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WO2001077189A1 - Procede pour produire un catalyseur a support pour la polymerisation d'olefines - Google Patents

Procede pour produire un catalyseur a support pour la polymerisation d'olefines Download PDF

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Publication number
WO2001077189A1
WO2001077189A1 PCT/EP2001/003821 EP0103821W WO0177189A1 WO 2001077189 A1 WO2001077189 A1 WO 2001077189A1 EP 0103821 W EP0103821 W EP 0103821W WO 0177189 A1 WO0177189 A1 WO 0177189A1
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butyl
iso
phenyl
propyl
sec
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Marc Oliver Kristen
Gerhard Hauck
Andrei Gonioukh
Carsten SÜLING
Wolf Spaether
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BASF SE
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BASF SE
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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
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/04—Monomers containing three or four carbon atoms
    • C08F210/06—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
    • 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
    • C08F110/02—Ethene
    • 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
    • C08F4/65908—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
    • C08F4/65916—Component covered by group C08F4/64 containing a transition metal-carbon bond supported on a carrier, e.g. silica, MgCl2, polymer
    • 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
    • C08F4/65925—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 non-bridged

Definitions

  • M is a transition metal from groups 5 to 10 of the Periodic Table of the Elements
  • A is selected from N, P or As,
  • a ' is selected from 0 or S
  • R 1 , R2 unsubstituted or substituted C 1 -C 8 alkyl, C 3 -C 5 cycloalkyl, C-Ci 5 aralkyl, Cg-C ⁇ aryl or five- or six-membered N-containing heteroaryl, R 3 , R4 hydrogen, unsubstituted or substituted C 1 -C 2 alkyl, C 3 -C 2 cycloalkyl, C 7 -C 5 aralkyl / C 6 -Ci 4 aryl or five- or six-membered N-containing heteroaryl,
  • R 5 to R 7 are independently selected from hydrogen, unsubstituted or substituted C 1 -C 4 alkyl, C 3 -C 2 cycloalkyl, C 7 -C 5 aralkyl, C 6 -C 4 aryl or five- or six-membered N -containing heteroaryl, halogen, -CC 6 alkoxy, N0 2 , SiR 8 R 9 R 10 or OSiR 8 R 9 R 10 , where adjacent residues can be linked together to form a 5- to 10-membered ring, including the parent body , R 8 to R 10 are independently selected independently of one another from hydrogen or unsubstituted or substituted C 1 -C 4 alkyl, C 3 -C 4 cycloalkyl, C 7 -Ci 5 aralkyl, C 6 -C 4 aryl; together with a molecularly defined activator of the general formulas II a to c
  • [LH] + is a Bronsted acid, where L is an electroneutral Lewis base, M 'is an element of Group 13 of the Periodic Table of the
  • Q 1 to Q 4 is independently selected from hydride, unsubstituted or substituted C 1 -C 4 alkyl,
  • a further compound which can be used as a catalytically active component for the polymerization of olefins, on a water-free porous support material.
  • the present invention relates to a process for the preparation of a supported catalyst for the polymerization of olefins.
  • the present invention further relates to a supported catalyst produced by the process according to the invention, and to a process for the polymerization of olefins using the catalyst according to the invention.
  • Polymers and copolymers of olefins are of great economic importance because the monomers are readily available in large quantities and because the polymers can be varied over a wide range by varying the production process or the processing parameters. Particular attention is paid to the catalyst used in the manufacturing process.
  • various types of single-site catalysts are of increasing importance, with central atoms in addition to Zr, for example in metallocene catalysts (H.-H. Brintzinger et al., Angew. Chem. 1995, 107, 1255) Ni or Pd (WO 96/23010) or Fe and Co (for example WO 98/27124) have also recently been examined in more detail.
  • the complexes of Ni, Pd, Fe and Co are also called late transition metal complexes.
  • Metallocene catalysts have disadvantages for large-scale use. The catalysts are very sensitive to impurities in the monomers available on an industrial scale, in the process gas and in the solvents used. Moisture and oxygen and CO are examples of disturbing impurities. Furthermore, the price for Zr as the central metal of the technically important zirconocenes is very high.
  • Ni or Pd complexes (WO 96/23010) catalyze the formation of highly branched, commercially less interesting polymers
  • the use of Fe or Co complexes leads to the formation of highly linear polyethylene.
  • GJP Britovsek et al. J. Am. Chem. Soc. 1999, 121, 8728 and VC Gibson et al. , J. Chem. Soc, Chem. Commun. 1998, 849 and in M. Brookhart et al., J " . Am. Chem. Soc.
  • aluminoxanes must be used in a large molar excess; 100 to 1000-fold excesses are common. This makes the cocatalyst a significant cost factor for the catalysts.
  • the catalysts activated with aluminoxanes are usually metered in a polymerization-active manner into the current process, for example gas phase, solution, suspension or bulk polymerization processes, and can lead to blockages, particularly in the metering lines.
  • Aluminoxanes are molecularly undefined substances whose ability to activate transition metal complexes strongly depends on the manufacturing process and impurities. The storage temperature and the storage time also play a role. Quality control is difficult.
  • - ⁇ Aluminoxanes must always be stored refrigerated, because otherwise they tend to gel. Aluminoxane gels are unsuitable as cocatalysts.
  • Aluminoxanes are marketed as solutions, so a lot of otherwise worthless solvent has to be transported.
  • Aluminoxanes, in particular those with C 1 -C 4 -alkyl radicals, and their solutions are pyrophoric and require increased security.
  • metallocene dialkyl compounds that are usually used are commercially available or that they can easily be obtained from the metallocene dichloride. This is often not the case with the corresponding complexes of late transition metals.
  • WO 98/27124 and WO 98/30612 relate to the polymerization of ethylene and propylene, in which case an Fe or Co complex of a tridentate pyridyldiimine ligand is first contacted with ethylene or propylene or another monomer; then MAO or an activator with a defined structure are added and finally an aluminum alkyl.
  • the procedure is such that a complex of a late transition metal, in this case an Fe or Co complex in the presence of ethylene, is first mixed with aluminum trialkyl and then with a strong Lewis acid such as B (C 6 F 5 ) 3rd
  • B (C 6 F 5 ) 3rd The low activity of the disclosed systems with 8 or 13 kg of polyethylene / (mol of Co) -h is disadvantageous. Such little active catalysts are unsuitable for technical processes.
  • WO 99/12981 relates to complexes of late transition metals with tridentate pyridyldiimine ligands as catalysts for the polymerization of 1-olefins.
  • Example 29 shows the polymerization with a molecularly defined activator, especially a tetrakis pentafluorophenyl borate, and (trimethylsilylmethyl) magnesium chloride as the alkylating agent.
  • the trimethylsilylmethyl anion is sterically very demanding and must be chosen because it can prevent reductive elimination of the alkyl groups on the late transition metal.
  • WO 99/46304 relates to catalyst systems for the polymerization and copolymerization of olefins based on supported complexes of late transition metals, which are deposited on a solid catalyst.
  • Alumina or molecularly defined activators are used as activators for the complexes, preference being given to silica gel, aluminum oxide or zirconium oxide as carrier materials and methylaluminoxane as activator.
  • the carrier materials are reacted with methylalumoxane prior to the actual deposition of the active components in order to rid them of moisture.
