CN113754813A - Preparation method of olefin-olefin alcohol copolymer - Google Patents
Preparation method of olefin-olefin alcohol copolymer Download PDFInfo
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- CN113754813A CN113754813A CN202010506189.7A CN202010506189A CN113754813A CN 113754813 A CN113754813 A CN 113754813A CN 202010506189 A CN202010506189 A CN 202010506189A CN 113754813 A CN113754813 A CN 113754813A
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- China
- Prior art keywords
- substituent
- alkyl
- olefin
- alkoxy
- halogen
- Prior art date
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- 229920001577 copolymer Polymers 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title abstract description 12
- -1 diimine metal complex Chemical class 0.000 claims abstract description 46
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 31
- 150000001336 alkenes Chemical class 0.000 claims abstract description 27
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000003054 catalyst Substances 0.000 claims abstract description 13
- 239000003607 modifier Substances 0.000 claims abstract description 8
- 229910000071 diazene Inorganic materials 0.000 claims abstract description 5
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 3
- 125000001424 substituent group Chemical group 0.000 claims description 109
- 229910052736 halogen Inorganic materials 0.000 claims description 37
- 150000002367 halogens Chemical class 0.000 claims description 37
- 238000000034 method Methods 0.000 claims description 21
- 238000006116 polymerization reaction Methods 0.000 claims description 21
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 20
- 239000005977 Ethylene Substances 0.000 claims description 20
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 20
- 125000003118 aryl group Chemical group 0.000 claims description 18
- 229910052739 hydrogen Inorganic materials 0.000 claims description 16
- 125000002947 alkylene group Chemical group 0.000 claims description 15
- 125000000027 (C1-C10) alkoxy group Chemical group 0.000 claims description 14
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims description 14
- 150000001875 compounds Chemical class 0.000 claims description 14
- 239000001257 hydrogen Substances 0.000 claims description 14
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims description 12
- 125000004191 (C1-C6) alkoxy group Chemical group 0.000 claims description 11
- 125000000217 alkyl group Chemical group 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 10
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 7
- 229920000098 polyolefin Polymers 0.000 claims description 7
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 claims description 6
- 125000006736 (C6-C20) aryl group Chemical group 0.000 claims description 6
- 125000003860 C1-C20 alkoxy group Chemical group 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- 150000008282 halocarbons Chemical class 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 125000003358 C2-C20 alkenyl group Chemical group 0.000 claims description 5
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 5
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 5
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 125000005865 C2-C10alkynyl group Chemical group 0.000 claims description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical group [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 4
- 125000003302 alkenyloxy group Chemical group 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 125000005133 alkynyloxy group Chemical group 0.000 claims description 4
- 229910052796 boron Inorganic materials 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 125000000000 cycloalkoxy group Chemical group 0.000 claims description 4
- 239000004711 α-olefin Substances 0.000 claims description 4
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 3
- 125000006374 C2-C10 alkenyl group Chemical group 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 2
- 125000005234 alkyl aluminium group Chemical group 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 150000002899 organoaluminium compounds Chemical group 0.000 claims description 2
- 229910052763 palladium Chemical group 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 6
- 150000001298 alcohols Chemical class 0.000 claims 1
- 229920000642 polymer Polymers 0.000 abstract description 27
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 48
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 21
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 18
- 239000000243 solution Substances 0.000 description 17
- 150000003254 radicals Chemical class 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 14
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 12
- 239000000203 mixture Substances 0.000 description 10
- 238000007334 copolymerization reaction Methods 0.000 description 9
- 239000000178 monomer Substances 0.000 description 8
- 230000037048 polymerization activity Effects 0.000 description 8
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 8
- XSNQECSCDATQEL-UHFFFAOYSA-N dihydromyrcenol Chemical compound C=CC(C)CCCC(C)(C)O XSNQECSCDATQEL-UHFFFAOYSA-N 0.000 description 7
- 229930008394 dihydromyrcenol Natural products 0.000 description 7
- 150000002431 hydrogen Chemical class 0.000 description 7
- 230000003472 neutralizing effect Effects 0.000 description 7
- 229910001220 stainless steel Inorganic materials 0.000 description 7
- 239000010935 stainless steel Substances 0.000 description 7
- 238000001035 drying Methods 0.000 description 6
- 238000010907 mechanical stirring Methods 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- UYOPRNGQFQWYER-UHFFFAOYSA-N 2-methylpent-4-en-2-ol Chemical compound CC(C)(O)CC=C UYOPRNGQFQWYER-UHFFFAOYSA-N 0.000 description 4
- HNVRRHSXBLFLIG-UHFFFAOYSA-N 3-hydroxy-3-methylbut-1-ene Chemical compound CC(C)(O)C=C HNVRRHSXBLFLIG-UHFFFAOYSA-N 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 4
- 229920000573 polyethylene Polymers 0.000 description 4
- PBKONEOXTCPAFI-UHFFFAOYSA-N 1,2,4-trichlorobenzene Chemical compound ClC1=CC=C(Cl)C(Cl)=C1 PBKONEOXTCPAFI-UHFFFAOYSA-N 0.000 description 3
- SRPFYGUVQUDURC-UHFFFAOYSA-N 3-hydroxydihydromyrcenol Natural products CC(C)(O)CCCC(C)(O)C=C SRPFYGUVQUDURC-UHFFFAOYSA-N 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 150000002085 enols Chemical class 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 239000004715 ethylene vinyl alcohol Substances 0.000 description 3
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- LWNGJAHMBMVCJR-UHFFFAOYSA-N (2,3,4,5,6-pentafluorophenoxy)boronic acid Chemical compound OB(O)OC1=C(F)C(F)=C(F)C(F)=C1F LWNGJAHMBMVCJR-UHFFFAOYSA-N 0.000 description 2
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- UBOXGVDOUJQMTN-UHFFFAOYSA-N 1,1,2-trichloroethane Chemical compound ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 2
- BZAZNULYLRVMSW-UHFFFAOYSA-N 2-Methyl-2-buten-3-ol Natural products CC(C)=C(C)O BZAZNULYLRVMSW-UHFFFAOYSA-N 0.000 description 2
- NVGOATMUHKIQQG-UHFFFAOYSA-N 2-Methyl-3-buten-1-ol Chemical compound OCC(C)C=C NVGOATMUHKIQQG-UHFFFAOYSA-N 0.000 description 2
- BDJFCIOMKXVJJM-UHFFFAOYSA-N 2-methyloct-7-en-2-ol Chemical compound CC(C)(O)CCCCC=C BDJFCIOMKXVJJM-UHFFFAOYSA-N 0.000 description 2
- ILPBINAXDRFYPL-UHFFFAOYSA-N 2-octene Chemical compound CCCCCC=CC ILPBINAXDRFYPL-UHFFFAOYSA-N 0.000 description 2
