WO1998030602A1 - A process for polymerizing olefins - Google Patents
A process for polymerizing olefins Download PDFInfo
- Publication number
- WO1998030602A1 WO1998030602A1 PCT/NL1997/000695 NL9700695W WO9830602A1 WO 1998030602 A1 WO1998030602 A1 WO 1998030602A1 NL 9700695 W NL9700695 W NL 9700695W WO 9830602 A1 WO9830602 A1 WO 9830602A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- catalyst
- olefins
- polymerization
- transition
- aryl
- Prior art date
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- 150000001336 alkenes Chemical class 0.000 title claims abstract description 27
- 238000000034 method Methods 0.000 title claims abstract description 9
- 230000000379 polymerizing effect Effects 0.000 title description 3
- 239000003426 co-catalyst Substances 0.000 claims abstract description 32
- 239000003054 catalyst Substances 0.000 claims abstract description 31
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 30
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 22
- 150000003624 transition metals Chemical class 0.000 claims abstract description 22
- 150000001875 compounds Chemical class 0.000 claims abstract description 19
- 125000003118 aryl group Chemical group 0.000 claims abstract description 14
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 11
- 125000002877 alkyl aryl group Chemical group 0.000 claims abstract description 10
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 10
- 125000003710 aryl alkyl group Chemical group 0.000 claims abstract description 10
- 229910052732 germanium Inorganic materials 0.000 claims abstract description 10
- 150000001768 cations Chemical class 0.000 claims abstract description 9
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 6
- 239000001257 hydrogen Substances 0.000 claims abstract description 6
- 229910052745 lead Inorganic materials 0.000 claims abstract description 6
- 229910052718 tin Inorganic materials 0.000 claims abstract description 6
- 239000012968 metallocene catalyst Substances 0.000 claims description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 8
- 229910052744 lithium Inorganic materials 0.000 claims description 8
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 11
- -1 5-trifluoromethylphenyl Chemical group 0.000 description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 239000011541 reaction mixture Substances 0.000 description 8
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 4
- 239000004411 aluminium Substances 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 239000012876 carrier material Substances 0.000 description 4
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 230000000737 periodic effect Effects 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 3
- 229960004132 diethyl ether Drugs 0.000 description 3
- 150000002430 hydrocarbons Chemical group 0.000 description 3
- 239000003446 ligand Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 2
- UXQAEOWCSOPBLF-UHFFFAOYSA-N 2,2,3,3-tetramethyloctane Chemical compound CCCCCC(C)(C)C(C)(C)C UXQAEOWCSOPBLF-UHFFFAOYSA-N 0.000 description 2
- 241000349731 Afzelia bipindensis Species 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical class B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 2
- 229910000085 borane Inorganic materials 0.000 description 2
- 150000001642 boronic acid derivatives Chemical class 0.000 description 2
- 238000012662 bulk polymerization Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 2
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 150000007517 lewis acids Chemical class 0.000 description 2
- IHLVCKWPAMTVTG-UHFFFAOYSA-N lithium;carbanide Chemical compound [Li+].[CH3-] IHLVCKWPAMTVTG-UHFFFAOYSA-N 0.000 description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 description 2
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical group C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 150000004756 silanes Chemical class 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- OLFPYUPGPBITMH-UHFFFAOYSA-N tritylium Chemical compound C1=CC=CC=C1[C+](C=1C=CC=CC=1)C1=CC=CC=C1 OLFPYUPGPBITMH-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 239000007848 Bronsted acid Substances 0.000 description 1
