WO1996020226A1 - Procede de fabrication de polymeres de composes vinylaromatiques, avec utilisation de melanges de systemes catalyseurs metallocenes - Google Patents

Procede de fabrication de polymeres de composes vinylaromatiques, avec utilisation de melanges de systemes catalyseurs metallocenes Download PDF

Info

Publication number
WO1996020226A1
WO1996020226A1 PCT/EP1995/004892 EP9504892W WO9620226A1 WO 1996020226 A1 WO1996020226 A1 WO 1996020226A1 EP 9504892 W EP9504892 W EP 9504892W WO 9620226 A1 WO9620226 A1 WO 9620226A1
Authority
WO
WIPO (PCT)
Prior art keywords
alkyl
compounds
catalyst systems
vinyl aromatic
polymers
Prior art date
Application number
PCT/EP1995/004892
Other languages
German (de)
English (en)
Inventor
Aktiengesellschaft Basf
Original Assignee
WÜNSCH, Josef
Fischer, David
Lux, Martin
Lilge, Dieter
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from DE19944446385 external-priority patent/DE4446385A1/de
Priority claimed from DE19500811A external-priority patent/DE19500811A1/de
Application filed by WÜNSCH, Josef, Fischer, David, Lux, Martin, Lilge, Dieter filed Critical WÜNSCH, Josef
Publication of WO1996020226A1 publication Critical patent/WO1996020226A1/fr

Links

Classifications

    • 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
    • C08F12/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F12/02—Monomers containing only one unsaturated aliphatic radical
    • C08F12/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • 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
    • C08F4/65908—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+
    • 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
    • C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
    • 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

