CN108864337B - Catalyst composition for olefin polymerization and olefin polymerization method - Google Patents
Catalyst composition for olefin polymerization and olefin polymerization method Download PDFInfo
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- CN108864337B CN108864337B CN201710335588.XA CN201710335588A CN108864337B CN 108864337 B CN108864337 B CN 108864337B CN 201710335588 A CN201710335588 A CN 201710335588A CN 108864337 B CN108864337 B CN 108864337B
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- 150000001336 alkenes Chemical class 0.000 title claims abstract description 126
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 124
- 239000003054 catalyst Substances 0.000 title claims abstract description 117
- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 102
- 238000000034 method Methods 0.000 title claims abstract description 52
- 239000000203 mixture Substances 0.000 title claims abstract description 47
- 239000002685 polymerization catalyst Substances 0.000 claims abstract description 103
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 54
- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract description 29
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 24
- 150000002367 halogens Chemical class 0.000 claims abstract description 24
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 19
- 239000001257 hydrogen Substances 0.000 claims abstract description 19
- 229910052751 metal Inorganic materials 0.000 claims abstract description 16
- 239000002184 metal Substances 0.000 claims abstract description 16
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 7
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 6
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 6
- HQWPLXHWEZZGKY-UHFFFAOYSA-N diethylzinc Chemical compound CC[Zn]CC HQWPLXHWEZZGKY-UHFFFAOYSA-N 0.000 claims description 89
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 70
- 239000005977 Ethylene Substances 0.000 claims description 70
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 claims description 57
- 230000008569 process Effects 0.000 claims description 39
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 21
- -1 Aluminum compound Chemical class 0.000 claims description 12
- 229910052759 nickel Inorganic materials 0.000 claims description 11
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical group [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- 239000003426 co-catalyst Substances 0.000 claims description 10
- 239000000178 monomer Substances 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- 150000002431 hydrogen Chemical class 0.000 claims description 8
- 150000004696 coordination complex Chemical class 0.000 claims description 7
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 229910052763 palladium Chemical group 0.000 claims description 5
- 239000004711 α-olefin Substances 0.000 claims description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical group [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 4
- 229910052735 hafnium Chemical group 0.000 claims description 4
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical group [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- ONBQEOIKXPHGMB-VBSBHUPXSA-N 1-[2-[(2s,3r,4s,5r)-3,4-dihydroxy-5-(hydroxymethyl)oxolan-2-yl]oxy-4,6-dihydroxyphenyl]-3-(4-hydroxyphenyl)propan-1-one Chemical compound O[C@@H]1[C@H](O)[C@@H](CO)O[C@H]1OC1=CC(O)=CC(O)=C1C(=O)CCC1=CC=C(O)C=C1 ONBQEOIKXPHGMB-VBSBHUPXSA-N 0.000 claims description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052796 boron Inorganic materials 0.000 claims description 3
- 229940126142 compound 16 Drugs 0.000 claims description 3
- 150000001925 cycloalkenes Chemical class 0.000 claims description 3
- 229910052733 gallium Inorganic materials 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- 125000006659 (C1-C20) hydrocarbyl group Chemical group 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- AXAZMDOAUQTMOW-UHFFFAOYSA-N dimethylzinc Chemical compound C[Zn]C AXAZMDOAUQTMOW-UHFFFAOYSA-N 0.000 claims description 2
- 150000002736 metal compounds Chemical class 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 2
- ORYGRKHDLWYTKX-UHFFFAOYSA-N trihexylalumane Chemical compound CCCCCC[Al](CCCCCC)CCCCCC ORYGRKHDLWYTKX-UHFFFAOYSA-N 0.000 claims description 2
- XCZXGTMEAKBVPV-UHFFFAOYSA-N trimethylgallium Chemical compound C[Ga](C)C XCZXGTMEAKBVPV-UHFFFAOYSA-N 0.000 claims description 2
- LFXVBWRMVZPLFK-UHFFFAOYSA-N trioctylalumane Chemical compound CCCCCCCC[Al](CCCCCCCC)CCCCCCCC LFXVBWRMVZPLFK-UHFFFAOYSA-N 0.000 claims description 2
- 150000003752 zinc compounds Chemical class 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical group C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims 3
- 125000000027 (C1-C10) alkoxy group Chemical group 0.000 claims 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims 1
- 150000001555 benzenes Chemical class 0.000 claims 1
- 229920001577 copolymer Polymers 0.000 claims 1
- 229910052725 zinc Inorganic materials 0.000 claims 1
- 239000011701 zinc Substances 0.000 claims 1
- 239000000460 chlorine Substances 0.000 abstract description 16
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052801 chlorine Inorganic materials 0.000 abstract description 3
- 125000005842 heteroatom Chemical group 0.000 abstract description 2
- 125000000962 organic group Chemical group 0.000 abstract description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 432
- 229920000642 polymer Polymers 0.000 description 60
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 30
- 229910052757 nitrogen Inorganic materials 0.000 description 29
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 28
- 229910001220 stainless steel Inorganic materials 0.000 description 28
- 239000010935 stainless steel Substances 0.000 description 28
- 230000000052 comparative effect Effects 0.000 description 13
- AFFLGGQVNFXPEV-UHFFFAOYSA-N n-decene Natural products CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 12
- 229920001400 block copolymer Polymers 0.000 description 9
- 238000009826 distribution Methods 0.000 description 9
- 229920002521 macromolecule Polymers 0.000 description 9
- 238000012546 transfer Methods 0.000 description 7
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 6
- 239000002904 solvent Substances 0.000 description 5
- 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 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- PBKONEOXTCPAFI-UHFFFAOYSA-N 1,2,4-trichlorobenzene Chemical group ClC1=CC=C(Cl)C(Cl)=C1 PBKONEOXTCPAFI-UHFFFAOYSA-N 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 3
- OXFCIXOXOWYRQI-UHFFFAOYSA-N bicyclo[2.2.1]hept-2-ene;toluene Chemical compound CC1=CC=CC=C1.C1C2CCC1C=C2 OXFCIXOXOWYRQI-UHFFFAOYSA-N 0.000 description 3
- 229910000071 diazene Inorganic materials 0.000 description 3
- 150000002430 hydrocarbons Chemical group 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 230000037048 polymerization activity Effects 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 description 2
- RAABOESOVLLHRU-UHFFFAOYSA-N diazene Chemical compound N=N RAABOESOVLLHRU-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000012968 metallocene catalyst Substances 0.000 description 2
- 125000002524 organometallic group Chemical group 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- 229920002725 thermoplastic elastomer Polymers 0.000 description 2
- PRBHEGAFLDMLAL-UHFFFAOYSA-N 1,5-Hexadiene Natural products CC=CCC=C PRBHEGAFLDMLAL-UHFFFAOYSA-N 0.000 description 1
- PCBPVYHMZBWMAZ-UHFFFAOYSA-N 5-methylbicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(C)CC1C=C2 PCBPVYHMZBWMAZ-UHFFFAOYSA-N 0.000 description 1
- VHNNPTGLWYHNHE-UHFFFAOYSA-N C1=CC2=CC=CC=C2C1[Zr]C1C2=CC=CC=C2C=C1 Chemical class C1=CC2=CC=CC=C2C1[Zr]C1C2=CC=CC=C2C=C1 VHNNPTGLWYHNHE-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical group [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 238000012644 addition polymerization Methods 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000005234 alkyl aluminium group Chemical group 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000012718 coordination polymerization Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 150000001923 cyclic compounds Chemical group 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- VGRFVJMYCCLWPQ-UHFFFAOYSA-N germanium Chemical compound [Ge].[Ge] VGRFVJMYCCLWPQ-UHFFFAOYSA-N 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 150000002391 heterocyclic compounds Chemical group 0.000 description 1
- PYGSKMBEVAICCR-UHFFFAOYSA-N hexa-1,5-diene Chemical compound C=CCCC=C PYGSKMBEVAICCR-UHFFFAOYSA-N 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003136 n-heptyl 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])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 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 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229920000428 triblock copolymer Polymers 0.000 description 1
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical group C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 1
- 239000003643 water by type Substances 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
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/02—Ethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/02—Ethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F295/00—Macromolecular compounds obtained by polymerisation using successively different catalyst types without deactivating the intermediate polymer
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The invention relates to the field of catalysts for olefin polymerization, and provides a catalyst composition for olefin polymerization and a method for olefin polymerization, wherein the catalyst composition comprises the following components in parts by weight: (1) a first olefin polymerization catalyst (A) selected from the group consisting of metal complexes of the formula I, wherein R1～R5，R7～R11Identical or different, selected from hydrogen, hydrocarbon radicals or halogens; m is a group IVA metal, X, which may be the same or different, is selected from the group consisting of halogen, hydrocarbyl, hydrocarbyloxy; l is a group VIA element; (2) a second olefin polymerization catalyst (B) selected from the group consisting of metal complexes represented by the general formula II wherein R1And R4Same or different, selected from C1‑C30Hydrocarbyl or C1‑C30A heterohydrocarbyl group; r2And R3Same or different and selected from hydrogen, chlorine, C1‑C20A hydrocarbon group, heteroatom-containing organic group; m is a group VIII metal; (3) a chain shuttling agent; (4) a cocatalyst. The catalyst can realize copolymerization at higher temperature.