- QBYBZANRRZESPD-UHFFFAOYSA-N CC1=CC2=CC=CC=C2C1[Zr](C)(C)C1C2=CC=CC=C2C=C1C Chemical compound CC1=CC2=CC=CC=C2C1[Zr](C)(C)C1C2=CC=CC=C2C=C1C QBYBZANRRZESPD-UHFFFAOYSA-N 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000008064 anhydrides Chemical group 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- ZJHMRPBTRSQNPI-UHFFFAOYSA-N benzo[b][1]benzosilole Chemical compound C1=CC=C2[Si]C3=CC=CC=C3C2=C1 ZJHMRPBTRSQNPI-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- CFBGXYDUODCMNS-UHFFFAOYSA-N cyclobutene Chemical compound C1CC=C1 CFBGXYDUODCMNS-UHFFFAOYSA-N 0.000 description 1
- ZXIJMRYMVAMXQP-UHFFFAOYSA-N cycloheptene Chemical compound C1CCC=CCC1 ZXIJMRYMVAMXQP-UHFFFAOYSA-N 0.000 description 1
- URYYVOIYTNXXBN-UPHRSURJSA-N cyclooctene Chemical compound C1CCC\C=C/CC1 URYYVOIYTNXXBN-UPHRSURJSA-N 0.000 description 1
- 239000004913 cyclooctene Substances 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 229940093499 ethyl acetate Drugs 0.000 description 1
- 235000019439 ethyl acetate Nutrition 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- RMBPEFMHABBEKP-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2C3=C[CH]C=CC3=CC2=C1 RMBPEFMHABBEKP-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000012685 gas phase polymerization Methods 0.000 description 1
- DHMQDGOQFOQNFH-UHFFFAOYSA-O glycinium Chemical compound [NH3+]CC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-O 0.000 description 1
- ZRALSGWEFCBTJO-UHFFFAOYSA-O guanidinium Chemical compound NC(N)=[NH2+] ZRALSGWEFCBTJO-UHFFFAOYSA-O 0.000 description 1
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- XBFJAVXCNXDMBH-GEDKWGBFSA-N molport-035-785-283 Chemical compound C1[C@@H](C23)C=C[C@H]1C3[C@@H]1C[C@H]2CC1 XBFJAVXCNXDMBH-GEDKWGBFSA-N 0.000 description 1
- XVDBWWRIXBMVJV-UHFFFAOYSA-N n-[bis(dimethylamino)phosphanyl]-n-methylmethanamine Chemical compound CN(C)P(N(C)C)N(C)C XVDBWWRIXBMVJV-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 1
- 150000002848 norbornenes Chemical class 0.000 description 1
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N o-biphenylenemethane Natural products C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 1
- PAYRUJLWNCNPSJ-UHFFFAOYSA-O phenylazanium Chemical compound [NH3+]C1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-O 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical compound Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- LFXVBWRMVZPLFK-UHFFFAOYSA-N trioctylalumane Chemical compound CCCCCCCC[Al](CCCCCCCC)CCCCCCCC LFXVBWRMVZPLFK-UHFFFAOYSA-N 0.000 description 1
- OBAJXDYVZBHCGT-UHFFFAOYSA-N tris(pentafluorophenyl)borane Chemical compound FC1=C(F)C(F)=C(F)C(F)=C1B(C=1C(=C(F)C(F)=C(F)C=1F)F)C1=C(F)C(F)=C(F)C(F)=C1F OBAJXDYVZBHCGT-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
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
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
-
- 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
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0803—Compounds with Si-C or Si-Si linkages
-
- 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
- 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
- the invention relates to a process for polymerizing olefins by bringing olefins into contact with a transition metal catalyst and a cocatalyst.
- a transition metal catalyst usually a co-catalyst is required to obtain an active catalyst system.
- Ziegler-Natta catalysts have been used for the polymerization of olefins since the Fifties. In order for these olefin polymerizations to proceed satisfactory with these Ziegler-Natta catalysts, co- catalysts need to be added. Usually aluminium- containing co-catalysts, such as, for example diethyl aluminium chloride, are used in combination with Ziegler-Natta catalysts.
- transition-metal catalysts such as for example metallocene catalysts
- metallocene catalysts have also been used for the polymerization of olefins.
- metallocene catalysts In order for olefin polymerizations with the aid of metallocene catalysts to proceed satisfactory, it is also necessary to use a co-catalyst.
- Aluminoxanes are used as co-catalysts in combination with metallocene catalysts.
- An example of an aluminoxane is methylaluminoxane (MAO) .
- a disadvantage of the use of aluminoxanes as co-catalysts in the polymerization of olefins with the aid of a metallocene catalyst is that a very large excess of the aluminoxane relative to the metallocene catalyst has to be applied in order for an active catalyst system to be obtained.
- the polyolefin produced contains a high concentration of aluminium, so that the aluminium will often need to be washed out of the polyolefin.
