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WO1999030821A1 - Catalyst compositions for olefin polymerization based on metallocene complexes and novel cocatalysts produced from trialkylaluminum compounds, sterically hindered phenols, and water - Google Patents

Catalyst compositions for olefin polymerization based on metallocene complexes and novel cocatalysts produced from trialkylaluminum compounds, sterically hindered phenols, and water Download PDF

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Publication number
WO1999030821A1
WO1999030821A1 PCT/US1998/024538 US9824538W WO9930821A1 WO 1999030821 A1 WO1999030821 A1 WO 1999030821A1 US 9824538 W US9824538 W US 9824538W WO 9930821 A1 WO9930821 A1 WO 9930821A1
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group
catalyst composition
ratio
groups
mmol
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PCT/US1998/024538
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French (fr)
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Yuri Viktorovich Kissin
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Mobil Oil Corporation
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Priority to AU14165/99A priority Critical patent/AU1416599A/en
Publication of WO1999030821A1 publication Critical patent/WO1999030821A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
    • B01J31/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
    • B01J31/143—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron of aluminium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2282—Unsaturated compounds used as ligands
    • B01J31/2295—Cyclic compounds, e.g. cyclopentadienyls
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
    • B01J2531/46—Titanium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
    • B01J2531/48—Zirconium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
    • B01J2531/49—Hafnium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
    • C08F4/65922—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not
    • C08F4/65927—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not two cyclopentadienyl rings being mutually bridged

