NL1004992C2 - Use of compounds containing Si, Ge, Sn or Pb as a cocatalyst in the polymerization of olefins. - Google Patents
Use of compounds containing Si, Ge, Sn or Pb as a cocatalyst in the polymerization of olefins. Download PDFInfo
- Publication number
- NL1004992C2 NL1004992C2 NL1004992A NL1004992A NL1004992C2 NL 1004992 C2 NL1004992 C2 NL 1004992C2 NL 1004992 A NL1004992 A NL 1004992A NL 1004992 A NL1004992 A NL 1004992A NL 1004992 C2 NL1004992 C2 NL 1004992C2
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- Netherlands
- Prior art keywords
- cocatalyst
- polymerization
- olefins
- transition metal
- aryl
- Prior art date
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- 238000006116 polymerization reaction Methods 0.000 title claims description 34
- 150000001336 alkenes Chemical class 0.000 title claims description 24
- 150000001875 compounds Chemical class 0.000 title claims description 22
- 229910052732 germanium Inorganic materials 0.000 title claims description 11
- 229910052718 tin Inorganic materials 0.000 title claims description 11
- 229910052745 lead Inorganic materials 0.000 title claims description 10
- 229910052710 silicon Inorganic materials 0.000 title claims description 9
- 239000003054 catalyst Substances 0.000 claims description 28
- 229910052723 transition metal Inorganic materials 0.000 claims description 20
- 150000003624 transition metals Chemical class 0.000 claims description 20
- 125000003118 aryl group Chemical group 0.000 claims description 13
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 8
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 8
- 150000001768 cations Chemical class 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 229910052744 lithium Inorganic materials 0.000 claims description 8
- 239000012968 metallocene catalyst Substances 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims 2
- 238000011835 investigation Methods 0.000 claims 2
- -1 for example Substances 0.000 description 15
- 229910052782 aluminium Inorganic materials 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 230000000737 periodic effect Effects 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 150000002430 hydrocarbons Chemical group 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 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 3
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 2
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-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
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 150000001642 boronic acid derivatives Chemical class 0.000 description 2
- 238000012662 bulk polymerization Methods 0.000 description 2
- 239000012876 carrier material 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
- 239000002270 dispersing agent Substances 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 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
- 239000003446 ligand Substances 0.000 description 2
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical group C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 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
- 229920000642 polymer Polymers 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 150000004756 silanes Chemical class 0.000 description 2
- 229920002554 vinyl polymer Polymers 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
- 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
- 230000006978 adaptation Effects 0.000 description 1
- 150000001298 alcohols Chemical class 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 class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical class B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 1
- 229910000085 borane Inorganic materials 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- CFBGXYDUODCMNS-UHFFFAOYSA-N cyclobutene Chemical compound C1CC=C1 CFBGXYDUODCMNS-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
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 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
- 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
- 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
- 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
- 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
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 1
- JQQSUOJIMKJQHS-UHFFFAOYSA-N pentaphenyl group Chemical group C1=CC=CC2=CC3=CC=C4C=C5C=CC=CC5=CC4=C3C=C12 JQQSUOJIMKJQHS-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 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
- 239000002002 slurry Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-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
- 238000005406 washing Methods 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Description
- 1 - PN 9086- 1 - PN 9086
TOEPASSING VAN VERBINDINGEN DIE Si. Ge, Sn of Pb 5 BEVATTEN ALS COKATALYSATOR BIJ DEAPPLICATION OF COMPOUNDS THAT Si. Ge, Sn or Pb 5 CONTAIN AS COCATALYSTATOR WITH THE
POLYMERISATIE VAN OLEFINENPOLYMERIZATION OF OLEFINS
De uitvinding betreft de toepassing van 10 verbindingen die Si, Ge, Sn of Pb bevatten als cokatalysator bij de polymerisatie van olefinen.The invention relates to the use of compounds containing Si, Ge, Sn or Pb as a cocatalyst in the polymerization of olefins.
Bij de polymerisatie van olefinen is meestal naast een overgangsmetaalkatalysator een cokatalysator nodig om een aktief katalysatorsysteem te verkrijgen.In the polymerization of olefins, in addition to a transition metal catalyst, a cocatalyst is usually required to obtain an active catalyst system.
