CN108359035B - Copolymerization method of ethylene and terminal alkenyl silane/siloxane - Google Patents
Copolymerization method of ethylene and terminal alkenyl silane/siloxane Download PDFInfo
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- CN108359035B CN108359035B CN201710057275.2A CN201710057275A CN108359035B CN 108359035 B CN108359035 B CN 108359035B CN 201710057275 A CN201710057275 A CN 201710057275A CN 108359035 B CN108359035 B CN 108359035B
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- ethylene
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- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 239000005977 Ethylene Substances 0.000 title claims abstract description 70
- 238000007334 copolymerization reaction Methods 0.000 title claims abstract description 46
- 238000000034 method Methods 0.000 title claims abstract description 42
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical compound [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 title claims abstract description 21
- -1 alkenyl silane Chemical group 0.000 title abstract description 33
- 229910000077 silane Inorganic materials 0.000 title abstract description 13
- 239000003054 catalyst Substances 0.000 claims abstract description 48
- 239000000203 mixture Substances 0.000 claims abstract description 17
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 15
- 150000002367 halogens Chemical group 0.000 claims abstract description 15
- 239000012986 chain transfer agent Substances 0.000 claims abstract description 13
- 239000001257 hydrogen Substances 0.000 claims abstract description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 12
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 9
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 6
- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 45
- 230000008569 process Effects 0.000 claims description 15
- 150000001875 compounds Chemical class 0.000 claims description 10
- 229910052759 nickel Inorganic materials 0.000 claims description 10
- 239000011701 zinc Substances 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 150000002430 hydrocarbons Chemical group 0.000 claims description 4
- 229930195734 saturated hydrocarbon Natural products 0.000 claims description 4
- 229930195735 unsaturated hydrocarbon Natural products 0.000 claims description 4
- 229910052796 boron Inorganic materials 0.000 claims description 3
- 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 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 229940126142 compound 16 Drugs 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 150000001642 boronic acid derivatives Chemical class 0.000 claims 1
- 229920000642 polymer Polymers 0.000 abstract description 49
- 230000037048 polymerization activity Effects 0.000 abstract description 17
- 150000001336 alkenes Chemical class 0.000 abstract description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 abstract description 5
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- 150000002739 metals Chemical class 0.000 abstract description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 152
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 53
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical class C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 49
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 33
- 238000006116 polymerization reaction Methods 0.000 description 28
- 238000006467 substitution reaction Methods 0.000 description 28
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 24
- 229910001220 stainless steel Inorganic materials 0.000 description 23
- 239000010935 stainless steel Substances 0.000 description 23
- 239000007789 gas Substances 0.000 description 20
- 238000003756 stirring Methods 0.000 description 20
- 238000002347 injection Methods 0.000 description 19
- 239000007924 injection Substances 0.000 description 19
- 239000000243 solution Substances 0.000 description 19
- 238000012423 maintenance Methods 0.000 description 18
- LFRDHGNFBLIJIY-UHFFFAOYSA-N trimethoxy(prop-2-enyl)silane Chemical compound CO[Si](OC)(OC)CC=C LFRDHGNFBLIJIY-UHFFFAOYSA-N 0.000 description 17
- 238000006243 chemical reaction Methods 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- 238000006386 neutralization reaction Methods 0.000 description 10
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 7
- HQWPLXHWEZZGKY-UHFFFAOYSA-N diethylzinc Chemical compound CC[Zn]CC HQWPLXHWEZZGKY-UHFFFAOYSA-N 0.000 description 7
- 239000003446 ligand Substances 0.000 description 7
- 150000003254 radicals Chemical class 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 150000001448 anilines Chemical class 0.000 description 6
- RAABOESOVLLHRU-UHFFFAOYSA-N diazene Chemical compound N=N RAABOESOVLLHRU-UHFFFAOYSA-N 0.000 description 6
- 229910000071 diazene Inorganic materials 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 229940126062 Compound A Drugs 0.000 description 5
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical class [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 238000006073 displacement reaction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 4
- 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 3
- PBKONEOXTCPAFI-UHFFFAOYSA-N 1,2,4-trichlorobenzene Chemical compound ClC1=CC=C(Cl)C(Cl)=C1 PBKONEOXTCPAFI-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 229910021585 Nickel(II) bromide Inorganic materials 0.000 description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 238000012718 coordination polymerization Methods 0.000 description 3
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 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 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- JLTDJTHDQAWBAV-UHFFFAOYSA-O dimethyl(phenyl)azanium Chemical compound C[NH+](C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-O 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- 229920001684 low density polyethylene Polymers 0.000 description 2
- 239000004702 low-density polyethylene Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- DNAJDTIOMGISDS-UHFFFAOYSA-N prop-2-enylsilane Chemical group [SiH3]CC=C DNAJDTIOMGISDS-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 125000005373 siloxane group Chemical group [SiH2](O*)* 0.000 description 2
- HYWCXWRMUZYRPH-UHFFFAOYSA-N trimethyl(prop-2-enyl)silane Chemical compound C[Si](C)(C)CC=C HYWCXWRMUZYRPH-UHFFFAOYSA-N 0.000 description 2
- 125000004417 unsaturated alkyl group Chemical group 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- NPNAXGKROXIVMJ-UHFFFAOYSA-N (2,3,4-trifluorophenyl)boron Chemical compound [B]C1=CC=C(F)C(F)=C1F NPNAXGKROXIVMJ-UHFFFAOYSA-N 0.000 description 1
- UFFBMTHBGFGIHF-UHFFFAOYSA-N (2,6-Me2C6H3)NH2 Natural products CC1=CC=CC(C)=C1N UFFBMTHBGFGIHF-UHFFFAOYSA-N 0.000 description 1
- RELMFMZEBKVZJC-UHFFFAOYSA-N 1,2,3-trichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1Cl RELMFMZEBKVZJC-UHFFFAOYSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- WKBALTUBRZPIPZ-UHFFFAOYSA-N 2,6-di(propan-2-yl)aniline Chemical compound CC(C)C1=CC=CC(C(C)C)=C1N WKBALTUBRZPIPZ-UHFFFAOYSA-N 0.000 description 1
- FOYHNROGBXVLLX-UHFFFAOYSA-N 2,6-diethylaniline Chemical compound CCC1=CC=CC(CC)=C1N FOYHNROGBXVLLX-UHFFFAOYSA-N 0.000 description 1
