NL1004991C2 - Polymerisation of olefin(s) - Google Patents
Polymerisation of olefin(s) Download PDFInfo
- Publication number
- NL1004991C2 NL1004991C2 NL1004991A NL1004991A NL1004991C2 NL 1004991 C2 NL1004991 C2 NL 1004991C2 NL 1004991 A NL1004991 A NL 1004991A NL 1004991 A NL1004991 A NL 1004991A NL 1004991 C2 NL1004991 C2 NL 1004991C2
- Authority
- NL
- Netherlands
- Prior art keywords
- cocatalyst
- olefins
- group
- polymerization
- transition metal
- Prior art date
Links
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 27
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title description 3
- 239000003054 catalyst Substances 0.000 claims abstract description 28
- 150000001875 compounds Chemical class 0.000 claims abstract description 25
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 20
- 150000003624 transition metals Chemical class 0.000 claims abstract description 20
- 125000005843 halogen group Chemical group 0.000 claims abstract description 18
- 125000003118 aryl group Chemical group 0.000 claims abstract description 12
- 229910052718 tin Inorganic materials 0.000 claims abstract description 11
- 229910052732 germanium Inorganic materials 0.000 claims abstract description 10
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 10
- 125000002877 alkyl aryl group Chemical group 0.000 claims abstract description 9
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 9
- 125000003710 aryl alkyl group Chemical group 0.000 claims abstract description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 9
- 239000001257 hydrogen Substances 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000006116 polymerization reaction Methods 0.000 claims description 33
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 10
- 150000001768 cations Chemical class 0.000 claims description 9
- 229910052745 lead Inorganic materials 0.000 claims description 9
- 239000012968 metallocene catalyst Substances 0.000 claims description 8
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 239000013589 supplement Substances 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
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 230000000737 periodic effect Effects 0.000 description 4
- 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
- LWNGJAHMBMVCJR-UHFFFAOYSA-N (2,3,4,5,6-pentafluorophenoxy)boronic acid Chemical compound OB(O)OC1=C(F)C(F)=C(F)C(F)=C1F LWNGJAHMBMVCJR-UHFFFAOYSA-N 0.000 description 2
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 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
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 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
- 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
- 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
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-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
- 229910018072 Al 2 O 3 Inorganic materials 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
- 229910004298 SiO 2 Inorganic materials 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
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 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
- 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
- 229910052794 bromium Inorganic materials 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 229910052906 cristobalite 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
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 229910052740 iodine Inorganic materials 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
- 229910001629 magnesium chloride 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
- 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
- 125000000538 pentafluorophenyl group Chemical group FC1=C(F)C(F)=C(*)C(F)=C1F 0.000 description 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-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
- 150000003254 radicals Chemical class 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 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
- 229910052682 stishovite Inorganic materials 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
- 229910052905 tridymite Inorganic materials 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
- 229910001845 yogo sapphire Inorganic materials 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
- 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
- C07F7/30—Germanium compounds
-
- 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
- C08F4/619—Component covered by group C08F4/60 containing a transition metal-carbon bond
- C08F4/61908—Component covered by group C08F4/60 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
- C08F4/619—Component covered by group C08F4/60 containing a transition metal-carbon bond
- C08F4/61912—Component covered by group C08F4/60 containing a transition metal-carbon bond in combination with an organoaluminium compound
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/619—Component covered by group C08F4/60 containing a transition metal-carbon bond
- C08F4/6192—Component covered by group C08F4/60 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/619—Component covered by group C08F4/60 containing a transition metal-carbon bond
- C08F4/6192—Component covered by group C08F4/60 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
- C08F4/61922—Component covered by group C08F4/60 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
- C08F4/61925—Component covered by group C08F4/60 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)
Abstract
Description
- 1 - PN 9087- 1 - PN 9087
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 AT THE
POLYMERISATIE VAN OLEFINENPOLYMERIZATION OF OLEFINS
10 De uitvinding betreft de toepassing van 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 15 nodig om een aktief katalysator systeem te verkrijgen.In the polymerization of olefins, a cocatalyst 15 is usually required in addition to a transition metal catalyst to obtain an active catalyst system.