- XEADMNUIVFYAHV-UHFFFAOYSA-N 3,5-dichloro-2-methyloct-7-en-2-ol Chemical compound CC(C)(C(CC(CC=C)Cl)Cl)O XEADMNUIVFYAHV-UHFFFAOYSA-N 0.000 description 2
- LPPRFCNPBUVGGK-UHFFFAOYSA-N 5-methylhept-6-en-2-ol Chemical compound CC(CCC(C)O)C=C LPPRFCNPBUVGGK-UHFFFAOYSA-N 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- 238000006136 alcoholysis reaction Methods 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- UFRKOOWSQGXVKV-UHFFFAOYSA-N ethene;ethenol Chemical compound C=C.OC=C UFRKOOWSQGXVKV-UHFFFAOYSA-N 0.000 description 2
- 239000005038 ethylene vinyl acetate Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 2
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N methylene hexane Natural products CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 2
- MKUWVMRNQOOSAT-UHFFFAOYSA-N methylvinylmethanol Natural products CC(O)C=C MKUWVMRNQOOSAT-UHFFFAOYSA-N 0.000 description 2
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 2
- 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 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 238000007127 saponification reaction Methods 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- YFIIENAGGCUHIQ-UHFFFAOYSA-N 1,1,1,2,2,3,3-heptachloropropane Chemical compound ClC(Cl)C(Cl)(Cl)C(Cl)(Cl)Cl YFIIENAGGCUHIQ-UHFFFAOYSA-N 0.000 description 1
- QVLAWKAXOMEXPM-UHFFFAOYSA-N 1,1,1,2-tetrachloroethane Chemical compound ClCC(Cl)(Cl)Cl QVLAWKAXOMEXPM-UHFFFAOYSA-N 0.000 description 1
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- VHSCQANAKTXZTG-UHFFFAOYSA-N 1,1,1-trifluoro-2-(trifluoromethyl)pent-4-en-2-ol Chemical compound FC(F)(F)C(C(F)(F)F)(O)CC=C VHSCQANAKTXZTG-UHFFFAOYSA-N 0.000 description 1
- HVCSXHFGNRDDQR-UHFFFAOYSA-N 1,1,2,2,3,3-hexachloropropane Chemical compound ClC(Cl)C(Cl)(Cl)C(Cl)Cl HVCSXHFGNRDDQR-UHFFFAOYSA-N 0.000 description 1
- FRRHZKFKOHHEJR-UHFFFAOYSA-N 1,1,2-trichloro-2-methylpropane Chemical compound CC(C)(Cl)C(Cl)Cl FRRHZKFKOHHEJR-UHFFFAOYSA-N 0.000 description 1
- GRSQYISVQKPZCW-UHFFFAOYSA-N 1,1,2-trichloropropane Chemical compound CC(Cl)C(Cl)Cl GRSQYISVQKPZCW-UHFFFAOYSA-N 0.000 description 1
- IXZVKECRTHXEEW-UHFFFAOYSA-N 1,2,3,4-tetrachlorobutane Chemical compound ClCC(Cl)C(Cl)CCl IXZVKECRTHXEEW-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
- OQPNDCHKFIHPBY-UHFFFAOYSA-N 1,2-dichloro-2-methylpropane Chemical compound CC(C)(Cl)CCl OQPNDCHKFIHPBY-UHFFFAOYSA-N 0.000 description 1
- KTWNITKLQPCZSL-UHFFFAOYSA-N 1,3-dichloro-2,2-dimethylpropane Chemical compound ClCC(C)(C)CCl KTWNITKLQPCZSL-UHFFFAOYSA-N 0.000 description 1
- YHRUOJUYPBUZOS-UHFFFAOYSA-N 1,3-dichloropropane Chemical compound ClCCCCl YHRUOJUYPBUZOS-UHFFFAOYSA-N 0.000 description 1
- KJDRSWPQXHESDQ-UHFFFAOYSA-N 1,4-dichlorobutane Chemical compound ClCCCCCl KJDRSWPQXHESDQ-UHFFFAOYSA-N 0.000 description 1
- LBKDGROORAKTLC-UHFFFAOYSA-N 1,5-dichloropentane Chemical compound ClCCCCCCl LBKDGROORAKTLC-UHFFFAOYSA-N 0.000 description 1
- JEKYMVBQWWZVHO-UHFFFAOYSA-N 1-chloro-2,2-dimethylpropane Chemical compound CC(C)(C)CCl JEKYMVBQWWZVHO-UHFFFAOYSA-N 0.000 description 1
- IWAKWOFEHSYKSI-UHFFFAOYSA-N 1-chloro-2-methylbutane Chemical compound CCC(C)CCl IWAKWOFEHSYKSI-UHFFFAOYSA-N 0.000 description 1
- CZHLPWNZCJEPJB-UHFFFAOYSA-N 1-chloro-3-methylbutane Chemical compound CC(C)CCCl CZHLPWNZCJEPJB-UHFFFAOYSA-N 0.000 description 1
- VFWCMGCRMGJXDK-UHFFFAOYSA-N 1-chlorobutane Chemical compound CCCCCl VFWCMGCRMGJXDK-UHFFFAOYSA-N 0.000 description 1
- SQCZQTSHSZLZIQ-UHFFFAOYSA-N 1-chloropentane Chemical compound CCCCCCl SQCZQTSHSZLZIQ-UHFFFAOYSA-N 0.000 description 1
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 1
- ZSLKGUQYEQVKQE-UHFFFAOYSA-N 1-prop-2-enylcyclohexan-1-ol Chemical compound C=CCC1(O)CCCCC1 ZSLKGUQYEQVKQE-UHFFFAOYSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- JEIHEDHVBGHZSI-UHFFFAOYSA-N 2,2,4,4-tetrachloropentane Chemical class CC(Cl)(Cl)CC(C)(Cl)Cl JEIHEDHVBGHZSI-UHFFFAOYSA-N 0.000 description 1
- GRCJVLMUNHFVRD-UHFFFAOYSA-N 2,3-dimethylhex-5-en-2-ol Chemical compound CC(O)(C)C(C)CC=C GRCJVLMUNHFVRD-UHFFFAOYSA-N 0.000 description 1
- MPNPXISFBDIFFW-UHFFFAOYSA-N 2,4,5-trimethylhept-6-en-2-ol Chemical compound CC(O)(C)CC(C)C(C)C=C MPNPXISFBDIFFW-UHFFFAOYSA-N 0.000 description 1
- YYWMKLMWCPTKDJ-UHFFFAOYSA-N 2,4-dimethylpent-4-en-2-ol Chemical compound CC(=C)CC(C)(C)O YYWMKLMWCPTKDJ-UHFFFAOYSA-N 0.000 description 1
- HMCCHLPSTZQUPB-UHFFFAOYSA-N 2,5-dimethylhept-1-en-4-ol Chemical compound CCC(C)C(O)CC(C)=C HMCCHLPSTZQUPB-UHFFFAOYSA-N 0.000 description 1
- XSNQECSCDATQEL-SECBINFHSA-N 2,6-dimethyl-7-octen-2-ol Chemical compound C=C[C@@H](C)CCCC(C)(C)O XSNQECSCDATQEL-SECBINFHSA-N 0.000 description 1
- SKKRPDNROZIXRQ-UHFFFAOYSA-N 2,6-dimethyloct-7-ene-2,3-diol Chemical compound C=CC(C)CCC(O)C(C)(C)O SKKRPDNROZIXRQ-UHFFFAOYSA-N 0.000 description 1
- OTTZHAVKAVGASB-HYXAFXHYSA-N 2-Heptene Chemical compound CCCC\C=C/C OTTZHAVKAVGASB-HYXAFXHYSA-N 0.000 description 1
- JRKCHZNIMYXNJD-UHFFFAOYSA-N 2-ethylbut-3-en-1-ol Chemical compound CCC(CO)C=C JRKCHZNIMYXNJD-UHFFFAOYSA-N 0.000 description 1
- CMAOLVNGLTWICC-UHFFFAOYSA-N 2-fluoro-5-methylbenzonitrile Chemical compound CC1=CC=C(F)C(C#N)=C1 CMAOLVNGLTWICC-UHFFFAOYSA-N 0.000 description 1
- OTTZHAVKAVGASB-UHFFFAOYSA-N 2-heptene Natural products CCCCC=CC OTTZHAVKAVGASB-UHFFFAOYSA-N 0.000 description 1
- WEPNJTDVIIKRIK-UHFFFAOYSA-N 2-methylhept-2-ene Chemical compound CCCCC=C(C)C WEPNJTDVIIKRIK-UHFFFAOYSA-N 0.000 description 1
- YZHZVFQOTFXKJK-UHFFFAOYSA-N 2-methylhept-6-en-2-ol Chemical compound CC(C)(O)CCCC=C YZHZVFQOTFXKJK-UHFFFAOYSA-N 0.000 description 1
- RVHXDRXNRJQLGG-UHFFFAOYSA-N 2-methylhex-5-en-2-ol Chemical compound CC(C)(O)CCC=C RVHXDRXNRJQLGG-UHFFFAOYSA-N 0.000 description 1
- IAFXHXHWWRHBHY-UHFFFAOYSA-N 2-methyloct-7-en-3-ol Chemical compound CC(C)C(O)CCCC=C IAFXHXHWWRHBHY-UHFFFAOYSA-N 0.000 description 1
- OVRDLJJMKGWDHY-UHFFFAOYSA-N 2-methylpent-1-en-1-ol Chemical compound CCCC(C)=CO OVRDLJJMKGWDHY-UHFFFAOYSA-N 0.000 description 1
- OWVUFBAJXKEVBE-UHFFFAOYSA-N 2-methylpent-3-en-2-ol Chemical compound CC=CC(C)(C)O OWVUFBAJXKEVBE-UHFFFAOYSA-N 0.000 description 1
- CTHUAOGQNZSMMC-UHFFFAOYSA-N 2-methylpent-4-en-1-ol Chemical compound OCC(C)CC=C CTHUAOGQNZSMMC-UHFFFAOYSA-N 0.000 description 1
- JYVLIDXNZAXMDK-UHFFFAOYSA-N 2-pentanol Substances CCCC(C)O JYVLIDXNZAXMDK-UHFFFAOYSA-N 0.000 description 1
- BELRNEPYFJNSPN-UHFFFAOYSA-N 2-phenylpent-4-en-2-ol Chemical compound C=CCC(O)(C)C1=CC=CC=C1 BELRNEPYFJNSPN-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- HVRJBYCEBWZUNM-UHFFFAOYSA-N 3,4-dimethylnon-8-en-4-ol Chemical compound CC(CC)C(CCCC=C)(O)C HVRJBYCEBWZUNM-UHFFFAOYSA-N 0.000 description 1
- HFYAEUXHCMTPOL-UHFFFAOYSA-N 3-Methyl-1-penten-3-ol Chemical compound CCC(C)(O)C=C HFYAEUXHCMTPOL-UHFFFAOYSA-N 0.000 description 1
- CEYUOZZFKHSVPX-UHFFFAOYSA-N 3-chloro-2-methyloct-7-en-2-ol Chemical compound CC(C)(C(CCCC=C)Cl)O CEYUOZZFKHSVPX-UHFFFAOYSA-N 0.000 description 1
- DUIPHFXLEWQRBE-UHFFFAOYSA-N 3-chloro-2-methyloct-7-ene-2,3-diol Chemical compound ClC(C(C)(O)C)(CCCC=C)O DUIPHFXLEWQRBE-UHFFFAOYSA-N 0.000 description 1
- LVSHOBFBQMQZQR-UHFFFAOYSA-N 3-ethylhept-6-en-2-ol Chemical compound CCC(C(C)O)CCC=C LVSHOBFBQMQZQR-UHFFFAOYSA-N 0.000 description 1
- DVSNFPYGEZVDFW-UHFFFAOYSA-N 3-ethyloct-7-en-3-ol Chemical compound CCC(O)(CC)CCCC=C DVSNFPYGEZVDFW-UHFFFAOYSA-N 0.000 description 1
- ZEWJFQRAPALZPS-UHFFFAOYSA-N 3-methylhept-6-en-2-ol Chemical compound CC(O)C(C)CCC=C ZEWJFQRAPALZPS-UHFFFAOYSA-N 0.000 description 1