Definitions

  • the invention relates to new catalyst compositions for olefin polymerization.
  • the invention relates to new cocatalysts for activating metallocene complexes of transition metals as olefin polymerization catalysts.
  • Catalyst compositions comprising metallocene complexes activated by alkylalumoxane cocatalysts (or activators), were introduced to the art of polymerization catalysis in the mid-1970s.
  • Alkylalumoxanes exhibit several inherent problems in use, such as a need for high [alumoxane]: [metallocene] ratios to produce highly active catalyst compositions, high reactivity towards impurities in feeds (such as moisture, alcohols, etc.) and flammability. Accordingly, some of the developments in this area of catalysis involved a search for alternative cocatalysts capable of activating metallocene complexes.
  • the class of alkylalumoxanes comprises oligomeric linear and/or cyclic compounds represented by the formulas R-[AI(R)-O] justify-AIR 2 for linear oligomeric alumoxanes and [-AI(R)-O-] for cyclic oligomeric alumoxanes where R is a C ⁇ -C 8 alkyl group. If R is the methyl group, the compound is called methylalumoxane or MAO. MAO has been the most popularly used cocatalyst in metallocene catalyst systems.
  • the present patent application describes catalyst systems for olefin polymerization based on metallocene complexes of zirconium, hafnium, or titanium which are activated by novel cocatalysts formed in reactions between trialkylaluminum compounds, sterically hindered 2,6-disubstituted phenols and water.
  • the invention relates to catalyst compositions for olefin polymerization comprising metallocene complexes and the cocatalysts of the invention.
  • the catalyst compositions may be homogeneous catalysts or a supported heterogeneous catalysts which comprise activated metallocene catalysts.
  • the metallocene complexes have the formula Cp x MA y B z in which Cp is an unsubstituted or substituted cyclopentadienyl group; M is zirconium, titanium or hafnium; and A and B belong to the group including a halogen atom, a hydrogen atom or an alkyl group.
  • the preferred transition metal atom M is zirconium.
  • the Cp group is an unsubstituted, a monosubstituted, disubstituted or a polysubstituted cyclopentadienyl group: and x is at least 1 and preferably is 2.
  • the substituents on the cyclopentadienyl group can be preferably linear or branched Ci- C 6 alkyl groups.
  • the cyclopentadienyl groups can also be a part of a bicyclic or a tricyclic moiety such as indenyl, tetrahydroindenyl, fluorenyl or a partially hydrogenated fluorenyl group, as well as a part of other substituted bicyclic or tricyclic moieties.
  • the cyclopentadienyl groups can be also bridged by polymethylene or dialkylsilyl groups such as -CH 2 -, -CH 2 -CH 2 -, -CR'R"- and -CR'R"-CR'R"- where R' and R" are short alkyl or phenyl groups or hydrogen atoms, -Si(CH 3 ) 2 -, -Si(C 6 H 5 ) 2 -, -Si(CH 3 )2-CH 2 -CH2-Si(CH 3 )2-. and similar bridging groups.
  • a and B substituents in the above formula of a metallocene complex are halogen atoms, they belong to the group of fluorine, chlorine, bromine or iodine; and y + z is 3 or less, provided that x + y + z equals the valence of M.
  • substituents A and B in the above formula of the metallocene complex are alkyl groups, they are preferably linear or branched C ⁇ -C 8 alkyl groups, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, ⁇ -hexyl or /7-octyl.
  • Suitable metallocene compounds include: bis(cyclopentadienyl)metal dihalides, bis(cyclopentadienyl)metal hydridohalides, bis(cyclopentadienyl)metal monoalkyl monohalides, bis(cyclopentadienyl)metal dialkyls, bis(indenyl)metal diahalides bis(tetrahydroindenyl)metal dihalides, and bis(fluorenyl)metal dihalides, wherein the metal is titanium, zirconium, or hafnium atoms; halide atoms are preferably chlorine; and the alkyl groups are d-C 6 alkyl groups.
  • metallocene complexes include bis(cyclopentadienyl)zirconium dichloride, bis(cyclopentadienyl)titanium dichloride, bis(cyclopentadienyl)hafnium dichloride, bis(cyclopentadienyl)zirconium dimethyl, bis(cyclopentadienyl)hafnium dimethyl, bis(cyclopentadienyl)zirconium hydridochloride, bis(cyclopentadienyl)hafnium hydridochloride, bis(/7-butylcyclopentadienyl)zirconium dichloride, bis(/7-butylcyclopentadienyl)hafnium dichloride, bis(/?-butylcyclopentadienyl)zirconium dimethyl, bis(n-butylcyclopentadienyl)hafnium dimethyl, bis(A7-but
  • Cocatalysts for metallocene complexes used in this invention are synthesized in reactions involving trialkylaluminum compounds, sterically hindered phenols, and water.
  • the trialkylaluminum compounds used for the preparation of the cocatalysts have the general formula of AIR 3 , wherein R are alkyl groups such as methyl, ethyl, n- propyl, ⁇ -butyl, isobutyl, n-hexyl, or n-octyl group.
  • the preferred trialkylaluminum compound is trimethylaluminum (TMA).
  • the sterically hindered phenols or polyphenols P ⁇ OH used for the preparation of the cocatalysts of the invention contain at least two substituents which are situated in the 2-nd and the 6-th positions of the benzene ring with respect to the hydroxyl group and are bulky alkyl, aryl, or alkylaryl groups such as a fe/ -butyl group, a phenyl group, or a benzyl group. It is noted that the empirical formula PhOH is used interchangeably with the phrase "sterically hindered phenols or polyphenols" herein.
  • the preferred substituents in the phenols are ferf-butyl and phenyl groups.
  • phenols include: 2,6-di-ferf-butylphenol, 2,6-diisopropylphenol, 2,6-diphenylphenol, 2,6-di-te/f-butyl-4-methylphenol, 2,6-diisopropyl ⁇ 4-methylphenol, 2,2-methylene-bis(2-terf-butyl-4-methylphenol), and 1 ,3,5-trimethyl-2,4,6-tris(3,5-di-ferf-butyl-4-hydroxybenzyl)benzene.
  • the sterically hindered phenol is reacted with a trialkylaluminum compound AIR 3 .
  • the reaction can be carried out in solution in a nonpolar solvent, such as a paraffinic hydrocarbon, a cycloalkane or an aromatic hydrocarbon, or with a neat trialkylaluminum compound, in a broad range of temperatures, from sub-zero to elevated temperatures.
  • the optimum reaction temperatures are from 10 to 70°C.
  • the reaction proceeds vigorously with the formation of an alkane RH.
  • the alkane RH evolves as a gas. It can be assumed that the reaction can be described by the following equations:
  • P ⁇ OH can vary from 10:1 to 1 :2; the most preferred ratio is 1 :1.
  • the product of the first stage is contacted with water.
  • This stage of the reaction can be carried out in the same solvent as that used in the first stage, in a broad range of temperatures, from sub-zero to elevated temperatures.
  • the optimum reaction temperatures are from 10 to 70°C.
  • the reaction is relatively slow and requires, depending on temperature, from 15 to 60 minutes to come to completion. It can be monitored by observing slow disappearance of drops of water on the bottom of the reaction vessel. The total amount of water can be added to the reaction vessel in one step or in several consecutive steps.