Definitions

  • the present invention relates to processes for the preparation of polymers of vinylaromatic compounds at temperatures in the range from 0 to 150 ° C. in the presence of catalyst systems.
  • the present invention further relates to the use of the polymers obtainable here for the production of moldings.
  • polymers of vinyl aromatic compounds are used in many areas, for example as packaging materials or as insulating coatings for metals or plastics, especially in electrical applications.
  • isotactic polystyrene A process for the production of isotactic polystyrene is described in GB-A 826 021. However, isotactic polystyrene crystallizes so slowly that it cannot be processed by injection molding.
  • Syndiotactic polystyrene by reacting styrene in the presence of a metallocene complex and a cocatalyst are described, for example, in EP-A 535 582 and EP-A 584 646.
  • Syndiotactic polystyrene has high chemical resistance, high rigidity, good dimensional stability and good dielectric properties.
  • the processes described in the cited documents lead to polymers with a narrow molecular weight distribution.
  • syndiotactic polymers of vinyl aromatic compounds with a broad molecular weight distribution are advantageous for some applications, for example housings for motors, electrical housings, large-area covers such as bonnets or door leaves, or plugs and cable sheathing.
  • B) contain a metallocenium ion-forming compound.
  • R 2 to R 6 independently hydrogen, C ⁇ ⁇ to C; 2 ⁇ alkyl, C 6 - to Ci 8 ⁇ aryl, halogen or where two adjacent radicals together represent cyclic groups having 4 to 15 carbon atoms.
  • Vinylaromatic compounds of the formula I are preferably used in which
  • R means hydrogen
  • R 2 to R 6 for hydrogen, C ⁇ ⁇ to Cj-alkyl, chlorine, phenyl,
  • Naphthalene derivatives or anthracene derivatives result.
  • Styrene p-methylstyrene, p-chlorostyrene, 2, 4-dimethylstyrene, 4-vinylbiphenyl, vinylnaphthalene or vinylanthracene.
  • Mixtures of different vinyl aromatic compounds can also be used, but preferably only one vinyl aromatic compound is used.
  • Particularly preferred vinyl aromatic compounds are styrene and p-methylstyrene.
  • component A) is preferably two different metallocene complexes of the general formula II
  • R 7 to R i hydrogen, C ⁇ to Cio-alkyl, 5- to 7-membered
  • Cycloalkyl which in turn may carry C ⁇ ⁇ to C ⁇ -alkyl groups as substituents, C ⁇ ⁇ to C-aryl or aryl alkyl and optionally two adjacent radicals can be C-atoms which together cycli ⁇ specific groups of 4 to 15, or Si (R 12 ) 3 ,
  • R 12 it Ci- to C. o-alkyl, C 6 - to cis-aryl or C 3 - to C 1 o ⁇ cycloalkyl, M a metal of III. to VI. Subgroup of the Periodic Table of the Elements or a metal from the lanthanide series
  • Z to Z 5 hydrogen, halogen, C ⁇ to Cio-alkyl, C ⁇ - bis
  • Particularly preferred metallocene complexes of the general formula II are those in which
  • M stands for a metal of subgroup IV of the Periodic Table of the Elements, in particular for titanium
  • Z : to Z 5 are C ⁇ to Cio-alkyl, C ⁇ ⁇ to Cio-alkoxy or halogen.
  • Metallocene complexes such as those described in EP-A 584 646 can also be used.
  • Mixtures of two different metallocene complexes have proven to be particularly suitable, but mixtures of up to 5 different metallocene complexes can also be used.
  • a mixture of pentamethylcyclopentadienyltrimethyl and pentamethylcyclopentadienyltrimethylate is particularly preferably used.
  • Such complex compounds can be synthesized by methods known per se, the reaction of the appropriately substituted, cyclic hydrocarbon anions with Halides of titanium, zirconium, hafnium, vanadium, niobium or tantalum are preferred.
  • component B In the process according to the invention for the preparation of polymers of vinylaromatic compounds, compounds which form metallocenium ions are used as component B).
  • open-chain or cyclic alumoxane compounds of the general formula III or IV are suitable
  • R 13 is a Cj to C 4 alkyl group, preferably methyl or ethyl group and m is an integer from 5 to 30, preferably 10 to 25.
  • oligomeric alumoxane compounds are usually prepared by reacting a solution of trialkylaluminum with water and include in EP-A 284 708 and US-A 4,794,096.
  • the oligomeric alumoxane compounds obtained are mixtures of different lengths, both linear and cyclic chain molecules, so that m is to be regarded as the mean.
  • the alumoxane compounds can also be present in a mixture with other metal alkyls, preferably with aluminum alkyls.
  • Other suitable compounds forming etallocenium ions are in particular strong, neutral Lewis acids, ionic compounds with Lewis acid cations and ionic compounds with Bronsted acids as the cation.
  • Main group of the periodic table means, in particular B, Al or Ga, preferably B,
  • Ci- to Cio-alkyl, C 6 - to cis-aryl, alkylaryl, arylalkyl, haloalkyl or haloaryl, each with 1 to 10 carbon atoms in the alkyl radical and 6 to 20 carbon atoms are in the aryl radical or fluorine, chlorine, bromine or iodine, in particular for haloaryls, preferably for pentafluorophenyl.
  • Q to Q z for single negatively charged residues, such as C 1 -C 28 -alkyl, C 6 to Cis-aryl, alkylaryl, arylalkyl,
  • Mercaptyl groups a represents integers from 1 to 6,
  • d corresponds to the difference a - z, but d is greater than or equal to 1.
  • Carbonium cations, oxonium cations and sulfonium cations as well as cationic transition metal complexes are particularly suitable.