  • These catalysts also contain MAO.
  • One or more compounds of the general formulas I a or b are used to prepare the catalyst: in which the variables are defined as follows:
  • M is a transition metal from groups 5 to 10 of the Periodic Table of the Elements, A is selected from N, P or As, A 'is selected from 0 or S, Nu 1 , Nu 2 N or P,
  • R 1 , R 2 unsubstituted or substituted C 1 -C 2 alkyl, C 3 -C 8 cycloalkyl, Cv-cis aralkyl, C 6 -C 4 aryl or five- or six-membered N-containing heteroaryl, R 3 , R 4 Hydrogen, unsubstituted or substituted C 1 -C 12 alkyl, C 3 -C 2 cycloalkyl, C 7 -C 5 aralkyl, C 6 ⁇ C 4 aryl or five- or six-membered N-containing heteroaryl,
  • R 5 to R 7 are independently selected from hydrogen, unsubstituted or substituted C 1 -C 2 alkyl, C 3 -Ci 2 cycloalkyl, C-Ci 5 aralkyl, C 6 -C 4 aryl or five- or six-membered N -containing heteroaryl, halogen, -CC 6 alkoxy, N0 2 , SiR 8 R 9 R 10 or OSiR 8 R 9 R 10 , where adjacent residues can be linked together to form a 5- to 10-membered ring, including the parent body ,
  • A is particularly preferably N, A 'is particularly preferably S,
  • Halogen such as fluorine, chlorine, bromine or iodine, particularly preferably X 1 and X 2 are chlorine, -C-C 4 alkoxy such as methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, iso-butoxy, sec-butoxy and tert-butoxy; particularly preferably methoxy, ethoxy, n-propoxy and n-butoxy;
  • -CC 2 -alkyl for example methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec.
  • substituted C ⁇ -C ⁇ alkyl groups include: mono- or poly-halogenated C ⁇ -C ⁇ 2 alkyl ⁇ groups such as fluoromethyl, difluoromethyl, trifluoromethyl,
  • Examples of substituted cycloalkyl groups are:
  • C -C 3 aralkyl preferably C to C 2 phenylalkyl such as benzyl, 1-phenethyl, 2-phenethyl, 1-phenyl-propyl, 2-phenyl-propyl, 3-phenyl-propyl, neophyl (1-methyl- l-phenylethyl), 1-phenylbutyl, 2-phenylbutyl, 3-phenylbutyl and 4-phenylbutyl, particularly preferably benzyl;
  • C 6 -C 4 aryl for example phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl and 9th -Phenanthryl, preferably phenyl, 1-naphthyl and 2-naphthyl, particularly preferably phenyl;
  • C 6 -C 4 aryl such as phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-A thryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl and 9th -Phenanthryl, identical or differently substituted by one or more C ⁇ -C 8 alkyl groups, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n -Pentyl, iso-pentyl, sec.-pentyl, neo-pentyl, 1, 2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec.-hexyl, n-heptyl, iso-heptyl and n-oct
  • C 3 -C 2 cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl and cyclododecyl; are preferred
  • Ci-C ⁇ alkoxy groups such as methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, iso-butoxy, sec-butoxy, tert-butoxy, n-pentoxy, iso-pentoxy, n-hexoxy and iso -Hexoxy, particularly preferably methoxy, ethoxy, n-propoxy and n-butoxy; C 6 -C 14 aryloxy groups such as phenoxy, ortho-cresyloxy, meta-cresyloxy, para-cresyloxy, ⁇ -naphthoxy, ⁇ -naphthoxy or 9-anthryloxy; - Silyl groups SiR 8 R 9 R 10 , where R 8 to R 10 are independently selected from hydrogen, C 1 -C 2 alkyl groups, C 7 -Ci 5 aralkyl and C 6 -Ci 4 aryl groups; preferred are the trimethylsilyl, triethyl
  • C 7 -Ci 5 aralkyl and C 6 -Ci 4 aryl groups are selected; preferred are the trimethylsilyloxy-, triethylsilyloxy-, triisopropylsilyloxy-, diethylisopropylsilyloxy-, dirnethethylthexylsilyloxy-, tert.-butyldimethylsilyloxy-, tert.-butyldiphenylsilyloxy-, tribenzylsilyloxy-tri-xyloxy-diylsilyl-, triphenylsilyl-, triphenyl- xylsilyl-, triphenylsilyl-, triphenyl- xylsilyl-, triphenyl- xylsilyl-, triphenyl- xylsilyl-, triphenyl- the trimethylsilyloxy group and the tert-butyldimethylsilyl
  • 2, 6-dimethylphenyl, 2,6-diisopropylphenyl, mesityl and 2, 6-dichlorophenyl are very particularly preferred; five- to six-membered nitrogen-containing heteroaryl radicals such as, for example, JV-pyrrolyl, pyrrol-2-yl, pyrrol-3-yl, N-imidazolyl, 2-imidazolyl, 4-imidazolyl, l, 2,4-triazol-3-yl, l, 2,4-triazol-4-yl, 2-pyridyl, 3-pyridyl, 4-pyridyl, 3-pyridazinyl, 4-pyridazinyl, 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl, N-indolyl and N-carbazolyl; five- to six-membered nitrogen-containing heteroaryl radicals such as, for example, N-pyrrolyl, pyrrol-2-yl, pyrrol
  • Ci-Cs-alkyl groups such as fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, bromomethyl, dibromomethyl, tribromomethyl, pentafluoroethyl, perfluoropropyl and perfluorobutyl, fluoromethyl, difluoromethyl, trifluoromethyl and perfluorobutyl are particularly preferred;
  • C3-C ⁇ 2 -cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl and cyclododecyl; cyclopentyl, cyclohexyl and cycloheptyl are preferred;
  • C 7 -Ci 3 aralkyl preferably C 7 -C 1 -phenylalkyl such as benzyl, 1-phenethyl, 2-phenethyl, 1-phenyl-propyl, 2-phenyl-propyl, 3-phenyl-propyl, neophyl (1 -Methyl-1-phenyl-ethyl1), 1-phenyl-buty1, 2-phenyl-buty1, 3-phenyl-buty1 and 4-phenyl-butyl, particularly preferably benzyl;
  • C 6 -C 4 aryl for example phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl and 9th -Phenanthryl, preferably phenyl, 1-naphthyl and 2-naphthyl, particularly preferably phenyl;
  • Halogen for example fluorine, chlorine, bromine or iodine, particularly preferably fluorine or chlorine;
  • Ci-C ß alkoxy groups such as methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, iso-butoxy, sec-butoxy, tert-butoxy, n-pentoxy, iso-pentoxy, n-hexoxy and iso -Hexoxy, particularly preferably methoxy, ethoxy, n-propoxy and n-butoxy; C 6 -Ci 4 aryloxy groups such as phenoxy, ortho-cresyloxy, meta-cresyloxy, para-cresyloxy, ⁇ -naphthoxy, ⁇ -naphthoxy or 9-anthryloxy; Silyl groups SiR 8 R 9 R 10 , where R 8 to R 10 are independently selected from hydrogen, Ci-Cs-alkyl groups, C 7 -Ci 5 -arykyl and C 6 -Ci 4 -aryl groups; trimethylsilyl, triethylsilyl,
  • -CC 2 -alkyl for example methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec.
