EP1121368A1 - Metallocenes a ponts rigides - Google Patents

Metallocenes a ponts rigides

Info

Publication number
EP1121368A1
EP1121368A1 EP99947464A EP99947464A EP1121368A1 EP 1121368 A1 EP1121368 A1 EP 1121368A1 EP 99947464 A EP99947464 A EP 99947464A EP 99947464 A EP99947464 A EP 99947464A EP 1121368 A1 EP1121368 A1 EP 1121368A1
Authority
EP
European Patent Office
Prior art keywords
fluorine
group
bis
trans
different
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
EP99947464A
Other languages
German (de)
English (en)
Inventor
Gerhard Erker
Stefanie KNÜPPEL
Cornelia Fritze
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Basell Polyolefine GmbH
Original Assignee
Basell Polypropylen GmbH
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 DE19847319A external-priority patent/DE19847319A1/de
Priority claimed from DE19847320A external-priority patent/DE19847320A1/de
Application filed by Basell Polypropylen GmbH filed Critical Basell Polypropylen GmbH
Publication of EP1121368A1 publication Critical patent/EP1121368A1/fr
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F17/00—Metallocenes
    • 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
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/04—Monomers containing three or four carbon atoms
    • C08F110/06—Propene
    • 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
    • C08F2420/00—Metallocene catalysts
    • C08F2420/10—Heteroatom-substituted bridge, i.e. Cp or analog where the bridge linking the two Cps or analogs is substituted by at least one group that contains a heteroatom
    • 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
    • C08F2420/00—Metallocene catalysts
    • C08F2420/11—Non-aromatic cycle-substituted bridge, i.e. Cp or analog where the bridge linking the two Cps or analogs is substituted by a non-aromatic cycle
    • 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
    • C08F2420/00—Metallocene catalysts
    • C08F2420/12—Long bridge, i.e. Cp or analog where the bridging unit linking the two Cps or analogs is composed of at least two atoms which are not part of a cycle and which are not an ethylene bridge