  • the triphenylmethyl cation, the silver cation and the 1, 1'-dimethylferrocenyl cation should be mentioned in particular.
  • non-coordinating counterions in particular boron compounds, as they are also mentioned in WO 91/09882, preferably tetrakis (pentafluorophenyl) borate.
  • Ionic compounds with Bronsted acids as cations and preferably also non-coordinating counterions are mentioned in WO 93/3067, the preferred cation is N, N-dimethylanilinium.
  • the vinyl aromatic compounds can be polymerized in solution, in bulk, in suspension or in the gas phase.
  • the process is preferably carried out in solution, with aromatic hydrocarbons such as benzene, toluene, ethylbenzene or xylenes as well as ethers such as diethyl ether, dibutyl ether, ethylene glycol dimethyl ether or tetrahydrofuran or aliphatic hydrocarbons such as propane, n-butane and isobutane as solvents or pentanes, and mixtures of the various solvents can be used, or in bulk.
  • aromatic hydrocarbons such as benzene, toluene, ethylbenzene or xylenes
  • ethers such as diethyl ether, dibutyl ether, ethylene glycol dimethyl ether or tetrahydrofuran or aliphatic hydrocarbons
  • propane, n-butane and isobutane as solvents or
  • the polymerization conditions are not critical per se, temperatures in the range from 0 to 150 ° C., preferably from 10 to 100 ° C., pressures from 0.1 to 100 bar, preferably from 1 to 5 bar and polymerization times from 0.1 to 24 are suitable Hours, preferably from 0.5 to 6 hours.
  • the metallocene complexes are preferably used without support, but they can also be used with support.
  • Suitable carrier materials are, for example, silica gels, preferably those of the formula Si0 2 • aAl 2 0 3 , in which a is a number in the range from 0 to 2, preferably 0 to 0.5; essentially aluminum silicates or silicon dioxide.
  • the carriers preferably have a particle diameter in the range from 1 to 200 ⁇ m on, in particular 30 to 80 microns. Products of this type are commercially available, for example as Silica Gel 332 from Grace.
  • Other carriers include finely divided polyolefins, for example finely divided polypropylene or polyethylene, but also polyethylene glycol, polybutylene terephthalate, polyethylene terephthalate, polyvinyl alcohol, polystyrene, polybutadiene, polycarbonates or their copolymers.
  • aluminum alkyls can also be used in the polymerization.
  • Trimethyl aluminum, triethyl aluminum, tri-iso-propyl aluminum, tri-n-propyl aluminum, tri-isobutyl aluminum and tri-n-butyl aluminum are particularly suitable, but in particular triisobutyl aluminum.
  • aluminum alkyls is particularly suitable when using strong neutral Lewis acids, ionic compounds with Lewis acid cations and ionic compounds with Bronsted acids as cations, as compounds forming metallocenium ions.
  • the molar ratio of the vinyl aromatic compound to the compound forming metallocenium ions is in the range from 10 2 : 1 to 10: 1, preferably in the range from 10 3 : 1 to 10 6 : 1.
  • the molar ratio of metallocenium ion-forming compound to the total molar amount of metallocene complexes is preferably in the range from 10 ⁇ 2 : 1 to 10 7 : 1, in particular in the range from 10 2 : 1 to 10 5 : 1.
  • the molar ratio of one metal ocene complex to the other metallocene complex is preferably in the range from 10 -3 : 1 to 10 3 : 1, in particular in the range from 10 ⁇ 2 : 1 to 10 2 : 1. If three or more metallocene complexes are used, the composition can vary so much that a metallocene complex is present up to a 1000-fold molar excess compared to the next most common metallocene complex. However, at most a 100-fold molar excess is preferred.
  • a molar ratio of aluminum alkyl to the total amount of metallocene complexes from 10,000: 1 to 10: 1, preferably from 1000: 1 to 100: 1, has therefore proven particularly suitable.
  • the process according to the invention is preferably carried out by initially introducing the vinylaromatic compound, optionally with a solvent, to temperatures in the range warmed from 40 to 80 ° C. and either the open-chain or cyclic alumoxane compound or the trialkyl aluminum and the strong, neutral Lewis acid, the ionic compound with Lewis acidic cation or the ionic compound with a Bronsted acid as a cation are added. Then you give the
  • the metallocene complexes can also be mixed beforehand with the compound forming the metallocenium ion and this mixture added to the reactor. Polymerization is then preferably carried out over a period of 45 to 90 minutes and the polymerization is terminated by adding methanol. The polymer obtained is preferably washed with methanol and dried at 40 to 100 ° C.
  • the process according to the invention is distinguished by the fact that it is technically inexpensive, the resulting polymers are syndiotactic and have a broad molecular weight distribution M w : M ⁇ of preferably 5 to 100 and are particularly suitable for the use of molding compositions in electrical or high-temperature resistant Applications.
  • the molar masses of the polymers prepared by the process according to the invention are in the range from 10,000 to 10,000,000 g / mol, preferably from 50,000 to 1,000,000 g / mol.
  • the molar mass distribution was determined by high-temperature GPC (G_elßermeations -_- chromatography) with 1,2,4-trichlorobenzene as solvent at 135 ° C. The calibration was carried out using narrowly distributed polystyrene standards.
  • the syndiotactic fraction determined by 13 C-NMR was> 96%.
  • the syndiotactic fraction determined by 3 C-NMR was> 96%.
  • the syndiotactic fraction determined by 13 C-NMR was> 96%.

