WO2001058970A1 - Propylene impact copolymers - Google Patents

Propylene impact copolymers Download PDF

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Publication number
WO2001058970A1
WO2001058970A1 PCT/US2001/004126 US0104126W WO0158970A1 WO 2001058970 A1 WO2001058970 A1 WO 2001058970A1 US 0104126 W US0104126 W US 0104126W WO 0158970 A1 WO0158970 A1 WO 0158970A1
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Prior art keywords
component
weight
rac
zirconium dichloride
dimethylsiladiyl
Prior art date
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PCT/US2001/004126
Other languages
French (fr)
Inventor
Terry J. Burkhardt
Dawn C. Wiser
Robert T. Li
Udo M. Stehling
William T. Haygood, Jr.
Francis C. Rix
Aspy K. Mehta
Original Assignee
Exxonmobil Chemical Patents Inc.
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Application filed by Exxonmobil Chemical Patents Inc. filed Critical Exxonmobil Chemical Patents Inc.
Priority to AT01910477T priority Critical patent/ATE286082T1/en
Priority to KR1020027010213A priority patent/KR20020074509A/en
Priority to EP01910477A priority patent/EP1254186B1/en
Priority to JP2001558115A priority patent/JP2003522259A/en
Priority to BR0108150-0A priority patent/BR0108150A/en
Priority to CA002398509A priority patent/CA2398509A1/en
Priority to DE60108075T priority patent/DE60108075T2/en
Publication of WO2001058970A1 publication Critical patent/WO2001058970A1/en

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Definitions

  • FIELD This invention relates to propylene impact copolymer compositions.
  • these unique and improved compositions can be produced using metallocene catalysts in commercial-scale processes.
  • Propylene impact copolymers are commonly used in a variety of applications where strength and impact resistance are desired such as molded and extruded automobile parts, household appliances, luggage and furniture. Propylene homopolymers are often unsuitable for such applications because they are too brittle and have low impact resistance particularly at low temperature, whereas propylene impact copolymers are specifically engineered for applications such as these.
  • a typical propylene impact copolymer contains two phases or components, a homopolymer component and a copolymer component. These two components are usually produced in a sequential polymerization process wherein the homopolymer produced in a first reactor is transferred to a second reactor where copolymer is produced and incorporated within the matrix of the homopolymer component.
  • the copolymer component has rubbery characteristics and provides the desired impact resistance, whereas the homopolymer component provides overall stiffness.
  • U.S. Patent No. 5,166,268 describes a "cold forming" process for producing propylene impact copolymers where finished articles are fabricated at temperatures below the melting point of the preform material, in this case, the propylene impact copolymer.
  • the patented process uses a propylene impact copolymer comprised of either a homopolymer or crystalline copolymer matrix (first component) and at least ten percent by weight of an "interpolymer" of ethylene and a small amount of propylene (the second component). Adding comonomer to the first component lowers its stiffness.
  • the ethylene/propylene copolymer second component enables the finished, cold-formed article to better maintain its shape.
  • nucleating agent is added to propylene impact copolymers having a numerical ratio of the intrinsic viscosity of the copolymer rubber phase (second component) to the intrinsic viscosity of the homopolymer phase (first component) which is near unity, and an ethylene content of the copolymer phase in the range of 38% to 60% by weight.
  • second component the intrinsic viscosity of the copolymer rubber phase
  • first component the intrinsic viscosity of the homopolymer phase
  • ethylene content of the copolymer phase in the range of 38% to 60% by weight.
  • U.S. Patent No. 5,250,631 describes a propylene impact copolymer having a homopolypropylene first component and an ethylene/butene/propylene terpolymer second component. Again, the goal is to obtain high impact strength coupled with resistance to stress whitening.
  • Propylene impact copolymers are also used to produce films as described in U.S. Patent No. 5,948,839.
  • the impact copolymer described in this patent contains a conventional first component and 25 to 45 weight percent ethylene/propylene second component having from 55 to 65 weight percent ethylene.
  • This impact copolymer composition has a melt flow of from 7 to 60 dg/min. Such films are used in articles such as diapers.
  • U.S. 5,990,242 approaches this problem by using an ethylene/butene (or higher ⁇ -olefin) copolymer second component, rather than a propylene copolymer, prepared using a hafnocene type metallocene.
  • hafnocene type metallocene such hafnium metallocenes in general are known for producing relatively higher molecular weight polymers; however, their activities are much lower than the more commonly used zirconocenes.
  • the second component molecular weights and intrinsic viscosities are lower than desired for good impact strength.
  • the present inventors have discovered new propylene impact copolymer compositions having the benefits of metallocene catalyzed polymers in addition to properties needed for high impact strength. Importantly, these polymers can be economically produced using commercial-scale processes.
  • the present invention provides reactor produced propylene impact copolymer compositions comprising:
  • Component A comprising propylene homopolymer or copolymer wherein the copolymer comprises 10% or less by weight ethylene, butene, hexene or octene comonomer;
  • Component B comprising propylene copolymer wherein the copolymer comprises from about 20% to about 70% by weight ethylene, butene, hexene and/or octene comonomer, and from about 80% to about 30% by weight propylene, wherein Component B:
  • (i) has a weight average molecular weight of at least 100,000; (ii) a composition distribution of greater than 60%; and (iii) an intrinsic viscosity of greater than 1.00 dl/g.
  • This invention also provides a process for producing propylene impact copolymer in a multiple stage process wherein Component A comprising propylene homopolymer or copolymer wherein the copolymer comprises 10% or less by weight ethylene, butene, hexene or octene comonomer is produced in a primary stage and Component B is produced in a subsequent stage, Component B comprising propylene copolymer wherein the copolymer comprises from about
  • Components A and/or B are polymerized using a metallocene selected from the group consisting of: rac-dimethylsiladiyl(2-iPr,4-phenylindenyl) 2 zirconium dichloride; rac-dimethylsiladiyl(2-iPr,4-[l -naphthyl]indenyl) 2 zirconium dichloride; rac-dimethylsiladiyl(2-iPr, 4-[3,5-dimethylphenyl]indenyl) 2 zirconium dichloride; rac-dimethylsiladiyl(2-iPr, 4-[ortho-methyl-phenyl]indenyl) 2 zirconium dichloride; and
  • Figure 1 is a plot of Notched Isod values as a function of Flexural Modulus data from Table 8.
  • the propylene impact copolymers (“ICPs”) of this invention comprise at least two major components, Component A and Component B.
  • Component A is preferably an isotactic propylene homopolymer, though small amounts of a comonomer may be used to obtain particular properties.
  • Such copolymers of Component A contain 10% by weight or less, preferably less than 6% by weight or less, comonomer such as ethylene, butene, hexene or octene. Most preferably less than 4% by weight ethylene is used.
  • the end result is usually a product with lower stiffness but with some gain in impact strength compared to homopolymer Component A.
  • Component A refers generally to the xylene insoluble portion of the ICP composition
  • Component B refers generally to the xylene soluble portion.
  • the xylene soluble portion clearly has both a high molecular weight component and a low molecular weight component, we have found that the low molecular weight component is attributable to amorphous, low molecular weight propylene homopolymer. Therefore, Component B in such circumstances refers only to the high molecular weight portion.
  • Component A preferably has a narrow molecular weight distribution Mw/Mn (“MWD”), i.e., lower than 4.0, preferably lower than 3.5, more preferably lower than 3.0, and most preferably 2.5 or lower. These molecular weight distributions are obtained in the absence of visbreaking using peroxide or other post reactor treatment designed to reduce molecular weight.
  • Component A preferably has a weight average molecular weight (Mw as determined by GPC) of at least 100,000, preferably at least 200,000 and a melting point (Mp) of at least 145°C, preferably at least 150°C, more preferably at least 152°C, and most preferably at least 155°C.
  • ICPs Another important feature of ICPs is the amount of amorphous polypropylene they contain.
  • the ICPs of this invention are characterized as having low amorphous polypropylene, preferably less than 3% by weight, more preferably less than 2% by weight, even more preferably less than 1% by weight and most preferably there is no measurable amorphous polypropylene.
  • Component B is most preferably a copolymer consisting essentially of propylene and ethylene although other propylene copolymers, ethylene copolymers or terpolymers may be suitable depending on the particular product properties desired.
  • propylene/butene, hexene or octene copolymers, and ethylene/butene, hexene or octene copolymers may be used, and propylene/ethylene/hexene-1 terpolymers may be used.
  • Component B is a copolymer comprising at least 40% by weight propylene, more preferably from about 80% by weight to about 30% by weight propylene, even more preferably from about 70% by weight to about 35% by weight propylene.
  • the comonomer content of Component B is preferably in the range of from about 20% to about 70% by weight comonomer, more preferably from about 30% to about 65% by weight comonomer, even more preferably from about 35% to about 60% by weight comonomer.
  • Most preferably Component B consists essentially of propylene and from about 20% to about 70% ethylene, more preferably from about 30% to about 65% ethylene, and most preferably from about 35% to about 60% ethylene.
  • Component B For other Component B copolymers, the comonomer contents will need to be adjusted depending on the specific properties desired. For example, for ethylene/hexene copolymers, Component B should contain at least 17% by weight hexene and at least 83% by weight ethylene.
  • Component B preferably has a narrow molecular weight distribution Mw/Mn ("MWD"), i.e., lower than 5.0, preferably lower than 4.0, more preferably lower than 3.5, even more preferably lower than 3.0 and most preferably 2.5 or lower. These molecular weight distributions should be obtained in the absence of visbreaking or peroxide or other post reactor treatment designed to reduce molecular weight.
  • Component B preferably has a weight average molecular weight (Mw as determined by GPC) of at least 100,000, preferably at least 150,000, and most preferably at least 200,000.
  • Component B preferably has an intrinsic viscosity greater than 1.00 dl/g, more preferably greater than 1.50 dl/g and most preferably greater than 2.00 dl/g.
  • intrinsic viscosity or "IN” is used conventionally herein to mean the viscosity of a solution of polymer such as Component B in a given solvent at a given temperature, when the polymer composition is at infinite dilution.
  • IN measurement involves a standard capillary viscosity measuring device, in which the viscosity of a series of concentrations of the polymer in the solvent at the given temperature are determined.
  • decalin is a suitable solvent and a typical temperature is 135°C. From the values of the viscosity of solutions of varying concentrations, the "value" at infinite dilution can be determined by extrapolation.
  • Component B preferably has a composition distribution (CD) of greater than 60%, more preferably greater than 65%, even more preferably greater than 70%o, even more preferably greater than 75%, still more preferably greater than 80%, and most preferably greater than 85%.
  • CD defines the compositional variation among polymer chains in terms of ethylene (or other comonomer) content of the copolymer as a whole. The measurement of CD is described in detail U.S. Patent No. 5,191,042 which is hereby fully incorporated by reference. CD is defined herein as the weight percent of the copolymer molecules having a comonomer content within 50% of the median total molar comonomer content. As described in U.S. Patent No.
  • CD is determined by first determining the mean ethylene (or other comonomer) content of the copolymer by a suitable test such as ASTM D-3900. Next, the copolymer sample is dissolved in solvent such as hexane and a number of fractions of differing composition are precipitated by the addition of incremental amounts of a liquid such as isopropanol in which the copolymer is insoluble. Generally from about 4 to 6 fractions are precipitated in this way and the weight and ethylene (or other comonomer) content of each fraction are determined after removing the solvent. From the weight of each fraction and its ethylene content, a plot is prepared of weight percent composition vs. cumulative weight percent of polymer, and a smooth curve is drawn through the points.
  • Component B of the ICPs preferably has low crystallinity, preferably less than 10% by weight of a crystalline portion, more preferably less than 5% by weight of a crystalline portion. Where there is a crystalline portion of Component
  • composition is preferably the same as or at least similar to (within 15% by weight) the remainder of Component B in terms of overall comonomer weight percent.
  • the ICPs of this invention are "reactor produced” meaning Components A and B are not physically or mechanically blended together. Rather, they are interpolymerized in at least one reactor. The final ICP as obtained from the reactor or reactors, however, can be blended with various other components including other polymers.
  • the preferred melt flow rate ("MFR") of these ICPs depends on the desired end use but is typically in the range of from about 0.2 dg min to about 200 dg/min, more preferably from about 5 dg/min to about 100 dg/min. Significantly, high MFRs, i.e., higher than 50 dg/min are obtainable. MFR is determined by a conventional procedure such as ASTM-1238 Cond. L.
  • the ICP preferably has a melting point of at least 145°C, preferably at least 150°C, more preferably at least 152°C, and most preferably at least 155°C.
  • the ICPs comprise from about 40% to about 95% by weight Component A and from about 5% to about 60% by weight Component B, preferably from about 50% to about 95% by weight Component A and from about 5% to about 50% Component B, even more preferably from about 60% to about 90% by weight
  • Component A and from about 10 % to about 40% by weight Component B.
  • the ICP consists essentially of Components A and B.
  • the overall comonomer (preferably ethylene) content of the total ICP is preferably in the range of from about 2% to about 30% by weight, preferably from about 5% to about 25% by weight, even more preferably from about 5% to about
  • additives may be incorporated into the ICP for various purposes.
  • Such additives include, for example, stabilizers, antioxidants, fillers, colorants, nucleating agents and mold release agents.
  • the ICP compositions of this invention may be prepared by conventional polymerization processes such as a two-step process. It is conceivable, although currently impractical, to commercially produce ICPs in a single reactor. Each step may be independently carried out in either the gas or liquid slurry phase. For example the first step may be conducted in the gas phase and the second in liquid slurry or vice versa. Alternatively, each phase may be the same.
  • the ICPs of this invention are produced in multiple reactors, preferably two or three, operated in series, Component B is preferably polymerized in a second, gas phase reactor. Component A is preferably polymerized first, in a liquid slurry or solution polymerization process.
  • Component A is made in at least two reactors in order to obtain fractions with varying melt flow rate. This has been found to improve the processability of the ICP.
  • stage is defined as that portion of a polymerization process during which one component of the ICP, Component A or Component B, is produced- One or multiple reactors may be used during each stage.
  • Hydrogen may be added to one or both reactors to control molecular weight, IN and MFR.
  • the use of hydrogen for such purposes is well known to those skilled in the art.
  • a metallocene catalyst system is used to produce the ICP compositions of this invention.
  • the most suitable metallocenes are those in the generic class of bridged, substituted bis(cyclopentadienyl) metallocenes, specifically bridged, substituted bis(indenyl) metallocenes known to produce high molecular weight, high melting, highly isotactic propylene polymers.
  • those of the generic class disclosed in U.S. Patent No. 5,770,753 should be suitable, however, it has been found that the exact polymer obtained is highly dependent on the metallocene's specific substitution pattern.
  • racemic metallocenes are most suitable for preparing the ICP compositions of this invention: rac-dimethylsiladiyl(2-iPr,4 ⁇ phenylindenyl) 2 zirconium dichloride; rac-dimethylsiladiyl(2-iPr,4-[ 1 - naphthyl]indenyl) 2 zirconium dichloride; rac-dimethylsiladiyl(2-iPr, 4-[3,5- dimethylphenyl]indenyl) 2 zircor ⁇ ium dichloride; rac-dimethylsiladiyl(2-iPr, 4-
  • Metallocenes are generally used in combination with some form of activator in order to create an active catalyst system.
  • activator is defined herein to be any compound or component, or combination of compounds or components, capable of enhancing the ability of one or more metallocenes to polymerize olefins.
  • Alkylalumoxanes such as methylalumoxane (MAO) are commonly used as metallocene activators. Generally alkylalumoxanes contain 5 to 40 of the repeating units:
  • R is a Cj-Cg alkyl including mixed alkyls.
  • Compounds in which R is methyl are particularly preferred.
  • Alumoxane solutions, particularly methylalumoxane solutions, may be obtained from commercial vendors as solutions having various concentrations. There are a variety of methods for preparing alumoxane, non-limiting examples of which are described in U.S. Patent No.
  • Ionizing activators may also be used to activate metallocenes. These activators are neutral or ionic, or are compounds such as tri(n-butyl)ammonium tetrakis(pentafluorophenyl)borate, which ionize the neutral metallocene compound. Such ionizing compounds may contain an active proton, or some other cation associated with, but not coordinated or only loosely coordinated to, the remaining ion of the ionizing compound. Combinations of activators may also be used, for example, alumoxane and ionizing activator combination, see for example, WO 94/07928.
  • ionic catalysts for coordination polymerization comprised of metallocene cations activated by non-coordinating anions appear in the early work in EP-A-0 277 003, EP-A-0 277 004 and US patent 5,198,401 and WO-A- 92/00333 (incorporated herein by reference for purposes of U.S. patent practice). These teach desirable methods of preparation wherein metallocenes (bisCp and monoCp) are protonated by an anion precursor such that an alkyl/hydride group is abstracted from a transition metal to make it both cationic and charge-balanced by the non-coordinating anion.
  • Suitable ionic salts include tetrakis-substituted borate or aluminum salts having fluorided aryl-constituents such as phenyl, biphenyl and napthyl.
  • noncoordinating 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.
  • “Compatible” noncoordinating anions are those which are not degraded to neutrality when the initially formed complex decomposes. Further, the anion will not transfer an anionic substituent or fragment to the cation so as to cause it to form a neutral four coordinate metallocene compound and a neutral by-product from the anion.
  • Particularly useful noncoordinating anions are those which are compatible, stabilize the metallocene cation in the sense of balancing its ionic charge in a +1 state, yet retain sufficient liability to permit displacement by an ethylenically or acetylenically unsaturated monomer during polymerization.
  • ionizing ionic compounds not containing an active proton but capable of producing both the active metallocene cation and a noncoordinating anion is also known. See, for example, EP-A-0 426 637 and EP-A- 0 573 403 (incorporated herein by reference for purposes of U.S. patent practice).
  • An additional method of making the ionic catalysts uses ionizing anion precursors which are initially neutral Lewis acids but form the cation and anion upon ionizing reaction with the metallocene compounds, for example the use of tris(pentafluorophenyl) borane. See EP-A-0 520 732 (incorporated herein by reference for purposes of U.S. patent practice).
  • Ionic catalysts for addition polymerization can also be prepared by oxidation of the metal centers of transition metal compounds by anion precursors containing metallic oxidizing groups along with the anion groups, see EP-A-0 495 375 (incorporated herein by reference for purposes of U.S. patent practice).
  • metal ligands include halogen moieties (for example, bis- cyclopentadienyl zirconium dichloride) which are not capable of ionizing abstraction under standard conditions, they 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 and EP- Al-0 570 982 (incorporated herein by reference for purposes of U.S. patent practice) for in situ processes describing the reaction of alkyl aluminum compounds with dihalo-substituted metallocene compounds prior to or with the addition of activating anionic compounds. '
  • the activator for the metallocene supported catalyst composition is a
  • NCA preferably the NCA is first added to the support composition followed by the addition of the metallocene catalyst.
  • the activator is MAO
  • the MAO and metallocene catalyst are dissolved together in solution.
  • the support is then contacted with the MAO/metallocene catalyst solution.
  • a porous particulate material such as for example, talc, inorganic oxides, inorganic chlorides and resinous materials such as polyolefin or polymeric compounds.
  • the support materials are porous inorganic oxide materials, which include those from the Periodic Table of Elements of Groups 2, 3, 4, 5, 13 or 14 metal oxides.
  • Silica, alumina, silica-alumina, and mixtures thereof are particularly preferable.
  • Other inorganic oxides that may be employed either alone or in combination with the silica, alumina or silica-alumina are magnesia, titania, zirconia, and the like.
  • the support material is porous silica which has a surface area in the range of from 10 to 700 " m-2/g, a total pore volume in the range of from 0.1 to 4.0 cc/g and an average particle size in the range of from 10 to 500 ⁇ m. More preferably, the surface area is in the range of from 50 to 500 m- ⁇ /g, the pore volume is in the range of from 0.5 to 3.5 cc/g and the average particle size is in the range of from 20 to 200 ⁇ m.
  • the surface area is in the range of from 100 to 400 m-2/g
  • the pore volume is in the range of from 0.8 to 3.0 cc/g
  • the average particle size is in the range of from 30 to 100 ⁇ m.
  • the average pore size of typical porous support materials is in the range of from 10 to 1000 A.
  • a support material is used that has an average pore diameter of from 50 to 50 ⁇ A, and most desirably from 75 to 35 ⁇ A. It may be particularly desirable to dehydrate the silica at a temperature of from 100°C to 800°C anywhere from 3 to 24 hours.
  • the metallocenes, activator and support material may be combined in any number of ways. Suitable support techniques are described in U. S Patent Nos.
  • the metallocenes and activator are combined and their reaction product supported on the porous support material as described in U. S. Patent No. 5,240,894 and WO 94/ 28034, WO 96/00243, and WO 96/00245 (each folly incorporated herein by reference for purposes of U.S. patent practice).
  • the metallocenes may be preactivated separately and then combined with the support material either separately or together. If the metallocenes are separately supported, then preferably, they are dried then combined as a powder before use in polymerization.
  • the total volume of reaction solution applied to porous support is desirably less than 4 times the total pore volume of the porous support, more desirably less than 3 times the total pore volume of the porous support and even more desirably in the range of from more than 1 to less than 2.5 times the total pore volume of the porous support.
  • Procedures for measuring the total pore volume of porous support are well known in the art. One such method is described in Volume 1, Experimental
  • the methods generally comprise either physical adsorption on traditional polymeric or inorganic supports that have been largely dehydrated and dehydroxylated, or using neutral anion precursors that are sufficiently strong Lewis acids to activate retained hydroxy groups in silica containing inorganic oxide supports such that the
  • Lewis acid becomes covalently bound and the hydrogen of the hydroxy group is available to protonate the metallocene compounds.
  • the supported catalyst system may be used directly in polymerization or the catalyst system may be prepolymerized using methods well known in the art.
  • Metallocene A racemic dimethylsiladiyl(2-isopropyl-4-phenylindenyl) 2 zirconium dichloride was obtained from commercial sources and used as received.
  • Metallocene B racemic dimethylsiladiyl(2-isopropyl-4-[l-naphthyl]indenyl) 2 zirconium dichloride was obtained from commercial sources and used as received.
  • Metallocene C racemic dimethylsiladiyl(2-isopropyl-4-[2-methyl- phenyl]indenyl) 2 zirconium dichloride was prepared as follows:
  • Metallocene D racemic dimethylsiladiyl(2- isopropyl-4-[3,5- dimethylphenyl]indenyl) 2 zirconium dichloride was prepared as follows:
  • Dimethylsiladiylbis[4-(3,5-dimethylphenyl)-2-isopropylindene] (2.1g, 3.6 mmol) was dissolved in 60 mL of Et 2 O. While stirring, 2.9 mL of n-BuLi (2.5M in hexane) was added and allowed to stir at room temperature for 2 hours. After this time, the solution was cooled to -35°C and ZrCl (0.83 g, 3.6 mmol) was added and allowed to stir at room temperature for 3 hours. The solvent was then removed in vacuo and the residue was taken up in toluene and filtered to remove
  • Metallocene E racemic diphenylsiladiyl(2-methyl-4-[l-naphthyl]indenyl) 2 zirconium dichloride was prepared as follows. Ph2Si(2-Methyl-4-ri-na ⁇ thyllindene)2
  • 4-[l-napthyl]indenyl lithium to form the ligand system with a Ph2Si bridge is a general one.
  • a wide variety of cyclopentadienyl or indenyl metal salts can be reacted with Ph2Si(OSO2CF3)2 when Ph2Si(Cl)2 is unreactive or slow with the cyclopentadienyl or indenyl metal salt reagent.
  • Ph2Si(2-Methyl-4-[l-napthyl]indenyl lithium)2 was prepared from addition of a 2.0 M solution of n-Butyl lithium and pentane (1.5 mL, 3.0 mmol) to a mixture of Ph2Si(2-Methyl, 4-napthyl indene)2 (1.0 g, 1.44 mmol) and diethyl ether (20 mL). After stirring for two hours, trimethyl tin chloride (0.6 g, 3.0 mmol) was added. The color changed instantly from an intense to light yellow. The ether was removed and the product extracted with pentane (3 x 20 mL). Removal of solvent yielded product. Yield 0.88 g, 60 %.
  • Comparison Metallocene 1 racemic dimethylsiladiyl(2-methyl-4-phenylindenyl) 2 zirconium dichloride was obtained from commercial sources and used as received.
  • Comparison Metallocene 2 racemic dimethylsiladiyl(2- methyl-4-[l- naphthyl]indenyl) 2 zirconium dichloride was obtained from commercial sources and used as received.
  • Comparison Metallocene 3 racemic dimethylsiladiyl(2-methyl-4-phenylindenyl) 2 zirconium dichloride was obtained from commercial sources and used as received.
  • Comparison Metallocene 4 racemic dimethylsiladiyl(2-ethyl-4-phenylindenyl)2 zirconium dichloride was obtained from commercial sources and used as received.
  • dimethylsiladiyl(2-iPr-4-phenyl indenyl)2 zirconium dichloride (A, 0.060 g) was added to the MAO-toluene solution (6.74 g, 7.2 mL) and stirred twenty minutes. This was filtered through a medium glass frit funnel and washed with toluene (14 mL). To the combined filtrates was added dehydrated silica (4.0 g, Davison 948 Regular, 600°C dehydration).
  • dimethylsiladiyl(2-iPr-4-phenylindenyl)2 zirconium dichloride F, 0.065 g was added to the MAO-toluene solution (5.1 g, 5.35 mL) and stirred fifteen minutes. This was filtered through a medium glass frit funnel and washed with toluene (11 mL). To the combined filtrates was added dehydrated silica (4.0 g, Davison 948 Regular, 600°C dehydration).
  • dimethylsiladiyl(2-iPr-4-phenylindenyl)2 zirconium dichloride (G, 0.065 g) was added to the MAO-toluene solution (5.1 g, 5.4 mL) and stirred fifty minutes. This was filtered through a medium glass frit funnel and washed with toluene (13 mL). To the combined filtrates was added dehydrated silica (4.0 g, Davison 948 Regular, 600°C dehydration). This slurry was stirred for twenty minutes, dried at 40 °C for ten minutes under vacuum on a rotary evaporator until the liquid evaporated and then the solid was further dried a total of about 3 hours. The supported catalyst was recovered as a purple, free flowing solid (5.45 g).
  • racemic dimethylsiladiyl(2-methyl-4- phenylindenyl) 2 zirconium dichloride (Comparison metallocene 3, 13.0 g) was dissolved in a MAO solution (300 mL). This was added to a MAO solution (800 mL diluted with 1600 mL toluene) and an additional 150 mL of toluene was added. This was mixed one hour. One half of this solution was added to dehydrated silica (802.2 g, Davison 948 Regular, 600°C dehydration) and stirred five minutes- The remaining solution was then added and stirred twenty minutes. Additional toluene was added (450 mL). This slurry was stirred for twenty minutes then dried at 46 °C for 11.5 hours under nitrogen flow. The supported catalyst was recovered as an orange, free flowing solid (1092.2 g) which was passed through a 25 mesh screen.
  • the polymerization procedure for producing homopolymers with the supported catalysts was as follows. In a clean, dry two liter autoclave which had been flushed with propylene vapor, TEAL scavenger (0.3 mL, 1.5M) was added. Hydrogen gas was added at this point. The reactor was closed and filled with 800 mL liquid propylene. After heating the reactor to 70 °C , the catalyst was added by washing in with propylene (200 mL). After the indicated time, typically one hour, the reactor was cooled, and the excess propylene vented- The polymer was removed and dried. Results are shown in Tables 1 A and 2A.
  • the polymerization procedure for producing ICP with the supported catalysts was as follows. In a clean, dry two liter autoclave which had been flushed with propylene vapor, TEAL scavenger (0.3 mL, 1.5M) was added.
  • Results are shown in Tables IB, 2B and 3-8.
  • DSC melting points were determined on commercial DSC instruments and are reported as the second melting point.
  • the polymer sample was heated to 230.0°C for ten minutes and then cooled from 230°C to 50°C at 10°C/minute. The sample is held at 50°C for five minutes.
  • the second melt is then recorded as the sample is heated from 50°C to 200°C at a rate of 10°C/minute.
  • the peak temperature is recorded as the second melting point.
  • the ICP polymer was dissolved in hot xylene and then allowed to cool overnight. After filtration the insolubes are dried. The xylene soluble portion was evaporated and the soluble material recovered. The IV of the recovered soluble material was measured in decalin at 135°C by using known methods and instruments such as a Schott A VSPro Viscosity Automatic Sampler. At very high ICP MFR this method can extract some low molecular weight isotactic PP and thus lower the observed IV.
  • the ICP products from the reactor were dry blended with additives (lOOOppm Irganox 3114; 600ppm Irgafos 168; 500ppm Kemamide U; 2000ppm sodium benzoate; 600ppm DSTDP), followed by compounding/pelletization on a laboratory extrusion line to make pellets. After pelletization, injection molded bars (127 mm x 12.7 mm x 3.2 mm) were fabricated using a Butler laboratory injection molding machine (Model No. 10/90V).
  • ASTM type tests were conducted on the molded samples to measure 1% secant flexual modulus (ASTM D-790A); Heat Distortion Temperature at 66 psi (455 kPa) (ASTM D-648); Izod impact strength (notched at 23°C and unnotched at -40°C, ASTM D-256).
  • the impact copolymers of this invention display improved impact properties as measured by the room temperature notched Izod values at similar Flexural Modulus. This can be seen by examining Table 8.
  • the ICP from inventive run 43 with inventive metallocene F has a Flexural Modulus of 151.8 kpsi (1046.9 MPa) with a Notched Izod of 1.57 ft-lb/inch (83.8 J/m) value
  • the ICP from inventive run 50 with inventive metallocene G has a Flexural Modulus of 158.3 kpsi (1091.5 MPa) with a Notched Izod of 1.7 ft-lb/inch (90.7 J/m) value.
  • the improved impact strength at comparable modulus results from a higher molecular weight, as measured by IV, of Component B.
  • the known metallocenes comparison 1 and 2 are limited to low values for this molecular weight as measured by the IV of Component B.
  • the maximum value of IN for the comparative metallocenes was a value of about 1.7 dl/g for run 9 (Table IB) with the ethylene/propylene at a 4.2/0.8 ratio.
  • Inventive metallocene B at this ratio produced an IV that ranged from 1.99 dl/g in run 13 to 2.338 dl/g in run 18.
  • the inventive metallocene D produced an ICP with an IV of 3.508 dl/g in run 40.