Definitions

  • the present invention relates to rigid-bridge metallocenes and a process for their preparation, and their use as a catalyst component for the production of polyolefins with the exception of cyclic polyolefins.
  • Lewis acidity can convert the neutral transition metal compound into a cation and stabilize it, known (EP-A 129 368, EP-A 351 392, EP-A 416 815).
  • Metallocenes are of great interest not only with regard to the polymerization or oligomerization of olefins. They can also be used as hydrogenation, epoxidation,
  • the polymerization properties of a metallocene compound can be controlled by the ligand system.
  • Derivatives of zirconocene dichloride in which the two substituted cyclopentadienyl groups are connected to one another, for example via a methyl, ethyl or dimethylsilyl bridge, can be used as catalysts for the isospecific polymerization of
  • Olefins are used (EP-A 316 155).
  • the present invention relates to bridged metallocene complexes with a rigid bridge and a process for their preparation.
  • the compound according to the invention is an organometallic compound of the formula
  • M is a metal from group 3, 4, 5 or 6 of the periodic table of the elements and lanthanides or actinides, preferably titanium, zirconium or hafnium
  • R 1 , R 5 are the same or different and are a hydrogen atom or a C1-C40- carbon-containing group, such as. B. methyl, ethyl, tert-butyl, cyclohexyl or octyl, C2-C25-alkenyl, C3-C-
  • R ⁇ identically or differently represents a hydrogen atom or a C-
  • R5 can be linked to one another in such a way that the radicals Rl or R 5 and the atoms of the cyclopentadienyl ring connecting them form a C4-C24-ing system which, in turn, can be substituted, m is 0, 1, 2, 3 or 4, p 0, 1, 2, 3 or 4,
  • R2 and R3 are the same or different and a hydrogen atom or a C ⁇ -C4Q- carbon-containing group, such as. B. methyl, ethyl, tert-butyl, cyclohexyl or octyl, C2-C25-alkenyl, C-3-Ci5-alkylalkenyl, Cö-C24-aryl, C5-C24-heteroaryl, e.g. B.
  • Ce-Ci o-fluoroaryl Cg-Ci o-aryloxy, C2-C ⁇ o-alkenyl, C7-C4o-arylalkyl, C7-C40-alkylaryl or C8-C4o-arylalkenyi, or two or more radicals R 1 or
  • R5 can be linked to one another in such a way that the radicals R1 or R ⁇ and the atoms of the cyclopentadienyl ring connecting them form a C4-C24 ring system, which in turn can be substituted,
  • R4 is an NR 7 R ⁇ group, wherein R 7 and R ⁇ are the same or different and a hydrogen atom or a C -) - C4o-kohienstoffumble group, such as. B. methyl,
  • -C-j2-amino, or the radicals R 7 and R ⁇ can be connected to one another in such a way that they form a C4-C24 ring system, which in turn can be substituted, n 0, 1, 2, 3 or 4 and X is the same or different and a hydrogen atom, a Ci-C 1-6 alkyl , a C-
  • Arylalkenyl, an OH group or a halogen atom is Arylalkenyl, an OH group or a halogen atom.
  • organometallic compound according to the invention examples but not limiting examples are:
  • M 1 M, R 1 , R 2 , R 3 , R 4 , R 5 , X, m, p and n have the same meaning as given above in formula I and m + p is 0, 1, 2 , 3 or 4 can be.
  • Strong bases such as lithium diisopropylamide, lithium hexamethyl disilazide, methyl lithium, butyllithium, potassium tert-butylate or potassium hydride are suitable as the base.
  • the reaction takes place at temperatures from -50 ° C to + 150 ° C, preferably at 0 ° C to 100 ° C.
  • Suitable solvents in which the reactions described are carried out are aliphatic or aromatic
  • Hydrocarbons which can be halogenated, such as but not exclusively pentane, hexane, cyclohexane, methylene chloride, dichloroethane, benzene, toluene, xylene, chlorobenzene, dichlorobenzene, ethers such as diethyl ether, dibutyl ether, tetrahydrofuran, anisole, dioxane, 1, 2-dimethoxyethane. Mixtures of two or more solvents can also be used. The implementation takes from 1 min to 20 days.
  • the compound of the formula I according to the invention can be isolated or used directly for further use.
  • the compound of formula (II) in the scheme above can be isolated, isolated or used directly for further use.
  • the compound of the formula I according to the invention can also be prepared in a one-pot reaction without isolation of intermediate and final stages.