  • the catalyst compositions of the invention can be used at the ratios between the amounts of the cocatalyst and a metallocene complex represented by the molar ratio between the Al compound used for the cocatalyst preparation and M in the metallocene complex in the [AI]coca.aiyst:[M] m ⁇ t a ⁇ iocene range from 20,000 to 1.0, preferably from 5,000 to 100.
  • the catalyst compositions may be formed from the metallocene complexes and the cocatalysts of this invention prior to their introduction into a polymerization reactor or in situ in a reactor by contacting the cocatalyst with a metallocene complex.
  • the support may be contacted with the cocatalyst to form the first contact product and then with the metallocene complex to form the second contact product; or the support can be contacted with the metallocene complex first and then with the cocatalyst.
  • the catalyst components, the metallocene complex and the cocatalyst of the invention can be pre-contacted and then impregnated into the support.
  • the catalyst of the invention is a supported particulate catalyst, it comprises 0.01 to 4.0 wt. %, preferably 0.1 to 2.0 wt. % transition metal provided by a metallocene complex.
  • Catalyst systems of the invention containing reaction products of trialkylaluminum compounds, sterically hindered phenols and water as cocatalysts and metallocene complexes of transition metals are highly active in various polymerization and copolymerization reactions of ethylene and alpha-olefins. If the [AIR 3 ]:[phenol] ratio used during the cocatalyst preparation is below 0.2:1 , the cocatalysts and the catalyst compositions based on them are air-stable and are not flammable, in contrast to trialkylaluminum compounds.
  • the catalysts of this invention can be fed to a solution reactor, a slurry reactor or a fluidized-bed gas-phase reactor for polymerization and copolymerization of ethylene and alpha-olefins.
  • the temperature of polymerization can range from 25° to 125°C, but more generally between 50° and 115°C, at pressures of less than 10000 psi.
  • the catalysts can be used, for example, to produce high density polyethylene resins or linear low density polyethylene resins which are copolymers of ethylene and higher alpha-olefins such as 1 -butene, 1 -pentene, 1 -hexene, 1 -octene, 4-methyl-1 - pentene, etc.
  • Such copolymers contain at least 80 wt.% of ethylene.
  • Examples 1-5 describe cocatalyst synthesis based on 2,6-di-ferf-butylphenol and trimethylaluminum at various [Phenol]: [AIMe 3 ]:[H 2 O] ratios.
  • Example 1 2,6-di-terf-butylphenol (DBP) in an amount of 0.551 g (2.7 mmol) was dissolved in 3 cc of toluene, the solution was flushed with purified nitrogen and slowly added to a 25-cc glass bottle sealed with a rubber septum and containing a mixture of 2 cc of 1.35 M solution of trimethylaluminum (TMA) in heptane and 5 cc of toluene. A rapid reaction ensued resulting in methane evolution (the gas was released from the bottle through a syringe needle); the reaction product remained dissolved in toluene.
  • DBP 2,6-di-terf-butylphenol
  • TMA trimethylaluminum
  • Example 2 A reaction between DBP (5.4 mmol) and TMA (2.7 mmol) was carried under conditions similar to those in Example 1 at an [DBP]:[TMA] ratio of 2:1 resulting in the formation of methylaluminum diphenoxide [CHsAI(OP 7) 2 ]. To bring the reaction to completion, the bottle was kept at 70°C for 30 minutes. Then the solution was cooled to room temperature and neat water was added to it in an amount of 24 ⁇ l (1.35 mmol) to achieve an [H 2 O]:[AI] ratio of 0.5. A relatively slow reaction with methane evolution continued for ca. 20 minutes and resulted in the formation of a uniform, light purple solution apparently containing tetraphenyldialuminate (P ⁇ O) 2 AI- O-AI(OP ⁇ ) 2 .
  • P ⁇ O tetraphenyldialuminate
  • Example 3 A similar reaction between DBP (2.7 mmol) and TMA (2.7 mmol) was carried at an [DBP]:[TMA] ratio of 1:1 resulting in the formation of (CH 3 ) 2 AI(OP ⁇ ). Then neat water was added to the solution in an amount of 24 ⁇ l (1.35 mmol) to achieve an [H 2 O]:[AI] ratio of 0.5. A reaction of methane evolution continued for Ca. 10 minutes and resulted in the formation of a uniform, magenta-colored solution apparently containing methylphenoxydialumoxane (P ⁇ O)(CH 3 )AI-O-AI(CH 3 )(OP/7).
  • P ⁇ O methylphenoxydialumoxane
  • Example 4 A similar reaction between DBP (2.7 mmol) and TMA (2.7 mmol) was carried in a toluene medium at an [DBP]:[TMA] ratio of 1 :1 resulting in the formation of (CH 3 ) 2 AI(OP ⁇ ). Then neat water was added to the solution in two steps, first in an amount of 24 ⁇ l (1.35 mmol) to achieve an [H 2 O]:[AI] ratio of 0.5 and apparently to produce methylphenoxydialumoxane
  • Example 5 A similar reaction between DBP (2.7 mmol) and TMA (2.7 mmol) was carried in a toluene medium at an [DBP]: [TMA] ratio of 1 :1 resulting in the formation of (CH 3 ) 2 AI(OP/7). Then neat water was added to the solution in two steps, first in an amount of 24 ⁇ l (1.35 mmol) to achieve an [H 2 O]:[AI] ratio of 0.5 and apparently to produce methylphenoxydialumoxane (P ⁇ O)(CH 3 )AI-O-AI(CH 3 )(OP/7) and then, in the second step, in an amount of 24 ⁇ l (1.35 mmol) to reach the total [H 2 O]:[AI] ratio of 1:1. Examples 6-8 describe cocatalyst syntheses based on 2,6-di-te/f-butylphenol and different organoaluminum compounds.
  • Example 6 DBP in an amount of 0.551 g (2.7 mmol) was dissolved in 3 cc of toluene, the solution was flushed with purified nitrogen and slowly added to a 25-cc glass bottle sealed with a rubber septum and containing a mixture of 1.8 cc of 1.53 M solution of triethylaluminum (TEAL) in heptane and 5 cc of toluene. A reaction ensued resulting in ethane evolution (the gas was released from the bottle through a syringe needle); the reaction product remained dissolved in toluene.
  • TEAL triethylaluminum
  • Example 7 A reaction between DBP (2.7 mmol) and triisobutylaluminum (TIBA, 2.7 mmol) was carried under similar conditions in a toluene medium at an [DBP]:[AI/-Bu 3 ] ratio of 1 :1 (practically no gas evolution was observed) resulting in the formation of an (/-C 4 H 9 ) 2 AI-OP? compound.
  • Examples 9 and 10 describe cocatalyst synthesis based on different hindered phenols and trimethylaluminum.
  • Example 9 2,6-diphenylphenol in an amount of 0.664 g (2.7 mmol) was dissolved in 5 cc of toluene, the solution was flushed with purified nitrogen and slowly added to a 25-cc glass bottle sealed with a rubber septum and containing a mixture of 2.0 cc of 1.35 M solution of TMA in heptane and 5 cc of toluene. A reaction ensued resulting in a gradual methane evolution (the gas was released from the bottle through a syringe needle); the reaction product remained dissolved in toluene.