  • C 7 -Ci 3 aralkyl preferably C 7 - to -C 2 phenylalkyl such as benzyl, 1-phenethyl, 2-phenethyl, 1-phenyl-propyl, 2-phenyl-propyl, 3-phenyl-propyl, neophyl (1- Methyl-1-phenylethyl), 1-phenylbutyl, 2-phenylbutyl, 3-phenylbutyl and 4-phenylbutyl, particularly preferably benzyl;
  • C6-Ci4-aryl for example phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl and 9-phenanthryl , preferably phenyl, 1-naphthyl and 2-naphthyl, particularly preferably phenyl;
  • C 6 -C aryl such as phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl and 9-phenanthryl , identical or differently substituted by one or more - -C 8 alkyl groups, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n- Pentyl, iso-pentyl, sec.-pentyl, neo-pentyl, 1, 2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec.-hexyl, n-heptyl, iso-heptyl and n-octyl;
  • the substituted C 1 -C 8 -alkyl groups may be mentioned as examples: mono- or poly-halogenated C 8 -C 8 -alkyl groups such as fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, bromomethyl, dibromomethyl, tribromomethyl, pentafluoroethyl, perfluoropropyl and perfluorobutyl , fluoromethyl, difluoromethyl, trifluoromethyl and perfluorobutyl are particularly preferred;
  • C 3 -C 2 cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl,
  • Cyclodecyl, cycloundecyl and cyclododecyl; cyclopentyl, cyclohexyl and cycloheptyl are preferred;
  • C 6 -Ci 4 aryl for example phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl and 9 -Phenanthryl, preferably phenyl, 1-naphthyl and 2-naphthyl, 10 particularly preferably phenyl;
  • Halogen for example fluorine, chlorine, bromine or iodine, particularly preferably fluorine or chlorine;
  • Ci-C ⁇ alkoxy groups such as methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, iso-butoxy, sec-butoxy, 15 tert-butoxy, n-pentoxy, iso-pentoxy, n-hexoxy and iso-hexoxy, particularly preferably methoxy, ethoxy, n-propoxy and n-butoxy;
  • Ci 4 aryloxy groups such as phenoxy, ortho-cresyloxy, meta-cresyloxy, para-cresyloxy, ⁇ -naphthoxy, ⁇ -naphtho-20 thoxy or 9-anthryloxy;
  • Silyl groups SiR 8 R 9 R 10 where R 8 to R 10 are independently selected from hydrogen, -CC 2 -alkyl groups, C 7 -Ci 5 aralkyl and C 6 -Ci 4 aryl groups; trimethylsilyl, triethylsilyl, triisopropylsilyl, diethylisopropylsilyl, dimethyl-thexylsilyl, tert-butyldimethylsilyl, tert.
  • Silyloxy groups OSiR 8 R 9 R 10 where R 8 to R 10 are independently selected from hydrogen, -CC 8 alkyl groups, C 7 -Ci 5 aralkyl and C 6 -Ci 4 aryl groups; trimethylsilyloxy-, triethylsily- 35 loxy-, triisopropylsilyloxy-, diethylisopropylsily- loxy-, dimethylthexylsilyloxy-, tert.
  • 2, 6-dimethylphenyl, 2,6-diisopropylphenyl, mesityl and 2, 6-dichlorophenyl are very particularly preferred; 45 - five- to six-membered nitrogen-containing heteroaryl radicals, such as N-pyrrolyl, pyrrol-2-yl, pyrrol-3-yl, N- - • imidazolyl, 2-imidazolyl, 4-imidazolyl, 1, 2,4-triazol-3- yl, l, 2,4-triazol-4-yl, 2-pyridyl, 3-pyridyl, 4-pyridyl, 3-pyridazinyl, 4-pyridazinyl, 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl, N- Indolyl and N-carbazolyl; five- to six-membered nitrogen-containing heteroaryl radicals such as, for example, N-pyrrolyl, pyrrol-2-yl, pyrrol-3
  • -C 8 alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl, sec-pentyl , neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec.-hexyl, n-heptyl, iso-heptyl and n-octyl; preferably -CC 6 alkyl such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl , neo-pentyl, 1, 2-d
  • Halogen for example fluorine, chlorine, bromine or iodine, particularly preferably fluorine or chlorine
  • Ci-C ⁇ -alkoxy groups such as methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, iso-butoxy, sec.-butoxy, tert.-butoxy, n-pentoxy, iso-pentoxy, n-hexoxy and iso- Hexoxy, particularly preferably methoxy, ethoxy, n-propoxy and n-butoxy
  • C 6 -C 4 aryloxy groups such as phenoxy, ortho-cresyloxy, meta-cresyloxy, para-cresyloxy, ⁇ -naphthoxy, ⁇ -naphthoxy or -anthryloxy;
  • Silyl groups SiR 8 R 9 R 10 where R 8 to R 10 are selected independently of one another from hydrogen, C 8 -C 8 alkyl groups, C 7 -Ci 5 aryl alkyl and C 6 -Ci 4 aryl groups; trimethylsilyl, triethylsilyl, triisopropylsilyl are preferred. Diethylisopropylsilyl-, dimethylthexylsilyl-, tert. -Butyldimethylsilyl-, tert.
  • s R 7 are independently selected from hydrogen
  • C 1 -C 2 alkyl for example methyl, ethyl, n-propyl, isopropyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl , neo-pentyl, 1, 2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec.-hexyl, n-heptyl, iso-heptyl, n-octyl, n-decyl or n-dodecyl; preferably -C 6 alkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl,
  • the substituted C 1 -C 2 -alkyl groups may be mentioned as examples: mono- or poly-halogenated C 1 -C 2 -alkyl groups such as fluoromethyl, difluoromethyl, trifluoromethyl,
  • -C 8 alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec.
