoborane(2-iso-propyl, 4-[3',5'-bis- trifluoromethylphenyl]indenyl)2zirconium dichloride; dimethylamidoborane(2-n-butyl, 4-[3',5'-bis- trifluoromethylphenyl]indenyl)2zirconium dichloride; dimethylamidoborane(2-iso-butyl, 4-[3',5'-bis- trifluoromethylphenyl]indenyl)2zirconium dichloride; dimethylamidoborane(2-sec-butyl, 4-[3',5'-bis- trifluoromethylphenyl]indenyl)2zirconium dichloride; dimethylamidoborane(2-tert-butyl, 4-[3',5'-bis- trifluoromethylphenyl]indenyl)2zirconium dichloride; dimethylamidoborane(2-ethyl, 4-[3',5'-di-iso-propylphenyl]indenyl)2zirconium dichloride; dimethylamidoborane(2-n-propyl, 4-[3',5'-di-iso-propylphenyl]indenyl)2zirconium dichloride dimethylamidoborane(2-iso-propyl, 4- [3 ' , 5 '-di-iso- propylphenyl]indenyl)2zirconium dichloride; dimethylamidoborane(2-n-butyl, 4-[3',5'-di-iso-propylphenyl]indenyl)2zirconium dichloride; dimethylamidoborane(2-iso-butyl, 4-[3',5'-di-iso-propylphenyl]indenyl)2zirconium dichloride; dimethylamidoborane(2-sec-butyl, 4-[3',5'-di-iso- propylphenyl]indenyl)2zirconium dichloride; dimethylamidoborane(2-tert-buty 1, 4- [3 ' ,5 '-di-iso- propylphenyl]indenyl)2zircor_ium dichloride; dimethylamidoborane(2-methyl, 4-[3',5'-di-phenylphenyl]indenyl)2zirconium dichloride; dimethylamidoborane(2-ethyl, 4-[3',5'-di-phenylphenyl]indenyl)2zirconium dichloride; dimethylamidoborane(2-n-propyl, 4-[3',5'-di-phenylphenyl]indenyl)2zirconium dichloride; dimethylamidoborane(2-iso-propyl, 4-[3',5'-di-phenylphenyl]indenyl)2zirconium dichloride; dimethylamidoborane(2-n-butyl, 4-[3',5'-di-phenylphenyl]indenyl)2zirconium dichloride; dimethylamidoborane(2-iso-butyl, 4-[3',5'-di-phenylphenyl]indenyl)2zirconium dichloride; dimethylamidoborane(2-sec-butyl, 4- [3 ',5'-di-phenylphenyl]indenyl)2zirconium dichloride; dimethylamidoborane(2-tert-butyl, 4-[3',5'-di-phenylphenyl]indenyl)2zirconium dichloride; dimethylamidoborane(2-methyl, 4-[3',5'-di-tbutylphenyl]indenyl)2 η4-l ,4- diphenyl- 1 ,3-butadiene; dimethylamidoborane(2-ethyl, 4-[3',5'-di-tbutylphenyl]indenyl)2 η4-l ,4-diphenyl- 1,3 -butadiene; dimethylamidoborane(2-n-propyl, 4-[3',5'-di-tbutylphenyl]indenyl)2η4-l,4- diphenyl- 1 ,3-butadiene; dimethylarnidoborane(2-iso-propyl, 4-[3',5'-di-tbutylphenyl]indenyl)2 η4-l ,4- diphenyl-l ,3-butadiene; dimethylamidoborane(2-n-butyl, 4-[3',5'-di-tbutylphenyl]indenyl)2 η4-l ,4- diphenyl- 1 ,3 -butadiene; dimethylamidoborane(2-iso-butyl, 4-[3',5'-di-tbutylphenyl]indenyl)2 η4-l ,4- diphenyl-l,3-butadiene; dimethylamidoborane(2-sec-butyl, 4-[3',5'-di-tbutylphenyl]indenyl)2η4-l,4- diphenyl-l,3-butadiene; dimethylamidoborane(2-tert-butyl, 4-[3',5'-di-tbutylphenyl]indenyl)2 η4-l ,4- diphenyl-l ,3-butadiene; dimethylamidoborane(2-ethyl, 4-[3',5'-bis-trifluoromethylphenyl]indenyl)2 η4-l ,4- diphenyl-l ,3-butadiene; dimethylamidoborane(2-n-propyl, 4-[3',5'-bis-trifluoromethylphenyl]indenyl)2η4- 1 ,4-diphenyl-l ,3-butadiene; dimethylamidoborane(2-iso-propyl, 4-[3',5'-bis- trifluoromethylphenyl]indenyl)2 η4-l ,4-diphenyl- 1 ,3-butadiene; dimethylamidoborane(2-n-butyl, 4-[3',5'-bis-trifluoromethylphenyl]indenyl)2η4- 1 ,4-diphenyl-l ,3-butadiene; dimethylamidoborane(2-iso-butyl, 4-[3',5'-bis-trifluoromethylphenyl]indenyl)2η4- 1 ,4-diphenyl- 1 ,3-butadiene; dimethylamidoborane(2-sec-butyl, 4-[3',5'-bis-trifluoromethylphenyl]indenyl)2η4- 1 ,4-diphenyl-l ,3-butadiene; dimethylamidoborane(2-tert-butyl, 4-[3',5'-bis-trifluoromethylphenyl]indenyl)2η4- 1 ,4-diphenyl- 1 ,3-butadiene; dimethylamidoborane(2-ethyl, 4-[3',5'-di-iso-propylphenyl]indenyl)2η4-l,4- diphenyl- 1 ,3 -butadiene; dimethylamidoborane(2-n-propyl, 4-[3',5'-di-iso-propylphenyl]indenyl)2 η4-l,4- diphenyl- 1 ,3 -butadiene; dimethylamidoborane(2-iso-propyl, 4-[3',5'-di-iso-propylphenyl]indenyl) η4-l,4- diphenyl- 1 ,3 -butadiene; dimethylamidoborane(2-n-butyl, 4-[3',5'-di-iso-propylphenyl]indenyl)2 η4-l,4- diphenyl- 1 ,3 -butadiene; dimethylamidoborane(2-iso-butyl, 4-[3',5'-di-iso-propylphenyl]indenyl)2 η4-l ,4- diphenyl- 1 ,3 -butadiene; dimethylamidoborane(2-sec-butyl, 4-[3',5'-di-iso-propylphenyl]indenyl)2η4-l,4- diphenyl-1 ,3-butadiene; dimethylamidoborane(2-tert-butyl, 4-[3',5'-di-iso-propylphenyl]indenyl)2 η4-l ,4- diphenyl- 1 ,3 -butadiene;
, dimethylamidoborane(2-methyl, 4-[3',5'-di-phenylphenyl]indenyl)2 η4-l ,4- diphenyl- 1 ,3-butadiene; dimethylamidoborane(2 -ethyl, 4-[3',5'-di-phenylphenyl]indenyl)2 η4-l ,4-diphenyl- 1,3 -butadiene; dimethylamidoborane(2-n-propyl, 4-[3',5'-di-phenylphenyl]indenyl)2 η -l ,4- diphenyl- 1 ,3 -butadiene; dimethylamidoborane(2-iso-propyl, 4-[3',5'-di-phenylphenyl]indenyl)2η4-l,4- diphenyl-l,3-butadiene; dimethylamidoborane(2-n-butyl, 4-[3',5'-di-phenylphenyl]indenyl)2 η4-l ,4- diphenyl- 1 ,3 -butadiene ; dimethylamidoborane(2-iso-butyl, 4-[3',5'-di-phenylphenyl]indenyl)2 η4-l ,4- diphenyl-l ,3-butadiene; dimethylamidoborane(2-sec-butyl, 4-[3',5'-di-phenylphenyl]indenyl)2η4-l,4- diphenyl- 1 ,3-butadiene; dimethylamidoborane(2-tert-butyl, 4-[3',5'-di-phenylphenyl]indenyl)2 η4-l ,4- diphenyl-l ,3-butadiene; dimethylamidoborane(2-methyl, 4-[3',5'-di-tbutylphenyl]indenyl)2 zirconium dimethyl; dimethylamidoborane(2-ethyl, 4-[3',5'-di-tbutylphenyl]mdenyl)2zirconium dimethyl; dimethylamidoborane(2-n-propyl, 4-[3',5'-di-tbutylphenyl]indenyl)2zirconium dimethyl; dimethylamidoborane(2-iso-propyl, 4-[3',5'-di-tbutylphenyl]indenyl)2zirconium dimethyl; dimethylamidoborane(2-n-butyl, 4-[3',5'-di-tbutylphenyl]indenyl)2zirconium dimethyl; dimethylamidoborane(2-iso-butyl, 4-[3',5'-di-tbutylphenyl]indenyl)2zirconium dimethyl; dimethylamidoborane(2-sec-butyl, 4-[3',5'-di-tbutylphenyl]indenyl)2zirconium dimethyl; dimethylamidoborane(2-tert-butyl, 4-[3',5'-di-tbutylphenyl]indenyl)2zirconium dimethyl; dimethylamidoborane(2-ethyl, 4-[3',5'-bis- trifluoromethylphenyl]indenyl)2zirconium dimethyl; dimethylamidoborane(2-n-propyl, 4-[3',5'-bis- trifluoromethylphenyl]indenyl)2zirconium dimethyl; dimethylamidoborane(2-iso-propyl, 4-[3',5'-bis- trifluoromethylphenyl]indenyl)2zirconium dimethyl; dimethylamidoborane(2-n-butyl, 4-[3',5'-bis- trifluoromethylphenyl]indenyl)2zirconium dimethyl; dimethylamidoborane(2-iso-butyl, 4-[3',5'-bis- trifluoromethylphenyl]indenyl)2zirconium dimethyl; dimethylamidoborane(2-sec-butyl, 4-[3 ',5'-bis- trifluoromethylphenyl]indenyl)2zirconium dimethyl; dimethylamidoborane(2-tert-butyl, 4-[3 ',5'-bis- trifluoromethylphenyl]indenyl)2zirconiιιm dimethyl; dimethylamidoborane(2-ethyl, 4-[3',5'-di-iso-propylphenyl]indenyl)2zirconium dimethyl; dimethylamidoborane(2-n-propyl, 4-[3',5'-di-iso-propylphenyl]indenyl)2zirconium dimethyl dimethylamidoborane(2-iso-propyl, 4-[3',5'-di-iso- propylphenyl]indenyl)2zirconium dimethyl; dimethylamidoborane(2-n-butyl, 4-[3,,5'-di-iso-propylphenyl]indenyl)2zirconium dimethyl; dimethylamidoborane(2-iso-butyl, 4-[3',5'-di-iso-propylphenyl]indenyl)2zirconium dimethyl; dimethylamidoborane(2-sec-butyl, 4-[3 ',5'-di-iso- propylphenyl]indenyl)2zirconium dimethyl; dimethylamidoborane(2-tert-butyl, 4- [3 ', 5 '-di-iso- propylphenyl]indenyl)2zirconium dimethyl; dimethylamidoborane(2-methyl, 4-[3',5'-di-phenylphenyl]indenyl)2zirconium dimethyl; dimethylamidoborane(2-ethyl, 4-[3',5'-di-phenylphenyl]indenyl)2zirconium dimethyl; dimethylamidoborane(2-n-propyl, 4-[3',5'-di-phenylphenyl]indenyl)2zirconium dimethyl; dimethylamidoborane(2-iso-propyl, 4-[3',5'-di-phenylphenyl]indenyl)2zirconium dimethyl; dimethylamidoborane(2-n-butyl, 4-[3',5'-di-phenylphenyl]indenyl)2zirconium dimethyl; dimethylamidoborane(2-iso-butyl, 4-[3',5'-di-phenylphenyl]indenyl)2zirconium dimethyl; dimethylamidoborane(2-sec-butyl, 4- [3 ', 5 '-di-phenylpheny l]indenyl)2zirconium dimethyl; dimethylamidoborane(2-tert-butyl, 4-[3',5'-di-phenylphenyl]indenyl)2zirconium dimethyl; diisopropylamidoborane(2-methyl, 4-[3',5'-di-tbutylphenyl]indenyl)2zirconium dichloride; diisopropylamidoborane(2-ethyl, 4-[3',5'-di-tbutylphenyl]indenyl)2zirconium dichloride; diisopropylamidoborane(2-n-propyl, 4-[3',5'-di-tbutylphenyl]indenyl)2zirconium dichloride; diisopropylamidoborane(2-iso-propyl, 4-[3',5'-di-tbutylphenyl]indenyl)2zirconium dichloride; diisopropylamidoborane(2-n-butyl, 4-[3',5'-di-tbutylphenyl]indenyl)2zirconium dichloride; diisopropylamidoborane(2-iso-butyl, 4-[3',5'-di-tbutylphenyl]indenyl)2zirconium dichloride; diisopropylamidoborane(2-sec-butyl, 4-[3',5'-di-tbutylphenyl]indenyl)2zirconium dichloride; diisopropylamidoborane(2-tert-butyl, 4-[3',5'-di-tbutylphenyl]indenyl)2zirconium dichloride; diisopropylamidoborane(2-ethyl, 4-[3',5'-bis- trifluoromethylphenyl]indenyl)2zirconium dichloride; diisopropylamidoborane(2-n-propyl, 4- [3 ', 5 '-bis- trifluoromethylphenyl]indenyl)2zirconium dichloride; diisopropylamidoborane(2-iso-propyl, 4-[3',5'-bis- trifluoromethylphenyl]indenyl)2zirconium dichloride; diisopropylamidoborane(2-n-butyl, 4-[3',5'-bis- trifluoromethylphenyl]indenyl)2zirconium dichloride; diisopropylamidoborane(2-iso-butyl, 4-[3',5'-bis- trifluoromethylphenyl]indenyl)2zirconium dichloride; diisopropylamidoborane(2-sec-butyl, 4-[3',5'-bis- trifluoromethylphenyl]indenyl)2zirconium dichloride; diisopropylamidoborane(2 -tert-butyl, 4-[3',5'-bis- trifluoromethylphenyl]indenyl)2zirconium dichloride; diisopropylamidoborane(2-ethyl, 4-[3',5'-di-iso-propylphenyl]indenyl)2zirconium dichloride; diisoproρylamidoborane(2-n-propyl, 4-[3',5'-di-iso- propylphenyl]indenyl)2zirconium dichloride diisoρropylamidoborane(2-iso-propyl, 4-[3',5'-di-iso- propylphenyl]indenyl)2zirconium dichloride; diisopropylamidoborane(2-n-butyl, 4-[3',5'-di-iso- propylphenyl]indenyl)2zirconium dichloride; diisopropylamidoborane(2-iso-butyl, 4-[3',5'-di-iso- propylphenyl]indenyl)2zirconium dichloride; diisopropylamidoborane(2-sec-butyl, 4-[3',5'-di-iso- propylphenyl]indeny_)2zirconium dichloride; diisopropylamidoborane(2-tert-butyl, 4-[3',5'-di-iso- propylphenyl]indenyl)2zirconium dichloride; diisopropylamidoborane(2-methyl, 4-[3',5'-di-phenylphenyl]indenyl)2zirconium dichloride; diisopropylamidoborane(2-ethyl, 4-[3',5'-di-phenylρhenyl]indenyl)2zirconium dichloride; diisopropylamidoborane(2-n-propyl, 4-[3',5'-di-phenylphenyl]indenyl)2zirconium dichloride; diisopropylamidoborane(2-iso-propyl, 4-[3',5'-di- phenylphenyl]indenyl)2zirconium dichloride; diisopropylamidoborane(2-n-butyl, 4-[3',5'-di-phenylphenyl]indenyl)2zirconium dichloride; diisopropylamidoborane(2-iso-butyl, 4-[3',5'-di-phenylphenyl]indenyl)2zirconium dichloride; diisopropylamidoborane(2-sec-butyl, 4-[3',5'-di-phenylphenyl]indenyl)2zirconium dichloride; diisopropylamidoborane(2-tert-butyl, 4-[3',5'-di-phenylphenyl]indenyl)2zirconium dichloride; diisopropylamidoborane(2-methyl, 4-[3',5'-di-tbutylphenyl]indenyl)2η4-l,4- diphenyl- 1 ,3-butadiene; diisopropylamidoborane(2-ethyl, 4-[3',5'-di-tbutylphenyl]indenyl)2η4-l,4- diphenyl-l,3-butadiene; diisopropylamidoborane(2-n-propyl, 4-[3',5'-di-tbutylphenyl]indenyl)2η4-l,4- diphenyl-1 ,3-butadiene; diisopropylamidoborane(2-iso-propyl, 4-[3',5'-di-tbutylphenyl]indenyl)2η4-l,4- diphenyl- 1 ,3 -butadiene; diisopropylamidoborane(2-n-butyl, 4-[3',5'-di-tbutylphenyl]indenyl)2 η4-l ,4- diphenyl- 1 ,3 -butadiene; diisopropylamidoborane(2-iso-butyl, 4-[3',5'-di-tbutylphenyl]indenyl)2 η4-l ,4- diphenyl- 1 ,3-butadiene; diisopropylamidoborane(2~sec-butyl, 4-[3',5'-di-tbutylphenyl]indenyl)2η4-l,4- diphenyl- 1 ,3 -butadiene; diisopropylamidoborane(2-tert-butyl, 4-[3',5'-di-tbutylphenyl]indenyl)2 η4- 1 ,4- diphenyl-l ,3-butadiene; diisopropylamidoborane(2-ethyl, 4-[3',5'-bis-trifluoromethylphenyl]indenyl)2η4- 1 ,4-diphenyl- 1 ,3-butadiene; diisopropylamidoborane(2-n-propyl, 4- [3 ' , 5 '-bis-trifluoromethylphenyl] indenyl)2 η4- 1 ,4-diphenyl- 1 ,3-butadiene; diisopropylamidoborane(2-iso-propyl, 4-[3',5'-bis- trifluoromethylphenyl]indenyl)2 η4- 1 ,4-diphenyl- 1 ,3-butadiene; diisopropylamidoborane(2-n-butyl, 4-[3',5'-bis-trifluoromethylphenyl]indenyl)2η4- 1 ,4-diphenyl- 1 ,3-butadiene; diisopropylamidoborane(2-iso-butyl, 4-[3',5'-bis-trifluoromethylphenyl]indenyl)2 η4- 1 ,4-diphenyl- 1 ,3-butadiene; diisopropylamidoborane(2-sec-butyl, 4-[3',5'-bis-trifluoromethylphenyl]indenyl)2 η4-l ,4-diphenyl- 1 ,3-butadiene; diisopropylamidoborane(2-tert-butyl, 4-[3',5'-bis-trifluoromethylphenyl]indenyl)2 η4- 1 ,4-diphenyl- 1 ,3 -butadiene; diisopropylamidoborane(2-ethyl, 4-[3',5'-di-iso-propylphenyl]indenyl)2η4-l,4- diphenyl- 1 ,3 -butadiene; diisopropylamidoborane(2-n-propyl, 4-[3',5'-di-iso-propylphenyl]indenyl) 2 η4-l,4- diphenyl-1 ,3-butadiene; diisopropylamidoborane(2-iso-propyl, 4-[3',5'-di-iso-propylphenyl]indenyl) η4- 1 ,4-diphenyl- 1 ,3 -butadiene; diisopropylamidoborane(2-n-butyl, 4-[3',5'-di-iso-propylphenyl]indenyl)2 η4-l ,4- diphenyl- 1 ,3-butadiene; diisopropylamidoborane(2-iso-butyl, 4-[3',5'-di-iso-propylphenyl]indenyl)2η4-l,4- diphenyl- 1 ,3 -butadiene; diisopropylamidoborane(2-sec-butyl, 4-[3',5'-di-iso-propylphenyl]indenyl)2 η4-l ,4- diphenyl-l ,3-butadiene; diisopropylamidoborane(2-tert-butyl, 4-[3',5'-di-iso-propylphenyl]indenyl)2 η4-l ,4- diphenyl- 1 ,3-butadiene; diisopropylamidoborane(2-methyl, 4-[3',5'-di-phenylphenyl]indenyl)2 η4-l ,4- diphenyl- 1 ,3-butadiene; diisopropylamidoborane(2-ethyl, 4-[3',5'-di-phenylphenyl]indenyl)2 η4-l ,4- diphenyl- 1 ,3-butadiene; diisopropylamidoborane(2-n-propyl, 4-[3',5'-di-phenylphenyl]indenyl)2 η4-l ,4- diphenyl-l ,3-butadiene; diisopropy lamidoborane(2-iso-propyl, 4- [3 ', 5 '-di-phenylpheny l]indenyl)2 η 4- 1 ,4- diphenyl-l,3-butadiene; diisopropylamidoborane(2-n-butyl, 4-[3',5'-di-phenylphenyl]indenyl)2 η4-l ,4- diphenyl- 1 ,3-butadiene; diisopropylamidoborane(2-iso-butyl, 4-[3',5'-di-phenylphenyl]indenyl)2 η4-l ,4- diphenyl- 1 ,3-butadiene; diisopropylamidoborane(2 -sec-butyl, 4-[3',5'-di-phenylphenyl]indenyl)2η4-l,4- diphenyl-1 ,3-butadiene; diisopropylamidoborane(2-tert-butyl, 4-[3',5'-di-phenylphenyl]indeny_)2η4-l,4- diρhenyl-1 ,3-butadiene; diisopropylamidoborane(2-methyl, 4-[3',5'-di-tbutylphenyl]indenyl)2zirconium dimethyl; diisopropylamidoborane(2-ethyl, 4-[3',5'-di-tbutylphenyl]indenyl)2zirconium dimethyl; diisopropylamidoborane(2-n-propyl, 4-[3',5'-di-tbutylphenyl]indenyl)2zirconium dimethyl; diisopropylamidoborane(2-iso-propyl, 4-[3',5'-di-tbutylphenyl]indenyl)2zirconium dimethyl; diisopropylamidoborane(2-n-butyl, 4-[3',5'-di-tbutylphenyl]indenyl)2zirconium dimethyl; diisopropylamidoborane(2-iso-butyl, 4-[3',5'-di-tbutylphenyl]indenyl)2zirconium dimethyl; diisopropylamidoborane(2-sec-butyl, 4-[3',5'-di-tbutylphenyl]indenyl)2zirconium dimethyl; diisopropylamidoborane(2-tert-butyl, 4-[3',5'-di-tbutylphenyl]indenyl)2zirconium dimethyl; diisopropylamidoborane(2-ethyl, 4-[3',5'-bis- trifluoromethylphenyl]indenyl)2zirconium dimethyl; diisopropylamidoborane(2-n-propyl, 4-[3',5'-bis- trifluoromethylphenyl]indenyl)2zirconium dimethyl; diisopropylamidoborane(2-iso-propyl, 4-[3',5'-bis- trifluoromethylphenyl]indenyl)2zirconium dimethyl; diisopropylamidoborane(2-n-butyl, 4-[3',5'-bis- trifluoromethylphenyl]indenyl)2zirconium dimethyl; diisopropylamidoborane(2-iso-butyl, 4-[3',5'-bis- trifluoromethylphenyl]indenyl)2zirconium dimethyl; diisopropylamidoborane(2-sec-butyl, 4- [3 ',5'-bis- trifluoromethylphenyl]indenyl)2zirconium dimethyl; diisopropylamidoborane(2-tert-butyl, 4-[3',5'-bis- trifluoromethylphenyl]indenyl)2zirconium dimethyl; diisopropylamidoborane(2-ethyl, 4~[3',5'-di-iso-propylphenyl]indenyl)2zircomum dimethyl; diisopropylamidoborane(2-n-propyl, 4-[3',5'-di-iso- propylphenyl]indenyl)2zirconium dimethyl diisopropylamidoborane(2~iso-propyl, 4-[3',5'-di-iso- propylphenyl]indenyl)2zirconium dimethyl; diisoρropylamidoborane(2-n-butyl, 4-[3',5'-di-iso- ρropylphenyl]indenyl)2zirconium dimethyl; diisopropylamidoborane(2-iso-butyl, 4-[3',5'-di-iso- propylphenyl]indenyl)2zirconium dimethyl; diisopropylamidoborane(2-sec-butyl, 4-[3',5'-di-iso- propylphenyl]indenyl)2zirconium dimethyl; diisopropylamidoborane(2-tert-butyl, 4-[3',5'-di-iso- proρylphenyl]indenyl)2zirconium dimethyl; diisopropylamidoborane(2-methyl, 4-[3',5'-di-phenylphenyl]indenyl)2zirconium dimethyl; diisopropylamidoborane(2-ethyl, 4-[3',5'-di-phenylphenyl]indenyl)2zirconium dimethyl; diisopropylamidoborane(2-n-propyl, 4-[3',5'-di-phenylphenyl]indenyl)2zirconium dimethyl; diisopropylamidoborane(2-iso-propyl, 4-[3',5'-di- phenylphenyl]indenyl)2zirconium dimethyl; diisopropylamidoborane(2-n-butyl, 4-[3',5'-di-phenylphenyl]indenyl)2zirconium dimethyl; diisopropylamidoborane(2-iso-butyl, 4-[3',5'-di-phenylphenyl]indenyl)2zirconium dimethyl; diisopropylamidoborane(2-sec-butyl, 4-[3',5'-di-phenylphenyl]indenyl)2zirconium dimethyl; diisopropylamidoborane(2-tert-butyl, 4-[3',5'-di-phenylphenyl]indenyl)2zirconium dimethyl; bis(trimethylsilyl)amidoborane(2-methyl, 4-[3',5'-di- tbutylphenyl]indenyl)2zirconium dichloride; bis(trimethylsilyl)amidoborane(2-ethyl, 4-[3',5'-di- tbutylphenyl]indenyl)2zirconium dichloride; bis(trimethylsilyl)amidoborane(2-n-propyl, 4-[3',5'-di- tbutylphenyl]indenyl)2zirconium dichloride; bis(trimethylsilyl)amidoborane(2-iso-propyl, 4-[3',5'-di- tbutylphenyl]indenyl)2zirconium dichloride; bis(trimethylsilyl)amidoborane(2-n-butyl, 4-[3',5'-di- tbutylphenyl]indenyl)2zirconium dichloride; bis(trimethylsilyl)amidoborane(2-iso-butyl, 4- [3 ' , 5 '-di- tbutylphenyl]indenyl)2zirconium dichloride; bis(trimethylsilyl)amidoborane(2-sec-butyl, 4-[3',5'-di- tbutylphenyl]indenyl)2zirconium dichloride; bis(trimethylsilyl)amidoborane(2-tert-butyl, 4- [3 ' , 5 '-di- tbutylphenyl]indenyl)2zirconium dichloride; bis(trimethylsilyl)amidoborane(2-ethyl, 4-[3',5'-bis- trifluoromethylphenyl]indenyl)2zirconium dichloride; bis(trimethylsilyl)amidoborane(2-n-propyl, 4- [3 ' ,5 '-bis- trifluoromethylphenyl]indenyl)2zirconium dichloride; bis(trimethylsilyl)amidoborane(2-iso-propyl, 4-[3',5'-bis- trifluoromethylphenyl]indenyl)2zirconium dichloride; bis(trimethylsilyl)amidoborane(2-n-butyl, 4-[3',5'-bis- trifluoromethylphenyl]indenyl)2zirconium dichloride; bis(trimethylsilyl)amidoborane(2-iso-butyl, 4- [3 ' ,5 '-bis- trifluoromethylphenyl]indenyl)2zirconium dichloride; bis(trimethylsilyl)amidoborane(2-sec-butyl, 4- [3 ' ,5 '-bis- trifluoromethylphenyl]indenyl)2zirconium dichloride; bis(trimethylsilyl)amidoborane(2-tert-butyl, 4-[3',5'-bis- trifluoromethylphenyl]indenyl)2zirconium dichloride; bis(trimethylsilyl)amidoborane(2-ethyl, 4-[3',5'-di-iso- propylphenyl]indenyl)2zirconium dichloride; bis(trimethylsilyl)amidoborane(2-n-propyl, 4-[3',5'-di-iso- propylphenyl]indenyl)2zirconium dichloride bis(trimethylsilyl)amidoborane(2-iso-propyl, 4-[3',5'-di-iso- propylphenyl]indenyl)2zirconium dichloride; bis(trimethylsilyl)amidoborane(2-n-buty 1, 4- [3 ', 5 '-di-iso- propylphenyl]indenyl)2zirconium dichloride; bis(trimethylsilyl)amidoborane(2-iso-butyl, 4- [3 ', 5 '-di-iso- propylphenyl]indenyl)2zirconium dichloride; bis(trimethylsilyl)amidoborane(2-sec-butyl, 4-[3',5'-di-iso- propylphenyl]indenyl)2zirconium dichloride; bis(trimethylsilyl)amidoborane(2-tert-butyl, 4-[3',5'-di-iso- propylphenyl]indenyl)2zirconium dichloride; bis(trimethylsilyl)amidoborane(2-methyl, 4-[3',5'-di- phenylphenyl]indenyl)2zirconium dichloride; bis(trimethylsilyl)amidoborane(2-ethyl, 4-[3',5'-di- phenylphenyl]indenyl)2zirconium dichloride; bis(trimethylsilyl)amidoborane(2-n-propyl, 4-[3',5'-di- phenylphenyl]indenyl)2zirconium dichloride; bis(trimethylsilyl)amidoborane(2-iso-propyl, 4-[3',5'-di- phenylphenyl]indenyl)2zirconium dichloride; bis(trimethylsilyl)amidoborane(2-n-butyl, 4-[3',5'-di- phenylphenyl]indenyl)2zirconium dichloride; bis(trimethylsilyl)amidoborane(2-iso-butyl, 4-[3',5'-di- phenylphenyl]indenyl)2zirconium dichloride; bis(trimethylsilyl)amidoborane(2-sec-butyl, 4-[3',5'-di- phenylphenyl]indenyl)2zirconium dichloride; bis(trimethylsilyl)amidoborane(2-tert-butyl, 4-[3',5'-di- phenylphenyl]indenyl)2zirconium dichloride; bis(trimethylsilyl)amidoborane(2-methyl, 4-[3',5'-di-tbutylphenyl]indenyl)2 η4-l ,4- diphenyl-l ,3-butadiene; bis(trimethylsilyl)amidoborane(2-ethyl, 4-[3',5'-di-tbutylphenyl]indenyl)2 η4-l ,4- diphenyl-l ,3-butadiene; bis(trimethylsilyl)amidoborane(2-n-propyl, 4-[3',5'-di-tbutylphenyl]indenyl)2η4- l,4-diphenyl-l,3-butadiene; bis(trimethylsilyl)amidoborane(2-iso-propyl, 4-[3',5'-di-tbutylphenyl]indenyl)2η4- 1 ,4-diphenyl- 1 ,3 -butadiene; bis(trimethylsilyl)amidoborane(2-n-butyl, 4-[3',5'-di-tbutylphenyl]indenyl)2η4- 1 ,4-diphenyl- 1 ,3-butadiene; bis(trimethylsilyl)amidoborane(2-iso-butyl, 4-[3',5'-di-tbutylphenyl]indenyl)2η4- 1 ,4-diphenyl- 1 ,3-butadiene; bis(trimethylsilyl)amidoborane(2-sec-butyl, 4-[3',5'-di-tbutylphenyl]indenyl)2η4- 1 ,4-diphenyl-l ,3-butadiene; bis(trimethylsilyl)amidoborane(2-tert-butyl, 4-[3',5'-di-tbutylphenyl]indenyl)2η4- 1 ,4-diphenyl-l ,3-butadiene; bis(trimethylsilyl)amidoborane(2-ethyl, 4-[3',5'-bis- trifluoromethylphenyl]indenyl)2η4-l,4-diphenyl-l,3-butadiene; bis(trimethylsilyl)amidoborane(2-n-propyl, 4-[3',5'-bis- trifluoromethylphenyl]indenyl)2 η4-l ,4-diphenyl-l ,3-butadiene; bis(trimethylsilyl)amidoborane(2-iso-propyl, 4-[3',5'-bis- trifluoromethylphenyl]indenyl)2 η4-l ,4-diphenyl-l ,3-butadiene; bis(trimethylsilyl)amidoborane(2-n-butyl, 4-[3',5'-bis- trifluoromethylphenyl]indenyl)2 η4-l ,4-diphenyl-l ,3-butadiene; bis(trimethylsilyl)amidoborane(2-iso-butyl, 4-[3',5'-bis- trifluoromethylphenyl]indenyl)2 η4-l ,4-diphenyl-l ,3-butadiene; bis(trimethylsilyl)amidoborane(2-sec-butyl, 4-[3',5'-bis- trifluoromethylphenyl]indenyl)2 η4-l ,4-diphenyl-l ,3-butadiene; bis(trimethylsilyl)amidoborane(2-tert-butyl, 4-[3',5'-bis- trifluoromethylphenyl]indenyl)2 η4- 1 ,4-diphenyl- 1 ,3-butadiene; bis(trimethylsilyl)amidoborane(2-ethyl, 4-[3',5'-di-iso-propylphenyl]indenyl)2η4-
1 ,4-diphenyl- 1 ,3 -butadiene; bis(trimethylsilyl)amidoborane(2-n-propyl, 4- [3 ',5'-di-iso-propylpheny_]indenyl) 2 η4- 1 ,4-diphenyl- 1 ,3-butadiene; bis(trimethylsilyl)amidoborane(2-iso-propyl, 4-[3',5'-di-iso-propylphenyl]indenyl) η4- 1 ,4-diphenyl- 1 ,3-butadiene; bis(trimethylsilyl)amidoborane(2-n-butyl, 4-[3',5'-di-iso-propylphenyl]indenyl)2 η4- 1 ,4-diphenyl-l ,3-butadiene; bis(trimet_ιylsilyl)anιidoborane(2-iso-butyl, 4-[3',5'-di-iso-propylphenyl]indenyl)2 η4- 1 ,4-diphenyl- 1 ,3 -butadiene; bis(trimethylsilyl)amidoborane(2-sec-butyl, 4-[3',5'-di-iso-propylphenyl]indenyl)2 η4- 1 ,4-diphenyl- 1 ,3-butadiene; bis(trimethylsilyl)amidoborane(2-tert-butyl, 4-[3',5'-di-iso-propylphenyl]indenyl)2 η4- 1 ,4-diphenyl- 1 ,3-butadiene; bis(trimethylsilyl)amidoborane(2-methyl, 4-[3',5'-di-phenylphenyl]indenyl)2η4-
1 ,4-diphenyl- 1 ,3 -butadiene; bis(trimethylsilyl)amidoborane(2-ethyl, 4-[3',5'-di-phenylphenyl]indenyl)2η4-l,4- diphenyl- 1 ,3 -butadiene; bis(trimethylsilyl)amidoborane(2-n-propyl, 4- [3 ',5'-di-phenylphenyl]indenyl)2 η4-
1 ,4-diphenyl- 1 ,3 -butadiene; bis(trimethylsilyl)amidoborane(2-iso-propyl, 4-[3',5'-di-phenylphenyl]indenyl)2 η4- 1 ,4-diphenyl- 1 ,3 -butadiene; bis(trimethylsilyl)amidoborane(2-n-butyl, 4-[3',5'-di-phenylphenyl]indenyl)2 η4- l,4-diphenyl-l,3-butadiene; bis(trimethylsilyl)amidoborane(2-iso-butyl, 4-[3',5'-di-phenylphenyl]indenyl)2η4-
1 ,4-diphenyl- 1 ,3-butadiene; bis(trimethylsilyl)amidoborane(2-sec-butyl, 4-[3',5'-di-phenylphenyl]indenyl)2η4- 1 ,4-diphenyl- 1 ,3-butadiene; bis(trimethylsilyl)amidoborane(2-tert-butyl, 4-[3 ',5'-di-phenylphenyl]indenyl)2 η4- 1 ,4-diphenyl- 1 ,3 -butadiene; bis(trimethylsilyl)amidoborane(2-methyI, 4-[3',5'-di- tbutylphenyl]indenyl)2zirconium dimethyl; bis(trimethylsilyl)amidoborane(2-ethyl, 4-[3',5'-di- tbutylphenyl]indenyl)2zirconium dimethyl; bis(trimethylsilyl)amidoborane(2-n-propyl, 4-[3',5'-di- tbutylphenyl]indenyl)2zirconium dimethyl; bis(trimethylsilyl)amidoborane(2-iso-propyl, 4-[3',5'-di- tbutylphenyl]indenyl)2zirconium dimethyl; bis(trimethylsilyl)amidoborane(2-n-butyl, 4-[3',5'-di- tbutylphenyl]indenyl)2zirconium dimethyl; bis(trimethylsilyl)amidoborane(2-iso-butyl, 4-[3',5'-di- tbutylphenyl]indenyl)2zirconium dimethyl; bis(trimethylsilyl)amidoborane(2-sec-butyl, 4-[3',5'-di- tbutylphenyl]indenyl)2zirconium dimethyl; bis(trimethylsilyl)amidoborane(2-tert-butyl, 4-[3',5'-di- tbutylphenyl]indenyl)2zirconium dimethyl; bis(trimethylsilyl)amidoborane(2-ethyl, 4-[3',5'-bis- trifluoromethylphenyl]indenyl)2zirconium dimethyl; bis(trimethylsilyl)amidoborane(2-n-propyl, 4-[3',5'-bis- trifluoromethylphenyl]indenyl)2zirconium dimethyl; bis(trimethylsilyl)amidoborane(2-iso-propyl, 4-[3',5'-bis- trifluoromethylphenyl]indenyl)2zirconium dimethyl; bis(trimethylsilyl)amidoborane(2-n-butyl, 4-[3',5'-bis- trifluoromethylphenyl]indenyl)2zirconium dimethyl; bis(trimethylsilyl)amidoborane(2-iso-butyl, 4-[3',5'-bis- trifluoromethylphenyl]indenyl)2zirconium dimethyl; bis(trimethylsilyl)amidoborane(2-sec-butyl, 4-[3',5'-bis- trifluoromethylphenyl]indenyl)2zirconium dimethyl; bis(trimethylsilyl)amidoborane(2-tert-butyl, 4-[3',5'-bis- trifluoromethylphenyl]indenyl)2zirconium dimethyl; bis(trimethylsilyl)amidoborane(2-ethyl, 4-[3',5'-di-iso- propylphenyl]indenyl)2zirconium dimethyl; bis(trimethylsilyl)amidoborane(2-n-propyl, 4-[3',5'-di-iso- propylphenyl]indenyl)2zirconium dimethyl bis(trimethylsilyl)amidoborane(2-iso-propyl, 4-[3',5'-di-iso- propylphenyl]indenyl)2zirconium dimethyl; bis(trimethylsilyl)amidoborane(2-n-butyl, 4-[3',5'-di-iso- propylphenyl]indenyl)2zirconium dimethyl; bis(trimethylsily_)amidoborane(2-iso-butyl, 4-[3',5'-di-iso- propylphenyl]indenyl)2zirconium dimethyl; bis(trimethylsilyl)amidoborane(2-sec-butyl, 4- [3 ' ,5 '-di-iso- propylphenyl]indenyl)2zirconium dimethyl; bis(trimethylsilyl)amidoborane(2-tert-butyl, 4-[3',5'-di-iso- propylphenyl]indenyl)2zirconium dimethyl; bis(trimethylsilyl)amidoborane(2-methyl, 4-[3',5'-di- phenylphenyl]_ndenyl)2zirconium dimethyl; bis(trimethylsilyl)amidoborane(2-ethyl, 4-[3',5'-di- phenylphenyl]indenyl)2zirconium dimethyl; bis(trimethylsilyl)amidoborane(2-n-propyl, 4-[3',5'-di- phenylphenyl]indenyl)2zirconium dimethyl; bis(trimethylsilyl)amidoborane(2-iso-propyl, 4-[3',5'-di- phenylphenyl]indenyl)2zirconium dimethyl; bis(trimethylsilyl)amidoborane(2-n-butyl, 4-[3',5'-di- phenylphenyl]indenyl)2zirconium dimethyl; bis(trimethylsilyl)amidoborane(2-iso-butyl, 4-[3',5'-di- phenylphenyl]indenyl)2zirconium dimethyl; bis(trimethylsilyl)amidoborane(2-sec-butyl, 4-[3',5'-di- phenylphenyl]indenyl)2zirconium dimethyl; and bis(trimethylsilyl)amidoborane(2-tert-butyl, 4-[3',5'-di- phenylphenyl]indenyl)2zirconium dimethyl.