- the object of the invention is to provide co- catalysts suitable for use in combination with a transition-metal catalyst for the polymerization of olefins which do not have this disadvantage.
- the invention relates to a cocatalyst having the formula XR 4 , wherein X represents Si or Ge and R represents an alkyl, aryl, arylalkyl or alkylaryl group, or to a cocatalyst having the formula [XR 5 ] ⁇ [Y] + , wherein X represents Si, Ge, Sn or Pb and R represents hydrogen or an alkyl, aryl, arylalkyl or alkylaryl group and Y represents a cation.
- an active catalyst system consisting of a transition-metal catalyst with one of the compounds according to the invention as co-catalyst is obtained which is suitable for the polymerization of olefins.
- the compounds according to the invention are used as co-catalyst for the polymerization of olefins, the required quantity of co-catalyst relative to the transition-metal catalyst is much smaller than when an aluminoxane is used a co-catalyst.
- Lewis acids or ion complexes are also used as coatalysts in combination with metallocene catalysts.
- Lewis acids are boranes, such as tris (pentafluorophenyl) borane
- ion complexes are borates, such as dimethylaniliniumtetrakis- (pentafluorophenyl) borate, triphenylcarbeniumtetrakis- (pentafluorophenyl) borate and trityltetrakis (3 , 5-trifluoromethylphenyl) borate .
- Boron-containing co-catalysts of this kind are described in for example EP-A-426 , 637 , EP-A-277,003 and EP-A-277, 004.
- Another advantage of the use of compounds according to the invention as co-catalysts in the polymerization of olefins is that the use of these compounds is generally cheaper than the use of aluminoxanes, boranes or borates.
- X is an atom from Group 14 of the Periodic Table of the Elements and can be chosen from the group comprising Si, Ge, Sn and Pb .
- X is Si, as Si is non- toxic.
- the R groups may be identical or different and can be chosen from the group comprising hydrogen and alkyl , aryl, arylalkyl or alkylaryl groups.
- the R group is preferably a hydrocarbon group containing 1-20 carbon atoms. Examples of suitable R groups are methyl, ethyl, propyl, isopropyl, hexyl, decyl and phenyl .
- two R groups may together form a bridged R 2 -group, for example a biphenyl-2,2' -diyl group and a diphenyl-2 , 2 ' - diylmethane group .
- at least two R groups together form a bridged aryl group.
- the compound having the formula XR 4 or [XR S ] " [Y] + contains two of such bridged aryl groups .
- the cation Y is for example a Bronsted acid which can donate a proton, a cation of an alkali metal or a carbene.
- cations are Li + , K + , Na + , H + , triphenylcarbenium, anilinium, guanidinium, glycinium, ammonium or a substituted ammonium cation, in which at most three hydrogen atoms have been replaced by a hydrocarbyl radical having 1-20 carbon atoms, or a substituted hydrocarbyl radical having 1-20 carbon atoms , in which one or more of the hydrogen atoms has or have been replaced by a halogen atom, phosphonium radicals, substituted phosphonium radicals, in which at most three hydrogen atoms have been replaced by a hydrocarbyl radical having 1-20 carbon atoms or a substituted hydrocarbyl radical having 1-20 carbon atoms, in which one or more of the hydrogen atoms has or have been replaced by a
- the cation is preferably dimethylanilinium, triphenylcarbenium or Li + .
- Compounds having the formula XR 4 are known from, for example, 'The chemistry of organic silicon compounds, E.S. Patai et al . , Wiley and Sons, 1989' . Anionic organosilicates were demonstrated for the first time in Angew. Chem. Int. Ed. Engl . 1996, 35, no. 10.
- lithium (2, 2' - biphenyldiyltrimethylsilicate) .4THF lithium (2 , 2 ' - biphenyldiyldimethylphenylsilicate) .4THF, lithium (2 , 2 ' - biphenyldiyldimethyl-t-butylsilicate) .4THF and lithium (pentaphenylsilicate) .4HMPA are mentioned.
- THF is tetrahydrofuran and HMPA is hexamethylphosphorus triamide.
- the above-mentioned compounds having the formula XR 4 can for example be synthesized according to the synthesis methods described in the above-mentioned publications .
- the compounds according to the invention can also be used on a carrier as co-catalysts in the polymerization of olefins.
