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WO1999030821A1 - Compositions de catalyseur pour la polymerisation d'olefines basees sur des complexes d'alliage organometallique et nouveaux cocatalyseurs produits a partir de composes de trialkylaluminium, de phenols entraves steriquement et d'eau - Google Patents

Compositions de catalyseur pour la polymerisation d'olefines basees sur des complexes d'alliage organometallique et nouveaux cocatalyseurs produits a partir de composes de trialkylaluminium, de phenols entraves steriquement et d'eau 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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English (en)
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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/fr

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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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  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
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  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Inorganic Chemistry (AREA)
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Abstract

L'invention concerne des compositions de catalyseur comprenant des complexes d'alliage organométallique d'un métal de transition de la formule CpxMAyBz et un cocatalyseur synthétisé dans des réactions entre des composés de trialkylalumium, des phénols disubstitués 2,6 entravés stériquement, et de l'eau.
PCT/US1998/024538 1997-12-18 1998-11-17 Compositions de catalyseur pour la polymerisation d'olefines basees sur des complexes d'alliage organometallique et nouveaux cocatalyseurs produits a partir de composes de trialkylaluminium, de phenols entraves steriquement et d'eau WO1999030821A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU14165/99A AU1416599A (en) 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

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US99316697A 1997-12-18 1997-12-18
US08/993,166 1997-12-18

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Cited By (2)

* 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

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2979497A (en) * 1957-02-12 1961-04-11 J W Ayers & Co Cyclic aluminum oxide acylates, alkoxides, and phenoxides
WO1994010180A1 (fr) * 1992-11-02 1994-05-11 Akzo N.V. Aryloxyaluminoxanes
US5391793A (en) * 1992-11-02 1995-02-21 Akzo Nobel N.V. Aryloxyaluminoxanes

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2979497A (en) * 1957-02-12 1961-04-11 J W Ayers & Co Cyclic aluminum oxide acylates, alkoxides, and phenoxides
WO1994010180A1 (fr) * 1992-11-02 1994-05-11 Akzo N.V. Aryloxyaluminoxanes
US5391793A (en) * 1992-11-02 1995-02-21 Akzo Nobel N.V. Aryloxyaluminoxanes

Cited By (3)

* 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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