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Abstract

Catalyst compositions comprising metallocene complexes of a transition metal of the formula CpxMAyBz and a cocatalyst synthesized in reactions between trialkylaluminum compounds, sterically hindered 2,6-disubstituted phenols, and water.

Description

CATALYST COMPOSITIONS FOR OLEFIN POLYMERIZATION BASED
ON METALLOCENE COMPLEXES AND NOVEL COCATALYSTS
PRODUCED FROM TRIALKYLALUMINUM COMPOUNDS,
STERICALLY HINDERED PHENOLS, AND WATER
The invention relates to new catalyst compositions for olefin polymerization. In particular, the invention relates to new cocatalysts for activating metallocene complexes of transition metals as olefin polymerization catalysts.
Catalyst compositions comprising metallocene complexes activated by alkylalumoxane cocatalysts (or activators), were introduced to the art of polymerization catalysis in the mid-1970s. Alkylalumoxanes exhibit several inherent problems in use, such as a need for high [alumoxane]: [metallocene] ratios to produce highly active catalyst compositions, high reactivity towards impurities in feeds (such as moisture, alcohols, etc.) and flammability. Accordingly, some of the developments in this area of catalysis involved a search for alternative cocatalysts capable of activating metallocene complexes.
The class of alkylalumoxanes comprises oligomeric linear and/or cyclic compounds represented by the formulas R-[AI(R)-O]„-AIR2 for linear oligomeric alumoxanes and [-AI(R)-O-] for cyclic oligomeric alumoxanes where R is a Cι-C8 alkyl group. If R is the methyl group, the compound is called methylalumoxane or MAO. MAO has been the most popularly used cocatalyst in metallocene catalyst systems.
It is an object of this invention to develop alternative cocatalysts for metallocene complexes, cocatalysts which synthesis does not require the use of MAO as a starting compound. The present patent application describes catalyst systems for olefin polymerization based on metallocene complexes of zirconium, hafnium, or titanium which are activated by novel cocatalysts formed in reactions between trialkylaluminum compounds, sterically hindered 2,6-disubstituted phenols and water.
The invention relates to catalyst compositions for olefin polymerization comprising metallocene complexes and the cocatalysts of the invention. The catalyst compositions may be homogeneous catalysts or a supported heterogeneous catalysts which comprise activated metallocene catalysts.
Contact of the cocatalysts and the metallocene complexes can occur prior to, or concurrently with, introduction of the metallocene complexes into a polymerization reactor.
The metallocene complexes have the formula CpxMAyBz in which Cp is an unsubstituted or substituted cyclopentadienyl group; M is zirconium, titanium or hafnium; and A and B belong to the group including a halogen atom, a hydrogen atom or an alkyl group. In the above formula of the metallocene complex, the preferred transition metal atom M is zirconium. In the above formula of the metallocene complex, the Cp group is an unsubstituted, a monosubstituted, disubstituted or a polysubstituted cyclopentadienyl group: and x is at least 1 and preferably is 2. The substituents on the cyclopentadienyl group can be preferably linear or branched Ci- C6 alkyl groups. The cyclopentadienyl groups can also be a part of a bicyclic or a tricyclic moiety such as indenyl, tetrahydroindenyl, fluorenyl or a partially hydrogenated fluorenyl group, as well as a part of other substituted bicyclic or tricyclic moieties. In the case when x is equal to 2, the cyclopentadienyl groups can be also bridged by polymethylene or dialkylsilyl groups such as -CH2-, -CH2-CH2-, -CR'R"- and -CR'R"-CR'R"- where R' and R" are short alkyl or phenyl groups or hydrogen atoms, -Si(CH3)2-, -Si(C6H5)2-, -Si(CH3)2-CH2-CH2-Si(CH3)2-. and similar bridging groups. If the A and B substituents in the above formula of a metallocene complex are halogen atoms, they belong to the group of fluorine, chlorine, bromine or iodine; and y + z is 3 or less, provided that x + y + z equals the valence of M. If the substituents A and B in the above formula of the metallocene complex are alkyl groups, they are preferably linear or branched Cι-C8 alkyl groups, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, π-hexyl or /7-octyl.
Suitable metallocene compounds include: bis(cyclopentadienyl)metal dihalides, bis(cyclopentadienyl)metal hydridohalides, bis(cyclopentadienyl)metal monoalkyl monohalides, bis(cyclopentadienyl)metal dialkyls, bis(indenyl)metal diahalides bis(tetrahydroindenyl)metal dihalides, and bis(fluorenyl)metal dihalides, wherein the metal is titanium, zirconium, or hafnium atoms; halide atoms are preferably chlorine; and the alkyl groups are d-C6 alkyl groups. Illustrative but nonlimiting examples of metallocene complexes include bis(cyclopentadienyl)zirconium dichloride, bis(cyclopentadienyl)titanium dichloride, bis(cyclopentadienyl)hafnium dichloride, bis(cyclopentadienyl)zirconium dimethyl, bis(cyclopentadienyl)hafnium dimethyl, bis(cyclopentadienyl)zirconium hydridochloride, bis(cyclopentadienyl)hafnium hydridochloride, bis(/7-butylcyclopentadienyl)zirconium dichloride, bis(/7-butylcyclopentadienyl)hafnium dichloride, bis(/?-butylcyclopentadienyl)zirconium dimethyl, bis(n-butylcyclopentadienyl)hafnium dimethyl, bis(A7-butylcyclopentadienyl)zirconium hydridochloride, bis(n-butylcyclopentadienyl)hafnium hydridochloride, bis(1,3-dimethylcyclopentadienyl)zirconium dichloride, bis(pentamethylcyclopentadienyl)zirconium dichloride, cyclopentadienylzirconium trichloride, bis(indenyl)zirconium dichloride, bis(4,5,6,7-tetrahydro-1-indenyl)zirconium dichloride, and ethylene[bis(4,5,6,7-tetrahydro-1 -indenyl)]zirconium dichloride.