[00102] In another embodiment scandium catalyst complexes may also be used in the processes of this invention with or without an activator, see
US6403773 for more information on these complexes.
[00103] In another embodiment, non-metallocene catalyst compounds, such as bisamide catalyst compounds, may be used. Bisamide catalyst compounds are defined to be bidentate bisamide catalyst compounds, pyridine bisamide catalyst compounds, and amine bisamide catalyst compounds.
[00104] Bidentate bisamide catalyst compounds are those represented by the following formula:
R
/
Figure imgf000067_0001
M is Ti, Zr, or Hf. R are the same or different alkyl, aryl, substituted alkyl, or substituted aryl radicals. X are the same or different alkyl, aryl, or halide radicals. Substituted alkyls and aryls can be alkyl-, aryl-, and halo-substituted. When X is a halide, the bisamide catalyst compound is typically first chemically modified to transform X into an abstractable ligand. This can be done by alkylation, for example.
[00105] Pyridine bisamide catalyst compounds are also useful herein.
Pyridine bisamide catalyst compounds are those compounds that have the following formula:
Figure imgf000068_0001
M is Ti, Zr, or Hf. R are the same or different alkyl, aryl, substituted alkyl, or substituted aryl radicals. X are the same or different alkyl, aryl, or halide radicals. Substituted alkyls and aryls can be alkyl-, aryl-, and halo-substituted. When X is a halide, the pyridine bisamide catalyst compound is typically first chemically modified to transform X into an abstractable ligand. This can be done by alkylation, for example.
[00106] Amine bisamide catalyst compounds are also useful herein. Amine bisamide catalyst compounds are those represented by the following formula:
Figure imgf000068_0002
M is Ti, Zr, or Hf. R and R are the same or different alkyl, aryl, substituted alkyl, or substituted aryl radicals. X are the same or different alkyl, aryl, or halide radicals. Substituted alkyl and aryls can be alkyl-, aryl-, and halo-substituted. When X is a halide, the amine bisamide catalyst compound must first be chemically modified to transform X into an abstractable ligand. This can be done by alkylation, for example. [00107] Additional compounds are suitable as olefin polymerization catalysts for use in this invention. These will be any of those Group-3-10 compounds that can be converted by ligand abstraction or bond scission into a cationic catalyst and stabilized in that state by a noncoordinating or weakly coordinating anion. That anion should be sufficiently labile to be displaced by an unsaturated monomer such as propylene.
[00108] Additional catalyst compounds that may be used herein include bisimide catalyst compounds represented by the formula:
Figure imgf000069_0001
where M is a group 8,9,10, metal, preferably a group 10 metal, preferably Pd, Pt orNi; n is the oxidation state of M and may be 2, 3, or 4; each X is independently a halogen or a substituted or unsubstituted hydrocarbyl group, a substituted or unsubstituted hydrocarboxy group, or a substituted or unsubstituted heteroatom containing group; y is 0 or 1 ; z is 0 or 1, where n = y + z + 2;
R1 is a heteroatom, a substituted C, to C50 hydrocarbyl group or an unsubstituted
Cx to C50 hydrocarbyl group;
R2 is a heteroatom, a substituted Cx to C50 hydrocarbyl group or an unsubstituted
Cx to C50 hydrocarbyl group;
R3 is a heteroatom, a substituted Cj to C50 hydrocarbyl group or an unsubstituted Cj to C50 hydrocarbyl group, preferably a phenyl group; R4 is a heteroatom, a substituted Cj to C50 hydrocarbyl group or an unsubstituted Cj to C50 hydrocarbyl group, preferably a phenyl group, where any adjacent R groups may form fused ring systems. [00109] Exemplary compounds include those described in the patent literature. International patent publications WO 96/23010, WO 97/48735 and Gibson, et al., Chem. Comm., pp. 849-850 (1998), which disclose diimine-based ligands for Group-8-10 compounds that undergo ionic activation and polymerize olefins. Polymerization catalyst systems from Group-5-10 metals, in which the active center is highly oxidized and stabilized by low-coordination-number, polyanionic, ligand systems, are described in U.S. Patent 5,502,124 and its divisional U.S. Patent 5,504,049. See also the Group-5 organometallic catalyst compounds of U.S. Patent 5,851,945 and the tridentate-ligand-containing, Group- 5-10, organometallic catalysts of U.S. Patent No. 6, 294, 495. Group-11 catalyst precursor compounds, activatable with ionizing cocatalysts, useful for olefin and vinylic polar molecules are described in WO 99/30822.
[00110] U.S. Patent 5,318,935 describes bridged and unbridged, bisamido catalyst compounds of Group-4 metals capable of α-olefins polymerization. Bridged bis(arylamido)Group-4 compounds for olefin polymerization are described by D. H. McConville, et al., in Organometallics 1995, 14, 5478-5480. This reference presents synthetic methods and compound characterizations. Further work appearing in D. H. McConville, et al, Macromolecules 1996, 29, 5241-5243, describes bridged bis(arylamido)Group-4 compounds that are polymerization catalysts for 1 -hexene. Additional invention-suitable transition metal compounds include those described in WO 96/40805. Cationic Group-3- or Lanthanide-metal olefin polymerization complexes are disclosed in copending U.S. Application Ser. No. 09/408,050, filed 29 September 1999. A monoanionic bidentate ligand and two monoanionic ligands stabilize those catalyst compounds, which can be used herein. [00111] The literature describes many additional suitable catalyst compound that can be used in this invention. See, for instance, N. C. Gibson, et al; "The Search for New-Generation Olefin Polymerization Catalysts: Life Beyond Metallocenes", Angew. Chem. Int. Ed, 38, 428-447 (1999).
Mixtures
[00112] In a preferred embodiment the processes of this invention may be used with two or more catalyst compounds at the same time or in series. In particular two different catalyst compounds can be activated with the same or different activators and introduced into the polymerization system at the same or different times.
[00113] As mentioned above, invention process can employ mixtures of catalyst compounds to select the properties that are desired from the polymer.
Mixed catalyst systems can be employed in invention processes to alter or select desired physical or molecular properties. For example, mixed catalyst systems can control the molecular weight distribution of isotactic polypropylene when used with the invention processes or for the invention polymers.
[00114] Mixed-catalyst systems can be used with the invention polymerization processes to tailor the composition distribution of copolymers with high catalyst productivity. These systems can also, optionally, be used with diene incorporation to facilitate long chain branching using mixed catalyst systems and high levels of vinyl terminated polymers.
[00115] In preferred embodiments two or more ofthe above catalysts compounds can be used together.
[00116] In another embodiment preferred catalyst combinations include any two or more of: μ-dimethyl silylbis(-2-methyl, 4-phenylindenyl) zirconium dichloride, μ-dimethyl silylbis(-2-methyl, 4-phenylindenyl) zirconium dimethyl,
1 , 1 '-bis(4-triethylsilylphenyl)methylene-(cyclopentadienyl)(2,7-di-tertiary-butyl-
9-fluorenyl)hafhium dichloride, 1 , 1 '-bis(4-triethylsilylphenyl)methylene-(cyclopentadienyl)(2,7-di-tertiary-butyl- 9-fluorenyl)hafhium dimethyl, dimethylsilyl(tetramethylcyclopentadienyl)(dodecylamido)titanium dimethyl, dimethylsilyl(tetramethylcyclopentadienyl)(dodecylamido)titanium dichloride, 1 , 1 '-bis(4-triethylsilylphenyl)methylene-(cyclopentadienyl)(2,7-di-tertiary-butyl- 9-fluorenyl)hafnium dichloride,
1 , 1 '-bis(4-triethylsilylphenyl)methylene-(cyclopentadienyl)(2,7-di-tertiary-butyl- 9-fluorenyl)hafnium dimethyl, dimethylsilylbis(indenyl)hafhium dichloride, dimethylsilylbis(indenyl)hafnium dimethyl, dimethylsilyl bis(2-methylindenyl) zirconium dichloride, dimethylsilyl bis(2-methylindenyl) zirconium dimethyl, dimethylsilyl bis(2-methylfluorenyl) zirconium dichloride, dimethylsilyl bis(2-methylfluorenyl) zirconium dimethyl, dimethylsilyl bis(2-methyl-5,7-propylindenyl) zirconium dichloride, dimethylsilyl bis(2-methyl-5,7-propylindenyl) zirconium dimethyl, dimethylsilyl bis(2-methyl-5-phenylindenyl) zirconium dichloride, dimethylsilyl bis(2-methyl-5-phenylindenyl) zirconium dimethyl, dimethylsilyl bis(2-ethyl-5-phenylindenyl) zirconium dichloride, dimethylsilyl bis(2-ethyl-5-phenylindenyl) zirconium dimethyl, dimethylsilyl bis(2-methyl-5-biphenylindenyl) zirconium dichloride, and dimethylsilyl bis(2-methyl-5-biphenylindenyl) zirconium dichloride dimethyl. [00117] A particularly preferred combination includes dimethylsilyl(tetramethylcyclopentadienyl)(dodecylamido)titanium dichloride and μ-dimethyl silylbis(-2-methyl, 4-phenylindenyl) zirconium dichloride. Another particularly preferred combination includes dimethylsilyl(tetramethylcyclopentadienyl)(dodecylamido)titanium methyl and μ- dimethyl silylbis(-2-methyl, 4-phenylindenyl) zirconium dimethyl. Another particularly preferred combination includes 1, l'-bis(4- triethylsilylphenyl)methylene-(cyclopentadienyl)(2,7-di-tertiary-butyl-9- fluorenyl)hafhium dichloride and μ-dimethyl silylbis(-2-methyl, 4-phenylindenyl) zirconium dichloride. Another particularly preferred combination includes 1, 1'- bis(4-triethylsilylphenyl)methylene-(cyclopentadienyl)(2,7-di-tertiary-butyl-9- fluorenyl)hafhium dimethyl and μ-dimethyl silylbis(-2-methyl, 4-phenylindenyl) zirconium dimethyl.
[00118] In another embodiment the catalyst compound is not dimethylmethenyl(flourenyl)(cyclopentadienyl)zirconium dichloride [Me2C(flu)(cp)ZrCl2].
Activators and Activation Methods for Catalyst Compounds
[00119] The catalyst compounds described herein are combined with activators for use in the processes of this invention. [00120] An activator is defined as any combination of reagents that increases the rate at which a metal complex polymerizes unsaturated monomers, such as olefins. An activator may also affect the molecular weight, degree of branching, comonomer content, or other properties ofthe polymer.
A. Alumoxane and Aluminum Alkyl Activators
[00121] In one embodiment, one or more alumoxanes are utilized as an activator in the processes ofthe invention. Alumoxanes, sometimes called aluminoxanes in the art, are generally oligomeric compounds containing -A1(R)- O- subunits, where R is an alkyl group. Examples of alumoxanes include methylalumoxane (MAO), modified methylalumoxane (MMAO), ethylalumoxane and isobutylalumoxane. Alkylalumoxanes and modified alkylalumoxanes are suitable as catalyst activators, particularly when the abstractable ligand is a halide. Mixtures of different alumoxanes and modified alumoxanes may also be used. For further descriptions, see U.S. Patents 4,665,208, 4,952,540, 5,041,584, 5,091,352, 5,206,199, 5,204,419, 4,874,734, 4,924,018, 4,908,463, 4,968,827, 5,329,032, 5,248,801, 5,235,081, 5,157,137, 5,103,031 and EP 0 561 476 Al, EP 0 279 586 BI, EP 0 516 476 A, EP 0 594218 Al and WO 94/10180. [00122] When the activator is an alumoxane (modified or unmodified), some embodiments select the maximum amount of activator at a 5000-fold molar excess Al/M over the catalyst compound (per metal catalytic site). The minimum activator-to-catalyst-compound is typically a 1:1 molar ratio. [00123] Alumoxanes may be produced by the hydrolysis ofthe respective trialkylaluminum compound. MMAO may be produced by the hydrolysis of trimethylaluminum and a higher trialkylaluminum such as triisobutylaluminum. MMAO's are generally more soluble in aliphatic solvents and more stable during storage. There are a variety of methods for preparing alumoxane and modified alumoxanes, non-limiting examples of which are described in U.S. Patent No. 4,665,208, 4,952,540, 5,091,352, 5,206,199, 5,204,419, 4,874,734, 4,924,018, 4,908,463, 4,968,827, 5,308,815, 5,329,032, 5,248,801, 5,235,081, 5,157,137, 5,103,031, 5,391,793, 5,391,529, 5,693,838, 5,731,253, 5,731,451, 5,744,656, 5,847,177, 5,854,166, 5,856,256 and 5,939,346 and European publications EP-A- 0 561 476, EP-B1-0 279 586, EP-A-0 594-218 and EP-B1-0 586 665, and PCT publications WO 94/10180 and WO 99/15534, all of which are herein fully incorporated by reference. It may be preferable to use a visually clear methylalumoxane. A cloudy or gelled alumoxane can be filtered to produce a clear solution or clear alumoxane can be decanted from the cloudy solution. Another preferred alumoxane is a modified methyl alumoxane (MMAO) cocatalyst type 3 A (commercially available from Akzo Chemicals, Inc. under the trade name Modified Methylalumoxane type 3 A, covered under patent number US 5,041,584).
[00124] Aluminum alkyl or organoaluminum compounds which may be utilized as activators (or scavengers) include trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n- octylaluminum and the like. B. Ionizing Activators
[00125] It is within the scope of this invention to use an ionizing or stoichiometric activator, neutral or ionic, such as fri (n-butyl) ammonium tetrakis (pentafluorophenyl) boron, a trisperfluorophenyl boron metalloid precursor or a trisperfluoronaphtyl boron metalloid precursor, polyhalogenated heteroborane anions (WO 98/43983), boric acid (U.S. Patent No. 5,942,459) or combination thereof as an activator in the processes of this invention. It is also within the scope of this invention to use neutral or ionic activators alone or in combination with alumoxane or modified alumoxane activators. [00126] Examples of neutral stoichiometric activators include tri- substituted boron, tellurium, aluminum, gallium and indium or mixtures thereof. The three substituent groups are each independently selected from alkyls, alkenyls, halogen, substituted alkyls, aryls, arylhalides, alkoxy and halides. Preferably, the three groups are independently selected from halogen, mono or multicyclic (including halosubstituted) aryls, alkyls, and alkenyl compounds and mixtures thereof, preferred are alkenyl groups having 1 to 20 carbon atoms, alkyl groups having 1 to 20 carbon atoms, alkoxy groups having 1 to 20 carbon atoms and aryl groups having 3 to 20 carbon atoms (including substituted aryls). More preferably, the three groups are alkyls having 1 to 4 carbon groups, phenyl, napthyl or mixtures thereof. Even more preferably, the three groups are halogenated, preferably fluorinated, aryl groups. Most preferably, the neutral stoichiometric activator is trisperfluorophenyl boron or frisperfluoronapthyl boron. [00127] Ionic stoichiometric activator compounds may contain an active proton, or some other cation associated with, but not coordinated to, or only loosely coordinated to, the remaining ion ofthe ionizing compound. Such compounds and the like are described in European publications EP-A-0 570 982, EP-A-0 520 732, EP-A-0 495 375, EP-B1-0 500 944, EP-A-0 277 003 and EP-A- 0 277 004, and U.S. Patent Nos. 5,153,157, 5,198,401, 5,066,741, 5,206,197, 5,241,025, 5,384,299 and 5,502,124 and U.S. Patent Application Serial No.
08/285,380, filed August 3, 1994, all of which are herein fully incorporated by reference.
[00128] Preferred activators include a cation and an anion component, and may be represented by the following formula:
Figure imgf000076_0001
Wf+ is a cation component having the charge f+
NCA " is a non-coordinating anion having the charge h- f is an integer from 1 to 3. h is an integer from 1 to 3. g and h are constrained by the relationship: (g) x (f) = (h) x (i).
[00129] The cation component, (W^+) may include Bronsted acids such as protons or protonated Lewis bases or reducible Lewis acids capable of protonating or abstracting a moiety, such as an akyl or aryl, from an analogous metallocene or Group 15 containing transition metal catalyst compound, resulting in a cationic transition metal species.
[00130] In a preferred embodiment, the activators include a cation and an anion component, and may be represented by the following formula:
Figure imgf000076_0002
wherein LB is a neutral Lewis base; H is hydrogen;
NCA is a non-coordinating anion having the charge h- f is an integer from 1 to 3, h is an integer from 1 to 3, g and h are constrained by the relationship: (g) x (f) = (h) x (i) [00131] The activating cation (W?+) may be a Bronsted acid, (LB-Hf+), capable of donating a proton to the transition metal catalyst compound resulting in a transition metal cation, including ammoniums, oxoniums, phosphoniums, silyliums and mixtures thereof, preferably ammoniums of methylamine, aniline, dimethylamine, diethylamine, N-methylaniline, diphenylamine, trimethylamine, triethylamine, N,N-dimethylaniline, methyldiphenylamine, pyridine, p-bromo N,N-dimethylaniline, p-nitro-N,N-dimethylaniline, phosphoniums from triethylphosphine, triphenylphosphine, and diphenylphosphine, oxoniums from ethers such as dimethyl ether diethyl ether, tetrahydrofuran and dioxane, sulfoniums from thioethers, such as diethyl thioethers and tetrahydrothiophene and mixtures thereof.
[00132] The activating cation (W^+) may also be an abstracting moiety such as silver, carboniums, tropylium, carbeniums, ferroceniums and mixtures, preferably carboniums and ferroceniums. Most preferably (W*+) is triphenyl carbonium or N, N-dimethylanilinium.
[00133] The anion component (NCA ") includes those having the formula
[ Qk] " wherein j is an integer from 1 to 3; k is an integer from 2 to 6; k - j = h; T is an element selected from Group 13 or 15 ofthe Periodic Table ofthe Elements, preferably boron or aluminum, and Q is independently a hydride, bridged or unbridged dialkylamido, halide, alkoxide, aryloxide, hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, and halosubstituted- hydrocarbyl radicals, said Q having up to 20 carbon atoms with the proviso that in not more than 1 occurrence is Q a halide. Preferably, each Q is a fluorinated hydrocarbyl group having 1 to 20 carbon atoms, more preferably each Q is a fluorinated aryl group, and most preferably each Q is a pentafluoryl aryl group.
Examples of suitable (NCA ~ also include diboron compounds as disclosed in U.S. Pat. No. 5,447,895, which is fully incorporated herein by reference. [00134] Additional suitable anions are known in the art and will be suitable for use with the catalysts ofthe invention. See in particular, U.S. patent 5,278,119 and the review articles by S. H. Strauss, "The Search for Larger and More Weakly Coordinating Anions", Chem. Rev., 93, 921-942 (1993) and C. A. Reed, "Carboranes: A New Class of Weakly Coordinating Anions for Strong Elecfrophiles, Oxidants and Superacids", Ace. Chem. Res., 31, 133 -139 (1998). [00135] Illustrative, but not limiting examples of boron compounds which may be used as an activating cocatalyst in the preparation ofthe improved catalysts of this invention are tri-substituted ammoiiium salts such as: trimethylammom'um tetraphenylborate, triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, tri(n-butyl)ammonium tetraphenylborate, tri(t-butyl)ammonium tetraphenylborate, N,N-dimethylanilinium tetraphenylborate, N,N-diethylanilinium tetraphenylborate, N,N-dimethyl-(2,4,6-trimethylanilinium) tetraphenylborate, trimethylammonium tetrakis(pentafluorophenyl)borate, triethylarr ιonium tetrakis(pentafluorophenyl)borate, tripropylammonium tetrakis(pentafluorophenyl)borate, tri(n-bu1yl)ammonium tetrakis(pentafluorophenyl)borate, tri(sec-butyl)ammonium tetrakis(pentaf_uorophenyι) borate, N,N-dimethylanilinium tetrakis(pentafluorophenyl) borate, N,N-diethylanilinium tetrakis(pentafluorophenyl) borate, N,N-dimethyl-(2,4,6-trimethylanilinium) tefrakis(pentafluorophenyl) borate, trimethylammonium tetrakis-(2,3 ,4,6-tetrafluorophenylborate, triethylammonium tetrakis-(2,3,4,6-tetrafluorophenyl) borate, tripropylammomum tetrakis-(2,3,4,6-tetrafluorophenyl) borate, tri(n-butyl)ammom'um tetrakis-(2,3,4,6-tetrafluoro-phenyl) borate, dimethyl(t-butyl)ammOnium tetrakis-(2,3,4,6-tetrafluorophenyl) borate, N,N-dimethylanilinium tetrakis-(2,3,4,6-tetrafluorophenyl) borate, N,N-diethylanilinium tetrakis-(2,3,4,6-tetrafluoro-phenyl) borate, and N,N-dimemyl-(2,4,6-frimethylam inium)tefrakis-(2,3,4,6-tetrafluorophenyl) borate; dialkyl ammonium salts such as: di-(i-propyl)ammoιιium tetrakis(pentafluorophenyl) borate, and dicyclohexylammonium tetrakis(pentafluorophenyl) borate; and tri-substituted phosphonium salts such as: triphenylphosphonium tetrakis(pentafluorophenyl) borate, tri(o- tolyl)phosphonium tetrakis(pentafluorophenyl) borate, and tri(2,6- dimethylphenyl)phosphonium tetrakis(pentafluorophenyl) borate. Most preferably, the ionic stoichiometric activatoris N,N-dimethylanilinium tetra(perfluorophenyl)borate and/or triphenylcarbenium tetra(perfluorophenyl)borate.
[00136] In one embodiment, an activation method using ionizing ionic compounds not containing an active proton but capable of producing an analogous metallocene catalyst cation and their non-coordinating anion are also contemplated, and are described in EP-A- 0 426 637, EP-A- 0 573 403 and U.S. Patent No. 5,387,568, which are all herein incorporated by reference. [00137] The term "non-coordinating anion" (NCA) means an anion which either does not coordinate to said cation or which is only weakly coordinated to said cation thereby remaining sufficiently labile to be displaced by a neutral Lewis base. "Compatible" non-coordinating anions are those which are not degraded to neutrality when the initially formed complex decomposes. Non-coordinating anions useful in accordance with this invention are those that are compatible, stabilize the metal cation in the sense of balancing its ionic charge, yet retain sufficient lability to permit displacement by an ethylenically or acetylenically unsaturated monomer during polymerization. These types of cocatalysts sometimes use tri-isobutyl aluminum or tri-octyl aluminum as a scavenger. [00138] Invention process also can employ cocatalyst compounds or activator compounds that are initially neutral Lewis acids but form a cationic metal complex and a noncoordinating anion, or a zwitterionic complex upon reaction with the invention compounds. For example, tris(pentafluorophenyl) boron or aluminum act to abstract a hydrocarbyl or hydride ligand to yield an invention cationic metal complex and stabilizing noncoordinating anion, see EP- A-0 427 697 and EP-A-0 520 732 for illustrations of analogous Group-4 metallocene compounds. Also, see the methods and compounds of EP-A-0 495 375. For formation of zwitterionic complexes using analogous Group 4 compounds, see U.S. Patents 5,624,878; 5,486,632; and 5,527,929. [00139] Additional neutral Lewis-acids are known in the art and are suitable for abstracting formal anionic ligands. See in particular the review article by E. Y.-X. Chen and T.J. Marks, "Cocatalysts for Metal-Catalyzed Olefin ι
Polymerization: Activators, Activation Processes, and Structure-Activity Relationships", Chem. Rev., 100, 1391-1434 (2000).
[00140] When the catalyst compound does not contain at least one hydride or hydrocarbyl ligand but does contain at least one functional group ligand, such as chloride, amido or alkoxy ligands, and the functional group ligands are not capable of discrete ionizing abstraction with the ionizing, anion pre-cursor compounds, these functional group ligands can be converted via known alkylation reactions with organometallic compounds such as lithium or aluminum hydrides or alkyls, alkylalumoxanes, Grignard reagents, etc. See EP-A-0 500 944, EP-Al-0 570 982 and EP-Al-0 612 768 for analogous processes describing the reaction of alkyl aluminum compounds with analogous dihalide substituted metallocene compounds prior to or with the addition of activating noncoordinating anion precursor compounds.
[00141] When the cations of noncoordinating anion precursors are Bronsted acids such as protons or protonated Lewis bases (excluding water), or reducible Lewis acids such as ferrocenium or silver cations, or alkali or alkaline earth metal cations such as those of sodium, magnesium or lithium, the catalyst-compound-to- activator molar ratio may be any ratio. Combinations ofthe described activator compounds may also be used for activation. For example, tris(perfluorophenyl) boron can be used with methylalumoxane. C. Non-ionizing Activators
[00142] Activators are typically strong Lewis-acids which may play either the role of ionizing or non-ionizing activator. Activators previously described as ionizing activators may also be used as non-ionizing activators. [00143] Abstraction of formal neutral ligands may be achieved with Lewis acids that display an affinity for the formal neutral ligands. These Lewis acids are typically unsaturated or weakly coordinated. Examples of non-ionizing activators include R10(Rπ)3, where R10 is a group 13 element and R11 is a hydrogen, a hydrocarbyl, a substituted hydrocarbyl, or a functional group. Typically, R11 is an arene or a perfluorinated arene. Non-ionizing activators also include weakly coordinated transition metal compounds such as low valent olefin complexes. [00144] Non-limiting examples of non-ionizing activators include BMe3,
BEt3, B(iBu)3, BPh3, B(C6F5)3, AlMe3, AlEt3, Al(iBu)3, AlPh3, B(C6F5)3,alumoxane, CuCl, Ni(l,5-cyclooctadiene)2.
[00145] Additional neutral Lewis-acids are known in the art and will be suitable for abstracting formal neutral ligands. See in particular the review article by E. Y.-X. Chen and T.J. Marks, "Cocatalysts for Metal-Catalyzed Olefin Polymerization: Activators, Activation Processes, and Structure- Activity Relationships", Chem. Rev., 100, 1391-1434 (2000).
[00146] Preferred non-ionizing activators include R10(Rn)3, where R10 is a group 13 element and R11 is a hydrogen, a hydrocarbyl, a substituted hydrocarbyl, or a functional group. Typically, R11 is an arene or a perfluorinated arene. [00147] More preferred non-ionizing activators include B(R12)3, where R12 is a an arene or a perfluorinated arene. Even more preferred non-ionizing activators include B(C6H5)3 and B(C6F5)3. A particularly preferred non-ionizing activator is B(C6F5)3. More preferred activators are ionizing and non-ionizing activators based on perfluoroaryl borane and perfluoroaryl borates such as PhNMe2H+ B(C6F5)4\ (C6H5)3C+ B(C6F5)4 ", and B(C6F5)3. [00148] Additional preferred activators that may be used with the catalysts compounds disclosed herein include those described in WO 03/064433 Al, which is incorporated by reference herein.
[00149] In general the catalyst compound(s) and the activator are combined in ratios of about 1000:1 to about 0.5:1. In a preferred embodiment the catalyst compounds and the activator are combined in a ratio of about 300:1 to about 1:1, preferably about 150:1 to about 1:1, for boranes, borates, aluminates, etc. the ratio is preferably about 1 :1 to about 10:1 and for alkyl aluminum compounds (such as diethylaluminum chloride combined with water) the ratio is preferably about 0.5:1 to about 10:1.
[00150] In a preferred embodiment the ratio ofthe first catalyst to the second or additional catalyst is 5:95 to 95:5, preferably 25:75 to 75:25, even more preferably 40:60 to 60:40.
[00151] In general the combined catalyst compounds and the activator are combined in ratios of about 1 : 10,000 to about 1 : 1 , in other embodiments the combined catalyst compounds and the activator are combined in ratios of 1 :1 to 100:1. When alumoxane or aluminum alkyl activators are used, the combined catalyst compound-to-activator molar ratio is from 1:5000 to 10:1, alternatively from 1:1000 to 10:1; alternatively, 1:500 to 2:1; or 1 :300 to 1:1. When ionizing activators are used, the combined catalyst compound-to-activator molar ratio is from 10:1 to 1:10; 5:1 to 1:5; 2:1 to 1:2; or 1.2:1 to 1:1. Multiple activators may be used, including using mixtures of alumoxanes or aluminum alkyls with ionizing activators.
Supports
[00152] In another embodiment the catalyst compositions of this invention include a support material or carrier. For example, the one or more catalyst components and/or one or more activators may be deposited on, contacted with, vaporized with, bonded to, or incorporated within, adsorbed or absorbed in, or on, one or more supports or carriers.
[00153] The support material is any ofthe conventional support materials.
Preferably the supported material is a porous support material, for example, talc, inorganic oxides and inorganic chlorides. Other support materials include resinous support materials such as polystyrene, functionalized or crosslinked organic supports, such as polystyrene divinyl benzene polyolefins or polymeric compounds, zeolites, clays, or any other organic or inorganic support material and the like, or mixtures thereof.
[00154] The preferred support materials are inorganic oxides that include those Group 2, 3, 4, 5, 13 or 14 metal oxides. The preferred supports include silica, which may or may not be dehydrated, fumed silica, alumina (WO 99/60033), silica-alumina and mixtures thereof. Other useful supports include magnesia, titania, zirconia, magnesium chloride (U.S. Patent No. 5,965,477), montmorillonite (European Patent EP-B1 0 511 665), phyllosilicate, zeolites, talc, clays (U.S. Patent No. 6,034,187) and the like. Also, combinations of these support materials may be used, for example, silica-chromium, silica-alumina, silica-titania and the like. Additional support materials may include those porous acrylic polymers described in EP 0 767 184 BI, which is incorporated herein by reference. Other support materials include nanocomposites as described in PCT WO 99/47598, aerogels as described in WO 99/48605, spherulites as described in U.S. Patent No. 5,972,510 and polymeric beads as described in WO 99/50311, which are all herein incorporated by reference.
[00155] It is preferred that the support material, most preferably an inorganic oxide, has a surface area in the range of from about 10 to about 700 m^/g, pore volume in the range of from about 0 to about 4.0 cc/g and average particle size in the range of from about 0.02 to about 50 μm. More preferably, the surface area ofthe support material is in the range of from about 50 to about 500 n_2/g, pore volume of from about 0 to about 3.5 cc/g and average particle size of from about 0.02 to about 20 μm. Most preferably the surface area ofthe support material is in the range is from about 100 to about 400 m^/g, pore volume from about 0 to about 3.0 cc/g and average particle size is from about 0.02 to about 10 μm.
[00156] Non-porous supports may also be used as supports in the processes described herein. For example, in a preferred embodiment the nonporous, fumed silica supports described in US 6590055 can be used in the practice of this invention.
[00157] Additional useful activators for use in the processes of this invention include clays that have been treated with acids ( such as H2SO4) and then combined with metal alkyls (such as triethylaluminum) as described in US 6,531,552 and EP 1 160 261 Al, which is incorporated by reference herein. [00158] Preferred activators include that may also be supports include ion- exchange layered silicate having an acid site of at most -8.2 pKa, the amount ofthe acid site is equivalent to at least 0.05 mmol/g of 2,6-dimethylpyridine consumed for neutralization. Preferred examples include chemically treated smectite group silicates, acid-treated smectite group silicates. Additional preferred examples ofthe ion-exchange layered silicate useful in this invention include layered silicates having a 1:1 type structure or a 2:1 type structure as described in "Clay Minerals (Nendo Kobutsu Gaku)" written by Haruo Shiramizu (published by Asakura Shoten in 1995). [00159] Examples of an ion-exchange layered silicate comprising the 1 : 1 layer as the main constituting layer include kaolin group silicates such as dickite, nacrite, kaolinite, metahalloysite, halloysite or the like, and serpentine group silicates such as chrysotile, lizaldite, antigorite or the like. Additional preferred examples ofthe ion-exchange layered silicate useful in this invention include ion- exchange layered silicates comprising the 2:2 layer as the main constituting layer include smectite group silicates such as montmorillonite, beidellite, nontronite, saponite, hectorite, stephensite or the like, vermiculite group silicates such as vermiculite or the like, mica group silicates such as mica, illite, sericite, glauconite or the like, and attapulgite, sepiolite, palygorskite, bentonite, pyrophyllite, talc, chlorites and the like. The clays are contacted with an acid, a salt, an alkali, an oxidizing agent, a reducing agent or a treating agent containing a compound intercalatable between layers of an ion-exchange layered silicate. The intercalation means to introduce other material between layers of a layered material, and the material to be introduced is called as a guest compound. Among these treatments, acid treatment or salt treatment is particularly preferable. The treated clay may then be contacted with an activator compound, such as TEAL, and the catalyst compound to polymerize olefins.
[00160] In another embodiment the polymerization system comprises less than 5 weight % polar species, preferably less than 4 weight %, more preferably less than 3 weight %, more preferably less than 2 weight %, more preferably less than 1 weight %, more preferably less than 1000 ppm, more preferably less than 750 ppm, more preferably less than 500 ppm, more preferably less than 250 ppm, more preferably less than 100 ppm, more preferably less than 50 ppm, more preferably less than 10 ppm. Polar species include oxygen containing compounds (except for alumoxanes) such as alcohols, oxygen, ketones, aldehydes, acids, esters and ethers.
[00161] In another embodiment the polymerization system comprises less than 5 weight % trimethylaluminum and/or triethylaluminum, preferably less than 4 weight %, more preferably less than 3 weight %, more preferably less than 2 weight %, more preferably less than 1 weight %, more preferably less than 1000 ppm, more preferably less than 750 ppm, more preferably less than 500 ppm, more preferably less than 250 ppm, more preferably less than 100 ppm, more preferably less than 50 ppm, more preferably less than 10 ppm. [00162] In another preferred embodiment the polymerization system comprises methylalumoxane and less than 5 weight % trimethylaluminum and or triethylaluminum, preferably less than 4 weight %, more preferably less than 3 weight %, more preferably less than 2 weight %, more preferably less than 1 weight %, more preferably less than 1000 ppm, more preferably less than 750 ppm, more preferably less than 500 ppm, more preferably less than 250 ppm, more preferably less than 100 ppm, more preferably less than 50 ppm, more preferably less than 10 ppm.
[00163] Preferred invention processes can use finely divided, supported catalysts to prepare propylene/1 -hexene copolymers with greater than 1.0 mole % hex- 1 -ene. In addition to finely divided supports, invention processes can use fumed silica supports in which the support particle diameter can range from 200 angstroms to 1500 angstroms, small enough to form a colloid with reaction media.
Polymerization Process
[00164] This invention relates to processes to polymerize olefins comprising contacting one or more olefins having at least three carbon atoms with a catalyst compound and an activator at in a supercritical polymerization medium in a reactor. One or more reactors in series or in parallel may be used in the present invention. Catalyst compound and activator may be delivered as a solution or slurry, either separately to the reactor, activated in-line just prior to the reactor, or preactivated and pumped as an activated solution or slurry to the reactor. A preferred operation is two solutions activated in-line. Polymerizations are carried out in either single reactor operation, in which monomer, comonomers, catalyst/activator, scavenger, and optional modifiers are added continuously to a single reactor or in series reactor operation, in which the above components are added to each of two or more reactors connected in series. The catalyst components can be added to the first reactor in the series. The catalyst component may also be added to both reactors, with one component being added to first reaction and another component to other reactors.
[00165] Invention methods also cover polymerization of propylene in high- pressure reactors where, preferably, the reactor is substantially unreactive with the polymerization reaction components and is able to withstand the high pressures and temperatures that occur during the polymerization reaction. Such reactors are known as high-pressure reactors for purposes of this disclosure. Withstanding these high pressures and temperatures will allow the reactor to maintain the propylene under supercritical conditions. Suitable reaction vessels include those known in the art to maintain supercritical or other high-pressure ethylene polymerization reactions. Suitable reactors are selected from autoclave, tubular, and autoclave/tubular reactors, among others.
[00166] The polymerization processes described herein operate well in autoclave and tubular reactors. Typically, autoclave reactors have length-to- diameter ratios of 1 : 1 to 20: 1 and are fitted with a high-speed (up to 1500 RPM) multiblade stirrer. Autoclave pressures are typically greater than 6 MPa with a maximum of typically less than 260 MPa. When the autoclave has a low length- to-diameter ratio (such as less than 4) propylene and other monomers are typically injected at only one position. But injection at two or more positions in the autoclave is also possible. For instance, in reactors where the length-to-diameter ratio is around 4-20, the reactor can contain up to six different injection positions. Additionally, in the larger autoclaves, one or more lateral fixing devices support the high-speed stirrer. These fixing devices can also divide the autoclave into two or more zones. Mixing blades on the stirrer can differ from zone to zone to allow for plug flow or back mixing, largely independently, in the separate zones. Two or more autoclaves with one or more zones can connect in series to tailor polymer structure.
[00167] Tubular reactors are also well suited for use in this invention, preferably tubular reactors capable of operating up to about 350MPa. Preferred tubular reactors are fitted with external cooling and one or more injection points along the (tubular) reaction zone. As in autoclaves, these injection points serve as entry points for monomers (such as propylene), one or more comonomer, catalyst, or mixtures of these. In tubular reactors, external cooling allows for increased monomer conversion relative to an autoclave, where the low surface-to-volume ratio hinders any significant heat removal. Tubular reactors have a special outlet valve that can send a pressure Shockwave backward along the tube. The Shockwave helps dislodge any polymer residue that has formed on reactor walls during operation. Another way of addressing wall deposits is to fabricate the tube with smooth, unpolished internal surfaces. Preferred tubular reactors can operate at pressures up to 360 MPa and preferably have lengths of 100-2000 meters and internal diameters usually less than 10 cm.