Description
Technical Field
The invention relates to the field of catalysts for olefin polymerization, and more particularly relates to a catalyst composition for olefin polymerization and a method for olefin polymerization.
Background
Polymers of block-type structure have often been superior in properties to random copolymers and blends for a long time. For example, triblock copolymers of Styrene and Butadiene (SBS) and their hydrogenated versions (SEBS) have excellent heat resistance and elasticity. Block copolymers, known as thermoplastic elastomers (TPEs), have "soft" or elastomeric segments in the polymer chain linking "hard" crystallizable moieties. These polymers exhibit the characteristics of elastomeric materials when the temperature reaches the melting point or glass transition temperature of the "hard" segment. At higher temperatures, these polymers become free flowing and exhibit thermoplastic properties. Existing methods for preparing block copolymers include anionic polymerization and controlled radical polymerization. However, these methods for preparing block copolymers require continuous addition of monomers and batch operations, and the kinds of monomers that can be used for polymerization in the above-mentioned methods are relatively small. For example, in the anionic polymerization of styrene and butadiene to form SBS type block copolymers, a stoichiometric amount of initiator is required per polymer chain and the resulting polymer has a very narrow molecular weight distribution Mw/Mn, preferably 1.0 to 1.3. In addition, anionic and radical polymerization are relatively slow, which affects the industrial development thereof.
It would be desirable to be able to achieve better control of the catalytic process for producing block copolymers, i.e., more than one polymer molecule can be formed per catalyst or initiator molecule during the polymerization process. In addition, it would be desirable to be able to produce multi-block copolymers having both highly crystalline and amorphous blocks or segments from a single monomer, such as ethylene.
Previous researchers have indicated that some homogeneous coordination polymerization catalysts can produce polymers with block structures by inhibiting chain transfer during polymerization. For example, block polymers are prepared by minimizing chain transfer agents and lowering the reaction temperature during polymerization, controlling beta-hydrogen transfer or chain transfer. Under the above conditions, it is believed that sequential addition of different monomers will result in the formation of polymers having sequences or segments with different monomer contents. Some examples of such catalyst compositions and methods are described in the Angew. chem. int. Ed. 2002,41, 2236-.
It is well known in the art to interrupt chain growth in olefin polymerization by utilizing certain metal alkyl compounds and other compounds, such as hydrogen, as chain transfer agents. In addition, alkylaluminum compounds are often used as scavengers or cocatalysts in olefin polymerization processes. In Macromolecules,2000,33, 9192-. In Macromolecules,2003,3026-3034 by Liu and Rytter, trimethylaluminum chain transfer agents have also been reported to catalyze the copolymerization of ethylene and 1-hexene in combination with similar catalysts.
In US 6,380,341 and US 6,169,151, it is reported that by using a "stereogenic" metallocene catalyst, an olefin polymer of a "block-like" structure is formed by interconverting polymerization characteristics exhibiting different reaction rates and the like between two stereo configurations of the catalyst.
It is well known that nickel and palladium alpha-diimine catalysts can form highly branched (highly branched) polymers by "chain transfer" during polymerization. Examples of such polymerizations are disclosed in chem.rev.,2000,100,1169-1203, macromol.chem.phys.,2004,205,897-906, and the like. Such long chain branched polymers may also be prepared by homopolymerization of ethylene catalyzed by, for example, 1-, and 2-t-butyldimethylsiloxy-substituted bis (indenyl) zirconium complexes with methylaluminoxane cocatalyst. Examples of such polymerizations are disclosed in j.mol.catal.a: chem.,1995,102, 59-65; macromolecules,1988,21, 617-622; J.mol.Catal.A. chem.,2002,185,57-64, J.am.chem.Soc.,1995,117, 6414-.
There are reports of chain shuttling polymerization using nickel diimine with metallocene catalysts under the action of diethylzinc (Macromolecules 2009,42,1834-1837), but the polymerization temperature is low, only 20 ℃. The existing alpha-nickel diimine catalyst has low ethylene polymerization activity at high temperature, the molecular weight of the prepared polyethylene is rapidly reduced along with the increase of polymerization temperature, and the existing late transition metal catalyst cannot meet the requirements of the existing ethylene polymerization device by a gas phase and solution method.
Disclosure of Invention
The present invention aims at solving the problems of the prior art and provides a catalyst composition for olefin polymerization and a method for olefin polymerization, wherein the catalyst A and the catalyst B can keep higher ethylene and C at higher temperature3～C16The obtained polymer has higher molecular weight and narrower molecular weight distribution, can prepare a block polymer under the action of a chain shuttling agent, and can pass through a comonomer C3～C16The selection and the amount of the alpha-olefin or the cycloolefine are controlled, and the structure and the crystallization property of the obtained polymer are controlled.
In order to achieve the above object, the present invention provides a catalyst composition for olefin polymerization, which is a mixture or a reaction product comprising the following components:
(1) a first olefin polymerization catalyst (A) selected from at least one metal complex represented by the general formula I:
in the general formula I, R1～R5，R7～R11Identical or different, each independently selected from hydrogen, hydrocarbyl or halogen, and optionally, R1And R4Are linked to each other to form a ring, and/or R2And R5Are connected with each other to form a ring; m is a group IVA metal, X, which may be the same or different, is selected from the group consisting of halogen, hydrocarbyl, hydrocarbyloxy; l is a group VIA element;
(2) a second olefin polymerization catalyst (B) selected from at least one metal complex represented by the general formula II:
in the general formula II, R1And R4Are the same or different and are each independently selected from C1-C30Or C is a hydrocarbon group1-C30A heterohydrocarbyl group of (a); r2And R3The same or different, each independently selected from hydrogen, chlorine, C1-C20A heteroatom-containing organic group, and optionally, R2And R3Forming rings mutually; m is a group VIII metal; x is the same or different and is selected from halogen, alkyl, alkoxy, acid radical or amino; n is an integer satisfying the valence of M;
(3) a chain shuttling agent;
(4) a cocatalyst.
According to the catalyst composition provided by the present invention, preferably, (1) a first olefin polymerization catalyst (a) is at least one selected from the group consisting of metal complexes represented by the general formula I:
in the general formula I, R1～R5，R7～R11The same or different, each independently selected from hydrogen and C1～C20Aliphatic hydrocarbon group of (C)6～C30Or halogen, and optionally, R1And R4Are linked to each other to form a ring, and/or R2And R5Are connected with each other to form a ring; m is selected from titanium, zirconium or hafnium, X, same or different, is selected from halogen, C1～C20Saturated hydrocarbon group of (C)2～C20Unsaturated hydrocarbon group of (C)1～C20Hydrocarbyloxy groups of (a); l is selected from O or S elements;
(2) a second olefin polymerization catalyst (B) selected from at least one metal complex represented by the general formula III:
in the general formula III, R1And R4Are the same or different and are each independently selected from C1-C20Or C is a hydrocarbon group1-C20A heterohydrocarbyl group of (a); r5～R8The same or different, each independently selected from hydrogen, chlorine, C1-C15A hydrocarbon group, a heterocyclic compound group, a non-cyclic compound group containing an oxygen, nitrogen, boron, sulfur, phosphorus, silicon, germanium or tin atom, and optionally, R5～R8Forming rings in pairs; m is a group VIII metal; x, which are identical or different, are selected from halogen, hydrocarbon or hydrocarbonoxy; n is an integer satisfying the valence of M;
(3) a chain shuttling agent;
(4) a cocatalyst.
According to the catalyst composition provided by the present invention, preferably, the first olefin polymerization catalyst (A) is at least one selected from the group consisting of metal complexes represented by the general formula IV,
in the general formula IV, R1～R5，R7，R9，R11The same or different, each independently selected from hydrogen and C1～C20Aliphatic hydrocarbon group of (C)6～C30Or halogen, and optionally, R1And R4Are linked to each other to form a ring, and/or R2And R5Are connected with each other to form a ring; x is halogen, M is titanium, zirconium or hafnium;
the second olefin polymerization catalyst (B) is at least one selected from metal complexes represented by the general formula V,
in the general formula V, R11-R20The same or different, each independently selected from hydrogen and C1-C10Saturated hydrocarbon group of (C)2-C10Unsaturated hydrocarbon group of (C)1-C10Alkoxy and halogen of (a); further preferably selected from hydrogen and C1～C6Alkyl of (C)2～C6Alkenyl of, C1～C6Alkoxy or halogen of (a); x is halogen, M is nickel or palladium.