  • C 1 -C 8 -alkyl groups such as fluoromethyl, difluoromethyl, tri-fluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, bromomethyl, dibromomethyl, tribromomethyl, pentafluoroethyl, perfluoropropyl and perfluorobutyl, particularly preferred are fluoromethyl, difluoromethyl, trifluoromethyl and per-;
  • C 3 -C ⁇ 2 -cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl and cyclododecyl; cyclopentyl, cyclohexyl and cycloheptyl are preferred;
  • C 7 -Ci 5 aralkyl preferably C 7 - to -CC-phenylalkyl such as benzyl, 1-phenethyl, 2-phenethyl, 1-phenyl-propyl, 2-phenyl-propyl, 3-phenyl-propyl, neophyl (1-Me - thyl-1-phenylethyl), 1-phenyl-butyl, 2-phenyl-butyl, 3-phenyl-butyl and 4-phenyl-butyl, particularly preferably benzyl;
  • C 6 -C 4 aryl for example phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl and 9th -Phenanthryl, preferably phenyl, 1-naphthyl and 2-naphthyl, particularly preferably phenyl; Halogen, for example fluorine, chlorine, bromine or iodine, particularly preferably fluorine or chlorine; C ⁇ -C 6 alkoxy groups such as methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, iso-butoxy, sec-butoxy, tert-butoxy, n-pentoxy, iso-pentoxy, n-hexoxy and iso -Hexoxy, particularly preferably methoxy, ethoxy, n-propoxy and n-butoxy
  • C 6 -Ci 4 aryloxy groups such as phenoxy, ortho-cresyloxy, meta-cresyloxy, para-cresyloxy, ⁇ -naphthoxy, ⁇ -naphthoxy or 9-anthryloxy;
  • Silyl groups SiR 8 R 9 R 10 where R 8 to R 10 are independently selected from hydrogen, -CC 2 alkyl groups, C 7 -Ci 5 aralkyl and C 6 -C ⁇ 4 aryl groups; the trimethylsilyl, triethylsilyl,
  • 2, 6-dimethylphenyl, 2,6-diisopropylphenyl, mesityl and 2, 6-dichlorophenyl are very particularly preferred; five- to six-membered nitrogen-containing heteroaryl radicals such as, for example, N-pyrrolyl, pyrrol-2-yl, pyrrol-3-yl, N-imidazolyl, 2-imidazolyl, 4-imidazolyl, 1, 2,4-triazol-3-yl, l, 2,4-triazol-4-yl, 2-pyridyl, 3-pyridyl, 4-pyridyl, 3-pyridazinyl, 4-pyridazinyl, 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl, N-indolyl and N-carbazolyl; five- to six-membered nitrogen-containing heteroaryl radicals such as, for example, N-pyrrolyl, pyrrol-2-yl, pyrrol-3-y
  • -C 8 alkyl groups such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl, sec.
  • C 1 -C 8 -alkyl groups such as fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, bromomethyl, dibromomethyl, tribromomethyl, pentafluoroethyl, perfluoropropyl and perfluorobutyl, particularly preferred are fluoromethyl, difluoromethyl, trifluoromethyl and per-;
  • C 3 -C 2 cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl and cyclododecyl; cyclopentyl, cyclohexyl and cycloheptyl are preferred;
  • C 6 -C 4 aryloxy groups such as phenoxy, orfciio-cresyloxy, meta-cresyloxy, para-cresyloxy, ⁇ -naphthoxy, ⁇ -naphthoxy or 9-anthryloxy; - Silyl groups SiR 8 R 9 R 10 , where R 8 to R 10 are independently selected from hydrogen, C ⁇ -C 8 alkyl groups, C 7 -C ⁇ 5 aralkyl and C 6 -Ci 4 aryl groups; preferred are the trimethylsilyl, triethylsilyl, triisopropylsilyl, diethylisopropylsilyl, dimethyl-thexylsilyl, tert.-butyldimethylsilyl, tert.-butyl-diphenylsilyl, tribenzylsilyl, tripenylsilyl and the tri-para-x; the trimethylsilyl group and the tert
  • Ci-C ⁇ -alkoxy such as methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, iso-butoxy, sec.-butoxy, tert.-butoxy, n-pentoxy, iso-pentoxy, n-hexoxy and iso -Hexoxy, particularly preferably methoxy, ethoxy, n-propoxy and n-butoxy, N0 2 ,
  • Silyl groups SiR 8 R 9 R 10 where R 8 to R 10 are independently selected from hydrogen, -C 8 alkyl groups, C -C aralkyl and C 6 -C 4 aryl groups; preferred are the trimethylsilyl, triethylsilyl, triisopropylsilyl, diethylisopropylsilyl, dimethylthexylsilyl, tert.-butyldimethylsilyl, tert.-butyldiphenylsilyl, tribenzylsilyl, triphenylsilyl and x-tri-para-groups; the trimethylsilyl group and the tert. -Butyldimethylsilyl distr;
  • Silyloxy groups OSiR 8 R 9 R 10 where R 8 to R 10 are independently selected from hydrogen, -CC 8 alkyl groups, C 7 -C ⁇ 5 aralkyl and c 6 ⁇ Ci 4 aryl groups; preferred are the trimethylsilyloxy, triethylsilyloxy, triisopropylsilyloxy, diethylisopropylsilyloxy, dirnethylthexylsilyloxy, tert.butyldimethylsilyloxy, tert. the trimethylsilyloxy group and the tert-butyldimethylsilyloxy group are particularly preferred.
  • two adjacent radicals can form a 5- to 10-membered ring with the inclusion of the parent aromatic.
  • R 5 and R 6 or in formula I b R 5 and R 7 together can be: - (CH 2 ) 3 - (trimethylene), - (CH 2 ) 4 ⁇ (tetramethylene), - (CH ) s- (pentamethylene),
  • a molecularly defined activator of the general formulas II a to c is also used, the activators being able to be represented as follows:
  • [LH] + is a Bronsted acid, where L is an electroneutral Lewis base, for example an amine of the general
  • Lewis bases L are trin-butylamine, N, N-dimethylaniline and N, N-dimethylbenzyl laminate.
  • M ' is an element of group 13 of the Periodic Table of the Elements, B and AI are preferred.
  • Q 1 to Q 4 is independently selected from
  • Hydride for example methyl, ethyl, n-propyl, isopropyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl, sec .-Pentyl, neo-pentyl, 1, 2-dimethyl-propyl, iso-amyl, n-hexyl, iso-hexyl, sec.-hexyl, n-heptyl, iso-heptyl, n-octyl, n-decyl or n dodecyl; preferably -C 6 alkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, is
  • the substituted C 1 -C 2 -alkyl groups may be mentioned as examples: mono- or multiply halogenated C 1 -C 2 -alkyl groups such as fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, bromomethyl, di-bromomethyl, tribromomethyl, pentafluoryl, perfluoropropyl and perfluorobutyl, particularly preferred are fluoromethyl, difluoromethyl, trifluoromethyl and perfluorobutyl; C 3 -C 2 cycloalkyl, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl and cyclododecyl; cyclopentyl, cyclohexyl
  • C-C ⁇ -aralkyl preferably C 7 - to -C 2 -phenylalkyl such as benzyl, 1-phenethyl, 2-phenethyl, 1-phenyl-propyl, 2-phenyl-propyl, 3-phenyl-propyl, neophyl (1-methyl 1-phenylethyl), 1-phenylbutyl, 2-phenylbutyl, 3-phenylbutyl and 4-phenylbutyl, particularly preferably benzyl;
  • C ⁇ -Ci 4 aryl for example phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl and 9 -Phenanthryl, preferably phenyl, 1-naphthyl and 2-naphthyl, particularly preferably phenyl; unsubstituted or substituted with C 6 -C aryl such as phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl and 9 -Phenanthryl, identical or different substituted by one or more
  • -C 8 alkyl groups such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl, sec-pentyl , neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec.-hexyl, n-heptyl, iso-heptyl and n-octyl; preferably Ci-C ⁇ - alkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl, sec-pentyl , neo-p
  • C 1 -C 4 alkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl and tert-butyl;
  • the substituted C ⁇ -C 8 -alkyl groups may be mentioned as examples: mono- or poly-halogenated C ⁇ -C 8 -alkyl groups such as fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, bromomethyl, dibromomethyl, tribromomethyl, pentafluoroethyl.