- NHEPUTZWBISVJH-UHFFFAOYSA-N 3-methylhept-6-en-3-ol Chemical compound CCC(C)(O)CCC=C NHEPUTZWBISVJH-UHFFFAOYSA-N 0.000 description 1
- GBARKLJMQRUBKV-UHFFFAOYSA-N 3-methylhex-5-en-3-ol Chemical compound CCC(C)(O)CC=C GBARKLJMQRUBKV-UHFFFAOYSA-N 0.000 description 1
- XHKCKQRCNHCJNV-UHFFFAOYSA-N 3-methyloct-7-en-3-ol Chemical compound CC(CC)(CCCC=C)O XHKCKQRCNHCJNV-UHFFFAOYSA-N 0.000 description 1
- ZAKMIMYVYWWNRS-UHFFFAOYSA-N 4-ethylnon-8-en-4-ol Chemical compound C(C)C(CCC)(CCCC=C)O ZAKMIMYVYWWNRS-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
- PYKQMQBNPLNLPS-UHFFFAOYSA-N 4-methylhept-1-en-4-ol Chemical compound CCCC(C)(O)CC=C PYKQMQBNPLNLPS-UHFFFAOYSA-N 0.000 description 1
- JSELNBHABZUYBU-UHFFFAOYSA-N 4-methylhept-6-en-2-ol Chemical compound CC(O)CC(C)CC=C JSELNBHABZUYBU-UHFFFAOYSA-N 0.000 description 1
- FBHBPWYIQNTBMB-UHFFFAOYSA-N 4-methylnon-8-en-4-ol Chemical compound CC(CCC)(CCCC=C)O FBHBPWYIQNTBMB-UHFFFAOYSA-N 0.000 description 1
- QGJZYOPWYGEGFR-UHFFFAOYSA-N 4-methyloct-7-en-2-ol Chemical compound CC(O)CC(C)CCC=C QGJZYOPWYGEGFR-UHFFFAOYSA-N 0.000 description 1
- JGTKGLUKURVOGV-UHFFFAOYSA-N 4-methyloct-7-en-3-ol Chemical compound CCC(O)C(C)CCC=C JGTKGLUKURVOGV-UHFFFAOYSA-N 0.000 description 1
- KPHPTSMXBAVNPX-UHFFFAOYSA-N 4-methylpent-4-en-2-ol Chemical compound CC(O)CC(C)=C KPHPTSMXBAVNPX-UHFFFAOYSA-N 0.000 description 1
- RLUDGGHEFUDPLJ-UHFFFAOYSA-N 4-propylhept-1-en-4-ol Chemical compound CCCC(O)(CCC)CC=C RLUDGGHEFUDPLJ-UHFFFAOYSA-N 0.000 description 1
- BKQGZHPQFPOPLC-UHFFFAOYSA-N 4-propylnon-8-en-4-ol Chemical compound CCCC(O)(CCC)CCCC=C BKQGZHPQFPOPLC-UHFFFAOYSA-N 0.000 description 1
- BZDOMSXLYCJAKU-UHFFFAOYSA-N 5-methyloct-7-en-3-ol Chemical compound CC(CC(CC)O)CC=C BZDOMSXLYCJAKU-UHFFFAOYSA-N 0.000 description 1
- DFVOXRAAHOJJBN-UHFFFAOYSA-N 6-methylhept-1-ene Chemical compound CC(C)CCCC=C DFVOXRAAHOJJBN-UHFFFAOYSA-N 0.000 description 1
- PMPISKBGRHSPEE-UHFFFAOYSA-N 6-methylhept-3-ene Chemical compound CCC=CCC(C)C PMPISKBGRHSPEE-UHFFFAOYSA-N 0.000 description 1
- LOOXFHXVVDRFPA-UHFFFAOYSA-N 6-methyloct-7-en-3-ol Chemical compound CCC(O)CCC(C)C=C LOOXFHXVVDRFPA-UHFFFAOYSA-N 0.000 description 1
- HSHUHVOEMVTVRS-UHFFFAOYSA-N 7-octen-2-ol Chemical compound CC(O)CCCCC=C HSHUHVOEMVTVRS-UHFFFAOYSA-N 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 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
- HQMRIBYCTLBDAK-UHFFFAOYSA-M bis(2-methylpropyl)alumanylium;chloride Chemical compound CC(C)C[Al](Cl)CC(C)C HQMRIBYCTLBDAK-UHFFFAOYSA-M 0.000 description 1
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 description 1
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 1
- 229960001701 chloroform Drugs 0.000 description 1
- GPTXWRGISTZRIO-UHFFFAOYSA-N chlorquinaldol Chemical compound ClC1=CC(Cl)=C(O)C2=NC(C)=CC=C21 GPTXWRGISTZRIO-UHFFFAOYSA-N 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000012718 coordination polymerization Methods 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
- 230000007123 defense Effects 0.000 description 1
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 1
- JLTDJTHDQAWBAV-UHFFFAOYSA-O dimethyl(phenyl)azanium Chemical compound C[NH+](C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-O 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229960003750 ethyl chloride Drugs 0.000 description 1
- UAIZDWNSWGTKFZ-UHFFFAOYSA-L ethylaluminum(2+);dichloride Chemical compound CC[Al](Cl)Cl UAIZDWNSWGTKFZ-UHFFFAOYSA-L 0.000 description 1
- 229920006242 ethylene acrylic acid copolymer Polymers 0.000 description 1
- 229920005680 ethylene-methyl methacrylate copolymer Polymers 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- AQTUHJABKZECGA-UHFFFAOYSA-N hept-1-en-4-ol Chemical compound CCCC(O)CC=C AQTUHJABKZECGA-UHFFFAOYSA-N 0.000 description 1
- RVXLYPSYVXXSQE-UHFFFAOYSA-N hept-6-en-2-ol Chemical compound CC(O)CCCC=C RVXLYPSYVXXSQE-UHFFFAOYSA-N 0.000 description 1
- XFXWEAWJVWCOBF-UHFFFAOYSA-N hept-6-en-3-ol Chemical compound CCC(O)CCC=C XFXWEAWJVWCOBF-UHFFFAOYSA-N 0.000 description 1
- LNPNXWKVAFKIBX-UHFFFAOYSA-N hex-5-en-2-ol Chemical compound CC(O)CCC=C LNPNXWKVAFKIBX-UHFFFAOYSA-N 0.000 description 1
- RZXDTJIXPSCHCI-UHFFFAOYSA-N hexa-1,5-diene-2,5-diol Chemical compound OC(=C)CCC(O)=C RZXDTJIXPSCHCI-UHFFFAOYSA-N 0.000 description 1
- VHHHONWQHHHLTI-UHFFFAOYSA-N hexachloroethane Chemical compound ClC(Cl)(Cl)C(Cl)(Cl)Cl VHHHONWQHHHLTI-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 1
- ULYZAYCEDJDHCC-UHFFFAOYSA-N isopropyl chloride Chemical compound CC(C)Cl ULYZAYCEDJDHCC-UHFFFAOYSA-N 0.000 description 1
- 125000000654 isopropylidene group Chemical group C(C)(C)=* 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229940073584 methylene chloride Drugs 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 125000006606 n-butoxy group Chemical group 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
- SNMVRZFUUCLYTO-UHFFFAOYSA-N n-propyl chloride Chemical compound CCCCl SNMVRZFUUCLYTO-UHFFFAOYSA-N 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
- VOKXPKSMYJLAIW-UHFFFAOYSA-N nickel;phosphane Chemical compound P.[Ni] VOKXPKSMYJLAIW-UHFFFAOYSA-N 0.000 description 1
- 125000003518 norbornenyl group Chemical class C12(C=CC(CC1)C2)* 0.000 description 1
- UXGHWJFURBQKCJ-UHFFFAOYSA-N oct-7-ene-1,2-diol Chemical compound OCC(O)CCCCC=C UXGHWJFURBQKCJ-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 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
- 238000004806 packaging method and process Methods 0.000 description 1
- BNIXVQGCZULYKV-UHFFFAOYSA-N pentachloroethane Chemical compound ClC(Cl)C(Cl)(Cl)Cl BNIXVQGCZULYKV-UHFFFAOYSA-N 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 230000035699 permeability Effects 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
- 229920001200 poly(ethylene-vinyl acetate) Polymers 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
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 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
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- CRNIHJHMEQZAAS-UHFFFAOYSA-N tert-amyl chloride Chemical compound CCC(C)(C)Cl CRNIHJHMEQZAAS-UHFFFAOYSA-N 0.000 description 1
- NBRKLOOSMBRFMH-UHFFFAOYSA-N tert-butyl chloride Chemical compound CC(C)(C)Cl NBRKLOOSMBRFMH-UHFFFAOYSA-N 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
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 125000003944 tolyl group Chemical group 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
- 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
- OBAJXDYVZBHCGT-UHFFFAOYSA-N tris(pentafluorophenyl)borane Chemical compound FC1=C(F)C(F)=C(F)C(F)=C1B(C=1C(=C(F)C(F)=C(F)C=1F)F)C1=C(F)C(F)=C(F)C(F)=C1F OBAJXDYVZBHCGT-UHFFFAOYSA-N 0.000 description 1
- 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
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/02—Ethene
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention relates to a preparation method of an olefin-olefin alcohol copolymer, and a product and application thereof. The preparation method of the olefin-olefin alcohol copolymer comprises the step of polymerizing olefin and olefin alcohol in the presence of a catalyst and a modifier, wherein the catalyst is a diimine metal complex shown in a formula I. The preparation method can obtain spherical and/or spheroidal polymers and has good prospect in industrial application.