Abstract

This invention relates to propylene impact copolymer compositions. In particular, these unique and improved compositions can be produced using conventional, commercial-scale processes.

Description

PROPYLENE IMPACT COPOLYMERS
FIELD This invention relates to propylene impact copolymer compositions. In particular, these unique and improved compositions can be produced using metallocene catalysts in commercial-scale processes.
BACKGROUND Propylene impact copolymers are commonly used in a variety of applications where strength and impact resistance are desired such as molded and extruded automobile parts, household appliances, luggage and furniture. Propylene homopolymers are often unsuitable for such applications because they are too brittle and have low impact resistance particularly at low temperature, whereas propylene impact copolymers are specifically engineered for applications such as these.
A typical propylene impact copolymer contains two phases or components, a homopolymer component and a copolymer component. These two components are usually produced in a sequential polymerization process wherein the homopolymer produced in a first reactor is transferred to a second reactor where copolymer is produced and incorporated within the matrix of the homopolymer component. The copolymer component has rubbery characteristics and provides the desired impact resistance, whereas the homopolymer component provides overall stiffness.
Many process variables influence the resulting impact copolymer and these have been extensively studied and manipulated to obtain various desired effects. For example U.S. Patent No. 5,166,268 describes a "cold forming" process for producing propylene impact copolymers where finished articles are fabricated at temperatures below the melting point of the preform material, in this case, the propylene impact copolymer. The patented process uses a propylene impact copolymer comprised of either a homopolymer or crystalline copolymer matrix (first component) and at least ten percent by weight of an "interpolymer" of ethylene and a small amount of propylene (the second component). Adding comonomer to the first component lowers its stiffness. The ethylene/propylene copolymer second component enables the finished, cold-formed article to better maintain its shape.
U.S. Patent No. 5,258,464 describes propylene impact copolymers with improved resistance to "stress whitening." Stress whitening refers to the appearance of white spots at points of impact or other stress. These otherwise conventional propylene impact copolymers have first and second components characterized by a numerical ratio of the second component intrinsic viscosity to the first component intrinsic viscosity which is near unity.
In U.S. Patent No. 5,362,782, nucleating agent is added to propylene impact copolymers having a numerical ratio of the intrinsic viscosity of the copolymer rubber phase (second component) to the intrinsic viscosity of the homopolymer phase (first component) which is near unity, and an ethylene content of the copolymer phase in the range of 38% to 60% by weight. These propylene impact copolymers are described as producing articles having good clarity as well as impact strength and resistance to stress whitening. The nucleating agents increase stiffness and impact strength.
U.S. Patent No. 5,250,631 describes a propylene impact copolymer having a homopolypropylene first component and an ethylene/butene/propylene terpolymer second component. Again, the goal is to obtain high impact strength coupled with resistance to stress whitening.
Propylene impact copolymers are also used to produce films as described in U.S. Patent No. 5,948,839. The impact copolymer described in this patent contains a conventional first component and 25 to 45 weight percent ethylene/propylene second component having from 55 to 65 weight percent ethylene. This impact copolymer composition has a melt flow of from 7 to 60 dg/min. Such films are used in articles such as diapers.
Recently, efforts have been made to prepare propylene impact copolymers using the newly developed metallocene catalysis technology in order to capitalize on the inherent benefits such catalysts provide. It is well known that homopolymers prepared with such "single-site" catalysts have narrow molecular weight distributions, and low extractables and a variety of other favorable properties associated therewith. Metallocene catalyzed copolymers have narrow composition distributions in addition to narrow molecular weight distribution and low extractables.
Unfortunately, known metallocenes are not able to provide copolymer components with high enough molecular weight under commercially relevant process conditions. The resulting propylene impact copolymers have poor impact strength compared to their conventionally catalyzed counterparts.
U.S. 5,990,242 approaches this problem by using an ethylene/butene (or higher α-olefin) copolymer second component, rather than a propylene copolymer, prepared using a hafnocene type metallocene. Such hafnium metallocenes in general are known for producing relatively higher molecular weight polymers; however, their activities are much lower than the more commonly used zirconocenes. In any event, the second component molecular weights and intrinsic viscosities are lower than desired for good impact strength.
The present inventors have discovered new propylene impact copolymer compositions having the benefits of metallocene catalyzed polymers in addition to properties needed for high impact strength. Importantly, these polymers can be economically produced using commercial-scale processes. SUMMARY
The present invention provides reactor produced propylene impact copolymer compositions comprising:
(a) From about 40% to about 95% by weight Component A based on the total weight of the impact copolymer, Component A comprising propylene homopolymer or copolymer wherein the copolymer comprises 10% or less by weight ethylene, butene, hexene or octene comonomer;
(b) From about 5% to about 60% by weight Component B based on the total weight of the impact copolymer, Component B comprising propylene copolymer wherein the copolymer comprises from about 20% to about 70% by weight ethylene, butene, hexene and/or octene comonomer, and from about 80% to about 30% by weight propylene, wherein Component B:
(i) has a weight average molecular weight of at least 100,000; (ii) a composition distribution of greater than 60%; and (iii) an intrinsic viscosity of greater than 1.00 dl/g.
This invention also provides a process for producing propylene impact copolymer in a multiple stage process wherein Component A comprising propylene homopolymer or copolymer wherein the copolymer comprises 10% or less by weight ethylene, butene, hexene or octene comonomer is produced in a primary stage and Component B is produced in a subsequent stage, Component B comprising propylene copolymer wherein the copolymer comprises from about
20% to about 70% by weight ethylene, butene, hexene and/or octene comonomer, and from about 80% to about 30% by weight propylene, wherein at least one of Components A and/or B are polymerized using a metallocene selected from the group consisting of: rac-dimethylsiladiyl(2-iPr,4-phenylindenyl)2zirconium dichloride; rac-dimethylsiladiyl(2-iPr,4-[l -naphthyl]indenyl)2zirconium dichloride; rac-dimethylsiladiyl(2-iPr, 4-[3,5-dimethylphenyl]indenyl)2zirconium dichloride; rac-dimethylsiladiyl(2-iPr, 4-[ortho-methyl-phenyl]indenyl)2zirconium dichloride; and rac-diphenylsiladiyl(2-methyl-4-[ 1 -naphthyl]indenyl)2zirconium dichloride.
BRIEF DESCRIPTION OF DRAWINGS Figure 1 is a plot of Notched Isod values as a function of Flexural Modulus data from Table 8.
DESCRIPTION
The propylene impact copolymers ("ICPs") of this invention comprise at least two major components, Component A and Component B. Component A is preferably an isotactic propylene homopolymer, though small amounts of a comonomer may be used to obtain particular properties. Typically such copolymers of Component A contain 10% by weight or less, preferably less than 6% by weight or less, comonomer such as ethylene, butene, hexene or octene. Most preferably less than 4% by weight ethylene is used. The end result is usually a product with lower stiffness but with some gain in impact strength compared to homopolymer Component A.
As used herein Component A refers generally to the xylene insoluble portion of the ICP composition, and Component B refers generally to the xylene soluble portion. Where the xylene soluble portion clearly has both a high molecular weight component and a low molecular weight component, we have found that the low molecular weight component is attributable to amorphous, low molecular weight propylene homopolymer. Therefore, Component B in such circumstances refers only to the high molecular weight portion.
Component A preferably has a narrow molecular weight distribution Mw/Mn ("MWD"), i.e., lower than 4.0, preferably lower than 3.5, more preferably lower than 3.0, and most preferably 2.5 or lower. These molecular weight distributions are obtained in the absence of visbreaking using peroxide or other post reactor treatment designed to reduce molecular weight. Component A preferably has a weight average molecular weight (Mw as determined by GPC) of at least 100,000, preferably at least 200,000 and a melting point (Mp) of at least 145°C, preferably at least 150°C, more preferably at least 152°C, and most preferably at least 155°C.
Another important feature of ICPs is the amount of amorphous polypropylene they contain. The ICPs of this invention are characterized as having low amorphous polypropylene, preferably less than 3% by weight, more preferably less than 2% by weight, even more preferably less than 1% by weight and most preferably there is no measurable amorphous polypropylene.
Component B is most preferably a copolymer consisting essentially of propylene and ethylene although other propylene copolymers, ethylene copolymers or terpolymers may be suitable depending on the particular product properties desired. For example, propylene/butene, hexene or octene copolymers, and ethylene/butene, hexene or octene copolymers may be used, and propylene/ethylene/hexene-1 terpolymers may be used. In a preferred embodiment though, Component B is a copolymer comprising at least 40% by weight propylene, more preferably from about 80% by weight to about 30% by weight propylene, even more preferably from about 70% by weight to about 35% by weight propylene. The comonomer content of Component B is preferably in the range of from about 20% to about 70% by weight comonomer, more preferably from about 30% to about 65% by weight comonomer, even more preferably from about 35% to about 60% by weight comonomer. Most preferably Component B consists essentially of propylene and from about 20% to about 70% ethylene, more preferably from about 30% to about 65% ethylene, and most preferably from about 35% to about 60% ethylene.
For other Component B copolymers, the comonomer contents will need to be adjusted depending on the specific properties desired. For example, for ethylene/hexene copolymers, Component B should contain at least 17% by weight hexene and at least 83% by weight ethylene. Component B, preferably has a narrow molecular weight distribution Mw/Mn ("MWD"), i.e., lower than 5.0, preferably lower than 4.0, more preferably lower than 3.5, even more preferably lower than 3.0 and most preferably 2.5 or lower. These molecular weight distributions should be obtained in the absence of visbreaking or peroxide or other post reactor treatment designed to reduce molecular weight. Component B preferably has a weight average molecular weight (Mw as determined by GPC) of at least 100,000, preferably at least 150,000, and most preferably at least 200,000.
Component B preferably has an intrinsic viscosity greater than 1.00 dl/g, more preferably greater than 1.50 dl/g and most preferably greater than 2.00 dl/g. The term "intrinsic viscosity" or "IN" is used conventionally herein to mean the viscosity of a solution of polymer such as Component B in a given solvent at a given temperature, when the polymer composition is at infinite dilution. According to the ASTM standard test method D 1601-78, IN measurement involves a standard capillary viscosity measuring device, in which the viscosity of a series of concentrations of the polymer in the solvent at the given temperature are determined. For Component B, decalin is a suitable solvent and a typical temperature is 135°C. From the values of the viscosity of solutions of varying concentrations, the "value" at infinite dilution can be determined by extrapolation.
Component B preferably has a composition distribution (CD) of greater than 60%, more preferably greater than 65%, even more preferably greater than 70%o, even more preferably greater than 75%, still more preferably greater than 80%, and most preferably greater than 85%. CD defines the compositional variation among polymer chains in terms of ethylene (or other comonomer) content of the copolymer as a whole. The measurement of CD is described in detail U.S. Patent No. 5,191,042 which is hereby fully incorporated by reference. CD is defined herein as the weight percent of the copolymer molecules having a comonomer content within 50% of the median total molar comonomer content. As described in U.S. Patent No. 5,191,042, CD is determined by first determining the mean ethylene (or other comonomer) content of the copolymer by a suitable test such as ASTM D-3900. Next, the copolymer sample is dissolved in solvent such as hexane and a number of fractions of differing composition are precipitated by the addition of incremental amounts of a liquid such as isopropanol in which the copolymer is insoluble. Generally from about 4 to 6 fractions are precipitated in this way and the weight and ethylene (or other comonomer) content of each fraction are determined after removing the solvent. From the weight of each fraction and its ethylene content, a plot is prepared of weight percent composition vs. cumulative weight percent of polymer, and a smooth curve is drawn through the points.
Component B of the ICPs preferably has low crystallinity, preferably less than 10% by weight of a crystalline portion, more preferably less than 5% by weight of a crystalline portion. Where there is a crystalline portion of Component
B, its composition is preferably the same as or at least similar to (within 15% by weight) the remainder of Component B in terms of overall comonomer weight percent.
The ICPs of this invention are "reactor produced" meaning Components A and B are not physically or mechanically blended together. Rather, they are interpolymerized in at least one reactor. The final ICP as obtained from the reactor or reactors, however, can be blended with various other components including other polymers.
The preferred melt flow rate ("MFR") of these ICPs depends on the desired end use but is typically in the range of from about 0.2 dg min to about 200 dg/min, more preferably from about 5 dg/min to about 100 dg/min. Significantly, high MFRs, i.e., higher than 50 dg/min are obtainable. MFR is determined by a conventional procedure such as ASTM-1238 Cond. L. The ICP preferably has a melting point of at least 145°C, preferably at least 150°C, more preferably at least 152°C, and most preferably at least 155°C. * The ICPs comprise from about 40% to about 95% by weight Component A and from about 5% to about 60% by weight Component B, preferably from about 50% to about 95% by weight Component A and from about 5% to about 50% Component B, even more preferably from about 60% to about 90% by weight
Component A and from about 10 % to about 40% by weight Component B. In the most preferred embodiment, the ICP consists essentially of Components A and B. The overall comonomer (preferably ethylene) content of the total ICP is preferably in the range of from about 2% to about 30% by weight, preferably from about 5% to about 25% by weight, even more preferably from about 5% to about
20% by weight, still more preferably from about 5% to about 15% by weight comonomer.
A variety of additives may be incorporated into the ICP for various purposes. Such additives include, for example, stabilizers, antioxidants, fillers, colorants, nucleating agents and mold release agents.
The ICP compositions of this invention may be prepared by conventional polymerization processes such as a two-step process. It is conceivable, although currently impractical, to commercially produce ICPs in a single reactor. Each step may be independently carried out in either the gas or liquid slurry phase. For example the first step may be conducted in the gas phase and the second in liquid slurry or vice versa. Alternatively, each phase may be the same. Preferably the ICPs of this invention are produced in multiple reactors, preferably two or three, operated in series, Component B is preferably polymerized in a second, gas phase reactor. Component A is preferably polymerized first, in a liquid slurry or solution polymerization process.
In an alternative embodiment, Component A is made in at least two reactors in order to obtain fractions with varying melt flow rate. This has been found to improve the processability of the ICP. As used herein "stage" is defined as that portion of a polymerization process during which one component of the ICP, Component A or Component B, is produced- One or multiple reactors may be used during each stage.
Hydrogen may be added to one or both reactors to control molecular weight, IN and MFR. The use of hydrogen for such purposes is well known to those skilled in the art.
Preferably a metallocene catalyst system is used to produce the ICP compositions of this invention. To date it appears that the most suitable metallocenes are those in the generic class of bridged, substituted bis(cyclopentadienyl) metallocenes, specifically bridged, substituted bis(indenyl) metallocenes known to produce high molecular weight, high melting, highly isotactic propylene polymers. Generally speaking, those of the generic class disclosed in U.S. Patent No. 5,770,753 (fully incorporated herein by reference) should be suitable, however, it has been found that the exact polymer obtained is highly dependent on the metallocene's specific substitution pattern.