  • Perfluoropropyl and perfluorobutyl particularly preferred are fluoromethyl, difluoromethyl, trifluoromethyl and perfluorobutyl;
  • C 3 -C 2 cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl and cyclododecyl; cyclopentyl, cyclohexyl and cycloheptyl are preferred;
  • Halogen for example fluorine, chlorine, bromine or iodine, preferably fluorine or chlorine and particularly preferably fluorine.
  • radicals Q1 to Q4 are the same and are selected from pentafluorophenyl, 3,5-bis-perfluoromethylphenyl or ortho-perfluorobiphenyl.
  • Ar is the same or different and selected from unsubstituted or substituted C 6 -C aryl such as phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3- Phenanthryl, 4-phenanthryl and 9-phenanthryl, identical or differently substituted by one or more C _.- C 8 alkyl groups, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec.- Butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec.-hexyl, n-heptyl ,
  • C 3 -C 2 cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl and cyclododecyl; cyclopentyl, cyclohexyl and cycloheptyl are preferred;
  • C 7 -Ci 5 aralkyl preferably C 7 to C 2 phenylalkyl such as benzyl, 1-phenethyl, 2-phenethyl, 1-phenyl-propyl, 2-phenyl-propyl, 3-phenyl-propyl, neophyl (1- Methyl-1-phenylethyl), 1-phenylbutyl, 2-phenylbutyl, 3-phenylbutyl and 4-phenylbutyl, particularly preferably benzyl;
  • C 6 -C 4 aryl for example phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl and 9-phenanthryl , preferably phenyl, 1-naphthyl and 2-naphthyl, particularly preferably phenyl;
  • Halogen for example fluorine, chlorine, bromine or iodine, preferably fluorine or chlorine and particularly preferably fluorine, or - NO 2 .
  • Ar is preferably phenyl.
  • Suitable carrier materials are, for example, porous metal oxides of metals from groups 2 to 14 or mixtures thereof, furthermore sheet silicates or amorphous silica gels such as diatomite, but also solid halides of metals from groups 1, 2 and 13.
  • Preferred examples of metal oxides from groups 2 to 14 are Si0 2 , B ⁇ 3 , AI 2 O 3 , MgO, CaO and ZnO.
  • Preferred layered silicates are montmorrilonite or bentonite; preferred halides are MgCl 2 or amorphous A1F 3 .
  • Other suitable carrier materials that can be used are polyethylene, polypropylene or polystyrene.
  • Particularly preferred carrier materials are spherical silica gels and aluminosilicate gels of the general formula Si0-a A10 3 , where a generally stands for a number in the range from 0 to 2, preferably 0 to 0.5.
  • silica gels are commercially available, for example silica gel SG 332, Sylopol 948 or Sylopol 952 or S 2101 from WR Grace or ES 70X from Crosfield.
  • Average particle diameters of 1-300 ⁇ m have proven successful as the particle size of the carrier material, preferably from 20 to 80 ⁇ m, the particle diameter being determined by known methods such as sieving methods.
  • the pore volume of these supports is 1.0 to 3.0 ml / g, preferably from 1.6 to 2.2 ml / g and particularly preferably from 1.7 to 1.9 ml / g.
  • the BET surface area is 200 to 750 m 2 / g, preferably 250 to 400 m 2 / g.
  • the carrier material is free of water. There are several ways of removing this water from carrier materials, which are usually supplied with a small amount of water.
  • One embodiment of the invention is calcining, and another embodiment of the invention is treatment with a metal alkyl compound.
  • the drying is carried out in such a way that the carrier material is dried by calcining.
  • the calcination is carried out at temperatures in the range from 500 to 800 ° C., preferably 600 to 750 ° C. If the temperature is chosen too high, the structure of the carrier material to be dried can be destroyed by sintering effects. If the temperature is chosen too low, the drying will be incomplete. It is also possible to run a temperature profile for drying, for example drying first at 300 ° C. for 2 to 4 hours, then increasing to 700 ° C. within one hour and leaving the temperature at this level for 3 hours before cooling again to room temperature.
  • this embodiment is only suitable for support materials whose melting temperature is above 800 ° C., that is to say for metal oxides of groups 2 to 14 of the periodic table of the elements and particularly expediently for silica gel or aluminum oxide gels.
  • This method is not suitable for drying polyethylene or polypropylene as a carrier material.
  • the carrier material is first reacted with a metal alkyl compound which reacts with physisorbed and chemisorbed water.
  • Preferred metal alkyl compounds are selected from LiR 11 , MgR 1: 1 R 12 or A1R 12 R 13 R 14 , in which R 11 to R 14 are selected independently of one another from unsubstituted or substituted --CC 2 alkyl, for example methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec.-butyl, tert.-butyl, n-pentyl, iso-pentyl, sec.-pentyl, neo-pentyl, 1, 2-dimethylpropyl, iso - Amyl, n-hexyl, iso-hexyl, sec.-hexyl, n-heptyl, iso-heptyl, n-octy
  • C 3 -Ci 2 cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl and cyclododecyl; cyclopentyl, cyclohexyl and cycloheptyl are preferred;
  • C 7 -Ci 3 aralkyl preferably C 7 to C 2 phenylalkyl such as benzyl, 1-phenethyl, 2-phenethyl, 1-phenyl-propyl, 2-phenyl-propyl, 3-phenyl-propyl, neophyl (1- Methyl-1-phenylethyl), 1-phenyl-butyl, 2-phenyl-butyl, 3-phenyl-butyl and 4-phenyl-butyl, particularly preferably benzyl;
  • C 6 -Ci 4 aryl for example phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl and 9 -Phenanthryl, preferably phenyl, 1-naphthyl and 2-naphthyl, particularly preferably phenyl.
  • R 12 to R 14 are particularly preferably the same.
  • alkylating agents are n-butyllithium, trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, trin-hexyl aluminum and butyl octyl magnesium ("BOMag").
  • mixtures of several alkylating agents can also be used to remove the moisture.
  • the solid support material is first pretreated thermally and then reacted with a metal alkyl compound.
  • the thermal pretreatment can be carried out at temperatures from 100 to 200 ° C., preferably 105 to 125 ° C. This procedure is particularly suitable if polyethylene, polypropylene or MgCl are to be used as carriers.
  • the carrier material reacted with the alkylating agent can then be separated from the solvent, for example by filtration, evaporation or centrifugation or a combination of several operations. After drying, the metal complex of the general formulas I a or b, the molecularly defined activator of the general formulas II a to c and the water-free carrier material are mixed together.
  • Solvents which are inert under the reaction conditions such as toluene, ortho-xylene, meta-xylene, para-xylene, ethylbenzene or mixtures thereof, have proven suitable.
  • alkanes such as n-heptane or isododecane are suitable as solvents, and mixtures of alkanes with toluene, ortho-xylene, meta-xylene, para-xylene or ethylbenzene are also suitable.
  • the molar ratios of complex I a or b to activator II a to c can be varied within certain limits.
  • Molar ratios I a (or b) to II a or II b or II c can be chosen from 10: 1 to 1:10, the ratios are preferably 2: 1 to 1: 2 and particularly preferably 1: 1.
  • Pressure and temperature conditions of the described reaction can be varied within wide limits. Working at normal pressure is preferred. Suitable temperatures from -20 ° C. to + 120 ° C. are preferred, 0 to 100 ° C. are preferred and 20 to 80 ° C. are particularly preferred.