Description
Technical Field
The invention belongs to the field of preparation of high molecular polymers, and particularly relates to a preparation method of an olefin-olefin alcohol copolymer.
Background
The polyolefin product has the characteristics of stable performance, excellent processing performance, good safety and stability, recycling and the like, so that the polyolefin product is widely applied to the fields of industry and agriculture, medical treatment and health, national defense industry, daily life and the like. However, the main chain of polyethylene is C-C bond and C-H bond with low reactivity, so that the printing property, the adhesive property, the air permeability and the compatibility with other materials of the polyethylene are poor, and the application of the polyethylene is limited. The polar group containing N, O, Si or halogen is introduced into polyolefin molecular chain by chemical synthesis method, which can improve chemical inertia, printing property, wettability and compatibility with other materials, endow new properties which are not possessed by raw materials, and widen application field. The current method commonly used in industry is to directly perform high-pressure radical copolymerization on ethylene and polar monomer to obtain polyethylene containing polar groups, such as ethylene-vinyl acetate, ethylene-methyl methacrylate, and ethylene-acrylic acid copolymer. Although the polar comonomer can be directly introduced into the polyolefin chain by high-pressure radical copolymerization, the method requires high-temperature and high-pressure conditions, and is high in energy consumption and expensive in equipment cost.
Ethylene-vinyl alcohol (EVOH or EVAL) copolymer is one of three barrier resins industrially produced in the world at present, has excellent gas barrier property, processability and biocompatibility, and is widely used for packaging of food and medicines, medical supplies and other products. Since vinyl alcohol cannot exist stably in the form of monomers, the product is usually prepared industrially as a two-step process: first, ethylene and vinyl acetate are polymerized through free radicals to generate ethylene-vinyl acetate (EVA); and the second step of alcoholysis reaction of the copolymer to obtain EVOH. However, a large amount of solvent is needed in the free radical polymerization process, the recovery is difficult, a large amount of alcohol solvent is needed in the alcoholysis process, the final saponification product contains a large amount of impurities such as sodium acetate, methyl acetate and the like, a large amount of water is needed for washing the product, and the energy consumption is high.
Compared with free radical polymerization, coordination polymerization for realizing the copolymerization of olefin isotropic monomers can obtain products with higher molecular weight under a milder condition, can conveniently regulate and control the insertion amount of polar monomers, can regulate the performance of the products in a wider range, has lower cost, and is one of the hotspots in the research field of polyolefin materials. Only a few reports have been made of the use of transition metal complexes to catalyze the copolymerization of ethylene with enol, such as Journal of Applied Polymer Science,2013,129(4): 1820-; ACS Catal, 2017,7(2):1308-1312, wherein a phosphine-nickel sulfonate catalyst (formula b) is adopted to catalyze the copolymerization of ethylene and hydroxyl-substituted norbornene; angewandte Chemie International Edition,2017,56(38): 11604-. However, in the existing reports, although the transition metal complex is adopted to successfully catalyze the copolymerization of the enol of ethylene with different structures, the product is a viscous solid with a random structure, and the product is easy to adhere and scale in polymerization equipment, thereby bringing difficulties to the procedures of further removing the solvent, granulating and the like of the product, and not meeting the requirements of industrial production.
Disclosure of Invention
It is an object of the present invention to overcome the disadvantages of the prior art and to provide a novel process for preparing olefin-olefin alcohol copolymers. Furthermore, the spherical and/or spheroidal polymer can be directly obtained by the method, the polymer has good appearance and good industrial application prospect.
In a first aspect, the present invention provides a process for preparing an olefin-olefin alcohol copolymer, comprising polymerizing an olefin and an olefin alcohol in the presence of a catalyst solvent and an improver to produce the olefin-olefin alcohol copolymer.
According to an embodiment of the invention, the catalyst comprises a procatalyst comprising a diimine metal complex according to formula I:
in the formula I, R1And R2The same or different, independently selected from C1-C30 hydrocarbyl containing or not containing substituent; r5-R10The aryl group is selected from hydrogen, halogen, hydroxyl, C1-C20 alkyl with or without substituent, C2-C20 alkenyl with or without substituent, C2-C20 alkynyl with or without substituent, C3-C20 cycloalkyl with or without substituent, C1-C20 alkoxy with or without substituent, C2-C20 alkenyloxy with or without substituent, C2-C20 alkynyloxy with or without substituent, C3-C20 cycloalkoxy with or without substituent, C6-C20 aryl with or without substituent, C7-C20 aralkyl with or without substituent and C7-C20 alkaryl with or without substituent.
M is a group VIII metal; x is selected from halogen, C1-C10 alkyl with or without substituent and C1-C10 alkoxy with or without substituent.
According to some embodiments of the invention, R1And R2Is selected from C1-C20 alkyl with or without substituent and/or C6-C20 aryl with or without substituent.
According to some embodiments of the invention, R1And/or R2Is a group of formula A:
in the formula A, R1-R5The aryl group is the same or different and is independently selected from hydrogen, halogen, hydroxyl, C1-C20 alkyl with or without substituent, C2-C20 alkenyl with or without substituent, C2-C20 alkynyl with or without substituent, C3-C20 cycloalkyl with or without substituent, C1-C20 alkoxy with or without substituent, C2-C20 alkenyloxy with or without substituent, C2-C20 alkynyloxy with or without substituent, C3-C20 cycloalkoxy with or without substituent, C6-C20 aryl with or without substituent, C7-C20 aralkyl with or without substituent and C7-C20 alkaryl with or without substituent; r1-R5Optionally forming a ring with each other.
According to some embodiments of the invention, R in formula A1-R5The aryl group is selected from hydrogen, halogen, hydroxyl, C1-C10 alkyl with or without substituent, C2-C10 alkenyl with or without substituent, C2-C10 alkynyl with or without substituent, C3-C10 cycloalkyl with or without substituent, C1-C10 alkoxy with or without substituent, C2-C10 alkenyloxy with or without substituent, C2-C10 alkynyloxy with or without substituent, C3-C10 cycloalkoxy with or without substituent, C6-C15 aryl with or without substituent, C7-C15 aralkyl with or without substituent and C7-C15 alkaryl with or without substituent.
According to some embodiments of the invention, M is selected from nickel and palladium.
According to some embodiments of the invention, X is selected from the group consisting of halogen, substituted or unsubstituted C1-C10 alkyl, and substituted or unsubstituted C1-C10 alkoxy, preferably from the group consisting of halogen, substituted or unsubstituted C1-C6 alkyl, and substituted or unsubstituted C1-C6 alkoxy.