Landscapes

  • 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)

Abstract

Procédé de fabrication de polymères de composés vinylaromatiques,à des températures comprises entre 0 et 150 DEG C, en présence de systèmes catalyseurs. On utilise, comme systèmes de ce genre, des systèmes renfermant comme constituants actifs A) au moins deux complexes métallocènes différents et B) un composé formant des ions métallocénium.
PCT/EP1995/004892 1994-12-23 1995-12-12 Procede de fabrication de polymeres de composes vinylaromatiques, avec utilisation de melanges de systemes catalyseurs metallocenes WO1996020226A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DEP4446385.5 1994-12-23
DE19944446385 DE4446385A1 (de) 1994-12-23 1994-12-23 Verfahren zur Herstellung von Polymerisaten von vinylaromatischen Verbindungen unter Verwendung von Mischungen von Metallocenkatalysatorsystemen
DE19500811A DE19500811A1 (de) 1995-01-13 1995-01-13 Verfahren zur Herstellung von Polymerisaten von vinylaromatischen Verbindungen unter Verwendung von Mischungen von Metallocenkatalysatorsystemen
DE19500811.1950113 1995-01-13

Publications (1)

Publication Number Publication Date
WO1996020226A1 true WO1996020226A1 (fr) 1996-07-04

Family

ID=25943282

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1995/004892 WO1996020226A1 (fr) 1994-12-23 1995-12-12 Procede de fabrication de polymeres de composes vinylaromatiques, avec utilisation de melanges de systemes catalyseurs metallocenes

Country Status (1)

Country Link
WO (1) WO1996020226A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102746436A (zh) * 2011-04-20 2012-10-24 中国石油化工股份有限公司 双峰宽分子量分布间规聚苯乙烯聚合物
CN102746435A (zh) * 2011-04-20 2012-10-24 中国石油化工股份有限公司 宽分子量分布间规聚苯乙烯聚合物制备方法
CN102746428A (zh) * 2011-04-20 2012-10-24 中国石油化工股份有限公司 双活性茂金属钛组合物及其制备方法
CN103539878A (zh) * 2012-07-12 2014-01-29 中国石油化工股份有限公司 双峰宽分子量分布间规聚苯乙烯聚合物制备方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0420134A2 (fr) * 1989-09-29 1991-04-03 Idemitsu Kosan Company Limited Procédé pour la préparation de polymères de styrène
EP0421659A2 (fr) * 1989-09-29 1991-04-10 The Dow Chemical Company Procédé de préparation d'un polymère vinyl-aromatique syndiotactique
US5276117A (en) * 1988-03-24 1994-01-04 Idemitsu Kosan Co., Ltd. Process for producing styrene-based polymers and catalysts for use therein
EP0584646A2 (fr) * 1992-08-14 1994-03-02 Idemitsu Petrochemical Co., Ltd. Procédé de préparation d'un polymère styrénique
WO1995003339A1 (fr) * 1993-07-23 1995-02-02 Idemitsu Kosan Co., Ltd. Catalyseur utilise pour produire une composition polymere a base d'un compose vinylique aromatique, et procede permettant de produire un polymere a base d'un compose vinylique aromatique au moyen dudit catalyseur

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5276117A (en) * 1988-03-24 1994-01-04 Idemitsu Kosan Co., Ltd. Process for producing styrene-based polymers and catalysts for use therein
EP0420134A2 (fr) * 1989-09-29 1991-04-03 Idemitsu Kosan Company Limited Procédé pour la préparation de polymères de styrène
EP0421659A2 (fr) * 1989-09-29 1991-04-10 The Dow Chemical Company Procédé de préparation d'un polymère vinyl-aromatique syndiotactique
EP0584646A2 (fr) * 1992-08-14 1994-03-02 Idemitsu Petrochemical Co., Ltd. Procédé de préparation d'un polymère styrénique
WO1995003339A1 (fr) * 1993-07-23 1995-02-02 Idemitsu Kosan Co., Ltd. Catalyseur utilise pour produire une composition polymere a base d'un compose vinylique aromatique, et procede permettant de produire un polymere a base d'un compose vinylique aromatique au moyen dudit catalyseur