- ODUZJBKKYBQIBX-UHFFFAOYSA-N 2,6-difluoroaniline Chemical compound NC1=C(F)C=CC=C1F ODUZJBKKYBQIBX-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 125000001494 2-propynyl group Chemical group [H]C#CC([H])([H])* 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- QGLAYJCJLHNIGJ-UHFFFAOYSA-N 4-bromo-2,6-dimethylaniline Chemical compound CC1=CC(Br)=CC(C)=C1N QGLAYJCJLHNIGJ-UHFFFAOYSA-N 0.000 description 1
- 125000004860 4-ethylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 125000000304 alkynyl group Chemical group 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 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
- 229940052810 complex b Drugs 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- AXAZMDOAUQTMOW-UHFFFAOYSA-N dimethylzinc Chemical compound C[Zn]C AXAZMDOAUQTMOW-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- HBWGDHDXAMFADB-UHFFFAOYSA-N ethenyl(triethyl)silane Chemical compound CC[Si](CC)(CC)C=C HBWGDHDXAMFADB-UHFFFAOYSA-N 0.000 description 1
- GCSJLQSCSDMKTP-UHFFFAOYSA-N ethenyl(trimethyl)silane Chemical compound C[Si](C)(C)C=C GCSJLQSCSDMKTP-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 239000004700 high-density polyethylene Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000001282 iso-butane Substances 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
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 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
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- IPLJNQFXJUCRNH-UHFFFAOYSA-L nickel(2+);dibromide Chemical compound [Ni+2].[Br-].[Br-] IPLJNQFXJUCRNH-UHFFFAOYSA-L 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- XPPWLXNXHSNMKC-UHFFFAOYSA-N phenylboron Chemical class [B]C1=CC=CC=C1 XPPWLXNXHSNMKC-UHFFFAOYSA-N 0.000 description 1
- 125000000286 phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229910001848 post-transition metal Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
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- 238000005086 pumping Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 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
- 238000001228 spectrum Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 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
- 125000003944 tolyl group Chemical group 0.000 description 1
- UMFJXASDGBJDEB-UHFFFAOYSA-N triethoxy(prop-2-enyl)silane Chemical compound CCO[Si](CC=C)(OCC)OCC UMFJXASDGBJDEB-UHFFFAOYSA-N 0.000 description 1
- SVGQCVJXVAMCPM-UHFFFAOYSA-N triethyl(prop-2-enyl)silane Chemical compound CC[Si](CC)(CC)CC=C SVGQCVJXVAMCPM-UHFFFAOYSA-N 0.000 description 1
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 1
- ORYGRKHDLWYTKX-UHFFFAOYSA-N trihexylalumane Chemical compound CCCCCC[Al](CCCCCC)CCCCCC ORYGRKHDLWYTKX-UHFFFAOYSA-N 0.000 description 1
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 1
- RKLXSINPXIQKIB-UHFFFAOYSA-N trimethoxy(oct-7-enyl)silane Chemical compound CO[Si](OC)(OC)CCCCCCC=C RKLXSINPXIQKIB-UHFFFAOYSA-N 0.000 description 1
- ZTRWVPZONVTXMB-UHFFFAOYSA-N trimethyl(oct-7-enyl)silane Chemical compound C[Si](C)(C)CCCCCCC=C ZTRWVPZONVTXMB-UHFFFAOYSA-N 0.000 description 1
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 1
- LFXVBWRMVZPLFK-UHFFFAOYSA-N trioctylalumane Chemical compound CCCCCCCC[Al](CCCCCCCC)CCCCCCCC LFXVBWRMVZPLFK-UHFFFAOYSA-N 0.000 description 1
- 125000002221 trityl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1C([*])(C1=C(C(=C(C(=C1[H])[H])[H])[H])[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/02—Ethene
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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 belongs to the field of olefin copolymerization reaction, and provides a copolymerization method of ethylene and terminal alkenyl silane/siloxane, which comprises the following steps: copolymerizing ethylene and terminal alkenyl silane/siloxane in the presence of a catalyst composition, wherein the catalyst composition comprises a main catalyst, a cocatalyst and an optional chain transfer agent, and the main catalyst is selected from at least one of complexes shown as a formula (I), wherein R is1~R10Each independently selected from hydrogen, saturated or unsaturated hydrocarbyl, hydrocarbyloxy, and the like; m is selected from group VIII metals and X is a halogen. The catalyst composition adopted by the method has higher polymerization activity in the copolymerization reaction of ethylene and terminal alkenyl silane/siloxane, can improve the content of comonomer and methyl on a polymer molecular chain, and has wide industrial application prospect.
Description
Technical Field
The invention belongs to the field of olefin copolymerization, and particularly relates to a copolymerization method of ethylene and terminal alkenyl silane/siloxane.
Background
The olefin copolymers containing vinylsilane or siloxane derivative groups can be used in a variety of applications, for example as various types of cable materials, pipes, adhesives, gaskets and crosslinked foams. Vinyl silane-based groups can be linked to olefin polymers by two methods: one method is to copolymerize olefins and vinylsilanes at high temperature and high pressure under the catalysis of a free radical initiator (e.g., US 3225018), the polymerization process is similar to the high-pressure homopolymerization of ethylene, and the structure of the obtained copolymer is similar to that of low-density polyethylene; another method is to graft an allyl-or vinyl-silane onto an existing polyolefin (e.g.US 3646155), which has the advantage that both low density polyethylene and high density polyethylene can be grafted on, but has the disadvantage that the grafting requires the additional use of free-radical initiators, which also complicates the preparation process. In addition, too little free radical initiator can result in too low a graft; too much free radical initiator may result in excessive crosslinking of the polymer. If the catalyst can catalyze the coordination polymerization of ethylene and the terminal alkenylsilane/siloxane groups, the polymerization process can be simplified, and the content of the terminal alkenylsilane/siloxane groups on a polymer chain can be controlled.
Currently, only a few documents report the use of transition metal complexes to catalyze the copolymerization of olefins with silicon-containing polar monomers (terminal alkenylsilanes/siloxanes). For example, WO 03/044066A 2 discloses that ethylene and allyl-or vinyl-silane can be copolymerized by using a late transition metal complex of a bidentate or tridentate ligand, however, the method needs to use expensive Modified Methylaluminoxane (MMAO) as a cocatalyst, and the polymerization is carried out under the higher ethylene polymerization pressure of 4.0-6.0 MPa, and the obtained polymer has low molecular weight and branching degree. Dalton reaction, 2015, 44(47):20745-20752 adopts pyridine diimine iron catalyst to catalyze the copolymerization of propylene and polar monomer containing silicon, the method still needs MMAO as cocatalyst, needs 30 ℃ or even lower temperature and 0 ℃ for polymerization reaction for 16 hours, has lower polymerization activity, and cannot carry out copolymerization reaction at higher temperature.