[00168] Reactor trains that pair autoclaves with tubular reactors can also serve in invention processes. In such instances, the autoclave typically precedes the tubular reactor. Such systems may have injection of additional catalyst and/or feed components at several points in the autoclave and more particularly along the tube length.
[00169] In both autoclaves and tubular reactors, at injection, feeds are preferably room temperature or below to provide maximum polymer production within the limits of maximum operating temperature. In autoclave operation, a preheater operates at startup, but not after the reaction reaches steady state if the first mixing zone has some back-mixing characteristics. In tubular reactors, the first section of double-jacketed tubing is heated rather than cooled and is operated continuously since a tubular reactor is by nature plug flow. In both multizone autoclaves and tubular reactors, catalyst can not only be injected at the inlet, but also optionally at one or more points along the reactor. The catalyst feeds injected at the inlet and other injection points can be the same or different in terms of content, density, concentration, etc. Choosing different catalyst feeds allows polymer design tailoring. At the reactor outlet valve, the pressure drops to levels below that which critical phase separation occurs. Therefore, the downstream vessel contains a polymer-rich phase and a polymer-lean phase. Typically, conditions in this vessel remain supercritical and temperature remains above the polymer product's crystallization temperature. The autoclave or tubular reactor effluent is depressurized on entering the high pressure separator (HPS). In polymerizations based on propylene alternative choices are open to the design relative to classic high pressure polyethylene process technology. [00170] At the reactor outlet valve the pressure drops to begin the separation of polymer and unreacted monomer, co-monomers, propane, etc. The temperature in this vessel will be maintained above the polymer product's crystallization point but the pressure may be below the critical point. The pressure need only be high enough that the propylene can be condensed against standard cooling water. The liquid recycle stream can then be recycled to the reactor with a liquid pumping system instead ofthe hyper-compressors required for polyethylene units. The relatively low pressure in this separator will reduce the monomer concentration in the liquid polymer phase which will result in a much lower polymerization rate. This polymerization rate may be low enough to operate this system without adding a catalyst poison or "killer". If a catalyst killer is required (e.g., to prevent reactions in the high pressure recycle) then provision must be made to remove any potential catalyst poisons from the recycled propylene rich monomer stream e.g. by the use of fixed bed adsorbents or by scavenging with an aluminum alkyl.
[00171] Alternatively, the HPS may be operated over propylene's critical pressure but within the propylene/polypropylene two phase region. This is the economically preferred method if polypropylene is to be produced with a revamped HPPE plant. The recycled HPS overhead is cooled and dewaxed before being returned to the suction ofthe secondary compressor, which is typical of HPPE plant operation.
[00172] The polymer from this intermediate or high pressure vessel will then go through another pressure reduction step to a low pressure separator. The temperature of this vessel will be maintained above the polymer melting point so that the polymer from this vessel can be fed as a liquid directly to an extruder or static mixer. The pressure in this vessel will be kept low by using a compressor to recover the unreacted monomers, etc to the condenser and pumping system referenced above.
[00173] In addition to autoclave reactors, tubular reactors, or reactors combining these, loop-type reactors function as well. In this reactor type, monomer enters and polymer exits continuously at different points along the loop, while an in-line pump continuously circulates the contents (reaction liquid). The feed/product takeoff rates control total average residence time. A cooling jacket removes reaction heat from the loop. Industrially a loop reactor is typically not operated at the high pressures encountered in autoclaves and tubes. [00174] Commercial low pressure loop reactors have diameters of 16 to 24 inches (41 to 61 cm) and lengths of 100 to 200+ meters. Operation in a single supercritical polypropylene in propylene solution phase is preferably at pressures of greater than 25 to 30 MPa. At these pressures smaller diameter thicker wall loop tubing is necessary resulting in potential difficulties in pump around efficiency and maximum allowable reactor capacity.
[00175] In addition to autoclave reactors, tubular reactors, or a combination of these reactors, loop-type reactors are useful in this invention. In this reactor type, monomer enters and polymer exits continuously at different points along the loop, while an in-line pump continuously circulates the contents (reaction liquid). The feed/product takeoff rates control total average residence time. A cooling jacket removes reaction heat from the loop. United States Patent No. 6,355,741 discusses a reactor with at least two loops that is useful in the practice of this invention provided that one or both operate at the supercritical conditions. United States Patent No. 5,326,835 describes a process said to produce polymer in a bimodal fashion. This process's first reactor stage is a loop reactor in which polymerization occurs in an inert, low-boiling hydrocarbon. After the loop reactor, the reaction medium transits into a gas-phase reactor where gas-phase polymerization occurs. Since two very different environments create the polymer, it shows a bimodal molecular weight distribution. This two stage procedure can be modified to work with the procedure ofthe instant application. For instance, a first stage loop reactor can use propylene as the monomer and a propylene-based reaction medium as the inert low-boiling hydrocarbon.
[00176] PCT publication WO 19/14766 describes a process comprising the steps of (a) continuously feeding olefinic monomer and a catalyst system, with a metallocene component and a cocatalyst component, to the reactor; (b) continuously polymerizing that monomer in a polymerization zone reactor under elevated pressure; (c) continuously removing the polymer/monomer mixture from the reactor; (d) continuously separating monomer from molten polymer; (e) reducing pressure to form a monomer-rich and a polymer-rich phase; and (f) separating monomer from the reactor. The polymerization zoning technique described in the above process can be practiced using the instant invention's process conditions. That is, the above process is suitable for use with this invention provided at least one polymerization zone makes the propylene or the reaction media containing propylene supercritical.
[00177] In general, feed inlet temperatures are generally at or below room temperature to provide cooling to the exothermic reaction in the reactor operating above the crystallization temperature ofthe polymer product. For a predominantly propylene containing feed with a catalyst producing significant polymer isotacticity the reactor temperature will be above 145°C.
[00178] The processes described herein may have residence times as short as 0.5 seconds and as long as several hours. In preferred embodiments the residence times are from 1 second to 30 minutes, preferably 5 seconds to 10 minutes, more preferably from 10 seconds to 5 minutes, more preferably from 10 seconds to 3 minutes. In some embodiments the residence time can be selected from 10, 30, 45, 50, 60, 120, and 150 seconds. Maximum residence times can be selected from 200, 300, 400, 500, or 600 seconds. In general, invention processes choose residence times of from 30-600 seconds; more particularly 45-400 or 60- 300 seconds. In general, invention processes choose residence times of from 30 sec to 1 hour; more particularly 30 sec to 30 minutes; 45-400, or 60-300 sec. In another embodiment the polymerization of propylene the residence times are up to 5 minutes.
[00179] In some embodiments, invention processes produce polymer at a rate of 560-10000 LB/w-Ft2. More particularly, production rates can range from 560-2000 or 600-1500.
[00180] Dividing the total quantity of polymer that is collected during the reaction time by the amount of propylene added to the reaction yields the conversion rate. The monomer-to-polymer conversion rate for the described processes is high. Invention processes can be run at conversion rates of 60 or less, 10-60, 20-60, 30-60, 40-60, 10-50, 20-50, 30-50, 40-50, 10-40, 20-40, or 30- 40 percent conversion, preferably greater than 30, or greater than 40 percent conversion.
[00181] Catalyst productivities range from 828 to 5940 kg PP/kg catalyst * hr. These high levels of catalyst productivity may result in low residual solids in the polymer product. Residual solid amount of less than 0.5 wt%, particularly less than 0.3 wt%, or more particularly less than 0.1 wt% total solids residue are preferred.
Comonomers, dual catalysts and polymer structure
[00182] In reactors with multiple injection points for catalyst and feed there exists the possibility to tailor the polymer design. Use of more than one catalyst having different molecular weight and stmctural capabilities allows a wide variety of product compositions (e.g. bimodal, linear mixed with long chain branched). [00183] The various olefins will have differing reactivity ratios for a given catalyst so a plug flow type operation will allow compositional tapering if for instance no feeds are injected down the reactor or compensation ofthe tapering if the more reactive monomer is injected preferentially along the tube. A single zone ideal back mixed autoclave reactor will not allow tapering of polymer composition but the use of multiple catalysts is still applicable. Operation of two such autoclaves in series or parallel can allow the use of tailoring by altering the composition of fresh feed to the second reactor.
Catalyst killing
[00184] The reactor effluent is depressurized to an intermediate pressure significantly below the cloud point pressure but nevertheless supercritical for that composition. This allows separation of a polymer rich phase for further purification and a propylene rich phase for recycle compression back to the reactor.
[00185] This separation is carried out in a vessel known as a high pressure separator (HPS). Since this vessel also has a significant residence time, the catalyst activity is killed by addition of a polar species such as water, alcohol or sodium/calcium stearate. The choice and quantity of killing agent will depend on the requirements for clean up ofthe recycle propylene and comonomers as well as the product properties, if the killing agent has low volatility. [00186] Alternatively the intermediate separation can be done at pressures well below the critical point so that the monomer concentration and therefore reactivity in the high pressure separator is relatively low. The relatively small amount of continued polymerization in this vessel may not be a problem so addition of catalyst deactivating compounds as is done in PE processes may be avoided presuming that no undesired reactions occur in the high or intermediate pressure recycle system. If no killing compounds are added then the killer removal step can be eliminated.
Choice of Propylene feed purity.
[00187] Propylene is available commercially at two levels of purity - polymer grade at 99.5% and chemical grade at about 93 to 95%. The choice of feed will set the level of purge required from the recycle to avoid over dilution of the feed by inert propane. The presence of propane in the reactor and HPS will raise the pressure ofthe cloud point curve for a given temperature but will decrease the polymerization efficiency due to a decrease in propylene (and other olefin) concentrations in the reactor. The elevation of cloud point pressure due to propane will widen the operating window ofthe HPS. In copolymerizations of propylene with limited amounts of ethylene, a similar effect in raising the cloud point pressure will be noted due to the presence of low levels of ethylene in the HPS.
Low Pressure Separator Operation
[00188] The LPS rurining at just above atmospheric pressure is just a simple sub critical flash of light components, reactants and oligomers thereof, for the sole purpose of producing a low volatile containing polymer melt entering the finishing extmder or static mixer.
Polymer Products
[00189] This invention also relates to a propylene polymer having a 1 ,3 regio defect population of greater than 5 per 10,000 monomer units, a melting point of 145°C or more, and a g' of 0.97 or less and an Mw greater than 20,000.
[00190] This invention also relates to a propylene polymer having a 1 ,3 regio defect population of greater than 5 per 10,000 monomer units, a melting point of 70°C or more (preferably 145°C or more), and a g' of 0.97 or more and an
Mw greater than 20,000.
[00191] This invention also relates to copolymer comprising propylene an a comonomer having a 1,3 regio defect population of greater than 5 per 10,000 monomer units, a melting point of 70°C or more (preferably 145°C or more), and a g' of 0.97 or less and an Mw greater than 10,000.
[00192] The polymers produced by invention processes may be in any structures including block, linear, radial, star, branched, and combinations of these.
[00193] Some invention embodiments produce polypropylene and copolymers of polypropylene with a unique microstructure. The process ofthe invention can be practiced such that novel isotactic and syndiotactic compositions are made. In other embodiments, the invention processes make crystalline polymers.
[00194] The processes ofthe invention produce propylene polymers with a melting point of 70 to 165°C, and a weight-average molecular weight of 2,000 to
1,000,000, 10,000 to 1,000,000,15,000 to 500,000, 25,000 to 250,000 or 35,000 to
150,000.
[00195] Invention processes produce polymer with a heat of fusion, ΔHf, of
1-30 J/g, 2-20 J/g, or 3-10 J/g. In another embodiment the process of this invention produce polymers having an Hf of up to 110 J/g, preferably 50 to 110
J/g, more preferably 70 to 100 J/g.
[00196] The processes described herein can produce polymers having little or no ash or residue from catalyst or supports. In a preferred embodiment the polymers produced herein comprise less than 1 weight % silica, preferably less than 0.1 weight % silica, preferably less than 100 ppm silica, preferably less than
10 ppm.
[00197] Dienes can be used as a comonomer to increase the molecular weight ofthe resulting polymer and to create long chain branching. Vinyl chloride can be used as a comonomer to increase the degree of vinyl termination in the polymer.
[00198] Invention processes can produce long-chain-branched polypropylene. Long-chain branching is achievable using invention process regardless of whether additional ,ω-diene or other diene such as vinylnorbomene are used. In a preferred embodiment, less than 0.5 wt% diene is used.
Alternatively, embodiments with less than 0.4 wt%, 0.3 wt%, 0.2 wt%, 1000 ppm,
500 ppm, 200 ppm, or 100 ppm.
[00199] In some embodiments, the present invention involves using as a comonomer an α,ω-diene and the olefin/α,ω-diene copolymers resulting from that use. Additionally, the present invention involves a copolymerization reaction of olefin monomers, wherein the reaction includes propylene and ethylene copolymerization with an α,ω-diene and the copolymers that are made. These copolymers may be employed in a variety of articles including, for example, films, fibers, such as spunbonded and melt blown fibers, fabrics, such as nonwoven fabrics, and molded articles. More particularly, these articles include, for example, cast films, oriented filnis, injection molded articles, blow molded articles, foamed articles, foam laminates and thermoformed articles. [00200] It should be noted that while linear α,ω-dienes are preferred, other dienes can also be employed to make polymers of this invention. These would include branched, substituted α,ω-dienes, such as 2-methyl-l,9-decadiene; cyclic dienes, such as vinylnorbomene; or aromatic types, such as divinyl benzene. [00201] Embodiments ofthe present invention include copolymers having from 98 to 99.999 weight percent olefin units, and from 0.001 to 2.000 weight percent α,ω-diene units. Copolymer embodiments may have a weight-average molecular weight from 50,000 to 2,000,000, crystallization temperatures from 50 °C to 140 °C and a melt flow rate (MFR) from 0.1 dg/min to 1500 dg/min. Note that the these embodiments display high crystallization temperatures intrinsically; there is no need for externally added nucleating agents.
[00202] In other embodiments, the copolymer includes from 90 to 99.999 weight percent of propylene units, from 0.000 to 8 weight percent of olefin units other than propylene units and from 0.001 to 2 weight percent α,ω-diene units. Copolymer embodiments may have weight-average molecular weights from 20,000 to 2,000,000, crystallization temperatures (without the addition of external nucleating agents) from 115 °C to 135 °C and MFRs from 0.1 dg/min to 100 dg/min. The accompanying olefin may be any of C2-C20 α-olefins, diolefins (with one internal olefin) and their mixtures thereof. More specifically, olefins include ethylene, butene- 1, pentene- 1, hexene- 1, heptene- 1, 4-methyl-l -pentene, 3- methyl- 1 -pentene, 4-methy 1-1 -hexene, 5-methyl-l -hexene, 1 -octene, 1 -decene, 1- undecene, and 1 -dodecene.
[00203] Copolymers of isotactic polypropylene made under supercritical conditions include ethylene and C4-C12 comonomers such as but- 1 -ene, 3- methylpent-1-ene, hex- 1 -ene, 4-methylpent-l-ene, and oct- 1 -ene. Invention process can prepare these copolymers without the use of solvent or in an environment with low solvent concentration.
[00204] In a preferred embodiment the polymers have a residual solid amount of less than 0.5 wt%, particularly less than 0.3 wt%, or more particularly less than 0.1 wt% total solids residue are preferred.
[00205] Preferred propylene polymers produced typically comprise 0 to 50 weight % of a comonomer, preferably 1 to 40 weight %, preferably 2 to 30 weight
%, preferably 4 to 20 weight %, preferably 5 to 15 weight %, preferably 5 to 10 weight %, and have one or more of:
1. a heat of fusion of 30 J/g or more, preferably 50 J/g or more, preferably 60 or more, preferably 70 or more, preferably 80 or more, preferably 90 or more, preferably 95 or more, preferably 100 or more, preferably 105 or more OR an Hf of 30 J/g or less, more preferably 20 J/g or less preferably 0;
2. a Branching Index (g'avg)of 1.0 or less, preferably 0.98 or less, preferably 0.97 or less, preferably 0.96 or less, preferably 0.95 or less, preferably 0.94 or less, preferably 0.93 or less, more preferably 0.92 or less, more preferably 0.91 or less, more preferably 0.90 or less;
3. a weight average molecular weight (as measured by GPC DRI) of 20,000 or more, preferably 50,000 to 2,000,000, preferably 100,000 to 1,000,000, preferably 150,000 to 900,000, preferably 200,000 to 800,000;
4. a melt flow rate of 0.5 dg/min or more, preferably 0.7 dg/min or more, preferably 1.0 dg/min or more, preferably between 0.1 and 1500 dg/min;
5. a percent crystallinity (%X) of 30 % or more, preferably between 40 and 50 %;
6. a melting temperature of 145 °C or more, preferably 150 °C or more, preferably 155°C or more, preferably between 145 and 160 °C;
7. a crystallization temperature of 25 °C or more, preferably 45 °C or more, preferably 65°C or more, preferably from 100°C; and
8. an Mw/Mn (as measured by GPC DRI) of about 1 to 20, preferably about 1.5 to 8, preferably 2 to 4. [00206] In another embodiment the polymers produced herein have a melt viscosity of less than 10,000 centipoises at 180 °C as measured on a Brookfield viscometer, preferably between 1000 to 3000 cps for some embodiments (such as packaging and adhesives) and preferably between 5000 and 10,000 for other applications.
Formulations
[00207] In some embodiments the polymer produced by this invention may be blended with one or more other polymers, including but not limited to, thermoplastic polymer(s) and/or elastomer(s).
[00208] A "thermoplastic polymer(s)" is a polymer that can be melted by heat and then cooled with out appreciable change in properties. Thermoplastic polymers typically include, but are not limited to, polyolefins, polyamides, polyesters, polycarbonates, polysulfones, polyacetals, polylactones, acrylonitrile- butadiene-styrene resins, polyphenylene oxide, polyphenylene sulfide, styrene- acrylonitrile resins, styrene maleic anhydride, polyimides, aromatic polyketones, or mixtures of two or more ofthe above. Preferred polyolefins include, but are not limited to, polymers comprising one or more linear, branched or cyclic C2 to C40 olefins, preferably polymers comprising propylene copolymerized with one or more C2 or C4 to C40 olefins, preferably a C3 to C20 alpha olefin, more preferably C3 to C10 α-olefins. More preferred polyolefins include, but are not limited to, polymers comprising ethylene including but not limited to ethylene copolymerized with a C3 to C40 olefin, preferably a C3 to C20 alpha olefin, more preferably propylene and or butene.
[00209] "Elastomers" encompass all natural and synthetic rubbers, including those defined in ASTM D1566). Examples of preferred elastomers include, but are not limited to, ethylene propylene rubber, ethylene propylene diene monomer rubber, styrenic block copolymer mbbers (including SI, SIS, SB, SBS, SEBS and the like, where S=styrene, I=isobutylene, and B=butadiene), butyl mbber, halobutyl rabber, copolymers of isobutylene and para-alkylstyrene, halogenated copolymers of isobutylene and para-alkylstyrene, natural rubber, polyisoprene, copolymers of butadiene with acrylonitrile, polychloroprene, alkyl acrylate rubber, chlorinated isoprene mbber, acrylonitrile chlorinated isoprene mbber, polybutadiene mbber (both cis and trans).
[00210] In another embodiment, the polymer produced by this invention is combined with one or more of isotactic polypropylene, highly isotactic polypropylene, syndiotactic polypropylene, random copolymer of propylene and ethylene and/or butene and/or hexene, polybutene, ethylene vinyl acetate, low density polyethylene (density 0.915 to less than 0.935 g/cm3) linear low density polyethylene, ultra low density polyethylene (density 0.86 to less than 0.90 g/cm3), very low density polyethylene (density 0.90 to less than 0.915 g/cm3), medium density polyethylene (density 0.935 to less than 0.945 g/cm3), high density polyethylene (density 0.945 to 0.98 g/cm3), ethylene vinyl acetate, ethylene methyl acrylate, copolymers of acrylic acid, polymethylmethacrylate or any other polymers polymerizable by a high-pressure free radical process, polyvinylchloride, polybutene- 1, isotactic polybutene, ABS resins, ethylene- propylene rabber (EPR), vulcanized EPR, EPDM, block copolymer, styrenic block copolymers, polyamides, polycarbonates, PET resins, crosslinked polyethylene, polymers that are a hydrolysis product of EN A that equate to an ethylene vinyl alcohol copolymer, polymers of aromatic monomers such as polystyrene, poly-1 esters, polyacetal, polyvinylidine fluoride, polyethylene glycols and/or polyisobutylene.
[00211] In another embodiment elastomers are blended with the polymer produced by this invention to form rubber toughened compositions. In some particularly preferred embodiments, the rabber toughened composition is a two (or more) phase system where the elastomer is a discontinuous phase and the polymer produced by this invention is a continuous phase. This blend may be combined with tackifiers and/or other additives as described herein. [00212] In another embodiment the polymer produced by this invention may be blended with elastomers or other soft polymers to form impact copolymers. In some embodiments the blend is a two (or more) phase system where the elastomer or soft polymer is a discontinuous phase and the polymer produced by this invention is a continuous phase. This blend may be combined with tackifiers and/or other additives as described herein. [00213] In some embodiments the polymers ofthe invention described above are combined with metallocene polyethylenes (mPEs) or metallocene polypropylenes (mPPs). The mPE and mPP homopolymers or copolymers are typically produced using mono- or bis-cyclopentadienyl transition metal catalysts in combination with an activator of alumoxane and/or a non-coordinating anion in solution, slurry, high pressure or gas phase. The catalyst and activator may be supported or unsupported and the cyclopentadienyl rings by may substituted or unsubstituted. Several commercial products produced with such catalyst/activator combinations are commercially available from ExxonMobil Chemical Company in Baytown, Texas under the tradenames EXCEED™, ACHIEVE™ and EXACT™. For more information on the methods and catalysts/activators to produce such homopolymers and copolymers see WO 94/26816; WO 94/03506; EPA 277,003; EPA 277,004; U.S. Pat. No. 5,153,157; U.S. Pat. No. 5,198,401; U.S. Pat. No. 5,240,894; U.S. Pat. No. 5,017,714; CA 1,268,753; U.S. Pat. No. 5,324,800; EPA 129,368; U.S. Pat. No. 5,264,405; EPA 520,732; WO 92 00333; U.S. Pat. No. 5,096,867; U.S. Pat. No. 5,507,475; EPA 426637; EPA 573 403; EPA 520 732; EPA 495 375; EPA 500944; EPA 570982; WO91/09882; WO94/03506 and U.S. Pat. No. 5,055,438.
[00214] In some embodiments the polymer of this invention is present in the above blends, at from 10 to 99 weight %, based upon the weight ofthe polymers in the blend, preferably 20 to 95 weight %, even more preferably at least 30 to 90 weight %, even more preferably at least 40 to 90 weight %, even more preferably at least 50 to 90 weight %, even more preferably at least 60 to 90 weight %, even more preferably at least 70 to 90 weight %. [00215] The blends described above may be produced by (a) mixing the polymers ofthe invention with one or more polymers (as described above), by (b) connecting reactors together in series to make in situ reactor blends or by (c) using more than one catalyst in the same reactor to produce multiple species of polymers. The polymers can be mixed together prior to being put into the extruder or may be mixed in an extruder.
[00216] Any ofthe above polymers may be functionalized. Functionalized means that the polymer has been contacted with an unsaturated acid or anhydride. Preferred unsaturated acids or anhydrides include any unsaturated organic compound containing at least one double bond and at least one carbonyl group. Representative acids include carboxylic acids, anhydrides, esters and their salts, both metallic and non-metallic. Preferably the organic compound contains an ethylenic unsaturation conjugated with a carbonyl group (-C=O). Examples include maleic, fumaric, acrylic, methacrylic, itaconic, crotonic, alpha-methyl crotonic, and cinnamic acids as well as their anhydrides, esters and salt derivatives. Maleic anhydride is particularly preferred. The unsaturated acid or anhydride is preferably present at about 0.1 weight % to about 5 weight %, preferably at about 0.5 weight % to about 4 weight %, even more preferably at about 1 to about 3 weight %, based upon the weight ofthe hydrocarbon resin and the unsaturated acid or anhydride.
[00217] Tackifiers may be blended with the polymers of this invention and/or with blends ofthe polymer produced by this inventions (as described above). Examples of useful tackifiers include, but are not limited to, aliphatic hydrocarbon resins, aromatic modified aliphatic hydrocarbon resins, hydrogenated polycyclopentadiene resins, polycyclopentadiene resins, gum rosins, gum rosin esters, wood rosins, wood rosin esters, tall oil rosins, tall oil rosin esters, polyterpenes, aromatic modified polyterpenes, terpene phenolics, aromatic modified hydrogenated polycyclopentadiene resins, hydrogenated aliphatic resin, hydrogenated aliphatic aromatic resins, hydrogenated terpenes and modified terpenes, and hydrogenated rosin esters. In some embodiments the tackifier is hydrogenated. In other embodiments the tackifier is non-polar. (Non-polar tackifiers are substantially free of monomers having polar groups. Preferably the polar groups are not present; however, if present, they are preferably not present at more that 5 weight %, preferably not more that 2 weight %, even more preferably no more than 0.5 weight %.) In some embodiments the tackifier has a sof ening point (Ring and Ball, as measured by ASTM E-28) of 80 °C to 140 °C, preferably 100 °C to 130 °C. In some embodiments the tackifier is functionalized. By functionalized is meant that the hydrocarbon resin has been contacted with an unsaturated acid or anhydride. Preferred unsaturated acids or anhydrides include any unsaturated organic compound containing at least one double bond and at least one carbonyl group. Representative acids include carboxylic acids, anhydrides, esters and their salts, both metallic and non-metallic. Preferably the organic compound contains an ethylenic unsaturation conjugated with a carbonyl group (-C=O). Examples include maleic, fumaric, acrylic, methacrylic, itaconic, crotonic, alpha-methyl crotonic, and cinnamic acids as well as their anhydrides, esters and salt derivatives. Maleic anhydride is particularly preferred. The unsaturated acid or anhydride is preferably present at about 0.1 weight % to about 10 weight %, preferably at about 0.5 weight % to about 7 weight %, even more preferably at about 1 to about 4 weight %, based upon the weight ofthe hydrocarbon resin and the unsaturated acid or anhydride.
[00218] The tackifier, if present, is typically present at about 1 weight % to about 50 weight %, based upon the weight ofthe blend, more preferably 10 weight % to 40 weight %, even more preferably 20 weight % to 40 weight %. Preferably however, tackifier is not present, or if present, is present at less than 10 weight %, preferably less than 5 weight %, more preferably at less than 1 weight %. [00219] In another embodiment the polymers of this invention, and/or blends thereof, further comprise a crosslinking agent. Preferred crosslinking agents include those having functional groups that can react with the acid or anhydride group. Preferred crosslinking agents include alcohols, multiols, amines, diamines and/or triamines. Examples of crosslinking agents useful in this invention include polyamines such as ethylenediamine, diethylenetriamine, hexamethylenediamine, diethylaminopropylamine, and/or menthanediamine. [00220] In another embodiment the polymers of this invention, and/or blends thereof, further comprise typical additives known in the art such as fillers, cavitating agents, antioxidants, surfactants, adjuvants, plasticizers, block, antiblock, color masterbatches, pigments, dyes, processing aids, UN stabilizers, neutralizers, lubricants, waxes, and/or nucleating agents. The additives may be present in the typically effective amounts well known in the art, such as 0.001 weight % to 10 weight %.
[00221] Preferred fillers, cavitating agents and/or nucleating agents include titanium dioxide, calcium carbonate, barium sulfate, silica, silicon dioxide, carbon black, sand, glass beads, mineral aggregates, talc, clay and the like. [00222] Preferred antioxidants include phenolic antioxidants, such as
Irganox 1010, Irganox, 1076 both available from Ciba-Geigy. Preferred oils include paraffinic or naphthenic oils such as Primol 352, or Primol 876 available from ExxonMobil Chemical France, S.A. in Paris, France. [00223] More preferred oils include aliphatic naphthenic oils, white oils or the like.
[00224] Preferred plasticizers and/or adjuvants include mineral oils, polybutenes, phthalates and the like. Particularly preferred plasticizers include phthalates such as diisoundecyl phthalate (DIUP), diisononylphthalate (DIΝP), dioctylphthalates (DOP) and polybutenes, such as Parapol 950 and Parapol 1300 available from ExxonMobil Chemical Company in Houston Texas. Additional Preferred plasticizers include those disclosed in WO0118109 A 1 and USSΝ 10/640,435, which are incorporated by reference herein. [00225] Preferred processing aids, lubricants, waxes, and/or oils include low molecular weight products such as wax, oil or low Mn polymer, (low meaning below Mn of 5000, preferably below 4000, more preferably below 3000, even more preferably below 2500). Preferred waxes include polar or non-polar waxes, functionalized waxes, polypropylene waxes, polyethylene waxes, and wax modifiers. Preferred waxes include ESCOMER™ 101. [00226] Preferred functionalized waxes include those modified with an alcohol, an acid, or a ketone. Functionalized means that the polymer has been contacted with an unsaturated acid or anhydride. Preferred unsaturated acids or anhydrides include any unsaturated organic compound containing at least one double bond and at least one carbonyl group. Representative acids include carboxylic acids, anhydrides, esters and their salts, both metallic and non-metallic. Preferably the organic compound contains an ethylenic ^saturation conjugated with a carbonyl group (-C= ). Examples include maleic, fumaric, acrylic, methacrylic, itaconic, crotonic, alpha-methyl crotonic, and cinnamic acids as well as their anhydrides, esters and salt derivatives. Maleic anhydride is particularly preferred. The unsaturated acid or anhydride is preferably present at about 0.1 weight % to about 10 weight %, preferably at about 0.5 weight % to about 7 weight %, even more preferably at about 1 to about 4 weight %, based upon the weight ofthe hydrocarbon resin and the unsaturated acid or anhydride. Preferred examples include waxes modified by methyl ketone, maleic anhydride or maleic acid. Preferred low Mn polymers include polymers of lower alpha olefins such as propylene, butene, pentene, hexene and the like. A particularly preferred polymer includes polybutene having an Mn of less than 1000. An example of such a polymer is available under the trade name PARAPOLT 950 from ExxonMobil Chemical Company. PARAPOLTM 950 is an liquid polybutene polymer having an Mn of 950 and a kinematic viscosity of 220cSt at 100 °C, as measured by ASTM D 445.
[00227] Preferred UN stabilizers and or antioxidants include Irganox 1010 and the like.
APPLICATIONS
[00228] The polymers of this invention (and blends thereof as described above) whether formed in situ or by physical blending are preferably used in any known thermoplastic or elastomer application. Examples include uses in molded parts, films, tapes, sheets, tubing, hose, sheeting, wire and cable coating, adhesives, shoesoles, bumpers, gaskets, bellows, films, fibers, elastic fibers, nonwovens, spunbonds, sealants, surgical gowns and medical devices.
Adhesives
[00229] The polymers of this invention or blends thereof can be used as adhesives, either alone or combined with tackifiers. The tackifier is typically present at about 1 weight % to about 50 weight %, based upon the weight ofthe , blend, more preferably 10 weight % to 40 weight %, even more preferably 20 weight % to 40 weight %. Other additives, as described above, may be added also.
[00230] The adhesives of this invention can be used in any adhesive application, including but not limited to, disposables, packaging, laminates, pressure sensitive adhesives, tapes labels, wood binding, paper binding, nonwovens, road marking, reflective coatings, and the like. In some embodiments the adhesives of this invention can be used for disposable diaper and napkin chassis constmction, elastic attachment in disposable goods converting, packaging, labeling, bookbinding, woodworking, and other assembly applications. Particularly preferred applications include: baby diaper leg elastic, diaper frontal tape, diaper standing leg cuff, diaper chassis construction, diaper core stabilization, diaper liquid transfer layer, diaper outer cover lamination, diaper elastic cuff lamination, feminine napkin core stabilization, feminine napkin adhesive strip, industrial filtration bonding, industrial filter material lamination, filter mask lamination, surgical gown lamination, surgical drape lamination, and perishable products packaging.
[00231] The adhesives described above may be applied to any substrate.
Preferred substrates include wood, paper, cardboard, plastic, thermoplastic, rabber, metal, metal foil (such as aluminum foil and tin foil), metallized surfaces, cloth, non-wovens (particularly polypropylene spun bonded fibers or non- wovens), spunbonded fibers, cardboard, stone, plaster, glass (including silicon oxide (SiOx)coatings applied by evaporating silicon oxide onto a film surface), foam, rock, ceramics, films, polymer foams (such as polyurethane foam), substrates coated with inks, dyes, pigments, PNDC and the like or combinations thereof. Additional preferred substrates include polyethylene, polypropylene, poly acrylates, acrylics, polyethylene terephthalate, or any ofthe polymers listed above as suitable for blends. Corona treatment, electron beam irradiation, gamma irradiation, microwave or silanization may modify any ofthe above substrates.
Films
[00232] The polymer produced by this invention described above and the blends thereof may be formed into monolayer or multilayer films. These films may be formed by any ofthe conventional techniques known in the art including extrasion, co-extrusion, extrusion coating, lamination, blowing, tenter frame, and casting. The film may be obtained by the flat film or tubular process, which may be followed by orientation in an uniaxial direction, or in two mutually perpendicular directions in the plane ofthe film. One or more ofthe layers ofthe film may be oriented in the transverse and/or longitudinal directions to the same or different extents. This orientation may occur before or after the individual layers are brought together. For example a polyethylene layer can be extrasion coated or laminated onto an oriented polypropylene layer or the polyethylene and polypropylene can be coextruded together into a film then oriented. Likewise, oriented polypropylene could be laminated to oriented polyethylene or oriented polyethylene could be coated onto polypropylene then optionally the combination could be oriented even further. Typically the films are oriented in the Machine Direction (MD) at a ratio of up to 15, preferably between 5 and 7, and in the Transverse Direction (TD) at a ratio of up to 15 preferably 7 to 9. However in another embodiment the film is oriented to the same extent in both the MD and TD directions. In another embodiment the layer comprising the polymer composition of this invention (and/or blends thereof) may be combined with one or more other layers. The other layer(s) may be any layer typically included in multilayer film structures. For example the other layer or layers may be: 1 • Polyolefins. Preferred polyolefins include homopolymers or copolymers of C2 to C40 olefins, preferably C2 to C20 olefins, preferably a copolymer of an α-olefin and another olefin or .α-olefin (ethylene is defined to be an α- olefin for purposes of this invention). Preferably homopolyethylene, homopolypropylene, propylene copolymerized with ethylene and or butene, ethylene copolymerized with one or more of propylene, butene or hexene, and optional dienes. Preferred examples include thermoplastic polymers such as ultra low density polyethylene, very low density polyethylene, linear low density polyethylene, low density polyethylene, medium density polyethylene, high density polyethylene, polypropylene, isotactic polypropylene, highly isotactic polypropylene, syndiotactic polypropylene, random copolymer of propylene and ethylene and/or butene and/or hexene, elastomers such as ethylene propylene rabber, ethylene propylene diene monomer rabber, neoprene, and blends of thermoplastic polymers and elastomers, such as for example, thermoplastic elastomers and rabber toughened plastics.
2. Polar polymers. Preferred polar polymers include homopolymers and copolymers of esters, amides, acrylates, anhydrides, copolymers of a C2 to C20 olefin, such as ethylene and/or propylene and/or butene with one or more polar monomers such as acetates, anhydrides, esters, alcohol, and or acrylics. Preferred examples include polyesters, polyamides, ethylene vinyl acetate copolymers, and polyvinyl chloride.
3. Cationic polymers. Preferred cationic polymers include polymers or copolymers of geminally disubstituted olefins, alpha-heteroatom olefins and/or styrenic monomers. Preferred geminally disubstituted olefins include isobutylene, isopentene, isoheptene, isohexane, isooctene, isodecene, and isododecene. Preferred α-heteroatom olefins include vinyl ether and vinyl carbazole, preferred styrenic monomers include styrene, alkyl styrene, para-alkyl styrene, alpha-methyl styrene, chloro-styrene, and brorno-para-methyl styrene. Preferred examples of cationic polymers include butyl rabber, isobutylene copolymerized with para methyl styrene, polystyrene, and poly-α-methyl styrene. 4. Miscellaneous. Other preferred layers can be paper, wood, cardboard, metal, metal foils (such as aluminum foil and tin foil), metallized surfaces, glass (including silicon oxide (SiO.x)coatings applied by evaporating silicon oxide onto a film surface), fabric, spunbonded fibers, and non- wovens (particularly polypropylene spun bonded fibers or non- wovens), and substrates coated with inks, dyes, pigments, PNDC and the like. The films may vary in thickness depending on the intended application, however films of a thickness from 1 to 250 μm are usually suitable. Films intended for packaging are usually from 10 to 60 μm thick. The thickness ofthe sealing layer is typically 0.2 to 50 μm. There may be a sealing layer on both the inner and outer surfaces ofthe film or the sealing layer may be present on only the inner or the outer surface. Additives such as block, antiblock, antioxidants, pigments, fillers, processing aids, UN stabilizers, neutralizers, lubricants, surfactants and/or nucleating agents may also be present in one or more than one layer in the films. Preferred additives include silicon dioxide, titanium dioxide, polydimethylsiloxane, talc, dyes, wax, calcium stearate, carbon black, low molecular weight resins and glass beads. In another embodiment, one or more layers may be modified by corona treatment, electron beam irradiation, gamma irradiation, or microwave. In some embodiments, one or both ofthe surface layers is modified by corona treatment. The films described herein may also comprise from 5 to 60 weight %, based upon the weight ofthe polymer and the resin, of a hydrocarbon resin. The resin may be combined with the polymer ofthe seal layer(s) or may be combined with the polymer in the core layer(s). The resin preferably has a softening point above 100°C, even more preferably from 130 to 180°C. Preferred hydrocarbon resins include those described above. The films comprising a hydrocarbon resin may be oriented in uniaxial or biaxial directions to the same or different degrees. [00233] The films described above may be used as stretch and/or cling films. Stretch/cling films are used in various bundling, packaging and palletizing operations. To impart cling properties to, or improve the cling properties of, a particular film, a number of well-known tackifying additives have been utilized. Common tackifying additives include polybutenes, terpene resins, alkali metal stearates and hydrogenated rosins and rosin esters. The well-known physical process referred to as corona discharge can also modify the cling properties of a film. Some polymers (such as ethylene methyl acrylate copolymers) do not need cling additives and can be used as cling layers without tackifiers. Stretch/clings films may comprise a slip layer comprising any suitable polyolefin or combination of polyolefins such as polyethylene, polypropylene, copolymers of ethylene and propylene, and polymers obtained from ethylene and/or propylene copolymerized with minor amounts of other olefins, particularly C4-C12 olefins. Particularly, preferred are polypropylene and linear low density polyethylene (LLDPE). Suitable polypropylene is normally solid and isotactic, i.e., greater than 90% hot heptane insolubles, having wide ranging melt flow rates of from about 0.1 to about 300 g/10 min. Additionally, the slip layer may include one or more anti-cling (slip and/or antiblock) additives, which may be added during the production ofthe polyolefin or subsequently blended in to improve the slip properties of this layer. Such additives are well-known in the art and include, for example, silicas, silicates, diatomaceous earths, talcs and various lubricants. These additives are preferably utilized in amounts ranging from about 100 ppm to about 20,000 ppm, more preferably between about 500 ppm to about 10,000 ppm, by weight based upon the weight ofthe slip layer. The slip layer may, if desired, also include one or more other additives as described above [00234] Polymers produced herein can be used for nonwovens, sealing layers, oriented polypropylene, and high-clarity thermoforming.