15 Vanaf de vijftiger jaren worden Ziegler-Natta katalysatoren toegepast bij de polymerisatie van olefinen. Voor het goed verlopen van olefinepolymerisaties met deze Ziegler-Natta katalysatoren is het toevoegen van cokatalysatoren 20 noodzakelijk. In combinatie met Ziegler-Natta katalysatoren worden veelal aluminium-bevattende cokatalysatoren toegepast, zoals bijvoorbeeld diethylaluminiumchlor ide.From the 1950s, Ziegler-Natta catalysts have been used in the polymerization of olefins. The addition of cocatalysts is necessary for the proper functioning of olefin polymerizations with these Ziegler-Natta catalysts. Aluminum-containing cocatalysts are often used in combination with Ziegler-Natta catalysts, such as, for example, diethyl aluminum chloride.
Recent worden ook andersoortige 25 overgangsmetaalkatalysatoren, zoals bijvoorbeeld metalloceenkatalysatoren, toegepast bij de polymerisatie van olefinen. Voor het goed verlopen van olefinepolymerisaties met metalloceenkatalysatoren is het ook noodzakelijk een cokatalysator te gebruiken. In 30 combinatie met metalloceenkatalysatoren worden als cokatalysator vaak aluminoxanen, Lewiszuren of ioncomplexen als cokatalysatoren toegepast. Een voorbeeld van een aluminoxaan is methylaluminoxaan (MAO).Recently, other kinds of transition metal catalysts, such as, for example, metallocene catalysts, have also been used in the polymerization of olefins. It is also necessary to use a cocatalyst to ensure proper olefin polymerizations with metallocene catalysts. In combination with metallocene catalysts, aluminoxanes, Lewis acids or ion complexes are often used as cocatalysts as a cocatalyst. An example of an aluminoxane is methylaluminoxane (MAO).
35 Voorbeelden van Lewiszuren zijn boranen, zoals bijvoorbeeld tris(pentafluorofenyl)boraan, en voorbeelden van ioncomplexen zijn boraten, zoals 1004992 - 2 - bijvoorbeeld dimethylaniliniumtetrakis-(pentafluorofenyl)boraat, trifenylcarbeniumtetrakis-(pentafluorofenyl)boraat en trityltetrakis(3,5-tr ifluoromethylfenyl)boraat.Examples of Lewis acids are boranes, such as, for example, tris (pentafluorophenyl) borane, and examples of ion complexes are borates, such as 1004992 - 2 - for example, dimethylanilinium tetrakis- (pentafluorophenyl) borate, triphenylcarbenium tetrakis- (pentafluorophenyl) borate (trityl-tetluoris-tristyl-tetluoris) borate.
5 Dergelijke boor-bevattende cokatalysatoren worden bijvoorbeeld beschreven in EP-A-426.637, EP-A-277.003 en EP-A-277.004.Such boron-containing cocatalysts are described, for example, in EP-A-426,637, EP-A-277,003 and EP-A-277,004.
Het toepassen van aluminoxanen als cokatalysator bij de polymerisatie van olefinen met 10 behulp van een metalloceenkatalysator heeft als nadeel dat een zeer grote overmaat van het aluminoxaan ten opzichte van de metalloceenkatalysator moet worden toegepast om een aktief katalysatorsysteem te verkrijgen. Hierdoor bevat het geproduceerde 15 polyolefine een hoge aluminiumconcentratie, waardoor uitwassen van het aluminium uit het polyolefine vaak noodzakelijk is.The use of aluminoxanes as a cocatalyst in the polymerization of olefins with the aid of a metallocene catalyst has the drawback that a very large excess of the aluminoxane relative to the metallocene catalyst must be used to obtain an active catalyst system. As a result, the polyolefin produced contains a high aluminum concentration, whereby washing out of the aluminum from the polyolefin is often necessary.
Doel van de uitvinding is het verschaffen van een groep van cokatalysatoren, die kunnen worden 20 toegepast in combinatie met een overgangsmetaal- katalysator bij de polymerisatie van olefinen, die dit nadeel niet bezit.The object of the invention is to provide a group of cocatalysts which can be used in combination with a transition metal catalyst in the polymerization of olefins, which does not have this drawback.
