WO2007005364A2 - Haloaluminoxane compositions - Google Patents

Haloaluminoxane compositions Download PDF

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Publication number
WO2007005364A2
WO2007005364A2 PCT/US2006/024778 US2006024778W WO2007005364A2 WO 2007005364 A2 WO2007005364 A2 WO 2007005364A2 US 2006024778 W US2006024778 W US 2006024778W WO 2007005364 A2 WO2007005364 A2 WO 2007005364A2
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Prior art keywords
composition
carbon atoms
haloaluminoxane
independently
general formula
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PCT/US2006/024778
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French (fr)
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WO2007005364A3 (en
Inventor
Rajeev S. Mathur
Samuel A. Sangokoya
Lubin Luo
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Albemarle Corporation
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Publication of WO2007005364A3 publication Critical patent/WO2007005364A3/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic System
    • C07F5/06—Aluminium compounds
    • C07F5/061—Aluminium compounds with C-aluminium linkage
    • C07F5/066—Aluminium compounds with C-aluminium linkage compounds with Al linked to an element other than Al, C, H or halogen (this includes Al-cyanide linkage)
    • C07F5/068—Aluminium compounds with C-aluminium linkage compounds with Al linked to an element other than Al, C, H or halogen (this includes Al-cyanide linkage) preparation of alum(in)oxanes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic System
    • C07F5/06—Aluminium compounds
    • C07F5/061—Aluminium compounds with C-aluminium linkage
    • C07F5/066—Aluminium compounds with C-aluminium linkage compounds with Al linked to an element other than Al, C, H or halogen (this includes Al-cyanide linkage)

Definitions

  • This invention relates to stabilized haloaluminoxane compositions that are of particular utility in the formation of new catalyst systems, to methods for the preparation of these stabilized haloaluminoxane compositions and catalyst systems, and to the use of such catalyst systems in the polymerization of olefin monomers, dienes, or the like.
  • Aluminoxane compositions are widely used in combination with various types of metallocenes and transition metal compounds to prepare catalyst systems for polymerizing olefin monomers.
  • certain limitations are associated with standard aluminoxane solutions, such as poor solubility, instability, and gel formation.
  • solutions of conventional aluminoxanes, such as methylaluminoxane (MAO) must be kept at lower temperatures to inhibit degradation via irreversible gel formation.
  • a fluorinated methylaluminoxane formulation may begin to show solid precipitation at a temperature of about -6°C, while a conventional methylaluminoxane formulation has a freezing temperature of less than about -35°C.
  • haloaluminoxanes are generally more stable to degradation than standard aluminoxanes, they are susceptible to slow irreversible degradation at higher temperatures, for example, at temperatures above about 45°C.
  • This invention encompasses stabilized haloaluminoxane compositions, methods for preparing stabilized haloaluminoxane compositions, supported and unsupported catalyst compositions comprising stabilized haloaluminoxane compositions, methods for preparing these catalyst compositions, and methods for polymerizing olefin monomers using these catalyst compositions.
  • haioaluminoxane compositions can be modified such that they have improved stability at lower and higher temperatures under inert, anhydrous conditions, while maintaining their solubility in hydrocarbon solvents, especially aromatic hydrocarbon solvents.
  • stabilized haioaluminoxane compositions of the invention also perform as well as, if not better than, standard haloaluminoxanes and conventional aluminoxanes when used as cocatalysts in the polymerization of olefins.
  • the present invention encompasses a stabilized haioaluminoxane composition comprising a contact product of:
  • halohydrocarbon having the general formula R n CX 4-P
  • siloxane having at least one labile halogen atom in the molecule, wherein each halogen atom is, independently, fluorine, chlorine, or bromine
  • X is, independently, a fluorine, a chlorine, or a bromine atom
  • R is, independently, a hydrogen atom, a hydrocarbyl group having from one to about twenty carbon atoms, or a halohydrocarbyl group having from one to about twenty carbon atoms,
  • R' is, independently, a hydrocarbyl group having from one to about twenty carbon atoms or a halohydrocarbyl group having from one to about twenty carbon atoms,
  • R" is an alkyl group having from two to about twenty carbon atoms
  • Q is, independently, a halide, a pseudohalide, or hydride.
  • Another aspect of the present invention encompasses a stabilized halomethylaluminoxane composition comprising the contact product of:
  • AIR" n Q 3 -n wherein: m is 1 or 2, inclusive, n is 1 , 2, or 3, inclusive,
  • R is, independently, a hydrogen atom, a hydrocarbyl group having from one to about twenty carbon atoms, or a fluorohydrocarbyl group having from one to about twenty carbon atoms,
  • R' is, independently, a hydrocarbyl group having from one to about twenty carbon atoms or a fluorohydrocarbyl group having from one to about twenty carbon atoms,
  • R" is an alkyl group having from two to about twenty carbon atoms
  • Yet another aspect of the present invention encompasses a stabilized haloaluminoxane composition comprising at least one aluminoxane, halogen atoms derived from a halogenation agent, and at least one additional alkylaluminum compound, wherein the amount of additional alkylaluminum compound present in the composition is in the range of about 1 mole % to about 5 mole % relative to the total composition.
  • a further aspect of the present invention encompasses a stabilized haloaluminoxane composition
  • a stabilized haloaluminoxane composition comprising at least one haloaluminoxane and at least one additional alkylaluminum compound, wherein the amount of additional alkylaluminum compound present in the composition is in the range of about 1 mole % to about 5 mole % relative to the total composition.
  • a still further aspect of the present invention encompasses a stabilized haloaluminoxane composition
  • a stabilized haloaluminoxane composition comprising at least one aluminoxane, halogen atoms derived from a halogenation agent, and at least one additional alkylaluminum compound, wherein the amount of additional alkylaluminum compound present in the composition is at least about 1 mole % relative to the total composition.
  • Another aspect of the present invention encompasses a stabilized haloaluminoxane composition comprising at least one haloaluminoxane and at least one additional alkylaluminum compound, wherein the amount of additional alkylaluminum compound present in the composition is at least about 1 mole % relative to the total composition.
  • the present invention also encompasses a stabilized haloaluminoxane composition which is stable to degradation at temperatures ranging from about -30 0 C to about 60 0 C for at least about thirty days.
  • Yet another aspect of the present invention encompasses a process to produce a stabilized haloaluminoxane composition comprising contacting, in an environment which is substantially inert and anhydrous:
  • halohydrocarbon having the general formula R n CX 4-0
  • siloxane having at least one labile halogen atom in the molecule, wherein each halogen atom is, independently, fluorine, chlorine, or bromine
  • X is, independently, a fluorine, chlorine, or bromine atom
  • R is, independently, a hydrogen atom, a hydrocarbyl group having from one to about twenty carbon atoms, or a halohydrocarbyl group having from one to about twenty carbon atoms,
  • R' is, independently, a hydrocarbyl group having from one to about twenty carbon atoms or a halohydrocarbyl group having from one to about twenty carbon atoms,
  • R" is an alkyl group having from two to about twenty carbon atoms
  • the present invention further encompasses a catalyst composition comprising a stabilized haloaluminoxane composition and at least one complex of a transition metal of Group 3, 4, 5, 6, 7, 8, 9, 10, or 11 of the Periodic Table of Elements, including the lanthanide and actinide series.
  • the catalyst composition can be unsupported or supported on an organic or inorganic carrier material.
  • This invention also encompasses a method for polymerizing olefin monomers comprising contacting at least one olefin monomer and a catalyst system comprising a stabilized haloaluminoxane composition in accordance with the present invention and at least one transition metal complex.
  • Figure 1 is a graph illustrating the accelerated aging over time for stabilized haloaluminoxanes as compared to conventional haloaluminoxanes.
  • the present invention provides stabilized haloaluminoxane compositions, methods for preparing stabilized haloaluminoxane compositions, supported and unsupported catalyst compositions comprising stabilized haloaluminoxane compositions of the present invention, and methods for polymerizing olefins using catalyst compositions comprising stabilized haloaluminoxane compositions of the present invention.
  • Stabilized haloaluminoxane compositions in accordance with the present invention comprise the contact product of:
  • X is, independently, a fluorine, chlorine, or bromine atom
  • R is, independently, a hydrogen atom, a hydrocarbyl group having from one to about twenty carbon atoms, or a halohydrocarbyl group having from one to about twenty carbon atoms,
  • R' is, independently, a hydrocarbyl group having from one to about twenty carbon atoms or a halohydrocarbyl group having from one to about twenty carbon atoms,
  • R" is an alkyl group having from two to about twenty carbon atoms
  • Q is, independently, a halide, a pseudohalide, or hydride.
  • Stabilized halomethylaluminoxane compositions in accordance with another aspect of the present invention comprise the contact product of:
  • AIR"nQ 3 -n wherein: m is 1 or 2, inclusive, n is 1 , 2, or 3, inclusive,
  • R is, independently, a hydrogen atom, a hydrocarbyl group having from one to about twenty carbon atoms, or a fluorohydrocarbyl group having from one to about twenty carbon atoms,
  • R' is, independently, a hydrocarbyl group having from one to about twenty carbon atoms or a fluorohydrocarbyl group having from one to about twenty carbon atoms,
  • R" is an alkyl group having from two to about twenty carbon atoms
  • Yet another aspect of the present invention encompasses a stabilized haloaluminoxane composition comprising at least one aluminoxane, halogen atoms derived from a halogenation agent, and at least one additional alkylaluminum compound, wherein the amount of additional alkylaluminum compound present in the composition is in a range of about 1 mole % to about 5 mole % relative to the total composition.
  • a further aspect of the present invention encompasses a stabilized haloaluminoxane composition comprising at least one haloaluminoxane and at least one additional alkylaluminum compound, wherein the amount of additional alkylaluminum compound present in the composition is in a range of about 1 mole % to about 5 mole % relative to the total composition.
  • a still further aspect of the present invention encompasses a stabilized haloaluminoxane composition
  • a stabilized haloaluminoxane composition comprising at least one aluminoxane, halogen atoms derived from a halogenation agent, and at least one additional alkylaluminum compound, wherein the amount of additional alkylaluminum compound present in the composition is at least about 1 mole % relative to the total composition.
  • Still yet another aspect of the present invention encompasses a stabilized haloaluminoxane composition
  • a stabilized haloaluminoxane composition comprising at least one haloaluminoxane and at least one additional alkylaluminum compound, wherein the amount of additional alkylaluminum compound present in the composition is at least about 1 mole % relative to the total composition.
  • the present invention also encompasses a stabilized haloaluminoxane composition which is stable to degradation at temperatures in a range from about -30 0 C to about 60 0 C for at least about 30 days.
  • Aluminoxanes can include any suitable hydrocarbylaluminoxanes having at least one hydrocarbyl moiety having from one to about twenty carbon atoms.
  • Such aluminoxanes include, but are not limited to, alkylaluminoxanes, cycloalkylaluminoxanes, arylaluminoxanes, aralkylaluminoxanes, or any combination thereof.
  • Hydrocarbylaluminoxanes can exist in the form of linear or cyclic polymers with the simplest monomeric compound being a tetraalkylaluminoxane, such as, tetramethylaluminoxane, (CHa) 2 AI-O-AI(CHs) 2 , or tetraethylaluminoxane, (C 2 H 5 ⁇ Al- O— AI(C 2 H 5 ) 2 .
  • the aluminoxanes can be oligomeric materials, sometimes referred to as polyalkylaluminoxanes, containing the repeating unit wherein R is a C 1 -Ci 0 alkyl group and n is an integer from about 4 to about 20.
  • aluminoxanes can contain linear, cyclic, cross- linked species, or any combination thereof.
  • hydrocarbylaluminoxanes for use in the invention include methylaluminoxanes (MAO), modified MAOs, ethylaluminoxanes (EAO), isobutylaluminoxanes (IBAO), n- propylaluminoxanes, n-octylaluminoxanes, phenylaluminoxanes, or any combination thereof.
  • the hydrocarbylaluminoxanes can also contain up to about 20 mole percent (based on aluminum atoms) of moieties derived from amines, alcohols, ethers, esters, phosphoric and carboxylic acids, thiols, aryl disiloxanes, alkyl disiloxanes, and the like to further improve activity, solubility and/or stability.
  • Aluminoxanes can be prepared as known in the art by the partial hydrolysis of hydrocarbylaluminum compounds.
  • Hydrocarbylaluminum compounds or mixtures of compounds capable of reacting with water to form an aluminoxane can be employed in the present invention. This includes, for example, trialkylaluminum, triarylaluminum, mixed alkyl-aryl aluminum, or any combination thereof.
  • the hydrocarbylaluminum compounds can be hydrolyzed by adding either free water or water- containing solids, which can be either hydrates or porous materials which have absorbed water.
  • Suitable hydrates include salt hydrates such as, but not limited to, CuSO 4 « 5H 2 O, AI 2 (SO 4 ) 3 *18H 2 O, FeSO 4 « 7H 2 O, AICI 3 « 6H 2 O, AI(NOs) 3 ⁇ H 2 O, MgSO 4 « 7H 2 O, MgCI 2 « 6H 2 O, ZnSO 4 « 7H 2 O, Na 2 SO 4 HOH 2 O, Na 3 PO 4 H 2H 2 O, LiBr » 2H 2 O, LiCI-H 2 O, Lil-2H 2 O, Lil*3H 2 O, KF'2H 2 O, NaBr « 2H 2 O, or any combination thereof.
  • salt hydrates such as, but not limited to, CuSO 4 « 5H 2 O, AI 2 (SO 4 ) 3 *18H 2 O, FeSO 4 « 7H 2 O, AICI 3 « 6H 2 O, AI(NOs) 3 ⁇ H 2 O, MgSO 4 « 7H 2 O, MgCI 2
  • Alkali or alkaline earth metal hydroxide hydrates can also be employed with the present invention.
  • Such alkali or alkaline earth metal hydroxide hydrates include, but are not limited to, NaOH » H 2 O, NaOH « 2H 2 O, Ba(OH) 2 *8H 2 O, KOH » 2H 2 O, CsOH « H 2 O, LiOH « H 2 O, or any combination thereof.
  • Mixtures of salt hydrates and alkali or alkaline earth metal hydroxide hydrates can also be used.
  • the molar ratios of free water or water in the hydrate or in porous materials, which include inorganic oxides such as alumina or silica, to total alkylaluminum compounds in the mixture can vary widely.
  • such molar ratios are in a range from about 2:1 to about 1:4. In another aspect of the present invention, such molar ratios are in a range from about 4:3 to about 2:7.
  • Suitable hydrocarbylaluminoxanes and processes for preparing hydrocarbylaluminoxanes which can be employed with the present invention, to name only a few, are described in U.S. Patent Nos. 4,908,463; 4,924,018; 5,003,095; 5,041 ,583; 5,066,631; 5,099,050; 5,157,008; 5,157,137; 5,235,081 ; 5,248,801, and 5,371,260.
  • the methyialuminoxanes can contain varying amounts of the aluminum value as unreacted trimethylaluminum (TMA), for example, from about 5 to about 35 mole percent.
  • TMA trimethylaluminum
  • the aluminoxanes have saturated hydrocarbyl groups having from one to about twenty carbon atoms.
  • the hydrocarbyl groups of the aluminoxanes have from one to about six carbon atoms.
  • Aluminoxanes which can be employed in the present invention include, but are not limited to, methylaluminoxane, ethylaluminoxane, n-propylaluminoxane, n-butylaluminoxane, isobutylaluminoxane, n-hexylaluminoxane, n-octylaluminoxane, decylaluminoxane, dodecylaluminoxane, tetradecylaluminoxane, hexadecylaluminoxane, octadecylaluminoxane, phenylaluminoxane, tolylaluminoxane, or any combination thereof.
  • the aluminoxane can contain up to about 15 mole percent (based on aluminum) of moieties formed from amines, alcohols, ethers, esters, phosphoric and carboxylic acids, thiols, alkyl disiloxanes, and the like to improve their activity, solubility, and/or stability.
  • the moiety is a bulky phenol.
  • Suitable bulky phenols include, but are not limited to, 2,6-dimethyl-4-(1 ,1- dimethylpropyl)phenol, 2,6-diisobutyl-4-methylphenol, 2,6-diisopropylphenol, 2,4,6- triisopropylphenol, 2,6-diisobutylphenol, 2,4,6-triisobutylphenol, 2,6-di-ferf-butylphenol, 2,4,6- tri-te/ ⁇ -butylphenol, or any combination thereof.
  • haloaluminoxanes can be described as two types of species.
  • One of these species is an ionic haloaluminoxane complex, which in theory is believed to be comprised of an organic cation and an aluminum anion site of the aluminoxane, where one of the species coordinated to the aluminum anion site is a halogen atom.
  • the ionic complexes are thought to exist only at the small number of aluminum anion sites of the aluminoxane, in particular those aluminum sites to which a halogen atom is coordinated.
  • ionic haloaluminoxane complex the entire species containing these ionic complexes is referred to as an ionic haloaluminoxane complex.
  • the other species is a partially halogenated aluminoxane, which in theory is believed to be comprised of a neutral aluminoxane where halogen atoms are coordinated to some of the aluminum atoms of the aluminoxane.
  • haloaluminoxane is used herein to refer to both ionic haloaluminoxane complexes and to partially halogenated aluminoxanes.
  • Stabilized haloaluminoxane compositions can comprise ionic haloaluminoxane complexes, partially halogenated aluminoxanes, or any combination thereof.
  • the amount of halogen atoms present in the haloaluminoxane composition is in a range from about 0.5 mole % to about 15 mole % halogen atoms relative to aluminum atoms.
  • These haloaluminoxane compositions can be formed from components comprising (a) at least one aluminoxane and (b) at least one halogenation agent.
  • Suitable halogenation agents include:
  • X is, independently, a fluorine, a chlorine, or a bromine atom
  • R is, independently, a hydrogen atom, a hydrocarbyl group having from one to about twenty carbon atoms, or a halohydrocarbyl group having from one to about twenty carbon atoms, and
  • Haloaluminoxanes can be prepared by a process comprising mixing, in an environment which is substantially inert and anhydrous, (a) at least one aluminoxane and (b) at least one halogenation agent, wherein the amount of halogen atoms is in the range of about 0.5 mole % to about 15 mole % halogen atoms relative to aluminum atoms, such that a haloaluminoxane composition is formed.
  • the ratio of halogen atoms to aluminum atoms are in a range from about 2 mole % to about 10 mole % halogen relative to aluminum. In yet another aspect of the present invention, the ratio of halogen atoms to aluminum atoms are in a range from about 2 mole % to about 6 mole % halogen atoms to aluminum atoms, although the optimum molar ratio will vary with each particular haloaluminoxane.
  • the process can be conducted in an environment which is substantially inert and anhydrous, such as, for example, in a substantially anhydrous liquid aromatic hydrocarbon solvent.
  • suitable anhydrous liquids include, but are not limited to, benzene, toluene, xylene, mesitylene, ethylbenzene, diethylbenzene, 1 ,2,4-triethylbenzene, 1,3,5-triethylbenzene, amylbenzene, tetrahydronaphthalene, or any combination thereof.
  • An alternative method for forming haloaluminoxanes is to have the halogenation agent present during the formation of the aluminoxane, for example, during the hydrolysis of the aluminum hydrocarbyl(s) used to form the aluminoxane.
  • the amount of halogen atoms can range from about 0.5 mole % to about 15 mole % relative to aluminum atoms.
  • haloaluminoxane components should be handled in an environment which is substantially inert, substantially moisture-free, and substantially oxygen-free.
  • environments include, but are not limited to, argon, nitrogen, or helium environments because of the sensitivity of such components and compositions to moisture and oxygen.
  • Haloaluminoxanes can include, but are not limited to, partially fluorinated methylaluminoxane, partially fluorinated ethylaluminoxane, partially fluorinated n- propylaluminoxane, partially fluorinated n-butylaluminoxane, partially fluorinated isobutylaluminoxane, partially fluorinated n-hexylaluminoxane, partially fluorinated n- octylaluminoxane, partially fluorinated phenylaluminoxane, partially chlorinated methylaluminoxane, partially chlorinated ethylaluminoxane, partially chlorinated n- propylaluminoxane, partially chlorinated n-butylaluminoxane, partially chlorinated isobutylaluminoxane, partially chlorinated n-hexylaluminoxane, partially chlorinated n- o
  • partially halogenated aluminoxanes and ionic haloaluminoxane complexes are those that have two or more different elements of halogen (for example, fluorine and chlorine; fluorine and bromine; chlorine and bromine; fluorine, chlorine, and bromine).
  • halogenation Agents for example, fluorine and chlorine; fluorine and bromine; chlorine and bromine; fluorine, chlorine, and bromine.
  • the halogenation agents of the present invention contain labile halogen atoms, i.e., halogen atoms that can react with aluminum sites in the aluminoxane.
  • Non-labile halogen atoms can also be present in the halogenation agent.
  • halogen atoms directly bound to aromatic rings have been observed to be non-labile.
  • Such halogen atoms remain bound to the aromatic ring when a halogenation agent containing such a moiety is brought into contact with an aluminoxane.
  • the halogenation agent is:
  • halohydrocarbon having the general formula R n CX 4-0
  • siloxane having at least one labile halogen atom in the molecule, wherein each halogen atom is, independently, fluorine, chlorine, or bromine
  • X is, independently, a fluorine, a chlorine, or a bromine atom.
  • R is, independently, a hydrogen atom, a hydrocarbyl group having from one to about twenty carbon atoms, or a halohydrocarbyl group having from one to about twenty carbon atoms;
  • R' is, independently, a hydrocarbyl group having from one to about twenty carbon atoms or a halohydrocarbyl group having from one to about twenty carbon atoms.
  • halohydrocarbon of the formula R n CX 4-0 ; wherein n is 1, 2, or 3, inclusive; X is, independently, a fluorine, a chlorine, or a bromine atom; and R is, independently, a hydrogen atom, a hydrocarbyl group having from one to about twenty carbon atoms, or a halohydrocarbyl group having from one to about twenty carbon atoms.
  • R can be a straight chain, branched, cycloalkyl, aryl, or aralkyl group.
  • the hydrocarbyl group is an aryl group.
  • the halohydrocarbon can also be a tertiary halohydrocarbon.
  • the halohydrocarbon has at least one R group which is an aryl group, for example, a phenyl group.
  • the halohydrocarbyl is a primary halohydfocarbon in which one R is an aryl group and the other R(s) are hydrogen atoms, or all of the other substituents are halogen atoms.
  • This group of halohydrocarbons can be represented by the general formula:
  • ArG n where Ar is an aromatic hydrocarbon ring system, which typically contains up to about 25 carbon atoms; G is -CX 3 , -CX 2 R, or -CXR 2 , in which X is, independently, a fluorine, a chlorine, or a bromine atom, and in which R is, independently, a hydrogen atom or Ci -4 alkyl group; and n is an integer from 1 to 5, inclusive.
  • Ar can contain up to about 12 carbon atoms or up to about 6 carbon atoms in the ring system.
  • n is 1 , 2, or 3, inclusive, or 1 or 2 inclusive, or 1.
  • G is a trihalomethyl group.
  • substituents on the aromatic ring(s) other than hydrogen and the group(s) containing labile halogen atom(s) can be electron-donating substituents.
  • Halogenation agents containing aromatic groups having electron-donating substituents were observed to have faster reaction rates than halogenation agents in which there were only hydrogen atoms on the aromatic ring.
  • Typical electron-donating substituents include, but are not limited to, hydrocarbyloxy groups and hydrocarbyl groups.
  • Suitable halohydrocarbons having an aryl group include, but are not limited to, ⁇ , ⁇ , ⁇ -trifluorotoluene, ⁇ , ⁇ -difluorotoluene, ⁇ -fluorotoluene, octafluorotoluene, 1 ,2- di(fluoromethyl)benzene, 1 ,3-di(fluoromethyl)benzene, 1 ,4-di(fluoromethyl)benzene, 1 ,2- bis(difluoromethyl)benzene, 1 ,3-bis(difluoromethyl)benzene, 1 ,4-bis(difluoromethyl)benzene, 1 ,3-bis(trifluoromethyl)benzene, 1 ,3,5-tris(trifluoromethyl)benzene, 4-methyl-1 - (trifluoromethyl)benzene, 3-methyl-1-(trifluoromethyl)benzene,
  • Suitable halohydrocarbons which do not have an aryl group include, but are not limited to, tert-butyl fluoride (2-methyl-2-fluoropropane), 3-methyl-3-fluoropentane, 3- methyl-3-fluorohexane, 1-methyl-i-fluorocyclohexane, 1 ,3-difluoro-1 ,3,5-methylcyclooctane, 2-methyl-2-fluoroheptane, 1 ,2-difluoro-i-methylcyclooctane, 2-methyl-2-chloropropane, tert- butyl chloride, 3-methyl-3-chloropentane, 3-chlorohexane, 3-methyl-3-chlorohexane, 1- methyl-1-chlorocyclohexane, 1 ,3-dichloro-1 ,3,5-methylcyclooctane, 2-methyl-2- chloroheptane, 1,2-d
  • Suitable halohydrocarbons which have at least two different elements of halogen that can be used include, but are not limited to, 1-chloro-3-fluoro-1 ,3,5- methylcyclooctane, 2-bromo-1 -fluoro-1 -methylcyclooctane, 2-chloro-1 -fluoro-1 - methylcyclooctane, 1 -(trichloromethyl)-4-(trifluoromethyl)benzene, 1 -(dichloromethyl)-3- (dibromomethyl)benzene, 1 -(bromomethyl)-2-(fluoromethyl)benzene, 1 -(chloromethyl)-4- (trifluoromethyl)benzene, 1-(dichloromethyl)-3-(fluoromethyl)benzene, 1-(bromomethyl)-3,5- bis(trifluoromethyl)benzene, 1 -(chloromethyl)-3,5-bis(trifluoro
  • the halohydrocarbon is selected from tert-butyl fluoride, tert-butyl chloride, tert-butyl bromide, ⁇ , ⁇ , ⁇ -trifluorotoluene, 4-methyl- 1-(trifluoromethyl)benzene, 3-methyl-1-(trifluoromethyl)benzene, triphenylfluoromethane, ⁇ , ⁇ , ⁇ -trichlorotoluene, 4-methyl-1-(trichloromethyl)benzene, 3-methyl-1- (trichloromethyl)benzene, triphenylchloromethane, ⁇ , ⁇ , ⁇ -tribromotoluene, 4-methyl-1- (tribromomethyl)benzene, 3-methyI-1-(tribromomethyl)benzene, triphenylbromomethane, or any combination thereof.