Disclosure of Invention
In order to solve the technical problems in the prior art, the invention provides a copolymerization method of ethylene and terminal alkenylsilane/siloxane, wherein a catalyst system in the method has higher polymerization activity, the molecular weight distribution of the obtained polymer is narrow, and the molecular weight and the branching degree of the polymer can be regulated and controlled in a wider range.
The invention provides a copolymerization method of ethylene and terminal alkenyl silane/siloxane, which comprises the following steps: copolymerizing ethylene and terminated alkenyl silane/siloxane in the presence of a catalyst composition, wherein the catalyst composition comprises a main catalyst, a cocatalyst and an optional chain transfer agent, and the main catalyst is selected from at least one of complexes shown in a formula (I):
in the formula (I), R1~R10The same or different, each independently selected from hydrogen, saturated or unsaturated alkyl, alkoxy or halogen; m is selected from group VIII metals and X is a halogen.
Compared with the conventional post-transition metal complex catalytic system adopting a bidentate or tridentate ligand, the catalyst composition adopted by the method has higher polymerization activity in the coordination copolymerization reaction of ethylene and terminal alkenyl silane/siloxane, can improve the content of a comonomer on a polymer molecular chain, can regulate and control the molecular weight and the branching degree of the polymer, and has wide industrial application prospect.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The invention provides a copolymerization method of ethylene and terminal alkenyl silane/siloxane, which comprises the following steps: copolymerizing ethylene with a terminal alkenylsilane/siloxane (comonomer) in the presence of a catalyst composition, wherein the catalyst composition comprises a procatalyst, a cocatalyst and optionally a chain transfer agent.
The procatalyst (i.e., single site catalyst) is selected from at least one of the complexes of formula (I):
in the formula (I), R1~R10The same or different, each independently selected from hydrogen, saturated or unsaturated alkyl, alkoxy or halogen; m is selected from group VIII metals and X is a halogen.
The halogen is F, Br, Cl or I.
Preferably, R1~R10Each independently selected from hydrogen and C1~C10A saturated or unsaturated hydrocarbon group of C1~C10Alkoxy or halogen of (a).
C1~C10The saturated or unsaturated hydrocarbon group of (1) specifically includes C1~C10Alkyl radical, C3~C10Cycloalkyl radical, C2~C10Alkenyl radical, C2~C10Alkynyl, C6~C10Aryl radical, C7~C10Aralkyl groups, and the like.
C1~C10Alkyl is 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.
C3~C10Examples of cycloalkyl groups may include, but are not limited to: cyclopropyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, 4-ethylcyclohexyl, 4-n-propylcyclohexyl and 4-n-butylcyclohexyl.
C6~C10Examples of aryl groups may include, but are not limited to: phenyl, 4-methylphenyl and 4-ethylphenyl.
C2~C10Examples of alkenyl groups may include, but are not limited to: vinyl and allyl.
C2~C10Examples of alkynyl groups may include, but are not limited to: ethynyl and propargyl.
C7~C10Examples of aralkyl groups may include, but are not limited to: phenylmethyl, phenylethyl, phenyl-n-propyl, phenyl-n-butyl, phenyl-t-butyl and phenyl-isopropyl.
C1~C10Non-limiting examples of alkoxy groups include: methoxy, ethoxy, propoxy, and the like.
More preferably, R1~R10Each independently selected from hydrogen and C1~C6Alkyl of (C)2~C6Alkenyl of, C1~C6Alkoxy or halogen of (a).
In the formula (I), M may be, for example, nickel, iron, cobalt, palladium, etc., and preferably nickel.
According to a preferred embodiment of the invention, the procatalyst is selected from at least one of the following complexes,
the complex 1: r1=R3=R4=R6=Me,R2=R5=H,X=Br;
And (2) the complex: r1=R3=R4=R6=Et,R2=R5=H,X=Br;
And (3) complex: r1=R3=R4=R6=iPr,R2=R5=H,X=Br;
The complex 4: r1=R2=R3=R4=R5=R6=Me,X=Br;
And (3) a complex 5: r1=R3=R4=R6=Me,R2=R5=Br,X=Br;
The complex 6: r1=R3=R4=R6=Me,R2=R5=Et,X=Br;
The complex 7: r1=R3=R4=R6=Et,R2=R5=Me,X=Br;
The complex 8: r1=R3=R4=R6=Et,R2=R5=Br,X=Br;
The complex 9: r1=R3=R4=R6=F,R2=R5=H,X=Br;
The complex 10: r1=R3=R4=R6=Cl,R2=R5=H,X=Br;
The complex 11: r1=R3=R4=R6=Br,R2=R5=H,X=Br;
The complex 12: r1=R3=R4=R6=Me,R2=R5=H,X=Cl;
The complex 13: r1=R3=R4=R6=Et,R2=R5=H,X=Cl;
The complex 14: r1=R3=R4=R6=iPr,R2=R5=H,X=Cl;
The complex 15: r1=R2=R3=R4=R5=R6=Me,X=Cl;
The compound 16: r1=R3=R4=R6=Me,R2=R5=Br,X=Cl;
The complex 17: r1=R3=R4=R6=Me,R2=R5=Et,X=Cl;
The complex 18: r1=R3=R4=R6=Et,R2=R5=Me,X=Cl;
The complex 19: r1=R3=R4=R6=Et,R2=R5=Br,X=Cl;
The complex 20: r1=R3=R4=R6=F,R2=R5=H,X=Cl;
The complex 21: r1=R3=R4=R6=Cl,R2=R5=H,X=Cl;
The complex 22: r1=R3=R4=R6=Br,R2=R5=H,X=Cl;
And in the complexes 1-22, R7~R10Are both hydrogen and M is nickel.
In the invention, the complex shown in the formula (I) can be prepared by the following method:
1) refluxing a compound A shown as a formula (I-I) and aniline or substituted aniline in a solvent under the action of a catalyst to prepare a diimine ligand compound shown as a formula (I-II):
2) reacting a diimine ligand compound of formula (I-II) with MX2Or MX2Carrying out coordination reaction on the derivative to obtain a complex shown as a formula (I);
wherein, to R1~R10And M, X are the same as above and will not be described further herein.