De uitvinding betreft het toepassen van verbindingen volgens de formule XR4, waarin X Si, Ge, 25 Sn of Pb is, R waterstof of een alkyl, aryl, arylalkyl of alkylarylgroep is, of van verbindingen volgens de formule [XRS]“[ Y] + , waarin X Si, Ge, Sn of Pb is, R waterstof of een alkyl, aryl, arylalkyl of alkylarylgroep is en Y een kation is, 30 als cokatalysator bij de polymerisatie van olefinen.The invention relates to the use of compounds of the formula XR4, wherein X is Si, Ge, Sn or Pb, R is hydrogen or an alkyl, aryl, arylalkyl or alkylaryl group, or of compounds of the formula [XRS] “[Y] +, wherein X is Si, Ge, Sn or Pb, R is hydrogen or an alkyl, aryl, arylalkyl or alkylaryl group and Y is a cation as a cocatalyst in the polymerization of olefins.
Hierdoor wordt bereikt dat een aktief katalysatorsysteem, bestaande uit een overgangsmetaal-katalysator en als cokatalysator een van de verbindingen volgens de uitvinding, wordt verkregen dat 35 geschikt is voor de polymerisatie van olefinen. Als de verbindingen volgens de uitvinding als cokatalysator voor de polymerisatie van olefinen worden toegepast, is 1004992 - 3 - de hoeveelheid van de cokatalysator die moet worden toegepast ten opzichte van de overgangsmetaalkatalysator veel lager dan bij de toepassing van een aluminoxaan als cokatalysator.This achieves the result that an active catalyst system consisting of a transition metal catalyst and one of the compounds according to the invention as cocatalyst, which is suitable for the polymerization of olefins, is obtained. When the compounds of the invention are used as a cocatalyst for the polymerization of olefins, 1004992-3 - the amount of the cocatalyst to be used relative to the transition metal catalyst is much lower than when using an aluminoxane as a cocatalyst.
5 Een verder voordeel van de toepassing van de verbindingen volgens de uitvinding als cokatalysator bij de polymerisatie van olefinen is dat het toepassen van deze verbindingen in de regel goedkoper is dan het toepassen van aluminoxanen of boraten.A further advantage of the use of the compounds according to the invention as a cocatalyst in the polymerization of olefins is that the use of these compounds is generally cheaper than the use of aluminoxanes or borates.
10 Als cokatalysator geschikte verbindingen zijn verbindingen volgens de formule XR4 en verbindingen volgens de formule [XRS]"( Υ]"-· X is een atoom uit groep 14 van het Periodiek Systeem der Elementen en kan worden gekozen uit Si, Ge, Sn en 15 Pb. Bij bijzondere voorkeur is X Si, omdat Si niet toxisch is.Suitable compounds as cocatalyst are compounds of the formula XR4 and compounds of the formula [XRS] "(Υ]" - X is an atom of group 14 of the Periodic Table of the Elements and can be selected from Si, Ge, Sn and 15 Pb X is particularly preferred because Si is non-toxic.
Hier en hierna wordt onder het Periodiek Systeem der Elementen verstaan het Periodiek Systeem dat is weergegeven aan de binnenzijde van de omslag van 20 het Handbook of Chemistry and Physics, 70th edition, 1989/1990 (New IUPAC Notation).Here and hereafter, the Periodic Table of Elements is understood to mean the Periodic Table shown on the inside cover of the Handbook of Chemistry and Physics, 70th edition, 1989/1990 (New IUPAC Notation).
De R-groepen kunnen gelijk of verschillend zijn en kunnen worden gekozen uit waterstof en alkyl, aryl, arylalkyl of alkylarylgroepen. Bij voorkeur is de R-25 groep een koolwaterstofgroep bevattende 1-20 koolstofatomen.The R groups can be the same or different and can be selected from hydrogen and alkyl, aryl, arylalkyl or alkylaryl groups. Preferably the R-25 group is a hydrocarbon group containing 1-20 carbon atoms.
Voorbeelden van geschikte R-groepen zijn methyl, ethyl, propyl, isopropyl, hexyl, decyl en fenyl. Ook kunnen 2 R-groepen tesamen een gebrugde R2-30 groep vormen, zoals bijvoorbeeld een bifenyl-2,2 diylgroep en een difenyl-2,2'-diylmethaangroep.Examples of suitable R groups are methyl, ethyl, propyl, isopropyl, hexyl, decyl and phenyl. Also, 2 R groups together may form a bridged R2-30 group, such as, for example, a biphenyl-2,2 diyl group and a diphenyl-2,2'-diylmethane group.