Melt Blown and Spun Bond Fabrics
[00235] Polymer made under supercritical conditions herein are useful for melt blown and spun bond fabrics. Invention processes can be used for making PP for spun bonded (SB) and melt blown (MB) fibers. Typical invention polymers have ash levels below 1000, 900, 700, 500, 400, 300, 200, 100, 50, 10, 1, 0.5, or 0.1 ppm. Some embodiments have ash levels of 1-500 ppb. All these characteristics combine to reduce polymer build-up on the die exits. These products can have high MFRs from 300-5000 useful for fiber applications.
Waxes
[00236] An appropriate choice of operating conditions and monomer and comonomer feeds yields polypropylene waxes from invention polymers and processes. Some invention embodiments are isotactic polypropylene waxes. As such these materials are well suited for viscosity modification in adhesives, as carriers for inks, and other applications. Some polypropylene waxes embodiments select melt viscosities of from 3-2000 cP at 180 °C. Some invention embodiments produce syndiotactic polypropylene waxes.
[00237] Invention process can prepare long chain branched isotactic- polypropylene at high monomer conversion (35+% and especially 45+%) conditions. Some embodiments use higher amounts of diluent to promote long chain branching.
[00238] Long chain branching is also favored by operating the polymerization under supercritical conditions, but with a polymer rich phase and a polymer lean phase. Doing this allows the polymer-rich phase to have a lower monomer concentration and a higher local concentration of vinyl terminated polymer. [00239] An appropriate choice of operating conditions and monomer and comonomer feeds, 180-200 °C and 20-150 MPa, yields polypropylene waxes from invention polymers and processes. Some invention embodiments are isotactic polypropylene waxes. As such these materials are well suited for viscosity modification in adhesives, films, and other applications. Some invention embodiments produce syndiotactic polypropylene waxes.
End Use Articles
[00240] Laminates comprising invention polymers can be used as a thermoformable sheet where the substrate is either sprayed or injection molded to couple it with the ionomer/tie-layer laminate sheet. The composite is formed into the desired shape to make the article, or composite article. Narious types of substrate materials form highly desirable articles. The laminate can be used with plastic substrates such as homopolymers, copolymers, foams, impact copolymers, random copolymers, and other applications. Specifically, some articles in which the present invention can be incorporated are the following: vehicle parts, especially exterior parts such as bumpers and grills, rocker panels, fenders, doors, hoods, trim, and other parts can be made from the laminates , composites and methods ofthe invention.
[00241] Other articles can also be named, for example: counter tops, laminated surface counter tops, pool liners/covers/boat covers, boat sails, cable jacketing, motorcycles/snowmobiles/outdoor vehicles, marine boat hulls/canoe interior and exterior, luggage, clothing/fabric (combined with non-wovens), tent material, GORETEX™, Gamma-radiation resistant applications, electronics housing (TV's, NCR's and computers), a wood replacement for decks and other outdoor building materials, prefab buildings, synthetic marble panels for constmction, wall covering, hopper cars, floor coating, polymer/wood composites, vinyl tile, bath/shower/toilet applications and translucent glass replacement, sidings, lawn/outdoor ftirniture, appliances such as refrigerators, washing machines, etc., children's toys, reflective signage and other reflective articles on roads and clothing, sporting equipment such as snowboards, surfboards, skis, scooters, wheels on in-line skates, CD's for scratch resistance, stadium seats, aerospace reentry shields, plastic paper goods, sports helmets, plastic microwaveable cookware, and other applications for coating plastics and metal where a highly glossy and scratch resistant surface is desirable, while not being subject to algae/discoloration.
[00242] The polypropylene copolymers described herein are suitable for applications such as molded articles, including injection and blow molded bottles and molded items used in automotive articles, such as automotive interior and exterior trims. Examples of other methods and applications for making polypropylene polymers and for which polypropylene polymers may be useful are described in the Encyclopedia of Chemical Technology, by Kirk-Otbmer, Fourth Edition, vol. 17, at pages 748-819, which are incorporated by reference herein. In those instances where the application is for molded articles, the molded articles may include a variety of molded parts, particularly molded parts related to and used in the automotive industry such as, for example, bumpers, side panels, floor mats, dashboards and instrument panels. Foamed articles are another application and examples where foamed plastics, such as foamed polypropylene, are useful may be found in Encyclopedia of Chemical Technology, by Kirk-Otbmer, Fourth Edition, vol. 11, at pages 730-783, which are incorporated by reference herein. Foamed articles are particularly useful for constmction and automotive applications. Examples of constmction applications include heat and sound insulation, industrial and home appliances, and packaging. Examples of automotive applications include interior and exterior automotive parts, such as bumper guards, dashboards and interior liners.
[00243] The poly olefinic compositions ofthe present invention are suitable for such articles as automotive components, wire and cable jacketing, pipes, agricultural films, geomembranes, toys, sporting equipment, medical devices, casting and blowing of packaging films, extrasion of tubing, pipes and profiles, sporting equipment, outdoor furniture (e.g., garden furniture) and playground equipment, boat and water craft components, and other such articles. In particular, the compositions are suitable for automotive components such as bumpers, grills, trim parts, dashboards and instrument panels, exterior door and hood components, spoiler, wind screen, hub caps, mirror housing, body panel, protective side molding, and other interior and external components associated with automobiles, tracks, boats, and other vehicles.
[00244] Other useful articles and goods may be formed economically by the practice of our invention including: crates, containers, packaging, labware, such as roller bottles for culture growth and media bottles, office floor mats, instrumentation sample holders and sample windows; liquid storage containers such as bags, pouches, and bottles for storage and IN infusion of blood or solutions; packaging material including those for any medical device or drags including unit-dose or other blister or bubble pack as well as for wrapping or containing food preserved by irradiation. Other useful items include medical tubing and valves for any medical device including infusion kits, catheters, and respiratory therapy, as well as packaging materials for medical devices or food which is irradiated including trays, as well as stored liquid, particularly water, milk, or juice, containers including unit servings and bulk storage containers as well as transfer means such as tubing, pipes, and such.
Molded Products
[00245] The polymers described above may also be used to prepare the molded products of this invention in any molding process, including but not limited to, injection molding, gas-assisted injection molding, extrasion blow molding, injection blow molding, injection stretch blow molding, compression molding, rotational molding, foam molding, thermoforming, sheet extrasion, and profile extrasion. The molding processes are well known to those of ordinary skill in the art. [00246] The compositions described herein may be shaped into desirable end use articles by any suitable means known in the art. Thermoforming, vacuum forming, blow molding, rotational molding, slush molding, transfer molding, wet lay-up or contact molding, cast molding, cold forming matched-die molding, injection molding, spray techniques, profile co-extrusion, or combinations thereof are typically used methods.
[00247] Thermoforming is a process of forming at least one pliable plastic sheet into a desired shape. An embodiment of a thermoforming sequence is described, however this should not be constmed as limiting the thermoforming methods useful with the compositions of this invention. First, an extradate film of the composition of this invention (and any other layers or materials) is placed on a shuttle rack to hold it during heating. The shuttle rack indexes into the oven which pre-heats the film before forming. Once the film is heated, the shuttle rack indexes back to the forming tool. The film is then vacuumed onto the forming tool to hold it in place and the forming tool is closed. The forming tool can be either "male" or "female" type tools. The tool stays closed to cool the film and the tool is then opened. The shaped laminate is then removed from the tool. [00248] Thermoforming is accomplished by vacuum, positive air pressure, plug-assisted vacuum forming, or combinations and variations of these, once the sheet of material reaches thermoforming temperatures, typically of from 140°C to 185°C or higher. A pre-stretched bubble step is used, especially on large parts, to improve material distribution. In one embodiment, an articulating rack lifts the heated laminate towards a male forming tool, assisted by the application of a vacuum from orifices in the male forming tool. Once the laminate is firmly formed about the male forming tool, the thermoformed shaped laminate is then cooled, typically by blowers. Plug-assisted forming is generally used for small, deep drawn parts. Plug material, design, and timing can be critical to optimization ofthe process. Plugs made from insulating foam avoid premature quenching of the plastic. The plug shape is usually similar to the mold cavity, but smaller and without part detail. A round plug bottom will usually promote even material distribution and uniform side-wall thickness. For a semicrystalline polymer such as polypropylene, fast plug speeds generally provide the best material distribution in the part.
[00249] The shaped laminate is then cooled in the mold. Sufficient cooling to maintain a mold temperature of 30°C to 65°C is desirable. The part is below 90 °C to 100 °C before ejection in one embodiment. For the good behavior in thermoforming, the lowest melt flow rate polymers are desirable. The shaped laminate is then trimmed of excess laminate material.
[00250] Blow molding is another suitable forming means, which includes injection blow molding, multi-layer blow molding, extrasion blow molding, and stretch blow molding, and is especially suitable for substantially closed or hollow objects, such as, for example, gas tanks and other fluid containers. Blow molding is described in more detail in, for example, CONCISE ENCYCLOPEDIA OF POLYMER SCIENCE AND ENGINEERING 90-92 (Jacqueline I. Kroschwitz, ed., John Wiley & Sons 1990).
[00251] In yet another embodiment ofthe formation and shaping process, profile co-extmsion can be used. The profile co-extrusion process parameters are as above for the blow molding process, except the die temperatures (dual zone top and bottom) range from 150°C - 235°C, the feed blocks are from 90°C - 250°C, and the water cooling tank temperatures are from 10°C - 40°C. [00252] One embodiment of an injection molding process is described as follows. The shaped laminate is placed into the injection molding tool. The mold is closed and the substrate material is injected into the mold. The substrate material has a melt temperature between 200°C and 300°C in one embodiment, and from 215°C and 250 °C and is injected into the mold at an injection speed of between 2 and 10 seconds. After injection, the material is packed or held at a predetermined time and pressure to make the part dimensionally and aesthetically correct. Typical time periods are from 5 to 25 seconds and pressures from 1,380 kPa to 10,400 kPa. The mold is cooled between 10 °C and 70°C to cool the substrate. The temperature will depend on the desired gloss and appearance desired. Typical cooling time is from 10 to 30 seconds, depending on part on the thickness. Finally, the mold is opened and the shaped composite article ejected. [00253] Likewise , molded articles may be fabricated by injecting molten polymer into a mold that shapes and solidifies the molten polymer into desirable geometry and thickness of molded articles. Sheet may be made either by extruding a substantially flat profile from a die, onto a chill roll, or alternatively by calendaring. Sheet will generally be considered to have a thickness of from 10 mils to 100 mils (254 μm to 2540 μm), although sheet may be substantially thicker. Tubing or pipe may be obtained by profile extrasion for uses in medical, potable water, land drainage applications or the like. The profile extrasion process involves the extrusion of molten polymer through a die. The extruded tubing or pipe is then solidified by chill water or cooling air into a continuous extruded articles. The tubing will generally be in the range of from 0.31 cm to 2.54 cm in outside diameter, and have a wall thickness of in the range of from 254 μm to 0.5 cm. The pipe will generally be in the range of from 2.54 cm to 254 cm in outside diameter, and have a wall thickness of in the range of from 0.5 cm to 15 cm. Sheet made from the products of an embodiment of a version ofthe present invention may be used to form containers. Such containers may be formed by thermoforming, solid phase pressure forming, stamping and other shaping techniques. Sheets may also be formed to cover floors or walls or other surfaces. [00254] In an embodiment ofthe thermoforming process, the oven temperature is between 160°C and 195°C, the time in the oven between 10 and 20 seconds, and the die temperature, typically a male die, between 10°C and 71°C. The final thickness ofthe cooled (room temperature), shaped laminate is from 10 μm to 6000 μm in one embodiment, from 200 μm to 6000 μm in another embodiment, and from 250 μm to 3000 μm in yet another embodiment, and from 500 μm to 1550 μm in yet another embodiment, a desirable range being any combination of any upper thickness limit with any lower thickness limit. [00255] In an embodiment ofthe injection molding process, wherein a substrate material in injection molded into a tool including the shaped laminate, the melt temperature ofthe substrate material is between 230°C and 255°C in one embodiment, and between 235°C and 250°C in another embodiment, the fill time from 2 to 10 seconds in one embodiment, from 2 to 8 seconds in another embodiment, and a tool temperature of from 25°C to 65°C in one embodiment, and from 27°C and 60°C in another embodiment. In a desirable embodiment, the substrate material is at a temperature that is hot enough to melt any tie-layer material or backing layer to achieve adhesion between the layers. [00256] In yet another embodiment ofthe invention, the compositions of this invention may be secured to a substrate material using a blow molding operation. Blow molding is particularly useful in such applications as for making closed articles such as fuel tanks and other fluid containers, playground equipment, outdoor furniture and small enclosed structures. In one embodiment of this process, Compositions of this invention are extmded through a multi-layer head, followed by placement ofthe uncooled laminate into a parison in the mold. The mold, with either male or female patterns inside, is then closed and air is blown into the mold to form the part.
[00257] It will be understood by those skilled in the art that the steps outlined above may be varied, depending upon the desired result. For example, the an extmded sheet ofthe compositions of this invention may be directly thermoformed or blow molded without cooling, thus skipping a cooling step. Other parameters may be varied as well in order to achieve a finished composite article having desirable features.
Non- Wovens and Fibers
[00258] The polymers described above may also be used to prepare the nonwoven fabrics and fibers of this invention in any nonwoven fabric and fiber making process, including but not limited to, melt blowing, spunbonding, film aperturing, and staple fiber carding. A continuous filament process may also be used. Preferably a spunbonding process is used. The spunbonding process is well known in the art. Generally it involves the extrasion of fibers through a spinneret. These fibers are then drawn using high velocity air and laid on an endless belt. A calender roll is generally then used to heat the web and bond the fibers to one another although other techniques may be used such as sonic bonding and adhesive bonding. The fabric may be prepared with mixed metallocene polypropylene alone, physically blended with other mixed metallocene polypropylene or physically blended with single metallocene polypropylene. Likewise the fabrics of this invention may be prepared with mixed metallocene polypropylene physically blended with conventional Ziegler-Natta produced polymer. If blended, the fabric of this invention is preferably comprised of at least 50% mixed metallocene polypropylene. With these nonwoven fabrics, manufacturers can maintain the desirable properties of fabrics prepared with metallocene produced polypropylene while increasing fabric strength and potentially increased line speed compared to fabrics made using conventional polymers.
EXAMPLES
Size-Exclusion Chromatography of Polymers
[00259] Molecular weight distribution was characterized using Size-
Exclusion Chromatography (SEC). Molecular weight (weight-average molecular weight, Mw, and number-average molecular weight, Mn) were determined using a High Temperature Size Exclusion Chromatograph (either from Waters Corporation or Polymer Laboratories), equipped with a differential refractive index detector (DRI), an online light scattering detector, and a viscometer. Experimental details not described below, including how the detectors were calibrated, are described in: T. Sun, P. Brant, R. R. Chance, and W. W. Graessley, Macromolecules, Volume 34, Number 19, 6812-6820, (2001). [00260] Three Polymer Laboratories PLgel 10mm Mixed-B columns were used. The nominal flow rate was 0.5 cm3 /min, and the nominal injection volume was 300 microliters. The various transfer lines, colximns and differential refractometer (the DRI detector) were contained in an oven maintained at 135°C. [00261] Solvent for the SEC experiment was prepared by dissolving 6 grams of butylated hydroxy toluene as an antioxidant in 4 liters of Aldrich reagent grade 1,2,4 frichlorobenzene (TCB). The TCB mixture was then filtered through a 0.7 μm glass pre-filter and subsequently through a 0.1 μm Teflon filter. The TCB was then degassed with an online degasser before entering the SEC. [00262] Polymer solutions were prepared by placing dry polymer in a glass container, adding the desired amount of TCB, then heating the mixture at 160 °C with continuous agitation for about 2 hours. All quantities were measured gravimetrically. The TCB densities used to express the polymer concentration in mass/volume units are 1.463 g/ml at room temperature and 1.324 g/ml at 135 °C. The injection concentration ranged from 1.0 to 2.0 mg/ml, with lower concentrations being used for higher molecular weight samples. [00263] Prior to running each sample the DRI detector and the injector were purged. Flow rate in the apparatus was then increased to 0.5 ml/minute, and the DRI was allowed to stabilize for 8-9 hours before injecting the first sample. The LS laser was turned on 1 to 1.5 hours before running samples by mnning the laser in idle mode for 20-30 minutes and then switching to full power in light regulation mode.
[00264] The concentration, c, at each point in the chromatogram is calculated from the baseline-subtracted DRI signal, IDRI, using the following equation: c = KDRIIDRI/(dn/dc) where KDRI is a constant determined by calibrating the DRI, and (dn/dc) is the same as described below for the LS analysis. Units on parameters throughout this description ofthe SEC method are such that concentration is expressed in g/cm3, molecular weight is expressed in g/mole, and intrinsic viscosity is expressed in dL/g. [00265] The light scattering detector used is either a Wyatt Technology
High Temperature mini-DAWN or a Precision Detector 2040 LALLS. The data is analyzed with the standard formulas for static light scattering
K c
+ 2A2c
ΔR(θ,c) MP(Θ)
Here, ΔR(θ,c) is the excess Rayleigh scattering intensity at scattering angle θ, c is the polymer concenfration, is the polymer molecular weight, A2 is the second virial coefficient ofthe solution, P(θ) is the form factor, and K0 is the optical constant for the system:
Figure imgf000120_0001
in which NA is Avogadro's number, and dn/dc is the refractive index increment for the system. For the LALLS detector we measure the scattering intensity at 15° and assume P(θ)=l. The concentrations used in the analyses are the values obtained from the DRI output. The refractive index n for TCB at 135 C for a 690 nm wavelength is 1.500. In addition, A2 = 0.0006 for propylene polymers and 0.0015 for butene polymers, and (dn/dc) = 0.104 for propylene polymers and 0.098 for butene polymers.
[00266] The viscometer used was a Niscotek Corporation high temperature viscometer which has four capillaries arranged in a Wheatstone bridge configuration with two pressure transducers. One transducer measures the total pressure drop across the detector, and the other, positioned between the two sides ofthe bridge, measures a differential pressure. The specific viscosity, ηs, for the solution flowing through the viscometer is calculated from their outputs. The intrinsic viscosity, [η], at each point in the chromatogram is calculated from the following equation: ηs = c[η] + 0.3(c[η])2 where c was determined from the DRI output.
[00267] The branching index (g') is calculated using the output of the SEC-
DRI-LS-NIS method as follows. The average intrinsic viscosity, [η]avg, of the sample is calculated by:
[η] = ∑ Ci Hi
where the summations are over the chromotographic slices, i, between the integration limits. The branching index g' is defined as:
Figure imgf000121_0001
where k = 0.0002288 and α = 0.705 for propylene polymers, and k = 0.00018 and α = 0.7 for butene polymers. Mv is the viscosity-average molecular weight based on molecular weights determined by LS analysis.
Differential Scanning Calorimetry
[00268] Melting point (Tm), heat of fusion (ΔHf), multiple melting peak, and any measurements related to detection of crystalline melting or crystallization are measured by Differential Scanning Calorimetry (DSC). A typical procedure used was as follows - Preferably, about 5 mg to about 9 mg of polymer that has aged at room temperature for at least 24 hours, is placed in a Differential Scanning Calorimeter. The sample is heated at about 10°C/minute to attain a final temperature of about 200°C. Subsequently, the sample is cooled to room temperature at about 10°C/min, during which the thermal output records the heat of crystallization. The crystallization temperature (Tcmax) is recorded as the temperature at the peak ofthe crystallization exotherm. The sample is then heated back to 200°C. The thermal output is recorded as the area under the melting peak, or peaks, of the sample which is typically at a maximum peak at about 160°C. The melting point is recorded as the temperature of the greatest heat absoφtion within the range of melting of the sample. In some cases, following the heating cycle the sample was cooled below room temperature prior to the second heating cycle.
[00269] The reaction temperature was from 150°C ± 3°C up to 190°C± 3°C
. Residence time was held constant at 300 seconds. Catalyst concentration was selected from 0.03 to 0.07 mol ppm metal feed based on estimated conversions of 10 and 20%. The mol ratio of aluminum/zirconium metal was approximately 10,000 in all tests. 99.8% pure propylene was obtained from Linde AG, Wiesbaden, in bombs of 33 kg. The propylene had a density of 1.91 kg/m3 (0°C, 1013 mbar), an Mw of 42.08 g/mol, a melting temperature of -185.25°C, a melting enthalpy of 69.9 kJ/kg, a boiling point at 1013 mbar of -47.75°C, a critical temperature of 91.85°C, a critical pressure of 46.2 bar (4.62MPa), and other CnHm of less than 1000 ppm. Methylalumoxane (Mw 58.01, density 0.93 g/ml at 20 ° C, 30 weight % in toluene, 13.0 to 14.5 % aluminum ) was obtained from Crompton GmbH. Tri-isobutyl aluminum (TIBAL) (Mw 198.33, density 0.789, g/ml at 20 ° C, 13.0 to 13.4 % aluminum ) was obtained from Crompton GmbH, Bergkamen. 95% pure hexane was obtained from Sigma- Aldrich, Deisenhofen. The hexane was purified by refluxing over a sodium-potassium alloy for 3 hours, followed by distillation under an inert atmosphere. The hexane had an Mw of 86.18 g/mol, a melting temperature of -95.53°C, a melting enthalpy of 147.8 kJ/kg, a boiling point at 1013 mbar of 68.75°C, a critical temperature of 234.25 ° C, a critical pressure of 29.7 bar (2.97MPa), an enthalpy of evaporation of 3335 kJ/kg, a non-volatiles level of less than 0.0015%, less than 0.02% water and less than 0.001% acids (CH3COOH).
[00270] 13C NMR was collected at 125C on a Varian NMR spectrometers.
Sample concentrations were approximately 10 wt% (wt/ vol) in perdeutero tetrachloroethane. 10-mm NMR tubes contained these samples. Acquisition conditions were a 90-degree pulse, ungated broadband decoupling, approximately 15 seconds between successive data acquisitions, a sweep width of 8000 Hz, digital resolution Of < 0.2 Hz with the final spectrum composed of at least 1000 time-averaged data acquisitions.
[00271] *H NMR was collected at 125C on Varian NMR spectrometers.
Sample concentrations were approximately 1.5 wt% (wt/vol) in perdeutero tetrachloroethane. 5-mm NMR tubes contained these samples. Acquisition conditions were < 45-degree pulse, approximately 8 seconds between successive data acquisitions, and a sweep width of at least 10 ppm with the final spectrum composed of at least 120 time-averaged data acquisitions.
Polymerization unit
[00272] The core ofthe unit was a polymerization autoclave (volume 100 mL), designed for a maximum pressure of 200 MPa (2000 Bar) and a maximum temperature of 300°C and containing a stirrer, magnetic drive, an electric heater (controlled by the thermocouple TIC-504), and a rapture disc. Pressure was measured with a pressure transducer (PIRC) and manometer. A thermocouple measured the temperature inside the autoclave. The autoclave was connected to the monomer and catalyst metering system and to the sampling device. Propylene was prepared in two tanks having a volume of 6 L each. It was fed by a membrane pump through the axis ofthe stirrer into the autoclave. The pressure in the propylene feed line was measured and indicated by a manometer. Hexane was metered through a feed line from a tank having a volume of 3 L using a second membrane pump. Thirty mL of catalyst solution was placed in a syringe type pump. As the catalyst solution was dispensed from the syringe, it was diluted with hexane before entering the reactor. The pressure in the catalyst feed line was measured with a manometer. [00273] After the autoclave, the pressure was released to ambient by an automatically operated outlet valve. The polymer samples were collected in receptacles below the outlet valve. Each receptacle was joined to the outlet valve one after the other. Unreacted propylene was released to a flare. The polymer that formed before steady state was reached was collected in a separate receptacle.
Polymerization Test procedure
Procedure I
[00274] In order to remove impurities, propylene was treated with tri-iso- butylaluminum (TIB A) as a scavenger for about a day. For this purpose a mixture of hexane and TIB A was metered into a tank. Afterwards propylene was taken from a bomb and condensed into the tank. For further purification the propylene was evaporated into a second tank and condensed. The metallocene catalyst was dissolved in a mixture of toluene and methyl alumoxane (MAO). This solution was stored under 2.5 MPa nitrogen. For each test 10 ml ofthe solution were placed in a syringe-type pump to be metered continuously into the autoclave. [00275] The catalyst feed was further diluted with hexane. Before treatment, the hexane itself was also treated with TIB A under 2.5 MPa nitrogen. The mixture of catalyst, hexane and a negligible quantity of TIB A was fed by pump to adjust a ratio of 90 mol propylene to 10 mol hexane and a pre-set catalyst concentration in the feed. The conversion was determined from the total quantity of polymer that was collected during the 600 seconds and the amount of propylene added to the reaction. The typical feed temperature at start-up was 150-158° C. Once polymerization was commenced, the autoclave temperature rose to a stable polymerization temperature of from 150 to 190° C. Table A reports conditions for the homopolymerizations using (μ-dimethylsilyl)bis(2-methy-4- phenylindenyl)zirconium dichloride (MW 628.82 g/mol)... Table A. Polymerization conditions for propylene homopolymerization
Metallocene Productivity Reaction Temperature
Concentration (kg PP/g Zr) Pressure (°C)
(Mol ppm) in 300 sec. (MPa)
PP1 0.05029 704.4 60 163
PP2 0.08565 1521.0 60 167
PP3 0.08565 1791.8 60 167
PP4 0.08565 1864.7 60 167
PP5 0.08565 1724.7 60 167
PP6 0.0441 690.8 80 162.5
PP7 0.0736 2352.1 80 168
PP8 0.0441 737.8 100 162.5
PP9 0.0602 2915.3 100 168
PP10 0.05250 3420.6 150 165
[00276] The data indicate that conversion increases with increasing catalyst concentration and with increasing pressure (Figure 1). Conversion is roughly proportional to pressure. The conversion was determined from the quantity of polymer obtained and the quantity of propylene fed into the reactor during sampling. Conversions greater than 40% were achieved. High catalyst productivities of 500 to 3400 kg PP/kg Zr or 95 to 495 kg PP/g μ- dimethylsilyl)bis(2-methy-4-phenylindenyl)zirconium dichloride catalyst were also observed. Catalyst productivity was evaluated from the quantity ofthe polymer sample and the quantity of catalyst metal fed during the time of collecting that sample.
Table B. Property data for PP1 to PP10.
IPP Sample Percent Mw (k) Mz (k) Melting Heat of g. 0 conversion Point °C Fusion J/g
PP1 8.50 27.2 46.1 145 81.9 1.00
PP2 31.30 20.4 33.5 1.00
PP3 36.90 21.4 36.4 0.96
PP4 38.40 20.8 34.2 0.96
PP5 35.50 20.9 34.2 0.97
PP6 7.30 30.0 45.4 0.97
PP7 41.60 24.4 41.5 0.97 24.7 44.1 0.96 29.5 43.3 0.81
PP8 7.80 35.4 54.3 142 87.8 1.00
PP9 42.20 25.5 43.9 146 87.2 0.95 25.5 44.4 0.96 26.9 47.0 0.89
PP10 43.20 31.8 55.7 0.96 31.2 56.1 0.97 29.7 52.3 0.99
(a) Ratio of intrinsic viscosity of sample to linear iPP standard (Achieve 1635).
Table C: Unsaturation Populations determined from !H NMR.
Sample vinyl vinylidene Vinyl ene(2° & 3°)
Per 1000 carbon atoms
PP-2 0.61 0.39 0.07
PP-6 1.12 0.75 0.05
PP-7 1.41 0.53 0.06
PP-8 1.08 0.65 0.13
PP-10 0.71 0.28 0.09
Table D: Repeat unit and end group structures - 13C NMR.
Figure imgf000127_0001
Propylene/Hex-1-ene copolymerization
[00277] Copolymerizations of propylene with hexene were run according to the procedure described above using (μ-dimethylsilyl)bis(2-methyl-4- phenylindenyl)zirconium dichloride and methylalumoxane as the catalyst compound and activator.. Reaction conditions for each ofthe examples and two comparative examples (PP-7 and PP-9) are set out in Table E. Table E. Polymerization conditions for propylene-Zhexene copolymers eight ratios
Metallocene Reaction hex- 1 -ene/ Conversion Productivity Temp
Concentration Pressure propylene (kg PP/g Zr)
(Mol ppm) (%) (MPa) (°C) (%)t
PH-1 15 0.09 38 1878 80 172.5
PH-2 15 0.09 39 1930 80 172.5
PH-3 15 0.05 14 1245 80 164
PH-4 15 0.05 16 1437 80 164 80
PH-6 25 0.10 30 1406 80 169
PH-7 25 0.075 11 701 80 162.5
PH-8 25 0.075 12 775 80 162.5
PH-9 25 0.090 27 1409 80 166
PH-10 25 0.090 29 1507 80 166
PP-9 NA 0.0602 42.2 2915.3 100 168
PP-7 NA 0.0736 41.6 2352.1 80 168
f weight ratio of hex- 1 -ene and propylene monomer added to the reaction.
Table F. Molecular weight (GPC-MALLS)
Mw(k) Mz(k)
PH-1 18.7 33.5
PH-2 17.6 30.1
PH-3 25.3 39.5
PH-4 25.8 38.6
(average) 21.85 35.4
PH-6 20.7 33.0
PH-7 28.0 43.2
PH-8 27.9 43.2
PH-9 21.7 34.9
PH-10 20.9 34.6
(average) 23.8 37.8
Table G. Unsaturations in Propylene/Hex-1-ene Copolymer ( JH NMR)
Figure imgf000129_0001
* Value in parentheses is % of total vinylidene signal that is singlet.
Table H.
Figure imgf000129_0002
[00278] PH-1 was evaluated for mechanical properties. Modulus was
8.9+2.1 kpsi, Peak Stress was 1043+121 psi, Strain at break was 508+55%, and Toughness was 2634+298 in-lb/in3.
Polypropylene Waxes
[00279] Wax-producing polymerizations were conducted in the autoclave described above. In each of these experiments, the polymerization temperature was 190°C and the residence time was 4 minutes. The catalyst for these polymerization reactions was (μ-dimethylsilyl)bis(2-methy-4- phenylindenyl)zirconium dichloride (MW 628.82 g/mol). The reactions used methylalumoxane as the activator.
Table I: Polypropylene wax polymerization
Pressure, % C3 kg Tm Mn (k) Mw(k) Mz(k)
MPa Conv. PP/g Zr (°C) GPC-DRI GPC-DRI GPC-DRI
PW-1 60 27.5 839 131.9 2.4 10.3 20.1
PW-2 60 25.4 777
PW-3 80 33.6 1027 131.0 2.7 11.7 23.1
PW-4 100 35 1069 132.0 2.9 12.5 24.1
PW-5 120 36.2 1106
PW-6 120 36.8 1124 133.8 3.1 13.7 26.2
PW-7 140 42.1 1285
PW-8 140 45.2 1381 127.4 2.5 12.5 25.2
PW-9 160 133.9 2.1 17.0 47.6 142
[00280] While certain representative embodiments and details have been shown to illustrate the invention, it will be apparent to skilled artisans that various process and product changes from those disclosed in this application may be made without departing from this invention's scope, which the appended claims define. [00281] All cited patents, test procedures, priority documents, and other cited documents are fully incorporated by reference to the extent that this material is consistent with this specification and for all jurisdictions in which such incoφoration is permitted.
[00282] Certain features ofthe present invention are described in terms of a set of numerical upper limits and a set of numerical lower limits. This specification discloses all ranges formed by any combination of these limits. All combinations of these limits are within the scope ofthe invention unless otherwise indicated.

Claims

Claims:
1. A polymer comprising propylene having: a) a 1,3 regio defect population of greater than 5 per 10,000 monomer units; b) a melting point of 140-165 °C; c) branching index of 0.97 or less, and d) weight average molecular weight of from 20,000-1,000,000.
2. The polymer of claim 1 , wherein the polymer further comprises up to 50 weight % of one or more comonomers independently selected from the group consisting of ethylene, but- 1 -ene, hex- 1 -ene, 4-methylpent-l-ene, dicyclopentadiene, norbornene, C4-C2000 α-olefins, C4-C2000 α,internal-diolefins, and C4-C2000 α,co-diolefins.
3. The composition of claim 1 or 2 wherein the weight average molecular weight is from 25,000-250,000.
4. The polymer of claim 1, 2 or 3 wherein the 1,3 regio defect population is greater than 10 per 10,000 monomer units.
5. The polymer of claim 1 , 2, 3, or 4 wherein the 1 ,3 regio defect population is greater than 15 per 10,000 monomer units.
6. The polymer of any of claims 1 to 5 wherein the 1,3 regio defect population is greater than 20 per 10,000 monomer units.
7. The polymer of any of claims 1 to 6 wherein the 1,3 regio defect population is greater than 25 per 10,000 monomer units.
8. The polymer of any of claims 1 to 7 wherein the polymer has less than 300 ppm silica.
9. The polymer of any ofthe above claims wherein the polymer has less than 300 ppm residue.
10. The polymer of any ofthe above claims wherein the polymer meso pentad mole fraction is 0.60-0.96.
11. The polymer of any ofthe above claims wherein the polymer meso pentad mole fraction is 0.70-0.96.
12. The polymer of any ofthe above claims wherein the polymer meso pentad mole fraction is 0.80-0.94.
13. The polymer of any of claims 1 to 12 wherein the total polymer comonomer content is greater than 0 wt% and less than 35 wt%.
14. The polymer of any of the above claims wherein the total polymer comonomer content is from 0.5 wt% to 30 wt%.
15. The polymer of any ofthe above claims wherein the branching index, g', is
Figure imgf000132_0001
16. The polymer of any ofthe above claims wherein the polymer has a heat of fusion of from 50 to 110 J/g and melting point of 145 to 165°C.
17. The polymer of any ofthe above claims wherein the polymer has a heat of fusion of from 0 to 30 J/g and g' of 0.95 or less.
18. The polymer of any of the above claims wherein the polymer has a heat of fusion of 0 to 30 J/g and melt viscosity of less than 10,000 cps at 180 °C.
19. The polymer of any ofthe above claims wherein the polymer has a heat of fusion of from 20 to 50 J/g and melt viscosity of between 1000 and 3000 cps at 180 °C.
20. A process to polymerize olefins comprising contacting, in a polymerization system, olefin monomers having three or more carbon atoms with:
1) a metallocene catalyst compound, a bisamide catalyst compound and/or a bisimide catalyst compound,
2) an activator,
3) optionally comonomer, and
4) optionally diluent or solvent, at a temperature above the cloud point temperature ofthe polymerization system and a pressure no lower than 10 MPa below the cloud point pressure ofthe polymerization system and less than 150 MPa, where the polymerization system comprises the monomers, any comonomer present, any diluent or solvent present, and the polymer product, and where the olefin monomers are present in the polymerization system at 40 weight
% or more.
21. The process of claim 20 wherein the catalyst compound comprises a metallocene catalyst compound and the pressure of the polymerization system is less than 125 MPa.
22. The process of any of claims 20 to 21 where the temperature is between 140 to l80°C.
23. The process of any of claims 20 to 21 wherein the catalyst compound comprises a metallocene catalyst compound, the pressure of the polymerization system is less than 100 MPa, and the temperature is between 140 to 180°C.
24. The process of any of claims 20 to 23 wherein the pressure ofthe polymerization system is above the cloud point pressure ofthe polymerization system.
25. The process of any of claims 20 to 23 wherein the pressure ofthe polymerization system is between 15 and 140 MPa.
26. The process of any of claims 20 to 23 wherein the pressure of the polymerization system is between 15 and 50 MPa.
27. The process of any of claims 20 to 26 wherein solvent and or diluent is present in the polymerization system at 0 to 25 wt %.
28. The process of any of claims 20 to 26 wherein solvent and or diluent is , present in the polymerization system at 0 to 10 wt %.
29. The process of any of claims 20 to 28 wherein the olefin monomers having three or more carbon atoms are present in the polymerization system at 55 wt % or more.
30. The process of any of claims 20 to 28 wherein the olefin monomers having three or more carbon atoms are present in the polymerization system at 75 wt % or more.
31. The process of any of claims 20 to 30 wherein the olefin monomer having three or more carbon atoms comprises propylene.
32. The process of claim 31 wherein comonomer is present at 1 to 45 mole%.
33. The process of any of claims 20 to 32 wherein the polymerization medium ofthe monomer, comonomers, solvents and diluents comprises from 55-100 wt% propylene monomer; from 0 to 45 wt% of a comonomer mixture comprising at least one comonomer selected from ethylene, but- 1 -ene, hex- 1 -ene, 4-methylpent- 1-ene, dicyclopentadiene, norbornene, C4-C2000 α-olefins, C4-C2000 α,internal- diolefins, and C4-C200o α,ω-diolefins.
34. The process of any of claims 20 to 33 wherein the comonomer comprises one or more of ethylene, butene, hexene, or octene.