We have found that the following racemic metallocenes are most suitable for preparing the ICP compositions of this invention: rac-dimethylsiladiyl(2-iPr,4~ phenylindenyl)2zirconium dichloride; rac-dimethylsiladiyl(2-iPr,4-[ 1 - naphthyl]indenyl)2zirconium dichloride; rac-dimethylsiladiyl(2-iPr, 4-[3,5- dimethylphenyl]indenyl)2zircorιium dichloride; rac-dimethylsiladiyl(2-iPr, 4-
[ortho-methyl-phenyl]indenyl)2zirconium dichloride; and rac-diphenylsiladiyl(2- methyl-4-[l-naphthyl]indenyl)2zirconium dichloride. It will be immediately apparent to those skilled in the art that certain modifications to these metallocene species are not likely to result in significantly modified ICP composition though activity or ease of synthesis may be impacted- While not wishing to be bound by theory, it is believed that the critical feature of these specific metallocenes is their substitution pattern on the base indenyl group. Thus, it is believed that changing the bridge, for example substituting carbon for silicon, or changing the metal to hafnium or titanium, or changing the metal dichloride to some other dihalide or dimethyl, will not significantly change the ICP compositions of this invention. On the other hand, substituting a group at any position on the indenyl for another or adding one or more groups or substitutents is likely to result in a significantly different composition which may or may not be an ICP of this invention.
Metallocenes are generally used in combination with some form of activator in order to create an active catalyst system. The term "activator" is defined herein to be any compound or component, or combination of compounds or components, capable of enhancing the ability of one or more metallocenes to polymerize olefins. Alkylalumoxanes such as methylalumoxane (MAO) are commonly used as metallocene activators. Generally alkylalumoxanes contain 5 to 40 of the repeating units:
R(A1R0)XA1R2 for linear species and (AlRO)x for cyclic species
where R is a Cj-Cg alkyl including mixed alkyls. Compounds in which R is methyl are particularly preferred. Alumoxane solutions, particularly methylalumoxane solutions, may be obtained from commercial vendors as solutions having various concentrations. There are a variety of methods for preparing alumoxane, 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, 5,103,031 and EP-A-0 561 476, EP-Bl-0 279 586, EP-A-0 594-218 and WO 94/10180, each fully incorporated herein by reference.
Ionizing activators may also be used to activate metallocenes. These activators are neutral or ionic, or are compounds such as tri(n-butyl)ammonium tetrakis(pentafluorophenyl)borate, which ionize the neutral metallocene compound. Such ionizing compounds may contain an active proton, or some other cation associated with, but not coordinated or only loosely coordinated to, the remaining ion of the ionizing compound. Combinations of activators may also be used, for example, alumoxane and ionizing activator combination, see for example, WO 94/07928.
Descriptions of ionic catalysts for coordination polymerization comprised of metallocene cations activated by non-coordinating anions appear in the early work in EP-A-0 277 003, EP-A-0 277 004 and US patent 5,198,401 and WO-A- 92/00333 (incorporated herein by reference for purposes of U.S. patent practice). These teach desirable methods of preparation wherein metallocenes (bisCp and monoCp) are protonated by an anion precursor such that an alkyl/hydride group is abstracted from a transition metal to make it both cationic and charge-balanced by the non-coordinating anion. Suitable ionic salts include tetrakis-substituted borate or aluminum salts having fluorided aryl-constituents such as phenyl, biphenyl and napthyl.
The term "noncoordinating 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" noncoordinating anions are those which are not degraded to neutrality when the initially formed complex decomposes. Further, the anion will not transfer an anionic substituent or fragment to the cation so as to cause it to form a neutral four coordinate metallocene compound and a neutral by-product from the anion. Particularly useful noncoordinating anions are those which are compatible, stabilize the metallocene cation in the sense of balancing its ionic charge in a +1 state, yet retain sufficient liability to permit displacement by an ethylenically or acetylenically unsaturated monomer during polymerization.
The use of ionizing ionic compounds not containing an active proton but capable of producing both the active metallocene cation and a noncoordinating anion is also known. See, for example, EP-A-0 426 637 and EP-A- 0 573 403 (incorporated herein by reference for purposes of U.S. patent practice). An additional method of making the ionic catalysts uses ionizing anion precursors which are initially neutral Lewis acids but form the cation and anion upon ionizing reaction with the metallocene compounds, for example the use of tris(pentafluorophenyl) borane. See EP-A-0 520 732 (incorporated herein by reference for purposes of U.S. patent practice). Ionic catalysts for addition polymerization can also be prepared by oxidation of the metal centers of transition metal compounds by anion precursors containing metallic oxidizing groups along with the anion groups, see EP-A-0 495 375 (incorporated herein by reference for purposes of U.S. patent practice).
Where the metal ligands include halogen moieties (for example, bis- cyclopentadienyl zirconium dichloride) which are not capable of ionizing abstraction under standard conditions, they 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 and EP- Al-0 570 982 (incorporated herein by reference for purposes of U.S. patent practice) for in situ processes describing the reaction of alkyl aluminum compounds with dihalo-substituted metallocene compounds prior to or with the addition of activating anionic compounds. '
Methods for supporting ionic catalysts comprising metallocene cations and NCA are described in U.S. Patent No. 5,643,847, U.S. Patent Application No.
09184358, filed November 2, 1998 and U.S. Patent Application No. 09184389, filed November 2, 1998 (all fully incorporated herein by reference for purposes of
U.S. patent practice).
When the activator for the metallocene supported catalyst composition is a
NCA, preferably the NCA is first added to the support composition followed by the addition of the metallocene catalyst. When the activator is MAO, preferably the MAO and metallocene catalyst are dissolved together in solution. The support is then contacted with the MAO/metallocene catalyst solution. Other methods and order of addition will be apparent to those skilled in the art. The catalyst systems used to prepare the compositions of this invention are preferably supported using a porous particulate material, such as for example, talc, inorganic oxides, inorganic chlorides and resinous materials such as polyolefin or polymeric compounds.
Preferably, the support materials are porous inorganic oxide materials, which include those from the Periodic Table of Elements of Groups 2, 3, 4, 5, 13 or 14 metal oxides. Silica, alumina, silica-alumina, and mixtures thereof are particularly preferable. Other inorganic oxides that may be employed either alone or in combination with the silica, alumina or silica-alumina are magnesia, titania, zirconia, and the like.
Preferably the support material is porous silica which has a surface area in the range of from 10 to 700"m-2/g, a total pore volume in the range of from 0.1 to 4.0 cc/g and an average particle size in the range of from 10 to 500 μm. More preferably, the surface area is in the range of from 50 to 500 m-^/g, the pore volume is in the range of from 0.5 to 3.5 cc/g and the average particle size is in the range of from 20 to 200 μm. Most desirably the surface area is in the range of from 100 to 400 m-2/g, the pore volume is in the range of from 0.8 to 3.0 cc/g and the average particle size is in the range of from 30 to 100 μm. The average pore size of typical porous support materials is in the range of from 10 to 1000 A. Preferably, a support material is used that has an average pore diameter of from 50 to 50θA, and most desirably from 75 to 35θA. It may be particularly desirable to dehydrate the silica at a temperature of from 100°C to 800°C anywhere from 3 to 24 hours.
The metallocenes, activator and support material may be combined in any number of ways. Suitable support techniques are described in U. S Patent Nos.
4,808,561 and 4,701,432 (each folly incorporated herein by reference). Preferably the metallocenes and activator are combined and their reaction product supported on the porous support material as described in U. S. Patent No. 5,240,894 and WO 94/ 28034, WO 96/00243, and WO 96/00245 (each folly incorporated herein by reference for purposes of U.S. patent practice). Alternatively, the metallocenes may be preactivated separately and then combined with the support material either separately or together. If the metallocenes are separately supported, then preferably, they are dried then combined as a powder before use in polymerization.
Regardless of whether the metallocenes and their activator are separately precontacted or whether the metallocenes and activator are combined at once, the total volume of reaction solution applied to porous support is desirably less than 4 times the total pore volume of the porous support, more desirably less than 3 times the total pore volume of the porous support and even more desirably in the range of from more than 1 to less than 2.5 times the total pore volume of the porous support. Procedures for measuring the total pore volume of porous support are well known in the art. One such method is described in Volume 1, Experimental
Methods in Catalyst Research, Academic Press, 1968, pages 67-96.
Methods of supporting ionic catalysts comprising metallocene cations and noncoordinating anions are described in WO 91/09882, WO 94/03506, WO 96/04319 and in co-pending U.S. Ser. No. 08/248,284, filed August 3 1994
(incorporated herein by reference for purposes of U.S. patent practice). The methods generally comprise either physical adsorption on traditional polymeric or inorganic supports that have been largely dehydrated and dehydroxylated, or using neutral anion precursors that are sufficiently strong Lewis acids to activate retained hydroxy groups in silica containing inorganic oxide supports such that the
Lewis acid becomes covalently bound and the hydrogen of the hydroxy group is available to protonate the metallocene compounds.
The supported catalyst system may be used directly in polymerization or the catalyst system may be prepolymerized using methods well known in the art.
For details regarding prepolymerization, see United States Patent Nos. 4,923,833 and 4,921,825, EP 0 279 863 and EP 0 354 893 each of which is folly incorporated herein by reference.
While the present invention has been described and illustrated by reference to particular embodiments, it will be appreciated by those of ordinary skill in the art, that the invention lends itself to many different variations not illustrated herein. For these reasons, then, reference should be made solely to the appended claims for purposes of determining the true scope of the present invention.
Although the appendant claims have single appendencies in accordance with U.S. patent practice, each of the features in any of the appendant claims can be combined with each of the features of other appendant claims or the main claim.
EXAMPLES
All air sensitive experiments are carried out in nitrogen purged dry boxes. All solvents were purchased from commercial sources. 4-Chloro-2- isopropylindene was purchased from commercial sources. Aluminum alkyls were purchased as hydrocarbon solutions from commercial sources. The commercial methylalumoxane ("MAO") was purchased from Albemarle as a 30 wt% solution in toluene.
METALLOCENE SYNTHESIS
Metallocene A: racemic dimethylsiladiyl(2-isopropyl-4-phenylindenyl)2 zirconium dichloride was obtained from commercial sources and used as received.
Metallocene B: racemic dimethylsiladiyl(2-isopropyl-4-[l-naphthyl]indenyl)2 zirconium dichloride was obtained from commercial sources and used as received. Metallocene C: racemic dimethylsiladiyl(2-isopropyl-4-[2-methyl- phenyl]indenyl)2 zirconium dichloride was prepared as follows:
4-(2-methylphenyl)-2-isopropylindene
4-Chloro-2-isopropylindene (9.8 g, 51 mmol) and NiCl2(PPh3)2 (1.8g, 2.8 mmol) are dissolved in 150 mL of Et2O. 2-Methylphenylmagnesium bromide (51 mmol) as an Et20 solution was added to the solution and the reaction was stirred overnight at room temperature. After overnight stirring, the reaction was slowly quenched with H20 to neutralize unreacted Grignard. The solution was subsequently treated with 100 mL of 10% HCl(aq) and neutralized with saturated sodium bicarbonate aqueous solution. The organic layer was dried with magnesium sulfate and the solvent was removed by rotary evaporation. The remaining residue was loaded onto a silica gel column and eluted with hexane. Yield was 6.6 g (52%).
Lithium 4-(2-methylphenyl)-2-isopropylindenide
4-(2-methylphenyl)-2-isopropylindene (6.6 g, 26.5 mmol) was dissolved in 80 mL of pentane. To this solution was added 10.6 mL of n-BuLi (2.5M in hexane) and the reaction was allowed to stir 4 hours at room temperature. A white solid precipitates from solution and was collected by frit filtration and washed with additional pentane. Yield was 5.8 g (88%).
Dimethylsiladiylbis[4-(2-methylphenyl)-2-isopropylindene]
SiMe2Cl2 (0.88 g, 6.8 mmol) was dissolved in 60 mL of THF. While stirring, lithium 4-(2-methylphenyl)-2-isopropylindenide (3.5 g, 13.7 mmol) was added as a dry powder and the contents are allowed to stir overnight at room temperature. The solvent was removed in vacuo and the residue was taken up in pentane and filtered to remove LiCl salts. The pentane was removed in vacuo to yield a flaky, white solid (3.0 g). Dimethylsiladiylbis[4-(2-methylphenyl)-2-isopropylindenyl]ZrCl
Dimethylsiladiylbis[4-(2-methylphenyl)-2-isopropylindene] (3.0 g, 5.4 mmol) was dissolved in 60 mL of Et2O. While stirring, 4.5 mL of n-BuLi (2.5M in hexane) was added and allowed to stir at room temperature for 2 hours. After this time, the solution was cooled to -35°C and ZrCl4 (1.25 g, 5.4 mmol) was added and allowed to stir at room temperature for 3 hours. The solvent was then removed in vacuo and the residue was taken up in a mixture of methylene chloride and pentane and filtered to remove LiCl salts. The filtrate was then concentrated and chilled to -35°C to induce crystallization. 0.26 g (6.7%) of pure racemic compound was obtained.
Metallocene D: racemic dimethylsiladiyl(2- isopropyl-4-[3,5- dimethylphenyl]indenyl)2 zirconium dichloride was prepared as follows:
4-(3 , 5-dimethylphenyl)-2-isopropylindene
4-Chloro-2-isoρropylindene (10.4 g, 54 mmol) and NiCl2(PPh3)2 (1.8 g, 2.8 mmol) are dissolved in 150 mL of Et2O. 3,5-dimethylphenylmagnesium bromide (54 mmol) as an Et20 solution was added under vigorous stirring and the reaction was stirred overnight at room temperature. After overnight stirring, the reaction was slowly quenched with H20 to neutralize unreacted Grignard. The solution was subsequently treated with 100 mL of 10% HC1 (aq) and neutralized with saturated sodium bicarbonate aqueous solution. The organic layer was dried
- with magnesium sulfate, and the solvent was removed by rotary evaporation. The remaining residue was loaded onto a silica gel column and eluted with hexane.
Yield was 5.5 g (39%). Lithium 4-(3,5-dimethylphenyl)-2-isopropyhndenide
4-(3,5-Dimethylphenyl)-2-isopropylindene (5.5 g, 21 mmol) was dissolved in 80 mL of pentane- To this solution was added 8.3 mL of n-BuLi (2.5M in hexane) and the reaction was allowed to stir 4 hours at room temperature. A white solid precipitates from solution and was collected by frit filtration and washed with additional pentane. Yield was 3.28 g (60%).
Dimethylsiladiylbis[4-(3,5-dimethylphenyl)-2-isopropylindene]
SiMe2Cl2 (0.69g, 5.4 mmol) was dissolved in 80 mL of THF. While stirring, lithium 4-(3,5-methylphenyl)-2-isopropylindenide (2.9 g, 10.8 mmol) was added as a dry powder and the contents are allowed to stir overnight at room temperature. The solvent was removed in vacuo and the residue was taken up in pentane and filtered to remove LiCl salts. The pentane was removed in vacuo to yield a flaky, white solid (2.1g, 67%)
Dimethylsiladiylbis[4-(3,5-dimethylphenyl)-2-isopropylindenyl]ZrCl2
Dimethylsiladiylbis[4-(3,5-dimethylphenyl)-2-isopropylindene] (2.1g, 3.6 mmol) was dissolved in 60 mL of Et2O. While stirring, 2.9 mL of n-BuLi (2.5M in hexane) was added and allowed to stir at room temperature for 2 hours. After this time, the solution was cooled to -35°C and ZrCl (0.83 g, 3.6 mmol) was added and allowed to stir at room temperature for 3 hours. The solvent was then removed in vacuo and the residue was taken up in toluene and filtered to remove
LiCl salts. The filtrate was then concentrated and chilled to -35°C to induce crystallization. 0.24 g (6.0%) of pure racemic compound was obtained.
Metallocene E: racemic diphenylsiladiyl(2-methyl-4-[l-naphthyl]indenyl)2 zirconium dichloride was prepared as follows. Ph2Si(2-Methyl-4-ri-naρthyllindene)2
2-Methyl-4-|T-napthyl]indenyl lithium (5.5 g, 21 mmol) was added to a solution of Ph2Si(OSO2CF3)2 (4.8 g, 10 mmol) and diethyl ether (50 mL). The mixture was stirred overnight then the product was isolated by filtration, washed with diethyl ether (4 x 50 mL) then dried in vacuo. Yield 4.71 g, 68 %.
The method described above reacting Ph2Si(OSO2CF3)2 with 2-Methyl-
4-[l-napthyl]indenyl lithium to form the ligand system with a Ph2Si bridge is a general one. A wide variety of cyclopentadienyl or indenyl metal salts can be reacted with Ph2Si(OSO2CF3)2 when Ph2Si(Cl)2 is unreactive or slow with the cyclopentadienyl or indenyl metal salt reagent.
Ph2Si(2-Methyl-4-ri -napthyllindenyl SnMe3)2
A slurry of Ph2Si(2-Methyl-4-[l-napthyl]indenyl lithium)2 was prepared from addition of a 2.0 M solution of n-Butyl lithium and pentane (1.5 mL, 3.0 mmol) to a mixture of Ph2Si(2-Methyl, 4-napthyl indene)2 (1.0 g, 1.44 mmol) and diethyl ether (20 mL). After stirring for two hours, trimethyl tin chloride (0.6 g, 3.0 mmol) was added. The color changed instantly from an intense to light yellow. The ether was removed and the product extracted with pentane (3 x 20 mL). Removal of solvent yielded product. Yield 0.88 g, 60 %.