In the invention C1～C20The aliphatic hydrocarbon group of (A) means C1～C20Alkane or C1～C20Cycloalkane of (a); c1～C20The alkane is C1～C20Straight chain alkyl or C3-C20Branched alkyl groups of (a). In the invention C1～C10The saturated hydrocarbon group of (A) means C1～C10Straight chain alkyl or C3-C10Non-limiting examples of branched alkyl groups of (a) include: methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl, neopentyl, n-hexyl, n-heptyl, n-octyl and n-decyl.
In the present invention, the first olefin polymerization catalyst (A) can be prepared by a conventional method, for example, the references Organometallics,1998,17, 2152-; macromolecules,1998, 31, 7588-; J.mol.Catal.A 2009,303, 102-. The disclosures of the foregoing documents are incorporated herein by reference in their entirety and are not described in detail herein.
According to the catalyst composition provided by the present invention, the polymerization activity of the second olefin polymerization catalyst (B) is lower than that of the first olefin polymerization catalyst (A). In the formula V, M may be, for example, nickel, iron, cobalt, palladium, etc., preferably nickel; x is selected from halogen.
Preferably, said second olefin polymerization catalyst (B)) At least one metal complex selected from the group consisting of the following; in the general formula V, R17-R20Are all hydrogen, M is nickel,
the complex 1: r11＝R13＝R14＝R16＝Me，R12＝R15＝H，X＝Br；
And (2) the complex: r11＝R13＝R14＝R16＝Et，R12＝R15＝H，X＝Br；
And (3) complex: r11＝R13＝R14＝R16＝iPr，R12＝R15＝H，X＝Br；
The complex 4: r11＝R12＝R13＝R14＝R15＝R16＝Me，X＝Br；
And (3) a complex 5: r11＝R13＝R14＝R16＝Me，R12＝R15＝Br，X＝Br；
The complex 6: r11＝R13＝R14＝R16＝Me，R12＝R15＝Et，X＝Br；
The complex 7: r11＝R13＝R14＝R16＝Et，R12＝R15＝Me，X＝Br；
The complex 8: r11＝R13＝R14＝R16＝Et，R12＝R15＝Br，X＝Br；
The complex 9: r11＝R13＝R14＝R16＝F，R12＝R15＝H，X＝Br；
The complex 10: r11＝R13＝R14＝R16＝Cl，R12＝R15＝H，X＝Br；
The complex 11: r11＝R13＝R14＝R16＝Br，R12＝R15＝H，X＝Br；
The complex 12: r11＝R13＝R14＝R16＝Me，R12＝R15＝H，X＝Cl；
The complex 13: r11＝R13＝R14＝R16＝Et，R12＝R15＝H，X＝Cl；
The complex 14: r11＝R13＝R14＝R16＝iPr，R12＝R15＝H，X＝Cl；
The complex 15: r11＝R12＝R13＝R14＝R15＝R16＝Me，X＝Cl；
The compound 16: r11＝R13＝R14＝R16＝Me，R12＝R15＝Br，X＝Cl；
The complex 17: r11＝R13＝R14＝R16＝Me，R12＝R15＝Et，X＝Cl；
The complex 18: r11＝R13＝R14＝R16＝Et，R12＝R15＝Me，X＝Cl；
The complex 19: r11＝R13＝R14＝R16＝Et，R12＝R15＝Br，X＝Cl；
The complex 20: r11＝R13＝R14＝R16＝F，R12＝R15＝H，X＝Cl；
The complex 21: r11＝R13＝R14＝R16＝Cl，R12＝R15＝H，X＝Cl；
The complex 22: r11＝R13＝R14＝R16＝Br，R12＝R15＝H，X＝Cl。
In the present invention, the second olefin catalyst (B) can be obtained by a complex preparation method disclosed in Macromolecules,2009,42,7789-7796, and the disclosure related content thereof is fully incorporated into the present invention for reference, and is not described herein again.
According to the catalyst composition provided by the invention, the molar ratio of the first olefin polymerization catalyst (a) to the second olefin polymerization catalyst (B) is preferably 1:100 to 100:1, and preferably 10:90 to 90: 10.
According to the catalyst composition provided by the invention, the chain shuttling agent can be selected by referring to the existing chain shuttling polymerization reaction; preferably, the chain shuttling agent is selected from the group consisting of at least one C1-C20Hydrocarbyl group IA, II A, IB, IIB metal compounds or complexes, more preferably selected from the group consisting of C-containing compounds1-C12Aluminum compound of hydrocarbon group, C1-C12Gallium compounds containing hydrocarbon radicals or containing C1-C12A zinc compound of a hydrocarbon group; the hydrocarbyl group is preferably an alkyl group.
Further preferably, the chain shuttling agent is selected from at least one of trialkylaluminum, dialkylzinc and trialkylgallium, more preferably from at least one of triethylaluminum, triisopropylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, dimethylzinc, diethylzinc and trimethylgallium.
According to the catalyst composition provided by the invention, the olefin polymerization catalyst is combined with a cocatalyst, so that the olefin polymerization catalyst has higher activity. The co-catalyst may be selected from Lewis acids, for example, preferably the co-catalyst is selected from C1-C30A hydrocarbyl-substituted group IIIA compound, more preferably at least one selected from the group consisting of alkylaluminoxanes, arylboranes and arylborates; further preferably at least one selected from the group consisting of methylaluminoxane, modified methylaluminoxane, triarylborane, and tetraarylborate.
According to the catalyst composition provided by the present invention, preferably, the molar ratio of aluminum in the co-catalyst to the sum of the first olefin polymerization catalyst (a) and the second olefin polymerization catalyst (B) is (10-20000):1, or the molar ratio of boron in the co-catalyst to the sum of the first olefin polymerization catalyst (a) and the second olefin polymerization catalyst (B) is (0.01-50): 1.
Preferably, the molar ratio of the sum of the first olefin polymerization catalyst (a) and the second olefin polymerization catalyst (B) to the chain shuttling agent is 1:1 to 1:20000, preferably 1:1 to 1: 1000.
The catalyst composition of the invention is used for olefin polymerization. In the polymerization reaction, an olefin polymerization catalyst consisting of two different active catalysts can be combined with the chain shuttling agent and other components to prepare block copolymers containing segments with different properties.
The present invention also provides a process for the polymerization of olefins, the process comprising: and contacting the catalyst composition with a monomer for copolymerization.
According to the method provided by the invention, preferably, the monomer is selected from ethylene and C3～C16And C3～C16At least one of the cyclic olefins of (1).
Said C is3～C16Examples of the α -olefin or cycloolefin of (b) include: propylene, 1-butene, 1-pentene, decene, cyclopentene, norbornene, 5-methyl-2-norbornene, 1, 5-hexadiene and the like.
Preferably, the olefin in the olefin polymerization process is ethylene, or ethylene and C3～C16Or a cyclic olefin (comonomer). In addition, the amount of the comonomer can be adjusted according to the melting point of the block copolymer to be prepared in practical application, and will not be described in detail herein.
According to the process of the present invention, the polymerization is carried out as a continuous polymerization, preferably as a continuous solution polymerization. Wherein the catalyst component, the shuttle agent(s), the monomer, and optionally the solvent, the coagent, the scavenger, and the polymerization coagent are continuously supplied to the reactor, and the polymerization product is continuously removed in the reaction vessel. The solvent used in the solution polymerization is not particularly limited, and may be a solvent conventionally used in olefin polymerization, for example, toluene.
According to one embodiment, preferably, the polymerization conditions comprise: the temperature is-20 to 150 ℃, preferably 20 to 100 ℃, and more preferably 40 to 100 ℃; the pressure is 0.1 to 10MPa, preferably 0.1 to 5 MPa.
Continuous solution polymerization processes utilizing the polymerization reaction conditions described above, particularly using two or more active polymerization catalyst components. Allows the use of increased reactor temperatures which results in the production of multi-block polymers or segmented polymers with high efficiency. Homogeneous and plug flow type reaction conditions may be used.
Shuttling from the chain shuttling agent to the catalyst under continuous solution polymerization conditions is an advantage over chain extension and forms the multi-block polymers of the present invention, especially linear multi-block polymers, with high efficiency.