Cocatalysts for metallocene complexes used in this invention are synthesized in reactions involving trialkylaluminum compounds, sterically hindered phenols, and water. The trialkylaluminum compounds used for the preparation of the cocatalysts have the general formula of AIR3, wherein R are alkyl groups such as methyl, ethyl, n- propyl, π-butyl, isobutyl, n-hexyl, or n-octyl group. The preferred trialkylaluminum compound is trimethylaluminum (TMA). The sterically hindered phenols or polyphenols PΛOH used for the preparation of the cocatalysts of the invention contain at least two substituents which are situated in the 2-nd and the 6-th positions of the benzene ring with respect to the hydroxyl group and are bulky alkyl, aryl, or alkylaryl groups such as a fe/ -butyl group, a phenyl group, or a benzyl group. It is noted that the empirical formula PhOH is used interchangeably with the phrase "sterically hindered phenols or polyphenols" herein. The preferred substituents in the phenols are ferf-butyl and phenyl groups. Illustrative but nonlimiting examples of the phenols include: 2,6-di-ferf-butylphenol, 2,6-diisopropylphenol, 2,6-diphenylphenol, 2,6-di-te/f-butyl-4-methylphenol, 2,6-diisopropyl~4-methylphenol, 2,2-methylene-bis(2-terf-butyl-4-methylphenol), and 1 ,3,5-trimethyl-2,4,6-tris(3,5-di-ferf-butyl-4-hydroxybenzyl)benzene.
In the first stage of the preparation of the cocatalyst, the sterically hindered phenol is reacted with a trialkylaluminum compound AIR3. The reaction can be carried out in solution in a nonpolar solvent, such as a paraffinic hydrocarbon, a cycloalkane or an aromatic hydrocarbon, or with a neat trialkylaluminum compound, in a broad range of temperatures, from sub-zero to elevated temperatures. The optimum reaction temperatures are from 10 to 70°C. The reaction proceeds vigorously with the formation of an alkane RH. In the case when the R group in he trialkylaluminum compound formula AIR3 is methyl or ethyl, the alkane RH evolves as a gas. It can be assumed that the reaction can be described by the following equations:
AIR3 + PΛOH → AIR20P/ϊ + RH
AIR3 + 2 PhOH → AIR(OPΛ) 2 + 2 RH, etc. and produces alkylaluminum phenoxides. The ratio between AIR3 and the phenol
PΛOH can vary from 10:1 to 1 :2; the most preferred ratio is 1 :1. In the second stage of the preparation of the cocatalyst, the product of the first stage is contacted with water. This stage of the reaction can be carried out in the same solvent as that used in the first stage, in a broad range of temperatures, from sub-zero to elevated temperatures. The optimum reaction temperatures are from 10 to 70°C. The reaction is relatively slow and requires, depending on temperature, from 15 to 60 minutes to come to completion. It can be monitored by observing slow disappearance of drops of water on the bottom of the reaction vessel. The total amount of water can be added to the reaction vessel in one step or in several consecutive steps. It is believed that this reaction produces products with an average structure P 7-O-[AI(R)-O]p-[AI(OPΛ)-O]q-AI(R)-OP 7 which can be described, in general terms, as phenylaluminates and in which the p:q ratio depends on the ratio between AIR3 and the phenol in the first stage of the cocatalyst preparation. If p:q is less than 0.2:1 the cocatalysts and the catalyst compositions based on them are air stable and are not flammable. The ratio between AIR3 used in the first stage of the cocatalyst preparation reaction and water used in the second stage of the cocatalyst preparation reaction can vary from 5:1 to 1 :1.5; the most preferred ratio is 1:1.
The catalyst compositions of the invention can be used at the ratios between the amounts of the cocatalyst and a metallocene complex represented by the molar ratio between the Al compound used for the cocatalyst preparation and M in the metallocene complex in the [AI]coca.aiyst:[M]mβtaιiocene range from 20,000 to 1.0, preferably from 5,000 to 100. The catalyst compositions may be formed from the metallocene complexes and the cocatalysts of this invention prior to their introduction into a polymerization reactor or in situ in a reactor by contacting the cocatalyst with a metallocene complex. If the catalyst composition is supported, the support may be contacted with the cocatalyst to form the first contact product and then with the metallocene complex to form the second contact product; or the support can be contacted with the metallocene complex first and then with the cocatalyst. Alternatively the catalyst components, the metallocene complex and the cocatalyst of the invention can be pre-contacted and then impregnated into the support. When the catalyst of the invention is a supported particulate catalyst, it comprises 0.01 to 4.0 wt. %, preferably 0.1 to 2.0 wt. % transition metal provided by a metallocene complex.
Catalyst systems of the invention containing reaction products of trialkylaluminum compounds, sterically hindered phenols and water as cocatalysts and metallocene complexes of transition metals are highly active in various polymerization and copolymerization reactions of ethylene and alpha-olefins. If the [AIR3]:[phenol] ratio used during the cocatalyst preparation is below 0.2:1 , the cocatalysts and the catalyst compositions based on them are air-stable and are not flammable, in contrast to trialkylaluminum compounds.
The catalysts of this invention can be fed to a solution reactor, a slurry reactor or a fluidized-bed gas-phase reactor for polymerization and copolymerization of ethylene and alpha-olefins. The temperature of polymerization can range from 25° to 125°C, but more generally between 50° and 115°C, at pressures of less than 10000 psi. The catalysts can be used, for example, to produce high density polyethylene resins or linear low density polyethylene resins which are copolymers of ethylene and higher alpha-olefins such as 1 -butene, 1 -pentene, 1 -hexene, 1 -octene, 4-methyl-1 - pentene, etc. Such copolymers contain at least 80 wt.% of ethylene.
EXAMPLES