racemic-Ph2Si(2-Methyl-4-[l-napthyl]indenyl)2ZrCl2
A 100 mL flask was charged with ZrCl4 (180 mg, 0.77 mmol), toluene (20 mL) then Ph2Si(2-Methyl-4-[l-napthyl]indenyl SnMe3)2 (815 mg, 0.8 mmol). The mixture was stirred overnight then heated in vacuo at 90 °C for 48h. The orange powder was taken up in toluene (5 mL) then filtered through a 0.45 μm filter. Diethyl ether (2-3 mL) was added to the toluene solution and the solution cooled to -30 °C. After prolonged cooling crystals were isolated then washed with cold toluene (3 1 mL) then pentane (3 x 5 mL). After further washing with toluene (3 x 1 mL) and hexane (3 x 5 mL) the sample was dried to obtain product- Yield 17 mg, 2.6%.
Comparison Metallocene 1 : racemic dimethylsiladiyl(2-methyl-4-phenylindenyl)2 zirconium dichloride was obtained from commercial sources and used as received.
Comparison Metallocene 2: racemic dimethylsiladiyl(2- methyl-4-[l- naphthyl]indenyl)2 zirconium dichloride was obtained from commercial sources and used as received.
Comparison Metallocene 3 : racemic dimethylsiladiyl(2-methyl-4-phenylindenyl)2 zirconium dichloride was obtained from commercial sources and used as received.
Comparison Metallocene 4: racemic dimethylsiladiyl(2-ethyl-4-phenylindenyl)2 zirconium dichloride was obtained from commercial sources and used as received.
SUPPORTED CATALYST SYSTEM SYNTHESIS
Supported Metallocene Catalyst System A
In a 100 mL round bottom flask dimethylsiladiyl(2-iPr-4-phenyl indenyl)2 zirconium dichloride (A, 0.060 g) was added to the MAO-toluene solution (6.74 g, 7.2 mL) and stirred twenty minutes. This was filtered through a medium glass frit funnel and washed with toluene (14 mL). To the combined filtrates was added dehydrated silica (4.0 g, Davison 948 Regular, 600°C dehydration). This slurry was stirred for twenty minutes, then dried at 40 °C for two minutes under vacuum on a rotary evaporator until the liquid evaporated and then the solid was further dried a total of about 2 hours and twenty minutes. The supported catalyst was recovered as a reddish purple, free flowing solid (5.71 g). Supported Metallocene Catalyst System B
In a 100 mL round bottom dimethylsiladiyl(2- isopropyl-4-[l- naphthyl]indenyl)2 zirconium dichloride (B, 0.069 g) was added to the MAO- toluene solution (6.74 g, 7.2 mL) and stirred twenty minutes. This was filtered through a medium glass frit funnel and washed with toluene (14 mL). To the combined filtrates was added dehydrated silica (4.0 g, Davison 948 Regular, 600°C dehydration). This slurry was stirred for thirty minutes, then dried at 40 °C for two minutes under vacuum on a rotary evaporator until the liquid evaporated and then the solid was dried a total of about 2 hours and twenty minutes. The supported catalyst was recovered as a light purple, free flowing solid (5.4 g).
Supported Metallocene Catalyst System C
In a 100 mL round bottom dimethylsiladiyl(2- isopropyl-4-[2-methyl- phenyl]indenyl)2 zirconium dichloride (C, 0.069 g) was added to the MAO- toluene solution (6.74 g, 7.2 mL) and stirred twenty minutes. This was filtered through a medium glass frit funnel and washed with toluene (14 L). To the combined filtrates was added dehydrated silica (4.0 g, Davison 948 Regular, 600°C dehydration). This slurry was stirred for thirty minutes then dried at 40 °C for two minutes under vacuum on a rotary evaporator until the liquid evaporated and then the solid was further dried a total of about 2 hours and twenty minutes. The supported catalyst was recovered as a light purple, free flowing solid (5.4 g).
Supported Metallocene Catalyst System D
In a 100 mL round bottom dimethylsiladiyl(2- isopropyl-4-[3,5- dimethylphenyl]indenyl)2 zirconium dichloride (D, 0066 g) was added to the MAO-toluene solution (6.74 g, 7.2 mL) and stirred twenty minutes. This was filtered through a medium glass frit funnel and washed with toluene (14 mL). To the combined filtrates was added dehydrated silica (4.0 g, Davison 948 Regular, 600°C dehydration). This slurry was stirred for twenty minutes then dried at 40 °C for two minutes under vacuum on a rotary evaporator until the liquid evaporated and then the solid was further dried a total of about 2 hours and twenty minutes. The supported catalyst was recovered as a purple, free flowing solid (5.11 g).
Supported Metallocene Catalyst System E
In a 100 mL round bottom diphenylsiladiyl(2-methyl-4-[l- naphthyl]indenyl)2 zirconium dichloride (E, 0.017 g) was added to the MAO- toluene solution (1.52 g) and stirred twenty minutes. This was filtered through a medium glass frit funnel and washed with toluene (3.2 mL). To the combined filtrates was added dehydrated silica (4.0 g, Davison 948 Regular, 600°C dehydration). This slurry was stirred for twenty minutes, then dried at 40 °C for two minutes under vacuum on a rotary evaporator until the liquid evaporated and then the solid was further dried a total of about 2 hours and twenty minutes. The supported catalyst was recovered as an orange, free flowing solid (1.06 g).
Supported Metallocene Catalyst System F
In a 100 mL round bottom flask dimethylsiladiyl(2-iPr-4-phenylindenyl)2 zirconium dichloride (F, 0.065 g) was added to the MAO-toluene solution (5.1 g, 5.35 mL) and stirred fifteen minutes. This was filtered through a medium glass frit funnel and washed with toluene (11 mL). To the combined filtrates was added dehydrated silica (4.0 g, Davison 948 Regular, 600°C dehydration). Toluene (2 mL) was added to this slurry, stirred for twenty minutes, dried at 40 °C for ten minutes under vacuum on a rotary evaporator until the liquid evaporated, and then the solid was further dried a total of about two hours and twenty three minutes. The supported catalyst was recovered as a light purple, free flowing solid (5.58 g). Supported Metallocene Catalyst System G
In a 100 mL round bottom flask dimethylsiladiyl(2-iPr-4-phenylindenyl)2 zirconium dichloride (G, 0.065 g) was added to the MAO-toluene solution (5.1 g, 5.4 mL) and stirred fifty minutes. This was filtered through a medium glass frit funnel and washed with toluene (13 mL). To the combined filtrates was added dehydrated silica (4.0 g, Davison 948 Regular, 600°C dehydration). This slurry was stirred for twenty minutes, dried at 40 °C for ten minutes under vacuum on a rotary evaporator until the liquid evaporated and then the solid was further dried a total of about 3 hours. The supported catalyst was recovered as a purple, free flowing solid (5.45 g).
Supported Comparison Metallocene Catalyst System 1
In a 100 mL round bottom racemic dimethylsiladiyl(2-methyl-4- phenylindenyl)2 zirconium dichloride (Comparison metallocene 1, 0.055 g) was added to the MAO toluene solution (6.74 g, 7.2 mL) and stirred twenty minutes. This was filtered through a medium glass frit funnel and washed with toluene (14 mL). To the combined filtrates was added dehydrated silica (4.0 g, Davison 948 Regular, 600°C dehydration). This slurry was stirred for twenty minutes then dried at 40 °C for two minutes under vacuum on a rotary evaporator until the liquid evaporated and then the solid was further dried a total of about 2 hours and twenty two minutes. The supported catalyst was recovered as a light orange, free flowing solid (5.63 g).
Supported Comparison Metallocene Catalyst System 2
In a 100 mL round bottom racemic dimethylsiladiyl(2- methyl-4-[l- naphthyl]indenyl)2 zirconium dichloride (Comparison metallocene 2, 0.064 g) was added to the MAO-toluene solution (6.74 g, 7.2 mL) and stirred twenty minutes-
This was filtered through a medium glass frit funnel and washed with toluene (14 mL). To the combined filtrates was added dehydrated silica (4.0 g, Davison 948 Regular, 600°C dehydration). This slurry was stirred for twenty minutes then dried at 40 °C for two minutes under vacuum on a rotary evaporator until the liquid evaporated and then the solid was further dried a total of about 2 hours. The supported catalyst was recovered as an orange, free flowing solid (4.72 g).
Supported Comparison Metallocene Catalyst System 3
In a two gallon mixer racemic dimethylsiladiyl(2-methyl-4- phenylindenyl)2 zirconium dichloride (Comparison metallocene 3, 13.0 g) was dissolved in a MAO solution (300 mL). This was added to a MAO solution (800 mL diluted with 1600 mL toluene) and an additional 150 mL of toluene was added. This was mixed one hour. One half of this solution was added to dehydrated silica (802.2 g, Davison 948 Regular, 600°C dehydration) and stirred five minutes- The remaining solution was then added and stirred twenty minutes. Additional toluene was added (450 mL). This slurry was stirred for twenty minutes then dried at 46 °C for 11.5 hours under nitrogen flow. The supported catalyst was recovered as an orange, free flowing solid (1092.2 g) which was passed through a 25 mesh screen.
Supported Comparison Metallocene Catalyst System 4
In a 100 mL round bottom racemic dimethylsiladiyl(2-ethyl-4- phenylindenyl)2 zirconium dichloride (Comparison metallocene 4, 0.065 g) was added to the MAO-toluene solution (5.1 g, 5.5 mL) and stirred fifteen minutes. This was filtered through a medium glass frit funnel and washed with toluene (11 mL). To the combined filtrates was added dehydrated silica (4.0 g, Davison 948 Regular, 600°C dehydration). After one addition mL toluene was added this slurry was stirred for twenty minutes then dried at 40 °C under vacuum on a rotary evaporator until the liquid evaporated and then the solid was further dried a total of 2 hours and 23 minutes. The supported catalyst was recovered as a pink, free flowing solid (5.56 g).
POLYMERIZATIONS
Isotactic Polypropylene Homopolymer
The polymerization procedure for producing homopolymers with the supported catalysts was as follows. In a clean, dry two liter autoclave which had been flushed with propylene vapor, TEAL scavenger (0.3 mL, 1.5M) was added. Hydrogen gas was added at this point. The reactor was closed and filled with 800 mL liquid propylene. After heating the reactor to 70 °C , the catalyst was added by washing in with propylene (200 mL). After the indicated time, typically one hour, the reactor was cooled, and the excess propylene vented- The polymer was removed and dried. Results are shown in Tables 1 A and 2A.
Impact Copolymers (ICP)
The polymerization procedure for producing ICP with the supported catalysts was as follows. In a clean, dry two liter autoclave which had been flushed with propylene vapor, TEAL scavenger (0.3 mL, 1.5M) was added.
Hydrogen gas was added at this point. The reactor was closed and filled with 800 mL liquid propylene. After heating the reactor to 70 °C, the catalyst was added by washing in with propylene (200 mL). After the indicated time, typically one hour, the reactor was vented to about 170 psig (1172 kPa) pressure and then an ethylene/propylene gas mixture was passed through the reactor at the rates indicated while maintaining 200 psig (1379 kPa). At the end of the gas phase stage, typically 90 to 150 minutes, the reactor was vented and cooled under N2. The granular ICP polymer was removed and dried- Results are shown in Tables 1 A and 2A. POLYMER ANALYSIS
Results are shown in Tables IB, 2B and 3-8. Molecular weight determinations were made by gel permeation chromatography (GPC) according to the following technique. Molecular weights and molecular weight distributions were measured using a Waters 150°C gel permeation chromatography equipped with Shodex (Showa Denko) AT-80 M S columns and a differential refractive index (DRI) detector operating at 145°C with 1,2,4-trichlorobenzene as the mobile phase at a 1.0 mL/min. flow rate. The sample injection volume was 300 microliters. The columns were calibrated using narrow polystyrene standards to generate a universal calibration curve. The polypropylene calibration curve was established using k = 8.33 X 10"5 and a = 0.800 as the Mark-Houwink coefficients. The numerical analyses were performed using Waters "Millennium" software.
DSC melting points were determined on commercial DSC instruments and are reported as the second melting point. The polymer sample was heated to 230.0°C for ten minutes and then cooled from 230°C to 50°C at 10°C/minute. The sample is held at 50°C for five minutes. The second melt is then recorded as the sample is heated from 50°C to 200°C at a rate of 10°C/minute. The peak temperature is recorded as the second melting point.
ICP POLYMER EXTRACTION METHOD
The ICP polymer was dissolved in hot xylene and then allowed to cool overnight. After filtration the insolubes are dried. The xylene soluble portion was evaporated and the soluble material recovered. The IV of the recovered soluble material was measured in decalin at 135°C by using known methods and instruments such as a Schott A VSPro Viscosity Automatic Sampler. At very high ICP MFR this method can extract some low molecular weight isotactic PP and thus lower the observed IV.
ICP POLYMER FRACTIONATION METHOD
The ICP samples were sent to Polyhedron Laboratories, Inc. to be fractionated and analyzed by GPC. A general description of the procedure is found in the reference J. C. Randall, J. Poly. Sci.: Part A Polymer Chemistry, Vol. 36, 1527-1542 (1998).
PHYSICAL PROPERTY MEASUREMENTS
The ICP products from the reactor were dry blended with additives (lOOOppm Irganox 3114; 600ppm Irgafos 168; 500ppm Kemamide U; 2000ppm sodium benzoate; 600ppm DSTDP), followed by compounding/pelletization on a laboratory extrusion line to make pellets. After pelletization, injection molded bars (127 mm x 12.7 mm x 3.2 mm) were fabricated using a Butler laboratory injection molding machine (Model No. 10/90V). ASTM type tests, were conducted on the molded samples to measure 1% secant flexual modulus (ASTM D-790A); Heat Distortion Temperature at 66 psi (455 kPa) (ASTM D-648); Izod impact strength (notched at 23°C and unnotched at -40°C, ASTM D-256).
The impact copolymers of this invention display improved impact properties as measured by the room temperature notched Izod values at similar Flexural Modulus. This can be seen by examining Table 8. For example, the ICP from inventive run 43 with inventive metallocene F has a Flexural Modulus of 151.8 kpsi (1046.9 MPa) with a Notched Izod of 1.57 ft-lb/inch (83.8 J/m) value, and the ICP from inventive run 50 with inventive metallocene G has a Flexural Modulus of 158.3 kpsi (1091.5 MPa) with a Notched Izod of 1.7 ft-lb/inch (90.7 J/m) value. The comparative examples shown in runs 46, 47 and 48 where the second values for each are 158.6 kpsi (1093.7 MPa), 155.8 kpsi (1074.1 MPa) and 155.7 kpsi (1073.5 -MPa) with an inferior notched Izods of 1.25 (66.7), 0.81 (43.2) and 0.74 (39.5) ft-lb/inch (J/m) values. Thus both inventive runs 43 and 50 have better impact strength as measured by notched Izod at similar Flexural modulus than the comparative runs.
This is further illustrated for all the data by plotting the notched Izod versus the Flexural Modulus for each the comparative examples relative to the inventive examples. As Figure 1 illustrates, the inventive examples have a higher impact property (notched Izod) at equivalent Flexural Modulus.
The improved impact strength at comparable modulus results from a higher molecular weight, as measured by IV, of Component B. The higher the molecular weight of component B, the better the impact test values.
The known metallocenes comparison 1 and 2 are limited to low values for this molecular weight as measured by the IV of Component B. The maximum value of IN for the comparative metallocenes was a value of about 1.7 dl/g for run 9 (Table IB) with the ethylene/propylene at a 4.2/0.8 ratio. Inventive metallocene B at this ratio produced an IV that ranged from 1.99 dl/g in run 13 to 2.338 dl/g in run 18. The inventive metallocene D produced an ICP with an IV of 3.508 dl/g in run 40. In fact, for all runs with inventive metallocene D the IV values were greater than 2.2 dl/g for all ICP products and ranged from 2.202 dl/g (run 39) to 3.667 dl/g (run 38). These high IV values will result in further improved impact properties.
All applications to which priority is claimed and all named testing procedures are fully incorporated herein by reference.
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Table 4
FTTR data
APPL RUN # Description Supported MFR % Xylene Sol % Xylene Insol Total C2 C2 in Comp. B Total Comp. B rV Of Comp. B
Metallocene (dl/g)
Catalyst System (dg/min) ( t%) ( t%) ( t%) (wt%) (wt%)
1 ICP E 114.0 25.6 74.5 10.24 50.8 20.2 0.979
2 Homo PP E 459.2 1 -2 98.8
3 Homo PP Comp. 1 58.95 0.6 99.4
4 ICP Comp. 1 127.16 20.4 79.7 7.82 50.04 15.6 0.708
9 ICP Comp. 2 4.98 23.5 76.2 9.74 51.52 18.9 1.713
10 Homo PP Comp. 2 3.12 0.9 99.1
13 ICP B 129.0 12.4 86.9
21 Homo PP E 10.3 0.7 99.3
22 ICP E 3.66 24 75.6 10.95 50.37 21.7 2.185
23 ICP E 7.01 20.9 79.3 6.46 36.4 17.7 2.11
24 ICP E 131.01 22 78.1 9.37 47.34 19.8 2.06
25 Homo PP E 681.8 2.1 98
Table 5
APPL Description Supported MFR —Xylene Solubles ('low' MW peak) — —Xylene ! Solubles ('high' MW peak)- Xylene Insolubles
RUN # Metallocene Cat. Syst.
(dg/min) Mn Mw Mz Mw/Mn Mn Mw Mz Mw/Mn Mn Mw Mz Mw/Mn
1 ICP E 114.0 1251 1554 1874 1.24 38015 74567 115589 1.96 12314 32426 54966 2.63
2 Homo PP E 459.2 1513 2013 2599 1.33 18384 30191 45639 1.64 17552 41149 67038 2.34
3 Homo PP Comp. 1 58.95 1441 1952 2630 1.35 14448 22536 35314 1.56 30510 63658 97817 2.09
4 ICP Comp. 1 127.16 981 1062 1140 1.08 15647 33205 51601 2.12 16342 42791 71409 2.62
9 ICP Comp. 2 4.98 987 1180 1433 1.2 48475 118629 214628 2.45 41276 106195 179010 2.57
10 Homo PP Comp. 2 3.12 1071 1376 1834 1.29 15113 30638 56220 2.03 61668 142260 249807 2.31
13 ICP B 21.1 941 1099 1308 1.17 44501 187149 515199 4.21 69282 167811 342963 2.42
21 Homo PP E 10.3 1114 1383 1715 1.24 12228 23656 42278 1.93 82347 184675 309914 2.24
22 ICP E 3.66 929 1153 1502 1.24 77378 211251 413832 2.73 97431 248553 471070 2.55
23 ICP E 7.01 982 1165 1403 1.19 57316 166144 312133 2.9 85158 206876 354334 2.43
24 ICP E 131.01 1515 2556 4282 1.69 74803 161031 319874 2.15 27750 76477 129002 2.76
25 Homo PP E 681.8 1430 1868 2472 1.31 10530 13500 17834 1.28 24398 76119 137103 3.12
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* Two impact/modulus tests were carried out because of differences in visual appearance of the samples from these runs.