Vanaf de vijftiger jaren worden Ziegler-Natta katalysatoren toegepast bij de polymerisatie van olefinen. Voor het goed verlopen van olefine-polymerisaties met deze Ziegler-Natta katalysatoren is 20 het toevoegen van cokatalysatoren noodzakelijk. In combinatie met Ziegler-Natta katalysatoren worden veelal aluminium-bevattende cokatalysatoren toegepast, zoals bijvoorbeeld diethylaluminiumchloride.Ziegler-Natta catalysts have been used in the polymerization of olefins since the 1950s. The addition of cocatalysts is necessary for successful olefin polymerizations with these Ziegler-Natta catalysts. Aluminum-containing cocatalysts, such as, for example, diethyl aluminum chloride, are often used in combination with Ziegler-Natta catalysts.
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 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 cocatalyst. An example of an aluminoxane is methylaluminoxane (MAO).
Voorbeelden van Lewiszuren zijn boranen, 35 zoals bijvoorbeeld tris(pentafluorofenyl)boraan, en voorbeelden van ioncomplexen zijn boraten, zoals 1004991 - 2 - bijvoorbeeld dimethylaniliniumtetrakis-(pentafluorofenyl)boraat, trifenylcarbenium-tetrakis(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 1004991 - 2 - for example, dimethylanilinium tetrakis (pentafluorophenyl) borate, triphenylcarbenium tetrakis (pentafluorophenyl) borate and trityltetrakis trifluoromethylphenyl) 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 aluminiumconcentrat ie, 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 25 XR4, waar in X Si, Ge, Sn of Pb is, R waterstof of een alkyl, aryl, arylalkyl of alkylarylgroep is, waarbij tenminste één R-groep één of 30 meer halogeenatomen bevat, of verbindingen volgens de formule [XRS]“[Y)+, waarin X Si, Ge, Sn of Pb is, R waterstof of een alkyl, aryl, arylalkyl of alkylarylgroep is, waarbij tenminste één R-groep één of 35 meer halogeenatomen bevat en Y een kation is, als cokatalysator bij de polymerisatie van olefinen.The invention relates to the use of compounds of the formula XR4, where in X is Si, Ge, Sn or Pb, R is hydrogen or an alkyl, aryl, arylalkyl or alkylaryl group, wherein at least one R group contains one or more halogen atoms or 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, wherein at least one R group is one or 35 more halogen atoms and Y is a cation, as a cocatalyst in the polymerization of olefins.
1004991 ‘ - 3 -1004991 "- 3 -
Door toepassing van deze verbindingen als cokatalysator bij de polymerisatie van olefinen wordt bereikt dat een aktief katalysatorsysteem wordt verkregen. Wanneer de verbindingen volgens de 5 uitvinding als cokatalysator voor de polymerisatie van olefinen worden toegepast, is 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.By using these compounds as a cocatalyst in the polymerization of olefins, an active catalyst system is obtained. When the compounds of the invention are used as a cocatalyst for the polymerization of olefins, 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.
10 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.
15 Als cokatalysator geschikte verbindingen zijn verbindingen volgens de formule XR4 en verbindingen volgens de formule [XRS]"[Y]+.Suitable compounds as cocatalyst are compounds of the formula XR4 and compounds of the formula [XRS] "[Y] +.
X is een atoom uit groep 14 van het Periodiek Systeem der Elementen en kan worden gekozen uit Si, Ge, Sn en 20 Pb. Bij bijzondere voorkeur is X Si, omdat Si niet toxisch is.X is a group 14 atom of the Periodic Table of Elements and can be selected from Si, Ge, Sn and 20 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 het 25 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. Tenminste één R-groep 30 bevat één of meer halogeenatomen. Dit houdt in dat in een verbinding volgens de formule XR4 of volgens de formule [XRS]~[Y]+ tenminste één halogeenatoom voorkomt dat geen onderdeel uitmaakt van het kation Y. Bij voorkeur is de R-groep een koolwaterstofgroep 35 bevattende 1-20 koolstofatomen. Voorbeelden van geschikte R-groepen zijn methyl, ethyl, propyl, isopropyl, hexyl, decyl en fenyl. Ook kunnen 2 R- 1004991 - 4 - groepen tesamen een gebrugde R2-groep vormen, zoals bijvoorbeeld een bifenyl-2,2'-diylgroep en een difenyl-2,2'-diylmethaangroep. Deze R-groepen kunnen één of meerdere halogeenatomen bevatten. Halogeenatomen zijn 5 F, Cl, Br en I. Combinaties van verschillende halogeenatomen kunnen voorkomen in één R-groep of verdeeld over verschillende R-groepen. Voorbeelden van R-groepen die een halogeenatoom bevatten zijn chloormethyl, 1,2-dibroomethyl, pentafluorfenyl en 10 octafluorbifenyl-2,2'-diyl.The R groups can be the same or different and can be selected from hydrogen and alkyl, aryl, arylalkyl or alkylaryl groups. At least one R group 30 contains one or more halogen atoms. This means that in a compound of the formula XR4 or of the formula [XRS] ~ [Y] + there is at least one halogen atom which is not part of the cation Y. Preferably the R group is a hydrocarbon group containing 1-20 carbon atoms. Examples of suitable R groups are methyl, ethyl, propyl, isopropyl, hexyl, decyl and phenyl. Also, 2 R-1004991-4 groups can together form a bridged R2 group, such as, for example, a biphenyl-2,2'-diyl group and a diphenyl-2,2'-diylmethane group. These R groups can contain one or more halogen atoms. Halogen atoms are 5 F, Cl, Br and I. Combinations of different halogen atoms can exist in one R group or divided over different R groups. Examples of R groups containing a halogen atom are chloromethyl, 1,2-dibromoethyl, pentafluorophenyl and octafluorobiphenyl-2,2'-diyl.