In step 1), the catalyst may be at least one selected from the group consisting of p-toluenesulfonic acid, acetic acid and formic acid. The solvent may be selected from at least one of toluene, methanol, ethanol and acetonitrile. The molar ratio of the compound A to aniline or substituted aniline is 1: 2 to 1: 10, preferably 1: 2 to 1: 3. The reflux temperature is 40-120 ℃, and preferably 65-110 ℃; the refluxing time is 0.5-7 days, preferably 1-2 days. Preferably, the amount of the catalyst is 0.01-20 mol% of the amount of the compound A.
The substituents on said substituted anilines are as defined for R1~R10However, R1~R10Not both being hydrogen, for example, the substituted aniline may be one or more of 2, 6-methylaniline, 2, 6-diethylaniline, 2, 6-diisopropylaniline, 2, 6-dimethyl-4-bromo-aniline and 2, 6-difluoroaniline.
In step 2), the diimine ligand compound is reacted with MX2Or MX2The molar ratio of the derivative (such as nickel halide or nickel halide derivative) may be 1: 1 to 1: 1.2. The nickel halide or nickel halide derivative may be selected from NiBr2、NiCl2、(DME)NiBr2Or (DME) NiCl2Wherein DME is an abbreviation for dimethyl ether. The temperature of the coordination reaction can be 0-60 ℃, and the reaction time is 0.5-12 h. The coordination reaction is carried out in an anhydrous and oxygen-free atmosphere, for example, under an inert atmosphere (usually nitrogen).
According to a particular embodiment, the synthesis of the complex may comprise the steps of:
a) refluxing compound A and substituted aniline in ethanol with acetic acid as catalyst for 1 day, filtering, removing solvent, dissolving the residue with dichloromethane, passing through alkaline alumina column, eluting with petroleum ether/ethyl acetate (20: 1), collecting the second eluate, and removing solvent to obtain yellow solid; or
b) Refluxing compound A and substituted aniline in toluene with p-toluenesulfonic acid as catalyst for 1 day, evaporating reaction solution to dryness, dissolving residue with dichloromethane, passing through alkaline alumina column, eluting with petroleum ether/ethyl acetate (20: 1), collecting second stream, and removing solvent to obtain yellow solid;
the yellow solid is determined as the diimine ligand compound through nuclear magnetism, infrared and element analysis characterization;
c) under the protection of inert gas, (DME) NiCl2Or (DME) NiBr2The dichloromethane solution is added dropwise to the solution of the diimine ligand compound at a molar ratio of 1: 1 to 1: 1.2, and the mixture is stirred at room temperatureAnd separating out a precipitate, filtering, washing with diethyl ether, drying in vacuum, and determining the obtained product as the complex shown in the formula (I) by elemental analysis and infrared characterization.
In addition, the complexes related to the following examples are prepared by using corresponding raw materials according to the synthesis method, and the details are not repeated.
In the present invention, the cocatalyst may be a conventional choice in coordination polymerization of olefins. Preferably, the cocatalyst is selected from at least one of alkylaluminoxane, arylboronium and borate.
The alkylaluminoxane is for example selected from Methylaluminoxane (MAO) and/or Modified Methylaluminoxane (MMAO).
More preferably, the cocatalyst is methylaluminoxane, so that the catalyst composition has higher copolymerization activity and the raw material cost can be reduced.
The aralkyl boron is substituted or unsubstituted phenyl boron, preferably, trifluorophenyl boron.
The borate is preferably N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate and/or triphenylmethyl tetrakis (pentafluorophenyl) borate.
In the catalyst composition, the molar ratio of aluminum in the cocatalyst to M (such as nickel) in the main catalyst may be (10-100000): 1, preferably (10-10000): 1, and more preferably (100-5000): 1; or the molar ratio of boron in the cocatalyst to M in the main catalyst can be (0.01-1000): 1, preferably (0.1-100): 1.
According to the invention, the selection and the addition amount of the chain transfer agent can control the molecular weight of the obtained polymer, and the molecular weight of the polymer can be regulated and controlled in a wide range. In the present invention, the type of the chain transfer agent is not particularly limited, and may be selected according to the type of the transition metal M.
According to one embodiment, the chain transfer agent is selected from trialkylaluminums and/or dialkylzinc.
Preferably, the chain transfer agent is selected from at least one of trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, dimethylzinc, and diethylzinc.
In this embodiment, the molar ratio of aluminum in the chain transfer agent to M in the main catalyst may be (1 to 10000): 1, preferably (1 to 1000): 1; or the molar ratio of zinc in the chain transfer agent to M in the main catalyst is (1-1000): 1.
The copolymerization process of the present invention can be carried out in the following manner: contacting the catalyst composition with ethylene, a terminal alkenylsilane/siloxane, in the presence of an organic solvent, under anhydrous and oxygen-free conditions. The main catalyst, the cocatalyst and other catalyst components can be added into the reactor respectively, or all the components can be added into the reactor after being mixed in advance, and the adding sequence or the mixing condition is not particularly limited.
The organic solvent may be selected from C3~C20Specific examples thereof include butane, isobutane, pentane, hexane, heptane, octane, cyclohexane, toluene, xylene, etc. Preferably, the organic solvent is toluene and/or hexane.
In the present invention, "terminal alkenyl" includes vinyl groups, α -alkenyl groups, and the double bond of the group is located at one end of the molecular chain.
Specifically, the terminal alkenylsilane is selected from at least one of compounds shown in a formula (II):
wherein m and n are 0 or positive integers, and are preferably integers of 0-20.
Non-limiting examples of the terminal alkenylsilanes include: vinyltrimethylsilane, vinyltriethylsilane, allyltriethylsilane, allyltri-n-butylsilane, 7-octenyltrimethylsilane, and the like.
The terminal alkenyl siloxane is selected from at least one of the compounds shown in the formula (III):
wherein p and q are each 0 or a positive integer, and each is preferably an integer of 0 to 20.
Non-limiting examples of the terminal alkenylsiloxanes include: vinyltrimethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, 7-octenyltrimethoxysilane and the like.
According to the copolymerization method of the invention, the dosage of the terminal alkenyl silane/siloxane is 0.01-3000 mmol/L, preferably 0.1-1000 mmol/L, and more preferably 1-500 mmol/L.
According to the invention, the amount of the main catalyst can be 0.00001-10 mmol/L, preferably 0.0001-1 mmol/L, and more preferably 0.001-0.5 mmol/L.
In the present invention, "mmol/L" means the concentration of the material in the reactor.
According to the invention, the temperature of the copolymerization reaction can be selected within a wide range, for example from-20 ℃ to 200 ℃, preferably from 40 ℃ to 120 ℃, more preferably from 60 ℃ to 110 ℃.