According to some embodiments of the invention, R5-R10The same or different, each is independently selected from hydrogen, halogen, hydroxyl, C1-C10 alkyl with or without substituent, and with or without substituentC2-C10 alkenyl containing substituent groups, C2-C10 alkynyl containing substituent groups or not, C3-C10 cycloalkyl containing substituent groups or not, C1-C10 alkoxy containing substituent groups or not, C2-C10 alkenyloxy containing substituent groups or not, C2-C10 alkynyloxy containing substituent groups or not, C3-C10 cycloalkoxy containing substituent groups or not, C6-C15 aryl containing substituent groups or not, C7-C15 aralkyl containing substituent groups or not, and C7-C15 alkaryl containing substituent groups or not.
According to some embodiments of the invention, R5-R10Each independently selected from hydrogen, C1-C10 alkyl, halogenated C1-C10 alkyl, C1-C10 alkoxy, halogenated C1-C10 alkoxy and halogen, more preferably from hydrogen, C1-C6 alkyl, halogenated C1-C6 alkyl, C1-C6 alkoxy, halogenated C1-C6 alkoxy and halogen.
According to some embodiments of the invention, the substituent is selected from the group consisting of halogen, hydroxy, C1-C10 alkyl, halogenated C1-C10 alkyl, C1-C10 alkoxy, and halogenated C1-C10 alkoxy; the substituents are preferably selected from halogen, hydroxy, C1-C6 alkyl, halogenated C1-C6 alkyl, C1-C6 alkoxy and halogenated C1-C6 alkoxy.
According to some embodiments of the invention, the C1-C6 alkyl group is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl and isobutyl, n-pentyl, isopentyl, n-hexyl, isohexyl, and 3, 3-dimethylbutyl.
According to some embodiments of the invention, the C1-C6 alkoxy group is selected from methoxy, ethoxy, n-propoxy, isopropoxy, n-and isobutoxy, n-pentoxy, isopentoxy, n-hexoxy, isohexoxy and 3, 3-dimethylbutoxy.
According to some embodiments of the invention, the halogen is selected from fluorine, chlorine, bromine and iodine.
According to some embodiments of the invention, the alkene alcohol is selected from one or more of the alkene alcohols represented by formula G:
in the formula G, L1-L3Each independently selected from H and C with or without substituent1-C30Alkyl radical, L4Is C having a pendant group1-C30An alkylene group.
According to some embodiments of the invention, the copolymer has a content of structural units derived from the alkene alcohol represented by formula G of 0.4 to 10.0 mol%.
According to some embodiments of the invention, in formula G, L1And L2Is H.
According to some embodiments of the invention, in formula G, L3Is H or C1-C30An alkyl group.
According to some embodiments of the invention, in formula G, L4Is C having a pendant group1-C30An alkylene group.
According to some embodiments of the invention, in formula G, L3Is H or C1-C20An alkyl group.
According to some embodiments of the invention, in formula G, L4Is C having a pendant group1-C20An alkylene group.
According to some embodiments of the invention, in formula G, L3Is H or C1-C10An alkyl group.
According to some embodiments of the invention, in formula G, L4Is C having a pendant group1-C10An alkylene group.
According to some embodiments of the invention, in formula G, L4Is C having a pendant group1-C6An alkylene group.
According to some embodiments of the invention, L1-L3Wherein said substituents are selected from halogen, C1-C10Alkyl radical, C1-C10Alkoxy radical, C6-C10One or more of aryl, cyano and hydroxyl.
According to some embodiments of the invention, L1-L3Wherein the substituent is selected from C1-C6 alkyl,One or more of halogen and C1-C6 alkoxy.
According to some embodiments of the invention, the pendant group in L4 is selected from halogen, C6-C20Aryl radical, C1-C20Alkyl and C1-C20One or more of alkoxy, said C6-C20Aryl radical, C1-C20Alkyl and C1-C20Alkoxy is optionally substituted by a substituent, preferably selected from halogen, C1-C10Alkyl radical, C1-C10Alkoxy radical, C6-C10One or more of aryl and hydroxyl.
According to a preferred embodiment of the invention, said L4The side group in (A) is selected from halogen and C6-C20Aryl radical, C1-C20Alkyl, hydroxy substituted C1-C20Alkyl and alkoxy substituted C1-C20One or more of alkyl; preferably, the side group is selected from halogen, C6-C20Aryl radical, C1-C10Alkyl, hydroxy substituted C1-C10Alkyl and alkoxy substituted C1-10One or more of alkyl; more preferably, the side group is selected from halogen, phenyl, C1-C6Alkyl and hydroxy substituted C1-C6One or more of alkyl, said C1-C6Alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl and hexyl.
According to a preferred embodiment of the invention, in formula G, L1And L2Is H, L3Is H or C1-C30Alkyl radical, L4Is C having a pendant group1-C30An alkylene group; said C is1-C30Alkyl is optionally substituted by a substituent, preferably selected from halogen, C1-C10Alkyl radical, C1-C10Alkoxy radical, C6-C10One or more of aryl, cyano and hydroxyl.
According to a preferred embodiment of the inventionIn the formula G, L1And L2Is H, L3Is H, C1-C10Alkyl or halogen substituted C1-C10Alkyl, preferably L3Is H or C1-C10An alkyl group; l is4Is C having a pendant group1-C20Alkylene radicals, e.g. L4Is methylene with side group, ethylene with side group, propylene with side group, butylene with side group, C with side group5Alkylene, C having pendant groups6Alkylene, C having pendant groups7Alkylene, C having pendant groups8Alkylene, C having pendant groups9Alkylene, C having pendant groups10Alkylene, C having pendant groups12Alkylene, C having pendant groups14Alkylene, C having pendant groups18Alkylene, C having pendant groups20Alkylene, preferably C, having pendant groups1-C10An alkylene group.
According to a preferred embodiment of the invention, in formula G, L1And L2Is H, L3Is H or C1-6An alkyl group; l is4Is C having a pendant group1-C10An alkylene group.
In the present invention, the carbon number n of the Cn alkylene group means the number of C's in the linear chain, excluding the number of C's in the pendant group, and is, for example, isopropylidene (-CH)2-CH(CH3) -) is referred to herein as C with a pendant group (methyl)2An alkylene group.
According to a preferred embodiment of the present invention, specific examples of the alkene alcohol represented by formula G include, but are not limited to: 2-methyl-3-buten-1-ol, 2-ethyl-3-buten-1-ol, 1-diphenyl-3-buten-1-ol, 2-methyl-3-buten-2-ol, 2-dimethyl-3-buten-1-ol, 3-methyl-1-penten-3-ol, 2, 4-dimethyl-4-penten-2-ol, 4-alkenyl-2-pentanol, 4-methyl-4-penten-2-ol, 2-phenyl-4-penten-2-ol, 2-methyl-3-buten-2-ol, 2-methyl-4-penten-2-ol, 2-methyl-3-buten-ol, 2-methyl-4-penten-2-ol, 2-methyl-4-penten-ol, 2-methyl-4-penten-2-ol, 2-methyl-penten-ol, 2-methyl-4-penten-2-ol, 2-methyl-penten-2-ol, and mixtures thereof, 2-allylhexafluoroisopropanol, 2-hydroxy-5-hexene, 3-buten-2-ol, 3-methyl-5-hexen-3-ol, 2-methyl-2-hydroxy-5-hexene, 1-allylcyclohexanol, 2, 3-dimethyl-2-hydroxy-5-hexene, 1-hepten-4-ol, 4-methyl-1-hepten-4-ol, 4-n-propyl-1-hepten-4-ol, 6-hepten-3-ol, 2-methyl-2-hydroxy-6-heptene, 5-methyl-2-hydroxy-6-heptene, 2-hydroxy-3-methyl-6-heptene, 2-hydroxy-3-ethyl-6-heptene, 2-hydroxy-4-methyl-6-heptene, 2-hydroxy-5-methyl-6-heptene, 2, 5-dimethyl-1-hepten-4-ol, 2, 6-dimethyl-7-octen-2-ol, 2-hydroxy-2, 4, 5-trimethyl-6-heptene, 2-methyl-3-hydroxy-7-octene, 3-methyl-3-hydroxy-6-heptene, 2-methyl-2-hydroxy-7-octene, 2-methyl-6-heptene, 2-hydroxy-6-heptene, 2-methyl-2-hydroxy-7-octene, 2-methyl-2-heptene, 2-methyl-2-1-heptene, 2-methyl-2-4-methyl-6-heptene, 2-methyl-4-heptene, 2-1-octene, 2-octene, 2-heptene, 2-octene, 2-one, 3-methyl-3-hydroxy-7-octene, 4-methyl-2-hydroxy-7-octene, 4-methyl-3-hydroxy-7-octene, 5-methyl-3-hydroxy-7-octene, 6-methyl-3-hydroxy-7-octene, 3-ethyl-3-hydroxy-7-octene, 1, 2-dihydroxy-7-octene, 2, 6-dimethyl-2, 6-dihydroxy-7-octene, 2, 6-dimethyl-2, 3-dihydroxy-7-octene, 2-methyl-2-hydroxy-3-chloro-7-octene, mixtures thereof, and mixtures thereof, 2-methyl-2-hydroxy-3, 5-dichloro-7-octene, 3, 4-dimethyl-4-hydroxy-8-nonene, 4-methyl-4-hydroxy-8-nonene, 4-ethyl-4-hydroxy-8-nonene, 4-propyl-4-hydroxy-8-nonene, 7-octen-2-ol, 3, 5-dichloro-2-methyl-7-octen-2-ol, 3-chloro-2-methyl-7-octen-2, 3-diol, and 2, 6-dimethyl-7-octen-2, 6-diol.