  • the halohydrocarbon is selected from a,a,a- trifluorotoluene, 4-methyl-1 -(trifluoromethyl)benzene, ⁇ , ⁇ , ⁇ -trichlorotoluene, triphenylchloromethane, ⁇ , ⁇ , ⁇ -tribromotoluene, triphenylbromomethane, or any combination thereof.
  • the halohydrocarbon is seleceted from ⁇ 7, ⁇ , ⁇ -trifluorotoluene, 4-methyl-1-(trifluoromethyl)benzene, triphenylchloromethane, ⁇ , ⁇ , ⁇ -tribromotoluene, or any combination thereof.
  • haloaluminoxanes of this invention is at least one siloxane having at least one labile halogen atom in the molecule, wherein each halogen atom is, independently, fluorine, chlorine, or bromine.
  • siloxanes have hydrocarbyl groups which typically contain from 1 to about 30 carbon atoms and can include linear and/or branched alkyl groups which contain from 1 to about 24 carbon atoms, cycloalkyl groups which contain from about 3 to about 24 carbon atoms, and alkylaryl or aryl groups which contain from about 6 to about 30 carbon atoms.
  • At least one hydrocarbyl group of the siloxane contains at least one labile halogen atom.
  • the siloxanes can be chosen from disiloxanes and linear or cyclic polysiloxanes. Siloxanes of the present invention can contain the Si-O-Si bond and are substantially free of Si-OH bonds. The siloxanes can contain mixed hydrocarbyl groups.
  • the polysiloxanes have a linear, branched, or cyclic backbone of alternating silicon and oxygen atoms.
  • the polysiloxane is acyclic, it can be represented by the empirical formula, Si n O n-I , wherein n is an integer of at least 3, and wherein the oxygen atoms are individually disposed between and connected to two silicon atoms as a -Si-O-Si- moiety.
  • n is 3, 4, 5, or 6, inclusive, or 3 or 4, inclusive.
  • Cyclic polysiloxanes can be represented by the empirical formula Si n O n , where n is an integer of at least 3, and wherein, as in the case of the acyclic polysiloxanes, the oxygen atoms are individually disposed between and connected to two silicon atoms as a -Si-O-Si- moiety.
  • the backbone of a polysiloxane containing 4 or more silicon atoms can be branched on one or more of the silicon atoms of the backbone. In such case, the silicon atom that carries the branch is bonded to three or four separate oxygen atoms, and each such oxygen atom is in turn bonded to an additional separate silicon atom.
  • siloxanes which can be employed in the present invention include, but are not limited to, (trifluoromethyl)pentamethyldisiloxane, tris(fluoromethyl)trimethyldisiloxane, (2,2-difluoroethyl)pentaethyldisiloxane, bis(1 ,2- difluoroethyl)triethyldisiloxane, bis(trifluoromethyl)tetramethyldisiloxane, (trifluoromethyl)trimethyldicyclohexyldisiloxane, tetramethylbis(2,2- difluorocyclohexyl)disiloxane, tetrarnethylbutyl(4,4,4-trifluorobutyl)disiloxane, bis(p- trifluoromethylphenyl)tetraphenyldisiloxane, diphenyltrimethyl(difluoromethyl)
  • Suitable siloxanes having two or more different elements of halogen include, but are not limited to, (fluoromethyl)(chloromethyl)(bromomethyl)trimethyldisiloxane, (2,2-dichloroethyl)(2,2-difluoroethyl)tetraethyldisiloxane, (1 ,2-dichloroethyl)(1 ,2- difluoroethyl)triethyldisiloxane, (trichloromethyl)(tribromomethyl)tetramethyldisiloxane, tetramethyl(2,2-dichlorocyclohexyl)(2,2-difluorocyclohexyl)disiloxane, (p- tribromomethylphenyl)(p-trifluoromethylphenyl)tetraphenyldisiloxane, tetraphenyl(chloromethyl)(fluoromethyl)(fluor
  • siloxanes are selected from trisiloxanes, tricyclosiloxanes, or siloxanes with at least one 3,3,3-trihalopropyl group.
  • siloxanes include, but are not limited to, 3,3,3-trifluoropropylheptamethyltrisiloxane, 3,3,3- trifluoropropylheptamethylcyclotrisiloxane, tri[rnethyl(3,3,3-trifluoropropyl)cyclopolysiloxane], tetra[methyl(3,3,3-trifluoropropyl)cyclopolysiloxane], poly[methyl(3,3,3- trifluoropropyl)siloxane], poly[dimethylsiloxane-co-methyl(3,3,3-trifluoropropyl)siloxane], 3,3,3- trichloropropylheptamethyltrisiloxane, S.S.
  • siloxanes are selected from 3,3,3-trifluoropropyIheptamethyltrisiloxane, 3,3,3-trifluoropropylheptamethylcyclotrisiloxane, poly[methyl(3,3,3-trifluoropropyl)siloxane], 3,3,3-trichloropropylheptamethyltrisiloxane, S ⁇ S-trichloropropylheptamethylcyclotrisiloxane, poly[methyl(3,3,3-trichloropropyl)siloxane], 3,3,3-tribromopropylheptamethyltrisiloxane, 3,3,3- tribromopropylheptamethylcyclotrisiloxane, poly[methyl(3,3,3-tribromopropyl)siloxane], or any combination thereof.
  • the siloxanes are poly[methyl(3,3,3- trifluoropropyl)siloxane], poly[methyl(3,3,3-trichloropropyl)siloxane], or poly[methyl(3,3,3- tribromopropyl)siloxane], or any combination thereof.
  • Still another type of halogenation agent that can be used in forming the haloaluminoxanes of the invention is at least one silane of the formula R ⁇ SiX 4-0 , where n is 1 , 2, or 3, inclusive, X is, independently, a fluorine, a chlorine, or a bromine atom, and R 1 is, independently, a hydrocarbyl group having from one to about twenty carbon atoms or a halohydrocarbyl group having from one to about twenty carbon atoms.
  • R' can be a straight chain, branched, cycloalkyl, aryl, or aralkyl group.
  • R 1 is an aryl group, for example, an aryl group having from about six to about twenty carbon atoms, such as a phenyl group.
  • R' is a straight chain or branched hydrocarbyl group, for example, a straight chain or branched hydrocarbyl group having from one to about twelve carbon atoms, or from one to about six carbon atoms, such as a methyl group.
  • Silanes that can be used as halogenation agents include, but are not limited to, trimethylfluorosilane, dimethyldifluorosilane, diethyldifluorosilane, diisopropyldifluorosilane, tert-butyltrifluorosilane, dicyclobutyldifluorosilane, tripentylfluorosilane, dicyclohexyldifluorosilane, triheptylfluorosilane, dicyclooctyldifluorosilane, triphenylfluorosilane, diphenyldifluorosilane, phenyltrifluorosilane, phenyldimethylfluorosilane, diphenylmethylfluorosilane, phenylmethyldifluorosilane, phenyldiisopropylfluorosilane, tritolylfluorosilane, ditolyldifluoros
  • the silanes are selected from triphenylfiuorosilane, triphenylchlorosilane, triphenylbromosilane, or any combination thereof.
  • the silanes have the general formula (CH 3 ) n SiX 4-n , where n is 1 , 2, or 3, inclusive, and X is, independently, a fluorine, a chlorine, or a bromine atom.
  • X is, independently, a fluorine, a chlorine, or a bromine atom.
  • a non- limiting example of such a silane is trimethylfluorosilane.
  • R' can be a straight chain, branched, cycloalkyl, aryl, or aralkyl group.
  • R' is an aryl group, for example, an aryl group having from about 6 to about 20 carbon atoms, such as a phenyl group.
  • R' can be a straight chain or branched hydrocarbyl group, for example, a straight chain or branched hydrocarbyl group having from one to about six carbon atoms, such as a methyl group.
  • Tin compounds that can be used as halogenation agents include, but are not limited to, trimethylfluorostannane, diethylfluorostannane, di-n-propyldifluorostannane, tri-n-butylfluorostannane, dipentyldifluorostannane, cyclohexyltrifluorostannane, diheptyldifluorostannane, trioctylfluorostannane, didodecyldifluorostannane, dichlorodimethylstannane, trichloromethylstannane, triethylchlorostannane, diisopropyldichlorostannane, dicyclobutyldichlorostannane, cyclopentyltrichlorostannane, trihexylchlorostannane, dicycloheptyldichlorostannane, octyltrichlor
  • the tin compound is selected from triphenylfluorostannane, triphenylchiorostannane, dichlorodimethylstannane, triphenylbromostannane, or any combination thereof.
  • the tin compound has the general formula (Chy n SnX t - n , where n is 1 , 2, or 3, inclusive, and X is, independently, a fluorine, a chlorine, or a bromine atom.
  • R' can be a straight chain, branched, cycloalkyl, aryl, or aralkyl group.
  • R' is a straight chain hydrocarbyl having from one to about ten carbon atoms.
  • Hydrocarbylaluminum halides that can be used as halogenation agents include, but are not limited to, methylaluminum difluoride, dimethylaluminum fluoride, ethylaluminum difluoride, diethylaluminum fluoride, isopropylaluminum difluoride, diisopropylaluminum fluoride, n-butylaluminum difluoride, isobutylaluminum difluoride, diisobutylaluminum fluoride, dipentylaluminum fluoride, cyclohexylaluminum difluoride, diheptylaluminum fluoride, dicyclooctylaluminum fluoride, nonylalumium difluoride, decylaluminum difluoride, diundecylaluminum fluoride,
  • hydrocarbylaluminum halides of the present invention are selected from methylaluminum difluoride, dimethylaluminum fluoride, methylaluminum dichloride, dimethylaluminum chloride, methylaluminum dibromide, dimethylaluminum bromide, or any combination thereof.
  • hydrocarbylaluminum halides are selected from methylaluminum difluoride or dimethylaluminum fluoride.
  • Mixtures can be used in which the halogen elements in the halogenation agents are the same or different. It can be advantageous to use a mixture of halogenation agents, depending on the desired product haloaluminoxane and the properties thereof (for example, degree of halogenation, solubility, or stability).
  • Alkylaluminum compounds employed in the present invention include trialkylaluminum compounds and substituted trialkylaluminum compounds having the following general formula, AIR" n Q3- n , wherein n is 1 , 2, or 3, inclusive;
  • Q is, independently, a halide, a pseudohalide, or hydride; and R" is an alkyl group having from two to about twenty carbon atoms.
  • Q can be any suitable anionic substituent, including halides, pseudohalides, and hydride.
  • halides include fluoride, chloride, bromide, and iodide.
  • Pseudohalides can include, for example, azides, cyanide, cyanate, thiocyanate, isocyanate, isothiocyanate, silicon groups, sulfur groups, nitrogen groups, oxygen groups, and phosphorous groups.
  • Silicon groups comprise silicon-containing groups, which include, but are not limited to, silyl groups such alkylsilyl groups, arylsilyl groups, arylalkylsilyl groups, siloxy groups, and the like.
  • silicon groups include trimethylsilyl and phenyloctylsilyl groups.
  • Sulfur groups comprise sulfur-containing groups, examples of which include, but are not limited to, -SR IV and the like, including substituted derivatives thereof.
  • Nitrogen groups are nitrogen- containing groups, which include, but are not limited to, -NR' V 2 and the like, including substituted derivatives thereof.
  • Oxygen groups are oxygen-containing groups, examples of which include, but are not limited to, alkoxy or aryloxy groups (-OR iv ), -OSiR lv 3 , -OPR iv 2 , - OAIR IV 2 , and the like, including substituted derivatives thereof.
  • alkoxy or aryloxy groups (-OR iv ) include, but are not limited to, methoxy, ethoxy, propoxy, butoxy, phenoxy, substituted phenoxy, and the like.
  • Phosphorus groups are phosphorus-containing groups, which include, but are not limited to, -PR' V 2 and the like, including substituted derivatives thereof.
  • R' v is selected from alkyl, cycloalkyl, aryl, aralkyl, substituted alky!, substituted aryl, or substituted aralkyl groups having from 1 to about 20 carbon atoms.
  • Suitable alkylaluminum compounds include, but are not limited to, tributylaluminum, triisobutylaluminum, tri-n-octylaluminum, or any combination thereof.
  • Substituted alkylaluminum compounds include, but are not limited to, dialkylaluminum halides and alkylaluminum dihalides.
  • the alkylaluminum compound is present in the stabilized haloaluminoxane composition in an amount sufficient to improve the stability to degradation at higher and lower temperatures.
  • the alkylaluminum compound can be employed in any amount, so long as it does not produce adverse effects on the stability or activation efficiency of the stabilized haloaluminoxane.
  • the alkylaluminum compound is present in the stabilized haloaluminoxane in a range of about 1 mole % to about 5 mole % relative to the total composition.
  • the amount of alkylaluminum compound present in the composition is at least about 1 mole % relative to the total stabilized haloaluminoxane composition.
  • Stabilized haloaluminoxane compositions of the present invention can optionally be supported on any suitable inorganic or organic carrier material.
  • Support materials used in accordance with this invention can be any finely divided inorganic solid support, such as talc; clay; inorganic oxides and mixed inorganic oxides including, but not limited to, silica, alumina, silica-alumina, or a mixture thereof; or any combination thereof.
  • Support materials can also be particulate, organic resinous support materials including, but not limited to, spheroidal, particulate, or finely-divided polyethylene, polyvinylchloride, polystyrene, or any combination thereof.
  • support materials are inorganic particulate supports or carrier materials such as magnesium halides, inorganic oxides, aluminum silicates, inorganic compositions containing inorganic oxides, or any combination thereof.
  • inorganic compositions containing inorganic oxides include, but are not limited to, kaolinite, attapulgtite, montmorillonite, illite, bentonite, halloysite, similar refractory clays, or any combination thereof.
  • examples of inorganic oxides, which include mixed inorganic oxides include, but are not limited to, silica, alumina, silica- alumina, magnesia, titania, zirconia, or any combination thereof.
  • the support is anhydrous or substantially anhydrous.
  • Inorganic oxides can be dehydrated to remove water.
  • the support can also be calcined or chemically treated with known conventional reagents to remove hydroxyl groups and/or water from the carrier.
  • Suitable conventional reagents include, but are not limited to aluminum alkyls, lithium alkyls, silylchloride, aluminoxanes, ionic aluminoxanates, or any combination thereof.
  • the specific particle size, surface area and pore volume of the support material determine the amount of support material that is desirable to employ in preparing the catalyst compositions, as well as affecting the properties of polymers formed with the aid of the catalyst compositions.
  • a suitable support such as silica typically will have a particle diameter in a range of about 0.1 micron to about 600 microns, or in a range of about 0.3 micron to about 100 microns; a surface area in a range of about 50 m 2 /g to about 1000 m 2 /g, or in a range of about 100 to about 500 m 2 /g; and a pore volume in a range of about 0.3 cc/g to about 5.0 cc/g, or in a range of about 0.5 cc/g to about 3.5 cc/g.
  • the support material can be heat treated at about 100 0 C to about 1000 0 C for a period of about 1 hour to about 100 hours, or, in another aspect of the present invention, from about 3 hours to about 24 hours.
  • the treatment can be carried out in a vacuum or while purging with a dry inert gas such as nitrogen.
  • the support material can be chemically dehydrated.
  • Chemical dehydration is accomplished by slurrying the support in an inert low-boiling solvent, such as, for example, heptane, in the presence of a dehydrating agent, such as, for example, triethylaluminum, in a moisture and oxygen-free environment.
  • an inert low-boiling solvent such as, for example, heptane
  • a dehydrating agent such as, for example, triethylaluminum
  • Stabilized haloaluminoxane compositions of the present invention are stable to degradation at temperatures ranging from about -30 0 C to about 60 0 C for at least about thirty days.
  • stabilized haloaluminoxane compositions in accordance with the present invention are stable to degradation at temperatures ranging from about - 3O 0 C to about 60°C for at least about ninety days.
  • stable to degradation it is meant that the stabilized haloaluminoxanes show minimal or no reversible or irreversible precipitation for extended periods of time.
  • stabilized haloaluminoxanes can remain substantially free of gel formation at temperatures ranging from about -30 0 C to about 60 0 C for at least about thirty days, or, in another aspect of the present invention, at least about ninety days. In another aspect of the present invention, stabilized haloaluminoxanes can remain substantially free of gel. formation at temperatures ranging from about -20°C to about 45 0 C for at least about thirty days, or, in yet another aspect of the present invention, at least about ninety days.
  • stabilized haloaluminoxanes can exhibit less than about two weight percent gel formation at temperatures ranging from about -30 0 C to about 60 0 C for at least about thirty days, or, in yet another aspect of the present invention, at least about ninety days. In yet another aspect, stabilized haloaluminoxanes can exhibit less than about two weight percent gel formation at temperatures ranging from about -20 0 C to about 45°C for at least about thirty days, or, in still another aspect of the present invention, at least about ninety days.
  • the stabilized haloaluminoxanes of the present invention can exhibit less than about five weight percent gel formation at temperatures ranging from about -30 0 C to about 60°C for at least about thirty days, or, in yet another aspect of the present invention, at least about ninety days. In another aspect, stabilized haloaluminoxanes of the present invention can exhibit less than about five weight percent gel formation at temperatures ranging from about -20 0 C to about 45°C for at least about thirty days, or, in yet another aspect of the present invention, at least about ninety days.
  • stabilized haloaluminoxanes can exhibit less than about 10 weight percent (wt.%) gel formation at temperatures ranging from about -30 0 C to about 60 0 C for at least about thirty days, or, in yet another aspect of the present invention, at least about ninety days.
  • the stabilized haloaluminoxanes can exhibit less than about 10 wt.% gel formation at temperatures ranging from about -20 0 C to about 45°C for at least about thirty days, or, in still another aspect of the present invention, at least about ninety days.
  • This invention encompasses methods for preparing stabilized haloaluminoxane compositions comprising contacting at least one aluminoxane, at least on halogenation agent, and at least one additional alkylaluminum compound, in any order.
  • the stabilized haloaluminoxane compositions of the present invention can be prepared by contacting at least one haloaluminoxane with at least one additional alkylaluminum compound.
  • the stabilized haloaluminoxane compositions of the present invention are obtained when these components are contacted in any sequence or order.
  • the aluminoxane can first be contacted with the halogenation agent to produce a haloaluminoxane.
  • the haloaluminoxane can then be contacted with the additional alkylaluminum compound to form a stabilized haloaluminoxane composition.
  • the present invention further encompasses methods to produce supported soluble stabilized haloaluminoxane compositions comprising contacting at least one aluminoxane, at least one halogenation agent, at least one additional alkylaluminum compound, and at least one organic or inorganic support material, in any order.
  • the stabilized haloaluminoxane composition can be prepared and subsequently contacted with a support material to form the supported composition.
  • the additional alkylaluminum compound is first contacted with a support material, and this mixture is subsequently contacted with a haloaluminoxane.
  • Preparation of the supported and unsupported stabilized haloaluminoxane composition is generally conducted under conventional inert atmospheres using substantially inert anhydrous materials. Typically, temperatures for preparation are in a range of about 20 0 C to about 80 0 C, although higher and lower temperatures are also suitable.
  • the alkylaluminum compound is present in the stabilized haloaluminoxane in a range of about 1 mole % to about 5 mole % relative to the total composition.
  • the amount of alkylaluminum compound present in the composition is at least about 1 mole % relative to the total stabilized haloaluminoxane composition.
  • This invention encompasses supported and unsupported catalyst compositions prepared using stabilized haloaluminoxane compositions.
  • Catalyst systems employed in the present invention can comprise the contact product of (a) at least one stabilized haloaluminoxane composition and (b) at least one complex of a transition metal of Group 3, 4, 5, 6, 7, 8, 9, 10 , or 11 of the Periodic Table of Elements, including the lanthanide series and the actinide series.
  • Stabilized haloaluminoxane compositions of the present invention can be used with any known transition metal catalyst compound in which the transition metal is a Group 3 to 11 transition metal of the Periodic Table of Elements, including compounds of a metal of the lanthanide or actinide series.
  • the Periodic Table of Elements referred to herein is that appearing on page 27 of the February 4, 1985 issue of Chemical & Engineering News.
  • Suitable catalyst compounds can also be described as d- and f- block metal compounds. See, for example, the Periodic Table of Elements appearing on page 225 of Moeller, et al., Chemistry, Second Edition, Academic Press, copyright 1984.
  • the metal constituent is a compound of Fe, Co, Ni, Pd, or V.
  • the metal constituent is a compound of the metals of Groups 4-6 (Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, and W).
  • the metal is a Group 4 metal, for example, titanium, zirconium, or hafnium.
  • the transition metal catalyst compounds used in this invention can be one or more of any Ziegler-Natta catalyst compound, any metallocene, any compound of constrained geometry, any late transition metal complex, or any other transition metal compound or complex reported in the literature or otherwise generally known in the art to be an effective catalyst compound when suitably activated, including mixtures of at least two different types of such transition metal compounds or complexes, such as for example a mixture of a metallocene and a Ziegler-Natta olefin polymerization catalyst compound.
  • transition metal compounds of the metals of Groups 3, 4, 5, and 6 which can be used as the transition metal component of the catalyst compositions of the present invention are compounds of such metals as scandium, titanium, zirconium, hafnium, cerium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, thorium and uranium, often referred to as Ziegler-Natta type olefin polymerization catalysts.
  • M represents the transition metal atom or a transition metal atom cation containing one or two oxygen atoms such as vanadyl, zirconyl, or uranyl
  • X represents a halogen atom
  • OR represents a hydrocarbyloxy group having up to about 18 carbon atoms, or up to about 8 carbon atoms, or an alkyl of up to about 4 carbon atoms, such as an alkyl, cycloalkyl, cycloalkylalkyl, aryl, or aralkyl group
  • n and m are positive integers except that either one of them (but not both) can be zero
  • n + m is the valence state of the transition metal.
  • hydrocarbyloxides and mixed halide/hydrocarbyloxides of the transition metals which can be employed in the present invention, include but are not limited to, Ti(OCHg) 4 , Ti(OCH 3 )CI 3 , Ti(OCH 3 )Br 3 , Ti(OCH 3 ) 2 l 2> Ti(OC 2 Hg) 4 , Ti(OC 2 Hs) 3 CI, Ti(OC 2 H 5 )Ci 3 , Ti(OC 2 H 5 )Br 3 , Ti(OC 4 H 9 )Br 3 , Ti(OC 2 H 5 )I 3 , Ti(OC 3 H 7 ) 2 CI 2 , Ti(O-iso-C 3 H 7 ) 3 CI, Ti(O-iso-C 3 H 7 ) 2 CI 2 , Ti(O-JSo-C 3 H 7 )CI 3 , Ti(OC 4 Hg) 3 CI, Ti(OC 4 Hg) 2 CI 2 , Ti(OC(OCHg) 2
  • Carboxylic acid salts and various chelates of the transition metal can also be used.
  • a few non-limiting examples of such salts and chelates include zirconyl acetate, uranyl butyrate, chromium acetate, chromium(lll) oxy-2-ethylhexanoate, chromium(lll) 2-ethylhexanoate, chromium(IU) dichloroethylhexanoate, chromium(ll) 2-ethylhexanoate, titanium(IV) 2-ethylhexanoate, bis(2,4-pentanedionate)titanium oxide, bis(2,4-pentanedionate)titanium dichloride, bis(2,4-pentanedionate)titanium dibutoxide, vanadyl acetylacetonate, chromium acetylacetonate, niobium acet
  • the transition metal compound is a well-known Ziegler-Natta catalyst compound, for example, those of the Group 4 metals, including the alkoxides, halides, and mixed halide/alkoxide compounds.
  • suitable transition metal compounds include TiCI 4 , ZrCI 4 , HfCI 4 , Or TiCI 3 . These compounds can also be used in chelated form in order to facilitate solubility. Suitable chelated catalysts of this type are known and reported in the literature.