The olefin polymerization method belongs to chain shuttling polymerization reaction, and the catalyst composition still has higher polymerization activity at high temperature (such as 60 ℃). During the polymerization, active chains can be alternately grown in the middle of the activities of two different catalysts (i.e., the first olefin polymerization catalyst a and the second olefin polymerization catalyst B) by the chain shuttling agent, and then block copolymers are produced. High molecular weight segmented polymers (multi-block polymers) are prepared comprising two or more, preferably more than three segments differing in density or other chemical or physical properties. The polymer has a molecular weight distribution M of less than 5.0, preferably less than 4.0w/Mn. Molecular weight distribution (M) of the block copolymerw/Mn) Preferably less than 5, more preferably less than 4.
The technical scheme of the invention has the following beneficial effects: in the catalyst composition of the present invention, the olefin polymerization catalyst can be matched with a chain shuttling agent at a higher temperature (for example, 60 ℃) to realize copolymerization of ethylene or ethylene and alpha-olefin or cycloolefin (comonomer), and under the condition of preparing a block polymer, the molecular weight of the polymer is higher, and the molecular weight distribution is narrower.
Detailed Description
Preferred embodiments of the present invention will be described in more detail below. While the preferred embodiments of the present invention have been described in the examples, it should be understood that the present invention may be embodied in various forms and should not be limited by the embodiments set forth herein.
Characterization of Polymer molecular weight (Mw) and molecular weight distribution (Mw/Mn):
the molecular weight and the distribution thereof are determined by Gel Permeation Chromatography (GPC), the instrument adopts Waters Alliance GPCV 2000, the solvent is 1,2, 4-trichlorobenzene, the sample concentration is lmg/ml, and the solvent flow rate is 1.0 ml/min; the measurement temperature was 150 ℃. Two measurements were made for each sample.
The following examples are presented to illustrate the catalyst composition and olefin polymerization process of the present invention.
Example 1
The first olefin polymerization catalyst A1 [ its structure is shown in formula (1), and its synthesis process is described in Organometallics,1998,17,2152-2154 ].
The structure of the second olefin polymerization catalyst B1 [ is shown as a formula (2), and the synthesis process is described in Macromolecules,2009,42,7789-7796 ].
The cocatalyst was methylaluminoxane and the shuttle agent was diethyl zinc (DEZ).
A1L stainless steel autoclave was evacuated and replaced with nitrogen, the process was repeated twice, and then evacuated again, 500 ml of toluene solvent was added under ethylene atmosphere, and the cocatalyst (6.5ml of 1.53M methylaluminoxane toluene solution) and DEZ (1ml of 1.5M DEZ toluene solution) were added through a syringe with the addition of toluene. Then catalyst A1(5ml of a 1.0mM toluene solution) and catalyst B1(5ml of a 1.0mM toluene solution) were added via syringe, ethylene was continuously introduced, the pressure was raised and maintained at 1.0MPa, polymerization was carried out at 60 ℃ for 30min, the temperature was reduced, the polymer was collected and weighed.
Specific polymerization results are listed in table 1.
Example 2
The first olefin polymerization catalyst A1 and the second olefin polymerization catalyst B1 were the same as in example 1.
The cocatalyst was methylaluminoxane and the shuttle agent was diethyl zinc (DEZ).
A1L stainless steel autoclave was evacuated and replaced with nitrogen, the process was repeated twice, and then evacuated again, 500 ml of toluene solvent was added under ethylene atmosphere, and the cocatalyst (6.5ml of 1.53M methylaluminoxane toluene solution) and DEZ (1ml of 1.5M DEZ toluene solution) were added through a syringe with the addition of toluene. Then catalyst A1(6ml of a 1.0mM toluene solution) and catalyst B1(4ml of a 1.0mM toluene solution) were added via syringe, ethylene was continuously introduced, the pressure was raised and maintained at 1.0MPa, polymerization was carried out at 60 ℃ for 30min, the temperature was reduced, the polymer was collected and weighed.
Specific polymerization results are listed in table 1.
Example 3
The first olefin polymerization catalyst A1 and the second olefin polymerization catalyst B1 were the same as in example 1.
The cocatalyst was methylaluminoxane and the shuttle agent was diethyl zinc (DEZ).
A1L stainless steel autoclave was evacuated and replaced with nitrogen, the process was repeated twice, and then evacuated again, 500 ml of toluene solvent was added under ethylene atmosphere, and the cocatalyst (6.5ml of 1.53M methylaluminoxane toluene solution) and DEZ (1ml of 1.5M DEZ toluene solution) were added through a syringe with the addition of toluene. Then, catalyst A1(2ml of a 1.0mM toluene solution) and catalyst B1(8ml of a 1.0mM toluene solution) were added via syringe, ethylene was continuously introduced, the pressure was raised and maintained at 1.0MPa, and polymerization was carried out at 60 ℃ for 30min, after which the temperature was reduced, and the polymer was collected and weighed.
Specific polymerization results are listed in table 1.
Comparative example 1
The first olefin polymerization catalyst A1 and the second olefin polymerization catalyst B1 were the same as in example 1.
The cocatalyst was methylaluminoxane and no shuttling agent was added.
A1L stainless steel autoclave was evacuated and replaced with nitrogen, the process was repeated twice, and then evacuated again, 500 ml of toluene solvent was added under ethylene atmosphere, and the cocatalyst (6.5ml of 1.53M methylaluminoxane solution in toluene) was added by syringe with the addition of toluene. Then catalyst A1(5ml of a 1.0mM toluene solution) and catalyst B1(5ml of a 1.0mM toluene solution) were added via syringe, ethylene was continuously introduced, the pressure was raised and maintained at 1.0MPa, polymerization was carried out at 60 ℃ for 30min, the temperature was reduced, the polymer was collected and weighed.
Specific polymerization results are listed in table 1.
Comparative example 2
The first olefin polymerization catalyst A1 and the second olefin polymerization catalyst B1 were the same as in example 1.
The cocatalyst was methylaluminoxane and no shuttling agent was added.
A1L stainless steel autoclave was evacuated and replaced with nitrogen, the process was repeated twice, and then evacuated again, 500 ml of toluene solvent was added under ethylene atmosphere, and the cocatalyst (6.5ml of 1.53M methylaluminoxane solution in toluene) was added by syringe with the addition of toluene. Then catalyst A1(6ml of a 1.0mM toluene solution) and catalyst B1(4ml of a 1.0mM toluene solution) were added via syringe, ethylene was continuously introduced, the pressure was raised and maintained at 1.0MPa, polymerization was carried out at 60 ℃ for 30min, the temperature was reduced, the polymer was collected and weighed.
Specific polymerization results are listed in table 1.
Comparative example 3
The first olefin polymerization catalyst A1 and the second olefin polymerization catalyst B1 were the same as in example 1.
The cocatalyst was methylaluminoxane and no shuttling agent was added.
A1L stainless steel autoclave was evacuated and replaced with nitrogen, the process was repeated twice, and then evacuated again, 500 ml of toluene solvent was added under ethylene atmosphere, and the cocatalyst (6.5ml of 1.53M methylaluminoxane solution in toluene) was added by syringe with the addition of toluene. Then, catalyst A1(2ml of a 1.0mM toluene solution) and catalyst B1(8ml of a 1.0mM toluene solution) were added via syringe, ethylene was continuously introduced, the pressure was raised and maintained at 1.0MPa, and polymerization was carried out at 60 ℃ for 30min, after which the temperature was reduced, and the polymer was collected and weighed.
Specific polymerization results are listed in table 1.
Comparative example 4
The first olefin polymerization catalyst A1 was identical to example 1, except that the second olefin polymerization catalyst B1 was not added.
The cocatalyst was methylaluminoxane and the shuttle agent was diethyl zinc (DEZ).
A1L stainless steel autoclave was evacuated and replaced with nitrogen, the process was repeated twice, and then evacuated again, 500 ml of toluene solvent was added under ethylene atmosphere, and the cocatalyst (3.2ml of 1.53M methylaluminoxane solution in toluene) and DEZ (0.5ml of 1.5M DEZ solution in toluene) were added by syringe with the addition of toluene. Then adding catalyst A1(5ml toluene solution with concentration of 1.0 mM) via syringe, introducing ethylene, increasing pressure to 1.0MPa, performing polymerization reaction at 60 deg.C for 30min, cooling, collecting polymer, and weighing.
Specific polymerization results are listed in table 1.
Comparative example 5
Second olefin polymerization catalyst B1 example 1 was repeated without addition of the first olefin polymerization catalyst A1.
The cocatalyst was methylaluminoxane and the shuttle agent was diethyl zinc (DEZ).