The pressure of the copolymerization reaction in the present invention is not particularly limited as long as the monomer can be subjected to coordination copolymerization. From the viewpoint of cost reduction and simplification of the polymerization process, the pressure of ethylene in the reactor is preferably 1 to 1000atm, more preferably 1 to 200atm, and still more preferably 1 to 50 atm.
The catalyst composition in the method can catalyze the monomer to carry out copolymerization reaction with high activity, so that the reaction can be completed in a short time, and the time of the copolymerization reaction can be 10-120 min, preferably 20-50 min.
In addition, after the time for the copolymerization reaction is reached, the method of the invention further comprises terminating the reaction by using a terminating agent, wherein the terminating agent can be a compound containing active hydrogen, such as water, alcohol, acid, amine and the like which are conventionally selected for coordination polymerization. In one embodiment, the terminator may be a 5-20 vol% acidified methanol or ethanol solution of hydrochloric acid, i.e., alcohol/concentrated hydrochloric acid (95/5-80/20 (vol/vol)).
The complex adopted by the method can be combined with a cocatalyst to realize the copolymerization reaction of ethylene and terminal alkenyl silane/siloxane under lower pressure, and the catalyst composition can still maintain higher catalytic activity even at high temperature (for example, above 90 ℃), namely, comonomer is successfully introduced into a polymer molecular chain; the method can realize the regulation and control of the molecular weight and the branching degree of the polymer, and the molecular weight distribution of the polymer is narrow, so that the method can be used for preparing the copolymer of ethylene and terminal alkenyl silane/siloxane with different physical properties.
The present invention will be described in detail with reference to examples, but the present invention is not limited to these examples.
In the following examples and comparative examples,
analyzing the relative content of Si element in the polymer by adopting X-ray fluorescence spectrum of PANALYTICAL company Axios-Advanced type, wherein the higher the content of Si is, the higher the content of comonomer is;
the methyl content of the polymer was tested using 13C NMR spectroscopy: on a 400MHz Bruker Avance 400 nuclear magnetic resonance spectrometer, a 10mm PASEX 13 probe is utilized, a polymer sample is dissolved by 1,2, 4-trichlorobenzene at 120 ℃ for analysis and test, wherein the higher the methyl content is, the higher the branching degree of the polymer is;
the molecular weight and molecular weight distribution of the polymer, PDI (PDI. Mw/Mn), were determined by P L-GPC 220 using trichlorobenzene as solvent at 150 deg.C (standard: PS, flow rate: 1.0M L/min, column: 3 × Plgel 10um M1 × ED-B300 × 7.5.5 nm).
Example 1
The mechanically stirred 1L stainless steel polymerization vessel was dried continuously at 130 ℃ for 6hrs, evacuated while hot and charged with N2Gas substitution 3 times, addition of 11.9mg (10. mu. mol) of complex 3, followed by vacuum and ethylene substitution 3 times, injection of 500m L of toluene, addition of 6.5m L of Methylaluminoxane (MAO) (1.53 mol/L in toluene), Al/Ni 1000, 5m L of allyltrimethoxysilane (28.7mmol), maintenance of 10atm of ethylene pressure at 70 ℃, stirring for 30min, and final neutralization with 5 vol% acidified ethanol solution of hydrochloric acid to give the polymer, polymerization activity and polymer performance parameters are shown in Table 1.
Example 2
The mechanically stirred 1L stainless steel polymerization vessel was dried continuously at 130 ℃ for 6hrs, evacuated while hot and charged with N2Gas substitution 3 times, addition of 11.9mg (10. mu. mol) of complex 3, followed by vacuum and ethylene substitution 3 times, injection of 500m L of toluene, addition of 6.5m L of Methylaluminoxane (MAO) (1.53 mol/L in toluene), Al/Ni 1000, 5m L of allyltrimethoxysilane (28.7mmol), maintenance of 10atm of ethylene pressure at 100 ℃, stirring for 30min, and final neutralization with 5 vol% acidified ethanol solution of hydrochloric acid to give the polymer, polymerization activity and polymer performance parameters are shown in Table 1.
Example 3
The mechanically stirred 1L stainless steel polymerization vessel was dried continuously at 130 ℃ for 6hrs, evacuated while hot and charged with N2Gas substitution 3 times, addition of 11.9mg (10. mu. mol) of complex 3, followed by vacuum and ethylene substitution 3 times, injection of 500m L of toluene, addition of 6.5m L of Methylaluminoxane (MAO) (1.53 mol/L in toluene), Al/Ni 1000, 10m L of allyltrimethoxysilane (57.4mmol), maintenance of 10atm of ethylene pressure at 70 ℃, stirring for 30min, and final neutralization with 5 vol% acidified ethanol solution of hydrochloric acid to give the polymer, polymerization activity and polymer performance parameters are shown in Table 1.
Example 4
The mechanically stirred 1L stainless steel polymerization vessel was dried continuously at 130 ℃ for 6hrs, evacuated while hot and charged with N2Gas substitution 3 times, addition of 11.9mg (10. mu. mol) of complex 3, followed by further vacuum and ethylene substitution 3 times, injection of 500m L of toluene, addition of 6.5m L of Methylaluminoxane (MAO) (1.53 mol/L in toluene), Al/Ni 1000, addition of 0.2m L of diethylzinc (1 mol/L in hexane), Zn/Ni 20, 5m L of allyltrimethoxysilane (28.7mmol), maintenance of 10atm of ethylene pressure at 70 ℃ and stirring for 30 min.
Example 5
A1L stainless steel polymerizer equipped with mechanical agitation was continuously operated at 130 ℃Drying for 6hrs, vacuum-pumping while hot and applying N2Gas substitution 3 times, addition of 11.9mg (10. mu. mol) of complex 3, followed by further vacuum and ethylene substitution 3 times, injection of 500m L of toluene, addition of 6.5m L of Methylaluminoxane (MAO) (1.53 mol/L in toluene), Al/Ni 1000, addition of 0.5m L of diethylzinc (1 mol/L in hexane), Zn/Ni 50, 5m L of allyltrimethoxysilane (28.7mmol), maintenance of 10atm of ethylene pressure at 70 ℃ and stirring for 30 min.