  • Metallocenes are another broad class of olefin polymerization catalyst compounds with which the stabilized haloaluminoxane compositions of this invention can be used in forming the catalyst compositions of this invention.
  • the term "metallocene” includes metal derivatives which contain at least one cyclopentadienyl (Cp) moiety.
  • Suitable metallocenes are well known in the art and include the metallocenes of Groups 3, 4, 5, 6, lanthanide and actinide metals, for example, the metallocenes which are described in U.S. Patent Nos.
  • Metallocene structures in this specification are to be interpreted broadly, and include structures containing 1 , 2, 3, or 4 Cp or substituted Cp rings.
  • metallocenes suitable for use in this invention can be represented by Formula (I): B a Cp b MXcY d (I) where Cp, independently in each occurrence, is a cyclopentadienyl-moiety-containing group which typically has in a range of 5 to about 24 carbon atoms; B is a bridging group or ansa group that links two Cp groups together or alternatively carries an alternate coordinating group such as alkylaminosilylalkyl, silylamido, alkoxy, siloxy, aminosilylalkyl, or analogous monodentate hetero atom electron donating groups; M is a d- or f-block metal atom; each X and each Y is, independently, a group that is bonded to the d- or f-block metal atom; a is 0
  • Cp is, independently, a cyclopentadienyl, indenyl, fluorenyl or related group that can 77-bond to the metal, or a hydrocarbyl-, halo-, halohydrocarbyl-, hydrocarbylmetalloid-, and/or halohydrocarbylmetalloid-substituted derivative thereof.
  • Cp typically contains up to 75 non-hydrogen atoms.
  • B if present, is typically a silylene (-SiR 2 -), benzo (C 6 H 4 ⁇ ), substituted benzo, methylene (-CH 2 -), substituted methylene, ethylene (- CH 2 CH 2 -), or substituted ethylene bridge.
  • M is a metal atom of Groups 4, 5, or 6 of the Periodic Table of Elements.
  • M is a Group 4 metal atom, such as hafnium, zirconium, or titanium.
  • X can be a divalent substituent such as an alkylidene group, a cyclometallated hydrocarbyl group, or any other divalent chelating ligand, two loci of which are singly bonded to M to form a cyclic moiety which includes M as a member.
  • Each X, and each Y, if present, can be, independently in each occurrence, a halogen atom, a hydrocarbyl group (alkyl, cycloalkyl, alkenyl, cycloalkenyl, aryl, aralkyl, etc.), hydrocarbyloxy, (alkoxy, aryloxy, efc.) siloxy, amino or substituted amino, hydride, acyloxy, triflate, and similar univalent groups that form stable metallocenes.
  • the sum of b, c, and d is a whole number, and is often from 3-5.
  • Cp such as borabenzene or substituted borabenzene, azaborole or substituted azaborole, and various other isoelectronic Cp analogs.
  • metallocenes In one group of metallocenes, b is 2, i.e., there are two cyclopentadienyl- moiety containing groups in the molecule, and these two groups can be the same or they can be different from each other. [00081] Another sub-group of useful metallocenes which can be used in the practice of this invention are metallocenes of the type described in WO 98/32776, published
  • metallocenes are characterized in that one or more cyclopentadienyl groups in the metallocene are substituted by one or more polyatomic groups attached via a
  • C 1 -C 8 hydrocarbyloxysilyl group a W-C 1 -C 8 hydrocarbylgermyl group, a W-C 1 -C 8 hydrocarbyloxygermyl group, or a mixed C 1 -C 8 hydrocarbyl and C 1 -C 8 hydrocarbyloxygermyl group.
  • metallocenes to which this invention is applicable include such compounds as: bis(cyclopentadienyl)zirconium dimethyl; bis(cyclopentadienyl)zirconium dichloride; bis(cyclopentadienyl)zirconium monomethylmonochloride; bis(cyclopentadienyl)titanium dichloride; bis(cyclopentadienyl)titanium difluoride; cyclopentadienylzirconium tri-(2-ethylhexanoate); bis(cyclopentadienyl)zirconium hydrogen chloride; bis(cyclopentadienyl)hafnium dichloride; racemic and meso dimethylsilanylene-bisCmethylcyclopentadienyOhafnium dichloride; racemic dimethylsilanylene-bis(indenyl)hafnium dichloride; racemic ethylene-bis(indenyl)zir
  • organometallic catalytic compounds with which the stabilized haloaluminoxanes of this invention can be used in forming the catalyst compositions of this invention are the late transition metal catalyst described, for example, in U.S. Patent Nos. 5,516,739 to Barborak, et al.; 5,561 ,216 to Barborak, et al.; 5,866,663 to Brookhart, et al; 5,880,241 to Brookhart, et al; and 6,114,483 to Coughlin, et al. Such catalysts are sometimes referred to herein collectively as "a Brookhart-type late transition metal catalyst compound or complex".
  • transition metal catalyst compounds and catalyst complexes that can be used in the practice of this invention include catfluoro nickel, palladium, iron, and cobalt complexes containing diimine and bisoxazoline ligands such as described in Johnson et al. WO 96/23010; palladium and nickel catalysts containing selected bidentate phosphorus-containing ligands such as described in EP 381 ,495; catfluoro ⁇ -diimine-based nickel and palladium complexes such as described by Johnson et al. in J. Am. Chem. Soc, 1995, 117, 6414, see also Brown et al. WO 97/17380; nickel complexes such as described by Johnson et al.
  • transition metal compounds include the following:
  • nickel compounds of the type described in U. S. Patent 5,880,323 nickel(ll) acetylacetonate; bis(acetonitrile)dichloro palladium(ll); bis(acetonitrile)bis(tetrafluoroborate)palladium(ll); (2,2'-bipyridine)dichloro palladium(ll); bis(cyclooctadienyl) nickel(O); palladium(ll) acetylacetonate; bis(salicylaldiminato) complexes of the type described by Matsui et. al. in Chemistry Letters 2000, pp. 554-555; cobalt dioctoate; cobaltocene;
  • transition metal compounds which can be used in forming the catalysts of this invention are transition metal compounds which can be represented by the formula:
  • M is a transition metal of Group 4 to 8 of the Periodic Table of Elements, including the lanthanide series and actinide series, and Y is, independently, a halide or pseudohalide, n is the valence of M, and m is an integer of from 0 to n-1.
  • pseudohalides are selected from alkoxide or oxyhalide groups.
  • M is a Group 4 metal.
  • Non-limiting examples of suitable transition metal compounds include, but are not limited to, transition metal halides and oxyhalides such as titanium dibromide, titanium tribromide, titanium tetrabromide, titanium dichloride, titanium trichloride, titanium tetrachloride, titanium trifluoride, titanium tetrafluoride, titanium diiodide, titanium tetraiodide, zirconium dibromide, zirconium tribromide, zirconium tetrabromide, zirconium dichloride, zirconium trichloride, zirconium tetrachloride, zirconium tetrafluoride, zirconium tetraiodide, hafnium tetrafluoride, hafnium tetrachloride, hafnium tetrabromide, hafnium tetraiodide, hafnium tetrafluoride, hafnium
  • suitable alkoxides and mixed halide/alkoxides of the transition metals are Ti(OCHs) 4 , Ti(OC 2 H 5 ) 4> Ti(OC 2 H 5 ) 3 CI, Ti(OC 2 H 5 )CI 3 , Ti(O-iso-C 3 H 7 )CI 3 , Ti(OC 4 Hg) 3 CI, Ti(OC 3 Hy) 2 Cl 2 , Ti(O-iso-C 3 H 7 ) 2 CI 2 , Ti(OC 17 H 18 ) 2 Br 2 , Zr(OC 2 H 5 ) 4 , Zr(OC 4 Hg) 4 , Zr(OC 5 Hn) 4 , ZrCI 3 (OC 2 H 5 ), ZrCI(OC 4 Hg) 3 , Hf(OC 4 Hg) 4 , Hf(OC 4 Hg) 3 CI, VO(OC 2 H 5 ) 3 , Cr(O-iso- C 4 Hg) 3 , Mp(OC 2 H 5 ) 3
  • the transition metal compounds are halides, oxyhalides, alkoxides, and mixed halide-alkoxides of the Group 4 to 6 metals.
  • the transition metal compound is a trivalent or tetravalent Group 4 metal halide, or a vanadium oxyhalide.
  • the Periodic Table of Elements referred to is that appearing on page 27 of the February 4, 1985 issue of Chemical & Engineering News.
  • the catalyst composition can optionally be supported on any suitable organic or inorganic carrier.
  • Support materials used in accordance with this invention can be any finely divided inorganic solid support, such as talc, clay, silica, alumina, silica-alumina, or any combination thereof.
  • Support materials can also be particulate, organic resinous support materials including, but not limited to, spheroidal, particulate, or finely-divided polyethylene, polyvinylchloride, polystyrene, or any combination thereof.
  • the specific particle size, surface area and pore volume of the support material determine the amount of support material that is desirable to employ in preparing the catalyst compositions, as well as affecting the properties of polymers formed with the aid of the catalyst compositions. These properties are frequently taken into consideration in choosing a support material for use in a particular aspect of the invention.
  • This invention encompasses methods for preparing supported and unsupported catalyst compositions comprising contacting at least one stabilized haloaluminoxane composition and at least one complex of a transition metal of Groups 3 to 11 of the Periodic Table of Elements.
  • the catalyst composition can be produced by contacting at least one aluminoxane compound, at least one halogenation agent, at least one additional alkylaluminum compound, and at least one complex of a transition metal of Groups 3 to 11 of the Periodic Table of Elements.
  • the catalyst composition can be produced by contacting at least one haloaluminoxane compound, at least one additional alkylaluminum compound, and at least one complex of a transition metal of Groups 3 to 11 of the Periodic Table of Elements.
  • a supported catalyst composition can be produced by contacting at least one aluminoxane compound, at least one halogenation agent, at least one additional alkylaluminum compound, at least one complex of a transition metal of Groups 3 to 11 of the Periodic Table of Elements, and at least one organic or inorganic support material.
  • a supported catalyst composition can be produced by contacting at least one haloaluminoxane compound, at least one additional alkylaluminum compound, at least one complex of a transition metal of Groups 3 to 11 of the Periodic Table of Elements, and at least one organic or inorganic support material.
  • the supported or unsupported catalyst composition is obtained when the components are contacted in any sequence or order.
  • the components can be fed to a reactor or separate vessel separately, in any order, or any two or more can be premixed and fed as a mixture, with the remaining components being fed before, during, or after the mixture is fed to the reactor.
  • Unsupported catalyst compositions in accordance with the present invention can be produced by contacting the transition metal complex with the stabilized haloaluminoxane composition before, during, or after its formation.
  • the transition metal complex before the stabilized haloaluminoxane composition is formed, the transition metal complex can be contacted with any one or any combination of (a) the at least one aluminoxane; (b) the at least one halogenation agent; or (c) the at least one additional alkylaluminum compound.
  • the transition metal complex can be added at any time during the formation of the stabilized haloaluminoxane composition.
  • the transition metal complex can be contacted with the stabilized haloaluminoxane composition after it is formed.
  • Temperatures for the preparation of unsupported catalyst compositions " of the present invention are in a range of about -100 0 C to about 300 0 C. In another aspect, preparation temperatures are in a range of about 0 0 C to about 80 0 C. Typically, the preparation is carried out at temperatures in a range of about 20 0 C to about 50 0 C, or at ambient room temperature. Holding times to allow for the completion of catalyst formation are in a range of about 10 seconds to about 60 minutes, depending on the reaction variables. [00093] Supported catalyst compositions are similarly formed by contacting the support material with the catalyst composition before, during, or after its formation.
  • Preparation can include contacting, in any order, the transition metal compound, a stabilized haloaluminoxane composition, and a support material in one or more suitable solvents or diluents.
  • suitable solvents and/or diluents include, but are not limited to, straight and branched-chain hydrocarbons such as isobutene, butane, pentane, .
  • cyclic and acyclic hydrocarbons such as cyclohexane, cycloheptane, methylcyclohexane, or methylcyclopentane; or aromatic and alkyl-substituted aromatic compounds such as benzene, toluene, or xylene.
  • Mixtures of different types of solvents and/or diluents can also be used, such as a mixture of one or more acyclic aliphatic hydrocarbons and one or more cycloaliphatic hydrocarbons; a mixture of one or more acyclic aliphatic hydrocarbons and one or more aromatic hydrocarbons; a mixture of one or more cycloaliphatic hydrocarbons and one or more aromatic hydrocarbons; or a mixture of one or more acyclic aliphatic hydrocarbons, one or more cycloaliphatic hydrocarbons, and one or more aromatic hydrocarbons.
  • the support material can first be contacted with the stabilized haloaluminoxane composition to form a supported stabilized haloaluminoxane composition which is subsequently contacted with the transition metal complex.
  • the support material can first be contacted with the transition metal complex to form a supported complex which is subsequently contacted with a stabilized haloaluminoxane composition.
  • the stabilized haloaluminoxane composition and the transition metal complex can be contacted together, and the resulting composition can be subsequently contacted with a support material.
  • the support material can be contacted with either the stabilized haloaluminoxane composition or the transition metal complex during its formation.
  • the support material can be contacted with one or more of the components used to form the stabilized haloaluminoxane composition or with one or more of the components used to form the transition metal complex.
  • catalyst components and catalyst compositions are generally handled under conventional inert atmospheres using substantially inert anhydrous materials, for example, in an environment that is substantially moisture-free and oxygen-free, such as, an argon, a nitrogen, or a helium environment.
  • Temperatures for each stage of the preparation of supported catalyst compositions of this invention are in a range of about - 100 0 C to about 300 0 C.
  • preparation temperatures are in a range of about 0 0 C to about 80°C.
  • the preparation is carried out temperatures in a range of about 20 0 C to about 50 0 C, or at ambient room temperature. Holding times to allow for the completion of catalyst formation can range from about 10 seconds to about 60 minutes, depending on the reaction variables.
  • Modified supported catalysts can be prepared in accordance with this invention by combining, in any order, at least one transition metal compound, at least one stabilized haloaluminoxane composition, at least one modifier, and a support material, in a suitable solvent and/or diluent.
  • a modifier can be defined as any compound containing a Lewis acidic or basic functionality, for example, tetraethoxysilane, phenyltri(ethoxy)silane, bis- tert-butylhydroxytoluene (BHT), or N,N-dimethylaniline.
  • the modified supported catalyst is formed by contacting a stabilized haloaluminoxane composition and the modifier in a suitable solvent to produce a slurry.
  • a transition metal compound is subsequently added to the slurry.
  • Suitable temperatures for these contacting steps are in a range of about -100°C to about 300 0 C, or, in another aspect of the present invention, a range of about 0 0 C to about 100°C. Holding times to allow for the completion of the reaction can range from about 10 seconds to about 60 minutes, depending on the reaction variables.
  • the mixture comprising the transition metal, modifier, and stabilized haloaluminoxane composition can then be contacted with the support material.
  • the molar ratio of stabilized haloaluminoxane composition to transition metal compound is generally from about 1 :1 to about 20000:1 , or, in another aspect of the present invention, from about 10:1 to about 1000:1.
  • the molar ratio of stabilized haloaluminoxane composition to modifier ranges from about 1 :1 to about 20000:1 , or, in another aspect of the present invention, from about 10:1 to about 1000:1.
  • the concentration of transition metal compound on the support is typically between about 0.01 wt% to about 100 wt%, or, in another aspect of the present invention, from about 0.1 wt% to about 20 wt%, based upon the weight of the support.
  • the amount of stabilized haloaluminoxane composition used varies depending upon the application and reaction conditions.
  • the stabilized haloaluminoxane is typically used in an amount sufficient to produce molar ratio of aluminum atoms derived from the stabilized haloaluminoxane composition to transition metal is in the range of about 20:1 to about 2000:1. In another aspect, the molar ratio is from about 20:1 to about 500:1.
  • the concentration of transition metal compound on the support is typically between about 0.01 wt% to about 100 wt%, or, in another aspect of the present invention, from about 0.1 wt% to about 20 wt%, based upon the weight of the support.
  • This invention encompasses a method for polymerizing olefin monomers comprising contacting under polymerization conditions at least one olefin monomer and a catalyst system comprising a stabilized haloaluminoxane composition of the present invention and at least one transition metal complex.
  • Catalyst compositions in accordance with the present invention are useful for the homopolymerization or copolymerization of olefinic monomers, for example, ⁇ -olefin monomers, cyclic olefin monomers, or vinylaromatic monomers.
  • Polymerizations using the catalysts of this invention can be carried out in any suitable manner known in the art.
  • Such polymerization processes include, but are not limited to, slurry polymerizations, gas phase polymerizations, solution polymerizations, and the like, including multi-reactor combinations thereof.
  • any polymerization zone known in the art to produce ethylene-containing polymers can be utilized.
  • a stirred reactor can be utilized for a batch process, or the reaction can be carried out continuously in a loop reactor or in a continuous stirred reactor.
  • the polymerization reactor can be any suitable type of reactor, for example, a gas phase reactor, tubular reactor, solution phase reactor, or a combination of two or more reactors.
  • the polymerization reaction typically occurs in a substantially inert atmosphere, that is, in an atmosphere substantially free of oxygen and under substantially anhydrous conditions as the reaction begins. Therefore a dry, inert atmosphere, for example, dry nitrogen or dry argon, is typically employed in the polymerization reactor.
  • a dry, inert atmosphere for example, dry nitrogen or dry argon
  • Conventional temperatures for polymerization range from about 0 0 C to about 16O 0 C and conventional pressures for polymerization range from about 1 kg/cm 2 to about 50 kg/cm 2 .
  • the polymerization can be carried out at both ambient temperature and pressure.
  • a particulate catalyst is typically dispersed in a suitable liquid reaction medium which can be comprised of one or more ancillary solvents or an excess amount of liquid monomer.
  • suitable ancillary solvents include, but are not limited to, aliphatic and aromatic liquid hydrocarbons such as heptane, isooctane, decane, toluene, xylene, ethylbenzene, mesitylene, or any combination thereof.
  • Slurry polymerization temperatures for this invention typically range from about 0 0 C to about 160 0 C, with a polymerization reaction temperature more typically operating between about 40 0 C to about 110 0 C.
  • the polymerization can take place under atmospheric, subatmospheric, or superatmospheric conditions, or any other polymerization reaction condition that does not adversely affect the polymerization reaction.
  • Typical diluents include, but are not limited to, isobutene, pentane, isopentane, hexane, heptane, toluene, or any combination thereof.
  • Gas phase polymerizations are typically conducted at temperatures in the range of about 50 0 C to 160 0 C, under superatmospheric pressures. However, the polymerization can take place at any temperature or pressure that does not adversely affect the polymerization reaction.
  • gas phase polymerizations can be performed in a stirred or fluidized bed of catalyst in a pressure vessel adapted to permit the separation of product particles from unreacted gases.
  • Thermostated ethylene, comonomer, hydrogen, and an inert diluent gas such as nitrogen can be introduced or reciruclated to maintain the particles at the desired polymerization reaction temperature.
  • An alkylaluminum, such as triethylaluminum, can be added as a scavenger of water, oxygen, and other impurities. In such cases, the alkylaluminum is typically employed as a solution in a suitable dry liquid hydrocarbon solvent such as toluene or xylene.
  • Concentrations of such solutions are typically in the range of about 5 x 10 "5 molar (M), but solutions of greater or lesser concentrations can be used.
  • Polymer product can be withdrawn continuously or semi-continuously at a rate that maintains a constant product inventory in the reactor.
  • Polymerization reactions in accordance with the present invention are carried out using a catalytically effective amount of a catalyst composition of this invention.
  • the amount of catalyst used depends on several factors, such as the type of polymerization being conducted, the polymerization conditions being used, and the type of reaction equipment in which the polymerization is being conducted.
  • the catalyst composition is used in a range of about 0.000001 to about 0.01 percent by weight of transition, lanthanide, or actinide metal based on the weight of the monomer(s) being polymerized.
  • conditions can be used for preparing unimodal or multimodal polymers.
  • multimodal polymers can be produced by using a mixture of different catalysts having different propagation and termination rate constants.
  • the product polymer can be recovered from the polymerization reactor by any suitable means.
  • the product is typically recovered by a physical separation technique, for example, decantation.
  • the recovered polymer is generally washed with one or more suitable volatile solvents to remove residual polymerization solvent or other impurities, and then dried, typically under reduced pressure, with or without the addition of heat.
  • the product after removal from the gas phase reactor is typically freed of residual monomer by means of a nitrogen purge, and can possibly be used without further catalyst deactivation or catalyst removal.
  • Polymers produced in accordance with this invention can be homopolymors, typically of ⁇ -olefins such as ethylene, propylene, 1-butene, styrene, or any combination thereof. Polymers can also be copolymers of two or more monomers, one of which is typically an ⁇ -olefin. Monomers useful in forming copolymers include one or mor& different a-o
  • Typical diolefin monomers which can be used to form terpolymers with ethylene and propylene include, but are not limited to, butadiene, hexadiene, norbornadiene, or any combination thereof.
  • Suitable acetylenic monomers include 1-heptyne or 1-octyne.
  • ethylene can be copolymerized with at least one ⁇ -olsfin having 3 to ⁇ carbon atoms, for example, propylene. [00011 Q] As used herein, the phrase "any combination thereof includes any mixture of the components listed therein.
  • a solution of fluorinat ⁇ d methylaluminoxane (FMAO) was prepared by treating a solution of about 30 wt% methylaluminoxane (MAO) in toluene with a s ⁇ lution of about 14.7 wt% dimethylaluminum fluoride (DMAF) in toluene.
  • the ratio of fluorine (F) atoms to aluminum (Al) atoms in the resulting FMAO [DMAF] solution was about 4:100 and the overall aluminum content was about 12.9 wt%.
  • a solution of FMAO was prepared by treating a solution of about 30 wt% MAO in toluene with a solution of trifluorotoluene (TFT) in toluene in an amount sufficient to produce a resulting FMAO [TFT] solution with a ratio of fluorine (F) atoms to aluminum (Al) atoms of about 4:100 and an overall aluminum content of about 10.5 wt%.
  • TFT trifluorotoluene
  • the ratio of fluorine atoms to aluminum atoms in the resulting FMAO [DMAF] solution was about 4:100 and the overall aluminum content was about 13.5 wt%.
  • About 9.79 g (0.027 mol) of TNOA was added to the FMAO [DMAF] solution with stirring to provide approximately 2.5 m ⁇ l% of the Al content from TNOA.
  • the solution was allowed to warm to ambient temperature (about 20 ⁇ C to about 30 0 C) over a period of about 30 minutes.
  • the mixture was placed in the freezer at about -20 0 C. No precipitation was observed upon prolonged chilling for a period of greater than about 3 months,
  • Each sample had a ratio of fluorine atoms to aluminum atoms of about 4:100. Sealed tubes of these samples were placed in an oil bath at a temperature of about 45 fl C for up to 3 months. Irreversible gel formation was evaluated for each sample.
  • Figure 1 shows the gel formation in each sample at 45 D C as a function of time.
  • Samples 4 and 6 stabilized haloalumi ⁇ oxanes show reduced irreversible gel formation as compared to corresponding conventional haloaluminoxanes at elevated temperatures. The precipitates observed in each sample did not redissolva.
  • Sample 4 and Sample 6 were used as co-catalysts in the polymerization o1 ethylene and compared to a MAO standard (13,6 wt% Ai).
  • Ethylene-bis(indenyl)zirconium dimethyl was employed as the polymerization catalyst and added in an amount to provide about 2.15 micromoles of zirconium in the reactor.
  • co-catalyst was added in an amount sufficient to produce a ratio of aluminum (Al) atoms to zirconium (Zr) atoms of about 400:1.
  • the reactor was maintained at a temperature of about 135°C and an ethylene pressure of about 140 pounds/square inch (psi), with about 1 mL of approximately 10 wt% triisobutylaluminum in isohexane used as a scavenger.
  • psi pounds/square inch
  • the stabilized haloaluminoxanes have comparable, if not better, activator efficiencies than standard aluminoxanes.

Abstract

The present invention provides stabilized haloaluminoxane compositions, methods for preparing stabilized haloaluminoxane compositions, catalyst compositions comprising stabilized haloaluminoxane compositions, and methods for polymerizing olefins employing catalyst compositions comprising stabilized haloaluminoxane compositions. Stabilized haloaluminoxane compositions of the present invention are less susceptible to degradation at higher and lower temperatures as compared to conventional aluminoxanes and haloaluminoxanes. The stabilized haloaluminoxane compositions are formed from at least one aluminoxane, at least one halogenation agent, and at least one additional alkylaluminum compound. The amount of additional alkylaluminum compound present in the composition is at least about 1 mole % relative to the total composition.

Description

HALOALUMINOXANE COMPOSITIONS
TECHNICAL FIELD OF THE INVENTION
[0001] This invention relates to stabilized haloaluminoxane compositions that are of particular utility in the formation of new catalyst systems, to methods for the preparation of these stabilized haloaluminoxane compositions and catalyst systems, and to the use of such catalyst systems in the polymerization of olefin monomers, dienes, or the like.