35. The process of any of claims 20-34 wherein the catalyst compound comprises a bisamide compound
36. The process of any of claims 20-34 wherein the catalyst compound comprises a bisimide catalyst compound.
37. The process of any of claims 20-34 wherein the catalyst compound is represented by the formula:
Figure imgf000136_0001
where M is selected from titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, or tungsten;
1 2
R and R are identical or different and are selected from hydrogen atoms, -C,,, alkyl groups, Cj-C10 alkoxy groups, C6-C10 aryl groups, C6-C10 aryloxy groups, C2- C10 alkenyl groups, C2-C40 alkenyl groups, C7-C40 arylalkyl groups, C7-C40 alkylaryl groups, C8-C40 arylalkenyl groups, OH groups or halogen atoms; or conjugated dienes that are optionally substituted with one or more hydrocarbyl, tri(hydrocarbyl)silyl groups or hydrocarbyl tri(hydrocarbyl)silylhydrocarbyl groups;
R3-R12 are the same or different and are selected from hydrogen atoms, halogen atoms, C,-C10 halogenated or unhalogenated alkyl groups, C6-C10 halogenated or unhalogenated aryl groups, C2-C10 halogenated or unhalogenated alkenyl groups, C7-C40 halogenated or unhalogenated arylalkyl groups, C7-C40 halogenated or unhalogenated alkylaryl groups, C8-C40 halogenated or unhalogenated arylalkenyl groups, -NR'2, -SR', -OR, -OSiR'3 or -PR'2 radicals in which R is one of a halogen atom, a CrC10 alkyl group, or a C6-C10 aryl group; or two or more adjacent
5 7 radicals R to R together with the atoms connecting them can form one or more rings;
R13 is selected from
R14 R14 R14 R14
I I I
-M3- -M3- M3- -0-M3-0-
Figure imgf000137_0001
Figure imgf000137_0002
I I I I I I -M3- C - -O-M3- - C — C - C —
Figure imgf000137_0003
-B(R14)-, -A1(R14)-, -Ge-, -Sn-, -O-, -S-, -SO-, -SO -, -N(R14)-, -CO-, -P(R14)- -
P(O)(R14)-, -B(NR1 R15)- and -B[N(SiR14R15R16)2]-, R14, R15'and R16 are each independently selected from hydrogen, halogen, C,-C20 alkyl groups, C6-C30 aryl groups, C,-C20 alkoxy groups, C2-C20 alkenyl groups, C7-C40 arylalkyl groups, C8- C40 arylalkenyl groups and C7-C40 alkylaryl groups, or R14 and R15, together with the atom(s) connecting them, form a ring; and M3 is selected from carbon, silicon, ι3 germanium and tin, or R is represented by the formula:
Figure imgf000137_0004
17 24 1 2 wherein R to R are as defined for R and R , or two or more adjacent radicals
17 24 20 21
R to R , including R and R , together with the atoms connecting them form one or more rings; M is carbon, silicon, germanium, or tin.
38. The process of any of claims 20-34 wherein the catalyst compound comprises one or more of: μ-dimethyl silylbis(-2-methyl, 4-phenylindenyl) zirconium dichloride, μ-dimethyl silylbis(-2-methyl, 4-phenylindenyl) zirconium dimethyl,
1 , 1 '-bis(4-triethylsilylphenyl)methylene-(cyclopentadienyl)(2,7-di-tertiary-butyl-
9-fluorenyl)hafnium dichloride,
1 , 1 '-bis(4-triethylsilylphenyl)methylene-(cyclopentadienyl)(2,7-di-tertiary-butyl-
9-fluorenyl)hafnium dimethyl, dimethylsilyl(tetramethylcyclopentadienyl)(dodecylamido)titanium dimethyl, dimethylsilyl(tetramethylcyclopentadienyl)(dodecylamido)titanium dichloride,
1 , 1 '-bis(4-triethylsilylphenyl)methylene-(cyclopentadienyl)(2,7-di-tertiary-butyl-
9-fluorenyl)hafhium dichloride,
1 , 1 '-bis(4-triethylsilylphenyl)methylene-(cyclopentadienyl)(2,7-di-tertiary-butyl-
9-fluorenyl)hafnium dimethyl, dimethylsilylbis(indenyl)hafiιium dichloride, dimethylsilylbis(indenyl)hafhium dimethyl, dimethylsilyl bis(2-methylindenyl) zirconium dichloride, dimethylsilyl bis(2-methylindenyl) zirconium dimethyl, dimethylsilyl bis(2-methylfluorenyl) zirconium dichloride, dimethylsilyl bis(2-methylfluorenyl) zirconium dimethyl, dimethylsilyl bis(2-methyl-5,7-propylindenyl) zirconium dichloride, dimethylsilyl bis(2-methyl-5,7-propylindenyl) zirconium dimethyl, dimethylsilyl bis(2-methyl-5-phenylindenyl) zirconium dichloride, dimethylsilyl bis(2-methyl-5-phenylindenyl) zirconium dimethyl, dimethylsilyl bis(2-ethyl-5-phenylindenyl) zirconium dichloride, dimethylsilyl bis(2-ethyl-5-phenylindenyl) zirconium dimethyl, dimethylsilyl bis(2-methyl-5-biphenylindenyl) zirconium dichloride, and dimethylsilyl bis(2-methyl-5-biphenylindenyl) zirconium dichloride dimethyl.
39. The process of any of claims 20-34 wherein the catalyst compound comprises two or more of: μ-dimethyl silylbis(-2-methyl, 4-phenylindenyl) zirconium dichloride, μ-dimethyl silylbis(-2-methyl, 4-phenylindenyl) zirconium dimethyl,
1 , 1 '-bis(4-triethylsilylphenyl)methylene-(cyclopentadienyl)(2,7-di-tertiary-butyl-
9-fluorenyl)hafnium dichloride,
1 , 1 '-bis(4-triethylsilylphenyl)methylene-(cyclopentadienyl)(2,7-di-tertiary-butyl-
9-fluorenyl)hafhium dimethyl, dimethylsilyl(tetramethylcyclopentadienyl)(dodecylamido)titanium dimethyl, dimethylsilyl(teframethylcyclopentadienyl)(dodecylamido)titanium dichloride,
1 , 1 '-bis(4-triethylsilylphenyl)methylene-(cyclopentadienyl)(2,7-di-tertiary-butyl-
9-fluorenyl)hafnium dichloride,
1 , 1 '-bis(4-triethylsilylphenyl)methylene-(cyclopentadienyl)(2,7-di-tertiary-butyl-
9-fluorenyl)hafhium dimethyl, dimethylsilylbis(indenyl)hafhium dichloride, dimethylsilylbis(indenyl)hafnium dimethyl, dimethylsilyl bis(2-methylindenyl) zirconium dichloride, dimethylsilyl bis(2-methylindenyl) zirconium dimethyl, dimethylsilyl bis(2-methylfluorenyl) zirconium dichloride, dimethylsilyl bis(2-methylfluorenyl) zirconium dimethyl, dimethylsilyl bis(2-methyl-5,7-propylindenyl) zirconium dichloride, dimethylsilyl bis(2-methyl-5,7-propylindenyl) zirconium dimethyl, dimethylsilyl bis(2-methyl-5-phenylindenyl) zirconium dichloride, dimethylsilyl bis(2-methyl-5-phenylindenyl) zirconium dimethyl, dimethylsilyl bis(2-ethyl-5-phenylindenyl) zirconium dichloride, dimethylsilyl bis(2-ethyl-5-phenylindenyl) zirconium dimethyl, dimethylsilyl bis(2-methyl-5-biphenylindenyl) zirconium dichloride, and dimethylsilyl bis(2-methyl-5-biphenylindenyl) zirconium dichloride dimethyl.
40. The process of any of claims 20-34 wherein the catalyst compound comprises:
1) dimethylsilyl(teframethylcyclopentadienyl)(dodecylamido)titariium dichloride and μ-dimethyl silylbis(-2-methyl, 4-phenylindenyl) zirconium dichloride;
2) dimethylsilyl(tetramethylcyclopentadienyl)(dodecylamido)titanium methyl and μ-dimethyl silylbis(-2-methyl, 4-phenylindenyl) zirconium dimethyl;
3) 1, 1 '-bis(4-triethylsilylphenyl)methylene-(cyclopentadienyl)(2,7-di- tertiary-butyl-9-fluorenyl)hafnium dichloride and μ-dimethyl silylbis(-2-methyl, 4-phenylindenyl) zirconium dichloride; or
4) 1, 1 '-bis(4-triethylsilylphenyl)methylene-(cyclopentadienyl)(2,7-di- tertiary-butyl-9-fluorenyl)hafhium dimethyl and μ-dimethyl silylbis(-2-methyl, 4- phenylindenyl) zirconium dimethyl.
41. The process of any of claims 20-40 wherein the activator comprises alumoxane.
42. The process of any of claims 20-40 wherein the activator comprises a non- coordinating anion.
43. The process of any of claims 20-40 wherein the activator comprises one or more of trimethylammonium tetraphenylborate, trisperfluorophenyl borate, trisperfluoronaphtyl borate, friethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, fri(n-butyl)ammom'um tetraphenylborate, fri(t-butyl)arnmonium tetraphenylborate, N,N-dimethylanilinium tetraphenylborate, N,N-diethylanilinium tetraphenylborate, N,N-dimethyl-(2,4,6-trimethylamlim'um) tetraphenylborate, trimemylam_ ιonium tetrakis(pentafluorophenyl)borate, friethylan__ιιonium tetrakis(pentafluorophenyl)borate, fripropylammonium tetrakis(pentafluorophenyl)borate, tri(n-butyl)anmιonium tetra__is(pentafluorophenyl)borate, fri(sec-bu1yl)ammoι_ium tetrakis(pentafluorophenyl) borate, N,N-dimethylanilinium tetrakis(pentafluorophenyl) borate, N,N-diethylanilinium tetrakis(pentafluorophenyl) borate, N,N-dimethyl-(2,4,6-trimethylanilinium) tetrakis(pentafluorophenyl) borate, trimethylammonium tetrakis-(2,3,4,6-tetrafluorophenylborate, triethylammonium tetrakis-(2,3,4,6-tetrafluorophenyl) borate, fripropylammonium tetrakis-(2,3,4,6-tetrafluorophenyl) borate, tri(n-butyl)ammonium tetrakis-(2,3,4,6-tetrafluoro-phenyl) borate, dimethyl(t-butyl)ammonium tetrakis-(2,3 ,4,6-tetrafluorophenyl) borate, N,N-dimethylanilinium tetrakis-(2,3 ,4,6-tetrafluorophenyl) borate, N,N-diethylanilinium tetrakis-(2,3,4,6-tetrafluoro-phenyl) borate, N,N-dimethyl-(2,4,6-frimemylanilinium)tetrakis-(2,3,4,6-tetrafluorophenyl) borate, dialkyl ammonium salts such as: di-(i-propyl)ammonium tetrakis(pentafluorophenyl) borate, dicyclohexylammonium tetrakis(pentafluorophenyl) borate, triphenylphosphonium tetrakis(pentafluorophenyl) borate, tri(o-tolyl)phosphonium tetrakis(pentafluorophenyl) borate, and tri(2,6-dimethylphenyl)phosphonium tetrakis(pentafluorophenyl) borate.
44. The process of any of claims 20-40 wherein the activator comprises N,N- dimethylamlimum tetra(perfluorophenyl)borate and/or triphenylcarbenium tetra(perfluorophenyl)borate
45. The process of any of claims 20 to 44 wherein the polymerization takes place in a tubular reactor.
46. The process of claim 45 wherein the tubular reactor has a length-to- diameter ratios of 1 : 1 to 20: 1.
47. The process of claim 45 wherein the tubular reactor has a length-to- diameter ratio of 4:1 to 20:1 and the reactor contains up to six different injection positions.
48. The process of claim 45 wherein the tubular reactor has a length of 100- 2000 meters and an internal diameter of less than 10 cm.
49. The process of claim 45 wherein the tubular reactor is operated in multiple zones.
50. The process of any of claims 20 to 44 wherein the polymerization takes place in an autoclave reactor.
51. The process of claim 50 wherein the autoclave reactor has a length-to- diameter ratios of 1 : 1 to 20: 1.
52. The process of claim 50 wherein the autoclave reactor has a length-to- diameter ratio of 4:1 to 20:1 and the reactor contains up to six different injection positions.
53. The process of claim 50 wherein the autoclave reactor is operated in multiple zones.
54. The process of claim 50 wherein the process comprises (a) continuously feeding olefin monomers, catalyst compound, and activator to the autoclave reactor; (b) continuously polymerizing the monomers in a polymerization zone reactor under elevated pressure; (c) continuously removing the polymer/monomer mixture from the reactor; (d) continuously separating monomer from molten polymer; (e) reducing pressure to form a monomer-rich and a polymer-rich phase; and (f) separating monomer from the polymer.
55. The process of any of claims 20 to 44 wherein the polymerization takes place in a loop reactor.
56. The process of claim 55 wherein the loop reactor has a diameter of 41 to 61 cm and a length of 100 to 200 meters.
57. The process of claim 55 wherein the loop reactor is operated at pressures of25 to 30 MPa.
58. The process of claim 55 where an in-line pump continuously circulates the polymerization system through the loop reactor.
59. The process of claim 55 wherein the process comprises (a) continuously feeding olefin monomers, catalyst compound, and activator to the loop reactor; (b) continuously polymerizing the monomers in a polymerization zone reactor under elevated pressure; (c) continuously removing the polymer/monomer mixture from the reactor; (d) continuously separating monomer from molten polymer; (e) reducing pressure to form a monomer-rich and a polymer-rich phase; and (f) separating monomer from the polymer.
60. The process of any of claims 20 to 59 wherein the polymerization takes place in multiple reactors.
61. The process of claim 60 wherein the polymerization takes places in a tubular reactor and then an autoclave reactor.
62. The process of claim 60 wherein the polymerization takes places in a tubular reactor and then a loop reactor.
63. The process of any of claims 20-62 wherein the residence time is less than 5 minutes.
64. A film comprising the polymer of any of claims 1 to 19.
65. A molded article comprising the polymer of any of claims 1 to 19.
66. An article comprising the polymer of any of claims 1 to 19.
67. A sheet comprising the polymer of any of claims 1 to 19.
68. A fiber comprising the polymer of any of claims 1 to 19.
69. A nonwoven comprising the polymer of any of claims 1 to 19.
70. A fabric comprising the polymer of any of claims 1 to 19.
72. An adhesive comprising the polymer of any of claims 1 to 19.
73. The process of any of claims 20-34 wherein the catalyst compound comprises one or more of: dimethylsiladiyl(2-methyl, 4-[3',5'-di-tbutylphenyl]indenyl)2zirconium dichloride; dimethylsiladiyl(2-ethyl, 4-[3',5'-di-tbutylphenyl]indenyl)2zirconium dichloride; dimethylsiladiyl(2-n-propyl, 4-[3',5'-di-tbutylphenyl]indenyl)2zirconium dichloride; dimethylsiladiyl(2-iso-propyl, 4-[3',5,-di-tbutylphenyl]indenyl)2zirconium dichloride; dimethylsiladiyl(2-n-butyl, 4-[3',5'-di-tbutylphenyl]indenyl)2zirconium dichloride; dimethylsiladiyl(2-iso-butyl, 4-[3',5'-di-tbutylphenyl]indenyl)2zirconium dichloride; dimethylsiladiyl(2-sec-butyl, 4- [3 ', 5 '-di-tbutylphenyl] indeny l)2zirconium dichloride; dimethylsiladiyl(2-tert-butyl, 4-[3',5'-di-tbutylphenyl]indenyl)2zirconium dichloride; dimethylsiladiyl(2-methyl, 4-[3',5'-di-tbutylphenyl]indenyl)2hafnium dichloride; dimethylsiladiyl(2-ethyl, 4-[3',5'-di-tbutylphenyl]indenyl)2hafnium dichloride; dimethylsiladiyl(2-n-propyl, 4-[3',5'-di-tbutylphenyl]indenyl)2hafhium dimethylsiladiyl(2-iso-propyl, 4-[3',5'-di-tbutylphenyl]indenyl)2hafiιium dichloride; dimethylsiladiyl(2-butyl, 4-[3',5'-di-tbutylphenyl]indenyl) 2hafnium dichloride;
9-silafluorendiyl(2-methyl, 4-[3',5'-di-tbutylphenyl]indenyl)2zirconium dichloride;
9-silafluorendiyl(2-ethyl, 4-[3',5'-di-tbutylphenyl]indenyl)2zirconium dichloride;
9-silafluorendiyl(2-n-propyl, 4-[3',5'-di-tbutylphenyl]indenyl)2zirconium dichloride;
9-silafluorendiyl(2-iso-propyl, 4-[3',5'-di-tbutylphenyl]indenyl)2zirconium dichloride;
9-silafluorendiyl(2-n-butyl, 4-[3',5'-di-tbutylphenyl]indenyl)2zirconium dichloride;
9-silafluorendiyl(2-iso-butyl, 4-[3',5'-di-tbutylphenyl]indenyl)2zirconium dichloride;
9-silafluorendiyl(2-sec-butyl, 4-[3',5'-di-tbutylphenyl]indenyl)2zirconium dichloride;
9-silafluorendiyl(2-tert-butyl, 4-[3',5'-di-tbutylphenyl]indenyl)2zirconium dichloride;
9-silafluorendiyl(2-methyl, 4-[3',5'-di-tbutylphenyl]indenyl) 2hafnium dichloride;
9-silafluorendiyl(2-ethyl, 4-[3',5'-di-tbutylphenyl]indenyl) 2hafnium dichloride; 9-silafluorendiyl(2-n-propyl, 4-[3',5'-di-tbutylphenyl]indenyl) 2hafhium dichloride; 9-silafluorendiyl(2-iso-propyl, 4-[3',5'-di-tbutylphenyl]indenyl)2hafiιium dichloride;
9-silafluorendiyl(2-n-butyl, 4-[3',5'-di-tbu1ylphenyl]indenyl)2hafhium dichloride; 9-silafluorendiyl(2-iso-butyl, 4-[3',5'-di-tbutylphenyl]indenyl)2hafhium dichloride; 9-silafluorendiyl(2-sec-butyl, 4-[3',5'-di-tbu1ylphenyl]indenyl)2hafhium dichloride; 9-silafluorendiyl(2-tert-butyl, 4-[3',5'-di-tbutylphenyl]indenyl)2hafnium dichloride; dimethylsiladiyl(2-methyl, 4-[3',5'-di-tbutylphenyl]indenyl)2zirconium dimethyl; dimethylsiladiyl(2-ethyl, 4-[3',5'-di-tbutylphenyl]indenyl)2zirconium dimethyl; dimethylsiladiyl(2-n-propyl, 4-[3',5'-di-tbutylphenyl]indenyl)2zirconium dimethyl; dimethylsiladiyl(2-iso-propyl, 4-[3',5'-di-tbutylphenyl]indenyl)2zirconium dimethyl; dimethylsiladiyl(2-n-butyl, 4-[3',5'-di-tbutylphenyl]indenyl)2zirconium dimethyl; dimethylsiladiyl(2-iso-butyl, 4-[3',5'-di-tbutylphenyl]indenyl)2zirconium dimethyl; dimethylsiladiyl(2-sec-butyl, 4-[3',5'-di-tbutylphenyl]indenyl)2zirconium dimethyl; dimethylsiladiyl(2-tert-butyl, 4-[3',5'-di-tbutylphenyl]indenyl)2zircomum dimethyl; dimethylsiladiyl(2-methyl, 4-[3',5'-di-tbutylphenyl]indenyl)2hafhium dimethyl; dimethylsiladiyl(2-ethyl, 4-[3',5'-di-tbutylphenyl]indenyl)2hafnium dimethyl; dimethylsiladiyl(2-n-propyl, 4-[3',5'-di-tbutylphenyl]indenyl)2hafnium dimethyl dimethylsiladiyl(2-iso-propyl, 4-[3',5'-di-tbutylphenyl]indenyl)2hafnium dimethyl; dimethylsiladiyl(2 -n-butyl, 4-[3',5'-di-tbutylphenyl]indenyl) 2hafrιium dimethyl; dimethylsiladiyl(2-iso-butyl, 4-[3',5'-di-tbutylphenyl]indenyl) 2hafnium dimethyl; dimethylsiladiyl(2-sec-butyl, 4-[3',5'-di-tbutylphenyl]indenyl) 2hafiιium dimethyl; dimethylsiladiyl(2-tert-butyl, 4-[3',5'-di-tbutylphenyl]indenyl) 2hafhium dimethyl; 9-silafluorendiyl(2-methyl, 4-[3',5'-di-tbutylphenyl]indenyl)2zirconium dimethyl; 9-silafluorendiyl(2-ethyl, 4-[3',5'-di-tbutylphenyl]indenyl)2zirconium dimethyl; 9-silafluorendiyl(2-n-propyl, 4-[3',5'-di-tbutylphenyl]indenyl)2zirconium dimethyl; 9-silafluorendiyl(2-iso-propyl, 4-[3',5'-di-tbutylphenyl]indenyl)2zirconium dimethyl;
9-silafluorendiyl(2-n-butyl, 4-[3',5'-di-tbutylphenyl]indenyl)2zirconium dimethyl;
9-silafluorendiyl(2-iso-butyl, 4-[3',5'-di-tbutylphenyl]indenyl)2zirconium dimethyl;
9-silafluorendiyl(2-sec-butyl, 4-[3',5'-di-tbutylphenyl]indenyl)2zirconium dimethyl;
9-silafluorendiyl(2-tert-butyl, 4-[3',5'-di-tbutylphenyl]indenyl)2zirconium dimethyl;
9-silafluorendiyl(2-methyl, 4-[3',5'-di-tbutylphenyl]indenyl) 2hafhium dimethyl;
9-silafluorendiyl(2-ethyl, 4-[3',5'-di-tbutylphenyl]indenyl) 2hafnium dimethyl;
9-silafluorendiyl(2-n-propyl, 4-[3',5'-di-tbutylphenyl]indenyl) 2hafnium dimethyl;
9-silafluorendiyl(2-iso-propyl, 4-[3',5'-di-tbutylphenyl]indenyl)2hafnium dimethyl;
9-silafluorendiyl(2-n-butyl, 4-[3',5'-di-tbutylphenyl]indenyl)2hafnium dimethyl;
9-silafluorendiyl(2-iso-butyl, 4-[3',5'-di-tbutylphenyl]indenyl)2hafnium dimethyl;
9-silafluorendiyl(2-sec-butyl, 4-[3',5'-di-tbutylphenyl]indenyl)2hafnium dimethyl;
9-silafluorendiyl(2-tert-butyl, 4-[3',5'-di-tbutylphenyl]indenyl)2hafnium dimethyl; dimethylsiladiyl(2-methyl, 4-[3',5'-bis-trifluoromethylphenyl]indenyl)2zirconium dichloride; dimethylsiladiyl(2-ethyl, 4- [3 ', 5 '-bis-trifluoromethylphenyl] indenyl)2zirconium dichloride; dimethylsiladiyl(2-n-propyl, 4-[3',5'-bis-frifluoromethylphenyl]indenyl)2zirconium dichloride; dimethylsiladiyl(2-iso-propyl, 4-[3',5'-bis- trifluoromethylphenyl]indenyl)2zirconium dichloride; dimethylsiladiyl(2-n-butyl, 4-[3',5'-bis-frifluoromethylphenyl]indenyl)2zirconium dichloride; dimethylsiladiyl(2-iso-butyl, 4-[3',5'-bis- trifluoromethylphenyl]indenyl)2zirconium dichloride; dimethylsiladiyl(2-sec-butyl, 4-[3',5'-bis- frifluoromethylphenyl]indenyl)2zirconium dichloride; dimethylsiladiyl(2-tert-butyl, 4-[3',5'-bis- trifluoromethylphenyl]indenyl)2zirconium dichloride; dimethylsiladiyl(2-methyl, 4-[3',5,-bis-trifluoromethylphenyl]indenyl)2hafnium dichloride; dimethylsiladiyl(2-ethyl, 4-[3',5'-bis-trifluoromethylphenyl]indenyl)2hafnium dichloride; dimethylsiladiyl(2-n-propyl, 4-[3',5'-bis- trifluoromethylphenyl]indenyl)2hafnium dichloride; dimethylsiladiyl(2-iso-propyl, 4-[3',5'-bis- trifluoromethylphenyl]indenyl)2hafnium dichloride; dimethylsiladiyl(2-n-butyl, 4-[3,,5'-bis- trifluoromemylphenyl]indenyl)2hafhium dichloride; dimethylsiladiyl(2-iso-butyl, 4-[3',5'-bis- frifluoromemylphenyljindenyl^hafhium dichloride; dimethylsiladiyl(2-sec-butyl, 4- [3 ', 5 '-bis- trifluoromethylpheny l]indenyl)2hafnium dichloride; dimethylsiladiyl(2-tert-butyl, 4-[3',5'-bis- trifluoromethylphenyl]indenyl)2hafhium dichloride;
9-silafluorendiyl(2-methyl, 4-[3',5'-bis-trifluoromethylphenyl]indenyl)2zirconium dichloride; dimethylsiladiyl(2-ethyl, 4-[3',5'-bis- trifluoromethylphenyl]indenyl)2hafnium dichloride;
9-silafluorendiyl(2-n-propyl, 4-[3',5'-bis- trifluoromethylphenyl]indenyl)2zirconium dichloride;
9-silafluorendiyl(2-iso-propyl, 4-[3',5'-bis- frifluoromethylphenyl]indenyl)2zirconium dichloride;
9-silafluorendiyl(2-n-butyl, 4-[3',5'-bis- trifluoromethylphenyl]indenyl)2zirconium dichloride; 9-silafluorendiyl(2-iso-butyl, 4-[3 ',5'-bis- trifluoromethylphenyl]indenyl)2zirconium dichloride; 9-silafluorendiyl(2-sec-butyl, 4-[3',5'-bis- ' trifluoromethylphenyl]indenyl)2zirconium dichloride; 9-silafluorendiyl(2-tert-butyl, 4-[3',5'-bis- trifluoromethylphenyl]indenyl)2zirconium dichloride;
9-silafluorendiyl(2-methyl, 4-[3',5'-bis-trifluoromemylphenyl]indenyl)2hafhium dichloride;
9-silafluorendiyl(2-ethyl, 4-[3',5'-bis-trifluoromethylphenyl]indenyl)2hafhium dichloride;
9-silafluorendiyl(2-n-propyl, 4-[3',5'-bis- trifluoromethylphenyl]indenyl)2 hafiiium dichloride;
9-silafluorendiyl(2-iso-propyl, 4-[3',5'-bis- trifluoromethylphenyl]indenyl)2 hafnium dichloride;
9-silafluorendiyl(2-n-butyl, 4-[3',5'-bis-trifluoromethylphenyl]indenyl)2hafnium dichloride;
9-silafluorendiyl(2-iso-butyl, 4-[3',5'-bis-trifluoromethylphenyl]indenyl)2hafnium dichloride;
9-silafluorendiyl(2-sec-butyl, 4-[3',5'-bis-trifluoromethylphenyl]indenyl)2hafhium dichloride;
9-silafluorendiyl(2-tert-butyl, 4-[3',5'-bis-trifluoromethylphenyl]indenyl)2hafnium dichloride; dimethylsiladiyl(2-methyl, 4-[3',5'-bis-trifluoromethylphenyl]indenyl)2zirconium dimethyl; dimemylsiladiyl(2-ethyl, 4-[3',5'-bis-frifluoromethylphenyl]indenyl)2zirconitιm dimethyl; dimethylsiladiyl(2-n-propyl, 4-[3',5'-bis-trifluoromethylphenyl]indenyl)2zirconium dimethyl; dimethylsiladiyl(2-iso-propyl, 4- [3 ',5'-bis- trifluoromethylphenyl]indenyl)2zirconium dimethyl; dimethylsiladiyl(2-n-butyl, 4-[3',5'-bis-trifluoromethylphenyl]indenyl)2zirconium dimethyl; dimethylsiladiyl(2-iso-butyl, 4-[3',5'-bis- trifluoromethylphenyl]indenyl)2zirconium dimethyl; dimethylsiladiyl(2-sec-butyl, 4-[3',5'-bis- trifluoromethylphenyl]indenyl)2zirconium dimethyl; dimethylsiladiyl(2-tert-butyl, 4-[3',5'-bis- trifluoromethylphenyl]indenyl)2zirconium dimethyl; dimethylsiladiyl(2-methyl, 4-[3',5'-bis-trifluoromethylphenyl]indenyl)2hafnium dimethyl; dimethylsiladiyl(2-ethyl, 4-[3',5'-bis-trifluoromethylphenyl]indenyl)2hafnium dimethyl; dimethylsiladiyl(2-n-propyl, 4-[3',5'-bis- trifluoromethylphenyl]indenyl)2hafnium dimethyl; dimethylsiladiyl(2-iso-propyl, 4-[3 ',5 '-bis- trifluoromethylphenyl]indenyl)2hafnium dimethyl ; dimethylsiladiyl(2-n-butyl, 4-[3',5'-bis- trifluoromethylphenyl]indenyl)2hafhium dimethyl; dimethylsiladiyl(2-iso-butyl, 4-[3',5'-bis- trifluoromethylphenyl]indenyl)2hafnium dimethyl; dimethylsiladiyl(2-sec-butyl, 4-[3',5'-bis- trifluoromethylphenyl]indenyl)2hafnium dimethyl; dimethylsiladiyl(2-tert-butyl, 4-[3 ',5'-bis- trifluoromethylphenyl]indenyl)2hafhium dimethyl;
9-silafluorendiyl(2-methyl, 4-[3',5'-bis-frifluoromethylphenyl]indenyl)2zirconium dimethyl; dimemylsiladiyl(2-e1_ yl, 4-[3',5'-bis- trifluorome ylphenyl]indenyl)2hafniιιm dimethyl;
9-silafluorendiyl(2-n-propyl, 4-[3',5'-bis- trifluoromethylphenyl]indenyl)2zirconium dimethyl; 9-silafluorendiyl(2-iso-propyl, 4-[3',5'-bis- trifluoromethylphenyl]indenyl)2zirconium dimethyl;
9-silafluorendiyl(2-n-butyl, 4-[3',5'-bis- trifluoromethylphenyl]indenyl)2zirconium dimethyl;
9-silafluorendiyl(2-iso-butyl, 4- [3 ', 5 '-bis- trifluoromethylphenyl]indenyl)2zirconium dimethyl;
9-silafluorendiyl(2-sec-butyl, 4-[3',5'-bis- trifluoromethylphenyl]indenyl)2zirconium dimethyl;
9-silafluorendiyl(2-tert-butyl, 4-[3',5'-bis- trifluoromethylphenyl]indenyl)2zirconium dimethyl;
9-silafluorendiyl(2-methyl, 4-[3',5'-bis-trifluoromethylphenyl]indenyl)2hafnium dimethyl;
9-silafluorendiyl(2-ethyl, 4-[3',5'-bis-trifluoromethylphenyl]indenyl)2hafnium dimethyl;
9-silafluorendiyl(2-n-propyl, 4-[3',5'-bis- trifluoromethylphenyl]indenyl)2 hafnium dimethyl;
9-silafluorendiyl(2-iso-propyl, 4-[3',5'-bis- frifluoromethylphenyl]indenyl)2 hafnium dimethyl;
9-silafluorendiyl(2-n-butyl, 4-[3',5'-bis-trifluoromethylphenyl]indenyl)2hafnium dimethyl;
9~silafluorendiyl(2-iso-butyl, 4- [3 ',5'-bis-trifluoromethylphenyl]indenyl)2hafnium dimethyl;
9-silafluorendiyl(2-sec-butyl, 4-[3',5'-bis-trifluoromethylphenyl]indenyl)2hafnium dimethyl;
9-silafluorendiyl(2-tert-butyl, 4-[3',5'-bis-trifluoromethylphenyl]indenyl)2ha__ιium dimethyl; dimethylsiladiyl(2-ethyl, 4-[3',5'-di-iso-propylphenyl]indenyl)2zirconium dichloride; dimethylsiladiyl(2-n-propyl, 4-[3',5'-di-iso-propylphenyl]indenyl)2zirconium dichloride dimethylsiladiyl(2-iso-propyl, 4-[3,,5'-di-iso-propylphenyl]indenyl)2zirconium dichloride; dimethylsiladiyl(2-n~butyl, 4-[3',5'-di-iso-propylphenyl]indenyl)2zirconium dichloride; dimethylsiladiyl(2-iso-butyl, 4-[3',5'-di-iso-propylphenyl]indenyl)2zirconium dichloride; dimethy lsiladiyl(2-sec-butyl, 4- [3 ',5 '-di-iso-propylphenyl]indenyl)2zirconium dichloride; dime /thylsiladiyl(2-tert-butyl, 4-[3',5'-di-iso-propylphenyl]indenyl)2zirconium dichloride; dimethylsiladiyl(2-ethyl, 4-[3',5'-di-iso-propylphenyl]indenyl)2hafnium dichloride; dimethylsiladiyl(2-n-propyl, 4-[3',5'-di-iso-propylphenyl]indenyl)2hafnium dichloride; dimethylsiladiyl(2-iso-propyl, 4-[3',5'-di- iso-propylphenyl]indenyl) 2hafnium dichloride; dimethylsiladiyl(2-n-butyl, 4-[3',5'-di- iso-propylphenyl]indenyl) 2hafhium dichloride; dimethylsiladiyl(2-iso-butyl, 4-[3',5'-di- iso-propylphenyl]indenyl) 2hafrιium dichloride; dinιethylsiladiyl(2-sec-butyl, 4-[3',5'-di- iso-propylphenyl]indenyl) 2hafnium dichloride; dimethylsiladiyl(2-tert-butyl, 4-[3',5'-di- iso-propylphenyl]indenyl) 2hafnium dichloride;
9-silafluorendiyl(2-ethyl, 4-[3',5'-di-iso-propylphenyl]indenyl)2zirconium dichloride;
9-silafluorendiyl(2-n-propyl, 4-[3',5'-di-iso-propylphenyl]indenyl)2zirconium dichloride;
9-silafluorendiyl(2-iso-propyl, 4-[3',5'-di-iso-propylphenyl]indenyl)2zirconium dichloride; 9-silafluorendiyl(2 -n-butyl, 4-[3',5,-di-iso-propylphenyl]indenyl)2zirconium dichloride;
9-silafluorendiyl(2-iso-butyl, 4-[3',5'-di-iso-propylphenyl]indenyl)2zirconium dichloride;
9-silafluorendiyl(2-sec-butyl, 4-[3',5'-di-iso-propylphenyl]indenyl)2zirconium dichloride;
9-silafluorendiyl(2-tert-butyl, 4-[3',5'-di-iso-propylphenyl]indenyl)2zirconium dichloride;
9-silafluorendiyl(2-ethyl, 4-[3',5'-di-iso-propylphenyl]indenyl)2hafhium dichloride;
9-silafluorendiy l(2-n-proρyl, 4- [3 ' , 5 '-di-iso-propylphenyl]indenyl)2hafnium dichloride;
9-silafluorendiyl(2-iso-propyl, 4-[3',5'-di-iso-propylphenyl]indenyl)2hafnium dichloride;
9-silafluorendiyl(2-n-butyl, 4-[3',5'-di-iso-propylphenyl]indenyl)2hafhium dichloride;
9-silafluorendiyl(2-iso-butyl, 4-[3',5'-di-iso-propylphenyl]indenyl)2haf_ιium dichloride;
9-silafluorendiyl(2-sec-butyl, 4-[3',5'-di-iso-propylphenyl]indenyl)2hafnium dichloride;
9-silafluorendiyl(2-tert-butyl, 4-[3',5'-di-iso-propylphenyl]indenyl)2hafnium dichloride; dimethylsiladiyl(2-ethyl, 4-[3',5'-di-iso-propylphenyl]indenyl)2zirconium dimethyl; dimethylsiladiyl(2-n-propyl, 4-[3',5'-di-iso-propylphenyl]indenyl)2zirconium dimethyl dimethylsiladiyl(2-iso-propyl, 4-[3',5'-di-iso-propylphenyl]indenyl)2zirconium dimethyl; dimethylsiladiyl(2-n-butyl, 4-[3',5'-di-iso-propylphenyl]indenyl)2zirconium dimethyl; dimethylsiladiyl(2 -isobutyl, 4-[3',5'-di-iso-propylphenyl]indenyl)2zirconium dimethyl; dimethylsiladiyl(2-sec-butyl, 4-[3',5'-di-iso-propylphenyl]indenyl)2zirconium dimethyl; dimethylsiladiyl(2-tert-butyl, 4-[3',5'-di-iso-propylphenyl]indenyl)2zirconium dimethyl; dimethylsiladiyl(2-ethyl, 4-[3',5'-di-iso-propylphenyl]indenyl) 2hafnium dimethyl; dimethylsiladiyl(2-n-propyl, 4-[3',5'-di- iso-propylphenyl]indenyl) 2hafnium dimethyl; dimethylsiladiyl(2-iso-propyl, 4-[3',5'-di- iso-propylphenyl]indenyl) 2hafhium dimethyl; dimethylsiladiyl(2-n-butyl, 4-[3',5'-di- iso-propylphenyl]indenyl) 2hafnium dimethyl; dimethylsiladiyl(2-iso-butyl, 4-[3',5'-di-iso-propylphenyl]indenyl)2zirconium dimethyl; dimethylsiladiyl(2-sec-butyl, 4-[3',5'-di-iso-propylphenyl]indenyl)2zirconium dimethyl; dimethylsiladiyl(2-tert-butyl, 4-[3',5'-di-iso-propylphenyl]indenyl)2zirconium dimethyl;
9-silafluorendiyl(2-ethyl, 4-[3',5'-di-iso-propylphenyl]indenyl)2zirconium dimethyl;
9-silafluorendiyl(2-n-propyl, 4-[3',5'-di-iso-propylphenyl]indenyl)2zirconium dimethyl;
9-silafluorendiyl(2-iso-propyl, 4- [3 ',5 '-di-iso-propylphenyl] indenyl)2zirconium dimethyl;
9-silafluorendiyl(2 -n-butyl, 4-[3',5'-di-iso-propylphenyl]indenyl)2zirconium dimethyl;
9-silafluorendiyl(2-iso-butyl, 4-[3',5'-di-iso-propylphenyl]indenyl)2zirconium dimethyl; 9-silafluorendiyl(2-sec-butyl, 4-[3',5'-di-iso-propylphenyl]indenyl)2zirconium dimethyl;
9-silafluorendiyl(2-tert-butyl, 4-[3',5'-di-iso-propylphenyl]indenyl)2zirconium dimethyl;
9-silafluorendiyl(2-ethyl, 4-[3',5'-di-iso-propylphenyl]indenyl) 2haf_ιium dimethyl;
9-silafluorendiyl(2-n-propyl, 4-[3',5'-di-iso-propylphenyl]indenyl)2hafhium dimethyl;
9-silafluorendiyl(2-iso-propyl, 4-[3',5'-di-iso-propylphenyl]indenyl)2hafnium dimethyl;
9-silafluorendiyl(2-n-butyl, 4-[3',5'-di-iso-propylphenyl]indenyl)2hafnium dimethyl;
9-silafluorendiyl(2-iso-butyl, 4-[3',5'-di-iso-propylphenyl]indenyl)2hafhium dimethyl;
9-silafluorendiyl(2-sec-butyl, 4-[3',5'-di-iso-propylphenyl]indenyl)2hafhium dimethyl;
9-silafluorendiyl(2-tert-butyl, 4-[3',5'-di-iso-propylphenyl]indenyl)2hafnium dimethyl; dimethylsiladiyl(2-methyl, 4- [3 ', 5 '-di-phenylpheny l]indenyl)2zirconium dichloride; dimethylsiladiyl(2-ethyl, 4-[3',5'-di-phenylphenyl]indenyl)2zirconium dichloride; dimethylsiladiyl(2-n-propyl, 4- [3 ', 5 '-di-pheny lphenyl]indenyl)2zirconium dichloride; dimethylsiladiyl(2-iso-propyl, 4-[3',5'-di-phenylphenyl]indenyl)2zirconium dichloride; dimethylsiladiyl(2-n-butyl, 4-[3',5,-di-phenylphenyl]indenyl)2zirconium dichloride; dimethylsiladiyl(2-iso-butyl, 4-[3',5'-di-phenylphenyl]indenyl)2zirconium dichloride; dimethylsiladiyl(2-sec-butyl, 4-[3',5'-di-phenylphenyl]indenyl)2zhconium dichloride; dimethylsiladiyl(2-tert-butyl, 4-[3',5'-di-phenylphenyl]indenyl)2zirconium dichloride; dimethylsiladiyl(2-methyl, 4-[3',5'-di-phenylphenyl]indenyl)2haf_ιium dichloride; dimethylsiladiyl(2-emyl, 4-[3',5'-di-phenylphenyl]indenyl)2hafiιium dichloride; dimethylsiladiyl(2-n-propyl, 4-[3',5'-di-phenylphenyl]indenyl)2hafhium dichloride; dimethylsiladiyl(2-iso-propyl, 4-[3',5'-di-phenylphenyl]indenyl)2hafnium dichloride; dimethylsiladiyl(2-n-butyl, 4-[3',5'-di-phenylphenyl]indenyl)2hafnium dichloride; dimethylsiladiyl(2-iso-butyl, 4- [3 ' , 5 '-di-phenylpheny l]indeny l)2hafhium dichloride; dimethylsiladiyl(2-sec-butyl, 4-[3',5'-di-phenylphenyl]indenyl)2hafhium dichloride; dimethylsiladiyl(2-tert-butyl, 4-[3',5'-di-phenylphenyl]indenyl)2hafnium dichloride;