Claims

CLA SWhat is claimed is:
1. A reactor produced propylene impact copolymer composition comprising:
(a) From about 40% to about 95% by weight Component A based on the total weight of the impact copolymer, Component A comprising propylene homopolymer or copolymer wherein the copolymer comprises 10% or less by weight ethylene, butene, hexene or octene comonomer;
(b) From about 5% to about 60% by weight Component B based on the total weight of the impact copolymer, Component B comprising propylene copolymer wherein the copolymer comprises from about 20% to about 70% by weight ethylene, butene, hexene and/or octene comonomer, and from about 80% to about 30% by weight propylene, wherein Component
B:
(i) has a weight average molecular weight of at least 100,000; (ii) a composition distribution of greater than 60%; and (iii) an intrinsic viscosity of greater than 1.00 dl/g.
2. The composition of claim 1 wherein Component A is a propylene homopolymer.
3. The composition of claim 1 wherein Component B consists essentially of propylene and from about 20% to about 70% by weight ethylene.
4. The composition of claim 1 wherein Component B consists essentially of propylene and from about 30% to about 65% by weight ethylene.
5. The composition of claim 1 wherein Component B has a molecular weight distribution of less than 3.5.
6. The composition of claim 1 wherein Component B has a weight average molecular weight of at least 200,000.
7. The composition of claim 1 wherein Component B has a composition distribution of greater than 70%.
8. The composition of claim 1 wherein Component B has an intrinsic viscosity of greater than 2.00 dl/g.
9. The composition of claim 1 wherem Component B has less than 10% by weight of a crystalline portion.
10. The composition of claim 1 wherein Component B has less than 10% by weight of a crystalline portion and the crystalline portion, if detectable, has the same comonomer content as the remainder of Component B.
11. The composition of claim 1 wherein Component A consists essentially of polypropylene homopolymer and has less than 2% by weight amorphous polypropylene.
12. The composition of claim 1 wherein Component A has a melting point of at least 155°C.
13. A reactor produced propylene impact copolymer composition comprising:
(a) From about 40% to about 95% by weight Component A based on the total weight of the impact copolymer, Component A comprising propylene homopolymer having a melting point of at least 155°C and less than 2% by weight amorphous polypropylene; (b) From about 5% to about 60% by weight Component B based on the total weight of the impact copolymer, Component B comprising propylene copolymer wherein the copolymer comprises from about 30% to about 65%» by weight ethylene and from about 70% to about 35% by weight propylene, wherein Component B:
(i) has a weight average molecular weight of at least 150,000; (ii) a molecular weight distribution of less than 3.5; (iii) a composition distribution of greater than 65%; and (iv) an intrinsic viscosity of greater than 2.00 dl/g.
(v) less than 10% by weight of a crystalline portion.
14. The composition of claim 13 consisting essentially of from about 60% to about 90% by weight Component A and from about 10% to about 40% by weight Component B .
15. The composition of claim 13 wherein Component B consists essentially of propylene and from about 35% to about 60% ethylene.
16. A propylene impact copolymer prepared in a two-stage polymerization process using a metallocene catalyst system comprising a metallocene selected from the group consisting of: rac-dimethylsiladiyl(2-iPr-4- phenylindenyl)2zirconium dichloride; rac-dimethylsiladiyl(2-iPr-4-[l- naphthyl]indenyl)2zirconium dichloride; rac-dimethyisiladiyl(2-iPr-4-[3,5- dimethylphenyl]indenyl)2zirconium dichloride; rac-dimethylsiladiyl(2-iPr-
4-[2-methyl-phenyl]indenyl)2zirconium dichloride; and rac- diphenylsiladiyl(2-methyl-4-[l-naphthyl]indenyl)2zirconium dichloride.
17. A propylene impact copolymer prepared in a two-stage polymerization process using a metallocene catalyst system comprising a metallocene selected from the group consisting of: rac-dimethylsiladiyl(2-iPr-4- phenylindenyf zirconium dichloride; rac-dimethylsiladiyl(2-iPr-4-[l- naphthyl]indenyl)2zirconium dichloride; rac-dimethylsiladiyl(2-iPr-4-[3,5- dimethylphenyl]indenyl)2zirconium dichloride; and rac-dimethylsiladiyl(2- iPr-4-[2-methyl-phenyl]indenyl)2zirconium dichloride.
18. A propylene impact copolymer prepared in a two-stage polymerization process using a metallocene catalyst system comprising a metallocene selected from the group consisting of: rac-dimethylsiladiyl(2-iPr-4- phenylindenyl) zirconium dichloride; rac-dimethylsiladiyl(2-iPr,4- [ 1 - naphthyl]indenyl)2zirconium dichloride; and rac-dimethylsiladiyl(2-iPr-4- [3,5-dimethylphenyl]indenyl) zirconium dichloride.
19. A propylene impact copolymer prepared in a two-stage polymerization process using a metallocene catalyst system comprising a metallocene selected from the group consisting of: rac-dimethylsiladiyl(2-iPr-4- phenylindenyl)2zirconium dichloride; and rac-dimethylsiladiyl(2-iPr-4-[lr naphthyl]indenyl)2zirconium dichloride.
20. A reactor produced propylene impact copolymer composition comprising:
(a) From about 40% to about 95% by weight Component A based on the total weight of the impact copolymer, Component A comprising propylene homopolymer having a melting point of at least 155°C and less than 2% by weight amorphous polypropylene;
(b) From about 5% to about 60% by weight Component B based on the total weight of the impact copolymer, Component B comprising propylene copolymer wherein the copolymer comprises from about 30% to about 65% by weight ethylene and from about 70% to about 35% by weight propylene, wherein Component B:
(i) has a weight average molecular weight of at least 150,000; (ii) a molecular weight distribution of less than 3.5; (iii) a composition distribution of greater than 65%; and (iv) an intrinsic viscosity of greater than 2.00 dl/g. (v) less than 10% by weight of a crystalline portion.
wherein the impact copolymer is prepared using a metallocene catalyst system comprising a metallocene selected from the group consisting of: rac-dimethylsiladiyl(2-iPr-4-phenylindenyl)2zirconium dichloride; rac- dimethylsiladiyl(2-iPr-4-[ 1 -naphthyl]indenyl)2zirconium dichloride; rac- dimethylsiladiyl(2-iPr-4-[3,5-dimethylphenyl]indenyl)2zirconium dichloride; rac-dimethylsiladiyl(2-iPr-4-[2-methyl- phenyl]indenyl)2zirconium dichloride; and rac-diphenylsiladiyl(2-methyl- 4-[l -naphthyl]indenyl) zirconium dichloride.
21. A process for producing a propylene impact copolymer comprising the steps of:
(a) polymerizing Component A in one stage; and
(b) polymerizing Component B in another stage in the presence of Component A,
wherein Component A comprises propylene homopolymer or copolymer containing 10% or less by weight ethylene, butene, hexene or octene comonomer, and Component B comprises propylene copolymer wherein the copolymer contains from about 20% to about 70% by weight ethylene, butene, hexene and/or octene comonomer, and from about 80% to about 30% by weight propylene, wherein at least one of Components A and/or B are polymerized using a metallocene selected from the group consisting of: rac-dimethylsiladiyl(2-iPr-4-phenylindenyl)2zirconium dichloride; rac- dimethylsiladiyl(2-iPr-4-[l-naphthyl]indenyl)2zirconium dichloride; rac- dimethylsiladiyl(2-iPr-4-[3,5-dimethylphenyl]indenyl)2zirconium dichloride; rac-dimethylsiladiyl(2-iPr-4-[2-methyl- phenyl]indenyl)2zirconium dichloride; and rac-diphenylsiladiyl(2-methyl- 4-[l -naphthyl]indenyl)2zirconium dichloride.
22. The process of claim 20 wherein the propylene impact copolymer is produced in two stages and Component A is produced in the first stage and
Component B is produced in the second stage.
23. The process of claim 21 wherein the second stage is a gas phase process.
24. The process of claim 21 wherein the first stage is a liquid slurry process and the second stage is a gas phase process.
25. The process of claim 20 wherein both components A and B are prepared using the same metallocene selected from the group consisting of: rac- dimethylsiladiyl(2-iPr-4-phenylindenyl)2zirconium dichloride; rac- dimethylsiladiyl(2-iPr-4-[ 1 -naphthyl]indenyl)2zirconium dichloride; rac- dimethylsiladiyl(2-iPr- 4-[3,5-dimethylphenyl]indenyl)2zirconium dichloride; rac-dimethylsiladiyl(2-iPr-4-[2-methyl- phenyl]indenyl)2zirconium dichloride; and rac-diphenylsiladiyl(2-methyl- 4-[l-naphthyl]indenyl)2zirconium dichloride.
26. The process of claim 20 wherein Component B (i) has a weight average molecular weight of at least 150,000; (ii) a molecular weight distribution of less than 2.5; (iii) a composition distribution of greater than 65%; and (iv) an intrinsic viscosity of greater than 2.00 dl/g. and (v) less than 10% by weight of a crystalline portion.
27. The process of claim 20 wherein Component A consists essentially of propylene homopolymer having a melting point of at least 155°C.
28. A process for producing a propylene impact copolymer comprising the steps of: (a) polymerizing Component A in a first stage wherein Component A consists essentially of propylene homopolymer; and then
(b) polymerizing Component B in a subsequent stage in the presence of Component A, wherein Component B comprises propylene copolymer wherein the copolymer contains from about 20% to about 70% by weight ethylene, butene, hexene and/or octene comonomer, and from about 80% to about 30% by weight propylene;
wherein both Components A and B are polymerized using a metallocene selected from the group consisting of: rac-dimethylsiladiyl(2-iPr-4- phenylindenyl)2zirconium dichloride; rac-dimethylsiladiyl(2-iPr-4-[l- naphthyl]indenyl)2zirconium dichloride; rac-dimethylsiladiyl(2-iPr-4-[3,5- dimethylphenyl]indenyl)2zirconium dichloride; rac-dimethylsiladiyl(2-iPr- 4-[2-methyl-phenyl]indenyl)2zirconium dichloride; and rac- diphenylsiladiyl(2-methyl-4-[l-naphthyl]indenyl)2zirconium dichloride.
29. The process of claim 28 wherein the metallocene is supported.
30. The process of claim 28 wherein the metallocene is activated with methylalumoxane.
31. The process of claim 28 wherein the metallocene is activated with an ionic activator.
32. The process of claim 28 wherein Component B (i) has a weight average molecular weight of at least 150,000; (ii) a molecular weight distribution of less than 3.0; (iii) a composition distribution of greater than 65%; and (iv) an intrinsic viscosity of greater than 2.00 dl/g. and (v) less than 10% by weight of a crystalline portion.
33. The process of claim 21 wherein Component A has a melting point of at least 155°C.
34. A process for producing a propylene impact copolymer comprising the steps of:
(a) polymerizing Component A in a first stage wherein Component A consists essentially of propylene homopolymer having a melting point of at least 155°C; and then
(b) polymerizing Component B in a subsequent stage in the presence of Component A, wherein Component B comprises propylene copolymer wherem the copolymer contains from about 20% to about 70% by weight ethylene, and from about 80% to about 30% by weight propylene, and wherein Component B (i) has a weight average molecular weight of at least 150,000; (ii) a molecular weight distribution of less than 3.5; (iii) a composition distribution of greater than 65%; and (iv) an intrinsic viscosity of greater than 2.00 dl/g. and (v) less than 10%> by weight of a crystalline portion;
wherein both Components A and B are polymerized using a metallocene selected from the group consisting of: rac-dimethylsiladiyl(2-iPr-4- phenylindenyl)2zirconium dichloride; rac-dimethylsiladiyl(2-iPr-4-[l- naphthyl]indenyl)2zirconium dichloride; rac-dimethylsiladiyl(2-iPr-4-[3,5- dimethylphenyl]indenyl)2zirconium dichloride; rac-dimethylsiladiyl(2-iPr-
4-[2-methyl-phenyl]indenyl)2zirconium dichloride; and rac- diphenylsiladiyl(2-methyl-4-[ 1 -naphthyl]indenyl)2zirconium dichloride.
PCT/US2001/004126 2000-02-08 2001-02-08 Propylene impact copolymers WO2001058970A1 (en)