According to a preferred embodiment of the invention, the cocatalyst is chosen from organoaluminum compounds and/or organoboron compounds.
According to a preferred embodiment of the invention, the organoaluminium compound is selected from alkylaluminoxanes or compounds of general formula AlRnX1 3-nWith an organoaluminum compound (alkylaluminum or alkylaluminum halide) of the general formula AlRnX1 3-nWherein R is H, C1-C20Saturated or unsaturated hydrocarbon radicals or C1-C20Saturated or unsaturated hydrocarbyloxy radicals, preferably C1-C20Alkyl radical, C1-C20Alkoxy radical, C7-C20Aralkyl or C6-C20An aryl group; x1Is halogen, preferably chlorine or bromine; 0<n is less than or equal to 3. Specific examples of the organoaluminum compound include, but are not limited to: trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, trioctylaluminum, diethylaluminum monohydrogen, diisobutylaluminum monohydrogen, diethylaluminum monochloride, diisobutylaluminum monochloride, ethylaluminum sesquichloride,Ethyl aluminum dichloride, Methylaluminoxane (MAO) and Modified Methylaluminoxane (MMAO). Preferably, the organoaluminum compound is Methylaluminoxane (MAO).
According to a preferred embodiment of the invention, the organoboron compound is selected from an aryl boron and/or a borate. The arylborole is preferably a substituted or unsubstituted phenylborone, more preferably tris (pentafluorophenyl) boron. The borate is preferably N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate and/or triphenylmethyl tetrakis (pentafluorophenyl) borate.
According to a preferred embodiment of the present invention, the concentration of the main catalyst in the reaction system is 0.00001 to 100mmol/L, for example, 0.00001mmol/L, 0.00005mmol/L, 0.0001mmol/L, 0.0005mmol/L, 0.001mmol/L, 0.005mmol/L, 0.01mmol/L, 0.05mmol/L, 0.1mmol/L, 0.3mmol/L, 0.5mmol/L, 0.8mmol/L, 1mmol/L, 5mmol/L, 8mmol/L, 10mmol/L, 20mmol/L, 30mmol/L, 50mmol/L, 70mmol/L, 80mmol/L, 100mmol/L and any value therebetween, preferably 0.0001 to 1mmol/L, more preferably 0.001 to 0.5 mmol/L.
According to a preferred embodiment of the present invention, when the cocatalyst is an organoaluminum compound, the molar ratio of aluminum in the cocatalyst to M in the procatalyst is (10-10000000):1, for example, 10:1, 20:1, 50:1, 100:1, 200:1, 300:1, 500:1, 700:1, 800:1, 1000:1, 2000:1, 3000:1, 5000:1, 10000:1, 100000:1, 1000000:1, 10000000:1 and any value therebetween, preferably (10-100000):1, more preferably (100-10000): 1; when the cocatalyst is an organoboron compound, the molar ratio of boron in the cocatalyst to M in the procatalyst is (0.1-1000):1, e.g., 0.1:1, 0.2:1, 0.5:1, 0.8:1, 1:1, 1.2:1, 1.4:1, 1.6:1, 1.8:1, 2:1, 2.5:1, 3:1, 4:1, 5:1, 8:1, 10:1, 20:1, 50:1, 100:1, 200:1, 300:1, 500:1, 700:1, 800:1, 1000:1, and any value therebetween, preferably (0.1-500): 1.
According to preferred embodiments of the present invention, the olefin comprises an olefin having from 2 to 16 carbon atoms, and in some embodiments of the present invention, the olefin comprises ethylene or alpha-olefins having from 3 to 16 carbon atomsAn olefin. In other embodiments of the present invention, the olefin is C3-C16A cyclic olefin, preferably a 5-or 6-membered ring. Preferably, the olefin is ethylene or an alpha-olefin having 3 to 16 carbon atoms, more preferably ethylene or C2-C10Alpha-olefins, such as ethylene, propylene, butene, pentene, hexene, heptene and octene.
According to a preferred embodiment of the present invention, the concentration of the olefin alcohol monomer represented by the formula G in the reaction system is 0.01 to 6000mmol/L, preferably 0.1 to 1000mmol/L, more preferably 1 to 500mmol/L, and may be, for example, 1mmol/L, 10mmol/L, 20mmol/L, 30mmol/L, 50mmol/L, 70mmol/L, 90mmol/L, 100mmol/L, 200mmol/L, 300mmol/L, 400mmol/L, 500mmol/L and any value therebetween.
According to a preferred embodiment of the invention, the modifier comprises a halogenated hydrocarbon, preferably selected from the group consisting of C1-C15 halogenated hydrocarbons, more preferably C1-C10 halogenated hydrocarbons, even more preferably C1-C6 halogenated alkanes.
According to a preferred embodiment of the invention, the improver comprises methyl chloride, methylene chloride, chloroform, ethyl chloride, 1, 2-dichloroethane, 1,1, 2-trichloroethane, 1,1, 1-trichloroethane, 1,1,2, 2-tetrachloroethane, 1,1,1, 2-tetrachloroethane, pentachloroethane, hexachloroethane, 2-chloropropane, chloro-n-propane, 1, 3-dichloropropane, 1,1, 2-trichloropropane, 1,1,2,2,3, 3-hexachloropropane, 1,1,1,2,2,3, 3-heptachloropropane, 1-chlorobutane, chloro-tert-butane, 1, 4-dichlorobutane, 1, 2-dichloroisobutane, 1,1, 2-trichloro-2-methylpropane, 1,2,3, 4-tetrachlorobutane, 1-chloropentane, 2-chloro-2-methylbutane, 1-chloro-3-methylbutane, 1-chloro-2, 2-dimethylpropane, 1-chloro-2-methylbutane, 1, 5-dichloropentane, 2, 2-dimethyl-1, 3-dichloropropane, 1,1,1- (trichloromethyl) ethane, tetrachloro-pentanes.
According to a preferred embodiment of the invention, the polymerization is carried out in an alkane solvent selected from C3-C20One or more alkanes, preferably selected from C3-C10Alkanes, for example, may be chosen from butane, isobutane, pentane, hexane, heptane,One or more of octane and cyclohexane, preferably one or more of hexane, heptane and cyclohexane.
According to a preferred embodiment of the invention, the volume ratio of solvent to modifier used for the polymerization is (1-5000):1, preferably (1.0-500): 1. For example, 1:1, 2:1, 5:1, 6:1, 7:1, 8:1, 9:1, 10:1, 15:1, 20:1, 50:1, 100:1, 200:1, 300:1, 500:1, 600:1, 800:1, 1000:1, 2000:1, and any value in between, preferably (1.0-500): 1.
According to a preferred embodiment of the present invention, the olefinic alcohol is pre-treated with a dehydroactive hydrogen, preferably with the use of a cocatalyst as described above, to remove hydroxyl active hydrogen from the olefinic alcohol. Preferably, the molar ratio of hydroxyl groups in the alkene alcohol to co-catalyst during pretreatment is from 10:1 to 1: 10.
According to a preferred embodiment of the invention, the reaction is carried out in the absence of water and oxygen.
According to a preferred embodiment of the invention, the conditions of the reaction include: the temperature of the reaction is-50 ℃ to 50 ℃, preferably-20 ℃ to 50 ℃, more preferably 0 ℃ to 50 ℃, and can be, for example, 0 ℃, 10 ℃,20 ℃, 30 ℃, 40 ℃, 50 ℃ and any value therebetween; and/or the reaction time is 10-200min, preferably 20-60 min. In the present invention, the reaction pressure is not particularly limited as long as the monomer can be subjected to coordination copolymerization. When the olefin is ethylene, the pressure of ethylene in the reactor is preferably 1 to 1000atm, more preferably 1 to 200atm, and still more preferably 1 to 50atm, from the viewpoint of cost reduction and simplification of the polymerization process. In the present invention, the "reaction system" is meant to include the totality of solvent, olefin alcohol monomer, catalyst, modifier and optionally chain transfer agent.
The invention also provides an olefin-olefin alcohol copolymer prepared by the preparation method, which comprises spherical and/or spheroidal polymers.
According to a preferred embodiment of the invention, the spherical and/or spheroidal polymers have an average particle size of 0.1 to 50.0mm, for example 0.1mm, 0.5mm, 1.0mm, 2.0mm, 3.0mm, 5.0mm, 8.0mm, 10.0mm, 15.0mm, 20.0mm, 25.0mm, 30.0mm, 35.0mm, 40.0mm, 45.0mm, 50.0mm and any value in between, preferably 0.5 to 20.0 mm.