A1L stainless steel autoclave was evacuated and replaced with nitrogen, the process was repeated twice, and then evacuated again, 500 ml of toluene solvent was added under ethylene atmosphere, and the cocatalyst (3.2ml of 1.53M methylaluminoxane solution in toluene) and DEZ (0.5ml of 1.5M DEZ solution in toluene) were added by syringe with the addition of toluene. Then adding catalyst B1(5ml toluene solution with concentration of 1.0 mM) via syringe, continuing to introduce ethylene, increasing pressure to and maintaining 1.0MPa, carrying out polymerization reaction at 60 deg.C for 30min, cooling, collecting polymer, and weighing.
Specific polymerization results are listed in table 1.
Example 4
The first olefin polymerization catalyst A1 was the same as in example 1,
the structure of the second olefin polymerization catalyst B2 is shown as a formula (3),
the cocatalyst was methylaluminoxane and the shuttle agent was diethyl zinc (DEZ).
A1L stainless steel autoclave was evacuated and replaced with nitrogen, the process was repeated twice, and then evacuated again, 500 ml of toluene solvent was added under ethylene atmosphere, and the cocatalyst (6.5ml of 1.53M methylaluminoxane toluene solution) and DEZ (1ml of 1.5M DEZ toluene solution) were added through a syringe with the addition of toluene. Then catalyst A1(5ml of a 1.0mM toluene solution) and catalyst B2(5ml of a 1.0mM toluene solution) were added via syringe, ethylene was continuously introduced, the pressure was raised and maintained at 1.0MPa, polymerization was carried out at 60 ℃ for 30min, the temperature was reduced, the polymer was collected and weighed.
Specific polymerization results are listed in table 1.
Example 5
The first olefin polymerization catalyst A2 [ the structure of which is shown in formula (4) ] is disclosed in Macromolecules,1998, 31,7588 and 7597.
The second olefin polymerization catalyst B1 was the same as in example 1,
the cocatalyst was methylaluminoxane and the shuttle agent was diethyl zinc (DEZ).
A1L stainless steel autoclave was evacuated and replaced with nitrogen, the process was repeated twice, and then evacuated again, 500 ml of toluene solvent was added under ethylene atmosphere, and the cocatalyst (6.5ml of 1.53M methylaluminoxane toluene solution) and DEZ (1ml of 1.5M DEZ toluene solution) were added through a syringe with the addition of toluene. Then catalyst A2(5ml of a 1.0mM toluene solution) and catalyst B1(5ml of a 1.0mM toluene solution) were added via syringe, ethylene was continuously introduced, the pressure was raised and maintained at 1.0MPa, polymerization was carried out at 60 ℃ for 30min, the temperature was reduced, the polymer was collected and weighed.
Specific polymerization results are listed in table 1.
Example 6
The first olefin polymerization catalyst A3 [ the structure of which is shown in formula (5) ] and the synthesis process of which is described in Macromolecules,1998, 31,7588-,
the second olefin polymerization catalyst B1 was the same as in example 1,
the cocatalyst was methylaluminoxane and the shuttle agent was diethyl zinc (DEZ).
A1L stainless steel autoclave was evacuated and replaced with nitrogen, the process was repeated twice, and then evacuated again, 500 ml of toluene solvent was added under ethylene atmosphere, and the cocatalyst (6.5ml of 1.53M methylaluminoxane toluene solution) and DEZ (1ml of 1.5M DEZ toluene solution) were added through a syringe with the addition of toluene. Then catalyst A3(5ml of a 1.0mM toluene solution) and catalyst B1(5ml of a 1.0mM toluene solution) were added via syringe, ethylene was continuously introduced, the pressure was raised and maintained at 1.0MPa, polymerization was carried out at 60 ℃ for 30min, the temperature was reduced, the polymer was collected and weighed.
Specific polymerization results are listed in table 1.
Example 7
The first olefin polymerization catalyst A4 [ the structure of which is shown as formula (6), and the synthetic process of which is disclosed in documents J.mol.Catal.A 2009,303,102-109 ],
the second olefin polymerization catalyst B1 was the same as in example 1,
the cocatalyst was methylaluminoxane and the shuttle agent was diethyl zinc (DEZ).
A1L stainless steel autoclave was evacuated and replaced with nitrogen, the process was repeated twice, and then evacuated again, 500 ml of toluene solvent was added under ethylene atmosphere, and the cocatalyst (6.5ml of 1.53M methylaluminoxane toluene solution) and DEZ (1ml of 1.5M DEZ toluene solution) were added through a syringe with the addition of toluene. Then catalyst A4(5ml of a 1.0mM toluene solution) and catalyst B1(5ml of a 1.0mM toluene solution) were added via syringe, ethylene was continuously introduced, the pressure was raised and maintained at 1.0MPa, polymerization was carried out at 60 ℃ for 30min, the temperature was reduced, the polymer was collected and weighed.
Specific polymerization results are listed in table 1.
Example 8
The first olefin polymerization catalyst A1 and the second olefin polymerization catalyst B1 were the same as in example 1.
The cocatalyst is Ph3CB(C6F5)4Tetrakis (pentafluorophenyl) borate and the shuttling agent is diethyl zinc (DEZ).
A1L stainless steel autoclave was evacuated and replaced with nitrogen, the process was repeated twice, and then evacuated again, 500 ml of a toluene solvent was added under an ethylene atmosphere, and a cocatalyst (10ml of 1.0mM Ph in accordance with the addition of toluene) was added3CB(C6F5)4Toluene solution of tetrakis (pentafluorophenyl) borate, 5ml of a 1.0M solution of triisobutylaluminum in toluene) and DEZ (1ml of a 1.5M solution in toluene) were added via syringe. Then catalyst A1(5ml of a 1.0mM toluene solution) and catalyst B1(5ml of a 1.0mM toluene solution) were added via syringe, ethylene was continuously introduced, the pressure was raised and maintained at 1.0MPa, polymerization was carried out at 60 ℃ for 30min, the temperature was reduced, the polymer was collected and weighed.
Specific polymerization results are listed in table 1.
Example 9
The first olefin polymerization catalyst A1 and the second olefin polymerization catalyst B1 were the same as in example 1.
The cocatalyst was methylaluminoxane and the shuttle agent was diethyl zinc (DEZ).
A1L stainless steel autoclave was evacuated and replaced with nitrogen, the process was repeated twice, and then evacuated again, 500 ml of toluene solvent was added under ethylene, and 20ml of decene, cocatalyst (6.5ml of 1.53M methylaluminoxane toluene solution) and DEZ (1ml of 1.5M DEZ toluene solution) were added by syringe with the addition of toluene. Then catalyst A1(8ml of a 1.0mM toluene solution) and catalyst B1(2ml of a 1.0mM toluene solution) were added via syringe, ethylene was continuously introduced, the pressure was raised and maintained at 1.0MPa, polymerization was carried out at 60 ℃ for 30min, the temperature was reduced, the polymer was collected and weighed.
Specific polymerization results are listed in table 2.
Example 10
The first olefin polymerization catalyst A1 and the second olefin polymerization catalyst B1 were the same as in example 1.
The cocatalyst was methylaluminoxane and the shuttle agent was diethyl zinc (DEZ).
A1L stainless steel autoclave was evacuated and replaced with nitrogen, the process was repeated twice, and then evacuated again, 500 ml of toluene solvent was added under ethylene, and 20ml of decene, cocatalyst (6.5ml of 1.53M methylaluminoxane toluene solution) and DEZ (1ml of 1.5M DEZ toluene solution) were added by syringe with the addition of toluene. Then catalyst A1(5ml of a 1.0mM toluene solution) and catalyst B1(5ml of a 1.0mM toluene solution) were added via syringe, ethylene was continuously introduced, the pressure was raised and maintained at 1.0MPa, polymerization was carried out at 60 ℃ for 30min, the temperature was reduced, the polymer was collected and weighed.
Specific polymerization results are listed in table 2.
Example 11
The first olefin polymerization catalyst A1 and the second olefin polymerization catalyst B1 were the same as in example 1.
The cocatalyst was methylaluminoxane and the shuttle agent was diethyl zinc (DEZ).
A1L stainless steel autoclave was evacuated and replaced with nitrogen, the process was repeated twice, and then evacuated again, 500 ml of toluene solvent was added under ethylene, and 20ml of decene, cocatalyst (6.5ml of 1.53M methylaluminoxane toluene solution) and DEZ (1ml of 1.5M DEZ toluene solution) were added by syringe with the addition of toluene. Then, catalyst A1(2ml of a 1.0mM toluene solution) and catalyst B1(8ml of a 1.0mM toluene solution) were added via syringe, ethylene was continuously introduced, the pressure was raised and maintained at 1.0MPa, and polymerization was carried out at 60 ℃ for 30min, after which the temperature was reduced, and the polymer was collected and weighed.