Bij voorkeur vormen tenminste 2 R-groepen tesamen een gebrugde arylgroep. Bij bijzondere voorkeur bevat de verbinding volgens de formule XR4 of [XRS]*[Y]+ 2 van 35 dergelijke gebrugde arylgroepen.Preferably at least 2 R groups together form a bridged aryl group. Particularly preferably, the compound of the formula XR4 or [XRS] * [Y] + 2 contains such bridged aryl groups.
Het kat ion Y, is bijvoorbeeld een Bronsted zuur dat een proton kan doneren, een kation van een alkalimetaal of 1004992 - 4 - een carbeen.The cat ion Y, for example, is a Bronsted acid that can donate a proton, a cation of an alkali metal or 1004992-4 - a carbene.
Voorbeelden van kationen zijn Li+, K+, Na+, H+, trifenylcarbenium, anilinium, guanidinium, glycinium, ammonium of een gesubstitueerd ammonium kation, waarin 5 ten hoogste 3 waterstofatomen zijn vervangen door een hydrocarbyl radicaal met 1-20 koolstofatomen, of een gesubstitueerd hydrocarbyl radicaal met 1-20 koolstofatomen, waarin 1 of meer van de waterstofatomen vervangen zijn door een halogeen atoom, fosfonium 10 radicalen, gesubstitueerde fosfonium radicalen, waarin ten hoogste 3 waterstofatomen vervangen zijn door een hydrocarbyl radicaal met 1-20 koolstofatomen of een gesubstitueerd hydrocarbyl radicaal met 1-20 koolstofatomen, waarin 1 of meer van de waterstofatomen 15 vervangen zijn door een halogeen atoom.Examples of cations are Li +, K +, Na +, H +, triphenylcarbenium, anilinium, guanidinium, glycinium, ammonium or a substituted ammonium cation, in which 5 at most 3 hydrogen atoms are replaced by a hydrocarbyl radical with 1-20 carbon atoms, or a substituted hydrocarbyl radical having 1-20 carbon atoms, wherein 1 or more of the hydrogen atoms have been replaced by a halogen atom, phosphonium radicals, substituted phosphonium radicals, in which at most 3 hydrogen atoms have been replaced by a hydrocarbyl radical with 1-20 carbon atoms or a substituted hydrocarbyl radical with 1-20 carbon atoms, in which 1 or more of the hydrogen atoms have been replaced by a halogen atom.
Bij voorkeur is het kation dimethylanilinium, trifenylcarbenium of Li+.Preferably the cation is dimethylanilinium, triphenylcarbenium or Li +.
Verbindingen volgens de formule XR4 en silicaten met 5 substituenten zijn bijvoorbeeld bekend 20 uit 'The chemistry of organic silicon compounds, E.S. Patai et al, Wiley and Sons, 1989'.Compounds of the formula XR4 and 5-substituent silicates are known, for example, from The Chemistry of Organic Silicon Compounds, E.S. Patai et al, Wiley and Sons, 1989 '.
Anionische organosilicaten zijn voor het eerst aangetoond in Angew. Chem. Int. Ed. Engl. 1996, 35, no.Anionic organosilicates have been first demonstrated in Angew. Chem. Int. Ed. Engl. 1996, 35, no.
10. In deze publicatie worden lithium(2,2'-25 bifenyldiyltrimethylsilicaat).4THF, 1ithium(2,2'- bifenyldiyldimethylfenylsilicaat).4THF, lithium(2,2 '-bifenyldiyldimethyl-t-butylsilicaat).4THF en 1ithium(pentafenylsilicaat).4HMPA genoemd. (THF is tetrahydrofuraan en HMPA is hexamethylfosfortriamide.) 30 De mogelijke toepassing van deze silicaten als cokatalysator bij de polymerisatie van olefinen wordt niet genoemd noch gesuggereerd.10. In this publication, lithium (2,2'-25 biphenyldiyltrimethylsilicate) .4THF, lithium (2,2'-biphenyldiyldimethylphenylsilicate) .4THF, lithium (2,2'-biphenyldiethyl dimethyl-t-butylsilicate) .4THF and lithium (pentaphenyl Called .4HMPA. (THF is tetrahydrofuran and HMPA is hexamethylphosphoric triamide.) The possible use of these silicates as a cocatalyst in the polymerization of olefins is neither mentioned nor suggested.
De bovengenoemde verbindingen volgens de formule XR4 zijn bijvoorbeeld te synthetiseren volgens de 35 synthesemethoden beschreven in de bovengenoemde publicaties.For example, the above compounds of the formula XR4 can be synthesized according to the synthesis methods described in the above publications.
