WO2001005850A1 - Systeme catalytique a base de complexes metalliques contenant du fluor - Google Patents

Systeme catalytique a base de complexes metalliques contenant du fluor Download PDF

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Publication number
WO2001005850A1
WO2001005850A1 PCT/EP2000/006180 EP0006180W WO0105850A1 WO 2001005850 A1 WO2001005850 A1 WO 2001005850A1 EP 0006180 W EP0006180 W EP 0006180W WO 0105850 A1 WO0105850 A1 WO 0105850A1
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WO
WIPO (PCT)
Prior art keywords
aluminum
ethylene
polymerization
group
catalyst system
Prior art date
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PCT/EP2000/006180
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German (de)
English (en)
Inventor
Sigurd Becke
Uwe Rosenthal
Original Assignee
Bayer Aktiengesellschaft
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Filing date
Publication date
Priority claimed from DE1999132409 external-priority patent/DE19932409A1/de
Priority claimed from US09/397,936 external-priority patent/US6303718B1/en
Application filed by Bayer Aktiengesellschaft filed Critical Bayer Aktiengesellschaft
Priority to EP00945860A priority Critical patent/EP1200487A1/fr
Priority to AU59810/00A priority patent/AU5981000A/en
Priority to JP2001511505A priority patent/JP2003505543A/ja
Priority to CA002379019A priority patent/CA2379019A1/fr
Publication of WO2001005850A1 publication Critical patent/WO2001005850A1/fr