- Si0 2 , A1 2 0 3 , MgCl 2 and polymer particles, such as polystyrene spherules can be mentioned as suitable carrier materials.
- These carrier materials can also be modified with for example silanes and/or aluminoxanes and/or aluminium alkyls .
- the supported co-catalysts can be synthesized prior to the polymerization, but they can also be formed in situ.
- Transition-metal catalysts are suitable as catalysts for the polymerization of olefins. Examples of such catalysts are described in US-A-5 , 096, 867 , WO- A-92/00333, EP-A-347 , 129 , EP-A-344 , 887 , EP-A-129 , 368 ,
- Supported transition-metal catalysts can be used. Si0 2 , Al 2 0 3 , MgCl 2 and polymer particles, such as polystyrene spherules, can be mentioned as suitable carrier materials. These carrier materials can also be modified with for example silanes and/or aluminoxanes and/or aluminium alkyls.
- the supported transition-metal catalysts can be synthesized prior to the polymerization, but they can also be formed in situ.
- metallocene catalysts are used for the polymerization of olefins in combination with a cocatalyst according to the invention.
- Metallocene catalysts are characterized by the presence in the transition-metal catalyst of one or more ⁇ -bound ligands, such as cyclopentadiene ligands (Cp) or cyclopentadiene-related ligands, for example indene and fluorene .
- Cp cyclopentadiene ligands
- Cp-related ligands for example indene and fluorene .
- transition-metal catalyst in which the transition metal is in a reduced oxidation state, as described in WO-A-96/13529, is more preferred.
- olefins for example ethylene, propylene, butene, hexene, octene and mixtures thereof and combinations with dienes
- olefins for example ethylene, propylene, butene, hexene, octene and mixtures thereof and combinations with dienes
- the catalyst system described above can also be used for the polymerization of vinylaromatic monomers, such as styrene and p-methylstyrene, for the polymerization of polar vinyl monomers, such as for example monomers containing alcohol, amine, alkyl halide, ether, amide, imine or anhydride groups, and for the polymerization of cyclic olefins, such as cyclobutene, cyclopentene, cyclohexene, cycloheptene, cyclooctene, norbornene, dimethanooctahydronaphthalene and substituted norbornenes.
- the amount of co-catalyst used relative to the amount of transition-metal catalyst (mol:mol) is normally 1:100-1000:1, preferably 1:5-250:1.
- the polymerizations can be carried out in the known manner and the use of the co-catalyst according to the invention does not necessitate any essential modification of these processes.
- the known polymerizations are carried out in suspension, solution, emulsion, gas phase or as bulk polymerization .
- the co-catalyst is used in suspension or gas-phase polymerization it is to be preferred to use the transition-metal catalyst or the co-catalyst according to the invention on a support. It is also possible to use both the catalyst and the co-catalyst on a support.
- the polymerizations are carried out at temperatures between -50°C and +350°C. Preferably between 50°C and 250°C.
- the pressures used generally lie between atmospheric pressure and 250 Mpa; for bulk polymerizations more in particular between 50 and 250 MPa, for the other polymerization processes between 0.5 and 25 MPa.
- dispersants and solvents substituted and unsubstituted hydrocarbons can for example be used, such as pentane, heptane and mixtures thereof. Aromatic, possibly perfluorinated hydrocarbons can also be considered.
- a monomer to be used in the polymerization can also be used as dispersant.
- the catalyst/cocatalyst mixture was introduced.
- the ethylene pressure was kept constant at 20 bars during the polymerisation. After 20 minutes the polymerization was stopped, the polymer was removed from the reactor and the yield was determined to be 3.63 g.