BACKGROUND OF THE INVENTION
[0002] Aluminoxane compositions are widely used in combination with various types of metallocenes and transition metal compounds to prepare catalyst systems for polymerizing olefin monomers. However, certain limitations are associated with standard aluminoxane solutions, such as poor solubility, instability, and gel formation. For example, solutions of conventional aluminoxanes, such as methylaluminoxane (MAO), must be kept at lower temperatures to inhibit degradation via irreversible gel formation.
[0003] Addition of small amounts of halogen to conventional aluminoxanes has been shown to impart a higher stability to decomposition at ambient and elevated temperatures. See, for example, U.S. Patent Application Serial No. 10/751 ,144, filed December 31 , 2003. However, such haloaluminoxane compositions generally freeze at higher temperatures than the corresponding non-halogenated aluminoxane solutions, resulting in a reversible "precipitation" upon cooling. Consequently, storage of haloaluminoxane compositions in colder climates may be problematic due to the precipitation of these haloaluminoxanes at lower temperatures. For example, a fluorinated methylaluminoxane formulation may begin to show solid precipitation at a temperature of about -6°C, while a conventional methylaluminoxane formulation has a freezing temperature of less than about -35°C. Furthermore, while haloaluminoxanes are generally more stable to degradation than standard aluminoxanes, they are susceptible to slow irreversible degradation at higher temperatures, for example, at temperatures above about 45°C.
[0004] It is therefore desirable to provide an aluminoxane formulation which is both stable to reversible precipitation at lower temperatures and irreversible precipitation at higher temperatures.
SUMMARY OF THE INVENTION
[0005] This invention encompasses stabilized haloaluminoxane compositions, methods for preparing stabilized haloaluminoxane compositions, supported and unsupported catalyst compositions comprising stabilized haloaluminoxane compositions, methods for preparing these catalyst compositions, and methods for polymerizing olefin monomers using these catalyst compositions. In the course of examining haioaluminoxane compositions, it was discovered that haioaluminoxane compositions can be modified such that they have improved stability at lower and higher temperatures under inert, anhydrous conditions, while maintaining their solubility in hydrocarbon solvents, especially aromatic hydrocarbon solvents. In addition to these desirable features, stabilized haioaluminoxane compositions of the invention also perform as well as, if not better than, standard haloaluminoxanes and conventional aluminoxanes when used as cocatalysts in the polymerization of olefins. [0006] In one aspect, the present invention encompasses a stabilized haioaluminoxane composition comprising a contact product of:
(a) at least one aluminoxane;
(b) at least one halogenation agent which is:
(i) at least one halohydrocarbon having the general formula RnCX4-P, (ii) at least one siloxane having at least one labile halogen atom in the molecule, wherein each halogen atom is, independently, fluorine, chlorine, or bromine,
(iii) at least one silane having the general formula RVSiX4-D,
(iv) at least one tin compound having the general formula RnSnX4-0,
(v) at least one hydrocarbylaluminum halide having the general formula
R^AIXs-m, or
(vi) any combination thereof; and
(c) at least one additional alkylaluminum compound having the general formula AIR"nQ3-n; wherein: m is 1 or 2, inclusive, n is 1 , 2, or 3, inclusive,
X is, independently, a fluorine, a chlorine, or a bromine atom,
R is, independently, a hydrogen atom, a hydrocarbyl group having from one to about twenty carbon atoms, or a halohydrocarbyl group having from one to about twenty carbon atoms,
R' is, independently, a hydrocarbyl group having from one to about twenty carbon atoms or a halohydrocarbyl group having from one to about twenty carbon atoms,
R" is an alkyl group having from two to about twenty carbon atoms, and
Q is, independently, a halide, a pseudohalide, or hydride. [0007] Another aspect of the present invention encompasses a stabilized halomethylaluminoxane composition comprising the contact product of:
(a) methylaluminoxane;
(b) at least one fluorination agent which is:
(i) at least one fluorohydrocarbon having the general formula RnCF4-1,, (ii) at least one siloxane having at least one labile fluorine atom in the molecule,
(iii) at least one silane having the general formula R nSiF4-D,
(iv) at least one tin compound having the general formula R^SnF4-P,
(v) at least one hydrocarbylaluminum fluoride having the general formula
R"mAIF3-m, or
(vi) any combination thereof; and
(c) at least one additional alkylaluminum compound having the general formula
AIR"nQ3-n; wherein: m is 1 or 2, inclusive, n is 1 , 2, or 3, inclusive,
R is, independently, a hydrogen atom, a hydrocarbyl group having from one to about twenty carbon atoms, or a fluorohydrocarbyl group having from one to about twenty carbon atoms,
R' is, independently, a hydrocarbyl group having from one to about twenty carbon atoms or a fluorohydrocarbyl group having from one to about twenty carbon atoms,
R" is an alkyl group having from two to about twenty carbon atoms, and
Q is, independently, a halide, a pseudohalide, or hydride. [0008] Yet another aspect of the present invention encompasses a stabilized haloaluminoxane composition comprising at least one aluminoxane, halogen atoms derived from a halogenation agent, and at least one additional alkylaluminum compound, wherein the amount of additional alkylaluminum compound present in the composition is in the range of about 1 mole % to about 5 mole % relative to the total composition.
[0009] A further aspect of the present invention encompasses a stabilized haloaluminoxane composition comprising at least one haloaluminoxane and at least one additional alkylaluminum compound, wherein the amount of additional alkylaluminum compound present in the composition is in the range of about 1 mole % to about 5 mole % relative to the total composition.
[00010] A still further aspect of the present invention encompasses a stabilized haloaluminoxane composition comprising at least one aluminoxane, halogen atoms derived from a halogenation agent, and at least one additional alkylaluminum compound, wherein the amount of additional alkylaluminum compound present in the composition is at least about 1 mole % relative to the total composition.
[00011] Another aspect of the present invention encompasses a stabilized haloaluminoxane composition comprising at least one haloaluminoxane and at least one additional alkylaluminum compound, wherein the amount of additional alkylaluminum compound present in the composition is at least about 1 mole % relative to the total composition.
[00012] The present invention also encompasses a stabilized haloaluminoxane composition which is stable to degradation at temperatures ranging from about -300C to about 600C for at least about thirty days.
[00013] Yet another aspect of the present invention encompasses a process to produce a stabilized haloaluminoxane composition comprising contacting, in an environment which is substantially inert and anhydrous:
(a) at least one aluminoxane;
(b) at least one halogenation agent which is:
(i) at least one halohydrocarbon having the general formula RnCX4-0, (ii) at least one siloxane having at least one labile halogen atom in the molecule, wherein each halogen atom is, independently, fluorine, chlorine, or bromine,
(Hi) at least one silane having the general formula RV1SiX4-,,,
(iv) at least one tin compound having the general formula RV1SnX4-11,
(v) at least one hydrocarbylaluminum halide having the general formula
R'mAIXs-m, or
(vi) any combination thereof; and
(c) at least one additional alkylaluminum compound having the general formula AIR"nQ3-n; wherein: m is 1 or 2, inclusive, n is 1, 2, or 3, inclusive,
X is, independently, a fluorine, chlorine, or bromine atom,
R is, independently, a hydrogen atom, a hydrocarbyl group having from one to about twenty carbon atoms, or a halohydrocarbyl group having from one to about twenty carbon atoms,
R' is, independently, a hydrocarbyl group having from one to about twenty carbon atoms or a halohydrocarbyl group having from one to about twenty carbon atoms,
R" is an alkyl group having from two to about twenty carbon atoms, and
Q is, independently, a halide, a pseudohalide, or hydride. [00014] The present invention further encompasses a catalyst composition comprising a stabilized haloaluminoxane composition and at least one complex of a transition metal of Group 3, 4, 5, 6, 7, 8, 9, 10, or 11 of the Periodic Table of Elements, including the lanthanide and actinide series. The catalyst composition can be unsupported or supported on an organic or inorganic carrier material.
[00015] This invention also encompasses a method for polymerizing olefin monomers comprising contacting at least one olefin monomer and a catalyst system comprising a stabilized haloaluminoxane composition in accordance with the present invention and at least one transition metal complex.
BRIEF DESCRIPTION OF THE DRAWINGS
[00016] Figure 1 is a graph illustrating the accelerated aging over time for stabilized haloaluminoxanes as compared to conventional haloaluminoxanes.
DETAILED DESCRIPTION OF THE INVENTION
[00017] The present invention provides stabilized haloaluminoxane compositions, methods for preparing stabilized haloaluminoxane compositions, supported and unsupported catalyst compositions comprising stabilized haloaluminoxane compositions of the present invention, and methods for polymerizing olefins using catalyst compositions comprising stabilized haloaluminoxane compositions of the present invention.
Stabilized Haloaluminoxane Compositions and Components
[00018] Stabilized haloaluminoxane compositions in accordance with the present invention comprise the contact product of:
(a) at least one aluminoxane;
(b) at least one halogenation agent which is:
(i) at least one halohydrocarbon having the general formula RnCX4-^ (ii) at least one siloxane having at least one labile halogen atom in the molecule, wherein each halogen atom is, independently, fluorine, chlorine, or bromine,
(iii) at least one silane having the general formula RV1SiX4-P,
(iv) at least one tiη compound having the general formula RVSnX4-0,
(v) at least one hydrocarbylaluminum halide having the general formula
R'πAIXs-m, or
(vi) any combination thereof; and
(c) at least one additional alkylaluminum compound having the general formula AIR"nQ3-n; wherein: m is 1 or 2, inclusive, n is 1 , 2 or 3, inclusive,
X is, independently, a fluorine, chlorine, or bromine atom,
R is, independently, a hydrogen atom, a hydrocarbyl group having from one to about twenty carbon atoms, or a halohydrocarbyl group having from one to about twenty carbon atoms,
R' is, independently, a hydrocarbyl group having from one to about twenty carbon atoms or a halohydrocarbyl group having from one to about twenty carbon atoms,
R" is an alkyl group having from two to about twenty carbon atoms, and
Q is, independently, a halide, a pseudohalide, or hydride.
[00019] Stabilized halomethylaluminoxane compositions in accordance with another aspect of the present invention comprise the contact product of:
(a) methylaluminoxane;
(b) at least one fluorination agent which is:
(i) at least one fluorohydrocarbon having the general formula RnCF4-0, (ii) at least one siloxane having at least one labile fluorine atom in the molecule,
(iii) at least one silane having the general formula R1 PSiF4-H,
(iv) at least one tin compound having the general formula R'nSnF4-n,
(v) at least one hydrocarbylaluminum fluoride having the general formula
R"mAIF3-m, or
(vi) any combination thereof; and
(c) at least one additional alkylaluminum compound having the general formula
AIR"nQ3-n; wherein: m is 1 or 2, inclusive, n is 1 , 2, or 3, inclusive,
R is, independently, a hydrogen atom, a hydrocarbyl group having from one to about twenty carbon atoms, or a fluorohydrocarbyl group having from one to about twenty carbon atoms,
R' is, independently, a hydrocarbyl group having from one to about twenty carbon atoms or a fluorohydrocarbyl group having from one to about twenty carbon atoms,
R" is an alkyl group having from two to about twenty carbon atoms, and
Q is, independently, a halide, a pseudohalide, or hydride. [00020] Yet another aspect of the present invention encompasses a stabilized haloaluminoxane composition comprising at least one aluminoxane, halogen atoms derived from a halogenation agent, and at least one additional alkylaluminum compound, wherein the amount of additional alkylaluminum compound present in the composition is in a range of about 1 mole % to about 5 mole % relative to the total composition.
[00021] A further aspect of the present invention encompasses a stabilized haloaluminoxane composition comprising at least one haloaluminoxane and at least one additional alkylaluminum compound, wherein the amount of additional alkylaluminum compound present in the composition is in a range of about 1 mole % to about 5 mole % relative to the total composition.
[00022] A still further aspect of the present invention encompasses a stabilized haloaluminoxane composition comprising at least one aluminoxane, halogen atoms derived from a halogenation agent, and at least one additional alkylaluminum compound, wherein the amount of additional alkylaluminum compound present in the composition is at least about 1 mole % relative to the total composition.
[00023] Still yet another aspect of the present invention encompasses a stabilized haloaluminoxane composition comprising at least one haloaluminoxane and at least one additional alkylaluminum compound, wherein the amount of additional alkylaluminum compound present in the composition is at least about 1 mole % relative to the total composition.
[00024] The present invention also encompasses a stabilized haloaluminoxane composition which is stable to degradation at temperatures in a range from about -300C to about 600C for at least about 30 days.
Aluminoxanes
[00025] Aluminoxanes can include any suitable hydrocarbylaluminoxanes having at least one hydrocarbyl moiety having from one to about twenty carbon atoms. Such aluminoxanes include, but are not limited to, alkylaluminoxanes, cycloalkylaluminoxanes, arylaluminoxanes, aralkylaluminoxanes, or any combination thereof. Hydrocarbylaluminoxanes can exist in the form of linear or cyclic polymers with the simplest monomeric compound being a tetraalkylaluminoxane, such as, tetramethylaluminoxane, (CHa)2AI-O-AI(CHs)2, or tetraethylaluminoxane, (C2H5^ Al- O— AI(C2H5)2. In one aspect of the invention, the aluminoxanes can be oligomeric materials, sometimes referred to as polyalkylaluminoxanes, containing the repeating unit
Figure imgf000010_0001
wherein R is a C1-Ci0 alkyl group and n is an integer from about 4 to about 20. The exact structure of aluminoxanes has not been defined and they can contain linear, cyclic, cross- linked species, or any combination thereof. Non-limiting examples of hydrocarbylaluminoxanes for use in the invention include methylaluminoxanes (MAO), modified MAOs, ethylaluminoxanes (EAO), isobutylaluminoxanes (IBAO), n- propylaluminoxanes, n-octylaluminoxanes, phenylaluminoxanes, or any combination thereof. The hydrocarbylaluminoxanes can also contain up to about 20 mole percent (based on aluminum atoms) of moieties derived from amines, alcohols, ethers, esters, phosphoric and carboxylic acids, thiols, aryl disiloxanes, alkyl disiloxanes, and the like to further improve activity, solubility and/or stability.
[00026] Aluminoxanes can be prepared as known in the art by the partial hydrolysis of hydrocarbylaluminum compounds. Hydrocarbylaluminum compounds or mixtures of compounds capable of reacting with water to form an aluminoxane can be employed in the present invention. This includes, for example, trialkylaluminum, triarylaluminum, mixed alkyl-aryl aluminum, or any combination thereof. The hydrocarbylaluminum compounds can be hydrolyzed by adding either free water or water- containing solids, which can be either hydrates or porous materials which have absorbed water. Because it is difficult to control the reaction by adding water, even with vigorous agitation of the mixture, the free water can be added in the form of a solution or a dispersion in an organic solvent. Suitable hydrates include salt hydrates such as, but not limited to, CuSO4 «5H2O, AI2(SO4)3*18H2O, FeSO4 «7H2O, AICI3 «6H2O, AI(NOs)3^H2O, MgSO4 «7H2O, MgCI2 «6H2O, ZnSO4 «7H2O, Na2SO4HOH2O, Na3PO4H 2H2O, LiBr»2H2O, LiCI-H2O, Lil-2H2O, Lil*3H2O, KF'2H2O, NaBr«2H2O, or any combination thereof. Alkali or alkaline earth metal hydroxide hydrates can also be employed with the present invention. Such alkali or alkaline earth metal hydroxide hydrates include, but are not limited to, NaOH»H2O, NaOH«2H2O, Ba(OH)2*8H2O, KOH»2H2O, CsOH«H2O, LiOH«H2O, or any combination thereof. Mixtures of salt hydrates and alkali or alkaline earth metal hydroxide hydrates can also be used. The molar ratios of free water or water in the hydrate or in porous materials, which include inorganic oxides such as alumina or silica, to total alkylaluminum compounds in the mixture can vary widely. In one aspect of the present invention such molar ratios are in a range from about 2:1 to about 1:4. In another aspect of the present invention, such molar ratios are in a range from about 4:3 to about 2:7. [00027] Suitable hydrocarbylaluminoxanes and processes for preparing hydrocarbylaluminoxanes which can be employed with the present invention, to name only a few, are described in U.S. Patent Nos. 4,908,463; 4,924,018; 5,003,095; 5,041 ,583; 5,066,631; 5,099,050; 5,157,008; 5,157,137; 5,235,081 ; 5,248,801, and 5,371,260. The methyialuminoxanes can contain varying amounts of the aluminum value as unreacted trimethylaluminum (TMA), for example, from about 5 to about 35 mole percent. [00028] In one aspect of the present invention, the aluminoxanes have saturated hydrocarbyl groups having from one to about twenty carbon atoms. In another aspect of the present invention, the hydrocarbyl groups of the aluminoxanes have from one to about six carbon atoms.
[00029] Aluminoxanes which can be employed in the present invention include, but are not limited to, methylaluminoxane, ethylaluminoxane, n-propylaluminoxane, n-butylaluminoxane, isobutylaluminoxane, n-hexylaluminoxane, n-octylaluminoxane, decylaluminoxane, dodecylaluminoxane, tetradecylaluminoxane, hexadecylaluminoxane, octadecylaluminoxane, phenylaluminoxane, tolylaluminoxane, or any combination thereof. [00030] The aluminoxane can contain up to about 15 mole percent (based on aluminum) of moieties formed from amines, alcohols, ethers, esters, phosphoric and carboxylic acids, thiols, alkyl disiloxanes, and the like to improve their activity, solubility, and/or stability. In another aspect of the present invention, the moiety is a bulky phenol. Suitable bulky phenols include, but are not limited to, 2,6-dimethyl-4-(1 ,1- dimethylpropyl)phenol, 2,6-diisobutyl-4-methylphenol, 2,6-diisopropylphenol, 2,4,6- triisopropylphenol, 2,6-diisobutylphenol, 2,4,6-triisobutylphenol, 2,6-di-ferf-butylphenol, 2,4,6- tri-te/ϊ-butylphenol, or any combination thereof.
Haloaluminoxanes
[00031] While not wishing to be bound by theory, it is believed that haloaluminoxanes can be described as two types of species. One of these species is an ionic haloaluminoxane complex, which in theory is believed to be comprised of an organic cation and an aluminum anion site of the aluminoxane, where one of the species coordinated to the aluminum anion site is a halogen atom. It is to be understood that the ionic complexes are thought to exist only at the small number of aluminum anion sites of the aluminoxane, in particular those aluminum sites to which a halogen atom is coordinated. For simplicity, the entire species containing these ionic complexes is referred to as an ionic haloaluminoxane complex. The other species is a partially halogenated aluminoxane, which in theory is believed to be comprised of a neutral aluminoxane where halogen atoms are coordinated to some of the aluminum atoms of the aluminoxane. The term "haloaluminoxane" is used herein to refer to both ionic haloaluminoxane complexes and to partially halogenated aluminoxanes. Stabilized haloaluminoxane compositions can comprise ionic haloaluminoxane complexes, partially halogenated aluminoxanes, or any combination thereof.
[00032] The amount of halogen atoms present in the haloaluminoxane composition is in a range from about 0.5 mole % to about 15 mole % halogen atoms relative to aluminum atoms. These haloaluminoxane compositions can be formed from components comprising (a) at least one aluminoxane and (b) at least one halogenation agent. Suitable halogenation agents include:
(i) at least one halohydrocarbon having the general formula RnCX4-0,
(ii) at least one siloxane having at least one labile halogen atom in the molecule, wherein each halogen atom is, independently, fluorine, chlorine, or bromine,
(iii) at least one silane having the general formula RVSiX4-11,
(iv) at least one tin compound having the general formula RVSnX4-0,
(v) at least one hydrocarbylaluminum halide having the general formula RV1AIX3-171, or
(vi) any combination thereof, wherein: m is 1 or 2, inclusive, n is 1 , 2, or 3, inclusive,
X is, independently, a fluorine, a chlorine, or a bromine atom,
R is, independently, a hydrogen atom, a hydrocarbyl group having from one to about twenty carbon atoms, or a halohydrocarbyl group having from one to about twenty carbon atoms, and
R1 is, independently, a hydrocarbyl group having from one to about twenty carbon atoms or a halohydrocarbyl group having from one to about twenty carbon atoms. [00033] Haloaluminoxanes can be prepared by a process comprising mixing, in an environment which is substantially inert and anhydrous, (a) at least one aluminoxane and (b) at least one halogenation agent, wherein the amount of halogen atoms is in the range of about 0.5 mole % to about 15 mole % halogen atoms relative to aluminum atoms, such that a haloaluminoxane composition is formed. In another aspect of the present invention, the ratio of halogen atoms to aluminum atoms are in a range from about 2 mole % to about 10 mole % halogen relative to aluminum. In yet another aspect of the present invention, the ratio of halogen atoms to aluminum atoms are in a range from about 2 mole % to about 6 mole % halogen atoms to aluminum atoms, although the optimum molar ratio will vary with each particular haloaluminoxane.
[00034] The process can be conducted in an environment which is substantially inert and anhydrous, such as, for example, in a substantially anhydrous liquid aromatic hydrocarbon solvent. Examples of suitable anhydrous liquids include, but are not limited to, benzene, toluene, xylene, mesitylene, ethylbenzene, diethylbenzene, 1 ,2,4-triethylbenzene, 1,3,5-triethylbenzene, amylbenzene, tetrahydronaphthalene, or any combination thereof. [00035] An alternative method for forming haloaluminoxanes is to have the halogenation agent present during the formation of the aluminoxane, for example, during the hydrolysis of the aluminum hydrocarbyl(s) used to form the aluminoxane. Again, in one aspect of the present invention, the amount of halogen atoms can range from about 0.5 mole % to about 15 mole % relative to aluminum atoms.
[00036] The haloaluminoxane components, as well as the resultant haloaluminoxane compositions, should be handled in an environment which is substantially inert, substantially moisture-free, and substantially oxygen-free. For example, such environments include, but are not limited to, argon, nitrogen, or helium environments because of the sensitivity of such components and compositions to moisture and oxygen. [00037] Haloaluminoxanes can include, but are not limited to, partially fluorinated methylaluminoxane, partially fluorinated ethylaluminoxane, partially fluorinated n- propylaluminoxane, partially fluorinated n-butylaluminoxane, partially fluorinated isobutylaluminoxane, partially fluorinated n-hexylaluminoxane, partially fluorinated n- octylaluminoxane, partially fluorinated phenylaluminoxane, partially chlorinated methylaluminoxane, partially chlorinated ethylaluminoxane, partially chlorinated n- propylaluminoxane, partially chlorinated n-butylaluminoxane, partially chlorinated isobutylaluminoxane, partially chlorinated n-hexylaluminoxane, partially chlorinated n- octylaluminoxane, partially chlorinated phenylaluminoxane, partially brominated methylaluminoxane, partially brominated ethylaluminoxane, partially brominated n- propylaluminoxane, partially brominated n-butylaluminoxane, partially brominated isobutylaluminoxane, partially brominated n-hexylaluminoxane, partially brominated n- octylaluminoxane, partially brominated phenylaluminoxane, fluoromethylaluminoxane, fluoroethylaluminoxane, fluoro-n-propylaluminoxane, fluoro-n-butylaluminoxane, fluoroisobutylaluminoxane, fluoro-n-hexylaluminoxane, fluoro-n-octylaluminoxane, fluorophenylaluminoxane, chloromethylaluminoxane, chloroethylaluminoxane, chloro-n- propylaluminoxane, chloro-n-butylaluminoxane, chloroisobutylaluminoxane, chloro-n- hexylaluminoxane, chloro-n-octylaluminoxane, chlorophenylaluminoxane, bromomethylaluminoxane, bromoethylaluminoxane, bromo-n-propylaluminoxane, bromo-n- butylaluminoxane, bromoisobutylaluminoxane, bromo-n-hexylaluminoxane, bromo-n- octylaluminoxane, and bromophenylaluminoxane. Also included as partially halogenated aluminoxanes and ionic haloaluminoxane complexes are those that have two or more different elements of halogen (for example, fluorine and chlorine; fluorine and bromine; chlorine and bromine; fluorine, chlorine, and bromine). Halogenation Agents
[00038] The halogenation agents of the present invention contain labile halogen atoms, i.e., halogen atoms that can react with aluminum sites in the aluminoxane. Non-labile halogen atoms can also be present in the halogenation agent. For example, halogen atoms directly bound to aromatic rings have been observed to be non-labile. Such halogen atoms remain bound to the aromatic ring when a halogenation agent containing such a moiety is brought into contact with an aluminoxane.
[00039] In one aspect of the present invention, the halogenation agent is:
(i) at least one halohydrocarbon having the general formula RnCX4-0, (ii) at least one siloxane having at least one labile halogen atom in the molecule, wherein each halogen atom is, independently, fluorine, chlorine, or bromine,
(Hi) at least one silane having the general formula R1 HSiX4-P,
(iv) at least one tin compound having the general formula R^SnX4-P,
(v) at least one hydrocarbylaluminum halide having the general formula
R'mAIXa-m, or
(vi) any combination thereof; wherein: m is 1 or 2, inclusive, n is 1 , 2, or 3, inclusive;
X is, independently, a fluorine, a chlorine, or a bromine atom. R is, independently, a hydrogen atom, a hydrocarbyl group having from one to about twenty carbon atoms, or a halohydrocarbyl group having from one to about twenty carbon atoms; and
R' is, independently, a hydrocarbyl group having from one to about twenty carbon atoms or a halohydrocarbyl group having from one to about twenty carbon atoms.