According to a preferred embodiment of the present invention, in the olefin-olefin alcohol copolymer, the content of the structural unit derived from the olefin alcohol represented by the formula G is 0.4 to 30.0 mol%, and for example, may be 0.4 mol%, 0.5 mol%, 0.7 mol%, 0.8 mol%, 1.0 mol%, 1.5 mol%, 2.0 mol%, 5.0 mol%, 8.0 mol%, 10.0 mol%, 15.0 mol%, 20.0 mol%, 25.0 mol%, 30.0 mol% and any value therebetween, preferably 0.7 to 10.0 mol%.
According to a preferred embodiment of the present invention, the weight average molecular weight of the olefin-olefin alcohol copolymer is 30000-500000, preferably 50000-400000.
According to a preferred embodiment of the present invention, the olefin-olefin alcohol copolymer has a molecular weight distribution of 4.0 or less, and for example, may be 0.1, 0.5, 1.0, 1.5, 2.0, 2.5, 3.0, 3.5, 4.0 and any value therebetween, and preferably, the molecular weight distribution is 1.0 to 4.0.
In the present invention, the particle size of a spherical or spheroidal polymer is herein considered to be equal to the diameter of a sphere having a volume equal to the volume of the particle.
According to still another aspect of the present invention, there is provided a use of the olefin-olefin alcohol copolymer as a polyolefin material.
The process for producing an olefin-olefin alcohol copolymer provided by the present invention uses a modifier. The technical problem to be solved by the invention is to provide a novel preparation method of olefin-olefin alcohol copolymer.
Furthermore, in the preparation method of the olefin-olefin alcohol copolymer provided by the invention, the spherical and/or spheroidal polymers with good shapes are directly prepared by selecting the olefin alcohol monomer for reaction, the catalyst and a proper modifier polymerization process without subsequent processing steps such as granulation and the like, and the obtained polymerization product is not easy to scale in a reactor and is convenient to transport.
Further, compared with the existing industrial process for preparing olefin-olefin alcohol copolymers, the method for preparing olefin-olefin alcohol copolymers provided by the invention omits the step of saponification reaction, and has simpler preparation process.
Symbols such as R used in different formulae or structural formulae herein1、R2、R3、R4、R5、R1-R10、R5X, M, A, etc., have the same definitions in each general formula or structural formula unless otherwise specified.
In the present invention, examples of the halogen include fluorine, chlorine, bromine, and iodine.
In the present invention, C1-C20Alkyl is C1-C20Straight chain alkyl or C3-C20Branched alkyl groups of (a), including but not limited to: 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-C20Examples of cycloalkyl groups include, but are not limited to: cyclopropyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, 4-ethylcyclohexyl, 4-n-propylcyclohexyl and 4-n-butylcyclohexyl.
C6-C20Examples of aryl groups include, but are not limited to: phenyl, 4-methylphenyl, 4-ethylphenyl, dimethylphenyl, vinylphenyl.
C2-C20Alkenyl means C1-C20Linear alkenyl of (A) or (C)3-C20Including but not limited to: vinyl, allyl, butenyl.
C7-C20Examples of aralkyl groups include, but are not limited to: phenylmethyl, phenylethyl, phenyl-n-propyl, phenyl-isopropyl, phenyl-n-butyl and phenyl-tert-butyl.
C7-C20Examples of alkaryl groups include, but are not limited to: tolyl, ethylphenyl, n-propylphenyl, isopropylphenyl, n-butylphenyl and tert-butylphenyl groups.
Detailed Description
The present invention will be described in detail with reference to examples, but the present invention is not limited to the examples.
The analytical characterization instrument used in the present invention was as follows:
comonomer content of the polymer (content of structural units derived from the olefin alcohol represented by formula G): by using13C NMR spectroscopy was carried out by dissolving a polymer sample in 1,2, 4-trichlorobenzene at 120 ℃ on a 400MHz Bruker Avance 400 NMR spectrometer using a 10mm PASEX 13 probe.
Molecular weight and molecular weight distribution PDI (PDI ═ Mw/Mn) of the copolymer: measured at 150 ℃ using PL-GPC220 in trichlorobenzene (standard: PS, flow rate: 1.0mL/min, column: 3 XPlgel 10um M1 XED-B300X 7.5 nm).
The activity measurement method comprises the following steps: weight of polymer (g)/nickel (mol). times.2.
Example 1
Continuously drying a 1L stainless steel polymerization kettle equipped with mechanical stirring at 130 deg.C for 6h, vacuumizing while hot, and adding N2Replace qi for 3 times. 500mL of hexane was poured into the polymerization system, and 3.8mg (6. mu. mol) of complex Ni1, 10mL of methylene chloride, 15mmol (3.0mL) of dihydromyrcenol, 15mL of AlEt3(1.0mol/L hexane solution), 10mL of MAO (1.53mol/L toluene solution), and the reaction was stirred at 30 ℃ under an ethylene pressure of 10atm for 30 min. Finally, the polymer was obtained by neutralizing the mixture with a 10 wt% ethanol solution acidified with hydrochloric acid. The polymerization activity and the polymer performance parameters are shown in Table 1.
Example 2
A1L stainless steel polymerizer equipped with a mechanical stirrer was continuously dried at 130 ℃ for 6 hours, evacuated while still hot and replaced with N2 gas 3 times. To the polymerization system was charged 500mL of hexane while adding 3.8mg (6. mu. mol) of complex Ni1, 50mL of dichloromethane, 15mmol (3.0mL) of dihydromyrcenol, 15mL of AlEt3(1.0mol/L in hexane), 10mL of MAO (1.53mol/L in toluene), and the reaction was stirred at 30 ℃ under an ethylene pressure of 10atm for 30 min. Finally, the polymer was obtained by neutralizing the mixture with a 10 wt% ethanol solution acidified with hydrochloric acid. The polymerization activity and the polymer performance parameters are shown in Table 1.
Example 3
Continuously drying a 1L stainless steel polymerization kettle equipped with mechanical stirring at 130 deg.C for 6h, vacuumizing while hot, and adding N2Replace qi for 3 times. 500mL of hexane was poured into the polymerization system, and 3.8mg (6. mu. mol) of complex Ni1, 100mL of methylene chloride, 15mmol (3.0mL) of dihydromyrcenol, 15mL of AlEt3(1.0mol/L hexane solution), 10mL of MAO (1.53mol/L toluene solution), and the reaction was stirred at 30 ℃ under an ethylene pressure of 10atm for 30 min. Finally, the polymer was obtained by neutralizing the mixture with a 10 wt% ethanol solution acidified with hydrochloric acid. The polymerization activity and the polymer performance parameters are shown in Table 1.
Example 4
Continuously drying a 1L stainless steel polymerization kettle equipped with mechanical stirring at 130 deg.C for 6h, vacuumizing while hot, and adding N2Replace qi for 3 times. 500mL of hexane was poured into the polymerization system, and 3.8mg (6. mu. mol) of complex Ni1, 200mL of methylene chloride, 15mmol (3.0mL) of dihydromyrcenol, 15mL of AlEt3(1.0mol/L hexane solution), 10mL of MAO (1.53mol/L toluene solution), and the reaction was stirred at 30 ℃ under an ethylene pressure of 10atm for 30 min. Finally, the polymer was obtained by neutralizing the mixture with a 10 wt% ethanol solution acidified with hydrochloric acid. The polymerization activity and the polymer performance parameters are shown in Table 1.
Example 5
Continuously drying a 1L stainless steel polymerization kettle equipped with mechanical stirring at 130 deg.C for 6h, vacuumizing while hot, and adding N2Replace qi for 3 times. 500mL of hexane was poured into the polymerization system, and 3.8mg (6. mu. mol) of complex Ni1, 400mL of methylene chloride, 15mmol (3.0mL) of dihydromyrcenol, 15mL of AlEt3(1.0mol/L hexane solution), 10mL of MAO (1.53mol/L toluene solution), and the reaction was stirred at 30 ℃ under an ethylene pressure of 10atm for 30 min. Finally, the polymer was obtained by neutralizing the mixture with a 10 wt% ethanol solution acidified with hydrochloric acid. The polymerization activity and the polymer performance parameters are shown in Table 1.
Example 6
Continuously drying a 1L stainless steel polymerization kettle equipped with mechanical stirring at 130 deg.C for 6h, vacuumizing while hot, and adding N2Replace qi for 3 times. 500mL of hexane was charged to the polymerization system while adding 3.8mg (6. mu. mol) of complex Ni1, 50mL of 1, 2-dichloroethane, 15mmol (3.0mL) of dihydromyrcenol, 15mL of AlEt3(1.0mol/L hexane solution), 10mL of MAO (1.53mol/L toluene solution), and the reaction was stirred at 30 ℃ under an ethylene pressure of 10atm for 30 min. Finally, the polymer was obtained by neutralizing the mixture with a 10 wt% ethanol solution acidified with hydrochloric acid. The polymerization activity and the polymer performance parameters are shown in Table 1.