Examples 1-5 describe cocatalyst synthesis based on 2,6-di-ferf-butylphenol and trimethylaluminum at various [Phenol]: [AIMe3]:[H2O] ratios.
Example 1. 2,6-di-terf-butylphenol (DBP) in an amount of 0.551 g (2.7 mmol) was dissolved in 3 cc of toluene, the solution was flushed with purified nitrogen and slowly added to a 25-cc glass bottle sealed with a rubber septum and containing a mixture of 2 cc of 1.35 M solution of trimethylaluminum (TMA) in heptane and 5 cc of toluene. A rapid reaction ensued resulting in methane evolution (the gas was released from the bottle through a syringe needle); the reaction product remained dissolved in toluene. Based on known chemistry of reactions between trialkylaluminum compounds and alcohols, the formation of dimethylaluminum phenoxide (CH3)2AI-OPΛ (where Ph is the 2,6-di-fetf-C4H9-C6H3-group) is expected in this reaction. In the next step, neat water in an amount of 39 μl (2.16 mmol) was added to the bottle at room temperature to bring the [H2O]:[AI] ratio to 0.8. Water droplets gradually reacted with the dimethylaluminum phenoxide with methane evolution and produced uniform, toluene-soluble product of light pink color which was expected to have an average structure
PΛ-O-AI(CH3)-O-AI(OPΛ)-O-AI(OP 7)-O-AI(OP/7)-O-AI(OP/j)-AI(CH3)-OPΛ.
Example 2. A reaction between DBP (5.4 mmol) and TMA (2.7 mmol) was carried under conditions similar to those in Example 1 at an [DBP]:[TMA] ratio of 2:1 resulting in the formation of methylaluminum diphenoxide [CHsAI(OP 7)2]. To bring the reaction to completion, the bottle was kept at 70°C for 30 minutes. Then the solution was cooled to room temperature and neat water was added to it in an amount of 24μl (1.35 mmol) to achieve an [H2O]:[AI] ratio of 0.5. A relatively slow reaction with methane evolution continued for ca. 20 minutes and resulted in the formation of a uniform, light purple solution apparently containing tetraphenyldialuminate (PΛO)2AI- O-AI(OPΛ)2.
Example 3. A similar reaction between DBP (2.7 mmol) and TMA (2.7 mmol) was carried at an [DBP]:[TMA] ratio of 1:1 resulting in the formation of (CH3)2AI(OPΛ). Then neat water was added to the solution in an amount of 24μl (1.35 mmol) to achieve an [H2O]:[AI] ratio of 0.5. A reaction of methane evolution continued for Ca. 10 minutes and resulted in the formation of a uniform, magenta-colored solution apparently containing methylphenoxydialumoxane (PΛO)(CH3)AI-O-AI(CH3)(OP/7).
Example 4. A similar reaction between DBP (2.7 mmol) and TMA (2.7 mmol) was carried in a toluene medium at an [DBP]:[TMA] ratio of 1 :1 resulting in the formation of (CH3)2AI(OPΛ). Then neat water was added to the solution in two steps, first in an amount of 24μl (1.35 mmol) to achieve an [H2O]:[AI] ratio of 0.5 and apparently to produce methylphenoxydialumoxane
(PhO)(CH3)AI-O-AI(CH3)(OP/7) and then, in the second step, in an amount of 22 μl (1.22 mmol) to reach the total [H2O)]:[AI] ratio of 0.9:1.
Example 5. A similar reaction between DBP (2.7 mmol) and TMA (2.7 mmol) was carried in a toluene medium at an [DBP]: [TMA] ratio of 1 :1 resulting in the formation of (CH3)2AI(OP/7). Then neat water was added to the solution in two steps, first in an amount of 24μl (1.35 mmol) to achieve an [H2O]:[AI] ratio of 0.5 and apparently to produce methylphenoxydialumoxane (PΛO)(CH3)AI-O-AI(CH3)(OP/7) and then, in the second step, in an amount of 24μl (1.35 mmol) to reach the total [H2O]:[AI] ratio of 1:1. Examples 6-8 describe cocatalyst syntheses based on 2,6-di-te/f-butylphenol and different organoaluminum compounds.
Example 6. DBP in an amount of 0.551 g (2.7 mmol) was dissolved in 3 cc of toluene, the solution was flushed with purified nitrogen and slowly added to a 25-cc glass bottle sealed with a rubber septum and containing a mixture of 1.8 cc of 1.53 M solution of triethylaluminum (TEAL) in heptane and 5 cc of toluene. A reaction ensued resulting in ethane evolution (the gas was released from the bottle through a syringe needle); the reaction product remained dissolved in toluene. Based on known chemistry of reactions between trialkylaluminum compounds and alcohols, the formation of diethylaluminum phenoxide (C2H5)2AI-OP/7 is expected in this reaction. In the next step, neat water was added to the solution in two steps, first in an amount of 24μl (1.35 mmol) to achieve an [H2O]:[AI] ratio of 0.5 and apparently to produce ethylaryloxydialumoxane (PΛO)(C2H5)AI-O-AI(C2H5)(OP 7) and then, in the second step, in an amount of 22μl (1.22 mmol) to reach the total [H2O]:[AI] ratio of 0.9:1. Water droplets gradually reacted with the diethylaluminum phenoxide with ethane evolution and produced a uniform, toluene-soluble product apparently containing oligomeric arylaluminates with predominantly -O-AI(-OPΛ)- groups flanked by a small amount of PΛO-AI(C2H5)-O- groups.
Example 7. A reaction between DBP (2.7 mmol) and triisobutylaluminum (TIBA, 2.7 mmol) was carried under similar conditions in a toluene medium at an [DBP]:[AI/-Bu3] ratio of 1 :1 (practically no gas evolution was observed) resulting in the formation of an (/-C4H9)2AI-OP? compound. Then neat water was added to the solution in two steps, first in an amount of 24μl (1.35 mmol) to achieve an [H2O]:[AI] ratio of 0.5 and apparently to produce isobutylphenoxydialumoxane (PΛO)(/-C4H9)AI-O-AI(/-C4H9)(OPΛ) and then, in the second step, in an amount of 22 μl (1.22 mmol) to reach the total [H2O)]:[AI] ratio of 0.9:1. Example 8. A reaction between DBP (2.7 mmol) and tri-n-octylaluminum (2.7 mmol) was carried under similar conditions in a toluene medium at an [DBP]:[AI/7- Oct3] ratio of 1 :1 resulting in the formation of (n-CβH17)2AI-OPΛ. Then neat water was added to the solution in two steps, first in an amount of 24μl (1.35 mmol) to achieve an [H2O]:[AI] ratio of 0.5 and apparently to produce n-octylaryloxydialumoxane (PA7O)(/7-C8Hi7)AI-O-AI(t?-C8H17)(OP/7) and then, in the second step, in an amount of 22 μl (1.22 mmol) to reach the total [H2O]:[AI] ratio of 0.9:1.