[00040] One type of halogenation agent that can be used to form the haloaluminoxanes of this invention is a halohydrocarbon of the formula RnCX4-0; wherein n is 1, 2, or 3, inclusive; X is, independently, a fluorine, a chlorine, or a bromine atom; and R is, independently, a hydrogen atom, a hydrocarbyl group having from one to about twenty carbon atoms, or a halohydrocarbyl group having from one to about twenty carbon atoms. R can be a straight chain, branched, cycloalkyl, aryl, or aralkyl group. In one aspect, when only one R is a hydrocarbyl group, the hydrocarbyl group is an aryl group. [00041] The halohydrocarbon can also be a tertiary halohydrocarbon. In one aspect, the halohydrocarbon has at least one R group which is an aryl group, for example, a phenyl group. In another aspect of the present invention, the halohydrocarbyl is a primary halohydfocarbon in which one R is an aryl group and the other R(s) are hydrogen atoms, or all of the other substituents are halogen atoms. This group of halohydrocarbons can be represented by the general formula:
ArGn, where Ar is an aromatic hydrocarbon ring system, which typically contains up to about 25 carbon atoms; G is -CX3, -CX2R, or -CXR2, in which X is, independently, a fluorine, a chlorine, or a bromine atom, and in which R is, independently, a hydrogen atom or Ci-4 alkyl group; and n is an integer from 1 to 5, inclusive. In one aspect of the present invention, Ar can contain up to about 12 carbon atoms or up to about 6 carbon atoms in the ring system. In another aspect of the present invention, n is 1 , 2, or 3, inclusive, or 1 or 2 inclusive, or 1. In yet another aspect, G is a trihalomethyl group.
[00042] In a further aspect, when there are substituents on the aromatic ring(s) other than hydrogen and the group(s) containing labile halogen atom(s), these other such substituents can be electron-donating substituents. Halogenation agents containing aromatic groups having electron-donating substituents were observed to have faster reaction rates than halogenation agents in which there were only hydrogen atoms on the aromatic ring. Typical electron-donating substituents include, but are not limited to, hydrocarbyloxy groups and hydrocarbyl groups.
[00043] Suitable halohydrocarbons having an aryl group include, but are not limited to, σ,σ,σ-trifluorotoluene, σ,σ-difluorotoluene, σ-fluorotoluene, octafluorotoluene, 1 ,2- di(fluoromethyl)benzene, 1 ,3-di(fluoromethyl)benzene, 1 ,4-di(fluoromethyl)benzene, 1 ,2- bis(difluoromethyl)benzene, 1 ,3-bis(difluoromethyl)benzene, 1 ,4-bis(difluoromethyl)benzene, 1 ,3-bis(trifluoromethyl)benzene, 1 ,3,5-tris(trifluoromethyl)benzene, 4-methyl-1 - (trifluoromethyl)benzene, 3-methyl-1-(trifluoromethyl)benzene, 1 ,3-bis(trifluoromethyl)-4- methylbenzene, 1 ,4-bis(trifluoromethyl)-2-methylbenzene, 1-ethyI-3,5- bis(trifluoromethyl)benzene, 1-isopropyl-4-(trifluoromethyl)benzene, 1-(fluoromethyl)-4-fluoro- 2-(trifluoromethyl)benzene, 1-(fluoromethyl)-2,4-bis(trifluoromethyl)benzene, 1-(1- fluoroethyl)benzene, 1 ,2-difluoroethylbenzene, 3,3'-bis(trifluoromethyl)biphenyl, 4,4'- bis(trifluoromethyl)biphenyl, 2,2'-bis(fluoromethyl)biphenyl, 3-(difluoromethyl)biphenyl, 1- (trifluoromethyl)naphthalene, 2-(trifluoromethyl)naphthalene, 1 -(difluoromethyl)naphthalene, 2~(difluorqmethyl)naphthalene, 1-(fluoromethyl)naphthalene, 1 ,8- bis(fluoromethyl)naphthalene, 1 -(fluoromethyl)-2-(methyl)naphthalene, 1 -isobutyl-2- trifluoromethyl-naphthalene, 1 -methyl-4-trifluorornethyl-naphthalene, 1 -n-butyl-5- trifluoromethyl-naphthalene, 1-(trifluoromethyl)anthracene, 2-(difluoromethyl)anthracene, 9- (fluoromethyl)anthracene, 9,10-bis(trifluoromethyl)anthracene, 9- (trifluoromethyl)phenanthrene, triphenylfluoromethane, difluorodiphenylmethane, a,a,a- trichlorotoluene, α,σ-dichlorotoluene, α-chlorotoluene, 1 ,3-bis(trichloromethyl)-4- methylbenzene, 1 ,4-bis(trichloromethyl)-2-methylbenzene, 4-methyl-1- (trichloromethyl)benzene, 3-methyl-1-(trichloromethyl)benzene, octachlorotoluene, 1,2- di(chloromethyl)benzene, 1 ,3-di(chloromethyl)benzene, 1 ,4-di(chloromethyl)benzene, 1 ,3,5- tris(trichloromethyl)benzene, 1 -ethyl-S.δ-bisCtrichloromethyObenzene, 1 -isopropyl-4- (trichloromethyl)benzene, 1 -(chloromethyl)-4-chloro-2-(trichloromethyl)benzene, 1 - (chloromethyl)-2,4-bis(trichloromethyl)benzene, 1-(1-chloroethyl)benzene, 1 ,2- dichloroethylbenzene, 3,3'-bis(trichloromethyl)biphenyl, 4,4'-bis(trichloromethyl)biphenyl, 2,2'- bis(chloromethyl)biphenyl, 3-(dichloromethyl)biphenyl, 1-(trichloromethyl)naphthalene, 2- (trichloromethyl)naphthalene, 1-(dichloromethyl)naphthalene, 2-(dichloromethyl)naphthaIene, 1-(chloromethyl)naphthalene, 1 ,8-bis(chloromethyl)naphthalene, 1-(chloromethyl)-2- (methyl)naphthalene, 1 -isobutyl^-trichloromethyl-naphthalene, 1 -methyl-4-trichloromethyl- naphthalene, i-n-butyl-5-trichloromethyI-naphthalene, 1-(trichloromethyl)anthracene, 2- (dichloromethyl)anthracene, 9-(chloromethyl)anthracene, 9,10- bis(trichloromethyl)anthracene, 9-(trichloromethyl)phenanthrene, triphenylchloromethane, dichlorodiphenylmethane, σ,σ,σ-tribromotoluene, σ,σ-dibromotoluene, σ-bromotoluene, 1 ,2- di(bromomethyl)benzene, 1 ,3-di(bromomethyl)benzene, 1 ,4-di(bromomethyl)benzene, 1 ,3- bis(tribromomethyl)benzene, 1 ,3,5-tris(tribromomethyl)benzene, 4-methyl-1- (tribromomethyl)benzene, 3-methyl-1-(tribromomethyI)benzene, 1 ,3-bis(tribromomethyl)-4- methylbenzene, 1,4-bis(tribromomethyl)-2-methylbenzene,1-ethyl-3,5- bis(tribromomethyl)benzene, 1 -isopropyl-4-(tribromomethyl)benzene, 1 -(bromomethyl)-2- (tribromomethyl)benzene, 1 -(bromomethyl)-2,4-bis(tribromomethyl)benzene, 1 -(1 - bromoethyl)benzene, 1 ,2-dibromoethylbenzene, 3,3'-bis(tribromomethyl)biphenyl, 4,4'- bis(tribromomethyl)biphenyl, 2,2'-bis(bromomethyl)biphenyl, 3-(dibromomethyl)biphenyl, 1- (tribromomethyl)naphthalene, 2-(tribromomethyl)naphthalene, 1-
(dibromomethyl)naphthalene, 2-(dibromomethyl)naphthalene, 1 -(bromomethyl)naphthalene, 1 ,8-bis(bromomethyl)naphthalene, 1-(bromomethyl)-2-(methyl)naphthalene, 1 -isobutyl-2- tribromomethyl-naphthalene, 1 -methyl-4-tribromomethyI-naphthalene, 1 -n-butyl-5- tribromomethyl-naphthalene, 1-(tribromomethyl)anthracene, 2-(dibromomethyl)anthracene, 9- (bromomethyl)anthracene, 9,10-bis(tribromonnethyl)anthracene, 9- (tribromomethyl)phenanthrene, triphenylbromomethane, dibromodiphenylmethane, or any combination thereof.
[00044] Suitable halohydrocarbons which do not have an aryl group include, but are not limited to, tert-butyl fluoride (2-methyl-2-fluoropropane), 3-methyl-3-fluoropentane, 3- methyl-3-fluorohexane, 1-methyl-i-fluorocyclohexane, 1 ,3-difluoro-1 ,3,5-methylcyclooctane, 2-methyl-2-fluoroheptane, 1 ,2-difluoro-i-methylcyclooctane, 2-methyl-2-chloropropane, tert- butyl chloride, 3-methyl-3-chloropentane, 3-chlorohexane, 3-methyl-3-chlorohexane, 1- methyl-1-chlorocyclohexane, 1 ,3-dichloro-1 ,3,5-methylcyclooctane, 2-methyl-2- chloroheptane, 1,2-dichloro-1-methylcyclooctane, 2-methyl-2-bromopropane, tert-butyl bromide, 3-methyl-3-bromopentane, 2-bromohexane, 3-bromohexane, 3-methyl-3- bromohexane, 1-methyl-i-bromocyclohexane, 1 ,3-dibromo-1 ,3,5-methylcyclooctane, 2- methyI-2-bromoheptane, 1 ,2-dibromo-1 -methylcyclooctane, or any combination thereof. [00045] Suitable halohydrocarbons which have at least two different elements of halogen that can be used include, but are not limited to, 1-chloro-3-fluoro-1 ,3,5- methylcyclooctane, 2-bromo-1 -fluoro-1 -methylcyclooctane, 2-chloro-1 -fluoro-1 - methylcyclooctane, 1 -(trichloromethyl)-4-(trifluoromethyl)benzene, 1 -(dichloromethyl)-3- (dibromomethyl)benzene, 1 -(bromomethyl)-2-(fluoromethyl)benzene, 1 -(chloromethyl)-4- (trifluoromethyl)benzene, 1-(dichloromethyl)-3-(fluoromethyl)benzene, 1-(bromomethyl)-3,5- bis(trifluoromethyl)benzene, 1 -(chloromethyl)-3,5-bis(trifluoromethyl)benzene, 1 - (tribromomethyl)-3-(trichloromethyl)-5-(trifluoromethyl)benzene, 1-ethyI-3-(trichloromethyl)-5- (trifluoromethyl)benzene, 1 -(chloromethyl)-4-chloro-2-(tribromomethyl)benzene, 1 - (fluoromethyl)-2,4-bis(trichloromethyl)benzene, 1 -(1 -bromoethyl)-3-(1 -fluoroethyl)benzene, 1 - (1 ,2-dichloroethyl)-4-(1-fluoroethyl)benzene, 1-trichloromethyl-4-trifluoromethyl-2, 3,5,6- tetrachlorobenzene, 3-(trichloromethyl)-3'-(trifluoromethyl)biphenyl, 4-(dichloromethyl)- 4'(difluoromethyl)-biphenyl, 2-(ch!oromethyl)-2'-(fluoromethyl)biphenyl, 1-(trichloromethyI)-2- (trifluoromethyl)naphthalene, 1-(difluoromethyl)-2-(dichloromethyl)naphthalene, 1- (bromomethyl)-8-(fluoromethyl)naphthalene, 9-(trifluoromethyl)-10- (trichloromethyl)anthracene, or any combination thereof.
[00046] In one aspect of the present invention, the halohydrocarbon is selected from tert-butyl fluoride, tert-butyl chloride, tert-butyl bromide, σ,σ,σ-trifluorotoluene, 4-methyl- 1-(trifluoromethyl)benzene, 3-methyl-1-(trifluoromethyl)benzene, triphenylfluoromethane, σ,α,σ-trichlorotoluene, 4-methyl-1-(trichloromethyl)benzene, 3-methyl-1- (trichloromethyl)benzene, triphenylchloromethane, σ,α,σ-tribromotoluene, 4-methyl-1- (tribromomethyl)benzene, 3-methyI-1-(tribromomethyl)benzene, triphenylbromomethane, or any combination thereof. In another aspect, the halohydrocarbon is selected from a,a,a- trifluorotoluene, 4-methyl-1 -(trifluoromethyl)benzene, σ,σ,α-trichlorotoluene, triphenylchloromethane, α,α,σ-tribromotoluene, triphenylbromomethane, or any combination thereof. In yet another aspect of the present invention, the halohydrocarbon is seleceted from <7,σ,σ-trifluorotoluene, 4-methyl-1-(trifluoromethyl)benzene, triphenylchloromethane, α,σ,α-tribromotoluene, or any combination thereof.
[00047] Another type of halogenation agent that can be used to form haloaluminoxanes of this invention is at least one siloxane having at least one labile halogen atom in the molecule, wherein each halogen atom is, independently, fluorine, chlorine, or bromine. These siloxanes have hydrocarbyl groups which typically contain from 1 to about 30 carbon atoms and can include linear and/or branched alkyl groups which contain from 1 to about 24 carbon atoms, cycloalkyl groups which contain from about 3 to about 24 carbon atoms, and alkylaryl or aryl groups which contain from about 6 to about 30 carbon atoms. At least one hydrocarbyl group of the siloxane contains at least one labile halogen atom. The siloxanes can be chosen from disiloxanes and linear or cyclic polysiloxanes. Siloxanes of the present invention can contain the Si-O-Si bond and are substantially free of Si-OH bonds. The siloxanes can contain mixed hydrocarbyl groups. The polysiloxanes have a linear, branched, or cyclic backbone of alternating silicon and oxygen atoms. If the polysiloxane is acyclic, it can be represented by the empirical formula, SinOn-I, wherein n is an integer of at least 3, and wherein the oxygen atoms are individually disposed between and connected to two silicon atoms as a -Si-O-Si- moiety. In one aspect of the present invention, n is 3, 4, 5, or 6, inclusive, or 3 or 4, inclusive. Cyclic polysiloxanes can be represented by the empirical formula SinOn, where n is an integer of at least 3, and wherein, as in the case of the acyclic polysiloxanes, the oxygen atoms are individually disposed between and connected to two silicon atoms as a -Si-O-Si- moiety. Whether cyclic or acyclic, the backbone of a polysiloxane containing 4 or more silicon atoms can be branched on one or more of the silicon atoms of the backbone. In such case, the silicon atom that carries the branch is bonded to three or four separate oxygen atoms, and each such oxygen atom is in turn bonded to an additional separate silicon atom.
[00048] Examples of siloxanes which can be employed in the present invention include, but are not limited to, (trifluoromethyl)pentamethyldisiloxane, tris(fluoromethyl)trimethyldisiloxane, (2,2-difluoroethyl)pentaethyldisiloxane, bis(1 ,2- difluoroethyl)triethyldisiloxane, bis(trifluoromethyl)tetramethyldisiloxane, (trifluoromethyl)trimethyldicyclohexyldisiloxane, tetramethylbis(2,2- difluorocyclohexyl)disiloxane, tetrarnethylbutyl(4,4,4-trifluorobutyl)disiloxane, bis(p- trifluoromethylphenyl)tetraphenyldisiloxane, diphenyltrimethyl(difluoromethyl)disiloxane, tetraphenylbis(fluoromethyl)disiloxane, bis(difluoromethyl)tetramethylcyclotrisiloxane, tetra(fluoromethyl)tetramethyltrisiloxane, 3,3,3-trifluoropropylheptamethyltrisiloxane, bis(3,3,3-trifluoropropyl)hexamethyltrisiloxane, 3,3,3- trifluoropropylheptamethylcyclotrisiloxane, (trifluoromethyl)heptamethylcyclotetrasiloxane, bis(/77-trifluoromethylphenyl)hexaphenylcyclotetrasiloxane, tri[methyl(3,3,3- trifluoropropyl)cyclopolysiloxane], tetra[methyl(3,3,3-trifluoropropyl)cyclopolysiloxane], poly[methyl(3,3,3-trifluoropropyl)siloxane], poly[dimethylsiloxane-co-methyl(3,3,3- trifluoropropyl)siloxane], (trichloromethyl)pentamethyldisiloxane, tris(chloromethyl)trimethyldisiloxane, 2,2-(dichloroethyl)pentaethyldisiloxane, bis(1 ,2- dichloroethyl)triethyldisiloxane, bis(trichloromethyl)tetramethyldisiloxane, (trichloromethyl)trimethyldicyclohexyldisiloxane, tetramethylbis(2,2- dichlorocyclohexy|)disiloxane, tetramethylbutyl(4,4,4-trichlorobutyl)disiloxane, bis(p- trichloromethylphenyl)tetraphenyldisiloxane, diphenyltrimethyKdichloromethyOdisiloxane, tetraphenylbis(chloromethyl)disiloxane, bis(dichloromethyl)tetramethylcyclotrisiloxane, tetra(chloromethyl)tetramethyltrisiloxane, 3,3,3-trichloropropylheptamethyltrisiloxane, bis(3,3,3-trichloropropyl)hexamethyltrisiloxane, 3,3,3- trichloropropylheptamethylcyclotrisiloxane, (trichloromethyOheptamethylcyclotetrasiloxane, bis^-trichloromethylphenyljhexaphenylcyclotetrasiloxane, tri[methyl(3,3,3- trichloropropyOcyclopolysiloxane], tetra[methyl(3,3,3-trichloropropyl)cyclopolysiloxane], poly[methyl(3,3,3-trichloropropyl)siloxane], poly[dimethylsiloxane-co-methyl(3,3,3- trichloropropyl)siioxane], (tribromomethyl)pentamethyldisiloxane, (2,2- dibromoethyl)pentaethyldisiloxane, tetramethylbis(2,2-dibromocyclohexyl)disiloxane, bis(p- tribromomethylphenyl)tetraphenyldisiloxane, bis(dibromomethyl)tetramethylcyclotrisiloxane, bis(3,3,3-tribromopropyl)hexamethyltrisiloxane, 3,3,3-tribromopropylheptamethyltrisiloxane, S.S.S-tribromopropylheptamethylcyclotrisiloxane, tri[methyl(3,3,3- tribromopropyl)cyclopolysiloxane], tetratmethyKS.S.S-tribromopropyOcyclopolysiloxane], poly[methyl(3,3,3-tribromopropyl)siloxane], and poly[dimethylsiloxane-co-methyl(3,3,3- tribromopropyl)siloxane], or any combination thereof.
[00049] Suitable siloxanes having two or more different elements of halogen include, but are not limited to, (fluoromethyl)(chloromethyl)(bromomethyl)trimethyldisiloxane, (2,2-dichloroethyl)(2,2-difluoroethyl)tetraethyldisiloxane, (1 ,2-dichloroethyl)(1 ,2- difluoroethyl)triethyldisiloxane, (trichloromethyl)(tribromomethyl)tetramethyldisiloxane, tetramethyl(2,2-dichlorocyclohexyl)(2,2-difluorocyclohexyl)disiloxane, (p- tribromomethylphenyl)(p-trifluoromethylphenyl)tetraphenyldisiloxane, tetraphenyl(chloromethyl)(fluoromethyl)disiloxane, (dichloromethyl)(difluoromethyl)tetramethylcyclotrisiloxane, bis(chloromethyl)bis(fluoromethyl)tetramethyltrisiloxane, (3,3,3~trichloropropyl)(3,3,3- trifluoropropyl)hexamethyltrisiloxane, (m-trichloromethylphenyl)(m- trifluoromethylphenyl)hexaphenylcyclotetrasiloxane, or any combination thereof. [00050] In one aspect, siloxanes are selected from trisiloxanes, tricyclosiloxanes, or siloxanes with at least one 3,3,3-trihalopropyl group. In another aspect, siloxanes include, but are not limited to, 3,3,3-trifluoropropylheptamethyltrisiloxane, 3,3,3- trifluoropropylheptamethylcyclotrisiloxane, tri[rnethyl(3,3,3-trifluoropropyl)cyclopolysiloxane], tetra[methyl(3,3,3-trifluoropropyl)cyclopolysiloxane], poly[methyl(3,3,3- trifluoropropyl)siloxane], poly[dimethylsiloxane-co-methyl(3,3,3-trifluoropropyl)siloxane], 3,3,3- trichloropropylheptamethyltrisiloxane, S.S.S-trichloropropylheptamethylcyclotrisiloxane, trifmethyKS.S.S-trichloropropyOcyclopolysiloxane], tetra[methyl(3,3,3- trichloropropyl)cyclopolysiloxane], poly[methyl(3,3,3-trichloropropyl)siloxane], polyfdimethylsiloxane-co-methyKS.S.S-trichloropropyOsiloxane], 3,3,3- tribromopropylheptamethyltrisiloxane, S.S.S-tribromopropylheptamethylcyclotrisiloxane, tri[methyl(3,3,3-tribromopropy|)cyclopolysiloxane], tetra[methyl(3,3,3- tribromopropyl)cyclopolysiloxane], poly[methyl(3,3,3-tribromopropyl)siloxane], poly[dimethylsiloxane-co-methyl(3,3,3-tribromopropyl)siloxane], or any combination thereof. In another aspect, siloxanes are selected from 3,3,3-trifluoropropyIheptamethyltrisiloxane, 3,3,3-trifluoropropylheptamethylcyclotrisiloxane, poly[methyl(3,3,3-trifluoropropyl)siloxane], 3,3,3-trichloropropylheptamethyltrisiloxane, S^S-trichloropropylheptamethylcyclotrisiloxane, poly[methyl(3,3,3-trichloropropyl)siloxane], 3,3,3-tribromopropylheptamethyltrisiloxane, 3,3,3- tribromopropylheptamethylcyclotrisiloxane, poly[methyl(3,3,3-tribromopropyl)siloxane], or any combination thereof. In a further aspect, the siloxanes are poly[methyl(3,3,3- trifluoropropyl)siloxane], poly[methyl(3,3,3-trichloropropyl)siloxane], or poly[methyl(3,3,3- tribromopropyl)siloxane], or any combination thereof.
[00051] Still another type of halogenation agent that can be used in forming the haloaluminoxanes of the invention is at least one silane of the formula R^SiX4-0, where n is 1 , 2, or 3, inclusive, X is, independently, a fluorine, a chlorine, or a bromine atom, and R1 is, independently, a hydrocarbyl group having from one to about twenty carbon atoms or a halohydrocarbyl group having from one to about twenty carbon atoms. R' can be a straight chain, branched, cycloalkyl, aryl, or aralkyl group. In one aspect, R1 is an aryl group, for example, an aryl group having from about six to about twenty carbon atoms, such as a phenyl group. In another aspect, R' is a straight chain or branched hydrocarbyl group, for example, a straight chain or branched hydrocarbyl group having from one to about twelve carbon atoms, or from one to about six carbon atoms, such as a methyl group. [00052] Silanes that can be used as halogenation agents include, but are not limited to, trimethylfluorosilane, dimethyldifluorosilane, diethyldifluorosilane, diisopropyldifluorosilane, tert-butyltrifluorosilane, dicyclobutyldifluorosilane, tripentylfluorosilane, dicyclohexyldifluorosilane, triheptylfluorosilane, dicyclooctyldifluorosilane, triphenylfluorosilane, diphenyldifluorosilane, phenyltrifluorosilane, phenyldimethylfluorosilane, diphenylmethylfluorosilane, phenylmethyldifluorosilane, phenyldiisopropylfluorosilane, tritolylfluorosilane, ditolyldifluorosilane, trimethylchlorosilane, dimethyldichlorosilane, methyltrichlorosilane, triethylchlorosilane, diethyldichlorosilane, ethyltrichlorosilane, di-n-propyldichlorosilane, triisopropylchlorosilane, isobutyltrichlorosilane, dipentyldichlorosilane, cyclohexyltrichlorosilane, dicycloheptyldichlorosilane, dodecyltrichlorosilane, tert-butyldimethylchlorosilane, octylmethyldichlorosilane, dimethyloctadecylchlorosilane, chlorodimethyl-tert-hexylsilane, benzyltrichlorosilane, triphenylchlorosilane, diphenyldichlorosilane, phenyltrichlorosilane, phenyldimethylchlorosilane, diphenylmethylchlorosilane, phenylmethyldichlorosilane, phenyldiisopropylchlorosilane, tert-butyldiphenylchlorosilane, tritolylchlorosilane, ditolyldichlorosilane, trimethylbromosilane, dimethyldibromosilane, methyltribromosilane, triethylbromosilane, diisopropyldibromosilane, n-propyltribromosilane, tert- butyltribromosilane, dicyclopentyldibromosilane, trihexylbromosilane, cycloheptyltribromosilane, dioctyldibromosilane, triphenylbromosilane, diphenyldibromosilane, phenyltribromosilane, phenyldimethylbromosilane, tolyltribromosilane, phenylisopropyldibromosilane, naphthyltribromosilane, phenylchlorodifluorosilane, phenyldichlorofluorosilane, phenyldibromochlorosilane, diphenylbromofluorosilane, phenylmethylchlorofluorosilane, diphenylchlorofluorosilane, phenylisopropylchlorofluorosilane, ditolylchlorofluorosilane, tolylbromodichlorosilane, ditolylbromofluorosilane, or any combination thereof. In one aspect, the silanes are selected from triphenylfiuorosilane, triphenylchlorosilane, triphenylbromosilane, or any combination thereof. In another aspect, the silanes have the general formula (CH3)nSiX4-n, where n is 1 , 2, or 3, inclusive, and X is, independently, a fluorine, a chlorine, or a bromine atom. A non- limiting example of such a silane is trimethylfluorosilane.