Bij voorkeur vormen tenminste 2 R-groepen tesamen een gebrugde arylgroep.Preferably at least 2 R groups together form a bridged aryl group.
Bij bijzondere voorkeur bevat de verbinding volgens de formule XR4 of [XRS]"[Y]* octafluorbifenyl-2,2 15 diylgroepen.Particularly preferably, the compound of the formula XR4 or [XRS] contains "[Y] * octafluorobiphenyl-2,2 diyl groups.
Het kation Y, is bijvoorbeeld een Bronsted zuur dat een proton kan doneren, een kation van een alkalimetaal of een carbeen.The cation Y, for example, is a Bronsted acid that can donate a proton, a cation of an alkali metal or a carbene.
Voorbeelden van kationen zijn Li-*, K+, Na+, 20 H+, trifenylcarbenium, anilinium, guanidinium, glycinium, ammonium of een gesubstitueerd ammonium kation, waarin ten hoogste 3 waterstofatomen zijn vervangen door een hydrocarbyl radicaal met 1-20 koolstofatomen, of een gesubstitueerd hydrocarbyl 25 radicaal met 1-20 koolstofatomen, waarin 1 of meer van de waterstofatomen vervangen zijn door een halogeen atoom, fosfonium radicalen, gesubstitueerde fosfonium radicalen, waarin ten hoogste 3 waterstofatomen vervangen zijn door een hydrocarbyl radicaal met 1-20 30 koolstofatomen of een gesubstitueerd hydrocarbyl radicaal met 1-20 koolstofatomen, waarin 1 of meer van de waterstofatomen vervangen zijn door een halogeen atoom.Examples of cations are Li- *, K +, Na +, 20 H +, triphenylcarbenium, anilinium, guanidinium, glycinium, ammonium or a substituted ammonium cation, in which at most 3 hydrogen atoms are replaced by a hydrocarbyl radical with 1-20 carbon atoms, or a substituted hydrocarbyl 25 radical of 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 are replaced by a hydrocarbyl radical of 1-20 carbon atoms or a substituted hydrocarbyl radical of 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, 35 trifenylcarbenium of Li+.Preferably the cation is dimethylanilinium, triphenylcarbenium or Li +.
Verbindingen volgens de formule XR4, die tenminste een halogeenatoom bevatten zijn bijvoorbeeld 1004991 - 5 - bekend uit 'Cohen and Massey, J. Organometal.Compounds of the formula XR4 containing at least one halogen atom are, for example, 1004991-5 known from Cohen and Massey, J. Organometal.
Chem.10(1967) 471-481', 'Tamborski et al., J. Organometal. Chem., 4(1965) 446-454' and 'Fearon and Gilman, J. Organometal. Chem., 10(1967) 409-419'.Chem. 10 (1967) 471-481 ', Tamborski et al., J. Organometal. Chem., 4 (1965) 446-454 'and' Fearon and Gilman, J. Organometal. Chem., 10 (1967) 409-419 '.