Specific polymerization results are listed in table 2.
Comparative example 6
The first olefin polymerization catalyst A1 and the second olefin polymerization catalyst B1 were the same as in example 1.
The cocatalyst was methylaluminoxane and no shuttling agent was added.
A1L stainless steel autoclave was evacuated and replaced with nitrogen, the process was repeated twice, and then evacuated again, 500 ml of toluene solvent was added under ethylene, and 20ml of decene, co-catalyst (6.5ml of 1.53M methylaluminoxane solution in toluene) were added by syringe with the addition of toluene. Then catalyst A1(5ml of a 1.0mM toluene solution) and catalyst B1(5ml of a 1.0mM toluene solution) were added via syringe, ethylene was continuously introduced, the pressure was raised and maintained at 1.0MPa, polymerization was carried out at 60 ℃ for 30min, the temperature was reduced, the polymer was collected and weighed.
Specific polymerization results are listed in table 2.
Comparative example 7
The first olefin polymerization catalyst A1 was identical to example 1, except that the second olefin polymerization catalyst B1 was not added.
The cocatalyst was methylaluminoxane and no shuttling agent was added.
A1L stainless steel autoclave was evacuated and replaced with nitrogen, the process was repeated twice, and then evacuated again, 500 ml of toluene solvent was added under ethylene, and 10ml of decene, cocatalyst (3.2ml of 1.53M methylaluminoxane toluene solution) and DEZ (0.5ml of 1.5M DEZ toluene solution) were added by syringe with the addition of toluene. Then adding catalyst A1(5ml toluene solution with concentration of 1.0 mM) via syringe, introducing ethylene, increasing pressure to 1.0MPa, performing polymerization reaction at 60 deg.C for 30min, cooling, collecting polymer, and weighing.
Specific polymerization results are listed in table 2.
Comparative example 8
Second olefin polymerization catalyst B1 example 1 was repeated without addition of the first olefin polymerization catalyst A1.
The cocatalyst was methylaluminoxane and no shuttling agent was added.
A1L stainless steel autoclave was evacuated and replaced with nitrogen, the process was repeated twice, and then evacuated again, 500 ml of toluene solvent was added under ethylene, and 10ml of decene, cocatalyst (3.2ml of 1.53M methylaluminoxane toluene solution) and DEZ (0.5ml of 1.5M DEZ toluene solution) were added by syringe with the addition of toluene. Then adding catalyst B1(5ml toluene solution with concentration of 1.0 mM) via syringe, continuing to introduce ethylene, increasing pressure to and maintaining 1.0MPa, carrying out polymerization reaction at 60 deg.C for 30min, cooling, collecting polymer, and weighing.
Specific polymerization results are listed in table 2.
Example 12
The first olefin polymerization catalyst A1 and the second olefin polymerization catalyst B1 were the same as in example 1.
The cocatalyst was methylaluminoxane and the shuttle agent was diethyl zinc (DEZ).
A1L stainless steel autoclave was evacuated and replaced with nitrogen, the process was repeated twice, and then evacuated again, 500 ml of a toluene solvent was added under an ethylene atmosphere, and 20ml of norbornene (5.0M norbornene toluene solution), cocatalyst (6.5ml of 1.53M methylaluminoxane toluene solution) and DEZ (1ml of 1.5M DEZ toluene solution) were added through a syringe with the addition of toluene. Then, catalyst A1(2ml of a 1.0mM toluene solution) and catalyst B1(8ml of a 1.0mM toluene solution) were added via syringe, ethylene was continuously introduced, the pressure was raised and maintained at 1.0MPa, and polymerization was carried out at 60 ℃ for 30min, after which the temperature was reduced, and the polymer was collected and weighed.
Specific polymerization results are listed in table 2.
Example 13
The first olefin polymerization catalyst A1 and the second olefin polymerization catalyst B1 were the same as in example 1.
The cocatalyst was methylaluminoxane and the shuttle agent was diethyl zinc (DEZ).
A1L stainless steel autoclave was evacuated and replaced with nitrogen, the process was repeated twice, and then evacuated again, 500 ml of a toluene solvent was added under an ethylene atmosphere, and 20ml of norbornene (5.0M norbornene toluene solution), cocatalyst (6.5ml of 1.53M methylaluminoxane toluene solution) and DEZ (1ml of 1.5M DEZ toluene solution) were added through a syringe with the addition of toluene. Then catalyst A1(5ml of a 1.0mM toluene solution) and catalyst B1(5ml of a 1.0mM toluene solution) were added via syringe, ethylene was continuously introduced, the pressure was raised and maintained at 1.0MPa, polymerization was carried out at 60 ℃ for 30min, the temperature was reduced, the polymer was collected and weighed.
Specific polymerization results are listed in table 2.
Example 14
The first olefin polymerization catalyst A1 and the second olefin polymerization catalyst B1 were the same as in example 1.
The cocatalyst was methylaluminoxane and the shuttle agent was diethyl zinc (DEZ).
A1L stainless steel autoclave was evacuated and replaced with nitrogen, the process was repeated twice, and then evacuated again, 500 ml of a toluene solvent was added under an ethylene atmosphere, and 20ml of norbornene (5.0M norbornene toluene solution), cocatalyst (6.5ml of 1.53M methylaluminoxane toluene solution) and DEZ (1ml of 1.5M DEZ toluene solution) were added through a syringe with the addition of toluene. Then catalyst A1(8ml of a 1.0mM toluene solution) and catalyst B1(2ml of a 1.0mM toluene solution) were added via syringe, ethylene was continuously introduced, the pressure was raised and maintained at 1.0MPa, polymerization was carried out at 60 ℃ for 30min, the temperature was reduced, the polymer was collected and weighed.
Specific polymerization results are listed in table 2.
Comparative example 9
The first olefin polymerization catalyst A1 and the second olefin polymerization catalyst B1 were the same as in example 1.
The cocatalyst was methylaluminoxane and no shuttling agent was added.
A1L stainless steel autoclave was evacuated and replaced with nitrogen, the process was repeated twice, and then evacuated again, 500 ml of a toluene solvent was added under an ethylene atmosphere, and 20ml of norbornene (5.0M norbornene in toluene), and a cocatalyst (6.5ml of 1.53M methylaluminoxane in toluene) were added by syringe with the addition of toluene. Then catalyst A1(5ml of a 1.0mM toluene solution) and catalyst B1(5ml of a 1.0mM toluene solution) were added via syringe, ethylene was continuously introduced, the pressure was raised and maintained at 1.0MPa, polymerization was carried out at 60 ℃ for 30min, the temperature was reduced, the polymer was collected and weighed.
Specific polymerization results are listed in table 2.
Example 15
The first olefin polymerization catalyst A1 was the same as in example 1, and the second olefin polymerization catalyst B2 was the same as in example 4.
The cocatalyst was methylaluminoxane and the shuttle agent was diethyl zinc (DEZ).
A1L stainless steel autoclave was evacuated and replaced with nitrogen, the process was repeated twice, and then evacuated again, 500 ml of toluene solvent was added under ethylene, and 20ml of decene, cocatalyst (6.5ml of 1.53M methylaluminoxane toluene solution) and DEZ (1ml of 1.5M DEZ toluene solution) were added by syringe with the addition of toluene. Then catalyst A1(5ml of a 1.0mM toluene solution) and catalyst B2(5ml of a 1.0mM toluene solution) were added via syringe, ethylene was continuously introduced, the pressure was raised and maintained at 1.0MPa, polymerization was carried out at 60 ℃ for 30min, the temperature was reduced, the polymer was collected and weighed.
Specific polymerization results are listed in table 2.
Example 16
The first olefin polymerization catalyst A2 was the same as in example 5, and the second olefin polymerization catalyst B1 was the same as in example 1.
The cocatalyst was methylaluminoxane and the shuttle agent was diethyl zinc (DEZ).
A1L stainless steel autoclave was evacuated and replaced with nitrogen, the process was repeated twice, and then evacuated again, 500 ml of toluene solvent was added under ethylene, and 20ml of decene, cocatalyst (6.5ml of 1.53M methylaluminoxane toluene solution) and DEZ (1ml of 1.5M DEZ toluene solution) were added by syringe with the addition of toluene. Then catalyst A2(5ml of a 1.0mM toluene solution) and catalyst B1(5ml of a 1.0mM toluene solution) were added via syringe, ethylene was continuously introduced, the pressure was raised and maintained at 1.0MPa, polymerization was carried out at 60 ℃ for 30min, the temperature was reduced, the polymer was collected and weighed.
Specific polymerization results are listed in table 2.