Example 6
The mechanically stirred 1L stainless steel polymerization vessel was dried continuously at 130 ℃ for 6hrs, evacuated while hot and charged with N2Gas substitution 3 times, addition of 11.3mg (10. mu. mol) of complex 2, followed by vacuum and ethylene substitution 3 times, injection of 500m L of toluene, addition of 6.5m L of Methylaluminoxane (MAO) (1.53 mol/L in toluene), Al/Ni 1000, 5m L of allyltrimethoxysilane (28.7mmol), maintenance of 10atm of ethylene pressure at 70 ℃, stirring for 30min, and final neutralization with 5 vol% acidified ethanol solution of hydrochloric acid to give the polymer, polymerization activity and performance parameters of the polymer are shown in Table 1.
Example 7
The mechanically stirred 1L stainless steel polymerization vessel was dried continuously at 130 ℃ for 6hrs, evacuated while hot and charged with N2Gas substitution 3 times, addition of 11.3mg (10. mu. mol) of complex 2, followed by further vacuum and ethylene substitution 3 times, injection of 500m L of toluene, addition of 6.5m L of Methylaluminoxane (MAO) (1.53 mol/L in toluene), Al/Ni 1000, addition of 0.5m L of diethylzinc (1 mol/L in hexane), Zn/Ni 50, 5m L of allyltrimethoxysilane (28.7mmol), maintenance of 10atm of ethylene pressure at 70 ℃ and stirring for 30 min.
Example 8
The mechanically stirred 1L stainless steel polymerization vessel was dried continuously at 130 ℃ for 6hrs, evacuated while hot and charged with N2Pneumatic deviceChanging 3 times, adding 10.7mg (10. mu. mol) of complex 1, then evacuating and replacing 3 times with ethylene, injecting 500m L of toluene, adding 6.5m L of Methylaluminoxane (MAO) (1.53 mol/L in toluene), making Al/Ni 1000, 5m L of allyltrimethoxysilane (28.7mmol), maintaining 10atm of ethylene pressure at 70 ℃, stirring for 30min, finally neutralizing with 5 vol% of hydrochloric acid acidified ethanol solution, obtaining the polymer, polymerization activity and performance parameters of the polymer are shown in Table 1.
Example 9
The mechanically stirred 1L stainless steel polymerization vessel was dried continuously at 130 ℃ for 6hrs, evacuated while hot and charged with N2Gas substitution 3 times, addition of 12.8mg (10. mu. mol) of complex 8, followed by vacuum and ethylene substitution 3 times, injection of 500m L of toluene, addition of 6.5m L of Methylaluminoxane (MAO) (1.53 mol/L in toluene), Al/Ni 1000, 5m L of allyltrimethoxysilane (28.7mmol), maintenance of 10atm of ethylene pressure at 70 ℃, stirring for 30min, and final neutralization with 5 vol% acidified ethanol solution of hydrochloric acid to give the polymer, polymerization activity and performance parameters of the polymer are shown in Table 1.
Example 10
The mechanically stirred 1L stainless steel polymerization vessel was dried continuously at 130 ℃ for 6hrs, evacuated while hot and charged with N2Gas substitution 3 times, addition of 11.0mg (10. mu. mol) of complex 14, followed by vacuum and ethylene substitution 3 times, injection of 500m L of toluene, addition of 6.5m L of Methylaluminoxane (MAO) (1.53 mol/L in toluene), Al/Ni 1000, 5m L of allyltrimethoxysilane (28.7mmol), maintenance of 10atm of ethylene pressure at 70 ℃, stirring for 30min, and final neutralization with 5 vol% acidified ethanol solution of hydrochloric acid to give the polymer, polymerization activity and performance parameters of the polymer are shown in Table 1.
Example 11
The mechanically stirred 1L stainless steel polymerization vessel was dried continuously at 130 ℃ for 6hrs, evacuated while hot and charged with N2Air-substituted 3 times, 11.9mg (10. mu. mol) of complex 3 are added, which is then again evacuated and substituted 3 times with ethylene, 500m L of toluene are injected and 6.5m L of Methylaluminoxane (MAO) (1.53 mol/L in toluene) are added to the solution and Al is/is presentNi 1000, 5m L7-octenyltrimethoxysilane (17.8mmol), ethylene pressure of 10atm was maintained at 70 ℃, and the reaction was stirred for 30 min.
Example 12
The mechanically stirred 1L stainless steel polymerization vessel was dried continuously at 130 ℃ for 6hrs, evacuated while hot and charged with N2Gas substitution 3 times, addition of 11.9mg (10. mu. mol) of complex 3, followed by further vacuum and ethylene substitution 3 times, injection of 500m L of toluene, addition of 6.5m L of Methylaluminoxane (MAO) (1.53 mol/L in toluene), Al/Ni 1000, addition of 0.2m L of diethylzinc (1 mol/L in hexane), Zn/Ni 20, 5m L7-octenyltrimethoxysilane (17.8mmol), maintenance of 10atm of ethylene pressure at 70 ℃ and stirring for 30 min.
Example 13
The mechanically stirred 1L stainless steel polymerization vessel was dried continuously at 130 ℃ for 6hrs, evacuated while hot and charged with N2Gas substitution 3 times, addition of 11.9mg (10. mu. mol) of complex 3, followed by further vacuum and ethylene substitution 3 times, injection of 500m L of toluene, addition of 6.5m L of Methylaluminoxane (MAO) (1.53 mol/L in toluene), Al/Ni 1000, addition of 0.5m L of diethylzinc (1 mol/L in hexane), Zn/Ni 50, 5m L7-octenyltrimethoxysilane (17.8mmol), maintenance of 10atm of ethylene pressure at 70 ℃ and stirring for 30 min.
Example 14
The mechanically stirred 1L stainless steel polymerization vessel was dried continuously at 130 ℃ for 6hrs, evacuated while hot and charged with N23 times replacement by gas, addition of 11.9mg (10. mu. mol) of complex 3, subsequent evacuation and replacement by ethylene 3 times, injection of 500m of toluene L and addition of 6.5m of L Methylaluminoxane (MAO) (1.53 mol/L in toluene) to convert Al/Ni to 1000, 5m of L vinyltrimethoxysilane(31.6 mmol). The reaction was carried out at 70 ℃ under an ethylene pressure of 10atm with stirring for 30 min. Finally, the polymer was obtained by neutralization with 5 vol% ethanol acidified with hydrochloric acid. The polymerization activity and the polymer performance parameters are shown in Table 1.
Example 15
The mechanically stirred 1L stainless steel polymerization vessel was dried continuously at 130 ℃ for 6hrs, evacuated while hot and charged with N2Gas substitution 3 times, addition of 11.9mg (10. mu. mol) of complex 3, followed by vacuum and ethylene substitution 3 times, injection of 500m L of toluene, addition of 6.5m L of Methylaluminoxane (MAO) (1.53 mol/L in toluene), Al/Ni 1000, 5m L of allyltrimethylsilane (22.1mmol), maintenance of 10atm of ethylene pressure at 70 ℃, stirring for 30min, and finally neutralization with 5 vol% of acidified ethanol solution of hydrochloric acid to give the polymer, polymerization activity and performance parameters of the polymer are shown in Table 1.