  • the reaction can also be carried out as a sequence by first reacting the metal complex of the general formulas I a or b with the molecularly defined activator and then depositing it on the support material.
  • the setting of a temperature profile has proven particularly useful for this embodiment of the present invention; the reaction of the complex of the late transition metal with the molecularly defined activator is preferably carried out at 60 to 100 °, especially if the activator is a salt.
  • the subsequent reaction with the carrier material is preferably carried out at room temperature.
  • the solid carrier material is impregnated with the mixture described above.
  • further solvent can be added or the fixation of the active components on the carrier material can be completed by a solvent in which the complex and activator are poorly soluble, such as, for example, n-pentane, n-heptane or isododane.
  • the amount of carrier added can be varied within wide limits. The usual procedure is to deposit about 5 to 200 ⁇ mol complex of the general formulas I a or b, based on 1 g of support material, on the support material. It is possible to separate higher amounts of complex, but this makes the catalyst very expensive, because usually the complex is significantly more expensive than the support material.
  • the solvent or solvents is usually removed in order to isolate the catalyst according to the invention.
  • the solvent can be removed by common techniques, such as evaporation or filtration, or a combination of several steps.
  • the catalyst can be washed with an inert solvent.
  • Another object of the present invention is a catalyst obtainable by the process described above.
  • the catalyst according to the invention is based on a support material which has been made water-free by calcination.
  • This particularly preferred catalyst is distinguished from the catalysts with late transition metals known from the prior art in that it contains no air or moisture-sensitive metal alkyl compounds such as, for example, aluminum alkyl compounds and can therefore be stored and transported without any special precautions.
  • the catalyst according to the invention produced by the process according to the invention is suitable for the polymerization and copolymerization of olefins.
  • a process for the polymerization and copolymerization of olefins using the catalyst according to the invention is a further subject of the present invention.
  • olefins are suitable as monomers: ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene or 1-undecene, ethylene being particularly preferred.
  • Suitable comonomers are ⁇ -olefins, such as 0.1 to 20 mol% of 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene or 1-undecene.
  • isobutene and styrene are also suitable comonomers, and cycloolefins such as, for example Cyclopentene, norbornene or norbornadiene as well as substituted norbornenes.
  • Pressure and temperature conditions during the polymerization can be chosen within wide limits.
  • a range from 0.5 bar to 4000 bar has proven to be suitable as the pressure, 10 to 75 bar or high-pressure conditions from 500 to 2500 bar are preferred.
  • a temperature of 0 to 120 ° C. has proven to be suitable, preferably 40 to 100 ° C. and particularly preferably 10 50 to 85 ° C.
  • the catalyst according to the invention can be treated again just before the polymerization with a metal alkyl compound which serves as an alkylating agent.
  • the alkylating agent is selected from the metal alkyl compounds listed above: LiR 11 or MgR 1: L R 12 or A1R 12 R 13 R 14 , in which R 11 to R 14 are as defined above.
  • Examples include metallocenes of the general formulas III a to e, furthermore Ni or Pd complexes, as described in WO 96/23010.
  • M '' is an element from the series Ti, Zr, Hf, V, Nb or Ta in the oxidation state +4; preferably Ti, Zr or Hf and particularly preferably Zr or Hf; X 3 and X 4 are independent of one another
  • Halogen such as fluorine, chlorine, bromine or iodine, chlorine and bromine being preferred; -C 1 -C 2 alkyl such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl , neo-pentyl, 1, 2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec.-hexyl, n-heptyl, iso-heptyl, n-octyl, n-nonyl, n-decyl, and n-dodecyl; preferably -C 6 alkyl such as methyl, ethyl, n-propyl, isopropyl, n-
  • C 3 -C 2 cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl and cyclododecyl; cyclopentyl, cyclohexyl and cycloheptyl, - C 7 - to C 2 o-aralkyl, preferably C 7 - to C ⁇ 2 -phenylalkyl such as benzyl, 1-phenethyl, 2-phenethyl, 1-phenyl-propyl, 2-phenyl are preferred propyl, 3-phenyl-propyl, 1-phenyl-butyl, 2-phenyl-butyl, 3-phenyl-butyl and 4-phenyl-butyl, particularly preferably benzyl, - C 6 -C 4
  • Halogen such as fluorine, chlorine, bromine or iodine, chlorine and bromine being preferred; C 1 -C 2 -alkyl such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, neo-pentyl, 1, 2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec.-hexyl, n-heptyl, iso-heptyl, n-octyl, n-nonyl, n-decyl, and n- dodecyl; preferably -C 6 alkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-
  • 3-phenanthryl, 4-phenanthryl and 9-phenanthryl preferably phenyl, 1-naphthyl and 2-naphthyl, particularly preferably phenyl, or -CC alkoxy groups, preferably CC ⁇ -alkoxy groups such as methoxy, ethoxy, n-propoxy, iso- Propoxy, n-butoxy, iso-butoxy, sec.-butoxy, tert.-butoxy, n-pentoxy, isopentoxy, n-hexoxy and iso-hexoxy, particularly preferably methoxy, ethoxy, n-propoxy and n-butoxy R and R 'together with E can form a saturated or unsaturated 4- to 9-membered ring; R 15 to R 22 are independently hydrogen,
  • Halogen such as fluorine, chlorine, bromine or iodine, chlorine and bromine being preferred;
  • - C 1 -C 2 alkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl , neo-pentyl, 1, 2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec.-hexyl, n-heptyl, iso-heptyl, n-octyl, n-nonyl, n-decyl, and n dodecyl;
  • preferred -C-C 5 alkyl such as methyl, ethyl, n-propyl, iso-propyl, n-
  • C 3 -Ci 2 ⁇ cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl and cyclododecyl; cyclopentyl, cyclohexyl and cycloheptyl are preferred;
  • C 7 - to C 2 o _ aralkyl C, preferably up to 2 C ⁇ phenylalkyl such as benzyl, 1-phenethyl, 2-phenethyl, 1-phenyl-propyl, 2-phenyl-propyl, 3-phenyl-propyl, 1-phenyl butyl, 2-phenyl-butyl, 3-phenyl-butyl and 4-phenyl-butyl, particularly preferably benzyl,
  • C 6 -C 1 aryl such as phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl and 9-phenanthryl, preferably phenyl, 1-naphthyl and 2-naphthyl, particularly preferred
  • Siloxy groups OSiR 8 R 9 R 10 where R 8 to R 10 independently of one another are hydrogen, C 1 -C 2 alkyl groups, C 3 -C 12 cycloalkyl groups, C 6 -C 4 aryl groups, substituted C 6 -Ci 4 aryl groups , -C-C ⁇ 2 alkoxy groups, benzyl groups and C 6 -C ⁇ 4 aryl groups are selected; preferred are the trimethylsilyloxy-, triethylsilyloxy-, triisopropylsilyloxy-, diethylisopropylsilyloxy-, dirnethylthexylsily- loxy-, tert.-butyldimethylsilyloxy-, tert.-butyldiphenylsilyloxy-, tribenzylsilyloxy- xoxy-triphenylsilyl-silyloxy-triphenylsilyl-silyloxy-triphenylsilyl
  • C 7 -Ci 5 aralkyl and C 6 -C ⁇ 4 aryl groups are selected; trimethylsilyl, triethylsilyl, triisopropylsilyl, diethylisopropylsilyl, dimethylthexylsilyl, tert-butyldimethylsilyl, tert.