  • the transition metal compounds according to the invention are highly active catalyst components for olefin polymerization. Depending on the substitution pattern of the ligands, the transition metal compounds can be obtained as a mixture of isomers.
  • the transition metal compounds are preferably used isomerically pure, but can also be used as a mixture of isomers.
  • the present invention further relates to a process for the preparation of a polyolefin by polymerizing one or more olefins in the presence of a
  • Catalyst system containing at least one transition metal compound according to the invention and at least one cocatalyst.
  • the term polymerization is understood to mean homopolymerization as well as copolymerization.
  • olefins examples include 1-olefins having 1 to 20 carbon atoms, such as ethylene, propene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene or 1-octene, styrene, or acyclic dienes such as 1,3-butadiene, isoprene, 1,4-hexadiene, cyclic olefins such as norbornene.
  • Propylene is preferably homopolymerized or propylene is copolymerized with one or more acyclic 1-olefins having 4 to 20 carbon atoms in the process according to the invention.
  • the polymerization is preferably carried out at a temperature of from -78 to 250.degree. C., particularly preferably from 50 to 200.degree.
  • the pressure is preferably 0.5 to 2000 bar, particularly preferably 5 to 64 bar.
  • the polymerization can be carried out in solution, in bulk, in suspension or in the gas phase, continuously or batchwise, in one or more stages.
  • the catalyst used in the process according to the invention preferably contains a transition metal compound. Mixtures of two or more transition metal compounds can also be used, e.g. for the production of polyolefins with a broad or multimodal molecular weight distribution.
  • any compound is suitable as a cocatalyst in the process according to the invention which, because of its Lewis acidity, can convert the neutral transition metal compound into a cation and stabilize it ("unstable coordination").
  • the cocatalyst or the anion formed from it should not undergo any further reactions with the cation formed (EP 427 697).
  • An aluminum compound and / or a boron compound as used in WO 971 1775 and German patent applications P19632557.9; P19733017.7 or P19744102.5 can be described, which are part of the description by citation.
  • the boron compound preferably has the formula R 12 X NH 4 - X BR 13 4 , R 12 X PH 4 - X BR 13 4 , R 2 3 CBR 13 or BR 13 3 , where x is a number from 1 to 4, preferably 3, means the R 12 radicals are the same or different, preferably the same, and -CC 10 alkyl or C6-C-i8-aryl, or two radicals R 12 together with the atoms connecting them form a ring, and the radicals R 13 are the same or are different, preferably the same, and are C 6 -C 18 aryl, which can be substituted by alkyl, haloalkyl or fluorine.
  • R 12 in particular represents ethyl, propyl, butyl or phenyl and R 13 represents phenyl,
  • Pentafluorophenyl 3,5-bistrifluoromethylphenyl, mesityl, xylyl or tolyl (EP-A-0,277,003; EP-A-0,277,004 and EP-A-0,426,638).
  • An aluminum compound such as aluminoxane and / or an aluminum alkyl is preferably used as the cocatalyst.
  • a cocatalyst is an aluminoxane (R 14 AIO) _ which can be cyclic and / or linear R 14, identical or different, is a hydrogen or a CC 20 hydrocarbon group, such as a CtC-ia alkyl group, a C 6 -C 6 ⁇ 8 aryl group or benzyl and z is an integer from 2 to 50, preferably 10 to 35.
  • R 14 AIO aluminoxane
  • R 14 radicals are preferably the same and denote hydrogen, methyl, isobutyl,
  • Phenyl or benzyl particularly preferably methyl.
  • the processes for producing the aluminoxanes are known.
  • the exact spatial structure of the aluminoxanes is not known (J. Am. Chem. Soc. (1993) 1 15, 4971). For example, it is conceivable that chains and rings combine to form larger two-dimensional or three-dimensional structures.
  • the preactivation of the transition metal compound is preferably carried out in solution performed.
  • the transition metal compound is preferably dissolved in a solution of the aluminoxane in an inert hydrocarbon.
  • An aliphatic or aromatic hydrocarbon is suitable as the inert hydrocarbon.
  • Toiuol is preferably used.