Ook kunnen de verbindingen volgens de uitvinding op 1004992 - 5 - drager worden toegepast als cokatalysator bij de polymerisatie van olefinen. Als geschikt dragermateriaal kunnen Si02, A1203, MgCl2 en polymeerdeeltjes, zoals polystyreenbolletjes, worden 5 genoemd. Deze dragermaterialen kunnen ook worden gemodificeerd met bijvoorbeeld silanen en/of aluminoxanen en/of aluminiumalkylen. De gedragen cokatalysatoren kunnen vooraf aan de polymerisatie worden gesynthetiseerd, maar kunnen ook in situ worden 10 gevormd.The compounds of the invention on 1004992-5 can also be used as cocatalyst in the polymerization of olefins. SiO 2, Al 2 O 3, MgCl 2 and polymer particles, such as polystyrene spheres, can be mentioned as a suitable carrier material. These support materials can also be modified with, for example, silanes and / or alumoxanes and / or aluminum alkyls. The supported cocatalysts can be synthesized prior to polymerization, but can also be formed in situ.
Als katalysator voor de polymerisatie van olefinen zijn overgangsmetaalkatalysatoren geschikt. Voorbeelden van dergelijke katalysatoren zijn bijvoorbeeld beschreven in US-A-5.096.867, WO-A-15 92/00333, EP-A-347.129, EP-A-344.887, EP-A-129.368, EP- A-476.671, EP-A-468.651, EP-A-416.815, EP-A-351.391, EP-A-351.392, EP-A-423.101, EP-A-503.422, EP-A-516.018, EP-A-490.256, EP-A-485.820, EP-A-376.154, DE-A-4.015.254, WO-A-96/13529, EP-A-530.908, WO-A-94/11406, 20 EP-A-672.676 en WO-A-96/23010. Ook overgangsmetaalkatalysatoren die metalen uit groep 3 van het Periodiek Systeem der Elementen en de lanthaniden bevatten, kunnen worden toegepast.Transition metal catalysts are suitable as a catalyst for the polymerization of olefins. Examples of such catalysts are described, for example, in US-A-5,096,867, WO-A-15 92/00333, EP-A-347,129, EP-A-344,887, EP-A-129,368, EP-A-476,671, EP -A-468.651, EP-A-416.815, EP-A-351.391, EP-A-351.392, EP-A-423.101, EP-A-503.422, EP-A-516.018, EP-A-490.256, EP-A -485,820, EP-A-376,154, DE-A-4,015,254, WO-A-96/13529, EP-A-530,908, WO-A-94/11406, EP-A-672,676 and WO-A- 96/23010. Transition metal catalysts containing Group 3 metals of the Periodic Table of the Elements and the Lanthanides can also be used.
Gedragen overgangsmetaalkatalysatoren kunnen worden 25 toegepast. Als geschikt dragermateriaal kunnen Si02, A1203, MgCl2 en polymeerdeeltjes, zoals polystyreenbolletjes, worden genoemd. Deze dragermaterialen kunnen ook worden gemodificeerd met bijvoorbeeld silanen en/of aluminoxanen en/of 30 aluminiumalkylen.Supported transition metal catalysts can be used. SiO 2, Al 2 O 3, MgCl 2 and polymer particles, such as polystyrene spheres, can be mentioned as a suitable carrier material. These support materials can also be modified with, for example, silanes and / or alumoxanes and / or aluminum alkyls.
De gedragen overgangsmetaalkatalysatoren kunnen vooraf aan de polymerisatie worden gesynthetiseerd, maar kunnen ook in situ worden gevormd.The supported transition metal catalysts can be synthesized before polymerization, but can also be formed in situ.
Bij voorkeur worden metalloceenkatalysatoren toegepast. 35 Metalloceenkatalysatoren kenmerken zich door de aanwezigheid van een of meerdere π-gebonden liganden, zoals voorbeeld cyclopentadieen- (Cp) of aan i 004992 - 6 - cyclopentadieen verwante liganden, zoals bijvoorbeeld indeen en fluoreen in de overgangsmetaalkatalysator.Metallocene catalysts are preferably used. Metallocene catalysts are characterized by the presence of one or more π-bonded ligands, such as, for example, cyclopentadiene (Cp) or ligands related to cyclopentadiene, such as, for example, indene and fluorene in the transition metal catalyst.