5 Verbindingen volgens de formule [ΧΚ5]"[Υ]^ zijn bekend uit Angew. Chem. Int. Ed. Engl. 1996, 35, no. 10. In deze publicatie worden lithium(2,2'-bifenyldiyltrimethylsilicaat).4THF, lithium(2,2'-bifenyldiyldimethylfenylsilicaat).4THF, lithium(2,2 '-10 bifenyldiyldimethyl-t-butylsilicaat).4THF en lithium(pentafenylsilicaat).4HMPA genoemd. (THF is tetrahydrofuraan en HMPA is hexamethylfosfortriamide.) Deze verbindingen bevatten echter geen halogeenatomen en over de mogelijke toepassing van deze verbindingen 15 als cokatalysator bij de polymerisatie van olefinen wordt niets gesuggereerd.Compounds of the formula [ΧΚ5] "[Υ] ^ are known from Angew. Chem. Int. Ed. Engl. 1996, 35, No. 10. In this publication, lithium (2,2'-biphenyldiyltrimethylsilicate). lithium (2,2'-biphenyldiyldimethylphenylsilicate) .4THF, lithium (2,2'-10 biphenyldiyldimethyl-t-butylsilicate) .4THF and lithium (pentaphenylsilicate) called .4HMPA. (THF is tetrahydrofuran and HMPA is hexamethylphosphoric triamide.) however, no halogen atoms and nothing is suggested about the possible use of these compounds as a cocatalyst in the polymerization of olefins.
De bovengenoemde verbindingen zijn te synthetiseren volgens de bij de vakman bekende synthesemethoden.The above compounds can be synthesized according to the synthesis methods known to the person skilled in the art.
20 Ook kunnen de verbindingen volgens de uitvinding op drager worden toegepast als cokatalysator bij de polymerisatie van olefinen. Als geschikt dragermateriaal kunnen Si02, Al203, MgCl2 en polymeerdeeltjes, zoals polystyreenbolletjes, worden 25 genoemd. Deze dragermaterialen kunnen ook worden gemodificeerd met bijvoorbeeld silanen en/of aluminoxanen en/of aluminiumalkylen.The supported compounds of the invention can also be used as a cocatalyst in the polymerization of olefins. Si02, Al2O3, MgCl2 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 cokatalysatoren kunnen vooraf aan de polymerisatie worden gesynthetiseerd, maar kunnen 30 ook in situ worden gevormd.The supported cocatalysts can be synthesized before polymerization, but can also be formed in situ.
Als katalysator voor de polymerisatie van olefinen kunnen allerlei typen overgangsmetaalkatalysatoren worden toegepast. Voorbeelden van dergelijke katalysatoren zijn 35 bijvoorbeeld beschreven in US-A-5.096.867, WO-A- 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, 1004991 - 6 - 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 en WO-A-96/23010 . Ook 5 overgangsmetaalkatalysatoren die metalen uit groep 3 van het Periodiek Systeem der Elementen en de Lanthaniden bevatten, kunnen worden toegepast.All kinds of transition metal catalysts can be used as the catalyst for the polymerization of olefins. Examples of such catalysts are described, for example, in US-A-5,096,867, WO-A-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, 1004991 - 6 - 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. Also 5 transition metal catalysts containing Group 3 metals of the Periodic Table of the Elements and Lanthanides can be used.
Gedragen overgangsmetaalkatalysatoren kunnen ook worden toegepast. Als geschikt dragermateriaal kunnen Si02, 10 A1203, MgClj en polymeerdeeltjes, zoals polystyreenbolletjes, worden genoemd. Deze dragermaterialen kunnen ook worden gemodificeerd met bijvoorbeeld silanen en/of aluminoxanen en/of a1umi n i uma1ky1en.Supported transition metal catalysts can also be used. SiO 2, Al 2 O 3, MgCl 3 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 nickels.
15 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 prior to polymerization, but can also be formed in situ.
Bij voorkeur worden metalloceenkatalysatoren toegepast. 20 Metalloceenkatalysatoren kenmerken zich door de aanwezigheid van een of meerdere π-gebonden liganden, zoals bijvoorbeeld cyclopentadieen- (Cp) of aan 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 cyclopentadiene-related ligands, such as, for example, indene and fluorene, in the transition metal catalyst.