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- Health & Medical Sciences (AREA)
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- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EA199900651A EA199900651A1 (ru) | 1997-01-14 | 1997-12-15 | Способ полимеризации олефинов |
EP97950490A EP0954539A1 (de) | 1997-01-14 | 1997-12-15 | Verfahren zur olefinpolymerisation |
CA002277909A CA2277909A1 (en) | 1997-01-14 | 1997-12-15 | A process for polymerizing olefins |
JP53077098A JP2002514246A (ja) | 1997-01-14 | 1997-12-15 | オレフィン重合法 |
AU53474/98A AU5347498A (en) | 1997-01-14 | 1997-12-15 | A process for polymerizing olefins |
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
NL1004992 | 1997-01-14 | ||
NL1004992A NL1004992C2 (nl) | 1997-01-14 | 1997-01-14 | Toepassing van verbindingen die Si, Ge, Sn of Pb bevatten als cokatalysator bij de polymerisatie van olefinen. |
US60/041,598 | 1997-03-17 |
Publications (1)
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WO1998030602A1 true WO1998030602A1 (en) | 1998-07-16 |
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Family Applications (1)
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PCT/NL1997/000695 WO1998030602A1 (en) | 1997-01-14 | 1997-12-15 | A process for polymerizing olefins |
Country Status (8)
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EP (1) | EP0954539A1 (de) |
JP (1) | JP2002514246A (de) |
CN (1) | CN1248980A (de) |
AU (1) | AU5347498A (de) |
CA (1) | CA2277909A1 (de) |
EA (1) | EA199900651A1 (de) |
NL (1) | NL1004992C2 (de) |
WO (1) | WO1998030602A1 (de) |
Cited By (19)
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---|---|---|---|---|
WO2002100866A1 (en) * | 2001-06-12 | 2002-12-19 | Dsm N.V. | Compound of formula (xr5-)(y+), process for synthesis |
WO2004046214A2 (en) | 2002-10-15 | 2004-06-03 | Exxonmobil Chemical Patents Inc. | Multiple catalyst system for olefin polymerization and polymers produced therefrom |
WO2005113622A1 (en) | 2004-04-15 | 2005-12-01 | Exxonmobil Chemical Patents Inc. | Multiple catalyst and reactor system for olefin polymerization and polymers produced therefrom |
EP1624000A1 (de) | 1999-05-06 | 2006-02-08 | Univation Technologies, LLC | Verfahren zur Herstellung von leichter zu verarbeitenden Polymeren |
WO2006049699A1 (en) | 2004-10-29 | 2006-05-11 | Exxonmobil Chemical Patents Inc | Catalyst compound containing divalent tridentate ligand |
EP1803747A1 (de) | 2005-12-30 | 2007-07-04 | Borealis Technology Oy | Oberflächemodifizierte Polymerisationskatalysatoren zur Herstellung von Polyolefinfilmen mit niedrigem Gelgehalt |
WO2010071798A1 (en) | 2008-12-18 | 2010-06-24 | Univation Technologies, Llc | Method for seed bed treatment for a polymerization reaction |
WO2011048527A1 (en) | 2009-10-19 | 2011-04-28 | Sasol Technology (Pty) Limited | Oligomerisation of olefinic compounds with reduced polymer formation |
WO2012074709A1 (en) | 2010-11-30 | 2012-06-07 | Univation Technologies, Llc | Processes for the polymerization of olefins with extracted metal carboxylate salts |
WO2012074710A1 (en) | 2010-11-30 | 2012-06-07 | Univation Technologies, Llc. | Catalyst composition having improved flow characteristics and methods of making and using the same |
WO2012158260A1 (en) | 2011-05-13 | 2012-11-22 | Univation Technologies, Llc | Spray-dried catalyst compositions and polymerization processes employing the same |
WO2014109832A1 (en) | 2013-01-14 | 2014-07-17 | Univation Technologies, Llc | Methods for preparing catalyst systems with increased productivity |
WO2014120494A1 (en) | 2013-01-30 | 2014-08-07 | Univation Technologies, Llc | Processes for making catalyst compositions having improved flow |
WO2015153082A1 (en) | 2014-04-02 | 2015-10-08 | Univation Technologies, Llc | Continuity compositions and methods of making and using the same |
WO2016145179A1 (en) | 2015-03-10 | 2016-09-15 | Univation Technologies, Llc | Spray dried catalyst compositions, methods for preparation and use in olefin polymerization processes |