[00053] Yet, another type of halogenation agent that can be used in forming the haloaluminoxanes of this invention is a tin compound of the formula R^SnX4-O, where n is 1 , 2, or 3, inclusive, X is, independently, a fluorine, a chlorine, or a bromine atom, and R' is, independently, a hydrocarbyl group having from one to about twenty carbon atoms or a halohydrocarbyl group having from one to about twenty carbon atoms. R' can be a straight chain, branched, cycloalkyl, aryl, or aralkyl group. In one aspect, R' is an aryl group, for example, an aryl group having from about 6 to about 20 carbon atoms, such as a phenyl group. In another aspect, R' can be a straight chain or branched hydrocarbyl group, for example, a straight chain or branched hydrocarbyl group having from one to about six carbon atoms, such as a methyl group.
[00054] Tin compounds that can be used as halogenation agents include, but are not limited to, trimethylfluorostannane, diethylfluorostannane, di-n-propyldifluorostannane, tri-n-butylfluorostannane, dipentyldifluorostannane, cyclohexyltrifluorostannane, diheptyldifluorostannane, trioctylfluorostannane, didodecyldifluorostannane, dichlorodimethylstannane, trichloromethylstannane, triethylchlorostannane, diisopropyldichlorostannane, dicyclobutyldichlorostannane, cyclopentyltrichlorostannane, trihexylchlorostannane, dicycloheptyldichlorostannane, octyltrichlorostannane, dinonyldichlorostannane, decyltrichlorostannane, dimethyldibromostannane, bromotriethylstannane, tribromoethylstannane, cyclopropyltribromostannane, di-n- butyldibromodstannane, pentyltribromostannane, dihexyldibromostannane, trihepylbromostannane, dicyclooctlydibromostannane, dimethylchlorobromostannane, diethylfluorobromostannane, isopropylfluorodichlorostannane, fluorotriphenylstannane, difluorodiphenylstannane, trifluorophenylstannane, fluorotritolylstannane, chlorotriphenylstannane, dichlorodiphenylstannane, trichlorophenylstannane, dichloroditolylstannane, bromotriphenylstannane, dibromodiphenylstannane, tribromophenylstannane, tolyltribromostannane, phenyldichlorobromostannane, diphenylfluorochlorostannane, diphenylfluorobromostannane, or any combination thereof. In one aspect, the tin compound is selected from triphenylfluorostannane, triphenylchiorostannane, dichlorodimethylstannane, triphenylbromostannane, or any combination thereof. In another aspect, the tin compound has the general formula (ChynSnXt-n, where n is 1 , 2, or 3, inclusive, and X is, independently, a fluorine, a chlorine, or a bromine atom.
[00055] Still another type of halogenation agent that can be used in forming the haloaluminoxanes of this invention include a hydrocarbylaluminum halide of the formula R'mAIX3.m, where m is 1 or 2, inclusive, X is, independently, a fluorine, a chlorine, or a bromine atom, and where R' is, independently, a hydrocarbyl group having from one to about twenty carbon atoms or a halohydrocarbyl group having from one to about twenty carbon atoms. R' can be a straight chain, branched, cycloalkyl, aryl, or aralkyl group. In one aspect, R' is a straight chain hydrocarbyl having from one to about ten carbon atoms. [00056] Hydrocarbylaluminum halides that can be used as halogenation agents include, but are not limited to, methylaluminum difluoride, dimethylaluminum fluoride, ethylaluminum difluoride, diethylaluminum fluoride, isopropylaluminum difluoride, diisopropylaluminum fluoride, n-butylaluminum difluoride, isobutylaluminum difluoride, diisobutylaluminum fluoride, dipentylaluminum fluoride, cyclohexylaluminum difluoride, diheptylaluminum fluoride, dicyclooctylaluminum fluoride, nonylalumium difluoride, decylaluminum difluoride, diundecylaluminum fluoride, phenylaluminum difluoride, diphenylaluminum fluoride, tolylaluminum difluoride, ditolylaluminum fluoride, methylaluminum dichloride, dimethylaluminum chloride, ethylaluminum dichloride, diethylaluminum chloride, diisopropylaluminum chloride, di-n-butylaluminum chloride, isobutylaluminum dichloride, pentylaluminum dichloride, dicyclohexylaluminum chloride, heptylaluminum dichloride, cyclooctylaluminum chloride, dinonylalumium chloride, didecylaluminum chloride, undecylaluminum chloride, phenylaluminum dichloride, diphenylaluminum chloride, tolylaluminum dichloride, ditolylaluminum chloride, methylaluminum dibromide, dimethylaluminum bromide, ethylaluminum dibromide, diethylaluminum bromide, isopropylaluminum dibromide, isobutylaluminum dibromide, diisobutylaluminum bromide, pentylaluminum bromide, cyclohexylaluminum bromide, heptylaluminum dibromide, cyclooctylaluminum bromide, dinonylalumium bromide, decylaluminum dibromide, undecylaluminum bromide, phenylaluminum dibromide, diphenylaluminum bromide, tolylaluminum dibromide, ditolylaluminum bromide, or any combination thereof. [00057] In one aspect, hydrocarbylaluminum halides of the present invention are selected from methylaluminum difluoride, dimethylaluminum fluoride, methylaluminum dichloride, dimethylaluminum chloride, methylaluminum dibromide, dimethylaluminum bromide, or any combination thereof. In another aspect, hydrocarbylaluminum halides are selected from methylaluminum difluoride or dimethylaluminum fluoride. [00058] Any combination of two or more halogenation agents can be employed in the present invention. This includes mixtures of different halogenation agents within the same type, mixtures of halogenation agents of different types, and mixtures of at least two different halogenation agents within the same type with at least one halogenation agent of a different type. Mixtures can be used in which the halogen elements in the halogenation agents are the same or different. It can be advantageous to use a mixture of halogenation agents, depending on the desired product haloaluminoxane and the properties thereof (for example, degree of halogenation, solubility, or stability).
Alkylaluminum Compounds
[00059] Alkylaluminum compounds employed in the present invention include trialkylaluminum compounds and substituted trialkylaluminum compounds having the following general formula, AIR"nQ3-n, wherein n is 1 , 2, or 3, inclusive;
Q is, independently, a halide, a pseudohalide, or hydride; and R" is an alkyl group having from two to about twenty carbon atoms. Q can be any suitable anionic substituent, including halides, pseudohalides, and hydride. Examples of halides include fluoride, chloride, bromide, and iodide. Pseudohalides can include, for example, azides, cyanide, cyanate, thiocyanate, isocyanate, isothiocyanate, silicon groups, sulfur groups, nitrogen groups, oxygen groups, and phosphorous groups. Silicon groups comprise silicon-containing groups, which include, but are not limited to, silyl groups such alkylsilyl groups, arylsilyl groups, arylalkylsilyl groups, siloxy groups, and the like. For example, silicon groups include trimethylsilyl and phenyloctylsilyl groups. Sulfur groups comprise sulfur-containing groups, examples of which include, but are not limited to, -SRIV and the like, including substituted derivatives thereof. Nitrogen groups are nitrogen- containing groups, which include, but are not limited to, -NR'V 2 and the like, including substituted derivatives thereof. Oxygen groups are oxygen-containing groups, examples of which include, but are not limited to, alkoxy or aryloxy groups (-ORiv), -OSiRlv 3, -OPRiv 2, - OAIRIV 2, and the like, including substituted derivatives thereof. Examples of alkoxy or aryloxy groups (-ORiv) include, but are not limited to, methoxy, ethoxy, propoxy, butoxy, phenoxy, substituted phenoxy, and the like. Phosphorus groups are phosphorus-containing groups, which include, but are not limited to, -PR'V 2 and the like, including substituted derivatives thereof. As employed herein, R'v is selected from alkyl, cycloalkyl, aryl, aralkyl, substituted alky!, substituted aryl, or substituted aralkyl groups having from 1 to about 20 carbon atoms.
[00060] Suitable alkylaluminum compounds include, but are not limited to, tributylaluminum, triisobutylaluminum, tri-n-octylaluminum, or any combination thereof. Substituted alkylaluminum compounds include, but are not limited to, dialkylaluminum halides and alkylaluminum dihalides.
[00061] The alkylaluminum compound is present in the stabilized haloaluminoxane composition in an amount sufficient to improve the stability to degradation at higher and lower temperatures. The alkylaluminum compound can be employed in any amount, so long as it does not produce adverse effects on the stability or activation efficiency of the stabilized haloaluminoxane. In one aspect of the present invention, the alkylaluminum compound is present in the stabilized haloaluminoxane in a range of about 1 mole % to about 5 mole % relative to the total composition. In another aspect of the present invention, the amount of alkylaluminum compound present in the composition is at least about 1 mole % relative to the total stabilized haloaluminoxane composition.
Optional Support Materials
[00062] Stabilized haloaluminoxane compositions of the present invention can optionally be supported on any suitable inorganic or organic carrier material. Support materials used in accordance with this invention can be any finely divided inorganic solid support, such as talc; clay; inorganic oxides and mixed inorganic oxides including, but not limited to, silica, alumina, silica-alumina, or a mixture thereof; or any combination thereof. Support materials can also be particulate, organic resinous support materials including, but not limited to, spheroidal, particulate, or finely-divided polyethylene, polyvinylchloride, polystyrene, or any combination thereof. In another aspect of this invention, support materials are inorganic particulate supports or carrier materials such as magnesium halides, inorganic oxides, aluminum silicates, inorganic compositions containing inorganic oxides, or any combination thereof. Examples of inorganic compositions containing inorganic oxides include, but are not limited to, kaolinite, attapulgtite, montmorillonite, illite, bentonite, halloysite, similar refractory clays, or any combination thereof. Examples of inorganic oxides, which include mixed inorganic oxides, include, but are not limited to, silica, alumina, silica- alumina, magnesia, titania, zirconia, or any combination thereof. In one aspect of the present invention, the support is anhydrous or substantially anhydrous. Inorganic oxides can be dehydrated to remove water. The support can also be calcined or chemically treated with known conventional reagents to remove hydroxyl groups and/or water from the carrier. Suitable conventional reagents include, but are not limited to aluminum alkyls, lithium alkyls, silylchloride, aluminoxanes, ionic aluminoxanates, or any combination thereof. [00063] The specific particle size, surface area and pore volume of the support material determine the amount of support material that is desirable to employ in preparing the catalyst compositions, as well as affecting the properties of polymers formed with the aid of the catalyst compositions. These properties are frequently taken into consideration in choosing a support material for use in a particular aspect of the invention. A suitable support such as silica typically will have a particle diameter in a range of about 0.1 micron to about 600 microns, or in a range of about 0.3 micron to about 100 microns; a surface area in a range of about 50 m2/g to about 1000 m2/g, or in a range of about 100 to about 500 m2/g; and a pore volume in a range of about 0.3 cc/g to about 5.0 cc/g, or in a range of about 0.5 cc/g to about 3.5 cc/g. It is also desirable to employ supports with pore diameters in a range of about 50 angstroms to about 500 angstroms. To ensure its use in dehydrated form the support material can be heat treated at about 1000C to about 10000C for a period of about 1 hour to about 100 hours, or, in another aspect of the present invention, from about 3 hours to about 24 hours. The treatment can be carried out in a vacuum or while purging with a dry inert gas such as nitrogen.
[00064] As an alternative, the support material can be chemically dehydrated.
Chemical dehydration is accomplished by slurrying the support in an inert low-boiling solvent, such as, for example, heptane, in the presence of a dehydrating agent, such as, for example, triethylaluminum, in a moisture and oxygen-free environment.
Stability of Stabilized Haloaluminoxane Compositions
[00065] Stabilized haloaluminoxane compositions of the present invention are stable to degradation at temperatures ranging from about -300C to about 600C for at least about thirty days. In one aspect, stabilized haloaluminoxane compositions in accordance with the present invention are stable to degradation at temperatures ranging from about - 3O0C to about 60°C for at least about ninety days. By "stable to degradation" it is meant that the stabilized haloaluminoxanes show minimal or no reversible or irreversible precipitation for extended periods of time. These stabilized haloaluminoxanes can remain substantially free of gel formation at temperatures ranging from about -300C to about 600C for at least about thirty days, or, in another aspect of the present invention, at least about ninety days. In another aspect of the present invention, stabilized haloaluminoxanes can remain substantially free of gel. formation at temperatures ranging from about -20°C to about 450C for at least about thirty days, or, in yet another aspect of the present invention, at least about ninety days. In a further aspect, stabilized haloaluminoxanes can exhibit less than about two weight percent gel formation at temperatures ranging from about -300C to about 600C for at least about thirty days, or, in yet another aspect of the present invention, at least about ninety days. In yet another aspect, stabilized haloaluminoxanes can exhibit less than about two weight percent gel formation at temperatures ranging from about -200C to about 45°C for at least about thirty days, or, in still another aspect of the present invention, at least about ninety days. In still a further aspect, the stabilized haloaluminoxanes of the present invention can exhibit less than about five weight percent gel formation at temperatures ranging from about -300C to about 60°C for at least about thirty days, or, in yet another aspect of the present invention, at least about ninety days. In another aspect, stabilized haloaluminoxanes of the present invention can exhibit less than about five weight percent gel formation at temperatures ranging from about -200C to about 45°C for at least about thirty days, or, in yet another aspect of the present invention, at least about ninety days. In a further aspect of the present invention, stabilized haloaluminoxanes can exhibit less than about 10 weight percent (wt.%) gel formation at temperatures ranging from about -300C to about 600C for at least about thirty days, or, in yet another aspect of the present invention, at least about ninety days. In yet another aspect of the present invention, the stabilized haloaluminoxanes can exhibit less than about 10 wt.% gel formation at temperatures ranging from about -200C to about 45°C for at least about thirty days, or, in still another aspect of the present invention, at least about ninety days.
Preparation of Stabilized Haloaluminoxane Compositions
[00066] This invention encompasses methods for preparing stabilized haloaluminoxane compositions comprising contacting at least one aluminoxane, at least on halogenation agent, and at least one additional alkylaluminum compound, in any order. Alternatively, the stabilized haloaluminoxane compositions of the present invention can be prepared by contacting at least one haloaluminoxane with at least one additional alkylaluminum compound. In this regard, the stabilized haloaluminoxane compositions of the present invention are obtained when these components are contacted in any sequence or order. For example, the aluminoxane can first be contacted with the halogenation agent to produce a haloaluminoxane. The haloaluminoxane can then be contacted with the additional alkylaluminum compound to form a stabilized haloaluminoxane composition. [00067] The present invention further encompasses methods to produce supported soluble stabilized haloaluminoxane compositions comprising contacting at least one aluminoxane, at least one halogenation agent, at least one additional alkylaluminum compound, and at least one organic or inorganic support material, in any order. For example, the stabilized haloaluminoxane composition can be prepared and subsequently contacted with a support material to form the supported composition. In another aspect, the additional alkylaluminum compound is first contacted with a support material, and this mixture is subsequently contacted with a haloaluminoxane. [00068] Preparation of the supported and unsupported stabilized haloaluminoxane composition is generally conducted under conventional inert atmospheres using substantially inert anhydrous materials. Typically, temperatures for preparation are in a range of about 200C to about 800C, although higher and lower temperatures are also suitable. [00069] In one aspect of the present invention, the alkylaluminum compound is present in the stabilized haloaluminoxane in a range of about 1 mole % to about 5 mole % relative to the total composition. In another aspect of the present invention, the amount of alkylaluminum compound present in the composition is at least about 1 mole % relative to the total stabilized haloaluminoxane composition.
Catalyst Compositions and Components
[00070] This invention encompasses supported and unsupported catalyst compositions prepared using stabilized haloaluminoxane compositions. Catalyst systems employed in the present invention can comprise the contact product of (a) at least one stabilized haloaluminoxane composition and (b) at least one complex of a transition metal of Group 3, 4, 5, 6, 7, 8, 9, 10 , or 11 of the Periodic Table of Elements, including the lanthanide series and the actinide series.
Transition Metal Complexes
[00071] Stabilized haloaluminoxane compositions of the present invention can be used with any known transition metal catalyst compound in which the transition metal is a Group 3 to 11 transition metal of the Periodic Table of Elements, including compounds of a metal of the lanthanide or actinide series. The Periodic Table of Elements referred to herein is that appearing on page 27 of the February 4, 1985 issue of Chemical & Engineering News. Suitable catalyst compounds can also be described as d- and f- block metal compounds. See, for example, the Periodic Table of Elements appearing on page 225 of Moeller, et al., Chemistry, Second Edition, Academic Press, copyright 1984. In one aspect of the present invention, the metal constituent is a compound of Fe, Co, Ni, Pd, or V. In another aspect, the metal constituent is a compound of the metals of Groups 4-6 (Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, and W). In yet another aspect, the metal is a Group 4 metal, for example, titanium, zirconium, or hafnium.
[00072] Thus, the transition metal catalyst compounds used in this invention can be one or more of any Ziegler-Natta catalyst compound, any metallocene, any compound of constrained geometry, any late transition metal complex, or any other transition metal compound or complex reported in the literature or otherwise generally known in the art to be an effective catalyst compound when suitably activated, including mixtures of at least two different types of such transition metal compounds or complexes, such as for example a mixture of a metallocene and a Ziegler-Natta olefin polymerization catalyst compound. [00073] Among the transition metal compounds of the metals of Groups 3, 4, 5, and 6 which can be used as the transition metal component of the catalyst compositions of the present invention are compounds of such metals as scandium, titanium, zirconium, hafnium, cerium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, thorium and uranium, often referred to as Ziegler-Natta type olefin polymerization catalysts. Compounds of this type can be represented by the formula MXn(OR)1n in which M represents the transition metal atom or a transition metal atom cation containing one or two oxygen atoms such as vanadyl, zirconyl, or uranyl, X represents a halogen atom, OR represents a hydrocarbyloxy group having up to about 18 carbon atoms, or up to about 8 carbon atoms, or an alkyl of up to about 4 carbon atoms, such as an alkyl, cycloalkyl, cycloalkylalkyl, aryl, or aralkyl group, n and m are positive integers except that either one of them (but not both) can be zero, and n + m is the valence state of the transition metal. Illustrative of some of the transition metal compounds which can be employed in the present invention include, but are not limited to, titanium dibromide, titanium tribromide, titanium tetrabromide, titanium dichloride, titanium trichloride, titanium tetrachloride, titanium trifluoride, titanium tetrafluoride, titanium diiodide, titanium triiodide, titanium tetraiodide, zirconium dibromide, zirconium tribromide, zirconium tetrabromide, zirconium dichloride, zirconium trichloride, zirconium tetrachloride, zirconium tetrafluoride, zirconium tetraiodide, hafnium tetrafluoride, hafnium tetrachloride, hafnium tetrabromide, hafnium tetraiodide, hafnium trichloride, hafnium tribromide, hafnium triiodide, vanadium dichloride, vanadium trichloride, vanadium tetrachloride, vanadium tetrabromide, vanadium tribromide, vanadium dibromide, vanadium trifluoride, vanadium tetrafluoride, vanadium pentafluoride, vanadium diiodide, vanadium triiodide, vanadium tetraiodide, vanadyl chloride, vanadyl bromide, niobium pentabromide, niobium pentachloride, niobium pentafluoride, tantalum pentabromide, tantalum pentachloride, tantalum pentafluoride, chromous bromide, chromic bromide, chromous chloride, chromic chloride, chromous fluoride, chromic fluoride, molybdenum dibromide, molybdenum tribromide, molybdenum tetrabromide, molybdenum dichloride, molybdenum trichloride, molybdenum tetrachloride, molybdenum pentachloride, molybdenum hexafluoride, lanthanum trichloride, cerous fluoride, cerous chloride, cerous bromide, cerous iodide, eerie fluoride, uranium trichloride, uranium tetrachloride, uranium tribromide, uranium tetrabromide, thorium tetrachloride, thorium tetrabromide, or any combination thereof. [00074] Among the hydrocarbyloxides and mixed halide/hydrocarbyloxides of the transition metals which can be employed in the present invention, include but are not limited to, Ti(OCHg)4, Ti(OCH3)CI3, Ti(OCH3)Br3, Ti(OCH3)2l2> Ti(OC2Hg)4, Ti(OC2Hs)3CI, Ti(OC2H5)Ci3, Ti(OC2H5)Br3, Ti(OC4H9)Br3, Ti(OC2H5)I3, Ti(OC3H7)2CI2, Ti(O-iso-C3H7)3CI, Ti(O-iso-C3H7)2CI2, Ti(O-JSo-C3H7)CI3, Ti(OC4Hg)3CI, Ti(OC4Hg)2CI2, Ti(OC4H9)CI3, Ti(OC6H5)CI3, Ti(O-P-CH3C6H4)CI3, Ti(OC6H13)2CI2, Ti(OC6H13)CI3, Ti(O-CyCIo-C6H11)CI3, Ti(OC8H17)2Br2> Ti(O-2-EtHex)4) Ti(OCi2H25)C) 3, Ti(OC17H1S)2Br2, Zr(OC2Hg)4, Zr(OC4H9)4, Zr(OC5Hn)4, ZrCI(OC2Hg)3, ZrCI2(OC2Hs)2, ZrCI3(OC2H5), ZrCI(OC4Hg)3, ZrCl2(OC4Hg)2, ZrCI3(OC4H9), Hf(OC4Hg)4, Hf(OC4Hg)3CI, VO(OC2H5)3l VOC!(OCH3)2, VOCI(OC2Hs)2, VOCI(OC3H7)2, VOCI(0-iso-C3H7)2, VOCI2(OCH3), VOCI2(OC2H5), VOCI2(OC3H7), VOCI2(O- ISO-C3H7), VOBr(OCH3)2, VOBr(OC2H5)2, VOBr(O-iso-C4H9)2, VOBr2(OC3H7), VOBr2(O-iso- C3H7), VOBr2(OC4H9), VOBr2(O-JSO-C4H9), VOI(OCH3)2, VOI(OC2H5)2> VOI2(OCH3), VOI2(O- cyclo-C3H5), VOI2(OC5H11), VOI2(O-CyCIo-C6H11), Cr(O-iso-C4Hg)3, Mo(OC2H5)3, or any combination thereof. Carboxylic acid salts and various chelates of the transition metal can also be used. A few non-limiting examples of such salts and chelates include zirconyl acetate, uranyl butyrate, chromium acetate, chromium(lll) oxy-2-ethylhexanoate, chromium(lll) 2-ethylhexanoate, chromium(IU) dichloroethylhexanoate, chromium(ll) 2-ethylhexanoate, titanium(IV) 2-ethylhexanoate, bis(2,4-pentanedionate)titanium oxide, bis(2,4-pentanedionate)titanium dichloride, bis(2,4-pentanedionate)titanium dibutoxide, vanadyl acetylacetonate, chromium acetylacetonate, niobium acetylacetonate, zirconyl acetylacetonate, chromium octylacetoacetate, or any combination thereof. Also, transition metal alkyls such as tetramethyl titanium, methyl titanium trichloride, tetraethyl zirconium, tetraphenyl titanium, or any combination thereof can be used.
[00075] In one aspect of the present invention, the transition metal compound is a well-known Ziegler-Natta catalyst compound, for example, those of the Group 4 metals, including the alkoxides, halides, and mixed halide/alkoxide compounds. For example, suitable transition metal compounds include TiCI4, ZrCI4, HfCI4, Or TiCI3. These compounds can also be used in chelated form in order to facilitate solubility. Suitable chelated catalysts of this type are known and reported in the literature.
[00076] Metallocenes are another broad class of olefin polymerization catalyst compounds with which the stabilized haloaluminoxane compositions of this invention can be used in forming the catalyst compositions of this invention. As used herein, the term "metallocene" includes metal derivatives which contain at least one cyclopentadienyl (Cp) moiety. Suitable metallocenes are well known in the art and include the metallocenes of Groups 3, 4, 5, 6, lanthanide and actinide metals, for example, the metallocenes which are described in U.S. Patent Nos. 2,864,843; 2,983,740; 4,665,046; 4,874,880; 4,892,851; 4,931 ,417; 4,952,713; 5,017,714; 5,026,798; 5,036,034; 5,064,802; 5,081,231; 5,145,819; 5,162,278; 5,245,019; 5,268,495; 5,276,208; 5,304,523; 5,324,800; 5,329,031; 5,329,033; 5,330,948, 5,347,025; 5,347,026; and 5,347,752, to name only a few. [00077] Metallocene structures in this specification are to be interpreted broadly, and include structures containing 1 , 2, 3, or 4 Cp or substituted Cp rings. Thus metallocenes suitable for use in this invention can be represented by Formula (I): BaCpbMXcYd (I) where Cp, independently in each occurrence, is a cyclopentadienyl-moiety-containing group which typically has in a range of 5 to about 24 carbon atoms; B is a bridging group or ansa group that links two Cp groups together or alternatively carries an alternate coordinating group such as alkylaminosilylalkyl, silylamido, alkoxy, siloxy, aminosilylalkyl, or analogous monodentate hetero atom electron donating groups; M is a d- or f-block metal atom; each X and each Y is, independently, a group that is bonded to the d- or f-block metal atom; a is 0 or 1 ; b is an integer from 1 to 3; c is at least 2; and d is 0 or 1. The sum of b, c, and d is sufficient to form a stable compound, and often is the coordination number of the d- or f- block metal atom.