Priority Applications (7)

Application Number Priority Date Filing Date Title
AT01910477T ATE286082T1 (en) 2000-02-08 2001-02-08 IMPACT RESISTANT PROPYLENE COPOLYMERS
KR1020027010213A KR20020074509A (en) 2000-02-08 2001-02-08 Propylene impact copolymers
EP01910477A EP1254186B1 (en) 2000-02-08 2001-02-08 Propylene impact copolymers
JP2001558115A JP2003522259A (en) 2000-02-08 2001-02-08 Propylene impact copolymer
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Cited By (50)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002070572A2 (en) * 2001-03-06 2002-09-12 Exxonmobil Chemical Patents Inc. Propylene polymers for films
WO2003002583A2 (en) 2001-06-29 2003-01-09 Exxonmobil Chemical Patents Inc. Metallocenes and catalyst compositions derived therefrom
WO2003045551A1 (en) * 2001-11-30 2003-06-05 Basell Polyolefine Gmbh Organometallic transition metal compound, biscyclopentadienyl ligand system, catalyst system and preparation of polyolefins
US6806316B2 (en) 1996-09-04 2004-10-19 Exxonmobil Chemical Patents Inc. Propylene polymers for oriented films
JP2005528412A (en) * 2002-04-23 2005-09-22 ダウ・グローバル・テクノロジーズ・インコーポレイテッド Alkaryl-substituted group 4 metal complex, catalyst, and olefin polymerization method
US7122498B2 (en) 2000-06-30 2006-10-17 Exxonmobil Chemical Patents Inc. Metallocenes and catalyst compositions derived therefrom
US7439312B2 (en) 2002-10-24 2008-10-21 Exxonmobil Chemical Patents Inc. Branched crystalline polypropylene
WO2009054833A2 (en) 2007-10-25 2009-04-30 Novolen Technology Holdings, C.V. Metallocene compounds, catalysts comprising them, process for producing an olefin polymer by use of the catalysts, and olefin homo and copolymers
WO2009077032A1 (en) * 2007-12-17 2009-06-25 Borealis Technology Oy Heterophasic polypropylene with high flowability and excellent low temperature impact properties
SG153790A1 (en) * 2007-12-26 2009-07-29 Sumitomo Chemical Co Polypropylene-based copolymer and film comprising the polypropylene- based copolymer
KR100954975B1 (en) * 2002-03-29 2010-04-30 구미아이 가가쿠 고교 가부시키가이샤 Genes Encoding Acetolactate Synthase
WO2010149705A1 (en) * 2009-06-26 2010-12-29 Basell Poliolefine Italia S.R.L. Polyolefin compositions
WO2011008582A1 (en) 2009-07-14 2011-01-20 Dow Global Technologies Inc. Vacuum thermoformed, extruded sheeting with improved reduced gloss
EP2426171A1 (en) 2010-08-30 2012-03-07 Borealis AG Heterophasic polypropylene with high flowability and enhanced mechanical properties
US8299287B2 (en) 2007-10-25 2012-10-30 Lammus Novolen Technology GmbH Metallocene compounds, catalysts comprising them, process for producing an olefin polymer by use of the catalysts, and olefin homo- and copolymers
US8304496B2 (en) 2005-05-12 2012-11-06 Dow Global Technologies Llc Thermoformed, extruded sheeting with reduced gloss
US8404773B2 (en) 2008-03-17 2013-03-26 Dow Global Technologies Llc Coating composition, method of producing the same, articles made therefrom, and method of making such articles
WO2013150057A1 (en) * 2012-04-05 2013-10-10 Borealis Ag High flow thermoplastic polyolefin with balanced mechanical performance and low shrinkage and clte
WO2015022127A1 (en) * 2013-08-14 2015-02-19 Borealis Ag Propylene composition with improved impact resistance at low temperature
WO2015108634A1 (en) 2014-01-15 2015-07-23 Exxonmobil Chemical Patents Inc. Propylene-based impact copolymers
WO2015126797A1 (en) 2014-02-24 2015-08-27 Dow Global Technologies Llc Thermoplastic polyolefin with reduced gloss for non-carpeted flooring
WO2016196339A3 (en) * 2015-06-05 2017-02-09 Exxonmobil Chemical Patents Inc. Production of heterophasic polymers in gas or slurry phase
US9637602B2 (en) 2013-12-18 2017-05-02 Borealis Ag BOPP film with improved stiffness/toughness balance
US9670293B2 (en) 2013-10-29 2017-06-06 Borealis Ag Solid single site catalysts with high polymerisation activity
US9708481B2 (en) 2013-10-24 2017-07-18 Borealis Ag Blow molded article based on bimodal random copolymer
US9751962B2 (en) 2013-11-22 2017-09-05 Borealis Ag Low emission propylene homopolymer with high melt flow
US9777142B2 (en) 2013-08-21 2017-10-03 Borealis Ag High flow polyolefin composition with high stiffness and toughness
US9802394B2 (en) 2013-10-11 2017-10-31 Borealis Ag Machine direction oriented film for labels
US9828698B2 (en) 2013-12-04 2017-11-28 Borealis Ag Phthalate-free PP homopolymers for meltblown fibers
WO2017204830A1 (en) 2016-05-27 2017-11-30 Exxonmobil Chemical Patents, Inc. Metallocene catalyst compositions and polymerization process therewith
US9890275B2 (en) 2013-08-21 2018-02-13 Borealis Ag High flow polyolefin composition with high stiffness and toughness
US10030109B2 (en) 2014-02-14 2018-07-24 Borealis Ag Polypropylene composite
US10040930B2 (en) 2013-09-27 2018-08-07 Abu Dhabi Polymers Co. Ltd (Borouge) Llc. Polymer composition with high XS, high Tm suitable for BOPP processing
US10100185B2 (en) 2014-02-06 2018-10-16 Borealis Ag Soft copolymers with high impact strength
US10100186B2 (en) 2014-02-06 2018-10-16 Borealis Ag Soft and transparent impact copolymers
US10227427B2 (en) 2014-01-17 2019-03-12 Borealis Ag Process for preparing propylene/1-butene copolymers
US10280235B2 (en) 2015-06-05 2019-05-07 Exxonmobil Chemical Patents Inc. Catalyst system containing high surface area supports and sequential polymerization to produce heterophasic polymers
US10280233B2 (en) 2015-06-05 2019-05-07 Exxonmobil Chemical Patents Inc. Catalyst systems and methods of making and using the same
US10287372B2 (en) 2015-06-05 2019-05-14 Exxonmobil Chemical Patents Inc. Bimodal propylene polymers and sequential polymerization
US10294316B2 (en) 2015-06-05 2019-05-21 Exxonmobil Chemical Patents Inc. Silica supports with high aluminoxane loading capability
US10329360B2 (en) 2015-06-05 2019-06-25 Exxonmobil Chemical Patents Inc. Catalyst system comprising supported alumoxane and unsupported alumoxane particles
US10450451B2 (en) 2014-05-20 2019-10-22 Borealis Ag Polypropylene composition for automotive interior applications
US10465025B2 (en) 2014-01-15 2019-11-05 Exxonmobil Chemical Patents Inc. Low comonomer propylene-based impact copolymers
US10519259B2 (en) 2013-10-24 2019-12-31 Borealis Ag Low melting PP homopolymer with high content of regioerrors and high molecular weight
US10723821B2 (en) 2015-06-05 2020-07-28 Exxonmobil Chemical Patents Inc. Supported metallocene catalyst systems for polymerization
WO2020170046A1 (en) * 2019-02-19 2020-08-27 Braskem S.A. No break polypropylene impact copolymers with melt flow rate higher than 90 g/10 min
US10759886B2 (en) 2015-06-05 2020-09-01 Exxonmobil Chemical Patents Inc. Single reactor production of polymers in gas or slurry phase
EP3722363A1 (en) * 2019-04-12 2020-10-14 Thai Polyethylene Co., Ltd. Impact copolymer polypropylene for thin-wall injection packaging
US10920053B2 (en) 2017-10-16 2021-02-16 Exxonmobil Chemical Patents Inc. Propylene impact copolymer blends with improved gloss
US11472828B2 (en) 2019-10-11 2022-10-18 Exxonmobil Chemical Patents Inc. Indacene based metallocene catalysts useful in the production of propylene polymers