  • C 1 -C 2 alkoxy groups preferably C 1 -C 6 alkoxy groups such as methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, iso-butoxy, sec.-butoxy, tert.-butoxy, n-pentoxy, iso- Pentoxy, n-hexoxy and iso-hexoxy, particularly preferably methoxy, ethoxy, n-propoxy and n-butoxy;
  • a special embodiment are metallocenes according to formula III b.
  • R 11 , R 16 , R 19 , R 20 and R 23 to R 30 are independently of one another - hydrogen
  • Halogen such as fluorine, chlorine, bromine or iodine, chlorine and bromine being preferred
  • -CC 2 -alkyl such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, neo-pentyl, 1, 2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec.-hexyl, n-heptyl, iso-heptyl, n-octyl, n-nonyl, n-decyl, and n- dodecyl; before- adds Ci-Ce-alkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl
  • C 3 -Ci 2 cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl and cyclododecyl; cyclopentyl, cyclohexyl and cycloheptyl are preferred; - C 7 - to C 2 o-aralkyl, preferably C 7 - to C 2 -phenylalkyl such as benzyl, 1-phenethyl, 2-phenethyl, 1-phenyl-propyl, 2-phenyl-propyl, 3-phenyl-propyl, 1st Phenyl butyl, 2-phenyl butyl, 3-phenyl butyl and 4-phenyl butyl, particularly preferably benzyl, C 6 ⁇ Ci 4 aryl
  • Silyl groups SiR 8 R 9 R 10 where R 8 to R 10 are independently selected from hydrogen, -CC-alkyl groups, C 7 -C ⁇ 5 aralkyl and C 6 -Ci 4 aryl groups; trimethylsilyl, triethylsilyl, triisopropylsilyl, diethylisopropylsilyl, dimethylhexylsilyl, tert-butyldimethylsilyl, and tert are preferred.
  • c ⁇ -c l2 ⁇ alkoxy groups preferably C 1 -C 6 alkoxy groups such as methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, iso-butoxy, sec-butoxy, tert-butoxy, n-pentoxy, iso-pen-toxy, n-hexoxy and iso-hexoxy, particularly preferably methoxy, ethoxy, n-propoxy and n-butoxy;
  • C 6 -C ⁇ 4 aryl groups which are themselves substituted by one or more C ⁇ -C ⁇ 2 alkyl, C ⁇ -C ⁇ groups 2 -alkenyl, C 3 -C ⁇ 2 -cyclo
  • R 15 to R 22 and R 31 and R 32 are independently hydrogen
  • Halogen such as fluorine, chlorine, bromine or iodine, chlorine and bromine being preferred;
  • -CC 2 -alkyl such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, neo-pentyl, 1, 2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec.-hexyl, n-heptyl, iso- Heptyl, n-octyl, n-nonyl, n-decyl, and n-dodecyl; preferably Ci-Cö-alkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, is
  • C3-C ⁇ 2 -cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl and cyclododecyl; cyclopentyl, cyclohexyl and cycloheptyl are preferred;
  • C7 to C 2 o _ aralkyl, C7 to Ci2 preferably phenylalkyl such as benzyl, 1-phenethyl, 2-phenethyl, 1-phenyl-propyl, 2-phenyl-propyl, 3-phenyl-propyl, 1-phenyl-butyl , 2-phenyl-butyl, 3-phenyl-butyl and 4-phenyl-butyl, particularly preferably benzyl,
  • C 6 -C 14 aryl such as phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl and 9-phenanthryl, are preferred Phenyl, 1-naphthyl and 2-naphthyl, particularly preferably phenyl,
  • Siloxy OSiR 8 R 9 R 10 wherein R 8 to R 10 are independently selected from are hydrogen, Ci 2 -alkyl, C 3 -C cloalkyl phenomenon 2 -Cy-, C6-Ci4-aryl groups, substituted C6-Ci4-aryl groups, C ⁇ -C ⁇ 2 alkoxy groups, benzyl groups and C6-Ci4 ⁇ aryl groups are selected; trimethylsilyloxy, triethylsilyloxy, triisopropylsilyloxy, diethylisopropylsilyloxy, dirnethylthexylsilyloxy, tert.-butyldimethylsilyloxy, tert.
  • Silyl groups SiR 8 R 9 R 10 where R 8 to R 10 are independently selected from hydrogen, -CC 2 -alkyl groups, C7-Ci5 ⁇ aralkyl and Ce-C ⁇ aryl groups; trimethylsilyl-, triethylsilyl-, triisopropylsilyl-, diethylisopropylsilyl-, dimethylthexyl- silyl, tert-butyldimethylsilyl, tert-butyldiphenylsilyl, tribenzylsilyl, triphenylsilyl and the tri-paraxylylsilyl group; the trimethylsilyl group and the tert are particularly preferred.
  • a special embodiment are metallocenes according to formula III d.
  • Formula III d is metallocenes according to formula III d.
  • R 15 to R 17 , R 19 to R 21 and R 23 to R 30 are independent of one another
  • Halogen such as fluorine, chlorine, bromine or iodine, chlorine and bromine being preferred
  • C ⁇ -C ⁇ alkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl, sec-pentyl, neo -Pentyl, 1, 2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec.-hexyl, n-heptyl, iso-heptyl, n-octyl, n-nonyl, n-decyl, and n-dodecyl ; preferably Ci-C ⁇ - al yl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec.-butyl, tert.-butyl
  • C 3 -C 2 cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl and cyclododecyl; cyclopentyl, cyclohexyl and cycloheptyl are preferred; - C 7 - to C 2 o-aralkyl, preferably C 7 - to C 2 phenylalkyl such as benzyl, 1-phenethyl, 2-phenethyl, 1-phenyl-propyl, 2-phenyl-propyl, 3-phenyl-propyl, 1 -Phenyl-butyl, 2-phenyl-butyl, 3-phenyl-butyl and 4-phenyl-butyl, particularly preferably benzyl, - C 6 -C
  • R 15 to R 18 are independently hydrogen
  • Halogen such as fluorine, chlorine, bromine or iodine, chlorine and bromine being preferred;
  • - -CC -alkyl such as methyl, ethyl, n-propyl, isopropyl, n-
  • 2- phenylalkyl such as benzyl, 1-phenethyl, 2-phenethyl, 1-phenyl-propyl, 2-phenyl-propyl, 3-phenyl-propyl, 1-phenyl-butyl, 2-phenyl-butyl, 3-phenyl-butyl and 4-phenylbutyl, particularly preferably benzyl, C 6 -C 4 aryl such as phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl,
  • 3-phenanthryl, 4-phenanthryl and 9-phenanthryl preferably phenyl, 1-naphthyl and 2-naphthyl, particularly preferably phenyl, siloxy groups OSiR 8 R 9 R 10 , where R 8 to R 10 independently of one another from hydrogen, C ⁇ - C 2 alkyl groups, C 3 -C 12 cycloalkyl groups, C 6 -C 4 aryl groups, substituted C 6 ⁇ C 4 aryl groups, C 1 -C 2 alkoxy groups, benzyl groups and C 6 -C aryl groups are selected; trimethylsilyloxy, triethylsilyloxy, triisopropylsilyloxy, diethylisopropylsilyloxy, dimethylthexylsilyloxy, tert.-butyldimethylsilyloxy, tert.-butyldiphenylsilyloxy, tribenzylsilyloxy, triphenyl
  • Silyl groups SiR 8 R 9 R 10 where R 8 to R 10 independently of one another from hydrogen, -CC 2 -alkyl groups,
  • C 7 -Ci 5 aralkyl and C 6 -Ci 4 aryl groups are selected; trimethylsilyl, triethylsilyl, triisopropylsilyl, diethylisopropylsilyl, dimethylthexylsilyl, tert-butyldimethylsilyl, tert.