[00078] Cp is, independently, a cyclopentadienyl, indenyl, fluorenyl or related group that can 77-bond to the metal, or a hydrocarbyl-, halo-, halohydrocarbyl-, hydrocarbylmetalloid-, and/or halohydrocarbylmetalloid-substituted derivative thereof. Cp typically contains up to 75 non-hydrogen atoms. B, if present, is typically a silylene (-SiR2-), benzo (C6H4<), substituted benzo, methylene (-CH2-), substituted methylene, ethylene (- CH2CH2-), or substituted ethylene bridge. In one aspect, M is a metal atom of Groups 4, 5, or 6 of the Periodic Table of Elements. In another aspect, M is a Group 4 metal atom, such as hafnium, zirconium, or titanium. X can be a divalent substituent such as an alkylidene group, a cyclometallated hydrocarbyl group, or any other divalent chelating ligand, two loci of which are singly bonded to M to form a cyclic moiety which includes M as a member. Each X, and each Y, if present, can be, independently in each occurrence, a halogen atom, a hydrocarbyl group (alkyl, cycloalkyl, alkenyl, cycloalkenyl, aryl, aralkyl, etc.), hydrocarbyloxy, (alkoxy, aryloxy, efc.) siloxy, amino or substituted amino, hydride, acyloxy, triflate, and similar univalent groups that form stable metallocenes. The sum of b, c, and d is a whole number, and is often from 3-5. When M is a Group 4 metal or an actinide metal, and b is 2, the sum of c and d is 2, c being at least 1. When M is a Group 3 or lanthanide metal, and b is 2, c is 1 and d is zero. When M is a Group 5 metal, and b is 2, the sum of c and d is 3, c being at least 2.
[00079] Also useful in this invention are compounds analogous to those of
Formula (I) where one or more of the Cp groups are replaced by cyclic unsaturated charged groups isoelectronic with Cp, such as borabenzene or substituted borabenzene, azaborole or substituted azaborole, and various other isoelectronic Cp analogs. See for example Krishnamurti, et al., U.S. Patent Nos. 5,554,775 and 5,756,611.
[00080] In one group of metallocenes, b is 2, i.e., there are two cyclopentadienyl- moiety containing groups in the molecule, and these two groups can be the same or they can be different from each other. [00081] Another sub-group of useful metallocenes which can be used in the practice of this invention are metallocenes of the type described in WO 98/32776, published
July 30, 1998. These metallocenes are characterized in that one or more cyclopentadienyl groups in the metallocene are substituted by one or more polyatomic groups attached via a
N, O, S, or P atom or by a carbon-to-carbon double bond. Examples of such substituents on the cyclopentadienyl ring include -OR, -SR, -NR2, -CH=, -CR=, and -PR2, where R can be the same or different and is a substituted or unsubstituted C1-C16 hydrocarbyl group, a W-C1-C8 hydrocarbylsilyl group, a W-C1-C8 hydrocarbyloxysilyl group, a mixed C1-C8 hydrocarbyl and
C1-C8 hydrocarbyloxysilyl group, a W-C1-C8 hydrocarbylgermyl group, a W-C1-C8 hydrocarbyloxygermyl group, or a mixed C1-C8 hydrocarbyl and C1-C8 hydrocarbyloxygermyl group.
[00082] Examples of metallocenes to which this invention is applicable include such compounds as: bis(cyclopentadienyl)zirconium dimethyl; bis(cyclopentadienyl)zirconium dichloride; bis(cyclopentadienyl)zirconium monomethylmonochloride; bis(cyclopentadienyl)titanium dichloride; bis(cyclopentadienyl)titanium difluoride; cyclopentadienylzirconium tri-(2-ethylhexanoate); bis(cyclopentadienyl)zirconium hydrogen chloride; bis(cyclopentadienyl)hafnium dichloride; racemic and meso dimethylsilanylene-bisCmethylcyclopentadienyOhafnium dichloride; racemic dimethylsilanylene-bis(indenyl)hafnium dichloride; racemic ethylene-bis(indenyl)zirconium dichloride;
(/75-indenyl)hafnium trichloride;
(/75-C5Me5)hafnium trichloride; racemic dimethylsilanylene-bis(indenyl)thorium dichloride; racemic dimethylsilanylene-bis(4,7-dimethyl-1 -indenyl)zirconium dichloride; racemic dimethyl-silanylene-bis(indenyl)uranium dichloride; racemic dimethylsilanylene-bis(2,3,5-trimethyl-1 -cyclopentadienyl)zirconium dichloride; racemic dimethyl-silanylene(3-methylcyclopentadienyl)hafnium dichloride; racemic dimethylsilanylene-bis(1-(2-methyl-4-ethyl)indenyI) zirconium dichloride; racemic dimethylsilanylene-bis(2-methyl~4,5,6,7-tetrahydro-1-indenyl) zirconium dichloride; bistøentamethylcyclopentadienyOthorium dichloride; bis(pentamethylcyclopentadienyl)uranium dichloride;
(tert-butylamido)dimethyl(tetramethyl-/75-cyclopentadienyl)silanetitanium dichloride;
(tert-butylamido)dimethyl(tetramethyl-/75-cyclopentadienyl)silane chromium dichloride; (tert-butylamido)dimethyl(-/75-cyclopentadienyl)siIanetitanium dichloride; (tert-butylamidoJdimethyKtetramethyl-^-cyclopentadienyOsilanemethyltitanium bromide; (tert-butylamido)(tetramethyl-/75-cyclopentadienyl)-1,2-ethanediyluranium dichloride; (tert-butylamidoJ^etramethyl-^-cyclopentadienylJ-i ^-ethanediyltitanium dichloride; (methylamido)(tetramethyl-/75-cyclopentadienyI)-1 ,2-ethanediylcerium dichloride; (methylamido)(tetramethyl-/75-cycIopentadienyl)-1 ,2-ethanediyltitanium dichloride; (ethylamido)(tetramethyl-/75-cyclopentadienyl)methylenetitanium dichloride; (tert-butylamido)dibenzyl(tetramethyI-/75-cyclopentadienyl)-siIaneben2ylvanadium chloride; (benzylamido)dimethyl(indenyl)silanetitanium dichloride;
(phenylphosphido)dimethyl(tetramethyl-/75-cyclopentadienyl)silanebenzyltitanium chloride; rac-dimethylsilylbis(2-methyl-1-indenyl)zirconium dimethyl; rac-ethylenebis(1 -indenyl)zirconium dimethyl; bis(methylcyclopentadienyl)titanium dimethyl; bis(methylcyclopentadienyl)zirconium dimethyl; bis(n-butylcyclopentadienyl)zirconium dimethyl; bis(dimethylcyclopentadienyl)zirconium dimethyl; bis(diethylcyclopentadienyl)zirconium dimethyl; bis(methyl-n-butylcyclopentadienyl)zirconium dimethyl; bis(n-propylcyclopentadienyl)zirconium dimethyl; bis(2-propylcyclopentadienyl)zirconium dimethyl; bis(methylethylcyclopentadienyl)zirconiurr) dimethyl; bis(indenyl)zirconium dimethyl; bis(methylindenyl)zirconium dimethyl; dimethylsilylenebis(indenyl)zirconium dimethyl; dimethylsilylenebis(2-methylindenyl)zirconium dimethyl; dimethylsilylenebis(2-ethylindenyl)zirconium dimethyl; dimethylsilylenebis(2-methyl-4-phenylindenyl)zirconium dimethyl; 1 ,2-ethylenebis(indenyl)zirconium dimethyl; 1 ,2-ethylenebis(methylindenyl)zirconium dimethyl; 2,2-propylidenebis(cyclopentadienyl)(fluorenyI)zirconium dimethyl; dimethylsilylenebis(6-phenylindenyl)zirconium dimethyl; bis(methylindenyl)zirconium benzyl methyl; ethylenebis[2-(tert-butyldimethylsiloxy)-1 -indenyl] zirconium dimethyl; dimethylsilylenebis(indenyl)chlorozirconium methyl; 5-(cyclopentadienyl)-5-(9-fluorenyl)1 -hexene zirconium dimethyl; dimethylsilylenebis(2-methylindenyl)hafnium dimethyl; dimethylsilylenebis(2-ethylindenyl)hafnium dimethyl; dimethylsilylenebis(2-methyl-4-phenylindenyl)hafniυm dimethyl; 2,2-propylidenebis(cyclopentadienyl)(fluorenyl)hafnium dimethyl; bis(9-fluorenyl)(methyl)(vinyl)silane zirconium dimethyl; bis(9-fluorenyl)(methyl)(prop-2-enyl)silane zirconium dimethyl; bis(9-fluorenyl)(methyl)(but-3-enyl)silane zirconium dimethyl; bis(9-fluorenyl)(methyl)(hex-5-enyl)silane zirconium dimethyl; bis(9-fluorenyl)(methyl)(oct-7-enyl)silane zirconium dimethyl; (cyclopentadienyl)(1-allylindenyl) zirconium dimethyl; bis(1 -allylindenyl)zirconium dimethyl;
(9-(prop-2-enyl)fluorenyl)(cyclopentadienyl)zirconium dimethyl; (9-(prop-2-enyl)fluorenyl)(pentamethylcyclopentadienyl)zirconium dimethyl; bis(9-(prop-2-eny))fluorenyl) zirconium dimethyl; (9-(cyclopent-2-enyl)fluorenyl)(cyclopentadienyl) zirconium dimethyl; bis(9-(cyclopent-2-enyl)(fluorenyl)zirconium dimethyl; 5-(2-methylcyclopentadienyl)-5(9-fluorenyl)-1 -hexene zirconium dimethyl; 1 -(9-fluorenyI)-1 -(cyclopentadienyl)-i -(but-3-enyI)-1 -(methyl)methane zirconium dimethyl; 5-(fluorenyl)-5-(cyclopentadienyl)-1 -hexene hafnium dimethyl; (9-fluorenyl)(1-allylindenyl)dimethylsilane zirconium dimethyl;
1-(2,7-di(alpha-methylvinyl)(9-fluorenyl)-1-(cyclopentadienyl)-1,1-dimethylmethane zirconium dimethyl;
1-(2,7-di(cyclohex-1-enyl)(9-fluorenyl))-1-(cyclopentadienyi)-1,1-methane zirconium dimethyl; 5-(cyclopentadienyl)-5-(9-fluorenyl)-1 -hexene titanium dimethyl; 5-(cyclopentadienyl)-5-(9-fluorenyl)1 -hexene titanium dimethyl; bis(9-fluorenyl)(methyl)(vinyl)silane titanium dimethyl; bis(9-fluoreny()(methyl)(prop~2-enyl)silane titanium dimethyl; bis(9-fluorenyl)(methyl)(but-3-enyl)silane titanium dimethyl; bis(9-fluorenyl)(methyl)(hex-5-enyl)silane titanium dimethyl; bis(9-fluorenyl)(methyl)(oct-7-enyl)silane titanium dimethyl; (cyclopentadienyl)(1-allylindenyl) titanium dimethyl; bis(1 -allylindenyl)titanium dimethyl;
(9-(prop-2-enyl)fluorenyl)(cyclopentadienyl)hafnium dimethyl; (9-(prop-2-enyl)fluorenyl)(pentamethylcyclopentadienyI)hafnium dimethyl; bis(9-(prop-2-enyl)fluorenyl) hafnium dimethyl; (9-(cyclopent-2-enyl)fluorenyI)(cyclopentadienyl) hafnium dimethyl; bis(9-(cyclopent-2-enyl)(fluorenyl)hafnium dimethyl; 5-(2-methylcyclopentadienyl)-5(9-fluorenyl)-1 -hexene hafnium dimethyl; 5-(fluorenyl)~5-(cyclopentadienyl)-1-octene hafnium dimethyl; (9-fIuorenyl)(1-allyIindenyl)dimethylsilane hafnium dimethyl;
(tert-butylamido)dimethyl(tetramethylcyclopentadienyl)silane titanium(1 ,3-pentadiene); (cyclopentadienyl)(9-fluorenyl)diphenylmethane zirconium dimethyl; (cyclopentadienyl)(9-fluorenyl)diphenylmethane hafnium dimethyl; dimethylsilanylene-bis(indenyl) thorium dimethyl; dimethylsilanylene-bis(4,7-dimethyl-1 -indenyl) zirconium dimethyl; dimethylsilanylene-bis(indenyl) uranium dimethyl; dimethylsilanylene-bis(2-methyl-4-ethyl-1 -indenyl) zirconium dimethyl; dimethylsilanylene-bis(2-methyl-4,5,6,7-tetrahydro-1 -indenyl) zirconium dimethyl; (tert-butylamido)dimethyl(tetramethyl-/75-cyclopentadienyl)silane titanium dimethyl; (tert-butylamido)dimethyl(tetramethyl-/75-cyclopentadienyl)silane chromium dimethyl; (tert-butylamido)dimethyl(tetramethyl-/75-cyclopentadienyl)silane titanium dimethyl; (phenylphosphido)dimethyl(tetramethyl-/75-cyclopentadienyl)silane titanium dimethyl; [dimethylsilanediylbis(indenyl)]scandium methyl; or any combination thereof. In many cases the metallocenes such as referred to above will exist as racemic mixtures, but pure enantiomeric forms or mixtures enriched in a given enantiomeric form can be used. [00083] Other organometallic catalytic compounds with which the stabilized haloaluminoxanes of this invention can be used in forming the catalyst compositions of this invention are the late transition metal catalyst described, for example, in U.S. Patent Nos. 5,516,739 to Barborak, et al.; 5,561 ,216 to Barborak, et al.; 5,866,663 to Brookhart, et al; 5,880,241 to Brookhart, et al; and 6,114,483 to Coughlin, et al. Such catalysts are sometimes referred to herein collectively as "a Brookhart-type late transition metal catalyst compound or complex".
[00084] Other transition metal catalyst compounds and catalyst complexes that can be used in the practice of this invention include catfluoro nickel, palladium, iron, and cobalt complexes containing diimine and bisoxazoline ligands such as described in Johnson et al. WO 96/23010; palladium and nickel catalysts containing selected bidentate phosphorus-containing ligands such as described in EP 381 ,495; catfluoro σ-diimine-based nickel and palladium complexes such as described by Johnson et al. in J. Am. Chem. Soc, 1995, 117, 6414, see also Brown et al. WO 97/17380; nickel complexes such as described by Johnson et al. in U.S. Patent No. 5,714,556; cobalt(lll) cyclopentadienyl catalytic systems such as described by Schmidt et al. in J. Am. Chem. Soc, 1985, 107, 1443, and by Brookhart et al. in Macromolecules, 1995, 28, 5378; anfluoro phosphorus, oxygen donors ligated to nickel(ll) such as described by Klabunde in U.S. Pat Nos. 4,716,205, 4,906,754, 5,030,606, and 5,175,326; Group 8-10 transition metal complexes coordinated with a bidentate ligand such as described in WO 98/40374; transition metal complexes with bidentate ligands containing pyridine or quinoline moieties such as described in U.S. Patent No. 5,637,660; quinolinoxy or pyridinoxy-substituted Group 4 transition metal trihalides such as described in U.S. Patent No. 6,020,493; nickel complexes such as described by bis(ylide)nickel complexes such as described by Starzewski et al. in Angew. Chem. Int. Ed. Engl., 1987, 26, 63, and U.S. Patent No. 4,691 ,036; neutral N, O, P, or S donor ligands in combination with a nickel(O) compound and an acid such as described in WO 97/02298; aminobis(imino)phosphorane nickel catalysts such as described by Fink et al. in U.S. Patent No. 4,724,273.
[00085] Illustrative, non-limiting additional examples of various types of transition metal compounds that can be employed include the following:
2,6-bis-[1-(1-methylphenylimino)ethyl]pyridine iron[ll] chloride; 2,6-bis[1-(1-ethylphenylimino)ethyl]pyridine iron[ll] chloride; 2,6-bis[1-(1-isopropylphenylimino)ethyl]pyridine iron[ll] chloride; 2,6-bis-(1-(2-methylphenylimino)ethyl)pyridine iron(ll) chloride; N,N'-di(trimethylsilyl)benzamidinato copper(ll); tridentate Schiff base complexes of cobalt and iron described by Mashima in Shokubai 1999, vol. 41, p. 58; nickel compounds of the type described in U. S. Patent 5,880,323; nickel(ll) acetylacetonate; bis(acetonitrile)dichloro palladium(ll); bis(acetonitrile)bis(tetrafluoroborate)palladium(ll); (2,2'-bipyridine)dichloro palladium(ll); bis(cyclooctadienyl) nickel(O); palladium(ll) acetylacetonate; bis(salicylaldiminato) complexes of the type described by Matsui et. al. in Chemistry Letters 2000, pp. 554-555; cobalt dioctoate; cobaltocene;
(cyclopentadienyl)(triphenylphosphino)cobalt(ll) diiodide; nickel compounds of the type described in JP 09-272709; or any combination thereof. [00086] In one aspect of the present invention, transition metal compounds which can be used in forming the catalysts of this invention are transition metal compounds which can be represented by the formula:
MXnYm where M is a transition metal of Group 4 to 8 of the Periodic Table of Elements, including the lanthanide series and actinide series, and Y is, independently, a halide or pseudohalide, n is the valence of M, and m is an integer of from 0 to n-1. In one aspect of the present invention, pseudohalides are selected from alkoxide or oxyhalide groups. In one aspect of the present invention, M is a Group 4 metal. Non-limiting examples of suitable transition metal compounds include, but are not limited to, transition metal halides and oxyhalides such as titanium dibromide, titanium tribromide, titanium tetrabromide, titanium dichloride, titanium trichloride, titanium tetrachloride, titanium trifluoride, titanium tetrafluoride, titanium diiodide, titanium tetraiodide, zirconium dibromide, zirconium tribromide, zirconium tetrabromide, zirconium dichloride, zirconium trichloride, zirconium tetrachloride, zirconium tetrafluoride, zirconium tetraiodide, hafnium tetrafluoride, hafnium tetrachloride, hafnium tetrabromide, hafnium tetraiodide, hafnium trichloride, hafnium tribromide, hafnium triiodide, hafnium oxychloride, vanadium dichloride, vanadium trichloride, vanadium tetrachloride, vanadium trifluoride, vanadium tetrafluoride, vanadium pentafluoride, vanadium triiodide, vanadium oxytrichloride, vanadium oxytribromide, niobium pentabromide, niobium pentachloride, niobium pentafluoride, tantalum pentabromide, tantalum pentachloride, tantalum pentafluoride, chromous bromide, chromic bromide, chromous chloride, chromic chloride, chromous fluoride, chromic fluoride, molybdenum dibromide, molybdenum tribromide, molybdenum tetrabromide, molybdenum dichloride, molybdenum trichloride, molybdenum tetrachloride, molybdenum pentachloride, molybdenum hexafluoride, lanthanum trichloride, cerous fluoride, cerous chloride, cerous bromide, cerous iodide, eerie fluoride, uranium trichloride, uranium tetrachloride, uranium tribromide, uranium tetrabromide, thorium tetrachloride, thorium tetrabromide, or any combination thereof.
[00087] Among suitable alkoxides and mixed halide/alkoxides of the transition metals are Ti(OCHs)4, Ti(OC2H5)4> Ti(OC2H5)3CI, Ti(OC2H5)CI3, Ti(O-iso-C3H7)CI3, Ti(OC4Hg)3CI, Ti(OC3Hy)2Cl2, Ti(O-iso-C3H7)2CI2, Ti(OC17H18)2Br2, Zr(OC2H5)4, Zr(OC4Hg)4, Zr(OC5Hn)4, ZrCI3(OC2H5), ZrCI(OC4Hg)3, Hf(OC4Hg)4, Hf(OC4Hg)3CI, VO(OC2H5)3, Cr(O-iso- C4Hg)3, Mp(OC2H5)3, or any combination thereof. Other transition metal compounds which can be employed in the present invention include, but are not limited to, amides such as Ti(NMe2)4, Zr(NMe2)4, Ti(NEt2)4, Zr(NEt2)4, and Ti(NBu2)4; carboxylic acid salts such as titanium oxalate, cobalt acetate, chromium acetate, nickel formate, thallium oxalate, and uranyl formate; or any combination thereof. In one aspect of the present invention, the transition metal compounds are halides, oxyhalides, alkoxides, and mixed halide-alkoxides of the Group 4 to 6 metals. In another aspect, the transition metal compound is a trivalent or tetravalent Group 4 metal halide, or a vanadium oxyhalide. The Periodic Table of Elements referred to is that appearing on page 27 of the February 4, 1985 issue of Chemical & Engineering News.
Optional Support Materials
[00088] The catalyst composition can optionally be supported on any suitable organic or inorganic carrier. Support materials used in accordance with this invention can be any finely divided inorganic solid support, such as talc, clay, silica, alumina, silica-alumina, or any combination thereof. Support materials can also be particulate, organic resinous support materials including, but not limited to, spheroidal, particulate, or finely-divided polyethylene, polyvinylchloride, polystyrene, or any combination thereof.
[00089] The specific particle size, surface area and pore volume of the support material determine the amount of support material that is desirable to employ in preparing the catalyst compositions, as well as affecting the properties of polymers formed with the aid of the catalyst compositions. These properties are frequently taken into consideration in choosing a support material for use in a particular aspect of the invention. Preparation of the Catalyst Composition
[00090] This invention encompasses methods for preparing supported and unsupported catalyst compositions comprising contacting at least one stabilized haloaluminoxane composition and at least one complex of a transition metal of Groups 3 to 11 of the Periodic Table of Elements. In another aspect, the catalyst composition can be produced by contacting at least one aluminoxane compound, at least one halogenation agent, at least one additional alkylaluminum compound, and at least one complex of a transition metal of Groups 3 to 11 of the Periodic Table of Elements. In a further aspect of the present invention, the catalyst composition can be produced by contacting at least one haloaluminoxane compound, at least one additional alkylaluminum compound, and at least one complex of a transition metal of Groups 3 to 11 of the Periodic Table of Elements. In yet another aspect of the present invention, a supported catalyst composition can be produced by contacting at least one aluminoxane compound, at least one halogenation agent, at least one additional alkylaluminum compound, at least one complex of a transition metal of Groups 3 to 11 of the Periodic Table of Elements, and at least one organic or inorganic support material. In still a further aspect of the present invention, a supported catalyst composition can be produced by contacting at least one haloaluminoxane compound, at least one additional alkylaluminum compound, at least one complex of a transition metal of Groups 3 to 11 of the Periodic Table of Elements, and at least one organic or inorganic support material.. In these aspects, the supported or unsupported catalyst composition is obtained when the components are contacted in any sequence or order. For example, the components can be fed to a reactor or separate vessel separately, in any order, or any two or more can be premixed and fed as a mixture, with the remaining components being fed before, during, or after the mixture is fed to the reactor.
[00091] Unsupported catalyst compositions in accordance with the present invention can be produced by contacting the transition metal complex with the stabilized haloaluminoxane composition before, during, or after its formation. For example, before the stabilized haloaluminoxane composition is formed, the transition metal complex can be contacted with any one or any combination of (a) the at least one aluminoxane; (b) the at least one halogenation agent; or (c) the at least one additional alkylaluminum compound. Alternatively, the transition metal complex can be added at any time during the formation of the stabilized haloaluminoxane composition. Additionally, the transition metal complex can be contacted with the stabilized haloaluminoxane composition after it is formed. [00092] Temperatures for the preparation of unsupported catalyst compositions "of the present invention are in a range of about -1000C to about 3000C. In another aspect, preparation temperatures are in a range of about 00C to about 800C. Typically, the preparation is carried out at temperatures in a range of about 200C to about 500C, or at ambient room temperature. Holding times to allow for the completion of catalyst formation are in a range of about 10 seconds to about 60 minutes, depending on the reaction variables. [00093] Supported catalyst compositions are similarly formed by contacting the support material with the catalyst composition before, during, or after its formation. Preparation can include contacting, in any order, the transition metal compound, a stabilized haloaluminoxane composition, and a support material in one or more suitable solvents or diluents. Suitable solvents and/or diluents include, but are not limited to, straight and branched-chain hydrocarbons such as isobutene, butane, pentane,.hexane, heptane, or octane; cyclic and acyclic hydrocarbons such as cyclohexane, cycloheptane, methylcyclohexane, or methylcyclopentane; or aromatic and alkyl-substituted aromatic compounds such as benzene, toluene, or xylene. Mixtures of different types of solvents and/or diluents can also be used, such as a mixture of one or more acyclic aliphatic hydrocarbons and one or more cycloaliphatic hydrocarbons; a mixture of one or more acyclic aliphatic hydrocarbons and one or more aromatic hydrocarbons; a mixture of one or more cycloaliphatic hydrocarbons and one or more aromatic hydrocarbons; or a mixture of one or more acyclic aliphatic hydrocarbons, one or more cycloaliphatic hydrocarbons, and one or more aromatic hydrocarbons.