  • the concentration of the aluminoxane in the solution is in the range from about 1% by weight to the saturation limit, preferably from 5 to 30% by weight, based in each case on the total amount of solution.
  • the transition metal compound can be used in the same concentration, but it is preferably used in an amount of 10-4 to 1 mol per mol of aluminoxane.
  • the preactivation time is 5
  • the transition metal compound is preferably in a concentration, based on the transition metal, of 10 "3 to 10 " 8 , preferably 10 "4 to 10 " 7 mol
  • Transition detail applied per dm 3 solvent or per dm 3 reactor volume is preferably used in a concentration of 10 "6 to 10 " 1 mol, preferably 10 "5 to 10 " 2 mol per dm 3 solvent or per dm 3 reactor volume.
  • the other cocatalysts mentioned are used in approximately equimolar amounts to the transition metal compound. In principle, however, higher concentrations are also possible.
  • an aluminum compound preferably an aluminum alkyl, such as trimethyl aluminum or triethyl aluminum
  • This cleaning can take place both in the polymerization system itself, or the olefin is brought into contact with the aluminum compound before the addition into the polymerization system and then separated off again.
  • Transition metal compound to carry out a prepolymerization the (or one of the) olefin (s) used in the polymerization is preferably used.
  • the catalyst used in the process according to the invention can be supported.
  • the support allows, for example, the grain morphology of the polyolefin produced to be controlled.
  • the transition metal compound can be reacted first with the support and then with the cocatalyst.
  • the cocatalyst can also first be supported and then reacted with the transition metal compound. It is also possible to slow the reaction product of transition metal compound and cocatalyst.
  • Suitable carrier materials are, for example, silica gels, aluminum oxides, solid aluminoxane or other inorganic carrier materials such as magnesium chloride.
  • a suitable carrier material is also a polyolefin powder in finely divided form.
  • Cocatalyst can, for example, as in WO 97/1 17775; EP-A-0, 567.952; EP-A-0,578,838; P19632558.7; P19634703.3; P19647070.6; 19757540.4 or P19804970.6.
  • the cocatalyst e.g. Aluminoxane
  • a carrier such as silica gels, aluminum oxides, solid aluminoxane, other inorganic carrier materials or a polyolefin powder in finely divided form and then reacted with the transition metal compound.
  • Oxides can be used as inorganic carriers, which have been generated by flame pyrocytic combustion of cement halides in a detonating gas flame, or can be produced as silica gel in certain particle size distributions and particle shapes. Further possibilities for producing a supported cocatalyst are described in EP-A-0,578,838.
  • the transition metal compound according to the invention is then applied to the supported cocatalyst by stirring the dissolved transition metal compound with the supported cocatalyst. The solvent is removed and replaced by a hydrocarbon in which both the cocatalyst and the transition metal compound are insoluble.
  • the reaction to the supported catalyst system takes place at a temperature of -20 to +120 C, preferably 0 to 100 C, particularly preferably at 15 to 40 C.
  • the transition metal compound is reacted with the supported cocatalyst in such a way that the cocatalyst as a suspension with 1 to 40% by weight, preferably with 5 to 20% by weight in an aliphatic, inert suspension medium such as n-decane, hexane, heptane, Diesel oil with a solution of the transition metal compound in an inert solvent such as toluene, hexane,
  • the reaction is carried out by intensive mixing, for example by stirring at a molar Al / catalyst ratio of 100/1 to 10000/1, preferably from 100/1 to 3000/1 and a reaction time of 5 to 120 minutes, preferably 10 to 60 minutes , particularly preferably 10 to 30 minutes under inert conditions.
  • a reaction time of 5 to 120 minutes, preferably 10 to 60 minutes , particularly preferably 10 to 30 minutes under inert conditions.
  • changes occur in the color of the reaction mixture, particularly during the use of the transition metal compound according to the invention with absorption maxima, the course of which allows the progress of the reaction to be monitored.
  • the supernatant solution is separated off, for example by filtration or decanting.