Families Citing this family (156)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7919561B2 (en) * 1996-09-04 2011-04-05 Exxonmobil Chemical Patents Inc. Process of producing thermoplastic polymer blends
US6635715B1 (en) * 1997-08-12 2003-10-21 Sudhin Datta Thermoplastic polymer blends of isotactic polypropylene and alpha-olefin/propylene copolymers
US6921794B2 (en) * 1997-08-12 2005-07-26 Exxonmobil Chemical Patents Inc. Blends made from propylene ethylene polymers
US7232871B2 (en) * 1997-08-12 2007-06-19 Exxonmobil Chemical Patents Inc. Propylene ethylene polymers and production process
WO2002083754A1 (en) 2001-04-12 2002-10-24 Exxonmobil Chemical Patents Inc. Propylene ethylene polymers and production process
EP1098934A1 (en) * 1998-07-01 2001-05-16 Exxon Chemical Patents Inc. Elastic blends comprising crystalline polymer and crystallizable polymers of propylene
JP2000072933A (en) * 1998-08-31 2000-03-07 Asahi Chem Ind Co Ltd Olefin elastomer composition
CA2398529A1 (en) * 2000-02-08 2001-08-16 Exxonmobil Chemical Patents Inc. Method of preparing group 14 bridged biscyclopentadienyl ligands
US6492465B1 (en) * 2000-02-08 2002-12-10 Exxonmobil Chemical Patents, Inc. Propylene impact copolymers
GB0008690D0 (en) * 2000-04-07 2000-05-31 Borealis Polymers Oy Process
US6870016B1 (en) * 2000-06-30 2005-03-22 Exxonmobil Chemical Patents Inc. Polymerization process and polymer composition
US7217463B2 (en) 2002-06-26 2007-05-15 Avery Dennison Corporation Machine direction oriented polymeric films and methods of making the same
US7998579B2 (en) * 2002-08-12 2011-08-16 Exxonmobil Chemical Patents Inc. Polypropylene based fibers and nonwovens
US7271209B2 (en) * 2002-08-12 2007-09-18 Exxonmobil Chemical Patents Inc. Fibers and nonwovens from plasticized polyolefin compositions
US7531594B2 (en) * 2002-08-12 2009-05-12 Exxonmobil Chemical Patents Inc. Articles from plasticized polyolefin compositions
CA2492839C (en) * 2002-08-12 2011-02-01 Exxonmobil Chemical Patents Inc. Plasticized polyolefin compositions
US8003725B2 (en) * 2002-08-12 2011-08-23 Exxonmobil Chemical Patents Inc. Plasticized hetero-phase polyolefin blends
ATE445651T1 (en) * 2002-09-06 2009-10-15 Basell Polyolefine Gmbh METHOD FOR COPOLYMERIZING ETHYLENE
US7700707B2 (en) 2002-10-15 2010-04-20 Exxonmobil Chemical Patents Inc. Polyolefin adhesive compositions and articles made therefrom
EP1558655B1 (en) 2002-10-15 2012-08-29 ExxonMobil Chemical Patents Inc. Multiple catalyst system for olefin polymerization and polymers produced therefrom
US7459500B2 (en) * 2002-11-05 2008-12-02 Dow Global Technologies Inc. Thermoplastic elastomer compositions
US20040147169A1 (en) 2003-01-28 2004-07-29 Allison Jeffrey W. Power connector with safety feature
EP1630197B1 (en) * 2003-05-28 2011-03-02 Mitsui Chemicals, Inc. Propylene polymer composition and use thereof
US8192813B2 (en) 2003-08-12 2012-06-05 Exxonmobil Chemical Patents, Inc. Crosslinked polyethylene articles and processes to produce same
CN1849350A (en) * 2003-09-11 2006-10-18 巴塞尔聚烯烃股份有限公司 Multistep process for preparing heterophasic propylene copolymers
CN1878806A (en) * 2003-09-11 2006-12-13 巴塞尔聚烯烃股份有限公司 Multistep process for preparing heterophasic propylene copolymers
US6995213B2 (en) * 2003-09-29 2006-02-07 Fina Technology, Inc. Oriented films prepared using impact copolymer polypropylene
JP4590037B2 (en) * 2003-09-30 2010-12-01 日本ポリプロ株式会社 Olefin polymerization catalyst component, α-olefin polymerization catalyst and method for producing α-olefin polymer
US7458839B2 (en) 2006-02-21 2008-12-02 Fci Americas Technology, Inc. Electrical connectors having power contacts with alignment and/or restraining features
CN101882718B (en) 2003-12-31 2012-11-21 Fci公司 Electrical power contacts and connectors comprising same
EP1718700B8 (en) 2004-02-12 2012-10-03 ExxonMobil Chemical Patents Inc. Plasticized polyolefin compositions
US20050234172A1 (en) * 2004-04-19 2005-10-20 Fina Technology, Inc. Random copolymer-impact copolymer blend
US20050234198A1 (en) * 2004-04-20 2005-10-20 Fina Technology, Inc. Heterophasic copolymer and metallocene catalyst system and method of producing the heterophasic copolymer using the metallocene catalyst system
CN101006132B (en) * 2004-07-30 2010-05-05 沙特基础工业公司 Propylene copolymer compositions with high transparency
EP1793997A1 (en) * 2004-09-10 2007-06-13 ExxonMobil Oil Corporation Cavitated opaque polymer film and methods related thereto
CN101065437B (en) 2004-10-04 2010-12-08 巴塞尔聚烯烃意大利有限责任公司 Elastomeric polyolefin compositions
US8389615B2 (en) 2004-12-17 2013-03-05 Exxonmobil Chemical Patents Inc. Elastomeric compositions comprising vinylaromatic block copolymer, polypropylene, plastomer, and low molecular weight polyolefin
US7384289B2 (en) 2005-01-31 2008-06-10 Fci Americas Technology, Inc. Surface-mount connector
KR100878869B1 (en) * 2005-03-18 2009-01-15 미쓰이 가가쿠 가부시키가이샤 Propylene polymer composition, use thereof, and process for production of thermoplastic polymer composition
US8513347B2 (en) 2005-07-15 2013-08-20 Exxonmobil Chemical Patents Inc. Elastomeric compositions
EP1917304B1 (en) * 2005-08-22 2011-06-22 Mitsui Chemicals, Inc. Propylene based resin composition
JP5379479B2 (en) * 2005-10-21 2013-12-25 バーゼル・ポリオレフィン・ゲーエムベーハー Polypropylene for injection molding
US7709577B2 (en) 2005-12-07 2010-05-04 Exxonmobil Chemical Patents Inc. Process of making polymer blends
US20090017710A1 (en) * 2006-02-02 2009-01-15 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
CN103121320B (en) 2006-06-14 2015-06-24 艾利丹尼森公司 Conformable and die-cuttable machine direction oriented labelstocks and labels, and process for preparing
US7726982B2 (en) 2006-06-15 2010-06-01 Fci Americas Technology, Inc. Electrical connectors with air-circulation features
BRPI0713492A2 (en) 2006-06-20 2012-01-24 Avery Dennison Corp multi-layer polymeric film for labeling hot melt adhesives and label and label thereof
ES2313510T5 (en) * 2006-07-10 2012-04-09 Borealis Technology Oy Branched Short Chain Polypropylene
US20080097774A1 (en) * 2006-08-29 2008-04-24 Rawls-Meehan Martin B Using a software application to configure a foam spring mattress
US8198373B2 (en) * 2006-10-02 2012-06-12 Exxonmobil Chemical Patents Inc. Plastic toughened plastics
US7256240B1 (en) * 2006-12-22 2007-08-14 Exxonmobil Chemical Patents Inc. Process of making polymer blends
US7905731B2 (en) 2007-05-21 2011-03-15 Fci Americas Technology, Inc. Electrical connector with stress-distribution features
WO2009035850A1 (en) * 2007-09-07 2009-03-19 Dow Global Technologies Inc. Filled tpo compositions with good low temperature ductility
US7762857B2 (en) * 2007-10-01 2010-07-27 Fci Americas Technology, Inc. Power connectors with contact-retention features
EP2062937A1 (en) * 2007-11-26 2009-05-27 Total Petrochemicals Research Feluy Heterophasic propylene copolymer for corrugated sheet and cast film applications
JP5156415B2 (en) * 2008-02-01 2013-03-06 トピー工業株式会社 High rigidity and high impact resistance resin composition
WO2009152345A1 (en) 2008-06-12 2009-12-17 3M Innovative Properties Company Biocompatible hydrophilic compositions
CN102105625B (en) * 2008-06-12 2015-07-08 3M创新有限公司 Melt blown fine fibers and methods of manufacture
US8062051B2 (en) 2008-07-29 2011-11-22 Fci Americas Technology Llc Electrical communication system having latching and strain relief features
US8246918B2 (en) * 2008-10-21 2012-08-21 Fina Technology, Inc. Propylene polymers for lab/medical devices
US7851554B2 (en) * 2008-10-27 2010-12-14 Exxonmobil Chemical Patents Inc. Propylene impact copolymers with balanced impact strength and stiffness
US8323049B2 (en) 2009-01-30 2012-12-04 Fci Americas Technology Llc Electrical connector having power contacts
USD619099S1 (en) 2009-01-30 2010-07-06 Fci Americas Technology, Inc. Electrical connector
US8366485B2 (en) 2009-03-19 2013-02-05 Fci Americas Technology Llc Electrical connector having ribbed ground plate
MX347301B (en) 2009-03-31 2017-04-21 3M Innovative Properties Co Dimensionally stable nonwoven fibrous webs and methods of making and using the same.
USD618181S1 (en) 2009-04-03 2010-06-22 Fci Americas Technology, Inc. Asymmetrical electrical connector
USD618180S1 (en) 2009-04-03 2010-06-22 Fci Americas Technology, Inc. Asymmetrical electrical connector
WO2011008589A1 (en) * 2009-07-14 2011-01-20 Dow Global Technologies Inc. Polypropylene impact copolymers having high melt flow and izod ductility
WO2011032917A1 (en) * 2009-09-21 2011-03-24 Basell Poliolefine Italia S.R.L. Polymer filament
EP2488583B1 (en) 2009-10-13 2014-01-15 Basell Poliolefine Italia S.r.l. Propylene polymer compositions
WO2011084670A1 (en) * 2009-12-17 2011-07-14 3M Innovative Properties Company Dimensionally stable nonwoven fibrous webs and methods of making and using the same
WO2011075619A1 (en) 2009-12-17 2011-06-23 3M Innovative Properties Company Dimensionally stable nonwoven fibrous webs, melt blown fine fibers, and methods of making and using the same
EP2539496B1 (en) 2010-02-23 2016-02-10 3M Innovative Properties Company Dimensionally stable nonwoven fibrous webs and methods of making and using the same
TW201221714A (en) 2010-10-14 2012-06-01 3M Innovative Properties Co Dimensionally stable nonwoven fibrous webs and methods of making and using the same
US8980415B2 (en) 2010-12-03 2015-03-17 Benoit Ambroise Antistatic films and methods to manufacture the same
PL2655505T3 (en) * 2010-12-20 2019-03-29 Braskem America, Inc. Propylene-based compositions of enhanced appearance and excellent mold flowability
US20120272468A1 (en) 2011-04-26 2012-11-01 The Procter & Gamble Company Oral Care Device Comprising A Synthetic Polymer Derived From A Renewable Resource And Methods Of Producing Said Device
US8809461B2 (en) * 2011-04-28 2014-08-19 Braskem America, Inc. Multimodal heterophasic copolymer and thermoformed articles from same
US8530581B2 (en) 2011-12-12 2013-09-10 Exxonmobil Chemical Patents Inc. Powder, compositions thereof, processes for making the same, and articles made therefrom
EP2624034A1 (en) 2012-01-31 2013-08-07 Fci Dismountable optical coupling device
USD727268S1 (en) 2012-04-13 2015-04-21 Fci Americas Technology Llc Vertical electrical connector
US8944831B2 (en) 2012-04-13 2015-02-03 Fci Americas Technology Llc Electrical connector having ribbed ground plate with engagement members
USD718253S1 (en) 2012-04-13 2014-11-25 Fci Americas Technology Llc Electrical cable connector
USD727852S1 (en) 2012-04-13 2015-04-28 Fci Americas Technology Llc Ground shield for a right angle electrical connector
US9257778B2 (en) 2012-04-13 2016-02-09 Fci Americas Technology High speed electrical connector
USD751507S1 (en) 2012-07-11 2016-03-15 Fci Americas Technology Llc Electrical connector
US9543703B2 (en) 2012-07-11 2017-01-10 Fci Americas Technology Llc Electrical connector with reduced stack height
US9676532B2 (en) 2012-08-15 2017-06-13 Avery Dennison Corporation Packaging reclosure label for high alcohol content products
MX2015002874A (en) 2012-09-11 2015-07-17 Sika Technology Ag Thermoplastic mixture with high flexibility and high melting point.
CN104755511B (en) 2012-10-31 2016-12-28 埃克森美孚化学专利公司 Propylene copolymer compositions and preparation method thereof
US9322114B2 (en) 2012-12-03 2016-04-26 Exxonmobil Chemical Patents Inc. Polypropylene fibers and fabrics
WO2014088827A1 (en) 2012-12-05 2014-06-12 Exxonmobil Chemical Patents Inc. Hdpe modified polyethylene blown film compositions having excellent bubble stability
CN106113851A (en) 2012-12-18 2016-11-16 埃克森美孚化学专利公司 Polyethylene film and manufacture method thereof
USD745852S1 (en) 2013-01-25 2015-12-22 Fci Americas Technology Llc Electrical connector
USD720698S1 (en) 2013-03-15 2015-01-06 Fci Americas Technology Llc Electrical cable connector
BR112015026427B1 (en) 2013-05-14 2020-07-21 Exxonmobil Chemical Patents Inc. ethylene-based polymers and articles made of the same
US20140355122A1 (en) 2013-05-28 2014-12-04 Tredegar Film Products Corporation Polyolefin Volumetric Diffuser
EP3011089B1 (en) * 2013-06-18 2020-12-02 ExxonMobil Chemical Patents Inc. Fibers and nonwoven materials prepared therefrom
US9938364B2 (en) 2013-07-17 2018-04-10 Exxonmobil Chemical Patents Inc. Substituted metallocene catalysts
EP3022236B1 (en) 2013-07-17 2017-11-15 ExxonMobil Chemical Patents Inc. Process using substituted metallocene catalysts and products therefrom
WO2015009471A1 (en) 2013-07-17 2015-01-22 Exxonmobil Chemical Patents Inc. Metallocenes and catalyst compositions derived therefrom
WO2015009473A1 (en) 2013-07-17 2015-01-22 Exxonmobil Chemical Patents Inc. Cyclopropyl substituted metallocene catalysts
EP3022234B1 (en) 2013-07-17 2018-12-26 ExxonMobil Chemical Patents Inc. Substituted metallocene catalysts
CN105358589B (en) 2013-07-17 2018-07-03 埃克森美孚化学专利公司 Metallocene and by its derivative carbon monoxide-olefin polymeric
US10006165B2 (en) 2013-09-30 2018-06-26 3M Innovative Properties Company Fibers and wipes with epoxidized fatty ester disposed thereon, and methods
CN105579630B (en) 2013-09-30 2018-03-23 3M创新有限公司 Fiber, cleaning piece and method
US20160235057A1 (en) 2013-09-30 2016-08-18 3M Innovative Properties Company Compositions, Wipes, and Methods
US9266910B2 (en) 2013-10-29 2016-02-23 Exxonmobil Chemical Patents Inc. Asymmetric polypropylene catalysts
US9376559B2 (en) 2013-11-22 2016-06-28 Exxonmobil Chemical Patents Inc. Reverse staged impact copolymers
WO2015085446A1 (en) 2013-12-10 2015-06-18 Exxonmobil Chemical Patents Inc. Methods for making multilayer films and films made thereby
BR112016013611B1 (en) 2013-12-20 2021-01-05 Saudi Basic Industries Corporation polyolefin compound, composition and article, heterophasic propylene copolymer and their uses
MX2016008028A (en) 2013-12-20 2017-05-12 Saudi Basic Ind Corp Heterophasic propylene copolymer.
AU2015270854B2 (en) 2014-06-02 2018-08-02 Avery Dennison Corporation Films with enhanced scuff resistance, clarity, and conformability
WO2016038211A1 (en) * 2014-09-12 2016-03-17 Borealis Ag Process for the preparation of copolymers of propylene
CN106795237B (en) 2014-10-03 2019-07-26 埃克森美孚化学专利公司 Polyethylene polymer, the film being made from it and its manufacturing method
JP6663096B2 (en) * 2015-02-19 2020-03-11 住友化学株式会社 Thermoplastic elastomer composition
CN107531035B (en) 2015-03-17 2022-11-22 埃克森美孚化学专利公司 Multilayer film and method for producing same
US10618989B2 (en) 2015-04-20 2020-04-14 Exxonmobil Chemical Patents Inc. Polyethylene composition
KR102537802B1 (en) 2015-06-11 2023-05-31 다우 글로벌 테크놀로지스 엘엘씨 Cable insulation comprising a blend of LDPE and polypropylene
CN109070531B (en) 2016-03-11 2020-09-18 埃克森美孚化学专利公司 Multilayer film and method for producing same
EP3445808A1 (en) 2016-04-22 2019-02-27 ExxonMobil Chemical Patents Inc. Polyethylene sheets
WO2018102091A1 (en) 2016-12-02 2018-06-07 Exxonmobil Chemical Patents Inc. Polyethylene films
WO2018106480A1 (en) 2016-12-06 2018-06-14 Exxonmobil Chemical Patents Inc. Multilayer films and methods of making the same
WO2018151903A1 (en) 2017-02-20 2018-08-23 Exxonmobil Chemical Patents Inc. Supported catalyst systems and processes for use thereof
WO2018187047A1 (en) 2017-04-06 2018-10-11 Exxonmobil Chemical Patents Inc. Cast films and processes for making the same
WO2018194740A1 (en) 2017-04-19 2018-10-25 Exxonmobil Chemical Patents Inc. Multilayer films and methods of making the same
WO2018226311A1 (en) 2017-06-08 2018-12-13 Exxonmobil Chemical Patents Inc. Polyethylene blends and extrudates and methods of making the same
WO2019027524A1 (en) 2017-08-02 2019-02-07 Exxonmobil Chemical Patents Inc. Multilayer films and methods of making the same
US10913808B2 (en) 2017-08-04 2021-02-09 Exxonmobil Chemical Patents Inc. Mixed catalysts with unbridged hafnocenes with -CH2-SiMe3 moieties
WO2019027586A1 (en) 2017-08-04 2019-02-07 Exxonmobil Chemical Patents Inc. Mixed catalysts with 2, 6-bis(imino)pyridy| iron complexes and bridged hafnocenes
CN111094366B (en) 2017-08-04 2022-06-24 埃克森美孚化学专利公司 Polyethylene compositions and films made therefrom
WO2019027605A1 (en) 2017-08-04 2019-02-07 Exxonmobil Chemical Patents Inc. Films made from polyethylene compositions and processes for making the same
US11691398B2 (en) 2017-11-28 2023-07-04 Exxonmobil Chemical Patents Inc. Multilayer films and methods of making the same
CN115850552A (en) 2017-12-01 2023-03-28 埃克森美孚化学专利公司 Catalyst system and polymerization process using the same
WO2019108327A1 (en) 2017-12-01 2019-06-06 Exxonmobil Chemical Patents Inc. Films comprising polyethylene composition
EP3749707A1 (en) 2018-02-05 2020-12-16 ExxonMobil Chemical Patents Inc. Enhanced processability of lldpe by addition of ultra-high molecular weight high density polyethylene
EP3807358B1 (en) 2018-06-13 2023-11-15 ExxonMobil Chemical Patents Inc. Polyolefin blend compositions
CN112313254B (en) 2018-06-19 2023-04-18 埃克森美孚化学专利公司 Polyethylene compositions and films made therefrom
WO2020068497A1 (en) 2018-09-25 2020-04-02 Exxonmobil Chemical Patents Inc. Multilayer films and methods of making the same
US20220056168A1 (en) 2018-11-01 2022-02-24 Exxonmobil Chemical Patents Inc. Slurry Trim Feeder Modifications
EP3873950A1 (en) 2018-11-01 2021-09-08 ExxonMobil Chemical Patents Inc. On-line adjustment of catalysts by trim and olefin polymerization
US20220033536A1 (en) 2018-11-01 2022-02-03 Exxonmobil Chemical Patents Inc. On-Line Adjustment of Mixed Catalyst Ratio By Trim and Olefin Polymerization with the Same
WO2020092584A2 (en) 2018-11-01 2020-05-07 Exxonmobil Chemical Patents Inc. In-line trimming of dry catalyst feed
US20220033535A1 (en) 2018-11-01 2022-02-03 Exxonmobil Chemical Patents Inc. On-Line Adjustment of Mixed Catalyst Ratio and Olefin Polymerization
WO2020139499A1 (en) 2018-12-26 2020-07-02 Exxonmobil Chemical Patents Inc. Multilayer metallized cast polypropylene films doped with hydrocarbon resin
WO2020167929A1 (en) 2019-02-13 2020-08-20 Exxonmobil Chemical Patents Inc. Methods for making films and films made thereby
WO2020167441A1 (en) 2019-02-13 2020-08-20 Exxonmobil Chemical Patents Inc. Oriented multilayer polyethylene films and laminates thereof
WO2020190507A1 (en) 2019-03-19 2020-09-24 Exxonmobil Chemical Patents Inc. Multilayer oriented films
US11180646B2 (en) 2019-08-20 2021-11-23 Exxonmobil Chemical Patents Inc. Films and methods of making the same
US11518154B2 (en) 2020-01-27 2022-12-06 Exxonmobil Chemical Patents Inc. Barrier films for packaging
WO2021167739A1 (en) 2020-02-18 2021-08-26 Exxonmobil Chemical Patents Inc. High tenacity handwrap stretch film for improved pallet stability
WO2021195070A1 (en) 2020-03-26 2021-09-30 Exxonmobil Chemical Patents Inc. Processes for making 3-d objects from blends of polypropylene and semi-amorphous polymers
CN116917353A (en) 2021-03-05 2023-10-20 埃克森美孚化学专利公司 Methods of making and using slurry catalyst mixtures
WO2022203461A1 (en) * 2021-03-26 2022-09-29 주식회사 엘지화학 Polypropylene resin composition and method for preparing same
WO2022203463A1 (en) * 2021-03-26 2022-09-29 주식회사 엘지화학 Polypropylene resin composition and non-woven fabric prepared using same
WO2023150480A1 (en) 2022-02-07 2023-08-10 Exxonmobil Chemical Patents Inc. C1 symmetric 5-ome-6-alkyl substituted metallocenes