Example 17
The first olefin polymerization catalyst A3 was the same as in example 6, and the second olefin polymerization catalyst B1 was the same as in example 1.
The cocatalyst was methylaluminoxane and the shuttle agent was diethyl zinc (DEZ).
A1L stainless steel autoclave was evacuated and replaced with nitrogen, the process was repeated twice, and then evacuated again, 500 ml of toluene solvent was added under ethylene, and 20ml of decene, cocatalyst (6.5ml of 1.53M methylaluminoxane toluene solution) and DEZ (1ml of 1.5M DEZ toluene solution) were added by syringe with the addition of toluene. Then catalyst A3(5ml of a 1.0mM toluene solution) and catalyst B1(5ml of a 1.0mM toluene solution) were added via syringe, ethylene was continuously introduced, the pressure was raised and maintained at 1.0MPa, polymerization was carried out at 60 ℃ for 30min, the temperature was reduced, the polymer was collected and weighed.
Specific polymerization results are listed in table 2.
Example 18
The first olefin polymerization catalyst A4 was the same as in example 7, and the second olefin polymerization catalyst B1 was the same as in example 1.
The cocatalyst was methylaluminoxane and the shuttle agent was diethyl zinc (DEZ).
A1L stainless steel autoclave was evacuated and replaced with nitrogen, the process was repeated twice, and then evacuated again, 500 ml of toluene solvent was added under ethylene, and 20ml of decene, cocatalyst (6.5ml of 1.53M methylaluminoxane toluene solution) and DEZ (1ml of 1.5M DEZ toluene solution) were added by syringe with the addition of toluene. Then catalyst A4(5ml of a 1.0mM toluene solution) and catalyst B1(5ml of a 1.0mM toluene solution) were added via syringe, ethylene was continuously introduced, the pressure was raised and maintained at 1.0MPa, polymerization was carried out at 60 ℃ for 30min, the temperature was reduced, the polymer was collected and weighed.
Specific polymerization results are listed in table 1.
Example 19
The first olefin polymerization catalyst A1 and the second olefin polymerization catalyst B1 were the same as in example 1.
The cocatalyst is Ph3CB(C6F5)4Tetrakis (pentafluorophenyl) borate and the shuttling agent is diethyl zinc (DEZ).
A1L stainless steel autoclave was evacuated and replaced with nitrogen, the process was repeated twice, and then evacuated again, 500 ml of toluene solvent was added under ethylene atmosphere, and 20ml of decene, co-catalyst (1ml of Ph at a concentration of 1.0 mM) and co-catalyst (1ml of toluene) were added3CB(C6F5)4Tetrakis (pentafluorophenyl) borate in toluene), triisobutylaluminum (5ml of 1.0M in toluene) and DEZ (1ml of 1.5M in toluene) were added by syringe. Then catalyst A1(5ml of a 1.0mM toluene solution) and catalyst B1(5ml of a 1.0mM toluene solution) were added via syringe, ethylene was continuously introduced, the pressure was raised and maintained at 1.0MPa, polymerization was carried out at 60 ℃ for 30min, the temperature was reduced, the polymer was collected and weighed.
Specific polymerization results are listed in table 2.
TABLE 1 homopolymerization results of ethylene
TABLE 2 ethylene and C3-C16As a result of copolymerization of alpha-olefins or cyclic olefins
In Table 1, "-" indicates that no test was performed.
As can be seen from tables 1 and 2, the molecular weight distribution of the polymer obtained in the examples using the catalyst composition of the present invention is significantly lower than that of the comparative examples (using catalyst A1 and catalyst B1, but without the addition of a chain shuttling agent). The comparative example using catalyst A alone, the polymer obtained under the same conditions was lower in molecular weight, the comparative example using catalyst B alone, the polymer obtained was higher in molecular weight, and the polymer molecular weight distributions Mw/Mn of examples 1-19 were lower, indicating that when a composition comprising catalyst A and catalyst B was used, copolymerization occurred under the action of the chain shuttling agent to form a block polymer, rather than the mixture of polymers prepared using catalyst A, B alone in the comparative examples, otherwise the Mw/Mn of the polymers obtained in examples 1-19 should be much greater than 4.
Having described embodiments of the present invention, the foregoing description is intended to be exemplary, not exhaustive, and not limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments.
Claims (21)
1. A catalyst composition for the polymerization of olefins, wherein the catalyst composition is a mixture or reaction product comprising:
(1) a first olefin polymerization catalyst (A) selected from at least one metal complex represented by the general formula I:
in the general formula I, R1～R5，R7～R11Identical or different, each independently selected from hydrogen, hydrocarbyl or halogen, and optionally, R1And R4Are linked to each other to form a ring, and/or R2And R5Are connected with each other to form a ring; m is a group IVA metal, X, which may be the same or different, is selected from the group consisting of halogen, hydrocarbyl, hydrocarbyloxy; l is a group VIA element;
(2) a second olefin polymerization catalyst (B) selected from at least one metal complex represented by the general formula II:
in the general formula II, R1And R4Are the same or different and are each independently selected from C1-C30A hydrocarbon group containing a benzene ring or C1-C30And said C is a heterohydrocarbyl group containing a benzene ring1-C30The benzene ring of the heterohydrocarbyl group containing a benzene ring is represented by C1-C10Alkoxy or halogen-substituted benzene ring of (1), said C1-C30A hydrocarbon group containing a benzene ring or C1-C30Each heterohydrocarbyl group containing a benzene ring independently has only one benzene ring; r2And R3Forming a ring with each other to form a canum; m is nickel or palladium; x is the same or different and is selected from halogen, alkyl, alkoxy, acid radical or amino; n is an integer satisfying the valence of M;
(3) a chain shuttling agent;
(4) a cocatalyst.
2. The catalyst composition of claim 1,
(1) a first olefin polymerization catalyst (A) selected from at least one metal complex represented by the general formula I:
in the general formula I, R1～R5，R7～R11The same or different, each independently selected from hydrogen and C1～C20Aliphatic hydrocarbon group of (C)6～C30Or halogen, and optionally, R1And R4Are linked to each other to form a ring, and/or R2And R5Are connected with each other to form a ring; m is selected from titanium, zirconium or hafnium, X, same or different, is selected from halogen, C1～C20Saturated hydrocarbon group of (C)2～C20Unsaturated hydrocarbon group of (C)1～C20Hydrocarbyloxy groups of (a); l is selected from O or S elements;
(3) a chain shuttling agent;
(4) a cocatalyst.
3. The catalyst composition according to claim 2, wherein the first olefin polymerization catalyst (A) is at least one selected from the group consisting of metal complexes represented by the general formula IV,
in the general formula IV, R1～R5，R7，R9，R11The same or different, each independently selected from hydrogen and C1～C20Aliphatic hydrocarbon group of (C)6～C30Or halogen, and optionally, R1And R4Are linked to each other to form a ring, and/or R2And R5Are connected with each other to form a ring; x is halogen, M is titanium, zirconium or hafnium;
the second olefin polymerization catalyst (B) is at least one selected from metal complexes represented by the general formula V,
in the general formula (V), R11-R20The same or different, each independently selected from hydrogen and C1-C10Saturated hydrocarbon group of (C)2-C10Unsaturated hydrocarbon group of (C)1-C10Alkoxy or halogen of (a); x is halogen, M is nickel or palladium.
4. The catalyst composition according to claim 3, wherein in the general formula (V), R11-R20The same or different, each independently selected from hydrogen and C1～C6Alkyl of (C)2～C6Alkenyl of, C1～C6Alkoxy or halogen of (a).