Bij bijzondere voorkeur wordt een overgangsmetaalkatalysator toegepast, waarin het 5 overgangsmetaal zich in een gereduceerde oxidatietoestand bevindt, zoals beschreven in WO-A-96/13529.Particular preference is given to using a transition metal catalyst in which the transition metal is in a reduced oxidation state, as described in WO-A-96/13529.
De polymerisatie van olefinen, bijvoorbeeld etheen, propeen, buteen, hexeen, octeen en mengsels 10 daarvan en combinaties met dieenen kunnen worden uitgevoerd in aanwezigheid van een overgangsmetaalkatalysator en de cokatalysator volgens de uitvinding. Ook kan het bovenbeschreven katalysator systeem worden toegepast voor de 15 polymerisatie van vinylaromatische monomeren, zoals bijvoorbeeld styreen en p-methylstyreen, voor de polymerisatie van polaire vinylmonomeren, zoals bijvoorbeeld alcoholen, amines, alkyl halides, ethers, amides, imines en anhydrides, en voor de polymerisatie 20 van cyclische olefines, zoals bijvoorbeeld cyclobuteen, cyclopenteen, cyclohexeen, cyclohepteen, cycloocteen, norborneen, dimethanooctahydronaftaleen en gesubstitueerde norbornenen.The polymerization of olefins, for example ethylene, propylene, butene, hexene, octene and mixtures thereof and combinations with dienes can be carried out in the presence of a transition metal catalyst and the cocatalyst according to the invention. The above-described catalyst system can also be used for the polymerization of vinyl aromatic monomers, such as, for example, styrene and p-methylstyrene, for the polymerization of polar vinyl monomers, such as, for example, alcohols, amines, alkyl halides, ethers, amides, imines and anhydrides, and for the polymerization of cyclic olefins, such as, for example, cyclobutene, cyclopentene, cyclohexene, cyclohepene, cyclooctene, norbornene, dimethano octahydronaphthalene and substituted norbornenes.
De hoeveelheid cokatalysator die wordt toegepast ten 25 opzichte van de hoeveelheid overgangsmetaalkatalysator (mol:mol) is normaliter 1:100-1000:1, bij voorkeur 1:5-250:1.The amount of cocatalyst used relative to the amount of transition metal catalyst (mol: mol) is normally 1: 100-1000: 1, preferably 1: 5-250: 1.
De polymerisaties kunnen op de daarvoor bekende wijze worden uitgevoerd en de toepassing van de cokatalysator 30 volgens de uitvinding maakt geen wezenlijke aanpassing van deze werkwijzen noodzakelijk. De bekende polymerisaties worden uitgevoerd in suspensie, solutie, emulsie, gasfase of als bulkpolymerisatie.The polymerizations can be carried out in the known manner and the use of the cocatalyst 30 according to the invention does not necessitate any substantial adaptation of these processes. The known polymerizations are carried out in suspension, solution, emulsion, gas phase or as bulk polymerization.
Voor toepassing van de cokatalysator in suspensie- of 35 gasfasepolymerisatie verdient het de voorkeur om de overgangsmetaalkatalysator of de cokatalysator volgens de uitvinding op een dragermateriaal toe te passen. Ook 1004992 - 7 - kunnen zowel de katalysator als de cokatalysator op drager worden toegepast.For use of the cocatalyst in slurry or gas phase polymerization, it is preferable to use the transition metal catalyst or the cocatalyst of the invention on a support material. Also 1004992-7 - both the catalyst and the cocatalyst on support can be used.
De polymerisaties worden uitgevoerd bij temperaturen tussen -50°C en +350°C. Bij voorkeur tussen 50°C en 5 250°CThe polymerizations are carried out at temperatures between -50 ° C and + 350 ° C. Preferably between 50 ° C and 250 ° C
Toegepaste drukken liggen in het algemeen tussen atmosferische druk en 250 MPa; voor bulkpolymerisaties meer in het bijzonder tussen 50 en 250 MPa, voor de overige polymerisatieprocessen tussen 0,5 en 25 MPa.Applied pressures are generally 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.
10 Als verdeel- en oplosmiddelen kunnen bijvoorbeeld gesubstitueerde en ongesubstitueerde koolwaterstoffen worden toegepast, zoals pentaan, heptaan en mengsels daarvan. Ook aromatische, eventueel geperfluoreer de koolwaterstoffen komen in aanmerking. Eveneens kan een 15 in de polymerisatie te gebruiken monomeer als verdeelmiddel toegepast worden.Substituted and unsubstituted hydrocarbons, such as pentane, heptane and mixtures thereof, can be used as dispersants and solvents. Aromatic, optionally perfluorinated hydrocarbons are also eligible. Also, a monomer to be used in the polymerization can be used as a dispersant.