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102746436A (zh) * 2011-04-20 2012-10-24 中国石油化工股份有限公司 双峰宽分子量分布间规聚苯乙烯聚合物
CN102746435A (zh) * 2011-04-20 2012-10-24 中国石油化工股份有限公司 宽分子量分布间规聚苯乙烯聚合物制备方法
CN102746428A (zh) * 2011-04-20 2012-10-24 中国石油化工股份有限公司 双活性茂金属钛组合物及其制备方法
CN103539878A (zh) * 2012-07-12 2014-01-29 中国石油化工股份有限公司 双峰宽分子量分布间规聚苯乙烯聚合物制备方法

Similar Documents

Publication Publication Date Title
DE4406963A1 (de) Metallocenkomplexe mit heterofunktionellen Gruppen am Cyclopentadienylsystem
EP0882076A1 (fr) Systemes de catalyseurs a supports
EP0868440B1 (fr) Procede de fabrication de copolymeres d'ethylene sous haute pression
EP0920463A1 (fr) Polymeres en etoile et leur preparation
DE4139262A1 (de) Getraegerte katalysatorsysteme zur polymerisation von c(pfeil abwaerts)2(pfeil abwaerts)- bis c(pfeil abwaerts)1(pfeil abwaerts)(pfeil abwaerts)0(pfeil abwaerts)-alkenen
DE4337233A1 (de) Verfahren zur Herstellung von Polymerisaten von C¶2¶- bis C¶1¶¶0¶-Alk-1-enen unter Verwendung von racemischen Metallocenkomplexen als Katalysatoren
WO1996020226A1 (fr) Procede de fabrication de polymeres de composes vinylaromatiques, avec utilisation de melanges de systemes catalyseurs metallocenes
EP0876408B1 (fr) Procede de preparation de polymeres d'alcenes en c 2 a c 10 en presence de complexes metallocenes avec des ligands cyclopentadienyles fonctionnalises cationiquement
DE19826403A1 (de) Übergangsmetallkomplexe
EP0861273B1 (fr) Procede de production de copolymeres a partir de composes vinylaromatiques et olefiniques par polymerisation en dispersion en presence de systemes catalyseurs metallocenes
EP0811023B1 (fr) Procede de production de polymeres de composes vinylaromatiques au moyen de systemes catalyseurs contenant des polymeres
EP0866812B1 (fr) Procede de production de copolymerisats de composes vinylaromatique en une seule etape, au moyen d'extrudeuses a deux vis
WO2004078765A2 (fr) Catalyseurs pour la polymerisation du styrene
EP0866813B1 (fr) Procede de production de polymerisats de composes vinylaromatiques en une seule etape, au moyen d'extrudeuses a deux vis
EP0815148B1 (fr) Procede de preparation de polymerisats de composes vinyliques aromatiques sous pression en presence d'hydrocarbures tres volatils
DE19500811A1 (de) Verfahren zur Herstellung von Polymerisaten von vinylaromatischen Verbindungen unter Verwendung von Mischungen von Metallocenkatalysatorsystemen
EP0931100B1 (fr) Systeme catalyseurs contenant des complexes metalliques d'une structure similaire a l'adamantane
DE4446385A1 (de) Verfahren zur Herstellung von Polymerisaten von vinylaromatischen Verbindungen unter Verwendung von Mischungen von Metallocenkatalysatorsystemen
EP0951490A1 (fr) Procede de preparation de polymerisats a base de composes vinylaromatiques par polymerisation en dispersion
DE19714548A1 (de) Thermoplastische Formmassen
DE19506554A1 (de) Verfahren zur Herstellung von Polymerisaten von vinylaromatischen Verbindungen unter Verwendung von Polymere enthaltenden Katalysatorsystemen
DE4425787A1 (de) Verfahren zur Herstellung von kammartigen Polypropylenen
WO1998057995A2 (fr) Systemes catalyseurs constitues de cyclopenta [i] phenanthrene et d'un complexe metallique

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): CN JP US

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FR GB GR IE IT LU MC NL PT SE

WA Withdrawal of international application
121 Ep: the epo has been informed by wipo that ep was designated in this application
122 Ep: pct application non-entry in european phase