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    • 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
    • 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
    • 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
    • C08F210/18—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers with non-conjugated dienes, e.g. EPT 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 present invention relates to a catalyst system based on fluorine-containing metal complexes, in particular a catalyst system consisting of metallocene fluorides and aluminum alkyls and the use of the catalyst system for the polymerization of unsaturated compounds, in particular for the polymerization and copolymerization of olefins and / or dienes.
  • cyclopentadienyl metal complexes in particular the use of metallocene complexes in a mixture with activating cocatalysts, for the polymerization of olefins and diolefins has long been known.
  • catalyst is unsuitable for industrial use because on the one hand the catalyst activity is too low and on the other hand the polymerization of 1-olefins is not possible.
  • Ethylene and / or 1-olefins consisting of metallocene dichlorides in a mixture with aluminoxanes, e.g. B. methylaluminoxane (MAO) are known.
  • aluminoxanes e.g. B. methylaluminoxane (MAO)
  • MAO methylaluminoxane
  • a large number of new metallocene catalysts or metallocene catalyst systems for the polymerization of olefinic compounds have been developed in recent years (for example EP 69 951, 129 368, 347 128, 347 129, 351 392, 485 821, 485 823).
  • Chlorine-containing metallocenes are usually used in combination with MAO.
  • Processes for olefin polymerization are also known, metallocene / aluminoxane catalysts (for example EP 308177, EP 575875) being prepared in situ.
  • WO 97/07141 uses fluorine-containing half-sandwich complexes of titanium in combination with MAO as catalysts for the production of polystyrene.
  • WO 98/36004 describes fluorine-containing complexes, preferably of titanium, preferably in combination with MAO as catalysts for the preparation of polybutadiene.
  • MAO aluminoxanes
  • MAO have disadvantages, as will be explained in more detail below.
  • MAO is a mixture of different aluminum compounds, the number and structure of which are not exactly known. Therefore, the polymerization of olefins with catalyst systems that contain MAO is not always reproducible.
  • MAO is not stable in storage and changes its composition under thermal stress.
  • MAO has the disadvantage of being used in large excesses in order to achieve high catalyst activities. This leads to a high aluminum content in the polymer.
  • MAO is also a cost-determining factor. High MAO surpluses are uneconomical for technical applications.
  • EP-A 277 003 and EP-A 277 004 describe ionic metallocenes which are prepared by reacting metallocenes with ionizing reagents.
  • EP-A 468 537 describes catalysts with an ionic structure which are formed by reacting metallocene dialkyl compounds with tetrakis (pentafluorophenyl) boron compounds. The ionic metallocenes are suitable as catalysts for the polymerization of olefins finen.
  • Reagents e.g. B. tetrakis (pentafluorophenyl) boron compounds are sometimes difficult to synthesize and their use is costly.
  • the object of the present invention was to find an aluminoxane-free composition which at least partially avoids the disadvantages of the prior art and whose use as a catalyst nevertheless enables high polymerization activities. Another object was to find a catalyst system with which the copolymerization of ethylene with 1-
  • Olefins in particular by the solution process, can also be obtained at higher polymerization temperatures (> 50 ° C.) copolymers with high molecular weights.
  • Another object was to find an aluminoxane-free catalyst system for the production of polyolefin rubbers, in particular for EP (D) M.
  • the present invention therefore relates to an aluminoxane-free catalyst system consisting of a) a fluorine-containing metal complex of the formula (I)
  • M is a metal from the group zirconium, hafnium, vanadium, niobium, tantalum,
  • A represents an anionic ligand which may be bridged once or more
  • F represents a fluorine atom
  • L is a nonionic ligand
  • b 1, 2, 3,
  • c 0, 1, 2, 3, 4, in particular 1, 2 or 3,
  • Y is the same or different and stands for hydrogen, a linear or branched C ⁇ - to C20-alkyl group, optionally substituted by silyl groups, a linear or branched C ⁇ - to Cjo-fluoroalkyl group, a Cß to CiQ-fluoroaryl group, one C ⁇ to CIQ alkoxy group, a Cg to C20 aryl group, a Cg to C20 aryloxy group, a C7 to C40 arylalkyl group, or a C7 to C40 alkylaryl group,
  • fluorine-containing metal complexes of the formula (I) are those in which
  • A is the same or different and represents a pyrazolyl borate of the formula R 1 B (N 2 C 3 R 2 3) 3, an alcoholate or phenolate of the formula OR 1 , a thiolate of the formula SR 1 , an amide of the formula NR ⁇ Siloxane of the formula OSiR ⁇ , an acetylacetonate of the formula (R 1 CO) 2 CR 1 , an amidinate of the formula R 1 C (NR 1 ), a cyclooctatetraenyl of the formula CgH ⁇ gq with q for 0, 1, 2, 3, 4 , 5, 6, 7, a cyclopentadienyl of the formula C5H q R 1 5 .
  • R 1 is the same or different and represents hydrogen, a C j - to C2o-alkyl group, a C ⁇ - to CiQ-fluoroalkyl group, a Cg to Cio-fluoroaryl group, a Cj to Cio alkoxy group, a Cg to C2o Aryl group, a C - to Cio-aryloxy group, a C 2 - bis
  • Cio-alkenyl group a C 7 - to C 4 o-arylalkyl group, a C 7 - to C 4 o -alkylaryl group, a Cg to C 4 o-arylalkenyl group, a C 2 - to Cjo-alkynyl group, one optionally by C ⁇ - C ⁇ o hydrocarbon radicals substituted silyl group, a boryl group, an amino group, a phosphinyl group or adjacent
  • Radicals R 1 form a ring system with the atoms connecting them
  • R 2 represents hydrogen or a C j -C j Q alkyl group
  • M, F, L and a, b, c have the meaning given above.
  • nonionic ligands L there are e.g. Ethers, thioethers, cyclic ethers, cyclic thioethers, amines or phosphines in question.
  • Further examples of nonionic ligands are substituted or unsubstituted aromatics, such as benzene, toluene, dimethylbenzene, trimethylbenzene, pentafluorobenzene, trifluoromethylbenzene,
  • L is preferably benzene, toluene, trimethylbenzene, naphthalene and anthracene.
  • fluorine-containing metal complexes of the formula (I) are those which contain an optionally substituted cyclopentadienyhing as a ligand and have fluorine atoms bonded directly to the metal atom M and M stands for zirconium and hafiiium. Catalyst systems with these catalyst components show good polymerization activity.
  • M is preferably zirconium or vanadium, particularly preferably zirconium.
  • a catalyst component which contains at least one bridge R 3 between at least two ligands A.
  • R 3 is preferred
  • R 4 and R 5 are the same or different and is a hydrogen atom, a halogen atom or a C ⁇ -C4o carbon-containing group, such as a C ⁇ -C2o-alkyl, a Cj-Cio-fluoroalkyl, a -C-C 10 alkoxy -, one
  • R 4 and R 5 each form one or more rings with the atoms connecting them and x is an integer from zero to 18, M 2 is silicon, germanium or tin; R 3 can also be two Link units of formula (I) together.
  • Emylenbis (4,5,6,7-tetrahyckomdenyl) hafhiumdifluorid
  • Fluorides of the metallocenes described in WO 98/01487 are also suitable as compounds of the formula (I).
  • the metallocene fluorides can be prepared, for example, according to J. Chem. Soc. (A), 1969, 2106-2116. The preparation of the compound ethylene bis (tetrahydroindenyl) zirconium difluoride is described in particular in Organometallics 1998, 17, page 2097.
  • Particularly suitable compounds of the formula (II) are compounds of the formula (Ha)
  • R, R, R, R and R are identical or different and represent hydrogen, a linear or branched C ⁇ - to C5-alkyl group, optionally substituted by silyl groups, a linear or branched C ⁇ - to C5-fluoroalkyl group, one C - to C5-alkoxy group, a Cg to C20 aryl group, a C - to C20 aryloxy group,
  • Z represents an optionally mono- or polysubstituted alkylene, alkenylene or alkynylene radical
  • n 0, 1
  • Y has the meaning given above.
  • R ⁇ is hydrogen or a C ⁇ -C4o carbon-containing group, such as a C ⁇ -C2o-lkyl-, a Ci-Cio-F ioralkyl-, a C j -Cio alkoxy, a C6-Ci 4 -aryl-, a Cg-C j o-fluoroaryl-, a Cö-Ci Q- aryloxy, a C 2 -C ⁇ o-alkenyl-, a C7-C o-arylalkyl-, a C7-C 4 o-alkylaryl-, or a Cg-C 4 o-arylalkenyl group, R 6 , R 7 , R 8 , R 9 , R 10 , Y, M 'and n have the meaning given above.