9-silafluorendiyl(2-methyl, 4-[3',5'-di-phenylphenyl]indenyl)2zirconium dichloride;
9-silafluorendiyl(2-ethyl, 4-[3',5'-di-phenylphenyl]indenyl)2zirconium dichloride;
9-silafluorendiyl(2-n-propyl, 4-[3',5'-di-phenylphenyl]indenyl)2zirconium dichloride;
9-silafluorendiyl(2-iso-propyl, 4-[3',5'-di-phenylphenyl]indenyl)2zirconium dichloride;
9-silafluorendiyl(2-n-butyl, 4-[3',5'-di-phenylphenyl]indenyl)2zirconium dichloride;
9-silafluorendiyl(2-iso-butyl, 4-[3',5'-di-phenylphenyl]indenyl)2zirconium dichloride;
9-silafluorendiyl(2-sec-butyl, 4-[3',5'-di-phenylphenyl]indenyl)2zirconium dichloride;
9-silafluorendiyl(2-tert-butyl, 4-[3',5'-di-phenylphenyl]indenyl)2zirconium dichloride;
9-silafluorendiyl(2-methyl, 4-[3',5'-di-phenylphenyl]indenyl)2hafnium dichloride; 9-silafluorendiyl(2-ethyl, 4-[3',5'-di-phenylphenyl]indenyl)2hafnium dichloride;
9-silafluorendiyl(2-n-propyl, 4-[3',5'-di-phenylphenyl]indenyl)2hafnium dichloride;
9-silafluorendiyl(2-iso-propyl, 4-[3',5'-di-phenylphenyl]indenyl)2hafnium dichloride;
9-silafluorendiyl(2-n-butyl, 4-[3',5'-di-phenylphenyl]indenyl)2hafhium dichloride;
9-silafluorendiyl(2-iso-butyl, 4-[3',5'-di-phenylphenyl]indenyl)2hafnium dichloride;
9-silafluorendiyl(2-sec-butyl, 4-[3',5'-di-phenylphenyl]indenyl)2hafnium dichloride;
9-silafluorendiyl(2-tert-butyl, 4-[3',5'-di-phenylphenyl]indenyl)2hafnium dichloride; dimethylsiladiyl(2-methyl, 4-[3',5'-di-phenylphenyl]indenyl)2zirconium dimethyl; dimethylsiladiyl(2-ethyl, 4-[3',5'-di-phenylphenyl]indenyl)2zirconium dimethyl; dimethylsiladiyl(2-n-propyl, 4-[3',5'-di-phenylphenyl]indenyl)2zirconium dimethyl; dimethylsiladiyl(2-iso-propyl, 4-[3',5'-di-phenylphenyl]indenyl)2zirconium dimethyl; dimethylsiladiyl(2-n-butyl, 4-[3',5'-di-phenylphenyl]indenyl)2zirconium dimethyl; dimethylsiladiyl(2-iso-butyl, 4-[3',5'-di-phenylphenyl]indenyl)2zirconium dimethyl; dimethylsiladiyl(2-sec-butyl, 4-[3',5'-di-phenylphenyl]indenyl)2zirconium dimethyl; dimethylsiladiyl(2-tert-butyl, 4-[3',5'-di-phenylphenyl]indenyl)2zirconium dimethyl; dimethylsiladiyl(2-methyl, 4-[3',5'-di-phenylphenyl]indenyl)2hafnium dimethyl; dimethylsiladiyl(2-emyl, 4-[3',5'-di-phenylphenyl]indenyl)2hafniιιm dimethyl; dimethylsiladiyl(2-n-propyl, 4-[3',5'-di-phenylphenyl]indenyl)2hafhium dimethyl; dimethylsiladiyl(2-iso-propyl, 4-[3',5'-di-phenylphenyl]indenyl)2haftιium dimethyl; dimethylsiladiyl(2-n-butyl, 4-[3',5'-di-phenylphenyl]indenyl)2hafnium dimethyl; dimethylsiladiyl(2-iso-butyl, 4- [3 ',5 '-di-phenylpheny 1] indenyl^hafnium dimethyl; dimethylsiladiyl(2-sec-butyl, 4-[3',5'-di-phenylphenyl]indenyl)2haf-_ium dimethyl; dimethylsiladiyl(2-tert-butyl, 4-[3',5'-di-phenylphenyl]indenyl)2hafhium dimethyl;
9-silafluorendiyl(2-methyl, 4-[3',5'-di-phenylphenyl]indenyl)2zirconium dimethyl;
9-silafluorendiyl(2-ethyl, 4-[3',5'-di-phenylphenyl]indenyl)2zirconium dimethyl;
9-silafluorendiyl(2-n-propyl, 4-[3',5'-di-phenylphenyl]indenyl)2zirconium dimethyl;
9-silafluorendiyl(2-iso-propyl, 4-[3',5'-di-phenylphenyl]indenyl)2zirconium dimethyl;
9-silafluorendiyl(2-n-butyl, 4-[3',5'-di-phenylphenyl]indenyl)2zirconium dimethyl;
9-silafluorendiyl(2-iso-butyl, 4-[3',5'-di-phenylphenyl]indenyl)2zirconium dimethyl;
9-silafluorendiyl(2-sec-butyl, 4-[3',5'-di-phenylphenyl]indenyl)2zirconium dimethyl;
9-silafluorendiyl(2-tert-butyl, 4-[3',5'-di-phenylphenyl]indenyl)2zirconium dimethyl;
9-silafluorendiyl(2-methyl, 4-[3',5'-di-phenylphenyl]indenyl)2hafhium dimethyl;
9-silafluorendiyl(2-ethyl, 4-[3',5'-di-phenylphenyl]indenyl)2hafnium dichloride;
9-silafluorendiyl(2-n-propyl, 4-[3',5'-di-phenylphenyl]indenyl)2hafnium dimethyl;
9-silafluorendiyl(2-iso-propyl, 4-[3',5'-di-phenylphenyl]indenyl)2hafhium dimethyl;
9-silafluorendiyl(2-n-butyl, 4-[3',5'-di-phenylphenyl]indenyl)2hafnium dimethyl;
9-silafluorendiyl(2-iso-butyl, 4-[3',5'-di-phenylphenyl]indenyl)2hafnium dimethyl;
9-silafluorendiyl(2-sec-butyl, 4-[3',5'-di-phenylphenyl]indenyl)2hafhium dimethyl;
9-silafluorendiyl(2-tert-butyl, 4-[3',5'-di-phenylphenyl]indenyl)2hafhium dimethyl; dimethylsiladiyl(2-methyl, 4-[3',5'-di-tbutylphenyl]indenyl)2η4-l,4-diphenyl-l,3- butadiene; dimethylsiladiyl(2-ethyl, 4-[3',5'-di-tbutylphenyl]indenyl)2η4-l,4-diphenyl-l,3- butadiene; dimethylsiladiyl(2-n-propyl, 4-[3',5'-di-tbutylphenyl]indenyl)2 η4-l ,4-diphenyl- 1,3 -butadiene; dimethylsiladiyl(2-iso-propyl, 4-[3',5'-di-tbutylphenyl]indenyl)2 η4-l ,4-diphenyl- 1,3 -butadiene; dimethylsiladiyl(2-n-butyl, 4-[3',5'-di-tbutylphenyl]indenyl)2 η4-l ,4-diphenyl-l ,3- butadiene; dimethylsiladiyl(2-iso-butyl, 4-[3',5'-di-tbutylphenyl]indenyl)2 η4-l ,4-diphenyl- 1,3 -butadiene; dimethylsiladiyl(2-sec-butyl, 4-[3',5'-di-tbutylphenyl]indenyl)2η4-l,4-diphenyl- 1,3-butadiene; dimethylsiladiyl(2-tert-butyl, 4-[3',5'-di-tbutylphenyl]indenyl)2 η4-l ,4-diphenyl- 1,3 -butadiene; dimethylsiladiyl(2 -ethyl, 4-[3',5'-bis-trifluoromethylphenyl]indenyl)2 η4-l ,4- diphenyl- 1 ,3-butadiene; dimethylsiladiyl(2-n-propyl, 4-[3',5'-bis-trifluoromethylphenyl]indenyl)2η4-l,4- diphenyl- 1 ,3 -butadiene; dimethylsiladiyl(2-iso-propyl, 4-[3',5'-bis- trifluoromethylphenyl]indenyl)2η4-l,4- diphenyl-l,3-butadiene; dimethylsiladiyl(2-n-butyl, 4-[3',5'-bis-trifluoromethylphenyl]indenyl)2 η4-l ,4- diphenyl-l ,3-butadiene; dimethylsiladiyl(2-iso-butyl, 4-[3',5'-bis-trifluoromethylphenyl]indenyl)2 η4-l ,4- diphenyl- 1 ,3-butadiene; dimethylsiladiyl(2-sec-butyl, 4-[3',5'-bis-frifluoromethylphenyl]indenyl)2 η4-l ,4- diphenyl- 1 ,3 -butadiene; dimethylsiladiyl(2-tert-butyl, 4-[3',5'-bis-trifluoromethylphenyl]indenyl)2 η4-l ,4- diphenyl-l,3-butadiene; dimethylsiladiyl(2-ethyl, 4-[3',5'-di-iso-propylphenyl]indenyl)2 η4-l ,4-diphenyl- 1,3 -butadiene; dimethylsiladiyl(2-n-propyl, 4-[3',5'-di-iso-propylphenyl]indenyl) 2 η4-l ,4- diphenyl-l,3-butadiene; dimethylsiladiyl(2-iso-propyl, 4-[3',5'-di-iso-propylphenyl]_ndeny_) η4-l ,4- diphenyl-l,3-butadiene; dimethylsiladiyl(2-n-butyl, 4-[3',5'-di-iso-propylphenyl]indenyl)2 η -l ,4-diphenyl- 1,3 -butadiene; dimethylsiladiyl(2-iso-butyl, 4-[3',5'-di-iso-propylphenyl]indenyl)2 η4-l ,4- diphenyl- 1 ,3-butadiene; dimethylsiladiyl(2-sec-butyl, 4-[3',5'-di-iso-propylphenyl]indenyl)2η4-l,4- diphenyl- 1 ,3 -butadiene; dimethylsiladiyl(2-tert-butyl, 4-[3',5'-di-iso-propylphenyl]indenyl)2 η4-l ,4- diphenyl-l,3-butadiene; dimethylsiladiyl(2-methyl, 4-[3',5'-di-phenylphenyl]indenyl)2η -l,4-diphenyl-l,3- butadiene; dimethylsiladiyl(2-ethyl, 4-[3',5'-di-phenylphenyl]indenyl)2η4-l,4-diphenyl-l,3- butadiene; dimethylsiladiyl(2-n-propyl, 4-[3',5'-di-phenylphenyl]indenyl)2 η4-l ,4-diphenyl- 1,3-butadiene; dimethylsiladiyl(2-iso-propyl, 4-[3',5'-di-phenylphenyl]indenyl)2η4-l,4-diphenyl- 1,3 -butadiene; dimethylsiladiyl(2-n-butyl, 4-[3',5'-di-phenylphenyl]indenyl)2 η4-l ,4-diphenyl-l ,3- butadiene; dimethylsiladiyl(2-iso-butyl, 4-[3',5'-di-phenylphenyl]indenyl)2 η4-l ,4-diphenyl- 1,3 -butadiene; dimethylsiladiyl(2-sec-butyl, 4-[3',5'-di-phenylphenyl]indenyl)2 η4-l ,4-diphenyl- 1,3-butadiene; dimethylsiladiyl(2-tert-butyl, 4-[3',5'-di-phenylphenyl]indenyl)2 η4-l ,4-diphenyl- 1,3-butadiene; 9-silafluorendiyl(2-methyl, 4-[3',5'-di-tbutylphenyl]indenyl)2η4-l,4-diphenyl-l,3- butadiene;
9-silafluorendiyl(2-ethyl, 4-[3,,5'-di-tbutylphenyl]indenyl)2η4-l,4-diphenyl-l,3- butadiene;
9-silafluorendiyl(2-n-propyl, 4-[3',5'-di-tbutylphenyl]indenyl)2 η4-l ,4-diphenyl- 1,3-butadiene;
9-silafluorendiyl(2-iso-propyl, 4-[3',5'-di-tbutylphenyl]indenyl)2 η4-l ,4-diphenyl- 1,3 -butadiene;
9-silafluorendiyl(2-n-butyl, 4-[3',5'-di-tbutylphenyl]indenyl)2 η4-l ,4-diphenyl-l ,3- butadiene;
9-silafluorendiyl(2-iso-butyl, 4-[3',5'-di-tbutylphenyl]indenyl)2 η4-l ,4-diphenyl- 1,3 -butadiene;
9-silafluorendiyl(2-sec-butyl, 4-[3',5'-di-tbutylphenyl]indenyl)2 η4-l ,4-diphenyl- 1,3 -butadiene;
9-silafluorendiyl(2-tert-butyl, 4-[3',5'-di-tbutylphenyl]indenyl)2 η4-l ,4-diphenyl- 1,3-butadiene;
9-silafluorendiyl(2-ethyl, 4-[3',5'-bis-trifluorome ylphenyl]indenyl)2 η4-l ,4- diphenyl-l ,3-butadiene;
9-silafluorendiyl(2-n-propyl, 4-[3',5'-bis-trifluoromethylphenyl]indenyl)2η4-l,4- diphenyl-1 ,3-butadiene;
9-silafluorendiyl(2-iso-propyl, 4-[3',5'-bis- trifluoromethylphenyl]indenyl)2 η4-l ,4- diphenyl-l ,3-butadiene;
9-silafluorendiyl(2-n-butyl, 4-[3',5'-bis-trifluoromethylphenyl]indenyl)2 η4-l ,4- diphenyl-l ,3-butadiene;
9-silafluorendiyl(2-iso-butyl, 4-[3',5'-bis-trifluoromethylphenyl]indenyl)2 η4-l ,4- diphenyl-l,3-butadiene;
9-silafluorendiyl(2-sec-butyl, 4-[3',5'-bis-trifluoromethylphenyl]indenyl)2η4-l,4- diphenyl-1 ,3-butadiene; 9-silafluorendiyl(2-tert-butyl, 4-[3',5'-bis-trifluoromethylphenyl]indenyl)2 η4-l ,4- diphenyl-l,3-butadiene;
9-silafluorendiyl(2-ethyl, 4-[3',5'-di-iso-propylphenyl]indenyl)2η4-l,4-diphenyl- 1,3-butadiene;
9-silafluorendiyl(2-n-propyl, 4-[3',5'-di-iso-propylphenyl]indenyl) 2 η4-l ,4- diphenyl-l,3-butadiene;
9-silafluorendiyl(2-iso-propyl, 4-[3',5'-di-iso-propylphenyl]indenyl) η4-l ,4- diphenyl- 1 ,3-butadiene;
9-silafluorendiyl(2-n-butyl, 4-[3',5'-di-iso-propylphenyl]indenyl)2 η4-l,4-diphenyl- 1,3 -butadiene;
9-silafluorendiyl(2-iso-butyl, 4-[3',5'-di-iso-propylphenyl]indenyl)2 η4-l ,4- diphenyl-l ,3-butadiene;
9-silafluorendiyl(2-sec-butyl, 4-[3',5'-di-iso-propylphenyl]indenyl)2 η4-l ,4- diphenyl-l ,3-butadiene;
9-silafluorendiyl(2-tert-butyl, 4-[3',5'-di-iso-propylphenyl]indenyl)2 η4-l ,4- diphenyl-l ,3-butadiene;
9-silafluorendiyl(2 -methyl, 4-[3',5'-di-phenylphenyl]indenyl)2 η4-l ,4-diphenyl-l ,3- butadiene;
9-silafluorendiyl(2-ethyl, 4-[3',5'-di-phenylphenyl]indenyl)2 η4-l ,4-diphenyl- 1,3- butadiene;
9-silafluorendiyl(2-n-propyl, 4-[3',5'-di-phenylphenyl]indenyl)2 η4-l ,4-diphenyl- 1,3-butadiene;
9-silafluorendiyl(2-iso-propyl, 4-[3',5'-di-phenylphenyl]indenyl)2 η4-l ,4-diphenyl- 1,3 -butadiene;
9-silafluorendiyl(2-n-butyl, 4-[3',5'-di-phenylphenyl]indenyl)2 η4-l ,4-diphenyl- 1,3 -butadiene;
9-silafluorendiyl(2-iso-butyl, 4-[3',5'-di-phenylphenyl]indenyl)2 η4-l ,4-diphenyl- 1,3 -butadiene; 9-silafluorendiyl(2-sec-butyl, 4-[3',5'-di-phenylphenyl]indenyl)2η4-l,4-diρhenyl-
1,3-butadiene;
9-silafluorendiyl(2-tert-butyl, 4-[3',5'-di-phenyIphenyl]indenyl)2η4-l,4-diρhenyl-
1,3 -butadiene; dimethylamidoborane(2-methyl, 4-[3',5'-di-tbutylphenyl]indenyl)2zirconium dichloride; dimethylamidoborane(2-ethyl, 4-[3',5'-di-tbutylphenyl]indenyl)2zirconium dichloride; dimethylamidoborane(2-n-propyl, 4-[3',5'-di-tbutylphenyl]indenyl)2zirconium dichloride; dimethylamidoborane(2-iso-propyl, 4-[3',5'-di-tbutylphenyl]indenyl)2zircor_ium dichloride; dimethylamidoborane(2 -n-butyl, 4-[3',5'-di-tbutylphenyl]indenyl)2zirconium dichloride; dimethylamidoborane(2-iso-butyl, 4-[3',5'-di-tbutylphenyl]indenyl)2zirconium dichloride; dimethylamidoborane(2-sec-butyl, 4-[3',5'-di-tbutylphenyl]indenyl)2zirconium dichloride; dimethylamidoborane(2-tert-butyl, 4-[3',5'-di-tbutylphenyl]indenyl)2zirconium dichloride; dimethylamidoborane(2-ethyl, 4-[3',5'-bis- frifluoromethylphenyljindenyl^zircor im dichloride; dimethylamidoborane(2-n-propyl, 4-[3',5'-bis- trifluoromethylphenyl]indenyl)2zirconium dichloride; dimethylamidoborane(2-iso-propyl, 4-[3',5'-bis- trifluoromethylphenyl]indenyl)2zirconium dichloride; dimethylamidoborane(2-n-butyl, 4-[3',5'-bis- trifluoromethylphenyl]indenyl)2zirconium dichloride; dimethylarnidoborane(2-iso-butyl, 4-[3',5'-bis- trifluoromethylphenyl]indenyl)2zirconium dichloride; dimethylamidoborane(2-sec-butyl, 4-[3',5'-bis- trifluoromethylphenyl]indenyl)2zirconium dichloride; dimethylamidoborane(2-tert-butyl, 4-[3',5'-bis- trifluoromethylphenyl]indenyl)2zirconium dichloride; dimethylamidoborane(2-ethyl, 4-[3',5'-di-iso-propylphenyl]indenyl)2zirconium dichloride; dimethylamidoborane(2-n-propyl, 4-[3',5'-di-iso-propylphenyl]indenyl)2zirconium dichloride dimethylamidoborane(2-iso~propyl, 4-[3',5'-di-iso- propylphenyl]indenyl)2zirconium dichloride; dimethylamidoborane(2-n-butyl, 4-[3',5'-di-iso-propylphenyl]indenyl)2zirconium dichloride; dimethylamidoborane(2-iso-butyl, 4-[3',5'-di-iso-propylphenyl]indenyl)2zirconium dichloride; dimethylamidoborane(2-sec-butyl, 4-[3',5'-di-iso- propylphenyl]indenyl)2zirconium dichloride; dimethylamidoborane(2-tert-butyl, 4-[3',5'-di-iso- propylphenyl]indenyl)2zirconium dichloride; dimethylamidoborane(2-methyl, 4-[3',5'-di-phenylphenyl]indenyl)2zirconium dichloride; dimethylamidoborane(2-ethyl, 4-[3',5'-di-phenylphenyl]indenyl)2zirconium dichloride; dimethylamidoborane(2-n-propyl, 4-[3',5'-di-phenylphenyl]indenyl)2zirconium dichloride; dimethylamidoborane(2-iso-propyl, 4-[3',5'-di-phenylphenyl]indenyl)2zirconium dichloride; dimethylamidoborane(2-n-butyl, 4-[3',5'-di-phenylphenyl]indenyl)2zirconium dichloride; dimethylamidoborane(2-iso-butyl, 4-[3',5'-di-phenylphenyl]indenyl)2zirconium dichloride; dimethylamidoborane(2-sec-butyl, 4-[3',5'-di-phenylphenyl]indenyl)2zirconium dichloride; dimethylamidoborane(2-tert-butyl, 4-[3',5'-di-phenylphenyl]indenyl)2zirconium dichloride; dimethylamidoborane(2-methyl, 4-[3',5'-di-tbutylphenyl]indenyl)2η4-l,4- diphenyl- 1 ,3-butadiene; dimethylamidoborane(2-ethyl, 4-[3',5'-di-tbutylphenyl]indenyl)2η4-l,4-diphenyl- 1,3 -butadiene; dimethylamidoborane(2-n-propyl, 4-[3',5'-di-tbutylphenyl]indenyl)2η4-l,4- diphenyl- 1 ,3-butadiene; dimethylamidoborane(2-iso-propyl, 4-[3',5'-di-tbutylphenyl]indenyl)2η4-l,4- diphenyl-l,3-butadiene; dimethyIamidoborane(2-n-butyl, 4-[3',5'-di-tbutylphenyl]indenyl)2η4-l,4- diphenyl-l,3-butadiene; dimethylamidoborane(2-iso-butyl, 4-[3',5'-di-tbutylphenyl]indenyl)2 η4-l ,4- diphenyl- 1 ,3-butadiene; dimethylamidoborane(2-sec-butyl, 4-[3',5'-di-tbutylphenyl]indenyl)2 η4-l ,4- diphenyl- 1 ,3-butadiene; dimethylamidoborane(2 -tert-butyl, 4-[3',5'-di-tbutylphenyl]indenyl)2 η4-l ,4- diphenyl-l ,3-butadiene; dimethylamidoborane(2-ethyl, 4-[3',5l-bis-trifluoromethylphenyl]indenyl)2 η4-l ,4- diphenyl- 1 ,3 -butadiene; dimethylamidoborane(2-n-propyl, 4-[3,,5'-bis-trifluoromethylphenyl]indenyl)2η4- 1 ,4-diphenyl- 1 ,3-butadiene; dimethylamidoborane(2-iso-propyl, 4-[3',5'-bis- trifluoromethylphenyl]indenyl)2 η4- 1 ,4-diphenyl- 1 ,3-butadiene; dimethylamidoborane(2 -n-butyl, 4-[3',5'-bis-trifluoromethylphenylJindenyl)2η4- l,4-diphenyl-l,3-butadiene; dimethylamidoborane(2-iso-butyl, 4-[3',5'-bis-trifluoromethylphenyl]indenyl)2η4- l,4-diphenyl-l,3-butadiene; dimethylamidoborane(2-sec-butyl, 4-[3',5'-bis-trifluoromethylphenyl]indenyl)2η4- l,4-diphenyl-l,3-butadiene; dimethylamidoborane(2-tert-butyl, 4-[3',5'-bis-trifluoromethylphenyl]indenyl)2η4- 1 ,4-diphenyl-l ,3-butadiene; dimethylamidoborane(2-ethyl, 4-[3',5'-di-iso-propylphenyl]indenyl)2η4-l,4- diphenyl- 1 ,3 -butadiene; dimethylamidoborane(2-n-propyl, 4-[3',5'-di-iso-propylphenyl]indenyl) 2 η4-l ,4- diphenyl- 1 ,3 -butadiene; dimethylamidoborane(2-iso-propyl, 4-[3',5'-di-iso-propylphenyl]indenyl) η4-l ,4- diphenyl-l ,3-butadiene; dimethylamidoborane(2-n-butyl, 4-[3',5'-di-iso-propylphenyl]indenyl)2 η4-l ,4- diphenyl- 1 ,3 -butadiene; dimethylamidoborane(2-iso-butyl, 4-[3',5'-di-iso-propylphenyl]indenyl)2η4-l,4- diphenyl- 1 ,3-butadiene; dimethylamidoborane(2-sec-butyl, 4-[3',5'-di-iso-propylphenyl]indenyl)2η4-l,4- diphenyl- 1 ,3-butadiene; dimethylamidoboraήe(2-tert-butyl, 4-[3',5'-di-iso-propylphenyl]indenyl)2η4-l,4- diphenyl-1 ,3-butadiene; dimethylamidoborane(2-methyl, 4-[3',5'-di-phenylphenyl]indenyl)2η4-l,4- diphenyl-1 ,3-butadiene; dimethylamidoborane(2-ethyl, 4-[3',5'-di-phenylphenyl]indenyl)2 η4-l ,4-diphenyl- 1,3-butadiene; dimethylamidoborane(2-n-propyl, 4-[3',5'-di-phenylphenyl]indenyl)2η4-l,4- diphenyl- 1 ,3-butadiene; dimethylamidoborane(2-iso-propyl, 4-[3',5'-di-phenylphenyl]indenyl)2η4-l,4- diphenyl-1 ,3-butadiene; dimethylamidoborane(2-n-butyl, 4-[3',5'-di-phenylphenyl]indenyl)2 η4-l ,4- diphenyl- 1 ,3-butadiene; dimethylamidoborane(2-iso-butyl, 4-[3',5'-di-phenylphenyl]indenyl)2 η4-l ,4- diphenyl-l ,3-butadiene; dimethylamidoborane(2-sec-butyl, 4-[3',5'-di-phenylphenyl]indenyl)2 η4-l ,4- diphenyl- 1 ,3 -butadiene; dimethylamidoborane(2-tert-butyl, 4- [3 ',5'-di-phenylphenyl]indenyl)2 η4- 1 ,4- diphenyl- 1 ,3-butadiene; dimethylamidoborane(2-methyl, 4-[3',5'-di-tbutylphenyl]indenyl)2 zirconium dimethyl; dimethylamidoborane(2-ethyl, 4-[3',5'-di-tbutylphenyl]indenyl)2zirconium dimethyl; dimethylamidoborane(2-n-propyl, 4-[3',5'-di-tbutylphenyl]indenyl)2zirconium dimethyl; dimethylamidoborane(2-iso-propyl, 4-[3',5'-di-tbutylphenyl]indenyl)2zirconium dimethyl; dimethylamidoborane(2-n-butyl, 4-[3',5'-di-tbutylphenyl]indenyl)2zirconium dimethyl; dimethylamidoborane(2-iso-butyl, 4-[3',5'-di-tbutylphenyl]indenyl)2zirconium dimethyl; dimethylamidoborane(2-sec-butyl, 4-[3',5'-di-tbutylphenyl]indenyl)2zirconium dimethyl; dimethylamidoborane(2-tert-butyl, 4-[3',5'-di-tbutylphenyl]indenyl)2zirconium dimethyl; dimethylamidoborane(2-ethyl, 4-[3',5'-bis- trifluoromethylphenyl]indenyl)2zirconium dimethyl; dimethylamidoborane(2-n-propyl, 4- [3 ', 5 '-bis- trifluoromethylphenyl]indenyl)2zirconium dimethyl; dimethylamidoborane(2-iso-propyl, 4-[3',5'-bis- trifluoromethylphenyl]indenyl)2zirconium dimethyl; dimethylamidoborane(2-n-butyl, 4-[3',5'-bis- trifluoromethylphenyl]indenyl)2zirconium dimethyl; dimethylamidoborane(2-iso-butyl, 4-[3',5'-bis- trifluoromethylphenyl]indenyl)2zirconium dimethyl; dimethylamidoborane(2-sec-butyl, 4- [3 ', 5 '-bis- trifluoromethylphenyl]indenyl)2zirconium dimethyl; dimethylamidoborane(2-tert-butyl, 4-[3',5'-bis- trifluoromethylphenyl]indenyl)2zirconium dimethyl; dimethylamidoborane(2-ethyl, 4-[3',5'-di-iso-propylphenyl]indenyl)2zirconium dimethyl; dimethylamidoborane(2-n-propyl, 4-[3',5'-di-iso-propylphenyl]indenyl)2zirconium dimethyl dimethylamidoborane(2-iso-propyl, 4-[3',5'-di-iso- propylphenyl]indenyl)2zirconium dimethyl; dimethylamidoborane(2-n-butyl, 4-[3',5'-di-iso-propylphenyl]indenyl)2zirconium dimethyl; dimethy lamidoborane(2-iso-butyl, 4- [3 ', 5 '-di-iso-propylpheny 1] indenyl)2zirconium dimethyl; dimethylamidoborane(2-sec-butyl, 4-[3',5'-di-iso- propylphenyl]indenyl)2zirconium dimethyl; dimethylamidoborane(2 -tert-butyl, 4-[3',5'-di-iso- propylphenyl]indenyl)2zirconium dimethyl; dimethylamidoborane(2 -methyl, 4-[3',5'-di-phenylphenyl]indenyl)2zirconium dimethyl; dimethylamidoborane(2-ethyl, 4-[3',5'-di-phenylphenyl]indenyl)2zirconium dimethyl; dimethylamidoborane(2-n-propyl, 4- [3 ',5'-di-phenylphenyl]indenyl)2zirconium dimethyl; dimethylamidoborane(2-iso-propyl, 4-[3',5'-di-phenylphenyl]indenyl)2zirconium dimethyl; dimemylamidoborane(2-n-butyl, 4-[3',5'-di-phenylphenyl]indenyl)2zirconium dimethyl; dimethylamidoborane(2-iso-butyl, 4-[3',5'-di-phenylphenyl]indenyl)2zirconium dimethyl; dimethylamidoborane(2-sec-butyl, 4-[3',5'-di-phenylphenyl]indenyl)2zirconium dimethyl; dimethy lamidoborane(2-tert-butyl, 4- [3 ',5,-di-phenylphenyl]indenyl)2zirconium dimethyl; diisoρropylamidoborane(2-methyl, 4-[3',5'-di-tbutylphenyl]indenyl)2zirconium dichloride; diisopropylamidoborane(2-ethyl, 4-[3',5'-di-tbutylphenyl]indenyl)2zirconium dichloride; diisopropylamidoborane(2-n-propyl, 4- [3 ', 5 '-di-tbutylphenyl] indenyl)2zirconium dichloride; diisopropylamidoborane(2-iso-propyl, 4-[3',5'-di-tbutylphenyl]indenyl)2zirconium dichloride; diisopropylamidoborane(2 -n-butyl, 4-[3',5'-di-tbutylphenyl]indenyl)2zirconium dichloride; diisopropylamidoborane(2-iso-butyl, 4-[3',5'-di-tbutylphenyl]indenyl)2zirconium dichloride; diisopropylamidoborane(2-sec-butyl, 4-[3',5'-di-tbutylphenyl]indenyl)2zirconium dichloride; diisopropylamidoborane(2-tert-butyl, 4-[3',5'-di-tbutylphenyl]indenyl)2zirconium dichloride; diisopropylamidoborane(2-ethyl, 4-[3',5'-bis- trifluoromethylphenyl]indenyl)2zirconium dichloride; diisopropylamidoborane(2-n-propyl, 4-[3',5'-bis- trifluoromethylphenyl]indenyl)2zirconium dichloride; diisopropylamidoborane(2-iso-propyl, 4-[3',5'-bis- frifluoromethylphenyl]indenyl)2zirconium dichloride; diisoproρylamidoborane(2-n-butyl, 4-[3',5'-bis- trifluoromethylphenyl]indenyl)2zirconium dichloride; diisopropylamidoborane(2-iso-butyl, 4-[3',5'-bis- trifluoromethylphenyl]indenyl)2zirconium dichloride; diisopropylamidoborane(2-sec-butyl, 4-[3 ',5'-bis- trifluoromethylphenyl]indenyl)2zircorrium dichloride; diisopropylamidoborane(2-tert-butyl, 4-[3',5'-bis- trifluoromethylphenyl]indenyl)2zirconium dichloride; diisopropylamidoborane(2-ethyl, 4-[3',5'-di-iso-propylphenyl]indenyl)2zirconium dichloride; diisopropylamidoborane(2-n-propyl, 4-[3',5'-di-iso- propylphenyl]indenyl)2zirconium< dichloride diisopropylamidoborane(2-iso-propyl, 4- [3 ', 5 '-di-iso- propylphenyl]indenyl)2zirconium dichloride; diisopropylamidoborane(2-n-butyl, 4-[3',5'-di-iso- propylphenyl]indenyl)2zirconium dichloride; diisopropylamidoborane(2-iso-butyl, 4-[3',5'-di-iso- propylphenyl]indenyl)2zirconium dichloride; diisopropylamidoborane(2-sec-butyl, 4-[3',5'-di-iso- propylphenyl]indenyl)2zirconium dichloride; diisopropylamidoborane(2-tert-butyl, 4-[3 ',5'-di-iso- propylphenyl]indenyl)2zirconium dichloride; diisopropylamidoborane(2-methyl, 4-[3',5'-di-phenylphenyI]indenyl)2zirconium dichloride; diisopropylamidoborane(2-ethyl, 4-[3',5'-di-phenylphenyl]indenyl)2zirconium dichloride; diisopropylamidoborane(2-n-propyl, 4-[3',5'-di-phenylphenyl]indenyl)2zirconium dichloride; diisopropylamidoborane(2-iso-propyl, 4-[3',5'-di- phenylphenyl]indenyl)2zirconium dichloride; diisopropylamidoborane(2-n-butyl, 4-[3',5'-di-phenylphenyl]indenyl)2zirconium dichloride; diisopropylamidoborane(2-iso-butyl, 4-[3',5'-di-phenylphenyl]indenyl)2zirconium dichloride; diisopropylamidoborane(2-sec-butyl, 4-[3',5'-di-phenylphenyl]indenyl)2zirconium dichloride; diisopropylamidoborane(2-tert-butyl, 4-[3',5'-di-phenylphenyl]indenyl)2zirconium dichloride; diisopropylamidoborane(2-methyl, 4-[3',5'-di-tbutylphenyl]indenyl)2 η4-l ,4- diphenyl- 1 ,3-butadiene; diisopropylamidoborane(2-ethyl, 4-[3',5'-di-tbutylphenyl]indenyl)2η4-l,4- diphenyl-1 ,3-butadiene; diisopropylamidoborane(2-n-propyl, 4- [3 ', 5 '-di-tbutylphenyl]indenyl)2 η 4- 1 ,4- diphenyl- 1 ,3-butadiene; diisopropylamidoborane(2-iso-propyl, 4-[3',5'-di-tbutylphenyl]indenyl)2 η4- 1 ,4- diphenyl- 1 ,3-butadiene; diisopropylamidoborane(2-n-butyl, 4-[3',5'-di-tbutylphenyl]indenyl)2η4-l,4- diphenyl- 1 ,3-butadiene; diisopropylamidoborane(2-iso-butyl, 4-[3',5'-di-tbutylphenyl]indenyl)2η4-l,4- diphenyl-1 ,3-butadiene; diisopropylamidoborane(2-sec-butyl, 4-[3',5'-di-tbutylphenyl]indenyl)2η4-l,4~ diphenyl-l,3-butadiene; diisopropylamidoborane(2-tert-butyl, 4-[3',5'-di-tbutylphenyl]indenyl)2η4-l,4- diphenyl- 1 ,3 -butadiene; diisopropylamidoborane(2-ethyl, 4-[3',5'-bis-trifluoromethylphenyl]indenyl)2η4- 1 ,4-diphenyl- 1 ,3-butadiene; diisopropylamidoborane(2-n-propyl, 4-[3',5'-bis-trifluoromethylphenyl]indenyl)2 η4- 1 ,4-diphenyl- 1 ,3 -butadiene; diisopropylamidoborane(2-iso-propyl, 4-[3',5'-bis- trifluoromethylphenyl]indenyl)2 η4- 1 ,4-diphenyl- 1 ,3-butadiene; diisopropylamidoborane(2-n-butyl, 4-[3',5'-bis-trifluoromethylphenyl]indenyl)2η4- 1 ,4-diphenyl- 1 ,3 -butadiene; diisopropylamidoborane(2-iso-butyl, 4-[3',5'-bis-trifluoromethylphenyl]indenyl)2 η4- 1 ,4-diphenyl- 1 ,3-butadiene; diisopropylamidoborane(2-sec-butyl, 4-[3',5'~bis-trifluoromethylphenyl]indenyl)2 η4- 1 ,4-diphenyl- 1 ,3-butadiene; diisopropylamidoborane(2-tert-butyl, 4-[3',5'-bis-trifluoromethylphenyl]indenyl)2 η4- 1 ,4-diphenyl-l ,3-butadiene; diisopropylamidoborane(2-ethyl, 4-[3',5'-di-iso-propylphenyl]indenyl)2 η4-l ,4- diphenyl- 1 ,3-butadiene; diisopropylamidoborane(2-n-propyl, 4-[3',5'-di-iso-propylphenyl]indenyl)2 η4-l,4- diphenyl-1 ,3-butadiene; diisopropylamidoborane(2~iso-propyl, 4-[3',5'-di-iso-propylphenyl]indenyl) η4- 1 ,4-diphenyl-l ,3-butadiene; diisopropylamidoborane(2-n-butyl, 4-[3',5'-di-iso-propylphenyl]indenyl)2 η4-l ,4- diphenyl- 1 ,3-butadiene; diisopropylamidoborane(2-iso-butyl, 4-[3',5'-di-iso-propylphenyl]indenyl)2 η4-l ,4- diphenyl- 1 ,3 -butadiene; diisopropylamidoborane(2-sec-butyl, 4-[3',5'-di-iso-propylphenyl]indenyl)2 η4-l ,4- diphenyl-l ,3-butadiene; diisopropylamidoborane(2-tert-butyl, 4-[3',5'-di-iso-propylphenyl]indenyl)2 η -l ,4- diphenyl- 1 ,3 -butadiene; diisopropylamidoborane(2-methyl, 4-[3',5'-di-phenylphenyl]indenyl)2η4-l,4- diphenyl-1 ,3-butadiene; diisopropylamidoborane(2-ethyl, 4-[3',5'-di-phenylphenyl]indenyl)2 η4- 1 ,4- diphenyl- 1 ,3 -butadiene; diisopropylamidoborane(2-n-propyl, 4-[3',5'-di-phenylphenyl]indenyl)2η4-l,4- diphenyl-1 ,3-butadiene; diisopropylamidoborane(2-iso-propyl, 4-[3',5'-di-phenylphenyl]indenyl)2 η4-l ,4- diphenyl-l ,3-butadiene; diisopropylamidoborane(2-n-butyl, 4-[3',5'-di-phenylphenyl]indenyl)2 η4-l ,4- diphenyl-l ,3-butadiene; diisopropylamidoborane(2-iso-butyl, 4-[3',5'-di-phenylphenyl]indenyl)2 η4-l ,4- diphenyl- 1 ,3 -butadiene ; diisopropylamidoborane(2-sec-butyl, 4-[3',5'-di-phenylphenyl]indenyl)2 η4-l ,4- diphenyl- 1 ,3 -butadiene ; diisopropylamidoborane(2-tert-butyl, 4-[3',5'-di-phenylphenyl]indenyl)2 η4-l ,4- diphenyl-l ,3-butadiene; diisopropylamidoborane(2-methyl, 4-[3',5'-di-tbutylphenyl]indenyl)2zirconium dimethyl; diisopropylamidoborane(2-ethyl, 4-[3',5'-di-tbutylphenyl]indenyl)2zirconium dimethyl; diisopropylamidoborane(2-n-propyl, 4-[3',5'-di-tbutylphenyl]indenyl)2zirconium dimethyl; diisopropylamidoborane(2-iso-propyl, 4-[3',5'-di-tbutylphenyl]indenyl)2zirconium dimethyl; diisopropylamidoborane(2-n-butyl, 4-[3',5'-di-tbutylphenyl]indenyl)2zirconium dimethyl; diisopropylamidoborane(2-iso-butyl, 4-[3',5'-di-tbutylphenyl]indenyl)2zirconium dimethyl; diisopropylamidoborane(2-sec-butyl, 4-[3',5'-di-tbutylphenyl]indenyl)2zirconium dimethyl; diisopropylamidoborane(2-tert-butyl, 4-[3',5'-di-tbutylphenyl]indenyl)2zirconium dimethyl; diisopropylamidoborane(2-ethyl, 4-[3',5'-bis- trifluoromethylphenyl]indenyl)2zirconium dimethyl; diisopropylamidoborane(2-n-propyl, 4-[3',5'-bis- trifluoromethylphenyl]indenyl)2zirconium dimethyl; diisopropylamidoborane(2-iso-propyl, 4-[3',5'-bis- frifluoromethylphenyl]indenyl)2zirconium dimethyl; diisopropylamidoborane(2-n-butyl, 4-[3',5'-bis- trifluoromethylphenyl]indenyl)2zirconium dimethyl; diisopropylamidoborane(2-iso-butyl, 4-[3',5'-bis- trifluoromethylphenyl]indenyl)2zirconium dimethyl; diisopropylamidoborane(2-sec-butyl, 4-[3',5'-bis- trifluoromethylphenyl]indenyl)2zirconium dimethyl; diisopropylamidoborane(2-tert-butyl, 4- [3 ' ,5 '-bis- trifluoromethylphenyl]indenyl)2zirconium dimethyl; diisopropylamidoborane(2-ethyl, 4-[3',5'-di-iso-propylphenyl]indenyl)2zirconium dimethyl; diisopropylamidoborane(2-n-propyl, 4-[3',5'-di-iso- propylphenyl]indenyl)2zirconium dimethyl diisopropylamidoborane(2-iso-propyl, 4-[3',5'-di-iso- propylphenyl]indenyl)2zirconium dimethyl; diisopropylamidoborane(2-n-butyl, 4-[3',5'-di-iso- propylphenyl] indeny l)2zirconium dimethyl; diisopropylamidoborane(2-iso-butyl, 4-[3',5'-di-iso- propylphenyl]indenyl)2zirconium dimethyl; diisopropylamidoborane(2-sec-butyl, 4- [3 ' ,5 '-di-iso- propylphenyl]indenyl)2zirconium dimethyl; diisopropylamidoborane(2-tert-butyl, 4-[3',5'-di-iso- propylphenyl]indenyl)2zirconium dimethyl; diisopropylamidoborane(2-methyl, 4-[3',5'-di-phenylphenyl]indenyl)2zirconium dimethyl; diisopropylamidoborane(2-ethyl, 4-[3',5'-di-phenylphenyl]indenyl)2zirconium dimethyl; diisopropylamidoborane(2-n-propyl, 4-[3',5'-di-phenylphenyl]indenyl)2zirconium dimethyl; diisopropylamidoborane(2-iso-propyl, 4-[3',5'-di- phenylphenyl]indenyl)2zirconium dimethyl; diisopropylamidoborane(2-n-butyl, 4-[3',5'-di-phenylphenyl]indenyl)2zirconium dimethyl; diisopropylamidoborane(2-iso-butyl, 4-[3',5'-di-phenylphenyl]indenyl)2zirconium dimethyl; diisopropylamidoborane(2-sec-butyl, 4-[3',5'-di-ρhenylphenyl]indenyI)2zirconium dimethyl; diisopropylamidoborane(2-tert-butyl, 4-[3',5'-di-phenylphenyl]indenyl)2zirconium dimethyl; bis(trimethylsilyl)amidoborane(2-methyl, 4-[3',5'-di- tbuty_pheny_]indenyl)2zirconium dichloride; bis(trimethylsilyl)amidoborane(2-ethyl, 4-[3',5'-di- tbutylphenyl]indenyl)2zirconium dichloride; bis(trimethylsilyl)amidoborane(2-n-propyl, 4-[3',5'-di- tbutylphenyl]indenyl)2zirconium dichloride; bis(trimethylsilyl)amidoborane(2-iso-propyl, 4-[3 ',5'-di- tbutylphenyl]indenyl)2zirconium dichloride; bis(trimethylsilyl)amidoborane(2-n-butyl, 4- [3 ', 5'-di- tbutylphenyl]indenyl)2zirconium dichloride; bis(trimethylsilyl)amidoborane(2-iso-butyl, 4-[3 ',5'-di- tbutylphenyl]indenyl)2zirconium dichloride; bis(trimethylsilyl)amidoborane(2-sec-butyl, 4-[3',5'-di- tbutylphenyl]indenyl)2zirconium dichloride; bis(trimethylsilyl)amidoborane(2-tert-butyl, 4-[3',5'-di- tbutylphenyl]indenyl)2zirconium dichloride; bis(trimethylsilyl)amidoborane(2-ethyl, 4-[3',5'-bis- trifluoromethylphenyl]indenyl)2zirconium dichloride; bis(trimethylsilyl)amidoborane(2-n-propyl, 4- [3 ' ,5 '-bis- trifluoromethylphenyl]indenyl)2zirconium dichloride; bis(trimethylsilyl)amidoborane(2-iso-propyl, 4-[3',5'-bis- trifluoromethylphenyl]indenyl)2zirconium dichloride; bis(trime ylsilyl)amidoborane(2-n-butyl, 4-[3',5'-bis- trifluoromethylphenyl]indenyl)2zirconium dichloride; bis(trimethylsilyl)amidoborane(2-iso-butyl, 4-[3',5'-bis- trifluoromethylphenyl]indenyl)2zirconium dichloride; bis(trimethylsilyl)amidoborane(2-sec-butyl, 4-[3',5'-bis- trifluoromethylphenyl]indenyl)2zirconium dichloride; bis(trimethylsilyl)amidoborane(2-tert-butyl, 4-[3',5'-bis- trifluoromethylphenyl]indenyl)2zirconium dichloride; bis(trimethylsilyl)amidoborane(2-ethyl, 4-[3',5'-di-iso- propylphenyl]indenyl)2zirconium dichloride; bis(trimethylsilyl)amidoborane(2-n-propyl, 4-[3',5'-di-iso- propylphenyl]indenyl)2zirconium dichloride bis(trimethylsilyl)amidoborane(2-iso-propyl, 4-[3',5'-di-iso- propylphenyl]indenyl)2zirconium dichloride; bis(trimethylsilyl)amidoborane(2-n-butyl, 4-[3',5'-di-iso- propylphenyl]indenyl)2zirconium dichloride; bis(trimethylsilyl)amidoborane(2-iso-butyl, 4- [3 ' ,5 '-di-iso- propylphenyl]indenyl)2zirconium dichloride; bis(trimethylsilyl)amidoborane(2-sec-butyl, 4-[3',5'-di-iso- propylphenyl]indenyl)2zirconium dichloride; bis(trimethylsilyl)amidoborane(2-tert-butyl, 4-[3',5'-di-iso- propylphenyl]indenyl)2zirconium dichloride; bis(trimethylsily l)amidoborane(2-methy 1, 4- [3 ', 5 '-di- phenylphenyl]indenyl)2zirconium dichloride; bis(trimethylsilyl)amidoborane(2-ethyl, 4-[3',5'-di- phenylphenyl]indenyl)2zirconium dichloride; bis(trimethylsilyl)amidoborane(2-n-propyl, 4-[3',5'-di- phenylphenyl]indenyl)2zirconium dichloride; bis(trimethylsilyl)amidoborane(2-iso-propyl, 4-[3',5'-di- phenylphenyl]indenyl)2zirconium dichloride; bis(trimethylsilyl)amidoborane(2-n-butyl, 4-[3',5'-di- phenylphenyl]indenyl)2zirconium dichloride; bis(trimethylsilyl)amidoborane(2-iso-butyl, 4-[3',5'-di- phenylphenyl]indenyl)2zirconium dichloride; bis(trimethylsilyl)amidoborane(2-sec-butyl, 4-[3',5'-di- phenylphenyl]indenyl)2zirconium dichloride; bis(trimethylsilyl)amidoborane(2-tert-butyl, 4-[3',5'-di- phenylphenyl]indenyl)2zirconium dichloride; bis(trimethylsilyl)amidoborane(2-methyl, 4-[3',5'-di-tbuty_phenyl]indenyl)2η4-l,4~ diphenyl-1 ,3-butadiene; bis(trimethylsilyl)amidoborane(2-ethyl, 4-[3',5'-di-tbutylphenyl]indenyl)2 η4- 1 ,4- diphenyl- 1 ,3-butadiene; bis(trimethylsilyl)amidoborane(2-n-propyl, 4-[3',5'-di-tbutylphenyl]indenyl)2η4- l,4-diphenyl-l,3-butadiene; bis(trimethylsilyl)amidoborane(2-iso-propyl, 4-[3',5'-di-tbutylphenyl]indenyl)2η4- l,4-diphenyl-l,3-butadiene; bis(trimethylsilyl)amidoborane(2-n-butyl, 4-[3',5'-di-tbutylphenyl]indenyl)2η4- l,4-diphenyl-l,3-butadiene; bis(trimethylsilyl)amidoborane(2-iso-butyl, 4-[3',5'-di-tbutylphenyl]indenyl)2η4-