WO2016172110A1 (en) | 2015-04-20 | 2016-10-27 | Univation Technologies, Llc | Bridged bi-aromatic ligands and transition metal compounds prepared therefrom |
WO2016172097A1 (en) | 2015-04-20 | 2016-10-27 | Univation Technologies, Llc | Bridged bi-aromatic ligands and olefin polymerization catalysts prepared therefrom |
WO2016176135A1 (en) | 2015-04-27 | 2016-11-03 | Univation Technologies, Llc | Supported catalyst compositions having improved flow properties and preparation thereof |
EP3372311A1 (de) | 2007-10-22 | 2018-09-12 | Univation Technologies, LLC | Film enthaltend eine polyethylenzusammensetzung mit verbesserten eigenschaften |
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1997
- 1997-01-14 NL NL1004992A patent/NL1004992C2/nl not_active IP Right Cessation
- 1997-12-15 EP EP97950490A patent/EP0954539A1/de not_active Withdrawn
- 1997-12-15 JP JP53077098A patent/JP2002514246A/ja active Pending
- 1997-12-15 AU AU53474/98A patent/AU5347498A/en not_active Abandoned
- 1997-12-15 EA EA199900651A patent/EA199900651A1/ru unknown
- 1997-12-15 WO PCT/NL1997/000695 patent/WO1998030602A1/en not_active Application Discontinuation
- 1997-12-15 CN CN97182024A patent/CN1248980A/zh active Pending
- 1997-12-15 CA CA002277909A patent/CA2277909A1/en not_active Abandoned
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EP1624000A1 (de) | 1999-05-06 | 2006-02-08 | Univation Technologies, LLC | Verfahren zur Herstellung von leichter zu verarbeitenden Polymeren |
WO2002100866A1 (en) * | 2001-06-12 | 2002-12-19 | Dsm N.V. | Compound of formula (xr5-)(y+), process for synthesis |
WO2004046214A2 (en) | 2002-10-15 | 2004-06-03 | Exxonmobil Chemical Patents Inc. | Multiple catalyst system for olefin polymerization and polymers produced therefrom |
WO2005113622A1 (en) | 2004-04-15 | 2005-12-01 | Exxonmobil Chemical Patents Inc. | Multiple catalyst and reactor system for olefin polymerization and polymers produced therefrom |
WO2006049699A1 (en) | 2004-10-29 | 2006-05-11 | Exxonmobil Chemical Patents Inc | Catalyst compound containing divalent tridentate ligand |
EP1803747A1 (de) | 2005-12-30 | 2007-07-04 | Borealis Technology Oy | Oberflächemodifizierte Polymerisationskatalysatoren zur Herstellung von Polyolefinfilmen mit niedrigem Gelgehalt |
EP3372311A1 (de) | 2007-10-22 | 2018-09-12 | Univation Technologies, LLC | Film enthaltend eine polyethylenzusammensetzung mit verbesserten eigenschaften |
EP3597294A1 (de) | 2007-10-22 | 2020-01-22 | Univation Technologies, LLC | Polyethylenzusammensetzungen mit verbesserten eigenschaften |
WO2010071798A1 (en) | 2008-12-18 | 2010-06-24 | Univation Technologies, Llc | Method for seed bed treatment for a polymerization reaction |
WO2011048527A1 (en) | 2009-10-19 | 2011-04-28 | Sasol Technology (Pty) Limited | Oligomerisation of olefinic compounds with reduced polymer formation |
WO2012074709A1 (en) | 2010-11-30 | 2012-06-07 | Univation Technologies, Llc | Processes for the polymerization of olefins with extracted metal carboxylate salts |
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WO2012158260A1 (en) | 2011-05-13 | 2012-11-22 | Univation Technologies, Llc | Spray-dried catalyst compositions and polymerization processes employing the same |
WO2014109832A1 (en) | 2013-01-14 | 2014-07-17 | Univation Technologies, Llc | Methods for preparing catalyst systems with increased productivity |
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WO2016172110A1 (en) | 2015-04-20 | 2016-10-27 | Univation Technologies, Llc | Bridged bi-aromatic ligands and transition metal compounds prepared therefrom |
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Also Published As
Publication number | Publication date |
---|---|
AU5347498A (en) | 1998-08-03 |
CN1248980A (zh) | 2000-03-29 |
JP2002514246A (ja) | 2002-05-14 |
EA199900651A1 (ru) | 1999-12-29 |
EP0954539A1 (de) | 1999-11-10 |
CA2277909A1 (en) | 1998-07-16 |
NL1004992C2 (nl) | 1998-07-15 |
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