Example 16
The mechanically stirred 1L stainless steel polymerization vessel was dried continuously at 130 ℃ for 6hrs, evacuated while hot and charged with N2Gas substitution 3 times, addition of 11.9mg (10. mu. mol) of complex 3, followed by further vacuum and ethylene substitution 3 times, injection of 500m L of toluene, addition of 6.5m L of Methylaluminoxane (MAO) (1.53 mol/L in toluene), setting Al/Ni to 1000, addition of 0.5m L of diethylzinc (1 mol/L in hexane), setting Zn/Ni to 50, 5m L of allyltrimethylsilane (22.1mmol), maintenance of 10atm of ethylene pressure at 70 ℃ and stirring for 30 min.
Example 17
The mechanically stirred 1L stainless steel polymerization vessel was dried continuously at 130 ℃ for 6hrs, evacuated while hot and charged with N23 times replacement by gas, addition of 11.9mg (10. mu. mol) of complex 3, subsequent evacuation and replacement by ethylene 3 times, injection of 500m L of toluene, addition of 6.5m L of Methylaluminoxane (MAO) (1.53 mol/L in toluene), setting Al/Ni to 1000, 5m L of allyltrimethoxysilane (28.7mmol), maintenance of 10atm of ethylene pressure at 40 ℃ and stirring for 30min, finally acidification with 5% by volume of hydrochloric acid in ethanolAnd neutralizing to obtain the polymer. The polymerization activity and the polymer performance parameters are shown in Table 1.
Example 18
The mechanically stirred 1L stainless steel polymerization vessel was dried continuously at 130 ℃ for 6hrs, evacuated while hot and charged with N2Gas substitution 3 times, addition of 11.9mg (10. mu. mol) of complex 3, followed by vacuum and ethylene substitution 3 times, injection of 500m L of toluene, addition of 6.5m L of Methylaluminoxane (MAO) (1.53 mol/L in toluene), Al/Ni 1000, 5m L of allyltrimethoxysilane (28.7mmol), maintenance of 10atm of ethylene pressure at 120 ℃, stirring for 30min, and final neutralization with 5 vol% acidified ethanol solution of hydrochloric acid to give the polymer, polymerization activity and polymer performance parameters are shown in Table 1.
Example 19
The mechanically stirred 1L stainless steel polymerization vessel was dried continuously at 130 ℃ for 6hrs, evacuated while hot and charged with N23 times by gas displacement, addition of 11.9mg (10. mu. mol) of complex 3, subsequent evacuation and 3 times by ethylene displacement, injection of 500m of L toluene, addition of 5m of L N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate in toluene (2 mmol/L in toluene), Ni/B ═ 1, 5m of L allyltrimethoxysilane (28.7mmol), maintenance of 10atm of ethylene pressure at 70 ℃ and stirring for 30min, and finally termination of the reaction with 5% by volume of hydrochloric acid in ethanol, the polymerization activity and the performance parameters of the polymer being shown in Table 1.
Comparative example 1
The mechanically stirred 1L stainless steel polymerization vessel was dried continuously at 130 ℃ for 6hrs, evacuated while hot and charged with N2The gas exchange was carried out 3 times, 6.6mg (10. mu. mol) of comparative catalyst A (complex A, structure formula (IV)) was added, followed by evacuation and 3 times replacement with ethylene, 500m L of toluene was injected, 6.5m L of Methylaluminoxane (MAO) (1.53 mol/L of toluene solution) was added to make Al/Ni 1000, 5m L of allyltrimethoxysilane (28.7mmol), ethylene pressure of 10atm was maintained at 70 ℃, the reaction was stirred for 30min, and finally neutralized with 5 vol% of ethanol acidified with hydrochloric acid, and only a small amount of polymer was formed, polymerization activity and polymer properties were as shown in Table 1.
Comparative example 2
The mechanically stirred 1L stainless steel polymerization vessel was dried continuously at 130 ℃ for 6hrs, evacuated while hot and charged with N2The gas exchange was carried out 3 times, 6.6mg (10. mu. mol) of comparative catalyst A was added, followed by further vacuum evacuation and 3 times replacement with ethylene, 500m L of toluene was injected, 6.5m L of Methylaluminoxane (MAO) (1.53 mol/L in toluene) was added to make Al/Ni 1000, 5m L of vinyltrimethoxysilane (28.7mmol), ethylene pressure was maintained at 70 ℃ at 10atm, the reaction was stirred for 30min, and finally neutralized with 5 vol% hydrochloric acid acidified ethanol solution, no polymer was formed.
Comparative example 3
The mechanically stirred 1L stainless steel polymerization vessel was dried continuously at 130 ℃ for 6hrs, evacuated while hot and charged with N2Air replacement 3 times, addition of 6.3mg (10. mu. mol) of comparative catalyst B (complex B, structure shown in formula (V)), followed by evacuation and replacement with ethylene 3 times, injection of 500m L toluene, addition of 6.5m L Methylaluminoxane (MAO) (1.53 mol/L in toluene) to make Al/Ni 1000, 5m L allyltrimethoxysilane (28.7mmol), maintenance of 10atm of ethylene pressure at 70 ℃, stirring for 30min, and final neutralization with 5 vol% HCl-acidified ethanol solution, no polymer formation.
Comparative example 4
The mechanically stirred 1L stainless steel polymerization vessel was dried continuously at 130 ℃ for 6hrs, evacuated while hot and charged with N2The reaction was carried out by gas displacement 3 times, addition of 6.0mg (10. mu. mol) of comparative catalyst C (complex C, structure formula (VI)), further evacuation and displacement with ethylene 3 times, injection of 500m L toluene, addition of 6.5m L Methylaluminoxane (MAO) (1.53 mol/L in toluene) to make Al/Ni 1000, 5m L allyltrimethoxysilane (28.7mmol), maintenance of 10atm of ethylene pressure at 70 ℃ and stirring for 30 min.Finally, the solution was neutralized with 5 vol% hydrochloric acid acidified ethanol solution, and no polymer was formed.
