WO2007005364A2 - Compositions d'haloaluminoxane - Google Patents

Compositions d'haloaluminoxane Download PDF

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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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composition
carbon atoms
haloaluminoxane
independently
general formula
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PCT/US2006/024778
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WO2007005364A3 (fr
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Rajeev S. Mathur
Samuel A. Sangokoya
Lubin Luo
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Albemarle Corporation
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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

La présente invention concerne des compositions d'haloaluminoxane stabilisées, des procédés pour préparer des compositions d'haloaluminoxane stabilisées, des compositions de catalyseur comprenant des compositions d'haloaluminoxane stabilisées, ainsi que des procédés pour polymériser des oléfines en utilisant des compositions de catalyseur comprenant des compositions d'haloaluminoxane stabilisées. Les compositions d'haloaluminoxane stabilisées selon cette invention sont moins enclines à la dégradation à des températures supérieures et inférieures que des aluminoxanes et des haloaluminoxanes conventionnels. Les compositions d'haloaluminoxane stabilisées sont formées à partir d'au moins un aluminoxane, d'au moins un agent d'halogénation et d'au moins un composé alkylaluminium supplémentaire. La quantité de composé alkylaluminium supplémentaire présent dans la composition s'élève à au moins environ 1 %molaire par rapport à la composition totale.
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JP2010538130A (ja) * 2007-08-29 2010-12-09 アルベマール・コーポレーシヨン ジアルキルアルミニウム陽イオンの前駆剤から生じるアルミノキサン触媒活性剤、同物質の製造方法、ならびにオレフィンの触媒および重合におけるその用途
WO2012071205A2 (fr) 2010-11-22 2012-05-31 Albemarle Corporation Compositions d'activateurs, leur préparation et leur utilisation en catalyse
WO2013162745A1 (fr) 2012-04-27 2013-10-31 Albemarle Corporation Compositions d'activateur, leur préparation et leur utilisation dans des catalyseurs

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010538130A (ja) * 2007-08-29 2010-12-09 アルベマール・コーポレーシヨン ジアルキルアルミニウム陽イオンの前駆剤から生じるアルミノキサン触媒活性剤、同物質の製造方法、ならびにオレフィンの触媒および重合におけるその用途
US8354485B2 (en) 2007-08-29 2013-01-15 Albemarle Corporation Aluminoxane catalyst activators derived from dialkylaluminum cation precursor agents, processes for making same, and use thereof in catalysts and polymerization of olefins
US8575284B2 (en) 2007-08-29 2013-11-05 Albemarle Corporation Aluminoxane catalyst activators derived from dialkylaluminum cation precursor agents, processes for making same, and use thereof in catalysts and polymerization of olefins
WO2012071205A2 (fr) 2010-11-22 2012-05-31 Albemarle Corporation Compositions d'activateurs, leur préparation et leur utilisation en catalyse
US8895465B2 (en) 2010-11-22 2014-11-25 Albemarle Corporation Activator compositions, their preparation, and their use in catalysis
WO2013162745A1 (fr) 2012-04-27 2013-10-31 Albemarle Corporation Compositions d'activateur, leur préparation et leur utilisation dans des catalyseurs

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