  • Ci 2 ⁇ alkoxy groups preferably Ci-C ⁇ alkoxy groups such as methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, iso-butoxy, sec.-butoxy, tert.-butoxy, n-pentoxy, iso-
  • Pentoxy, n-hexoxy and iso-hexoxy particularly preferably methoxy, ethoxy, n-propoxy and n-butoxy; C 6 -C 4 aryl groups which are themselves substituted by one or more C ⁇ -C ⁇ 2 alkyl, C ⁇ -C ⁇ groups 2 -alkenyl, C 3 -C ⁇ 2 -cycloalkyl, C 6 -C 4 aryl groups,
  • Siloxy groups OSiR 8 R 9 R 10 or -CC 2 alkoxy groups these groups being specified as above; where two adjacent radicals can together form a saturated or unsaturated 4- to 9-membered ring, preferably 5- to 8-membered. For example, two residues can be together: - (CH 2 ) 3 -.
  • metallocenes of the formulas III a-e are:
  • a metal complex of the general formulas I a or b is deposited together with a further transition metal complex, preferably with a metallocene of the general formulas III a to e, on the same support, this process is also referred to as co-transfer.
  • the metal complexes I a or b and metallocene III a to e can be used in the molar ratio 1:20 to 20: 1, preferably 1:10 to 10: 1, for the co-transfer.
  • the polymerization process according to the invention can be carried out in various embodiments, the modern polymerization processes such as suspension processes, bulk polymers risk or gas phase processes can be used.
  • Stirred tanks, tubular reactors, loop reactors and stirred tank cascades are suitable as systems, whereby stirred tanks and loop reactors can also be connected in cascade. No morphology problems of the polymer (chunks, wall coverings, blockages in pipes or heat exchangers) are observed.
  • the catalysts according to the invention can also be used together with one or more other polymerization catalysts known per se. So they can be used together with Ziegler-Natta catalysts, supported metallocene catalysts of the transition metals of groups IV to VI of the Periodic Table of the Elements, catalysts of the late transition metals (WO 96/23010), or chromium oxide catalysts according to Phillips.
  • the catalysts and catalyst blends according to the invention have furthermore proven to be hydrogen-controllable, i.e. by adding hydrogen, the molecular weight of the polymers obtainable by the catalyst system according to the invention can be reduced. If enough hydrogen is added, waxes are obtained, the required hydrogen concentration also depending on the type of polymerization system used.
  • the present invention also relates to a process for polymerizing olefins with the catalyst according to the invention in the presence of hydrogen as regulator.
  • calcined silica gel is understood to mean a silica gel which has been dried at 1 mbar and 600 ° C. for 8 hours.
  • the polymer viscosity was determined according to ISO 1628-3.
  • ATE triethyl aluminum
  • TIBAL triisobutyl aluminum
  • TMA trimethyl aluminum
  • Polyethylene was obtained in the form of a free-flowing semolina. Yield: 285 g, productivity: 4380 g PE / g catalyst, viscosity: 8.0 dl / gg) g) ethylene-hexene copolymerization with catalyst mixture: The procedure was as in f), in addition, 40 ml of 1-hexene were added in the autoclave submitted.
  • Polyethylene was obtained in the form of a free-flowing semolina. See Table 4 for details.
  • silica gel ES 70X (from Crosfield, baked at 120 ° C./1 mbar / 8 hours) were suspended in 1300 ml of n-heptane in a 2000 ml four-necked flask. With stirring, within 1 hour

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Abstract

L'invention concerne un procédé pour produire un catalyseur à support pour la polymérisation d'oléfines, caractérisé en ce que l'on dépose, sur un matériau support poreux sans eau, un ou plusieurs composés de formule générale (Ia) ou (Ib), avec un activateur moléculairement défini de formule générale (IIa) à (IIc), (IIa): [(L-H)]+[(M')Q<1>Q<2>Q<3>Q<4>]-; (IIb): [(CAr3)]+[(M')Q<1>Q<2>Q<3>Q<4>]-; (IIc): [(M')Q<1>Q<2>Q<3>], et éventuellement un autre composé qui peut être utilisé comme composant à effet catalytique pour la polymérisation d'oléfines.
PCT/EP2001/003821 2000-04-08 2001-04-04 Procede pour produire un catalyseur a support pour la polymerisation d'olefines Ceased WO2001077189A1 (fr)

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DE10017666.6 2000-04-08
DE2000117666 DE10017666A1 (de) 2000-04-08 2000-04-08 Verfahren zur Herstellung eines geträgerten Katalysators zur Polymerisation von Olefinen

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017161466A1 (fr) * 2016-03-22 2017-09-28 亚培烯科技(嘉兴)有限公司 Nouveau catalyseur d'alpha-oléfine linéaire, et préparation et application de ce dernier
CN114316101A (zh) * 2022-01-17 2022-04-12 万华化学集团股份有限公司 一种茂金属催化剂和制备方法及其催化烯烃聚合的用途

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999046304A1 (fr) * 1998-03-12 1999-09-16 Bp Chemicals Limited Catalyseur de polymerisation
WO2001014391A1 (fr) * 1999-08-20 2001-03-01 Basf Aktiengesellschaft Composes a base de bisimidine, leurs complexes de metaux de transition et leur utilisation en tant que catalyseurs
EP1099714A1 (fr) * 1999-11-12 2001-05-16 BP Chemicals Limited Catalyseur de polymérisation

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999046304A1 (fr) * 1998-03-12 1999-09-16 Bp Chemicals Limited Catalyseur de polymerisation
WO2001014391A1 (fr) * 1999-08-20 2001-03-01 Basf Aktiengesellschaft Composes a base de bisimidine, leurs complexes de metaux de transition et leur utilisation en tant que catalyseurs
EP1099714A1 (fr) * 1999-11-12 2001-05-16 BP Chemicals Limited Catalyseur de polymérisation

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017161466A1 (fr) * 2016-03-22 2017-09-28 亚培烯科技(嘉兴)有限公司 Nouveau catalyseur d'alpha-oléfine linéaire, et préparation et application de ce dernier
CN114316101A (zh) * 2022-01-17 2022-04-12 万华化学集团股份有限公司 一种茂金属催化剂和制备方法及其催化烯烃聚合的用途
CN114316101B (zh) * 2022-01-17 2023-10-17 万华化学集团股份有限公司 一种茂金属催化剂和制备方法及其催化烯烃聚合的用途

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