  • Particularly suitable compounds of the formula (II) are triethyl aluminum, diethyl aluminum hydride, triisobutyl aluminum, diisobutyl aluminum hydride, triisohexyl aluminum, tris (2,3,3-trimethyl-butyl) aluminum, tris (2,3-dimethyl-hexyl) aluminum, tris (2,3-dimethyl-butyl) aluminum, tris- (2,3-dimethyl-pentyl) aluminum, tris- (2,3-dimethyl-heptyl) aluminum, tris- (2-methyl-3-ethyl-pentyl) aluminum, tris- (2-methyl-3-ethyl-hexyl) aluminum, tris- (2-methyl-3-ethyl-heptyl) aluminum, tris- (2-methyl-3-propyl-hexyl) aluminum, tris- ( 2-ethyl-3-methyl-butyl) aluminum, tris- (2-ethyl-3-methyl-pent
  • trialkyl aluminum compounds and dialkyl aluminum hydrides can be prepared according to the method described in Liebigs Annalen der Chemie, Volume
  • Another object of the present invention is the use of the new
  • the polymerization is understood to be both the homo- and the copolymerization of the unsaturated compounds mentioned. the.
  • C2-C ⁇ o _ alkenes such as ethylene, propylene, 1-butene, 1-pentene and 1-hexene, 1-octene, isobutylene and arylalkenes such as styrene are used in the polymerization.
  • conjugated dienes such as 1,3-butadiene, isoprene, 1,3-pentadiene, and non-conjugated dienes, such as 1,4-hexadiene, 1,5-heptadiene, 5,7-dimethyl-1, 6-octadiene, 7-methyl-1, 6-octadiene, 4-vinyl-1-cyclohexene, 5-ethylidene-2-norbornene, 5-vinyl-2-norbornene and dicyclopentadiene.
  • the catalysts of the invention are suitable for the production of rubbers based on copolymers of ethylene with one or more of the ⁇ -olefins mentioned and the dienes mentioned.
  • the catalysts of the invention are particularly suitable for the preparation of EP (D) M.
  • the catalyst system according to the invention is suitable for the polymerization of cyclo-olefins such as norbornene, cyclopentene, cyclohexene, cyclooctane and the copolymerization of cycloolefins with ethylene or ⁇ -olefins.
  • the polymerization can be carried out in the liquid phase, in the presence or absence of an inert solvent, or in the gas phase.
  • Aromatic hydrocarbons such as benzene and / or toluene or aliphatic hydrocarbons such as propane, hexane, heptane, octane, isobutane, cyclohexane or mixtures of the various hydrocarbons are suitable as solvents.
  • Suitable carrier materials are e.g. To name: inorganic or organic polymeric carriers, such as silica gel, zeolites, carbon black, activated carbon, aluminum oxide, polystyrene and polypropylene.
  • Carrier materials are preferably thermally and / or chemically pretreated in order to set the water content or the OH group concentration in a defined manner or to keep it as low as possible.
  • Chemical pretreatment can consist, for example, of reacting the support with aluminum alkyl.
  • Inorganic carriers are usually kept at 100 ° C to 1000 ° C for 1 to 100 hours before use heated.
  • the surface area of such inorganic supports, in particular of silica (SiO 2 ) is between 10 and 100 m 2 / g, preferably between 100 and 800 m 2 / g.
  • the particle diameter is between 0.1 and 500 micrometers ( ⁇ ), preferably between 10 and 200 ⁇ .
  • the polymerization is generally carried out at pressures of 1 to 1,000, preferably 1 to 100.
  • the polymerization can be carried out in conventional reactors, continuously or batchwise.
  • the pressures often do not exceed 30 bar, preferably 20 bar.
  • one or more reactors or reaction zones e.g. worked in a reactor cascade; in the case of several reactors, different polymerization conditions can be set.
  • the polymerization is usually carried out at temperatures in the range from 0 ° C to
  • 200 ° C preferably from 20 ° C to 150 ° C, particularly preferably from 40 ° C to 120 ° C, very particularly preferably from 60 ° C to 120 ° C.
  • the molar ratio of polymerizable monomer to the compound of formula (I) is in the range from 1 x 10 10 : 1 to 100: 1, preferably from 1 x 10 8 : 1 to
  • the molar ratio of the compound of formula (II) to the compound of formula (I) is in the range from 10,000: 1 to 0.1: 1, preferably 1000: 1 to 1: 1.
  • the polymers obtainable in the process according to the invention are particularly suitable for the production of moldings of all kinds.
  • Witco Triisobutylaluminium (TIBA), tri- (2,4,4-trimethylpentyl) aluminum
  • TIOA ethylene bis (tetrahydroindenyl) zirconium dichloride
  • DLBAC Diisobutyl aluminum chloride
  • TMA Trimethylaluminium
  • MCAT Emylenebis (tetrahydroindenyl) zirconium difluoride
  • Tri- (2-phenyl-propyl) aluminum was produced in accordance with the literature specification in Annalen der Chemie, volume 629, 1960, page 18.
  • Polymer characterization The intrinsic viscosity was determined in an Ubbelohde capillary viscometer at 140 ° C in o-dichlorobenzene as solvent (multi-point measurement).
  • the DSC measurements were carried out on a device from Perkin-Elmer called Differential Scarming Calorimeter DSC-2 according to the following specification: two heating -90 ° C, up to + 180 ° D, heating rate 20K / min, rapid cooling with 320K / min to -90 ° C, nitrogen purging, weighed out 12.3 mg sample mass in standard capsules.
  • the LR composition of the polymer composition was determined in accordance with ASTM D 3900.
  • the Mooney viscosity ML (1 + 4) 125 ° C. was determined in accordance with ASTM 1646 / DIN 53523. example 1
  • Example 1 The polymerization from Example 1 was repeated, with the difference that the fluorine-free compound ethylene bis (tetrahydroindenyl) zirconium dichloride was used instead of ethylene bis (tetrahydroindenyl) zirconium difluoride. There was no polymerization.
  • Temperature sensors, a temperature control device, a catalyst lock and monomer metering devices for ethylene and propylene have been equipped
  • Example 3 The polymerization from Example 3 was repeated, with the difference that 1.0 ml of a 2.0 molar solution of trimethylaluminum in toluene was used instead of 0.3 ml of TIBA. There was no polymerization.
  • Example 6 The polymerization from Example 3 was repeated, with the difference that 1.0 ml of a 2.0 molar solution of diisobutylaluminum chloride in toluene was used instead of 0.3 ml of TUBA. There was no polymerization.
  • Example 6 The polymerization from Example 3 was repeated, with the difference that 1.0 ml of a 2.0 molar solution of diisobutylaluminum chloride in toluene was used instead of 0.3 ml of TUBA. There was no polymerization.
  • Example 6 The polymerization from Example 3 was repeated, with the difference that 1.0 ml of a 2.0 molar solution of diisobutylaluminum chloride in toluene was used instead of 0.3 ml of TUBA. There was no polymerization.
  • Temperature sensors, a temperature control device, a catalyst lock and monomer metering devices for ethylene and propylene, 500 ml of toluene (freshly absolute), 1 ml of TLBA and 5 ml of ENB were presented.
  • the inside temperature was set to 60 ° C with a thermostat.
  • 11 g of ethylene and 25 g of propylene were metered in.
  • the polymerization was started by adding a mixture of 1.25 ⁇ mol of ethylene bis (tetrahydroindenyl) zirconium difluoride and 0.25 ml of TUBA, dissolved in 5 ml of toluene.
  • Example 7 The polymerization from Example 7 was repeated, with the difference that instead of ethylene bis (tetrahydroindenyl) zirconium difluoride, the fluorine-free compound ethylene bis (tetrahydroindenyl) zirconium dichloride was used. There was no polymerization.
  • Example 9 The polymerization from Example 9 was repeated, with the difference that 9 g
  • Temperature sensors, a temperature control device, a catalyst lock and monomer metering devices for ethylene and propylene, 500 ml hexane (freshly absolute) and 1.5 g (3.9 mmol) TPPA were presented.
  • the inside temperature was set to 60 ° C with a thermostat. 10 g of ethylene and 50 g of propylene were then metered in. By adding 2.5 ml of
  • Example 13 The polymerization from Example 13 was repeated, with the difference that 70 g of propylene and 10 g of ethylene were introduced into the autoclave.
  • Example 13 The polymerization from Example 13 was repeated, with the difference that 10 g of ethylene, 50 g of propylene and 2.5 ml of ENB were introduced into the autoclave.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