1 ,4-diphenyl-l ,3-butadiene; bis(trimethylsilyl)amidoborane(2-sec-butyl, 4-[3',5'-di-tbutylphenyl]indenyl)2η4-
1 ,4-diphenyl- 1 ,3 -butadiene; bis(trimethylsilyl)amidoborane(2-tert-butyl, 4-[3',5'-di-tbutylphenyl]indenyl)2η4-
1 ,4-diphenyl- 1 ,3 -butadiene; bis(trimethylsilyl)amidoborane(2-ethyl, 4-[3',5'-bis- trifluoromethylphenyl]indenyl)2η -l,4-diphenyl-l,3-butadiene; bis(trimethylsilyl)amidoborane(2-n-propyl, 4-[3',5'-bis- trifluoromethylphenyl]indenyl)2η4-l,4-diphenyl-l,3-butadiene; bis(trimethylsilyl)amidoborane(2-iso-propyl, 4-[3',5'-bis- trifluoromethylphenyl]indenyl)2 η4-l ,4-diphenyl-l ,3-butadiene; bis(trimethylsilyl)amidoborane(2-n-butyl, 4-[3',5'-bis- trifluoromethy lphenyl] indenyl)2 η4- 1 ,4-diphenyl- 1 ,3 -butadiene; bis(trimethylsilyl)amidoborane(2-iso-butyl, 4-[3',5'-bis- trifluoromethylphenyl]indenyl)2 η4-l ,4-diphenyl-l ,3-butadiene; bis(trimethylsilyl)amidoborane(2-sec-butyl, 4-[3',5'-bis- trifluoromethylphenyl]indenyl)2η4-l,4-diphenyl-l,3-butadiene; bis(trimethylsilyl)amidoborane(2-tert-butyl, 4-[3',5'-bis- trifluoromethylphenyl]indenyl)2 η4-l ,4-diphenyl-l ,3-butadiene; bis(trimethylsilyl)amidoborane(2-ethyl, 4-[3',5'-di-iso-propylphenyl]indenyl)2η4-
1 ,4-diphenyl- 1 ,3 -butadiene; bis(trimethylsilyl)amidoborane(2-n-propyl, 4-[3',5'-di-iso-propylphenyl]indenyl)2 η4- 1 ,4-diphenyl-l ,3-butadiene; bis(trimethylsilyl)amidoborane(2-iso-propyl, 4-[3',5'-di-iso-propylphenyl]indenyl) η4- 1 ,4-diphenyl- 1 ,3-butadiene; bis(trimethylsilyl)amidoborane(2-n-butyl, 4-[3',5'-di-iso-propylphenyl]indenyl)2 η4- 1 ,4-diphenyl- 1 ,3-butadiene; bis(trimethylsilyl)amidoborane(2-iso-butyl, 4-[3',5'-di-iso-propylphenyl]indenyl)2 η4- 1 ,4-diphenyl- 1 ,3-butadiene; bis(trimethylsilyl)amidoborane(2-sec-butyl, 4-[3',5'-di-iso-propylphenyl]indenyl)2 η4- 1 ,4-diphenyl-l ,3-butadiene; bis(trimethylsilyl)amidoborane(2-tert-butyl, 4-[3',5'-di-iso-propylphenyl]indenyl)2 η4- 1 ,4-diphenyl- 1 ,3-butadiene; bis(trimethylsilyl)amidoborane(2-methyl, 4-[3',5'-di-phenylphenyl]indenyl)2η4-
1 ,4-diphenyl- 1 ,3-butadiene; bis(trimethylsilyl)amidoborane(2-ethyl, 4-[3',5'-di-phenylphenyl]indenyl)2η4-l,4- diphenyl-1 ,3-butadiene; bis(trimethylsilyl)amidoborane(2-n-propyl, 4-[3',5'-di-phenylphenyl]indenyl)2η4- l,4-diphenyl-l,3-butadiene; bis(trimethylsilyl)amidoborane(2-iso-propyl, 4-[3',5'-di-phenylphenyl]indenyl)2 η4-l,4-diphenyl-l,3-butadiene; bis(trimethylsilyl)amidoborane(2-n-butyl, 4-[3',5'-di-phenylphenyl]indenyl)2 η4-
1 ,4-diphenyl- 1 ,3-butadiene; bis(trimethylsilyl)amidoborane(2-iso-butyl, 4-[3',5'-di-phenylphenyl]indenyl)2η4-
1 ,4-diphenyl- 1 ,3-butadiene; bis(trimethylsilyl)amidoborane(2-sec-butyl, 4-[3',5'-di-phenylphenyl]indenyl)2η4-
1 ,4-diphenyl-l ,3-butadiene; bis(trimethylsilyl)amidoborane(2-tert-butyl, 4-[3',5'-di-phenylphenyl]indenyl)2η4-
1 ,4-diphenyl- 1 ,3-butadiene; bis(trimethylsilyl)amidoborane(2-methyl, 4-[3',5'-di- tbutylphenyl]indenyl)2zirconium dimethyl; bis(trimethylsilyl)amidoborane(2-ethyl, 4- [3 ', 5 '-di- tbutylphenyl]indenyl)2zirconium dimethyl; bis(trimethylsily l)amidoborane(2-n-propyl, 4- [3 ',5 '-di- tbutylphenyl]indenyl)2zirconium dimethyl; bis(trimethylsilyl)amidoborane(2-iso-propyl, 4-[3',5'-di- tbutylphenyl]indenyl)2zirconium dimethyl; bis(trimethylsilyl)amidoborane(2-n-butyl, 4-[3',5'-di- tbutylphenyl]indenyl)2zirconium dimethyl; bis(trimethylsilyl)amidoborane(2-iso-butyl, 4-[3',5'-di- tbutylphenyl]indenyl)2zirconium dimethyl; bis(trimethylsilyl)amidoborane(2-sec-butyl, 4-[3',5'-di- tbutylphenyl]indenyl)2zirconium dimethyl; bis(trimethylsilyl)amidoborane(2-tert-butyl, 4-[3',5'-di- tbutylphenyl]indenyl)2zirconium dimethyl; bis(trimethylsilyl)amidoborane(2-ethyl, 4-[3',5'-bis- trifluoromethylphenyl]indenyl)2zirconium dimetliyl; bis(trimethylsilyl)amidoborane(2-n-propyl, 4-[3',5'-bis- trifluoromethylphenyl]indenyl)2zirconium dimethyl; bis(trimethylsilyl)amidoborane(2-iso-propyl, 4-[3',5'-bis- trifluoromethylphenyl]indenyl)2zirconium dimethyl; bis(trimethylsilyl)amidoborane(2-n-butyl, 4-[3',5'-bis- trifluoromethylphenyl]indenyl)2zirconium dimethyl; bis(trimethylsilyl)amidoborane(2-iso-butyl, 4-[3',5'-bis- trifluoromethylphenyl]indenyl)2zirconium dimethyl; bis(trimethylsilyl)amidoborane(2-sec-butyl, 4-[3',5'-bis- trifluoromethylphenyl]indenyl)2zirconium dimethyl; bis(trimethylsilyl)amidoborane(2-tert-butyl, 4- [3 ',5 '-bis- trifluoromethy_phenyl]indenyl)2zirconium dimethyl; bis(trimethylsilyl)amidoborane(2-ethyl, 4-[3',5'-di-iso- propylphenyl]indenyl)2zirconium dimethyl; bis(trimethylsilyl)amidoborane(2-n-propyl, 4-[3',5'-di-iso- propy lpheny 1] indeny l)2zirconium dimethyl bis(trimethylsilyl)amidoborane(2-iso-propyl, 4-[3',5'-di-iso- propylphenyl] indeny ^zirconium dimethyl; bis(trimethylsilyl)amidoborane(2-n-butyl, 4-[3',5'-di-iso- propylphenyl] indeny l)2zirconium dimethyl; bis(trimethylsilyl)amidoborane(2-iso-butyl, 4-[3',5'-di-iso- propylphenyl]indenyl)2zirconium dimethyl; bis(trimethylsilyl)amidoborane(2-sec-butyl, 4-[3',5'-di-iso- propylphenyl]indenyl)2zirconium dimethyl; bis(trimethylsilyl)amidoborane(2-tert-butyl, 4-[3',5'-di-iso- propylphenyl]indenyl)2zirconium dimethyl; bis(trimethylsilyl)amidoborane(2-methyl, 4-[3',5'-di- phenylphenyl]indenyl)2zirconium dimethyl; bis(frimethylsilyl)amidoborane(2-ethyl, 4-[3',5'-di- phenylphenyl]indenyl)2zirconium dimethyl; bis(trimethylsilyl)amidoborane(2-n-propyl, 4-[3',5'-di- phenylphenyl]indenyl)2zirconium dimethyl; bis(trimethylsilyl)amidoborane(2-iso-propyl, 4-[3',5'-di- phenylphenyl]indenyl)2zirconium dimethyl; bis(trimethylsilyl)amidoborane(2-n-butyl, 4-[3',5'-di- phenylphenyl]indenyl)2zirconium dimethyl; bis(trimethylsilyl)amidoborane(2-iso-butyl, 4-[3',5'-di- phenylphenyl]indenyl)2zirconium dimethyl; bis(trimethylsilyl)amidoborane(2-sec-butyl, 4-[3',5'-di- phenylρhenyl]indenyl)2zirconium dimethyl; and bis(trimethylsilyl)amidoborane(2-tert-butyl, 4-[3',5'-di- phenylphenyl]indenyl)2zirconium dimethyl.
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Cited By (84)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005061565A1 (en) * 2003-12-17 2005-07-07 Exxonmobil Chemical Patents Inc. Radiation tolerant copolymers
WO2006025917A2 (en) * 2004-06-21 2006-03-09 Exxonmobil Chemical Patents Inc. Polymerization process
WO2006025949A2 (en) * 2004-07-08 2006-03-09 Exxonmobil Chemical Patents Inc. Polymer production at supercritical conditions
EP1674504A1 (en) * 2004-12-22 2006-06-28 Total Petrochemicals Research Feluy Geo-membrane applications
US7087690B2 (en) 2000-11-07 2006-08-08 Symyx Technologies, Inc. Substituted pyridyl amine catalysts and processes for polymerizing crystalline polymers
WO2008076589A1 (en) 2006-12-20 2008-06-26 Exxonmobil Chemical Patents Inc. Phase separator and monomer recycle for supercritical polymerization process
WO2008079483A1 (en) 2006-12-22 2008-07-03 Exxonmobil Chemical Patents Inc. Process of making polymer blends
WO2008079509A1 (en) 2006-12-22 2008-07-03 Exxonmobil Chemical Patents Inc. Process of making polymer blends
WO2008079565A1 (en) * 2006-12-20 2008-07-03 Exxonmobil Chemical Patents Inc. Polymer production at supercritical conditions
WO2008109212A1 (en) * 2007-03-06 2008-09-12 Exxonmobil Chemical Patents Inc. Polymer production under supersolution conditions
US7449530B2 (en) 2004-06-21 2008-11-11 Exxonmobil Chemical Patents Inc. Polymerization process
WO2008150572A1 (en) * 2007-06-04 2008-12-11 Exxonmobil Chemical Patents Inc. Super-solution homogeneous propylene polymerization
WO2009035580A1 (en) 2007-09-13 2009-03-19 Exxonmobil Research And Engineering Company In-line process for producing plasticized polymers and plasticized polymer blends
EP2070953A1 (en) * 2007-12-11 2009-06-17 Total Petrochemicals Research Feluy Activating supports based on phosphonium complexes
WO2009123663A1 (en) 2007-12-20 2009-10-08 Exxonmobil Chemical Patents Inc. Isotactic polypropylene produced from supercritical polymerization process
WO2010014344A2 (en) 2008-08-01 2010-02-04 Exxonmobil Chemical Patents Inc. Catalyst system and process for olefin polymerization
US7799841B2 (en) 2006-08-25 2010-09-21 Borealis Technology Oy Polypropylene foam
EP2231727A1 (en) * 2007-12-20 2010-09-29 ExxonMobil Research and Engineering Company Bulk homogeneous polymerization process for ethylene propylene copolymers
US7872086B2 (en) 2008-01-17 2011-01-18 Tonen Chemical Corporation Polymeric material and its manufacture and use
WO2011019474A2 (en) 2009-08-14 2011-02-17 Exxonmobil Chemical Patents Inc. Catalyst system, process for olefin polymerization, and polymer compositions produced therefrom
US7914899B2 (en) 2006-07-10 2011-03-29 Borealis Technology Oy Electrical insulation film
US7915367B2 (en) 2006-12-28 2011-03-29 Borealis Technology Oy Process for the manufacture of branched polypropylene
WO2011071900A2 (en) 2009-12-07 2011-06-16 Univation Technologies, Llc Methods for reducing static charge of a catalyst and methods for using the catalyst to produce polyolefins
WO2011103402A1 (en) 2010-02-22 2011-08-25 Univation Technologies, Llc Catalyst systems and methods for using same to produce polyolefin products
WO2011103280A1 (en) 2010-02-18 2011-08-25 Univation Technologies, Llc Methods for operating a polymerization reactor
EP2368896A1 (en) 2010-03-01 2011-09-28 ExxonMobil Chemical Patents Inc. Mono-indenyl transition metal compounds and polymerization therewith
WO2011129956A1 (en) 2010-04-13 2011-10-20 Univation Technologies, Llc Polymer blends and films made therefrom
WO2012009216A1 (en) 2010-07-16 2012-01-19 Univation Technologies, Llc Systems and methods for measuring particle accumulation on reactor surfaces
WO2012009215A1 (en) 2010-07-16 2012-01-19 Univation Technologies, Llc Systems and methods for measuring static charge on particulates
WO2012015898A1 (en) 2010-07-28 2012-02-02 Univation Technologies, Llc Systems and methods for measuring velocity of a particle/fluid mixture
US8142902B2 (en) 2006-08-25 2012-03-27 Borealis Technology Oy Extrusion coated substrate
EP2450403A1 (en) * 2007-12-20 2012-05-09 ExxonMobil Research and Engineering Company Polypropylene ethylene-propylene copolymer blends and in-line process to produce them
WO2012074709A1 (en) 2010-11-30 2012-06-07 Univation Technologies, Llc Processes for the polymerization of olefins with extracted metal carboxylate salts
WO2012074710A1 (en) 2010-11-30 2012-06-07 Univation Technologies, Llc. Catalyst composition having improved flow characteristics and methods of making and using the same
WO2012082674A1 (en) 2010-12-17 2012-06-21 Univation Technologies, Llc Systems and methods for recovering hydrocarbons from a polyolefin purge gas product
WO2012088235A2 (en) 2010-12-21 2012-06-28 Dow Global Technologies Llc Olefin-based polymers and dispersion polymerizations
WO2012087560A1 (en) 2010-12-22 2012-06-28 Univation Technologies, Llc Additive for polyolefin polymerization processes
US8247052B2 (en) 2006-09-25 2012-08-21 Borealis Technology Oy Coaxial cable
WO2012158260A1 (en) 2011-05-13 2012-11-22 Univation Technologies, Llc Spray-dried catalyst compositions and polymerization processes employing the same
US8378047B2 (en) 2006-07-10 2013-02-19 Borealis Technology Oy Biaxially oriented polypropylene film
WO2013028283A1 (en) 2011-08-19 2013-02-28 Univation Technologies, Llc Catalyst systems and methods for using same to produce polyolefin products
WO2013070601A2 (en) 2011-11-08 2013-05-16 Univation Technologies, Llc Methods of preparing a catalyst system
WO2013070602A1 (en) 2011-11-08 2013-05-16 Univation Technologies, Llc Methods for producing polyolefins with catalyst systems
US8598287B2 (en) 2007-10-22 2013-12-03 Univation Technologies, Llc Metallocene catalysts and their use in polymerization processes
WO2014106143A1 (en) 2012-12-28 2014-07-03 Univation Technologies, Llc Supported catalyst with improved flowability
WO2014120494A1 (en) 2013-01-30 2014-08-07 Univation Technologies, Llc Processes for making catalyst compositions having improved flow
WO2014123598A1 (en) 2013-02-07 2014-08-14 Univation Technologies, Llc Preparation of polyolefin
US8814862B2 (en) 2005-05-12 2014-08-26 Innovatech, Llc Electrosurgical electrode and method of manufacturing same
WO2014143421A1 (en) 2013-03-15 2014-09-18 Univation Technologies, Llc Tridentate nitrogen based ligands for olefin polymerisation catalysts
WO2014149361A1 (en) 2013-03-15 2014-09-25 Univation Technologies, Llc Ligands for catalysts
WO2014197169A1 (en) 2013-06-05 2014-12-11 Univation Technologies, Llc Protecting phenol groups
WO2015153082A1 (en) 2014-04-02 2015-10-08 Univation Technologies, Llc Continuity compositions and methods of making and using the same
WO2016028278A1 (en) 2014-08-19 2016-02-25 Univation Technologies, Llc Fluorinated catalyst supports and catalyst systems
WO2016028277A1 (en) 2014-08-19 2016-02-25 Univation Technologies, Llc Fluorinated catalyst supports and catalyst systems
WO2016028276A1 (en) 2014-08-19 2016-02-25 Univation Technologies, Llc Fluorinated catalyst supports and catalyst systems
WO2016118599A1 (en) 2015-01-21 2016-07-28 Univation Technologies, Llc Methods for controlling polymer chain scission
WO2016118566A1 (en) 2015-01-21 2016-07-28 Univation Technologies, Llc Methods for gel reduction in polyolefins
WO2016145179A1 (en) 2015-03-10 2016-09-15 Univation Technologies, Llc Spray dried catalyst compositions, methods for preparation and use in olefin polymerization processes
WO2016164451A1 (en) 2015-04-08 2016-10-13 Univation Technologies, Llc Closed reactor transitions between metallocene catalysts
WO2016172197A1 (en) 2015-04-20 2016-10-27 Exxonmobil Chemical Patents Inc. Multimodal and broad molecular weight high density polyethylene
WO2016176135A1 (en) 2015-04-27 2016-11-03 Univation Technologies, Llc Supported catalyst compositions having improved flow properties and preparation thereof
US9630206B2 (en) 2005-05-12 2017-04-25 Innovatech, Llc Electrosurgical electrode and method of manufacturing same
EP3309182A2 (en) 2007-11-15 2018-04-18 Univation Technologies, LLC Polymerization catalysts, methods of making; methods of using, and polyolefinproducts made therefrom
WO2018151903A1 (en) 2017-02-20 2018-08-23 Exxonmobil Chemical Patents Inc. Supported catalyst systems and processes for use thereof
WO2019027587A1 (en) 2017-08-04 2019-02-07 Exxonmobil Chemical Patents Inc. Polyethylene compositions and films prepared therefrom
WO2019162760A1 (en) 2018-02-05 2019-08-29 Exxonmobil Chemical Patents Inc. A Corporation Of State Of Delaware Enhanced processability of lldpe by addition of ultra-high molecular weight high density polyethylene
WO2019210030A1 (en) 2018-04-26 2019-10-31 Exxonmobil Chemical Patents Inc. Non-coordinating anion type activators containing cation having branched alkyl groups
WO2019246069A1 (en) 2018-06-19 2019-12-26 Exxonmobil Chemical Patents Inc. Polyethylene compositions and films prepared therefrom
WO2021119089A1 (en) 2019-12-11 2021-06-17 Exxonmobil Chemical Patents Inc. Processes for introduction of liquid activators in olefin polymerization reactions
WO2021126523A1 (en) 2019-12-19 2021-06-24 Exxonmobil Chemical Patents Inc. Production of impact copolymer polypropylene using metallocene and ziegler-natta catalysts in parallel reactors
WO2021188361A1 (en) 2020-03-20 2021-09-23 Exxonmobil Chemical Patents Inc. Linear alpha-olefin copolymers and impact copolymers thereof
WO2021194831A1 (en) 2020-03-25 2021-09-30 Exxonmobil Chemical Patents Inc. Alkylation of transition metal coordination catalyst complexes
WO2021202091A1 (en) 2020-03-30 2021-10-07 Exxonmobil Chemical Patents Inc. Comb-block copolymers and methods thereof
WO2021222280A2 (en) 2020-05-01 2021-11-04 Exxonmobil Chemical Patents Inc. Linear low density polyethylene for film applications
WO2021222016A2 (en) 2020-05-01 2021-11-04 Exxonmobil Chemical Patents Inc. Linear low density polyethylene for film applications
WO2021257264A1 (en) 2020-06-16 2021-12-23 Exxonmobil Chemical Patents Inc. Metallocene catalysts for producing vinyl-terminated polyalphaolefins and methods associated therewith
WO2021262842A1 (en) 2020-06-26 2021-12-30 Exxonmobil Chemical Patents Inc. COPOLYMERS OF ETHYLENE, α-OLEFIN, NON-CONJUGATED DIENE, AND ARYL-SUBSTITUTED CYCLOALKENE, METHODS TO PRODUCE, BLENDS, AND ARTICLES THEREFROM
WO2021262838A1 (en) 2020-06-26 2021-12-30 Exxonmobil Chemical Patents Inc. Copolymers composed of ethylene, a-olefin, non-conjugated diene, and substituted styrene and articles therefrom
WO2022035484A1 (en) 2020-08-10 2022-02-17 Exxonmobil Chemical Patents Inc. Methods for delivery of non-aromatic solutions to polymerization reactors
WO2022035585A1 (en) 2020-08-13 2022-02-17 Exxonmobil Chemical Patents Inc. Cyclic containing polymer compositions obtained using transition metal bis(phenolate) catalyst complexes and process for production thereof
WO2022076216A1 (en) 2020-10-08 2022-04-14 Exxonmobil Chemical Patents Inc. Supported catalyst systems and processes for use thereof
WO2022087121A1 (en) 2020-10-22 2022-04-28 Exxonmobil Chemical Patents Inc. Multidentate lewis base catalysts and methods for use thereof
WO2022093814A1 (en) 2020-10-28 2022-05-05 Exxonmobil Chemical Patents Inc. Non-aromatic hydrocarbon soluble olefin polymerization catalysts and use thereof
WO2022250822A1 (en) 2021-05-24 2022-12-01 Exxonmobil Chemical Patents Inc. Biphasic polymerization processes

Families Citing this family (72)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006500470A (en) * 2002-09-20 2006-01-05 エクソンモービル・ケミカル・パテンツ・インク Supercritical polymerization method and polymer produced thereby
US8008412B2 (en) * 2002-09-20 2011-08-30 Exxonmobil Chemical Patents Inc. Polymer production at supersolution conditions
US7803307B2 (en) * 2004-06-07 2010-09-28 Interplex Qlp, Inc. Ultra high-temperature plastic package and method of manufacture
WO2006019494A1 (en) * 2004-07-14 2006-02-23 Exxonmobil Chemical Patents Inc. Polymer production at supercritical conditions
KR20070087670A (en) * 2004-12-21 2007-08-28 다우 글로벌 테크놀로지스 인크. Polypropylene-based adhesive compositions
US8022142B2 (en) * 2008-12-15 2011-09-20 Exxonmobil Chemical Patents Inc. Thermoplastic olefin compositions
US7297653B2 (en) 2005-07-21 2007-11-20 Exxonmobil Chemical Patents Inc. Fluorophenylborates and their use as activators in catalyst systems for olefin polymerization
US20070031653A1 (en) * 2005-08-02 2007-02-08 Toray Plastics (America), Inc. Multi-layer barrier film structure
WO2007088204A2 (en) * 2006-02-02 2007-08-09 Basell Polyolefine Gmbh Propylene melt blown resins, propylene melt blown resin fibers and non-woven fabric made from the same, and methods of making the same
EP1881011B1 (en) * 2006-06-02 2018-12-19 Agilent Technologies, Inc. Method of preparing spheroid polymer particles having a narrow size distribution by dispersion polymerization, particles obtainable by said method and use of said particles
CN101563374B (en) * 2006-12-20 2012-09-05 埃克森美孚化学专利公司 Phase separator and monomer recycle for supercritical polymerization process
US8143352B2 (en) * 2006-12-20 2012-03-27 Exxonmobil Research And Engineering Company Process for fluid phase in-line blending of polymers
JP5060791B2 (en) * 2007-01-26 2012-10-31 独立行政法人森林総合研究所 Method for drying wood, method for penetrating chemicals into wood and drying apparatus
US20080205800A1 (en) * 2007-02-28 2008-08-28 Toray Plastics (America), Inc. Transparent biaxially oriented polypropylene film with low moisture vapor and oxygen transmission rate
US8080610B2 (en) * 2007-03-06 2011-12-20 Exxonmobil Research And Engineering Company Monomer recycle process for fluid phase in-line blending of polymers
US20080287614A1 (en) * 2007-05-15 2008-11-20 Sonoco Development, Inc. Polypropylene-Based Polymer Blend of Enhanced Melt Strength
US7745552B2 (en) * 2007-06-29 2010-06-29 Exxonmobil Research And Engineering Company Fouling prevention in polymerization reactors
EP2201042B1 (en) * 2007-09-13 2012-06-27 ExxonMobil Research and Engineering Company In-line blending of plasticizers with a base polymer
US8507628B2 (en) * 2007-10-02 2013-08-13 Fina Technology, Inc. Propylene based polymers for injection stretch blow molding
US7994237B2 (en) * 2007-12-20 2011-08-09 Exxonmobil Research And Engineering Company In-line process to produce pellet-stable polyolefins
US7528222B1 (en) 2008-01-15 2009-05-05 Exxonmobil Chemical Patents Inc. Olefin polymerization process
US8318875B2 (en) * 2008-01-18 2012-11-27 Exxonmobil Chemical Patents Inc. Super-solution homogeneous propylene polymerization and polypropylenes made therefrom
US8067512B2 (en) * 2008-04-10 2011-11-29 Exxonmobil Research And Engineering Company Monomer/solvent separation and recycle process for propylene containing polymers
US7939610B2 (en) * 2008-05-22 2011-05-10 Exxonmobil Research And Engineering Company Polymerization processes for broadened molecular weight distribution
US8802797B2 (en) 2008-06-20 2014-08-12 Exxonmobil Chemical Patents Inc. Vinyl-terminated macromonomer oligomerization
US8283419B2 (en) * 2008-06-20 2012-10-09 Exxonmobil Chemical Patents Inc. Olefin functionalization by metathesis reaction
US8399725B2 (en) * 2008-06-20 2013-03-19 Exxonmobil Chemical Patents Inc. Functionalized high vinyl terminated propylene based oligomers
US8372930B2 (en) 2008-06-20 2013-02-12 Exxonmobil Chemical Patents Inc. High vinyl terminated propylene based oligomers
US8283428B2 (en) * 2008-06-20 2012-10-09 Exxonmobil Chemical Patents Inc. Polymacromonomer and process for production thereof
US8399586B2 (en) 2008-09-05 2013-03-19 Exxonmobil Research And Engineering Company Process for feeding ethylene to polymerization reactors
CN102300883B (en) * 2009-01-29 2014-08-20 埃克森美孚化学专利公司 Polypropylene Nonwoven Fibers And Fabrics And Methods For Making Same
US9090000B2 (en) 2009-03-26 2015-07-28 Fina Technology, Inc. Injection stretch blow molded articles and random copolymers for use therein
BRPI1010093B1 (en) 2009-07-16 2019-12-10 Dow Global Technologies Llc solution polymerization process
KR101507211B1 (en) 2009-07-31 2015-03-30 헨켈 유에스 아이피 엘엘씨 Low application temperature hot melt adhesive
JP5707404B2 (en) * 2009-08-20 2015-04-30 アイキューエルピー，リミティッドライアビリティ カンパニー Ultra-high temperature plastic chip package and manufacturing method thereof
WO2011113685A1 (en) * 2010-03-17 2011-09-22 Borealis Ag Polymer composition for w&c application with advantageous electrical properties
JP5606144B2 (en) * 2010-05-12 2014-10-15 出光興産株式会社 Method for producing polyolefin
CN102464748B (en) * 2010-11-16 2013-07-03 中国石油化工股份有限公司 Propylene copolymer macromonomer and preparation method thereof
JP6457716B2 (en) 2011-01-14 2019-01-23 ダブリュー・アール・グレイス・アンド・カンパニー−コネチカット Process for the preparation of modified metallocene catalysts, catalysts produced and their use
WO2012099675A1 (en) 2011-01-19 2012-07-26 Exxonmobal Chemical Patents Inc. Method and apparatus for managing the conversion of hydrocarbons into olefins
WO2012099680A2 (en) 2011-01-19 2012-07-26 Exxonmobil Chemical Patents Inc. Method and apparatus for converting hydrocarbons into olefins
WO2012099679A1 (en) 2011-01-19 2012-07-26 Exxonmobil Chemical Patents Inc. Method and apparatus for converting hydrocarbons into olefins
WO2012099671A1 (en) 2011-01-19 2012-07-26 Exxonmobil Chemical Patent Inc. Method and apparatus for converting hydrocarbons into olefins using hydroprocessing and thermal pyrolysis
WO2012099678A1 (en) 2011-01-19 2012-07-26 Exxonmobil Chemical Patents Inc. Method and apparatus for managing for hydrogen content through the conversion of hydrocarbons into olefins
WO2012099676A2 (en) 2011-01-19 2012-07-26 Exxonmobil Chemical Patents Inc. Process and apparatus for converting hydrocarbons
US9868680B2 (en) 2011-01-19 2018-01-16 Exxonmobil Chemical Patents Inc. Method and apparatus for converting hydrocarbons into olefins
WO2012099677A2 (en) 2011-01-19 2012-07-26 Exxonmobil Chemical Patents Inc. Method and apparatus for converting hydrocarbons into olefins
KR20140107260A (en) 2011-12-19 2014-09-04 다우 글로벌 테크놀로지스 엘엘씨 Ethylene-based polymers prepared by dispersion polymerization
EP2925795B1 (en) 2012-12-03 2018-12-26 ExxonMobil Chemical Patents Inc. Propylene polymers
US9322114B2 (en) 2012-12-03 2016-04-26 Exxonmobil Chemical Patents Inc. Polypropylene fibers and fabrics
CA2798036C (en) 2012-12-05 2020-01-21 Nova Chemicals Corporation Reduction of fouling in high pressure reactors
EP2860031B1 (en) 2013-10-11 2016-03-30 Borealis AG Machine direction oriented film for labels
WO2015059229A1 (en) * 2013-10-24 2015-04-30 Borealis Ag Low melting pp homopolymer with high content of regioerrors and high molecular weight
CA2927448C (en) 2013-11-22 2017-01-17 Borealis Ag Low emission propylene homopolymer with high melt flow
EP3077426B1 (en) 2013-12-04 2022-10-05 Borealis AG Phthalate-free pp homopolymers for meltblown fibers
US10227427B2 (en) 2014-01-17 2019-03-12 Borealis Ag Process for preparing propylene/1-butene copolymers
ES2767498T3 (en) 2014-02-06 2020-06-17 Borealis Ag Transparent and smooth impact copolymers
CN105934475A (en) 2014-02-06 2016-09-07 北欧化工公司 Soft copolymers with high impact strength
WO2015147215A1 (en) 2014-03-28 2015-10-01 三井化学株式会社 ETHYLENE/α-OLEFIN COPOLYMER AND LUBRICATING OIL
EP2947118B1 (en) 2014-05-20 2017-11-29 Borealis AG Polypropylene composition for automotive interior applications
CN107889472B (en) 2015-05-11 2021-09-07 格雷斯公司 Process for preparing modified clay supported metallocene polymerization catalysts, the catalysts prepared and their use
WO2016183008A1 (en) 2015-05-11 2016-11-17 W.R. Grace & Co.-Conn. Process to produce modified clay, modified clay produced and use thereof
WO2017073153A1 (en) * 2015-10-26 2017-05-04 東洋紡株式会社 Adhesive composition and hot-melt adhesive
JP7296691B2 (en) * 2016-02-16 2023-06-23 三井化学株式会社 Transition metal compound, catalyst for olefin polymerization, and method for producing olefin polymer
KR101810317B1 (en) * 2016-04-06 2017-12-19 롯데케미칼 주식회사 High melt strength polypropylene resin composition
WO2018022263A1 (en) 2016-07-29 2018-02-01 Exxonmobil Chemical Patents Inc. Polymerization processes using high molecular weight polyhydric quenching agents
CN107125062A (en) * 2016-12-05 2017-09-05 广东乐将生物科技有限公司 A kind of novel degradable mulch film and its application method
CN109913078B (en) * 2019-03-15 2021-03-30 广东工业大学 Bio-fiber road sealing material and preparation method thereof
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CN111560091A (en) * 2020-05-29 2020-08-21 南京金陵塑胶化工有限公司 Production process of random copolymerization polypropylene
CN113484102B (en) * 2021-07-12 2022-12-06 吉林化工学院 Petroleum refining gas sampler and sampling method of carbon fiber composite material
FR3126402A1 (en) * 2021-08-31 2023-03-03 Airbus Operations IMPROVED TWO-PART BUS-BAR SUPPORT INCLUDING A CLIP BETWEEN THE TWO PARTS.