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0641807A2 (en) * 1993-08-13 1995-03-08 Mitsui Petrochemical Industries, Ltd. Olefin polymerization catalyst and process for preparing polypropylene and a propylene block copolymer
EP0657500A1 (en) * 1993-06-30 1995-06-14 Mitsui Petrochemical Industries, Ltd. Polypropylene composition

Family Cites Families (30)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
US5258464A (en) 1990-01-29 1993-11-02 Shell Oil Company Impact copolymer compositions
US5118757A (en) 1990-03-26 1992-06-02 Shell Oil Company Polymer production
US5166268A (en) 1990-04-12 1992-11-24 Union Carbide Chemicals & Plastics Technology Corporation Process for cold forming propylene copolymers
US5362782A (en) 1990-05-14 1994-11-08 Shell Oil Company Polymer compositions
US5250631A (en) 1990-06-13 1993-10-05 Shell Oil Company Polymer compositions
DE4130429A1 (en) 1991-09-13 1993-03-18 Basf Ag METHOD FOR PRODUCING MULTI-PHASE BLOCK COPOLYMERISATS BASED ON ALK-1-ENEN
US5830821A (en) 1991-11-30 1998-11-03 Targor Gmbh Process for olefin preparation using metallocenes having benzo-fused indenyl derivatives as ligands
TW294669B (en) 1992-06-27 1997-01-01 Hoechst Ag
DE59309424D1 (en) 1992-08-15 1999-04-15 Targor Gmbh Process for the production of polyolefins
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
WO1995027741A1 (en) * 1994-04-11 1995-10-19 Mitsui Petrochemical Industries, Ltd. Process for producing propylene polymer composition, and propylene polymer composition
CA2157400C (en) 1994-04-11 2003-07-29 Takashi Ueda Process for preparing propylene polymer composition, and propylene polymer composition
JP3357186B2 (en) 1994-07-14 2002-12-16 三菱化学株式会社 Method for producing propylene block copolymer
KR100359370B1 (en) 1995-02-07 2003-02-11 미쓰이 가가쿠 가부시키가이샤 Manufacturing method of olefin polymer
US5674630A (en) 1995-05-08 1997-10-07 Union Carbide Chemicals & Plastics Technology Corporation Polymer compositions and cast films
JPH09151294A (en) 1995-09-29 1997-06-10 Mitsubishi Chem Corp Talc-containing propylene resin composition
US5712344A (en) 1996-01-04 1998-01-27 Union Carbide Chemicals & Plastics Technology Corporation Modified polypropylene impact copolymer compositions
JPH09208881A (en) 1996-02-07 1997-08-12 Mitsubishi Chem Corp Propylene resin composition for coating
SG67392A1 (en) 1996-05-27 1999-09-21 Sumitomo Chemical Co Propylene/ethylene-alpha-olefin block copolymer and process for producing the same
AU1211197A (en) 1997-01-10 1998-08-03 Chisso Corporation Propylene/ethylene copolymer, process for the production thereof, and molded articles thereof
WO1998040331A1 (en) 1997-03-07 1998-09-17 Targor Gmbh Preparation of preparing substituted indanones
US6303696B1 (en) 1997-04-11 2001-10-16 Chisso Corporation Propylene (co)polymer composition using metallocene catalyst
US6635715B1 (en) * 1997-08-12 2003-10-21 Sudhin Datta Thermoplastic polymer blends of isotactic polypropylene and alpha-olefin/propylene copolymers
US6201069B1 (en) * 1997-08-29 2001-03-13 Chisso Corporation Polypropylene/propylene-ethylene copolymer composition and process for the preparation thereof
DE19739946A1 (en) 1997-09-11 1999-03-18 Targor Gmbh Process for the production of metallocenes
US5942587A (en) 1997-11-21 1999-08-24 Exxon Chemical Patents Inc. Ethylene polymers with a norbornene comonomer for LLDPE like resins of improved toughness and processibility for film production
US5986009A (en) * 1997-12-03 1999-11-16 The Dow Chemical Company Blends of polypropylenes
US6469100B2 (en) 1998-06-04 2002-10-22 Japan Polychem Corporation Propylene block copolymer and resin composition
US6492465B1 (en) * 2000-02-08 2002-12-10 Exxonmobil Chemical Patents, Inc. Propylene impact copolymers

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0657500A1 (en) * 1993-06-30 1995-06-14 Mitsui Petrochemical Industries, Ltd. Polypropylene composition
EP0641807A2 (en) * 1993-08-13 1995-03-08 Mitsui Petrochemical Industries, Ltd. Olefin polymerization catalyst and process for preparing polypropylene and a propylene block copolymer

Cited By (81)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7026040B2 (en) 1996-09-04 2006-04-11 Exxon Mobil Chemical Patents Inc. Oriented films from improved propylene polymers
US6583227B2 (en) 1996-09-04 2003-06-24 Exxonmobil Chemical Patents Inc. Propylene polymers for films
US6806316B2 (en) 1996-09-04 2004-10-19 Exxonmobil Chemical Patents Inc. Propylene polymers for oriented films
US7122498B2 (en) 2000-06-30 2006-10-17 Exxonmobil Chemical Patents Inc. Metallocenes and catalyst compositions derived therefrom
WO2002070572A3 (en) * 2001-03-06 2002-11-07 Exxonmobil Chem Patents Inc Propylene polymers for films
WO2002070572A2 (en) * 2001-03-06 2002-09-12 Exxonmobil Chemical Patents Inc. Propylene polymers for films
WO2003002583A2 (en) 2001-06-29 2003-01-09 Exxonmobil Chemical Patents Inc. Metallocenes and catalyst compositions derived therefrom
WO2003002583A3 (en) * 2001-06-29 2004-03-04 Exxonmobil Chem Patents Inc Metallocenes and catalyst compositions derived therefrom
WO2003045551A1 (en) * 2001-11-30 2003-06-05 Basell Polyolefine Gmbh Organometallic transition metal compound, biscyclopentadienyl ligand system, catalyst system and preparation of polyolefins
US7109278B2 (en) 2001-11-30 2006-09-19 Basell Polyolefine Gmbh Organometallic transition metal compound, biscyclopentadienyl ligand system, catalyst system and preparation of polyolefins
KR100954975B1 (en) * 2002-03-29 2010-04-30 구미아이 가가쿠 고교 가부시키가이샤 Genes Encoding Acetolactate Synthase
US8030547B2 (en) 2002-03-29 2011-10-04 Kumiai Chemical Industry Co., Ltd. Gene coding for acetolactate synthase
JP2005528412A (en) * 2002-04-23 2005-09-22 ダウ・グローバル・テクノロジーズ・インコーポレイテッド Alkaryl-substituted group 4 metal complex, catalyst, and olefin polymerization method
US7439312B2 (en) 2002-10-24 2008-10-21 Exxonmobil Chemical Patents Inc. Branched crystalline polypropylene
US8304496B2 (en) 2005-05-12 2012-11-06 Dow Global Technologies Llc Thermoformed, extruded sheeting with reduced gloss
US8299287B2 (en) 2007-10-25 2012-10-30 Lammus Novolen Technology GmbH Metallocene compounds, catalysts comprising them, process for producing an olefin polymer by use of the catalysts, and olefin homo- and copolymers
WO2009054833A2 (en) 2007-10-25 2009-04-30 Novolen Technology Holdings, C.V. Metallocene compounds, catalysts comprising them, process for producing an olefin polymer by use of the catalysts, and olefin homo and copolymers
US8507706B2 (en) 2007-10-25 2013-08-13 Lummus Novolen Technology Gmbh Metallocene compounds, catalysts comprising them, process for producing an olefin polymer by use of the catalysts, and olefin homo- and copolymers
EP2075284A1 (en) * 2007-12-17 2009-07-01 Borealis Technology OY Heterophasic polypropylene with high flowability and excellent low temperature impact properties
WO2009077032A1 (en) * 2007-12-17 2009-06-25 Borealis Technology Oy Heterophasic polypropylene with high flowability and excellent low temperature impact properties
EP2363433A1 (en) * 2007-12-17 2011-09-07 Borealis Technology OY Heterophasic polypropylene with high flowability and excellent low temperature impact properties
US8445598B2 (en) 2007-12-17 2013-05-21 Borealis Technology Oy Heterophasic polypropylene with high flowability and excellent low temperature impact properties
RU2451041C2 (en) * 2007-12-17 2012-05-20 Бореалис Текнолоджи Ой Heterophase polypropylene having high fluidity and excellent low-temperature impact properties
SG153790A1 (en) * 2007-12-26 2009-07-29 Sumitomo Chemical Co Polypropylene-based copolymer and film comprising the polypropylene- based copolymer
US8404773B2 (en) 2008-03-17 2013-03-26 Dow Global Technologies Llc Coating composition, method of producing the same, articles made therefrom, and method of making such articles
US8569418B2 (en) 2009-06-26 2013-10-29 Basell Poliolefine Italia S.R.L. Polyolefin compositions
WO2010149705A1 (en) * 2009-06-26 2010-12-29 Basell Poliolefine Italia S.R.L. Polyolefin compositions
WO2011008582A1 (en) 2009-07-14 2011-01-20 Dow Global Technologies Inc. Vacuum thermoformed, extruded sheeting with improved reduced gloss
US8431651B2 (en) 2009-07-14 2013-04-30 Dow Global Technologies Llc Vacuum thermoformed, extruded sheeting with improved reduced gloss
WO2012028252A1 (en) 2010-08-30 2012-03-08 Borealis Ag Heterophasic polypropylene with high flowability and enhanced mechanical properties
EP2426171A1 (en) 2010-08-30 2012-03-07 Borealis AG Heterophasic polypropylene with high flowability and enhanced mechanical properties
US9074085B2 (en) 2010-08-30 2015-07-07 Borealis Ag Heterophasic polypropylene with high flowability and enhanced mechanical properties
WO2013150057A1 (en) * 2012-04-05 2013-10-10 Borealis Ag High flow thermoplastic polyolefin with balanced mechanical performance and low shrinkage and clte
US9120922B2 (en) 2012-04-05 2015-09-01 Borealis Ag High flow thermoplastic polyolefin with balanced mechanical performance and low shrinkage and CLTE
KR101512279B1 (en) 2012-04-05 2015-04-14 보레알리스 아게 High flow thermoplastic polyolefin with balanced mechanical performance and low shrinkage and clte
WO2015022127A1 (en) * 2013-08-14 2015-02-19 Borealis Ag Propylene composition with improved impact resistance at low temperature
RU2648673C2 (en) * 2013-08-14 2018-03-28 Бореалис Аг Propylene composition with improved impact resistance at low temperature
US9670347B2 (en) 2013-08-14 2017-06-06 Borealis Ag Propylene composition with improved impact resistance at low temperature
KR101820613B1 (en) 2013-08-14 2018-01-19 보레알리스 아게 Propylene composition with improved impact resistance at low temperature
US9890275B2 (en) 2013-08-21 2018-02-13 Borealis Ag High flow polyolefin composition with high stiffness and toughness
US9777142B2 (en) 2013-08-21 2017-10-03 Borealis Ag High flow polyolefin composition with high stiffness and toughness
US10040930B2 (en) 2013-09-27 2018-08-07 Abu Dhabi Polymers Co. Ltd (Borouge) Llc. Polymer composition with high XS, high Tm suitable for BOPP processing
US9802394B2 (en) 2013-10-11 2017-10-31 Borealis Ag Machine direction oriented film for labels
US10519259B2 (en) 2013-10-24 2019-12-31 Borealis Ag Low melting PP homopolymer with high content of regioerrors and high molecular weight
US9708481B2 (en) 2013-10-24 2017-07-18 Borealis Ag Blow molded article based on bimodal random copolymer
US9670293B2 (en) 2013-10-29 2017-06-06 Borealis Ag Solid single site catalysts with high polymerisation activity
US9751962B2 (en) 2013-11-22 2017-09-05 Borealis Ag Low emission propylene homopolymer with high melt flow
US9828698B2 (en) 2013-12-04 2017-11-28 Borealis Ag Phthalate-free PP homopolymers for meltblown fibers
US9637602B2 (en) 2013-12-18 2017-05-02 Borealis Ag BOPP film with improved stiffness/toughness balance
EP3094681B1 (en) 2014-01-15 2021-01-20 ExxonMobil Chemical Patents Inc. Propylene-based impact copolymers
US9745395B2 (en) 2014-01-15 2017-08-29 Exxonmobil Chemical Patents Inc. Propylene-based impact copolymers
US9309334B2 (en) 2014-01-15 2016-04-12 Exxonmobil Chemical Patents Inc. Propylene-based impact copolymers
US10465025B2 (en) 2014-01-15 2019-11-05 Exxonmobil Chemical Patents Inc. Low comonomer propylene-based impact copolymers
WO2015108634A1 (en) 2014-01-15 2015-07-23 Exxonmobil Chemical Patents Inc. Propylene-based impact copolymers
US10227427B2 (en) 2014-01-17 2019-03-12 Borealis Ag Process for preparing propylene/1-butene copolymers
US10100186B2 (en) 2014-02-06 2018-10-16 Borealis Ag Soft and transparent impact copolymers
US10100185B2 (en) 2014-02-06 2018-10-16 Borealis Ag Soft copolymers with high impact strength
US10030109B2 (en) 2014-02-14 2018-07-24 Borealis Ag Polypropylene composite
WO2015126797A1 (en) 2014-02-24 2015-08-27 Dow Global Technologies Llc Thermoplastic polyolefin with reduced gloss for non-carpeted flooring
US10450451B2 (en) 2014-05-20 2019-10-22 Borealis Ag Polypropylene composition for automotive interior applications
US10294316B2 (en) 2015-06-05 2019-05-21 Exxonmobil Chemical Patents Inc. Silica supports with high aluminoxane loading capability
US10570219B2 (en) 2015-06-05 2020-02-25 Exxonmobil Chemical Patents Inc. Production of heterophasic polymers in gas or slurry phase
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US11192961B2 (en) 2015-06-05 2021-12-07 Exxonmobil Chemical Patents Inc. Production of heterophasic polymers in gas or slurry phase
US10280233B2 (en) 2015-06-05 2019-05-07 Exxonmobil Chemical Patents Inc. Catalyst systems and methods of making and using the same
WO2016196339A3 (en) * 2015-06-05 2017-02-09 Exxonmobil Chemical Patents Inc. Production of heterophasic polymers in gas or slurry phase
US10280235B2 (en) 2015-06-05 2019-05-07 Exxonmobil Chemical Patents Inc. Catalyst system containing high surface area supports and sequential polymerization to produce heterophasic polymers
US10287372B2 (en) 2015-06-05 2019-05-14 Exxonmobil Chemical Patents Inc. Bimodal propylene polymers and sequential polymerization
US10723821B2 (en) 2015-06-05 2020-07-28 Exxonmobil Chemical Patents Inc. Supported metallocene catalyst systems for polymerization
US10329360B2 (en) 2015-06-05 2019-06-25 Exxonmobil Chemical Patents Inc. Catalyst system comprising supported alumoxane and unsupported alumoxane particles
US10759886B2 (en) 2015-06-05 2020-09-01 Exxonmobil Chemical Patents Inc. Single reactor production of polymers in gas or slurry phase
US10280240B2 (en) 2016-05-27 2019-05-07 Exxonmobil Chemical Patents Inc. Metallocene catalyst compositions and polymerization process therewith
US11492425B2 (en) 2016-05-27 2022-11-08 Exxonmobil Chemical Patents Inc. Metallocene catalyst compositions and polymerization process therewith
WO2017204830A1 (en) 2016-05-27 2017-11-30 Exxonmobil Chemical Patents, Inc. Metallocene catalyst compositions and polymerization process therewith
US11059918B2 (en) 2016-05-27 2021-07-13 Exxonmobil Chemical Patents Inc. Metallocene catalyst compositions and polymerization process therewith
US10920053B2 (en) 2017-10-16 2021-02-16 Exxonmobil Chemical Patents Inc. Propylene impact copolymer blends with improved gloss
US11396592B2 (en) 2019-02-19 2022-07-26 Braskem S.A. No break polypropylene impact copolymers with melt flow rate higher than 90 g/10 min
WO2020170046A1 (en) * 2019-02-19 2020-08-27 Braskem S.A. No break polypropylene impact copolymers with melt flow rate higher than 90 g/10 min
WO2020208198A1 (en) 2019-04-12 2020-10-15 Thai Polyethylene Co., Ltd Impact copolymer polypropylene for thin-wall injection packaging
EP3722363A1 (en) * 2019-04-12 2020-10-14 Thai Polyethylene Co., Ltd. Impact copolymer polypropylene for thin-wall injection packaging
US11472828B2 (en) 2019-10-11 2022-10-18 Exxonmobil Chemical Patents Inc. Indacene based metallocene catalysts useful in the production of propylene polymers

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