La présente invention concerne un système catalytique à base de complexes métalliques contenant du fluor, notamment un système catalytique constitué de fluorures de métallocène et d'alkyles d'aluminium. Cette invention concerne également l'utilisation de ce système catalytique pour la polymérisation de composés insaturés, notamment pour la polymérisation et la copolymérisation d'oléfines et/ou de diènes.
PCT/EP2000/006180 1999-07-14 2000-07-03 Systeme catalytique a base de complexes metalliques contenant du fluor WO2001005850A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
EP00945860A EP1200487A1 (fr) 1999-07-14 2000-07-03 Systeme catalytique a base de complexes metalliques contenant du fluor
AU59810/00A AU5981000A (en) 1999-07-14 2000-07-03 Catalyst system that is based on fluorine-containing metal complexes
JP2001511505A JP2003505543A (ja) 1999-07-14 2000-07-03 フッ素含有金属錯体をベースとする触媒系
CA002379019A CA2379019A1 (fr) 1999-07-14 2000-07-03 Systeme catalytique a base de complexes metalliques contenant du fluor

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DE19932409.3 1999-07-14
DE1999132409 DE19932409A1 (de) 1999-07-14 1999-07-14 Zusammensetzung auf Basis von fluorhaltigen Metallkomplexen
US09/397,936 1999-09-17
US09/397,936 US6303718B1 (en) 1999-09-17 1999-09-17 Composition based on fluorine-containing metal complexes