TABLE 1
As can be seen from Table 1, the catalyst compositions of the examples have a copolymerization activity of up to 14.30 × 106g·mol-1(Ni)·h-1. Compared with the complexes of comparative examples 1 to 4, the complexes adopted in examples 1 to 19 have significantly improved copolymerization activity when used as a main catalyst, the obtained polymer has a molecular weight significantly higher than that of the comparative example, the contents of the comonomer and methyl are also significantly improved, the molecular weight distribution of the polymer is lower than that of the comparative example, and the branching degree and the molecular weight of the polymer can be regulated and controlled in a wider range.
Having described embodiments of the present invention, the foregoing description is intended to be exemplary, not exhaustive, and not limited to the disclosed embodiments. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the illustrated embodiments.
Claims (18)
1. A method of copolymerizing ethylene with a terminal alkenylsilane/siloxane, the method comprising: copolymerizing ethylene and a terminal alkenylsilane/siloxane in the presence of a catalyst composition, wherein the catalyst composition comprises a main catalyst, a cocatalyst and optionally a chain transfer agent, wherein the main catalyst is at least one selected from complexes represented by the formula (I):
in the formula (I), R1~R10Are the same or different, wherein R2、R5And R7~R10Each independently selected from hydrogen, saturated or unsaturated hydrocarbyl, hydrocarbyloxy or halogen; r1、R3、R4And R6Each independently selected from saturated or unsaturated hydrocarbyl, hydrocarbyloxy or halogen; m is nickel and X is halogen.
2. The copolymerization process according to claim 1, wherein in the formula (I), R is2、R5And R7~R10Each independently selected from hydrogen and C1~C10A saturated or unsaturated hydrocarbon group of C1~C10Alkoxy or halogen of (a); r1、R3、R4And R6Each independently selected from C1~C10A saturated or unsaturated hydrocarbon group of C1~C10Alkoxy or halogen of (a).
3. The copolymerization process according to claim 2, wherein R2、R5And R7~R10Each independently selected from hydrogen and C1~C6Alkyl of (C)2~C6Alkenyl of, C1~C6Alkoxy or halogen of (a); r1、R3、R4And R6Each independently selected from C1~C6Alkyl of (C)2~C6Alkenyl of, C1~C6Alkoxy or halogen of (a).
4. The copolymerization process according to claim 1, wherein the procatalyst is selected from at least one of the following complexes,
the complex 1: r1=R3=R4=R6=Me,R2=R5=H,X=Br;
And (2) the complex: r1=R3=R4=R6=Et,R2=R5=H,X=Br;
And (3) complex: r1=R3=R4=R6=iPr,R2=R5=H,X=Br;
The complex 4: r1=R2=R3=R4=R5=R6=Me,X=Br;
And (3) a complex 5: r1=R3=R4=R6=Me,R2=R5=Br,X=Br;
The complex 6: r1=R3=R4=R6=Me,R2=R5=Et,X=Br;
The complex 7: r1=R3=R4=R6=Et,R2=R5=Me,X=Br;
The complex 8: r1=R3=R4=R6=Et,R2=R5=Br,X=Br;
The complex 9: r1=R3=R4=R6=F,R2=R5=H,X=Br;
The complex 10: r1=R3=R4=R6=Cl,R2=R5=H,X=Br;
The complex 11: r1=R3=R4=R6=Br,R2=R5=H,X=Br;
The complex 12: r1=R3=R4=R6=Me,R2=R5=H,X=Cl;
The complex 13: r1=R3=R4=R6=Et,R2=R5=H,X=Cl;
The complex 14: r1=R3=R4=R6=iPr,R2=R5=H,X=Cl;
The complex 15: r1=R2=R3=R4=R5=R6=Me,X=Cl;
The compound 16: r1=R3=R4=R6=Me,R2=R5=Br,X=Cl;
The complex 17: r1=R3=R4=R6=Me,R2=R5=Et,X=Cl;
The complex 18: r1=R3=R4=R6=Et,R2=R5=Me,X=Cl;
The complex 19: r1=R3=R4=R6=Et,R2=R5=Br,X=Cl;
The complex 20: r1=R3=R4=R6=F,R2=R5=H,X=Cl;
The complex 21: r1=R3=R4=R6=Cl,R2=R5=H,X=Cl;
The complex 22: r1=R3=R4=R6=Br,R2=R5=H,X=Cl;
And in the complexes 1-22, R7~R10Are both hydrogen and M is nickel.
5. The copolymerization process of claim 1, wherein the cocatalyst is selected from at least one of alkylaluminoxanes, arylborohydrides and borates.
6. The copolymerization process according to claim 1, wherein the chain transfer agent is selected from trialkylaluminums and/or dialkylzinc.
7. The copolymerization method of claim 5, wherein the molar ratio of aluminum in the cocatalyst to M in the main catalyst is (10-100000): 1; or the molar ratio of boron in the cocatalyst to M in the main catalyst is (0.01-1000): 1.
8. The copolymerization method of claim 6, wherein the molar ratio of aluminum in the chain transfer agent to M in the main catalyst is (1-10000): 1; or the molar ratio of zinc in the chain transfer agent to M in the main catalyst is (1-1000): 1.
9. The copolymerization process according to claim 1, wherein the terminal alkenylsilane is selected from at least one compound of formula (II) and the terminal alkenylsiloxane is selected from at least one compound of formula (III):
in the formula (II), m and n are respectively 0 or a positive integer;
in the formula (III), p and q are each 0 or a positive integer.
10. The copolymerization process according to claim 9, wherein in the formula (II), m and n are each an integer of 0 to 20;
in the formula (III), p and q are each an integer of 0 to 20.
11. The copolymerization process according to claim 1, wherein the temperature of the copolymerization reaction is from-20 ℃ to 200 ℃;
the pressure of ethylene is 1 to 1000 atm.
12. The copolymerization process according to claim 11, wherein the temperature of the copolymerization reaction is 40 to 120 ℃.
13. The copolymerization process according to claim 12, wherein the temperature of the copolymerization reaction is 60 to 110 ℃.
14. The copolymerization process according to claim 11, wherein the pressure of ethylene is 1 to 200 atm.
15. The copolymerization process according to claim 1, 9, 10, 11, 12, 13 or 14, wherein the terminal alkenylsilane/siloxane is used in an amount of 0.01 to 3000 mmol/L.
16. The copolymerization process according to claim 15, wherein the terminal alkenylsilane/siloxane is used in an amount of 0.1 to 1000 mmol/L.
17. The copolymerization method according to claim 1, wherein the amount of the main catalyst is 0.00001 to 100 mmol/L.
18. The copolymerization process according to claim 17, wherein the amount of the procatalyst used is from 0.001 to 1 mmol/L.
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