10049921004992
Claims (9)
Priority Applications (8)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| NL1004992A NL1004992C2 (en) | 1997-01-14 | 1997-01-14 | Use of compounds containing Si, Ge, Sn or Pb as a cocatalyst in the polymerization of olefins. |
| PCT/NL1997/000695 WO1998030602A1 (en) | 1997-01-14 | 1997-12-15 | A process for polymerizing olefins |
| AU53474/98A AU5347498A (en) | 1997-01-14 | 1997-12-15 | A process for polymerizing olefins |
| EA199900651A EA199900651A1 (en) | 1997-01-14 | 1997-12-15 | METHOD OF POLYMERIZATION OF OLEFINS |
| JP53077098A JP2002514246A (en) | 1997-01-14 | 1997-12-15 | Olefin polymerization method |
| EP97950490A EP0954539A1 (en) | 1997-01-14 | 1997-12-15 | A process for polymerizing olefins |
| CN97182024A CN1248980A (en) | 1997-01-14 | 1997-12-15 | Process for polymerizing olefins |
| CA002277909A CA2277909A1 (en) | 1997-01-14 | 1997-12-15 | A process for polymerizing olefins |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| NL1004992 | 1997-01-14 | ||
| NL1004992A NL1004992C2 (en) | 1997-01-14 | 1997-01-14 | Use of compounds containing Si, Ge, Sn or Pb as a cocatalyst in the polymerization of olefins. |
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| Publication Number | Publication Date |
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| NL1004992C2 true NL1004992C2 (en) | 1998-07-15 |
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| NL1004992A NL1004992C2 (en) | 1997-01-14 | 1997-01-14 | Use of compounds containing Si, Ge, Sn or Pb as a cocatalyst in the polymerization of olefins. |
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| Country | Link |
|---|---|
| EP (1) | EP0954539A1 (en) |
| JP (1) | JP2002514246A (en) |
| CN (1) | CN1248980A (en) |
| AU (1) | AU5347498A (en) |
| CA (1) | CA2277909A1 (en) |
| EA (1) | EA199900651A1 (en) |
| NL (1) | NL1004992C2 (en) |
| WO (1) | WO1998030602A1 (en) |
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| US6339134B1 (en) | 1999-05-06 | 2002-01-15 | Univation Technologies, Llc | Polymerization process for producing easier processing polymers |
| US20040267037A1 (en) * | 2001-06-12 | 2004-12-30 | Sirik Deerenberg | Compound according to the formula (xr5-)(y+)and a process for the synthesis of such a compound |
| US7223822B2 (en) | 2002-10-15 | 2007-05-29 | Exxonmobil Chemical Patents Inc. | Multiple catalyst and reactor system for olefin polymerization and polymers produced therefrom |
| WO2004046214A2 (en) | 2002-10-15 | 2004-06-03 | Exxonmobil Chemical Patents Inc. | Multiple catalyst system for olefin polymerization and polymers produced therefrom |
| EP1805226A1 (en) | 2004-10-29 | 2007-07-11 | Exxonmobil Chemical Patents Inc. | Catalyst compound containing divalent tridentate ligand |
| EP1803747A1 (en) | 2005-12-30 | 2007-07-04 | Borealis Technology Oy | Surface-modified polymerization catalysts for the preparation of low-gel polyolefin films |
| TW200932762A (en) | 2007-10-22 | 2009-08-01 | Univation Tech Llc | Polyethylene compositions having improved properties |
| BRPI0922454A2 (en) | 2008-12-18 | 2018-05-22 | Univation Tech Llc | seedbed treatment method for a polymerization reaction |
| EP2490990B1 (en) | 2009-10-19 | 2013-12-04 | Sasol Technology (Proprietary) Limited | Oligomerisation of olefinic compounds with reduced polymer formation |
| KR101832541B1 (en) | 2010-11-30 | 2018-02-26 | 유니베이션 테크놀로지즈, 엘엘씨 | Catalyst composition having improved flow characteristics and methods of making and using the same |
| BR112013012741B1 (en) | 2010-11-30 | 2020-04-28 | Univation Tech Llc | polymerization process |
| WO2012158260A1 (en) | 2011-05-13 | 2012-11-22 | Univation Technologies, Llc | Spray-dried catalyst compositions and polymerization processes employing the same |