5. The catalyst composition according to claim 3, wherein the second olefin polymerization catalyst (B) is selected from at least one of the following metal complexes; in the general formula V, R17-R20Are all hydrogen, M is nickel,
the complex 1: r11＝R13＝R14＝R16＝Me，R12＝R15＝H，X＝Br；
And (2) the complex: r11＝R13＝R14＝R16＝Et，R12＝R15＝H，X＝Br；
And (3) complex: r11＝R13＝R14＝R16＝iPr，R12＝R15＝H，X＝Br；
The complex 4: r11＝R12＝R13＝R14＝R15＝R16＝Me，X＝Br；
And (3) a complex 5: r11＝R13＝R14＝R16＝Me，R12＝R15＝Br，X＝Br；
The complex 6: r11＝R13＝R14＝R16＝Me，R12＝R15＝Et，X＝Br；
The complex 7: r11＝R13＝R14＝R16＝Et，R12＝R15＝Me，X＝Br；
The complex 8: r11＝R13＝R14＝R16＝Et，R12＝R15＝Br，X＝Br；
The complex 9: r11＝R13＝R14＝R16＝F，R12＝R15＝H，X＝Br；
The complex 10: r11＝R13＝R14＝R16＝Cl，R12＝R15＝H，X＝Br；
The complex 11: r11＝R13＝R14＝R16＝Br，R12＝R15＝H，X＝Br；
The complex 12: r11＝R13＝R14＝R16＝Me，R12＝R15＝H，X＝Cl；
The complex 13: r11＝R13＝R14＝R16＝Et，R12＝R15＝H，X＝Cl；
The complex 14: r11＝R13＝R14＝R16＝iPr，R12＝R15＝H，X＝Cl；
The complex 15: r11＝R12＝R13＝R14＝R15＝R16＝Me，X＝Cl；
The compound 16: r11＝R13＝R14＝R16＝Me，R12＝R15＝Br，X＝Cl；
The complex 17: r11＝R13＝R14＝R16＝Me，R12＝R15＝Et，X＝Cl；
The complex 18: r11＝R13＝R14＝R16＝Et，R12＝R15＝Me，X＝Cl；
The complex 19: r11＝R13＝R14＝R16＝Et，R12＝R15＝Br，X＝Cl；
The complex 20: r11＝R13＝R14＝R16＝F，R12＝R15＝H，X＝Cl；
The complex 21: r11＝R13＝R14＝R16＝Cl，R12＝R15＝H，X＝Cl；
The complex 22: r11＝R13＝R14＝R16＝Br，R12＝R15＝H，X＝Cl。
6. The catalyst composition according to claim 4, wherein the second olefin polymerization catalyst (B) is selected from at least one of the following metal complexes; in the general formula V, R17-R20Are all hydrogen, M is nickel,
the complex 1: r11＝R13＝R14＝R16＝Me，R12＝R15＝H，X＝Br；
And (2) the complex: r11＝R13＝R14＝R16＝Et，R12＝R15＝H，X＝Br；
And (3) complex: r11＝R13＝R14＝R16＝iPr，R12＝R15＝H，X＝Br；
The complex 4: r11＝R12＝R13＝R14＝R15＝R16＝Me，X＝Br；
And (3) a complex 5: r11＝R13＝R14＝R16＝Me，R12＝R15＝Br，X＝Br；
The complex 6: r11＝R13＝R14＝R16＝Me，R12＝R15＝Et，X＝Br；
The complex 7: r11＝R13＝R14＝R16＝Et，R12＝R15＝Me，X＝Br；
The complex 8: r11＝R13＝R14＝R16＝Et，R12＝R15＝Br，X＝Br；
The complex 9: r11＝R13＝R14＝R16＝F，R12＝R15＝H，X＝Br；
Fitting togetherAn object 10: r11＝R13＝R14＝R16＝Cl，R12＝R15＝H，X＝Br；
The complex 11: r11＝R13＝R14＝R16＝Br，R12＝R15＝H，X＝Br；
The complex 12: r11＝R13＝R14＝R16＝Me，R12＝R15＝H，X＝Cl；
The complex 13: r11＝R13＝R14＝R16＝Et，R12＝R15＝H，X＝Cl；
The complex 14: r11＝R13＝R14＝R16＝iPr，R12＝R15＝H，X＝Cl；
The complex 15: r11＝R12＝R13＝R14＝R15＝R16＝Me，X＝Cl；
The compound 16: r11＝R13＝R14＝R16＝Me，R12＝R15＝Br，X＝Cl；
The complex 17: r11＝R13＝R14＝R16＝Me，R12＝R15＝Et，X＝Cl；
The complex 18: r11＝R13＝R14＝R16＝Et，R12＝R15＝Me，X＝Cl；
The complex 19: r11＝R13＝R14＝R16＝Et，R12＝R15＝Br，X＝Cl；
The complex 20: r11＝R13＝R14＝R16＝F，R12＝R15＝H，X＝Cl；
The complex 21: r11＝R13＝R14＝R16＝Cl，R12＝R15＝H，X＝Cl；
The complex 22: r11＝R13＝R14＝R16＝Br，R12＝R15＝H，X＝Cl。
7. The catalyst composition according to claim 1, wherein the molar ratio of the first olefin polymerization catalyst (a) to the second olefin polymerization catalyst (B) is from 1:100 to 100: 1.
8. The catalyst composition according to claim 7, wherein the molar ratio of the first olefin polymerization catalyst (A) to the second olefin polymerization catalyst (B) is from 10:90 to 90: 10.
9. The catalyst composition of any of claims 1-8, wherein the chain shuttling agent is selected from the group consisting of containing at least one C1-C20Hydrocarbyl group IA, II A, IB, IIB metal compounds or complexes.
10. The catalyst composition of any of claims 1-8, wherein the chain shuttling agent is selected from the group consisting of C-containing1-C12Aluminum compound of hydrocarbon group, C1-C12Gallium compounds containing hydrocarbon radicals or containing C1-C12A zinc compound of a hydrocarbon group.
11. The catalyst composition of claim 9, wherein the hydrocarbyl group is an alkyl group.
12. The catalyst composition of claim 10, wherein the hydrocarbyl group is an alkyl group.
13. The catalyst composition of claim 10, wherein the chain shuttling agent is selected from at least one of a trialkyl aluminum, a dialkyl zinc, and a trialkyl gallium.
14. The catalyst composition of claim 13, wherein the chain shuttling agent is selected from at least one of triethylaluminum, triisopropylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, dimethylzinc, diethylzinc, and trimethylgallium.
15. The catalyst composition of any of claims 1-8, wherein the co-catalyst is selected from the group consisting of C1-C30Hydrocarbyl-substituted group IIIA compounds.
16. The catalyst composition of claim 15 wherein said cocatalyst is selected from at least one of alkylaluminoxane, arylborane, and arylborate.
17. The catalyst composition of claim 16, wherein said cocatalyst is selected from at least one of methylaluminoxane, modified methylaluminoxane, triarylborane, and tetraarylborate.
18. The catalyst composition according to claim 1, wherein the molar ratio of aluminum in the co-catalyst to the sum of the first olefin polymerization catalyst (a) and the second olefin polymerization catalyst (B) is (10-20000):1, or the molar ratio of boron in the co-catalyst to the sum of the first olefin polymerization catalyst (a) and the second olefin polymerization catalyst (B) is (0.01-50): 1;
the molar ratio of the sum of the first olefin polymerization catalyst (A) and the second olefin polymerization catalyst (B) to the chain shuttling agent is 1: 1-1: 20000.
19. The catalyst composition of claim 18, wherein the molar ratio of the sum of the first olefin polymerization catalyst (a) and the second olefin polymerization catalyst (B) to the chain shuttling agent is from 1:1 to 1: 1000.
20. A process for the polymerization of olefins, the process comprising: contacting the catalyst composition of any one of claims 1-19 with a monomer for copolymerization to form a copolymer.
21. The method of claim 20, wherein the monomer is selected from ethylene, C3～C16At least one of α -olefin and cycloolefin; the polymerization conditions include: the temperature is-20 to 150 ℃, and the pressure is 0.1 to 10 MPa.
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| JP7175426B2 (en) * | 2020-07-31 | 2022-11-18 | ポリプラスチックス株式会社 | Method for producing cyclic olefin copolymer |
| JP7073467B2 (en) * | 2020-10-02 | 2022-05-23 | ポリプラスチックス株式会社 | Method for Producing Cyclic Olefin Copolymer |
| CN114853964B (en) * | 2021-02-04 | 2023-12-22 | 中国石油天然气股份有限公司 | Cycloolefin block copolymer and process for producing the same |
| CN115246893B (en) * | 2021-04-28 | 2023-10-13 | 中国石油化工股份有限公司 | Catalyst composition for preparing bimodal polyolefin, and preparation method and application thereof |
| CN115246896B (en) * | 2021-04-28 | 2023-08-15 | 中国石油化工股份有限公司 | Double/multi-metal catalyst and preparation method and application thereof |
| CN113248548A (en) * | 2021-05-19 | 2021-08-13 | 青岛科技大学 | Preparation method and application of single metallocene catalyst |
| CN116023537B (en) * | 2021-10-26 | 2024-05-07 | 中国石油化工股份有限公司 | Catalyst composition for olefin polymerization and preparation method and application thereof |
| CN115109189B (en) * | 2022-06-15 | 2024-01-30 | 宁夏清研高分子新材料有限公司 | Preparation method of cycloolefin copolymer material, catalyst system and application thereof |
| CN116333004A (en) * | 2023-03-30 | 2023-06-27 | 青岛科技大学 | Preparation of 2, 6-diisopropylthiophenol single metallocene catalyst and application of catalyst in preparation of functionalized polyolefin |
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