25 Bij bijzondere voorkeur wordt een overgangsmetaalkatalysator toegepast, waarin het 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 30 etheen, propeen, buteen, hexeen, octeen en mengsels daarvan en combinaties met dieenen kunnen worden uitgevoerd in aanwezigheid van een overgangsmetaalkatalysator en de cokatalysator volgens de uitvinding. Ook kan het bovenbeschreven 35 katalysatorsysteem worden toegepast voor de polymerisatie van vinylaromatische monomeren, zoals bijvoorbeeld styreen en p-methylstyreen, voor de 1004991 - 7 - polymerisatie van polaire vinylmonomeren, zoals bijvoorbeeld alcoholen, amines, alkyl halides, ethers, amides, imines en anhydrides, en voor de polymerisatie van cyclische olefines, zoals bijvoorbeeld cyclobuteen, 5 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 opzichte van de hoeveelheid overgangsmetaalkatalysator 10 (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 10 (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 volgens de uitvinding maakt geen wezenlijke aanpassing 15 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 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 gasfasepolymerisatie verdient het de voorkeur om de 20 overgangsmetaalkatalysator of de cokatalysator volgens de uitvinding op een dragermateriaal toe te passen. Ook kunnen zowel de katalysator als de cokatalysator op drager worden toegepast. De polymerisaties worden uitgevoerd bij temperaturen tussen -50°C en +350°C, bij 25 voorkeur tussen 50°C en 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 polymerisatie-processen tussen 0,5 en 25 MPa. Als verdeel- en 30 oplosmiddelen kunnen bijvoorbeeld gesubstitueerde en ongesubstitueerde koolwaterstoffen worden toegepast, zoals pentaan, heptaan en mengsels daarvan. Ook aromatische, eventueel geperfluoreerde koolwaterstoffen komen in aanmerking. Eveneens kan een in de 35 polymerisatie te gebruiken monomeer als verdeelmiddel toegepast worden.For use of the cocatalyst in slurry or gas phase polymerization, it is preferable to use the transition metal catalyst or the cocatalyst according to the invention on a support material. Both the catalyst and the cocatalyst on a support can also be used. The polymerizations are carried out at temperatures between -50 ° C and + 350 ° C, preferably between 50 ° C and 250 ° C. 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. Substituted and unsubstituted hydrocarbons, such as pentane, heptane and mixtures thereof, may be used as dispersants and solvents. Aromatic, optionally perfluorinated hydrocarbons are also eligible. A monomer to be used in the polymerization can also be used as a dispersing agent.
10049911004991
Claims (8)
Priority Applications (12)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| NL1004991A NL1004991C2 (en) | 1997-01-14 | 1997-01-14 | Polymerisation of olefin(s) |
| AU53475/98A AU5347598A (en) | 1997-01-14 | 1997-12-15 | A process for polymerizing olefins |
| ES97950491T ES2226005T3 (en) | 1997-01-14 | 1997-12-15 | A PROCEDURE FOR POLYMERIZING OLEFINS. |
| EA199900650A EA199900650A1 (en) | 1997-01-14 | 1997-12-15 | METHOD OF POLYMERIZATION OF OLEFINS |
| CA002277886A CA2277886A1 (en) | 1997-01-14 | 1997-12-15 | A process for polymerizing olefins |
| AT97950491T ATE272078T1 (en) | 1997-01-14 | 1997-12-15 | METHOD FOR OLEFIN POLYMERIZATION |
| EP97950491A EP0954540B1 (en) | 1997-01-14 | 1997-12-15 | A process for polymerizing olefins |
| JP53077198A JP2002514247A (en) | 1997-01-14 | 1997-12-15 | Olefin polymerization method |
| PCT/NL1997/000696 WO1998030603A1 (en) | 1997-01-14 | 1997-12-15 | A process for polymerizing olefins |
| DE69730047T DE69730047T2 (en) | 1997-01-14 | 1997-12-15 | PROCESS FOR OLEFIN POLYMERIZATION |
| CN97182023A CN1248979A (en) | 1997-01-14 | 1997-12-15 | Process for polymerizing olefins |
| US09/352,842 US6218487B1 (en) | 1997-01-14 | 1999-07-13 | Process for polymerizing olefins |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| NL1004991 | 1997-01-14 | ||
| NL1004991A NL1004991C2 (en) | 1997-01-14 | 1997-01-14 | Polymerisation of olefin(s) |
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| Publication Number | Publication Date |
|---|---|
| NL1004991C2 true NL1004991C2 (en) | 1998-07-15 |
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| Country | Link |
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| EA (1) | EA199900650A1 (en) |
| NL (1) | NL1004991C2 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE641076A (en) * | 1962-12-14 | 1964-04-01 |
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|---|---|---|---|---|
| BE641076A (en) * | 1962-12-14 | 1964-04-01 |
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