Examples 9 and 10 describe cocatalyst synthesis based on different hindered phenols and trimethylaluminum. Example 9. 2,6-diphenylphenol in an amount of 0.664 g (2.7 mmol) was dissolved in 5 cc of toluene, the solution was flushed with purified nitrogen and slowly added to a 25-cc glass bottle sealed with a rubber septum and containing a mixture of 2.0 cc of 1.35 M solution of TMA in heptane and 5 cc of toluene. A reaction ensued resulting in a gradual methane evolution (the gas was released from the bottle through a syringe needle); the reaction product remained dissolved in toluene. Based on known chemistry of reactions between trialkylaluminum compounds and alcohols, formation of dimethylaluminum phenoxide (CH3)2AI-OPΛ' (where Ph' is 2,6- di-Ph-C6H3) is expected in this reaction. In the next step, neat water was added to the solution in an amount of 29 μl (1.6 mmol) to achieve an [H2O]:[AI] ratio to 0.6. Example 10. 2,2-methylene-bis(2-terf-butyl-4-methylphenol) in an amount of
0.84 g (2.7 mmol) was dissolved in 8 cc of toluene and the solution was slowly added to a glass bottle containing 2.7 mmol of TMA (heptane solution) and was mixed for 1 hour. The reaction is expected to produce CH3-A\(Ph") where Ph" is a bidentate ligand derived from 2,2-methylene-bis(2-ferf-butyl-4-methylρhenol) and attached to the Al atom through two oxygen atoms. After the end of methane evolution, neat water (24μl,1.35 mmol) was added to the solution to produce aryldialuminate Ph"A\- O-AIP/7".
Comparative Example 1. Cocatalyst synthesis based on sterically nonhindered phenol and trimethylaluminum. Phenol in an amount of 0.259 g (2.75 mmol) was dissolved in 3 cc of toluene, the solution was flushed with purified nitrogen and slowly added to a 25-cc glass bottle sealed with a rubber septum and containing a mixture of 2.0 cc of 1.35 M solution of TMA in heptane and 5 cc of toluene. A reaction ensued resulting in a rapid methane evolution (the gas was released from the bottle through a syringe needle); the reaction product remained dissolved in toluene. Based on known chemistry of reactions between trialkylaluminum compounds and alcohols, formation of dimethylaluminum phenoxide (CH3)2AI-OC6H5 is expected in this reaction. Then neat water was added to the solution in two steps, first in an amount of 24μl (1.35 mmol) to achieve an [H2O]:[AI] ratio of 0.5 and apparently to produce methylphenoxydialumoxane (C6H5O)(CH3)AI-O-AI(CH3)(OC6H5) and then, in the second step, in an amount of 22μl (1.22 mmol) to reach the total [H2O]:[AI] ratio of 1.9:1.
Example 11. Polymerization experiments.
All cocatalyst compositions of Examples 1-10 were tested in ethylene/1 -hexene copolymerization reactions using a bridged metallocene complex C2H4(indenyl)2ZrCI2 as a catalyst. The copolymerization reactions were carried out in a 500-cc stainless- steel autoclave equipped with a stirrer, a thermocouple, and several ports for adding reaction components. Prior to polymerization, the reactor was purged with nitrogen at 105-110°C for 1 hour. Polymerization reactions were carried out at 80°C in n- heptane (230 cc) as a solvent, at a 0.64 mol/1 1 -hexene concentration in solution and at a total reaction pressure of ca. 180 psig. Trialkylaluminum compounds, TMA, TEAL or TIBA, were added to the mixtures of the solvent and 1 -hexene as impurity scavengers. The amount of the cocatalysts (expressed as mmol of Al) in all experiments was 2.7 mmol. Reaction conditions and product properties are listed in Table 1 :
Table 1. Polymerization reactions with C2H4(lnd)2ZrCI2 and reaction products of sterically hindered phenols, alkylaluminum compounds and water.
Example Cocatalyst of C2H4(lnd)2ZrCI2, Time, Yield, Productivity
# Example mmol min g g/mmol Zr CHa
11-1 1 1.47.10"3 127 10.2 6,940 1:6%
11-2 2 1.47.10"3 120 5.5 3,740 1.5%
11-3 3 1.47.10 * 120 9.4 6,600 1.5%
11-4 4 1.47.10"3 30 24.8 16,900 1.5%
11-5 5 1.47.10"3 120 8.6 19,500 1.7%
11-7 6 1.47.10 * 120 7.0 4,800 1.8%
11-8 7 1.47.10"3 120 32.4 22,000 1.3%
11-9 8 1.47.10-3 120 24.1 16,400 1.4%
11-10 9 1.47.10- 60 5.8 3,940 1.8%
11-11 10 1.47.103 120 15.0 10,200 1.4%
11-12 Comparative 1.47.10-3 120 -2.5 -1,500 3.1% Example 1
a Hexene content in a copolymer, mol.%.
The data in the table demonstrate that the products of reactions between trialkylaluminum compounds, sterically hindered phenols and water are all effective cocatalysts for metallocene complexes in olefin polymerization reactions and produce ethylene/1 -hexene copolymers of the same composition. Nonhindered phenols produce inferior cocatalysts (Example 11-12). Comparison of results in Examples 11- 1 through 11-5 indicates that the most effective cocatalysts (in Examples 11-4 and 11-5) are formed at an [H2O]:[AI] ratio close to 1 :1 when nearly all AI-CH3 bonds remaining after the reaction between TMA and a sterically hindered phenol further react with water and produce oligomeric arylaluminates, whereas both dialumoxanes (cocatalysts in Examples 11-2 and 11-3) exhibit the lowest activity.
Comparison of polymerization results in Examples 11-7, 11-8 and 11-9 shows that arylaluminates produced from various trialkylaluminum compounds are all active cocatalysts and that the products generated from TIBA and tri-tj- octylaluminum have activities similar to those of the products generated from TMA. Thus it is apparent that there has been provided, in accordance with the invention a synthesis that fully satisfies the objects, aims, and advantages set forth above. While the invention has been described in conjunction with specific embodiments thereof, it is evident that many alternatives, modifications, and variations will be apparent to those skilled in the art in light of the foregoing description. Accordingly, it is intended to embrace all such alternatives, modifications, and variations as fall within the spirit and broad scope of the appended claims.