  • the remaining solid is washed 1-5 times with an inert suspending agent such as toluene, n-decane, hexane, Diesel oil, dichloromethane to remove soluble constituents in the catalyst formed, in particular to remove unreacted and thus soluble transition metal compound.
  • an inert suspending agent such as toluene, n-decane, hexane, Diesel oil, dichloromethane to remove soluble constituents in the catalyst formed, in particular to remove unreacted and thus soluble transition metal compound.
  • the supported catalyst system thus produced can be dried in vacuo as
  • an inert solvent customary for the Ziegler low-pressure process is used.
  • an aliphatic or cycloaliphatic hydrocarbon such as propane, butane, hexane, heptane, isooctane, cyclohexane, methylcyclohexane.
  • a gasoline or hydrogenated diesel oil fraction can also be used.
  • Toluene can also be used.
  • Polymerization is preferably carried out in the liquid monomer.
  • the supported catalyst system from a transition metal compound according to the invention and a supported cocatalyst or from an inventive one
  • Transition metal compound and an organoaluminum compound on a polyolefin powder in finely divided form another aluminum alkyl compound such as trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, trioctyl aluminum or isoprenyl aluminum can be added to the polymerization system (for example to separate existing catalyst poisons into the reactor in the olefin). This is added to the polymerization system in a concentration of 100 to 0.01 mmol AI per kg reactor content. Triisobutylaluminum and triethylaluminum are preferred in a concentration of 10 to 0.1 mmol Al per kg reactor content. As a result, the molar Al / catalyst ratio can be chosen to be small in the synthesis of a supported catalyst system.
  • another aluminum alkyl compound such as trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, trioctyl aluminum or isoprenyl aluminum
  • the monomers become gaseous or liquid added.
  • the duration of the polymerization is arbitrary, since the catalyst system to be used in the process according to the invention shows only a slight time-dependent drop in the polymerization activity.
  • the compounds were characterized by DSC, 1 H-HMR, 13 C-NMR or IR spectroscopy.
  • Example 3 Synthesis of 6-methyl-6 ' -N, N-morpholino aminofulven: 10 g of 6-methyl-6 ' -N, N-dimethy! Aminofulven are refluxed with 150 ml of morpholine for 5 days. The solvent is then removed on a rotary evaporator.
  • Example 4 Synthesis of (6-dimethylamino-5-vinyl) cyclopentadienyllithium: At -78 ° C a suspension of 6 g of 6-methyl-6 '-dimethyiaminofulven in 80 ml of tetrahydrofuran with 27.7 ml of a 1.6 molar Methyilithiumites in diethyl ether was added. The mixture is allowed to thaw slowly and stirred at room temperature for 12 h. The resulting solution is concentrated in an oil pump vacuum and stirred for a further 2 hours with pentane. Allow to settle and decant the pentane phase. The precipitate is dried in an oil pump vacuum. Yield: 7 g (6-dimethylamino-5-vinyl) cyclopentadienyllithium (89%)
  • Example 5 Synthesis of (6-pyrrolidino-5-vinyl) cyclopentadienyllithium: At -78 ° C, a suspension of 5 g of 6-methyl-6 ' -N, N-pyrrolindinoaminofuiven in
  • Example 6 Synthesis of (6-morpholino-5-vinyl) cyclopentadienyllithium: At -78 ° C, a suspension of 6.94 g of 6-methyl-6 ' -N, N-morpholinoaminofuiven in 80 ml of tetrahydrofuran with 24 ml of a 1.75 molar methyl lithium solution added in diethyl ether. Allow to thaw slowly and stir for 12 hours
  • Example 11 Synthesis of 9-N-pyrrolidino-trans-6,9-bis (cyclopentadienyl) butadienyldichlorohafnium: At -78 ° C., 1.5 g of 6-pyrrolidino-5-vinylcyclopentadienyllithium in 60 ml
  • Example 12 Synthesis of 9-N, N-dimethylamino-trans-6,9-bis (cyclopentadienyl) butadienyldichlorotitanium: At -78 ° C. 1 g (6-N, N-dimethylamino-5-vinyl) cyclopentadienylilithium in 60 ml
  • the polymerization is started by injection of 18 mg of 9-N, N-dimethylamino-trans-6,9-bis (cyclopentadieny) butadienyldichiorozirconium, dissolved in toluene. After 40 minutes, the polymerization is stopped by degassing the excess monomer and carefully adding hydrochloric acid methanol.
  • Example 19 In a 1 liter autoclave, 200 ml of toluene, 2.3 g of norbornene, dissolved in 100 ml