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5408017A (en) * 1987-01-30 1995-04-18 Exxon Chemical Patents Inc. High temperature polymerization process using ionic catalysts to produce polyolefins
EP0846696A1 (en) * 1996-12-09 1998-06-10 Mitsubishi Chemical Corporation Catalyst for polymerization of alpha-olefins
US6160072A (en) * 1997-05-02 2000-12-12 Ewen; John A. Process for polymerizing tactioselective polyolefins in condensed phase using titanocenes
US6218488B1 (en) * 1998-03-04 2001-04-17 Exxon Mobil Chemical Patents Inc. Polymerization process for olefin copolymers using bridged hafnocene compounds
US6225432B1 (en) * 1998-08-26 2001-05-01 Exxon Chemical Patents Inc. Branched polypropylene compositions
WO2001044318A1 (en) * 1999-12-15 2001-06-21 Basell Technology Company B.V. Metallocene compounds, process for their preparation and their use in catalytic systems for the polymerization of olefins
US6355741B1 (en) * 1999-09-10 2002-03-12 Fina Research, S.A. Process for producing polyolefins
WO2002070572A2 (en) * 2001-03-06 2002-09-12 Exxonmobil Chemical Patents Inc. Propylene polymers for films
WO2002090399A1 (en) * 2001-05-04 2002-11-14 Borealis Technology Oy Polymerization process for producing copolymers

Family Cites Families (88)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US540817A (en) * 1895-06-11 Garment-supporter
BE420895A (en) 1936-02-04 1900-01-01
US2852501A (en) 1954-10-05 1958-09-16 Monsanto Chemicals Polymerization of ethylene
US3725378A (en) 1958-12-17 1973-04-03 Monsanto Co Polymerization of ethylene
US3294772A (en) 1963-06-17 1966-12-27 Phillips Petroleum Co Supercritical polymerization
US4153774A (en) 1976-02-17 1979-05-08 Basf Aktiengesellschaft Manufacture of high pressure polyethylene
US4135044A (en) 1977-08-08 1979-01-16 Exxon Research & Engineering Co. Process for achieving high conversions in the production of polyethylene
ZA844157B (en) 1983-06-06 1986-01-29 Exxon Research Engineering Co Process and catalyst for polyolefin density and molecular weight control
US4530914A (en) 1983-06-06 1985-07-23 Exxon Research & Engineering Co. Process and catalyst for producing polyethylene having a broad molecular weight distribution
US5324800A (en) 1983-06-06 1994-06-28 Exxon Chemical Patents Inc. Process and catalyst for polyolefin density and molecular weight control
IN172494B (en) 1986-12-19 1993-09-04 Exxon Chemical Patents Inc
DE3615563A1 (en) 1986-05-09 1987-11-12 Basf Ag METHOD FOR PRODUCING COPOLYMERISATES OF ETHYLENE WITH VINYL ESTERS IN A TUBE REACTOR AT PRESSURES ABOVE 500 BAR
US5084534A (en) 1987-06-04 1992-01-28 Exxon Chemical Patents, Inc. High pressure, high temperature polymerization of ethylene
DE3743321A1 (en) 1987-12-21 1989-06-29 Hoechst Ag 1-OLEFIN POLYMER WAX AND METHOD FOR THE PRODUCTION THEREOF
US5382631A (en) 1988-09-30 1995-01-17 Exxon Chemical Patents Inc. Linear ethylene interpolymer blends of interpolymers having narrow molecular weight and composition distributions
US5382630A (en) 1988-09-30 1995-01-17 Exxon Chemical Patents Inc. Linear ethylene interpolymer blends of interpolymers having narrow molecular weight and composition distribution
DE3904468A1 (en) 1989-02-15 1990-08-16 Hoechst Ag POLYPROPYLENE WAX AND METHOD FOR THE PRODUCTION THEREOF
DE3929693A1 (en) 1989-09-07 1991-03-14 Hoechst Ag METHOD FOR PRODUCING A POLYOLEFIN WAX
US5026798A (en) 1989-09-13 1991-06-25 Exxon Chemical Patents Inc. Process for producing crystalline poly-α-olefins with a monocyclopentadienyl transition metal catalyst system
US5504169A (en) 1989-09-13 1996-04-02 Exxon Chemical Patents Inc. Process for producing amorphous poly-α-olefins with a monocyclopentadienyl transition metal catalyst system
US5324799A (en) 1990-03-06 1994-06-28 Akihiro Yano Polyethylene and process of production thereof
PL166690B1 (en) 1990-06-04 1995-06-30 Exxon Chemical Patents Inc Method of obtaining polymers of olefins
US5272236A (en) 1991-10-15 1993-12-21 The Dow Chemical Company Elastic substantially linear olefin polymers
DE4030379A1 (en) 1990-09-26 1992-04-02 Basf Ag POLYMER WAXES OF PROPYLENE WITH HIGH HARDNESS AND CRYSTAL INITY
FI89929C (en) 1990-12-28 1993-12-10 Neste Oy Process for homo- or copolymerization of ethylene
FI86867C (en) 1990-12-28 1992-10-26 Neste Oy FLERSTEGSPROCESS FOR FRAMSTAELLNING AV POLYETEN
GB9103527D0 (en) 1991-02-20 1991-04-10 Exxon Chemical Patents Inc Hp catalyst killer
DE4130299A1 (en) 1991-09-12 1993-03-18 Basf Ag METHOD FOR PRODUCING HIGH PRESSURE POLYPROPYLENE
GB9125934D0 (en) * 1991-12-05 1992-02-05 Exxon Chemical Patents Inc Process for polymerising olefinic feeds under pressure
TW285680B (en) 1992-03-31 1996-09-11 Hoechst Ag
ES2100388T3 (en) 1992-05-26 1997-06-16 Hoechst Ag PROCEDURE FOR PREPARING POLYOLEFIN WAXES.
TW294669B (en) 1992-06-27 1997-01-01 Hoechst Ag
TW303368B (en) 1992-08-08 1997-04-21 Hoechst Ag
US5332706A (en) 1992-12-28 1994-07-26 Mobil Oil Corporation Process and a catalyst for preventing reactor fouling
EP0812854B2 (en) 1993-06-07 2011-04-20 Mitsui Chemicals, Inc. Novel transition metal compound, olefin polymerization catalyst comprising said compound, process for olefin polymerization using said catalyst and propylene homo- and copolymer
ES2154664T3 (en) 1993-11-24 2001-04-16 Targor Gmbh METALOCENOS, PROCEDURES FOR OBTAINING, AND YOUR EMPLOYMENT AS CATALYSTS.
NO178790C (en) * 1993-12-13 1996-06-05 Borealis Holding As Process for preparing olefin polymers in an autoclave reactor
DE4406963A1 (en) 1994-03-03 1995-09-07 Basf Ag Metallocene complexes with heterofunctional groups on the cyclopentadienyl system
JPH10507212A (en) 1994-06-24 1998-07-14 エクソン・ケミカル・パテンツ・インク Polymerization method and catalyst system useful for this polymerization method
US5552489A (en) 1994-07-22 1996-09-03 Exxon Chemical Patents Inc. Tackifiers and a process to obtain tackifiers
US6300451B1 (en) 1994-10-24 2001-10-09 Exxon Chemical Patents Inc. Long-chain branched polymers and their production
US5880241A (en) 1995-01-24 1999-03-09 E. I. Du Pont De Nemours And Company Olefin polymers
JPH08208535A (en) 1995-02-03 1996-08-13 Mitsui Toatsu Chem Inc Production of alkylbenzene
FI951970A (en) 1995-04-25 1996-10-26 Borealis As Olefin polymers containing polar groups and a process for their preparation
GB2300425A (en) * 1995-05-01 1996-11-06 Kobe Steel Europ Ltd Nucleation of diamond films using an electrode
US6143682A (en) 1995-06-07 2000-11-07 Exxon Chemical Patents Inc. Bimetallocyclic transition metal catalyst systems
US5882750A (en) 1995-07-03 1999-03-16 Mobil Oil Corporation Single reactor bimodal HMW-HDPE film resin with improved bubble stability
FI954475A (en) 1995-09-21 1997-03-22 Borealis As Olefin polymers containing polar groups and processes for their preparation
FI105820B (en) * 1995-10-10 2000-10-13 Borealis Tech Oy Process for the preparation of homopolymers or copolymers of propylene
EA000521B1 (en) 1995-10-10 1999-10-28 Бореалис А/С Process for making propylene homo or copolymers
JPH11513717A (en) 1995-10-14 1999-11-24 ビーエーエスエフ アクチェンゼゲルシャフト Method for producing ethylene copolymer under high pressure
JPH09176235A (en) * 1995-12-25 1997-07-08 Mitsui Toatsu Chem Inc Method for polymerizing propylene
JPH09216916A (en) 1996-02-13 1997-08-19 Tosoh Corp Production of ethylene/alpha-olefin copolymer
FI102476B (en) 1996-05-31 1998-12-15 Borealis As New transition metal complexes and method for their preparation
US6127497A (en) 1996-06-17 2000-10-03 Exxon Chemical Patents Inc. Elevated pressure polymerization processes with late transition metal catalyst systems
ES2158567T3 (en) * 1996-06-17 2001-09-01 Exxonmobil Chem Patents Inc CATALYTIC SYSTEMS OF MIXED TRANSITION METALS FOR THE POLYMERIZATION OF OLEFINS.
JPH1045834A (en) 1996-08-07 1998-02-17 Mitsubishi Chem Corp Polymerization of propylene
ATE202365T1 (en) * 1996-08-13 2001-07-15 Basell Polyolefine Gmbh SUPPORTED CATALYST SYSTEM, METHOD FOR THE PRODUCTION THEREOF AND ITS USE FOR THE POLYMERIZATION OF OLEFINS
JP3421202B2 (en) 1996-10-09 2003-06-30 三菱化学株式会社 Propylene polymerization method and propylene polymer obtained using the same
DE19648895A1 (en) 1996-11-26 1998-05-28 Clariant Gmbh Polar modified polypropylene waxes
JP3883243B2 (en) 1997-01-22 2007-02-21 矢崎総業株式会社 Simple exchange lighting system
AU6147398A (en) 1997-02-05 1998-08-25 Penn State Research Foundation, The Metal catalyzed synthesis of hyperbranched ethylene and/or alpha-olefin polymers
CN1117104C (en) 1997-06-06 2003-08-06 出光石油化学株式会社 Olefinic polymer
FI111847B (en) 1997-06-24 2003-09-30 Borealis Tech Oy A process for the preparation of copolymers of propylene
FI972946A (en) 1997-07-11 1999-01-12 Borealis As Novel metallocene compounds for polymerization of ethylenically unsaturated monomers
JP3846193B2 (en) 1997-09-04 2006-11-15 チッソ株式会社 Propylene copolymer and process for producing the same
US6184327B1 (en) 1997-12-10 2001-02-06 Exxon Chemical Patents, Inc. Elastomeric propylene polymers
KR20010033302A (en) 1997-12-19 2001-04-25 린다 에스 잘리 Nickel diimine catalysts with methylalumoxane as cocatalyst, method of polymerization of olefins therewith and polymers produced
DE19804970A1 (en) 1998-02-07 1999-08-12 Aventis Res & Tech Gmbh & Co Catalyst system
KR100653018B1 (en) 1998-12-21 2006-11-30 엑손모빌 케미칼 패턴츠 인코포레이티드 Branched semi-crystalline ethylene-propylene compositions
JP2002534538A (en) 1999-01-08 2002-10-15 ザ ボード オブ トラスティーズ オブ ザ リーランド スタンフォード ジュニア ユニバーシティ Ethylene copolymer having narrow composition distribution and high melting point and method for producing the same
US6620896B1 (en) 1999-02-23 2003-09-16 Eastman Chemical Company Mixed olefin polymerization catalysts, processes employing such catalysts, and polymers obtained therefrom
FI990948A0 (en) 1999-04-27 1999-04-27 Borealis As Non-crosslinked polyethylene
DE60029817T2 (en) 1999-10-06 2006-11-30 Idemitsu Kosan Co. Ltd. CALANDER-SHAPED AND SPRAYED POLYPROPYLENE-BASED OBJECT
JP2001163924A (en) * 1999-12-03 2001-06-19 Japan Polychem Corp Branched propylene polymer and manufacturing method thereof
US20020013440A1 (en) * 1999-12-10 2002-01-31 Agarwal Pawan Kumar Propylene diene copolymers
CN1227272C (en) 1999-12-20 2005-11-16 埃克森化学专利公司 Process for preparation polyolefin resins using supported ionic catalysts
GB0013571D0 (en) 2000-06-06 2000-07-26 Power X Limited Switching system
EP1191042A1 (en) * 2000-09-26 2002-03-27 Atofina Process for polymerisation of 1,1difluoroethylen at high pressure
EP1195391A1 (en) 2000-10-05 2002-04-10 ATOFINA Research Production of polypropylene
ATE337341T1 (en) 2000-10-25 2006-09-15 Exxonmobil Chem Patents Inc METHOD AND DEVICE FOR CONTINUOUS SOLUTION POLYMERIZATION
WO2002046246A2 (en) * 2000-12-04 2002-06-13 Univaton Technologies, Llc Polimerization process
BR0116317A (en) 2000-12-20 2005-04-05 Exxonmobil Chem Patents Inc Olefin polymerization process to produce branched polymer compositions
US20060025545A1 (en) 2002-09-20 2006-02-02 Patrick Brant Polymer production at supercritical conditions
JP2006500470A (en) * 2002-09-20 2006-01-05 エクソンモービル・ケミカル・パテンツ・インク Supercritical polymerization method and polymer produced thereby
US8008412B2 (en) 2002-09-20 2011-08-30 Exxonmobil Chemical Patents Inc. Polymer production at supersolution conditions
DE602005010255D1 (en) 2004-07-08 2008-11-20 Exxonmobil Chem Patents Inc CATALYST SYSTEM FOR OLEFIN POLYMERIZATION AND METHOD FOR ITS USE
WO2006019494A1 (en) 2004-07-14 2006-02-23 Exxonmobil Chemical Patents Inc. Polymer production at supercritical conditions

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5408017A (en) * 1987-01-30 1995-04-18 Exxon Chemical Patents Inc. High temperature polymerization process using ionic catalysts to produce polyolefins
EP0846696A1 (en) * 1996-12-09 1998-06-10 Mitsubishi Chemical Corporation Catalyst for polymerization of alpha-olefins
US6160072A (en) * 1997-05-02 2000-12-12 Ewen; John A. Process for polymerizing tactioselective polyolefins in condensed phase using titanocenes
US6218488B1 (en) * 1998-03-04 2001-04-17 Exxon Mobil Chemical Patents Inc. Polymerization process for olefin copolymers using bridged hafnocene compounds
US6225432B1 (en) * 1998-08-26 2001-05-01 Exxon Chemical Patents Inc. Branched polypropylene compositions
US6355741B1 (en) * 1999-09-10 2002-03-12 Fina Research, S.A. Process for producing polyolefins
WO2001044318A1 (en) * 1999-12-15 2001-06-21 Basell Technology Company B.V. Metallocene compounds, process for their preparation and their use in catalytic systems for the polymerization of olefins
WO2002070572A2 (en) * 2001-03-06 2002-09-12 Exxonmobil Chemical Patents Inc. Propylene polymers for films
WO2002090399A1 (en) * 2001-05-04 2002-11-14 Borealis Technology Oy Polymerization process for producing copolymers

Cited By (111)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7087690B2 (en) 2000-11-07 2006-08-08 Symyx Technologies, Inc. Substituted pyridyl amine catalysts and processes for polymerizing crystalline polymers
US7807769B2 (en) 2002-09-20 2010-10-05 Exxonmobil Chemical Patents Inc. Isotactic polypropylene produced from supercritical polymerization process
WO2005061565A1 (en) * 2003-12-17 2005-07-07 Exxonmobil Chemical Patents Inc. Radiation tolerant copolymers
US7449530B2 (en) 2004-06-21 2008-11-11 Exxonmobil Chemical Patents Inc. Polymerization process
WO2006025917A3 (en) * 2004-06-21 2006-10-12 Exxonmobil Chem Patents Inc Polymerization process
US7858714B2 (en) 2004-06-21 2010-12-28 Exxonmobil Chemical Patents Inc. Polymerization process
WO2006025917A2 (en) * 2004-06-21 2006-03-09 Exxonmobil Chemical Patents Inc. Polymerization process
WO2006025949A2 (en) * 2004-07-08 2006-03-09 Exxonmobil Chemical Patents Inc. Polymer production at supercritical conditions
WO2006025949A3 (en) * 2004-07-08 2006-08-31 Exxonmobil Chem Patents Inc Polymer production at supercritical conditions
JP2008506018A (en) * 2004-07-08 2008-02-28 エクソンモービル・ケミカル・パテンツ・インク Polymer production under supercritical conditions
EP1674504A1 (en) * 2004-12-22 2006-06-28 Total Petrochemicals Research Feluy Geo-membrane applications
WO2006067180A1 (en) * 2004-12-22 2006-06-29 Total Petrochemicals Research Feluy Geo-membrane applications
EA012733B1 (en) * 2004-12-22 2009-12-30 Тотал Петрокемикалс Рисерч Фелюй Geo-membranes
US8814863B2 (en) 2005-05-12 2014-08-26 Innovatech, Llc Electrosurgical electrode and method of manufacturing same
US11246645B2 (en) 2005-05-12 2022-02-15 Innovatech, Llc Electrosurgical electrode and method of manufacturing same
US10463420B2 (en) 2005-05-12 2019-11-05 Innovatech Llc Electrosurgical electrode and method of manufacturing same
US9630206B2 (en) 2005-05-12 2017-04-25 Innovatech, Llc Electrosurgical electrode and method of manufacturing same
US8814862B2 (en) 2005-05-12 2014-08-26 Innovatech, Llc Electrosurgical electrode and method of manufacturing same
US8378047B2 (en) 2006-07-10 2013-02-19 Borealis Technology Oy Biaxially oriented polypropylene film
US7914899B2 (en) 2006-07-10 2011-03-29 Borealis Technology Oy Electrical insulation film
US7799841B2 (en) 2006-08-25 2010-09-21 Borealis Technology Oy Polypropylene foam
US8142902B2 (en) 2006-08-25 2012-03-27 Borealis Technology Oy Extrusion coated substrate
US8247052B2 (en) 2006-09-25 2012-08-21 Borealis Technology Oy Coaxial cable
WO2008079565A1 (en) * 2006-12-20 2008-07-03 Exxonmobil Chemical Patents Inc. Polymer production at supercritical conditions
WO2008076589A1 (en) 2006-12-20 2008-06-26 Exxonmobil Chemical Patents Inc. Phase separator and monomer recycle for supercritical polymerization process
WO2008079509A1 (en) 2006-12-22 2008-07-03 Exxonmobil Chemical Patents Inc. Process of making polymer blends
WO2008079483A1 (en) 2006-12-22 2008-07-03 Exxonmobil Chemical Patents Inc. Process of making polymer blends
US7915367B2 (en) 2006-12-28 2011-03-29 Borealis Technology Oy Process for the manufacture of branched polypropylene
US8008417B2 (en) 2007-01-19 2011-08-30 Toray Tonen Specialty Separator Godo Kaisha Polymeric material and its manufacture and use
CN101600742B (en) * 2007-03-06 2014-07-09 埃克森美孚化学专利公司 Polymer production under supersolution conditions
WO2008109212A1 (en) * 2007-03-06 2008-09-12 Exxonmobil Chemical Patents Inc. Polymer production under supersolution conditions
CN101679556B (en) * 2007-06-04 2012-06-06 埃克森美孚化学专利公司 Super-solution homogeneous propylene polymerization
WO2008150572A1 (en) * 2007-06-04 2008-12-11 Exxonmobil Chemical Patents Inc. Super-solution homogeneous propylene polymerization
WO2009035580A1 (en) 2007-09-13 2009-03-19 Exxonmobil Research And Engineering Company In-line process for producing plasticized polymers and plasticized polymer blends
US8598287B2 (en) 2007-10-22 2013-12-03 Univation Technologies, Llc Metallocene catalysts and their use in polymerization processes
EP3309182A2 (en) 2007-11-15 2018-04-18 Univation Technologies, LLC Polymerization catalysts, methods of making; methods of using, and polyolefinproducts made therefrom
EP2070953A1 (en) * 2007-12-11 2009-06-17 Total Petrochemicals Research Feluy Activating supports based on phosphonium complexes
US8338324B2 (en) 2007-12-11 2012-12-25 Total Petrochemicals Research Feluy Activating supports based on phosphonium complexes
WO2009123663A1 (en) 2007-12-20 2009-10-08 Exxonmobil Chemical Patents Inc. Isotactic polypropylene produced from supercritical polymerization process
CN101903423B (en) * 2007-12-20 2014-04-30 埃克森美孚研究工程公司 Bulk homogeneous polymerization process for ethylene propylene copolymers
EP2231727A4 (en) * 2007-12-20 2011-05-04 Exxonmobil Res & Eng Co Bulk homogeneous polymerization process for ethylene propylene copolymers
EP2231727A1 (en) * 2007-12-20 2010-09-29 ExxonMobil Research and Engineering Company Bulk homogeneous polymerization process for ethylene propylene copolymers
EP2450403A1 (en) * 2007-12-20 2012-05-09 ExxonMobil Research and Engineering Company Polypropylene ethylene-propylene copolymer blends and in-line process to produce them
US7872086B2 (en) 2008-01-17 2011-01-18 Tonen Chemical Corporation Polymeric material and its manufacture and use
US8580902B2 (en) 2008-08-01 2013-11-12 Exxonmobil Chemical Patents Inc. Catalyst system, process for olefin polymerization, and polymer compositions produced therefrom
EP2853549A2 (en) 2008-08-01 2015-04-01 ExxonMobil Chemical Patents Inc. Process for olefin polymerization
WO2010014344A2 (en) 2008-08-01 2010-02-04 Exxonmobil Chemical Patents Inc. Catalyst system and process for olefin polymerization
WO2011019474A2 (en) 2009-08-14 2011-02-17 Exxonmobil Chemical Patents Inc. Catalyst system, process for olefin polymerization, and polymer compositions produced therefrom
US8835587B2 (en) 2009-08-14 2014-09-16 Exxonmobil Chemical Patents Inc. Catalyst system, process for olefin polymerization, and polymer compositions produced therefrom
WO2011071900A2 (en) 2009-12-07 2011-06-16 Univation Technologies, Llc Methods for reducing static charge of a catalyst and methods for using the catalyst to produce polyolefins
WO2011103280A1 (en) 2010-02-18 2011-08-25 Univation Technologies, Llc Methods for operating a polymerization reactor
WO2011103402A1 (en) 2010-02-22 2011-08-25 Univation Technologies, Llc Catalyst systems and methods for using same to produce polyolefin products
EP2368896A1 (en) 2010-03-01 2011-09-28 ExxonMobil Chemical Patents Inc. Mono-indenyl transition metal compounds and polymerization therewith
WO2011129956A1 (en) 2010-04-13 2011-10-20 Univation Technologies, Llc Polymer blends and films made therefrom
WO2012009215A1 (en) 2010-07-16 2012-01-19 Univation Technologies, Llc Systems and methods for measuring static charge on particulates
WO2012009216A1 (en) 2010-07-16 2012-01-19 Univation Technologies, Llc Systems and methods for measuring particle accumulation on reactor surfaces
WO2012015898A1 (en) 2010-07-28 2012-02-02 Univation Technologies, Llc Systems and methods for measuring velocity of a particle/fluid mixture
WO2012074709A1 (en) 2010-11-30 2012-06-07 Univation Technologies, Llc Processes for the polymerization of olefins with extracted metal carboxylate salts
WO2012074710A1 (en) 2010-11-30 2012-06-07 Univation Technologies, Llc. Catalyst composition having improved flow characteristics and methods of making and using the same
WO2012082674A1 (en) 2010-12-17 2012-06-21 Univation Technologies, Llc Systems and methods for recovering hydrocarbons from a polyolefin purge gas product
US9388254B2 (en) 2010-12-21 2016-07-12 Dow Global Technologies Llc Olefin-based polymers and dispersion polymerizations
WO2012088235A2 (en) 2010-12-21 2012-06-28 Dow Global Technologies Llc Olefin-based polymers and dispersion polymerizations
EP3091038A1 (en) 2010-12-21 2016-11-09 Dow Global Technologies LLC Olefin-based polymers and dispersion polymerizations
WO2012087560A1 (en) 2010-12-22 2012-06-28 Univation Technologies, Llc Additive for polyolefin polymerization processes
WO2012158260A1 (en) 2011-05-13 2012-11-22 Univation Technologies, Llc Spray-dried catalyst compositions and polymerization processes employing the same
WO2013028283A1 (en) 2011-08-19 2013-02-28 Univation Technologies, Llc Catalyst systems and methods for using same to produce polyolefin products
WO2013070601A2 (en) 2011-11-08 2013-05-16 Univation Technologies, Llc Methods of preparing a catalyst system
US9234060B2 (en) 2011-11-08 2016-01-12 Univation Technologies, Llc Methods of preparing a catalyst system
WO2013070602A1 (en) 2011-11-08 2013-05-16 Univation Technologies, Llc Methods for producing polyolefins with catalyst systems
WO2014106143A1 (en) 2012-12-28 2014-07-03 Univation Technologies, Llc Supported catalyst with improved flowability
EP4039366A1 (en) 2012-12-28 2022-08-10 Univation Technologies, LLC Supported catalyst with improved flowability
WO2014120494A1 (en) 2013-01-30 2014-08-07 Univation Technologies, Llc Processes for making catalyst compositions having improved flow
WO2014123598A1 (en) 2013-02-07 2014-08-14 Univation Technologies, Llc Preparation of polyolefin
EP4223802A2 (en) 2013-02-07 2023-08-09 Univation Technologies, LLC Polymerization catalyst
WO2014149361A1 (en) 2013-03-15 2014-09-25 Univation Technologies, Llc Ligands for catalysts
WO2014143421A1 (en) 2013-03-15 2014-09-18 Univation Technologies, Llc Tridentate nitrogen based ligands for olefin polymerisation catalysts
WO2014197169A1 (en) 2013-06-05 2014-12-11 Univation Technologies, Llc Protecting phenol groups
EP3287473A1 (en) 2013-06-05 2018-02-28 Univation Technologies, LLC Protecting phenol groups
WO2015153082A1 (en) 2014-04-02 2015-10-08 Univation Technologies, Llc Continuity compositions and methods of making and using the same
WO2016028276A1 (en) 2014-08-19 2016-02-25 Univation Technologies, Llc Fluorinated catalyst supports and catalyst systems
WO2016028277A1 (en) 2014-08-19 2016-02-25 Univation Technologies, Llc Fluorinated catalyst supports and catalyst systems
WO2016028278A1 (en) 2014-08-19 2016-02-25 Univation Technologies, Llc Fluorinated catalyst supports and catalyst systems
WO2016118566A1 (en) 2015-01-21 2016-07-28 Univation Technologies, Llc Methods for gel reduction in polyolefins
WO2016118599A1 (en) 2015-01-21 2016-07-28 Univation Technologies, Llc Methods for controlling polymer chain scission
EP3915759A1 (en) 2015-01-21 2021-12-01 Univation Technologies, LLC Method for controlling polymer chain scission
WO2016145179A1 (en) 2015-03-10 2016-09-15 Univation Technologies, Llc Spray dried catalyst compositions, methods for preparation and use in olefin polymerization processes
WO2016164451A1 (en) 2015-04-08 2016-10-13 Univation Technologies, Llc Closed reactor transitions between metallocene catalysts
WO2016171810A1 (en) 2015-04-20 2016-10-27 Exxonmobil Chemical Patents Inc. Supported catalyst systems and processes for use thereof
WO2016172197A1 (en) 2015-04-20 2016-10-27 Exxonmobil Chemical Patents Inc. Multimodal and broad molecular weight high density polyethylene
WO2016176135A1 (en) 2015-04-27 2016-11-03 Univation Technologies, Llc Supported catalyst compositions having improved flow properties and preparation thereof
WO2018151903A1 (en) 2017-02-20 2018-08-23 Exxonmobil Chemical Patents Inc. Supported catalyst systems and processes for use thereof
WO2019027587A1 (en) 2017-08-04 2019-02-07 Exxonmobil Chemical Patents Inc. Polyethylene compositions and films prepared therefrom
WO2019162760A1 (en) 2018-02-05 2019-08-29 Exxonmobil Chemical Patents Inc. A Corporation Of State Of Delaware Enhanced processability of lldpe by addition of ultra-high molecular weight high density polyethylene
WO2019210030A1 (en) 2018-04-26 2019-10-31 Exxonmobil Chemical Patents Inc. Non-coordinating anion type activators containing cation having branched alkyl groups
WO2019246069A1 (en) 2018-06-19 2019-12-26 Exxonmobil Chemical Patents Inc. Polyethylene compositions and films prepared therefrom
WO2021119089A1 (en) 2019-12-11 2021-06-17 Exxonmobil Chemical Patents Inc. Processes for introduction of liquid activators in olefin polymerization reactions
WO2021126523A1 (en) 2019-12-19 2021-06-24 Exxonmobil Chemical Patents Inc. Production of impact copolymer polypropylene using metallocene and ziegler-natta catalysts in parallel reactors
WO2021188361A1 (en) 2020-03-20 2021-09-23 Exxonmobil Chemical Patents Inc. Linear alpha-olefin copolymers and impact copolymers thereof
WO2021194831A1 (en) 2020-03-25 2021-09-30 Exxonmobil Chemical Patents Inc. Alkylation of transition metal coordination catalyst complexes
WO2021202091A1 (en) 2020-03-30 2021-10-07 Exxonmobil Chemical Patents Inc. Comb-block copolymers and methods thereof
WO2021222016A2 (en) 2020-05-01 2021-11-04 Exxonmobil Chemical Patents Inc. Linear low density polyethylene for film applications
WO2021222280A2 (en) 2020-05-01 2021-11-04 Exxonmobil Chemical Patents Inc. Linear low density polyethylene for film applications
WO2021257264A1 (en) 2020-06-16 2021-12-23 Exxonmobil Chemical Patents Inc. Metallocene catalysts for producing vinyl-terminated polyalphaolefins and methods associated therewith
WO2021262838A1 (en) 2020-06-26 2021-12-30 Exxonmobil Chemical Patents Inc. Copolymers composed of ethylene, a-olefin, non-conjugated diene, and substituted styrene and articles therefrom
WO2021262842A1 (en) 2020-06-26 2021-12-30 Exxonmobil Chemical Patents Inc. COPOLYMERS OF ETHYLENE, α-OLEFIN, NON-CONJUGATED DIENE, AND ARYL-SUBSTITUTED CYCLOALKENE, METHODS TO PRODUCE, BLENDS, AND ARTICLES THEREFROM
WO2022035484A1 (en) 2020-08-10 2022-02-17 Exxonmobil Chemical Patents Inc. Methods for delivery of non-aromatic solutions to polymerization reactors
WO2022035585A1 (en) 2020-08-13 2022-02-17 Exxonmobil Chemical Patents Inc. Cyclic containing polymer compositions obtained using transition metal bis(phenolate) catalyst complexes and process for production thereof
WO2022076216A1 (en) 2020-10-08 2022-04-14 Exxonmobil Chemical Patents Inc. Supported catalyst systems and processes for use thereof
WO2022087121A1 (en) 2020-10-22 2022-04-28 Exxonmobil Chemical Patents Inc. Multidentate lewis base catalysts and methods for use thereof
WO2022093814A1 (en) 2020-10-28 2022-05-05 Exxonmobil Chemical Patents Inc. Non-aromatic hydrocarbon soluble olefin polymerization catalysts and use thereof
WO2022250822A1 (en) 2021-05-24 2022-12-01 Exxonmobil Chemical Patents Inc. Biphasic polymerization processes

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