Claims

CLAIMS:
1. A catalyst composition for polymerization and copolymerization of alpha- olefins comprising the contact product of a metallocene complex of a transition metal of the formula CpxMAyBz wherein x is 1 or 2; M is titanium, zirconium or hafnium; Cp is a cyclopentadienyl group, a substituted cyclopentadienyl group, a cyclopentadienyl group that is a part of a bicyclic or a tricyclic moiety or, when x is 2, the cyclopentadienyl groups are optionally bridged; and each of A and B is selected from the group consisting of a halogen atom, a hydrogen atom, an alkyl group, or combinations thereof; providing that x+y+z is equal to the valence of M; and a cocatalyst produced in a two-step reaction comprising (i) reacting a trialkylaluminum compound AIR3 with a phenol or polyphenol PΛOH substituted in the 2-nd and the 6-th positions with respect to the hydroxyl group, at the [AIR3]:[PΛOH] ratio in the 10:1 to 1 :2 range, and
(ii) reacting the product of step (i) with water at the [AI]:[H2O] ratio in the 5:1 to 1 :1.5 range.
2. The catalyst composition of Claim 1 , wherein x is 2.
3. The catalyst composition of Claim 1 or 2, wherein M is Zr.
4. The catalyst composition of Claim 1 , 2 or 3, wherein A and B are Cl.
5. The catalyst composition of Claim 4, wherein Cp is n-butylcyclopentadienyl group.
6. The catalyst composition of Claim 4 wherein Cp is a tetrahydroindenyl group and where the two tetrahydroindenyl groups are linked by an ethylene bridge.
7. The catalyst composition of Claim 4 wherein Cp is an indenyl group and where the two indenyl groups are linked by an ethylene bridge.
8. The catalyst composition of Claim 4 wherein Cp is a tetrahydroindenyl group and where the two tetrahydroindenyl groups are linked by a dimethylsilyl bridge.
9. The catalyst composition of Claim 1 wherein the alkyl group R in the trialkylaluminum compound is selected from a group comprising methyl, ethyl, propyl, isopropyl, /7-butyl, isobutyl, n-pentyl, isopentyl, n-hexyl, isohexyl, n-heptyl, isoheptyl, π-octyl, or isooctyl groups.
10. The catalyst composition of Claim 9 wherein the [AIR3]:[PΛOH] ratio is 1.0.
11. The catalyst composition of Claim 9 wherein the [AIR3]:[PΛOH] ratio is 2.0.
12. The catalyst component of Claim 10, wherein the [AI]:[H2O] ratio is 1.0.
13. The catalyst component of Claim 11 , wherein the [AI]:[H2O] ratio is 1.0.
14. The catalyst component of Claim 1 , wherein the catalyst composition comprising the contact product of the metallocene complex of a transition metal and the cocatalyst is supported on an inert porous support.
PCT/US1998/024538 1997-12-18 1998-11-17 Catalyst compositions for olefin polymerization based on metallocene complexes and novel cocatalysts produced from trialkylaluminum compounds, sterically hindered phenols, and water WO1999030821A1 (en)

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Cited By (2)

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US7034173B2 (en) 2000-05-24 2006-04-25 Basell Polyolefine Gmbh Chemical products suited for use as co-catalysts, method for the preparation thereof and their use in catalyst systems for producing polyolefins
US20180002464A1 (en) * 2014-12-31 2018-01-04 Dow Global Technologies Llc A polyolefin composition and method of producing the same

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WO1994010180A1 (en) * 1992-11-02 1994-05-11 Akzo N.V. Aryloxyaluminoxanes
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WO1994010180A1 (en) * 1992-11-02 1994-05-11 Akzo N.V. Aryloxyaluminoxanes
US5391793A (en) * 1992-11-02 1995-02-21 Akzo Nobel N.V. Aryloxyaluminoxanes

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7034173B2 (en) 2000-05-24 2006-04-25 Basell Polyolefine Gmbh Chemical products suited for use as co-catalysts, method for the preparation thereof and their use in catalyst systems for producing polyolefins
US20180002464A1 (en) * 2014-12-31 2018-01-04 Dow Global Technologies Llc A polyolefin composition and method of producing the same
US10351646B2 (en) * 2014-12-31 2019-07-16 Dow Global Technologies Llc Polyolefin composition and method of producing the same

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