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)

Abstract

L'invention concerne des métallocènes à ponts rigides et un procédé permettant de les préparer, ainsi que leur utilisation comme constituants de catalyseurs pour préparer des polyoléfines.
EP99947464A 1998-10-14 1999-10-05 Metallocenes a ponts rigides Ceased EP1121368A1 (fr)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
DE19847319A DE19847319A1 (de) 1998-10-14 1998-10-14 Verfahren zur Herstellung von Cycloolefincopolymeren unter Verwendung von Metallocenen mit starrer Brücke
DE19847320A DE19847320A1 (de) 1998-10-14 1998-10-14 Metallocene mit starrer Brücke
DE19847320 1998-10-14
DE19847319 1998-10-14
PCT/EP1999/007381 WO2000021972A1 (fr) 1998-10-14 1999-10-05 Metallocenes a ponts rigides

Publications (1)

Publication Number Publication Date
EP1121368A1 true EP1121368A1 (fr) 2001-08-08

Family

ID=26049508

Family Applications (1)

Application Number Title Priority Date Filing Date
EP99947464A Ceased EP1121368A1 (fr) 1998-10-14 1999-10-05 Metallocenes a ponts rigides

Country Status (3)

Country Link
EP (1) EP1121368A1 (fr)
JP (1) JP2002527446A (fr)
WO (1) WO2000021972A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10038709A1 (de) * 2000-08-09 2002-02-28 Aventis Pharma Gmbh Substituierte und unsubstituierte Benzooxathiazole sowie daraus abgeleitete Verbindungen

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO0021972A1 *

Also Published As

Publication number Publication date
JP2002527446A (ja) 2002-08-27
WO2000021972A1 (fr) 2000-04-20

Similar Documents

Publication Publication Date Title
EP0816372B1 (fr) Composé d'un métal de transition
EP1325926B1 (fr) Métallocènes
EP0781783B1 (fr) Systèmes catalytiques à base de métallocène comportant une base de Lewis présentant un encombrement stérique
DE19739946A1 (de) Verfahren zur Herstellung von Metallocenen
EP0779295B1 (fr) Métallocènes
EP1033371A1 (fr) Complexe de métaux de transition, système catalyseur, procédé de préparation et son utilisation pour la polymérisation de polyoléfines
EP0723971A2 (fr) Métallocènes et leur utilisation comme composant d'un catalyseur
EP0742225A1 (fr) Composé organométallique
EP1284981B1 (fr) Procede de preparation de composes de metaux de transition et leur utilisation pour polymeriser des olefines
EP0749985A2 (fr) Composés de métallocène stéréo rigides
EP0707010B1 (fr) Métallocènes
EP1000092B1 (fr) Catalyseurs a base de complexes metalliques de fulvene
DE69310139T2 (de) Dimere und tetramere cyclopentdienyl-gruppe 6b-alpha-olefinpolymerisationskatalysatore und verfahren zur olefinpolymerisation
DE19847320A1 (de) Metallocene mit starrer Brücke
EP0837068A2 (fr) Métallocènes stéréorigides
EP1992630B1 (fr) Composés non metallocènes fixés de façon covalente, procédé de fabrication de ceux-ci et utilisation pour la polymerisation
EP1121368A1 (fr) Metallocenes a ponts rigides
EP1084159A1 (fr) Systeme catalyseur compose de metallocenes comprenant des substituants fluores
WO1997023512A1 (fr) Compose metallique de transition
DE19847319A1 (de) Verfahren zur Herstellung von Cycloolefincopolymeren unter Verwendung von Metallocenen mit starrer Brücke
EP0749975B1 (fr) Composé d'un métal de transition
WO2003080684A1 (fr) Metallocenes «a geometrie contrainte', leur procede de production et leur utilisation pour la polymerisation d'olefines
DE19756742A1 (de) Verfahren zur Herstellung von Fulven-Metallkomplexen
WO2002034758A1 (fr) Composition a base de complexes monofluorometalliques
EP0812853A2 (fr) Composés contenant un métal de transition

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20010405

AK Designated contracting states

Kind code of ref document: A1

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

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

17Q First examination report despatched

Effective date: 20020305

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION HAS BEEN REFUSED

18R Application refused

Effective date: 20020831