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WO2001005850A1 true WO2001005850A1 (fr) 2001-01-25

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JP (1) JP2003505543A (fr)
AU (1) AU5981000A (fr)
CA (1) CA2379019A1 (fr)
WO (1) WO2001005850A1 (fr)

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Publication number Priority date Publication date Assignee Title
US6894131B2 (en) * 1998-08-21 2005-05-17 Univation Technologies, Llc Polymerization process using a metallocene catalyst system

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3576763A (en) * 1966-06-10 1971-04-27 Du Pont Organic vanadyl fluorides and their use in coordination catalysts
EP0834515A2 (fr) * 1996-10-04 1998-04-08 Kanto Kagaku Kabushiki Kaisha Composés organométalliques et leur application comme catalyseurs de polymérisation d'oléfines
WO2000011047A1 (fr) * 1998-08-21 2000-03-02 Univation Technologies Llc Procede de polymerisation faisant appel a un systeme ameliore de catalyseur de type metallocene a ligand volumineux

Family Cites Families (5)

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JP3465322B2 (ja) * 1993-11-04 2003-11-10 東ソー株式会社 イオン性メタロセン化合物、その製造方法、およびそれを用いたオレフィン重合用触媒
JPH07216014A (ja) * 1994-01-28 1995-08-15 Idemitsu Petrochem Co Ltd オレフィン重合用触媒及びオレフィン系重合体の製造方法
WO1997007141A1 (fr) * 1995-08-18 1997-02-27 Targor Gmbh Constituants de catalyseur et systeme catalyseur a haut degre d'activite de polymerisation utilises pour produire des polymeres
JP3765629B2 (ja) * 1996-10-07 2006-04-12 旭化成ケミカルズ株式会社 オレフィン重合触媒およびその触媒を用いたポリオレフィンの製造方法
EP0960144B1 (fr) * 1997-02-17 2002-05-29 Bayer Aktiengesellschaft Nouveau systeme catalyseur, son utilisation pour polymeriser des dienes en solution, en suspension ou en phase gazeuse et utilisation des caoutchoucs dieniques produits a l'aide dudit systeme catalyseur

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3576763A (en) * 1966-06-10 1971-04-27 Du Pont Organic vanadyl fluorides and their use in coordination catalysts
EP0834515A2 (fr) * 1996-10-04 1998-04-08 Kanto Kagaku Kabushiki Kaisha Composés organométalliques et leur application comme catalyseurs de polymérisation d'oléfines
WO2000011047A1 (fr) * 1998-08-21 2000-03-02 Univation Technologies Llc Procede de polymerisation faisant appel a un systeme ameliore de catalyseur de type metallocene a ligand volumineux

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CA2379019A1 (fr) 2001-01-25
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EP1200487A1 (fr) 2002-05-02

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