[00094] The support material can first be contacted with the stabilized haloaluminoxane composition to form a supported stabilized haloaluminoxane composition which is subsequently contacted with the transition metal complex. Alternatively, the support material can first be contacted with the transition metal complex to form a supported complex which is subsequently contacted with a stabilized haloaluminoxane composition. In another aspect of this invention, the stabilized haloaluminoxane composition and the transition metal complex can be contacted together, and the resulting composition can be subsequently contacted with a support material. In further aspect of the present invention, the support material can be contacted with either the stabilized haloaluminoxane composition or the transition metal complex during its formation. For example, the support material can be contacted with one or more of the components used to form the stabilized haloaluminoxane composition or with one or more of the components used to form the transition metal complex.
[00095] Because of the sensitivity of the catalyst components and catalyst compositions to moisture and oxygen, these components and compositions are generally handled under conventional inert atmospheres using substantially inert anhydrous materials, for example, in an environment that is substantially moisture-free and oxygen-free, such as, an argon, a nitrogen, or a helium environment. Temperatures for each stage of the preparation of supported catalyst compositions of this invention are in a range of about - 1000C to about 3000C. In another aspect, preparation temperatures are in a range of about 00C to about 80°C. Typically, the preparation is carried out temperatures in a range of about 200C to about 500C, or at ambient room temperature. Holding times to allow for the completion of catalyst formation can range from about 10 seconds to about 60 minutes, depending on the reaction variables.
[00096] Modified supported catalysts can be prepared in accordance with this invention by combining, in any order, at least one transition metal compound, at least one stabilized haloaluminoxane composition, at least one modifier, and a support material, in a suitable solvent and/or diluent. A modifier can be defined as any compound containing a Lewis acidic or basic functionality, for example, tetraethoxysilane, phenyltri(ethoxy)silane, bis- tert-butylhydroxytoluene (BHT), or N,N-dimethylaniline.
[00097] In one aspect of the present invention, the modified supported catalyst is formed by contacting a stabilized haloaluminoxane composition and the modifier in a suitable solvent to produce a slurry. A transition metal compound is subsequently added to the slurry. Suitable temperatures for these contacting steps are in a range of about -100°C to about 3000C, or, in another aspect of the present invention, a range of about 00C to about 100°C. Holding times to allow for the completion of the reaction can range from about 10 seconds to about 60 minutes, depending on the reaction variables. The mixture comprising the transition metal, modifier, and stabilized haloaluminoxane composition can then be contacted with the support material.
[00098] In the case of modified supported catalysts, the molar ratio of stabilized haloaluminoxane composition to transition metal compound is generally from about 1 :1 to about 20000:1 , or, in another aspect of the present invention, from about 10:1 to about 1000:1. The molar ratio of stabilized haloaluminoxane composition to modifier ranges from about 1 :1 to about 20000:1 , or, in another aspect of the present invention, from about 10:1 to about 1000:1. The concentration of transition metal compound on the support is typically between about 0.01 wt% to about 100 wt%, or, in another aspect of the present invention, from about 0.1 wt% to about 20 wt%, based upon the weight of the support. [00099] The amount of stabilized haloaluminoxane composition used varies depending upon the application and reaction conditions. The stabilized haloaluminoxane is typically used in an amount sufficient to produce molar ratio of aluminum atoms derived from the stabilized haloaluminoxane composition to transition metal is in the range of about 20:1 to about 2000:1. In another aspect, the molar ratio is from about 20:1 to about 500:1. [000100] The concentration of transition metal compound on the support is typically between about 0.01 wt% to about 100 wt%, or, in another aspect of the present invention, from about 0.1 wt% to about 20 wt%, based upon the weight of the support.
Polymerization Process
[000101] This invention encompasses a method for polymerizing olefin monomers comprising contacting under polymerization conditions at least one olefin monomer and a catalyst system comprising a stabilized haloaluminoxane composition of the present invention and at least one transition metal complex. Catalyst compositions in accordance with the present invention are useful for the homopolymerization or copolymerization of olefinic monomers, for example, σ-olefin monomers, cyclic olefin monomers, or vinylaromatic monomers.
[000102] Polymerizations using the catalysts of this invention can be carried out in any suitable manner known in the art. Such polymerization processes include, but are not limited to, slurry polymerizations, gas phase polymerizations, solution polymerizations, and the like, including multi-reactor combinations thereof. Thus, any polymerization zone known in the art to produce ethylene-containing polymers can be utilized. For example, a stirred reactor can be utilized for a batch process, or the reaction can be carried out continuously in a loop reactor or in a continuous stirred reactor. The polymerization reactor can be any suitable type of reactor, for example, a gas phase reactor, tubular reactor, solution phase reactor, or a combination of two or more reactors.
[000103] The polymerization reaction typically occurs in a substantially inert atmosphere, that is, in an atmosphere substantially free of oxygen and under substantially anhydrous conditions as the reaction begins. Therefore a dry, inert atmosphere, for example, dry nitrogen or dry argon, is typically employed in the polymerization reactor. Conventional temperatures for polymerization range from about 00C to about 16O0C and conventional pressures for polymerization range from about 1 kg/cm2 to about 50 kg/cm2. Generally, the polymerization can be carried out at both ambient temperature and pressure. [000104] For slurry polymerizations, a particulate catalyst is typically dispersed in a suitable liquid reaction medium which can be comprised of one or more ancillary solvents or an excess amount of liquid monomer. Suitable ancillary solvents include, but are not limited to, aliphatic and aromatic liquid hydrocarbons such as heptane, isooctane, decane, toluene, xylene, ethylbenzene, mesitylene, or any combination thereof. Slurry polymerization temperatures for this invention typically range from about 00C to about 1600C, with a polymerization reaction temperature more typically operating between about 400C to about 1100C. The polymerization can take place under atmospheric, subatmospheric, or superatmospheric conditions, or any other polymerization reaction condition that does not adversely affect the polymerization reaction. Typical diluents include, but are not limited to, isobutene, pentane, isopentane, hexane, heptane, toluene, or any combination thereof. [000105] Gas phase polymerizations are typically conducted at temperatures in the range of about 500C to 1600C, under superatmospheric pressures. However, the polymerization can take place at any temperature or pressure that does not adversely affect the polymerization reaction. These gas phase polymerizations can be performed in a stirred or fluidized bed of catalyst in a pressure vessel adapted to permit the separation of product particles from unreacted gases. Thermostated ethylene, comonomer, hydrogen, and an inert diluent gas such as nitrogen can be introduced or reciruclated to maintain the particles at the desired polymerization reaction temperature. An alkylaluminum, such as triethylaluminum, can be added as a scavenger of water, oxygen, and other impurities. In such cases, the alkylaluminum is typically employed as a solution in a suitable dry liquid hydrocarbon solvent such as toluene or xylene. Concentrations of such solutions are typically in the range of about 5 x 10"5 molar (M), but solutions of greater or lesser concentrations can be used. Polymer product can be withdrawn continuously or semi-continuously at a rate that maintains a constant product inventory in the reactor.
[000106] Polymerization reactions in accordance with the present invention are carried out using a catalytically effective amount of a catalyst composition of this invention. The amount of catalyst used depends on several factors, such as the type of polymerization being conducted, the polymerization conditions being used, and the type of reaction equipment in which the polymerization is being conducted. In one aspect of this invention, the catalyst composition is used in a range of about 0.000001 to about 0.01 percent by weight of transition, lanthanide, or actinide metal based on the weight of the monomer(s) being polymerized.
[000107] When conducting polymerization reactions pursuant to this invention, conditions can be used for preparing unimodal or multimodal polymers. For example, multimodal polymers can be produced by using a mixture of different catalysts having different propagation and termination rate constants.
[000108] After polymerization and deactivation of the catalyst, the product polymer can be recovered from the polymerization reactor by any suitable means. When conducting the process with a slurry or dispersion of the catalyst in a liquid medium, the product is typically recovered by a physical separation technique, for example, decantation. The recovered polymer is generally washed with one or more suitable volatile solvents to remove residual polymerization solvent or other impurities, and then dried, typically under reduced pressure, with or without the addition of heat. When conducting the process as a gas phase polymerization, the product after removal from the gas phase reactor is typically freed of residual monomer by means of a nitrogen purge, and can possibly be used without further catalyst deactivation or catalyst removal.
[000109] Polymers produced in accordance with this invention can be homopolymors, typically of α-olefins such as ethylene, propylene, 1-butene, styrene, or any combination thereof. Polymers can also be copolymers of two or more monomers, one of which is typically an α-olefin. Monomers useful in forming copolymers include one or mor& different a-o|efin, diolefin, cyclic olefin, or acetylenic monomers. Examples of olefins that can be polymerized in the presence of a catalyst composition of the present invention include, but are not limited to, α-olefins having from 2 to about 20 carbon atoms, such as ethylene, propylene, 1-butene, 1-hexenβ, 4-methyl-1-pentene, 1-octene, 1-deceπe, 1-dodeceneF 1- tetradecene, 1-hexadecene, or 1-octadecenβ. Typical diolefin monomers which can be used to form terpolymers with ethylene and propylene include, but are not limited to, butadiene, hexadiene, norbornadiene, or any combination thereof. Suitable acetylenic monomers include 1-heptyne or 1-octyne. In one aspect of the present invention, ethylene can be copolymerized with at least one α-olsfin having 3 to θ carbon atoms, for example, propylene. [00011 Q] As used herein, the phrase "any combination thereof includes any mixture of the components listed therein.
EXAMPLES
[000111] The following examples are presented for purposes of illustration, and are not intended to impose limitations on the scope of the invention. All experiments were conducted under dry nitrogen, with a water and oxygen content of less than about 1 ppm.
EXAMPLE 1
Treatment of fluorineted methylaluminaxane with 1 rnol% tri-n-octylaluminum [000112] A solution of fluorinatβd methylaluminoxane (FMAO) was prepared by treating a solution of about 30 wt% methylaluminoxane (MAO) in toluene with a sαlution of about 14.7 wt% dimethylaluminum fluoride (DMAF) in toluene. The ratio of fluorine (F) atoms to aluminum (Al) atoms in the resulting FMAO [DMAF] solution was about 4:100 and the overall aluminum content was about 12.9 wt%. About 16.7 g of the FMAO [DMAF] solution (2.15 g Al; 79.B mmol Al) was treated with about 0<30 g (0.Θ2 mmol) of tri-n- octylaluminum (TNOA) to provide approximately 1 mol% of the Al content from TNOA. The mixture was shaken and placed in the freezer at about -20βC. Na precipitation was SΘΘΠ after about 72 hours, although some precipitation was observed after about 7 days. The precipitate dissolved upon warming to ambient temperature (about 2Q0C to about 30°C). EXAMPLE 2
Treatment of flυoπnated methylsluminoxane with 2,5 mol% tri-n-ootylaluminυm [000113] About 14.5 g of tha FMAO [DMAF] solution prepared in Example 1 (1.87 g Al; 69.3 mmol Al) was treated with about 0.64 g (1.75 mmol) of TNOA to provide approximately 2,5 mol% of the Al content from TNOA. The mixture was shaken and placed in a freezer at about -20ήC. No precipitation was observed upon extended aging for a period of about 3 months.
EXAMPLE 3
Treatment of 'fluorinatθd methylaluminoxanβ with 1 mol% tri-n-octylaluminum [000114] A solution of FMAO was prepared by treating a solution of about 30 wt% MAO in toluene with a solution of trifluorotoluene (TFT) in toluene in an amount sufficient to produce a resulting FMAO [TFT] solution with a ratio of fluorine (F) atoms to aluminum (Al) atoms of about 4:100 and an overall aluminum content of about 10.5 wt%. About 17.6 g of the FMAO [TFT] solution (1.84 g Al; 68.3 mmol Al) was treated with about 0.26 g (0.71 mmol) of TNOA to provide approximately 1 mol% of the Al content from TNOA. The mixture was shaken and placed in the freezer at about -20DC. Precipitation was observed after about 30 minutes, but dissolved upon warming to ambient temperature (about 2O0C to about 3O0C).
EXAMPLE 4
Treatment offluoπnated methylaluminoxane with 2.5 mol% tri-n-octylaluminum [000115] About 16.Θ g of the FMAO [TFT] solution prepared in Example 3 (1.77 g Al; 65.8 mmol Al) was treated with about 0.60 g (1.64 mmol) of TNOA to provide approximately 2,5 mol% of the Al content from TNOA. The mixture was shaken and placed in the freezer at about -2QβC. No precipitation was observed after about 72 hours,
EXAMPLE 5
Large scale treatment of fluαrinated mβthylaluminoxane with -2.5- mol% tri-n-octylaluminum [000116] At a temperature of about O0C to about 5X1 a solution of FMAO was prepared by treating about 205.6 g of a solution of about 30 wt% MAO in toluene (13.B wt% Al; 28.4 g Al, 1.05 mol Al) with about 13.2 g of a solution of about 25.4 wt% DMAF in toluene (3.4 g DMAF; 1.2 g Al; 0.044 mol Al). The ratio of fluorine atoms to aluminum atoms in the resulting FMAO [DMAF] solution was about 4:100 and the overall aluminum content was about 13.5 wt%. About 9.79 g (0.027 mol) of TNOA was added to the FMAO [DMAF] solution with stirring to provide approximately 2.5 mαl% of the Al content from TNOA. The solution was allowed to warm to ambient temperature (about 20αC to about 300C) over a period of about 30 minutes. The mixture was placed in the freezer at about -200C. No precipitation was observed upon prolonged chilling for a period of greater than about 3 months,
EXAMPLE 6 Large scale treatment αffluorinatθcj methylaluminαxanθ with 2.5 mol% tή-n-octylaluminum
[000117] While stirring at ambient temperature, about 194,5 g of the FMAO [TFT] solution prepared in Example 3 (20.4 g Al; 0.76 mol Al) was treated with about 7.1 g (0.019 mol) of neat TNOA to provide approximately 2.5 mol% of the Al content from TNOA. The mixture was stirred for an additional 30 minutes at ambient temperature (about 20 "C to about 3Q"C) and placed in the freezer at about -206C. No precipitation was observed upon prolonged chilling for a period of greater than about 3 months.
COMPARATIVE EXAMPLE 7 Precipitation of standard haloaluminoxanes at low&r temperatures
[000118] Samples of the untreated FMAO solutions prepared in Examples 1 and 3 were placed in the freezer. Solid formation was observed at approximately -120C for the FMAO [DMAF] solution from Example 1 and approximately -6DC for the FMAO [TFT] solution from Example 3. As the mixtures were warmed, the solids dissolved and clear solutions were seen for both samples at about O0C
EXAMPLE θ Comparison of accelerated aging for stabilized and conventional haloaliiminoxanes
[000119] Six haloaluminoκane samples were prepared in a manner similar to that described in Examples 1-7 to provide the samples listed in Table I:
TABLE I
Figure imgf000045_0001
[000120] Each sample had a ratio of fluorine atoms to aluminum atoms of about 4:100. Sealed tubes of these samples were placed in an oil bath at a temperature of about 45flC for up to 3 months. Irreversible gel formation was evaluated for each sample. Figure 1 shows the gel formation in each sample at 45DC as a function of time. As indicated in the graph, Samples 4 and 6 (stabilized haloalumiπoxanes) show reduced irreversible gel formation as compared to corresponding conventional haloaluminoxanes at elevated temperatures. The precipitates observed in each sample did not redissolva.
EXAMPLE θ
Comparison of activator efficiency far stabilized haloaluminoxanes and conventional aluminoxanβs
[000121] Sample 4 and Sample 6 were used as co-catalysts in the polymerization o1 ethylene and compared to a MAO standard (13,6 wt% Ai). Ethylene-bis(indenyl)zirconium dimethyl was employed as the polymerization catalyst and added in an amount to provide about 2.15 micromoles of zirconium in the reactor. In each trial, co-catalyst was added in an amount sufficient to produce a ratio of aluminum (Al) atoms to zirconium (Zr) atoms of about 400:1. The reactor was maintained at a temperature of about 135°C and an ethylene pressure of about 140 pounds/square inch (psi), with about 1 mL of approximately 10 wt% triisobutylaluminum in isohexane used as a scavenger. The results of each polymerization run after a polymerization time of about 30 minutes are indicated in Table II; Table Il
Figure imgf000046_0001
[000122] As shown in the table, the stabilized haloaluminoxanes have comparable, if not better, activator efficiencies than standard aluminoxanes.

Claims

1. A haloaluminoxane composition comprising a contact product of at least one aluminoxane, halogen atoms derived from a halogenation agent, and at least one additional alkylaluminum compound, wherein the amount of additional alkylaluminum compound present in the composition is in a range of about 1 mole % to about 5 mole % relative to the total composition.
2. A composition according to Claim 1 , wherein the additional alkylaluminum compound has at least one alkyl group having at least two carbon atoms.
3. A composition according to Claim 1 , wherein the composition is a contact product of:
(a) at least one aluminoxane;
(b) at least one halogenation agent which is:
(i) at least one halohydrocarbon having the general formula RnCX4-11, (ii) at least one siloxane having at least one labile halogen atom in the molecule, wherein each halogen atom is, independently, fluorine, chlorine, or bromine,
(iii) at least one silane having the general formula R1 I1SiX4-11,
(iv) at least one tin compound having the general formula RVSnX4-0,
(v) at least one hydrocarbylaluminum halide having the general formula
R'mAIX3-m, or
(vi) any mixture thereof; and
(c) at least one additional alkylaluminum compound having the general formula AIR"nQ3-n; wherein: m is 1 or 2, n is 1 , 2 or 3, inclusive,
X is, independently, a fluorine, a chlorine, or a bromine atom, .
Q is, independently, a halide, a pseudohalide, or hydride,
R is, independently, a hydrogen atom, a hydrocarbyl group having from one to about, twenty carbon atoms, or a halohydrocarbyl group having from one to about twenty carbon atoms,
R1 is, independently, a hydrocarbyl group having from one to about twenty carbon atoms or a halohydrocarbyl group having from one to about twenty carbon atoms,
R" is an alkyl group having from two to about twenty carbon atoms.
4. A composition according to Claim 1 , wherein the amount of halogen atoms present in said composition is in a range of about 0.5 mole % to about 15 mole % relative to aluminum atoms derived from the at least one aluminoxane.
5. A composition according to Claim 1 , wherein the halogen is fluorine, chlorine, or bromine.
6. A composition according to Claim 1 , wherein the aluminoxane has saturated hydrocarbyl groups having from one to about twenty carbon atoms.
7. A composition according to Claim 1 , wherein said aluminoxane is methylaluminoxane, ethylaluminoxane, n-butylaluminoxane, or isobutylaluminoxane.
8. A composition according to Claim 1 , wherein the aluminoxane is methylaluminoxane and the halogen is fluorine.
9. A composition comprising the aluminoxane composition of Claim 1 and at least one support material.
10. A composition according to Claim 9, wherein the support material is silica, alumina, silica-alumina, clay, a modified clay composition, or any combination thereof.
11. A composition according to Claim 9, wherein the support material is spheroidal, particulate, or finely-divided polyethylene, polyvinylchloride, polystyrene, or any combination thereof.
12. A composition according to Claim 1 , wherein the additional alkylaluminum compound has the general formula AIR"mX3-m, wherein m is 1 or 2, inclusive;
X is, independently, a fluorine, a chlorine, or a bromine atom; and
R" is an alkyl group having from two to about twenty carbon atoms.
13. A composition according to Claim 1 , wherein the additional alkylaluminum compound is tri-n-octylaluminum.
14. A catalyst composition comprising the composition of Claim 1 and at least one complex of a transition metal of Groups 3, 4, 5, 6, 7, 8, 9, 10, or 11 of the Periodic Table of Elements, including the Ianthanide series and the actinide series.
15. A catalyst composition according to Claim 14, further comprising a support material.
16. A composition according to Claim 1 , wherein the composition is substantially free of gel formation for at least about thirty days at temperatures ranging from about -300C to about 600C.
17. A composition according to Claim 1 , wherein the composition exhibits less than about 10 wt.% gel formations for at least about thirty days at temperatures in a range of about -300C to about 60°C.
18. A composition according to Claim 1 , wherein the composition is substantially free of gel formation for at least about thirty days at temperatures in a range of about -200C to about 45°C.
19. A composition according to Claim 1 , wherein the composition exhibits less than about 10 wt. % gel formation for at least about thirty days at temperatures in a range of about -20°C to about 45°C.
20. A haloaluminoxane composition comprising at least one haloaluminoxane and at least one additional alkylaluminum compound, wherein the amount of additional alkylaluminum compound present in the composition is in a range of about 1 mole % to about 5 mole % relative to the total composition.
21. A composition according to Claim 20, wherein the additional alkylaluminum compound has at least one alkyl group having at least two carbon atoms.
22. A composition according to Claim 20, wherein the haloaluminoxane is a partially halogenated aluminoxane.
23. A haloaluminoxane composition comprising a contact product of at least one aluminoxane, halogen atoms derived from a halogenation agent, and at least one additional alkylaluminum compound, wherein the amount of additional alkylaluminum compound present in the composition is at least about 1 mole % relative to the total composition.
24. A haloaluminoxane composition comprising a contact product of at least one haloaluminoxane and at least one additional alkylaluminum compound, wherein the amount of additional alkylaluminum compound present in the composition is at least about 1 mole % relative to the total composition.
25. A haloaluminoxane composition which is substantially free of gel formation for at least about thirty days at temperatures in a range of about -300C to about 600C.
26. A haloaluminoxane composition comprising the contact product of:
(a) at least one aluminoxane;
(b) at least one halogenation agent which is:
(i) at least one halohydrocarbon having the general formula RnCX4-H, -■ (ii) at least one siloxane having at least one labile halogen atom in the molecule, wherein each halogen atom is, independently, fluorine, chlorine, or bromine,
(iii) at least one silane having the general formula RYiSiX4-11,
(iv) at least one tin compound having the general formula RV1SnX4-0,
(v) at least one hydrocarbylaluminum halide having the general formula
R'mAIXs-m, or
(vi) any mixture thereof; and
(c) at least one additional alkylaluminum compound having the general formula
AIR"nQ3-n; wherein: m is 1 or 2, n is 1 , 2, or 3, inclusive,
X is, independently, a fluorine, a chlorine, or a bromine atom,
R is, independently, a hydrogen atom, a hydrocarbyl group having from one to about twenty carbon atoms, or a halohydrocarbyl group having from one to about twenty carbon atoms, R' is, independently, a hydrocarbyl group having from one to about twenty carbon" atoms or a halohydrocarbyl group having from one to about twenty carbon atoms, R" is an alkyl group having from two to about twenty carbon atoms.
27. A process to produce a haloaluminoxane composition comprising contacting, in a substantially inert, substantially anhydrous environment:
(d) at least one aluminoxane;
(b) at least one halogenation agent which is:
(i) at least one halohydrocarbon having the general formula RnCX4-0, (ii) at least one siloxane having at least one labile halogen atom in the molecule, wherein each halogen atom is, independently, fluorine, chlorine, or bromine,
(iii) at least one silane having the general formula RV1SiX4-,,,
(iv) at least one tin compound having the general formula R'nSnX4-n,
(v) at least one hydrocarbylaluminum halide having the general formula R'mAIX3-m, or
(iv) any mixture thereof; and
(c) at least one additional alkylaluminum compound having the general formula AIR"nQ3-n, wherein: m is 1 or 2, n is 1, 2, or 3, inclusive,
X is, independently, a fluorine, a chlorine, or a bromine atom,
Q is, independently, a halide, a pseudohalide, or hydride,
R is, independently, a hydrogen atom, a hydrocarbyl group having from one to about twenty carbon atoms, or a halohydrocarbyl group having from one to about twenty carbon atoms;
R1 is, independently, a hydrocarbyl group having from one to about twenty carbon atoms or a halohydrocarbyl group having from one to about twenty carbon atoms, and
R" is an alkyl group having from two to about twenty carbon atoms.
28. A process according to Claim 27, wherein the halogenation agent is at least one siloxane, at least one silane, at least one tin compound, or at least one hydrocarbylaluminum halide.
29. A process according to Claim 28, wherein the at least one siloxane is a trisiloxane or a tricyclosilixane.
30. A process for producing a polyolefin polymer comprising contacting, under polymerization conditions, at least one olefinic monomer and the catalyst composition of Claim 14.
PCT/US2006/024778 2005-07-01 2006-06-26 Haloaluminoxane compositions WO2007005364A2 (en)

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Publication number Priority date Publication date Assignee Title
JP2010538130A (en) * 2007-08-29 2010-12-09 アルベマール・コーポレーシヨン Aluminoxane catalyst activators derived from dialkylaluminum cation precursors, processes for producing the same, and their use in olefin catalysis and polymerization
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WO2013162745A1 (en) 2012-04-27 2013-10-31 Albemarle Corporation Activator compositions, their preparation, and their use in catalysts

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