| US9938361B2 (en) | 2013-01-14 | 2018-04-10 | Univation Technologies, Llc | Methods for preparing catalyst systems with increased productivity |
| JP2016506979A (en) | 2013-01-30 | 2016-03-07 | ユニベーション・テクノロジーズ・エルエルシー | Process for making a catalyst composition with improved flow |
| RU2677897C2 (en) | 2014-04-02 | 2019-01-22 | ЮНИВЕЙШН ТЕКНОЛОДЖИЗ, ЭлЭлСи | Continuity compositions and methods of making and using 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 |
| WO2016172097A1 (en) | 2015-04-20 | 2016-10-27 | Univation Technologies, Llc | Bridged bi-aromatic ligands and olefin polymerization catalysts prepared therefrom |
| BR112017022494A2 (en) | 2015-04-20 | 2018-07-17 | Univation Tech Llc | bridged biaromatic ligands and transition metal compounds prepared therefrom |
| WO2016176135A1 (en) | 2015-04-27 | 2016-11-03 | Univation Technologies, Llc | Supported catalyst compositions having improved flow properties and preparation thereof |
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| FR1134740A (en) * | 1954-08-16 | 1957-04-17 | Du Pont | Preparation of polyethylene and ethylene copolymers |
| US2992190A (en) * | 1957-09-13 | 1961-07-11 | Du Pont | Olefin polymerization catalyst |
| US3166547A (en) * | 1959-09-15 | 1965-01-19 | Union Carbide Corp | Polymerization of alpha-monoolefins in an aqueous diluent |
| US3332927A (en) * | 1966-02-14 | 1967-07-25 | Cabot Corp | Process for polymerization |
| EP0780405A1 (en) * | 1995-12-21 | 1997-06-25 | ENICHEM S.p.A. | Process for the preparation of crystalline vinylaromatic polymers with a predominantly syndiotactic structure |
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| JPH07109305A (en) * | 1993-10-12 | 1995-04-25 | Showa Denko Kk | Production of ethylene polymer |
| AU4146896A (en) * | 1994-10-31 | 1996-05-23 | W.R. Grace & Co.-Conn. | In situ dehydroxylation of supports and preparation of supported metallocene polyolefin catalysts |
-
1997
- 1997-01-14 NL NL1004992A patent/NL1004992C2/en not_active IP Right Cessation
- 1997-12-15 CN CN97182024A patent/CN1248980A/en active Pending
- 1997-12-15 JP JP53077098A patent/JP2002514246A/en active Pending
- 1997-12-15 AU AU53474/98A patent/AU5347498A/en not_active Abandoned
- 1997-12-15 EA EA199900651A patent/EA199900651A1/en unknown
- 1997-12-15 EP EP97950490A patent/EP0954539A1/en not_active Withdrawn
- 1997-12-15 CA CA002277909A patent/CA2277909A1/en not_active Abandoned
- 1997-12-15 WO PCT/NL1997/000695 patent/WO1998030602A1/en not_active Application Discontinuation
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| FR1134740A (en) * | 1954-08-16 | 1957-04-17 | Du Pont | Preparation of polyethylene and ethylene copolymers |
| US2992190A (en) * | 1957-09-13 | 1961-07-11 | Du Pont | Olefin polymerization catalyst |
| US3166547A (en) * | 1959-09-15 | 1965-01-19 | Union Carbide Corp | Polymerization of alpha-monoolefins in an aqueous diluent |
| US3332927A (en) * | 1966-02-14 | 1967-07-25 | Cabot Corp | Process for polymerization |
| EP0780405A1 (en) * | 1995-12-21 | 1997-06-25 | ENICHEM S.p.A. | Process for the preparation of crystalline vinylaromatic polymers with a predominantly syndiotactic structure |
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Also Published As
| Publication number | Publication date |
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| CA2277909A1 (en) | 1998-07-16 |
| AU5347498A (en) | 1998-08-03 |
| WO1998030602A1 (en) | 1998-07-16 |
| CN1248980A (en) | 2000-03-29 |
| EA199900651A1 (en) | 1999-12-29 |
| EP0954539A1 (en) | 1999-11-10 |
| JP2002514246A (en) | 2002-05-14 |
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