Example 7 (comparative)
Continuously drying a 1L stainless steel polymerization kettle equipped with mechanical stirring at 130 deg.C for 6h, vacuumizing while hot, and adding N2Replace qi for 3 times. To the polymerization system was charged 500mL of hexane while adding 3.8mg (2.5. mu. mol) of complex Ni1, 15mmol (3.0mL) of dihydromyrcenol, 15mL of AlEt3(1.0mol/L in hexane), 10mL of MAO (1.53mol/L in toluene), and the reaction was stirred at 30 ℃ under an ethylene pressure of 10atm for 30 min. Finally, the polymer was obtained by neutralizing the mixture with a 10 wt% ethanol solution acidified with hydrochloric acid. The polymerization activity and the polymer performance parameters are shown in Table 1.
TABLE 1
As can be seen from Table 1, in the preparation method of the invention, when the catalyst catalyzes the copolymerization of ethylene and enol, the polymerization activity is higher, and the obtained polymer has higher sphericity. By regulating and controlling the polymerization conditions, a copolymerization product with good particle morphology can be prepared.
It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not set any limit to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.
Claims (10)
1. A process for producing an olefin-olefin alcohol copolymer, which comprises polymerizing an olefin and an olefin alcohol in the presence of a catalyst and an improver to produce the olefin-olefin alcohol copolymer,
wherein the catalyst comprises a main catalyst and an optional cocatalyst, and the main catalyst comprises a diimine metal complex shown as a formula I:
in the formula I, the compound is shown in the specification,
R1and R2The same or different, independently selected from C1-C30 hydrocarbyl containing or not containing substituent; r5-R10The aryl group is the same or different and is independently selected from hydrogen, halogen, hydroxyl, C1-C20 alkyl with or without substituent, C2-C20 alkenyl with or without substituent, C2-C20 alkynyl with or without substituent, C3-C20 cycloalkyl with or without substituent, C1-C20 alkoxy with or without substituent, C2-C20 alkenyloxy with or without substituent, C2-C20 alkynyloxy with or without substituent, C3-C20 cycloalkoxy with or without substituent, C6-C20 aryl with or without substituent, C7-C20 aralkyl with or without substituent and C7-C20 alkaryl with or without substituent;
m is a group VIII metal;
x is selected from halogen, C1-C10 alkyl with or without substituent and C1-C10 alkoxy with or without substituent.
2. The method of claim 1, wherein R is1And R2Selected from substituted or unsubstituted C1-C20 alkyl and or substituted or unsubstituted C6-C20 aryl, preferably R1And/or R2Is a group of formula A:
in the formula A, R1-R5The aryl group is the same or different and is independently selected from hydrogen, halogen, hydroxyl, C1-C20 alkyl with or without substituent, C2-C20 alkenyl with or without substituent, C2-C20 alkynyl with or without substituent, C3-C20 cycloalkyl with or without substituent, C1-C20 alkoxy with or without substituent, C2-C20 alkenyloxy with or without substituent, C2-C20 alkynyloxy with or without substituent, C3-C20 cycloalkoxy with or without substituent, C6-C20 aryl with or without substituent, C7-C20 aralkyl with or without substituent and C7-C20 alkaryl with or without substituent; r1-R5Optionally forming a ring with each other;
preferably, in formula A, R1-R5The aryl group is the same or different and is independently selected from hydrogen, halogen, hydroxyl, C1-C10 alkyl with or without substituent, C2-C10 alkenyl with or without substituent, C2-C10 alkynyl with or without substituent, C3-C10 cycloalkyl with or without substituent, C1-C10 alkoxy with or without substituent, C2-C10 alkenyloxy with or without substituent, C2-C10 alkynyloxy with or without substituent, C3-C10 cycloalkoxy with or without substituent, C6-C15 aryl with or without substituent, C7-C15 aralkyl with or without substituent and C7-C15 alkaryl with or without substituent;
preferably, M is selected from nickel and palladium; x is selected from halogen, C1-C10 alkyl with or without substituent and C1-C10 alkoxy with or without substituent, more preferably from halogen, C1-C6 alkyl with or without substituent and C1-C6 alkoxy with or without substituent.
3. The method of claim 1 or 2, wherein R is5-R10The aryl group is the same or different and is independently selected from hydrogen, halogen, hydroxyl, C1-C10 alkyl with or without substituent, C2-C10 alkenyl with or without substituent, C2-C10 alkynyl with or without substituent, C3-C10 cycloalkyl with or without substituent, C1-C10 alkoxy with or without substituent, C2-C10 alkenyloxy with or without substituent, C2-C10 alkynyloxy with or without substituent, C3-C10 cycloalkoxy with or without substituent, C6-C15 aryl with or without substituent, C7-C15 aralkyl with or without substituent and C7-C15 alkaryl with or without substituent;
preferably, R5-R10Each independently selected from hydrogen, C1-C10 alkyl, halogenated C1-C10 alkyl, C1-C10 alkoxy, halogenated C1-C10 alkoxy and halogen, more preferably from hydrogen, C1-C6 alkyl, halogenated C1-C6 alkyl, C1-C6 alkoxy, halogenated C1-C6 alkoxy and halogen.
4. A process according to any one of claims 1 to 3, wherein the olefin comprises an olefin having 2 to 16 carbon atoms, preferably the olefin comprises ethylene or an alpha-olefin having 3 to 16 carbon atoms, and/or the olefinic alcohol is selected from one or more olefinic alcohols of formula G:
in the formula G, L1-L3Each independently selected from H and C with or without substituent1-C30Alkyl radical, L4Is C having a pendant group1-C30An alkylene group;
preferably, the copolymer has a content of structural units derived from the olefin alcohol represented by the formula G of 0.4 to 10.0 mol%;
preferably, L1And L2Is H, L3Is H or C1-C30Alkyl radical, L4Is C having a pendant group1-C30An alkylene group;
more preferably, L1And L2Is H, L3Is H or C1-C20Alkyl radical, L4Is C having a pendant group1-C20An alkylene group;
still more preferably, L1And L2Is H, L3Is H or C1-C10Alkyl radical, L4Is C having a pendant group1-C10An alkylene group;
further preferably, L1And L2Is H, L3Is H or C1-C10Alkyl radical, L4Is C having a pendant group1-C6An alkylene group.
5. The method of claim 4, wherein L is1-L3Wherein said substituents are selected from halogen, C1-C10Alkyl radical, C1-C10Alkoxy radical, C6-C10One or more of aryl, cyano and hydroxy; more preferably L1-L3Wherein the substituent is selected from one or more of C1-C6 alkyl, halogen and C1-C6 alkoxy;
the side group in L4 is selected from halogen and C6-C20Aryl radical, C1-C20Alkyl and C1-C20One or more of alkoxy, said C6-C20Aryl radical, C1-C20Alkyl and C1-C20Alkoxy is optionally substituted by a substituent, preferably selected from halogen, C1-C10Alkyl radical, C1-C10Alkoxy radical, C6-C10One or more of aryl and hydroxyl.
6. A method according to any of claims 1 to 5, characterised in that the modifier comprises a halogenated hydrocarbon, preferably selected from C1-C15 halogenated hydrocarbons, more preferably C1-C10 halogenated hydrocarbons, even more preferably C1-C6 halogenated alkanes.
7. The process according to any one of claims 1 to 6, wherein the polymerization is carried out in the presence of a solvent,
preferably, the solvent is an alkane solvent, preferably one or more of C3-20 alkanes, more preferably C3-C10 alkanes;
preferably, the volume ratio of the solvent to the modifier is (1-5000):1, preferably (1.0-500): 1.
8. A process according to any one of claims 1 to 7, wherein the cocatalyst is selected from organoaluminium compounds and/or organoboron compounds; the organic aluminum compound is selected from one or more of alkyl aluminoxane, alkyl aluminum and alkyl aluminum halide; the organoboron compound is selected from an aryl boron and/or a borate;
preferably, when the cocatalyst is an organoaluminum compound, the molar ratio of aluminum in the cocatalyst to M in the diimine metal complex is (10-10)7):1, preferably (10-100000) 1, more preferably (100-; when the cocatalyst is an organoboron compound, the molar ratio of boron in the cocatalyst to M in the diimine metal complex is (0.1-1000):1, preferably (0.1-500): 1.
9. An olefin-olefin alcohol copolymer prepared according to the process of any one of claims 1 to 8, which is spherical and/or spheroidal, and/or which has a particle size of from 0.1 to 50 mm.
10. Use of an olefin-olefin alcohol copolymer prepared according to the process of any one of claims 1 to 8 or of the olefin-olefin alcohol copolymer of claim 9 as a polyolefin material.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1044282A (en) * | 1988-12-30 | 1990-08-01 | 联合碳化化学品及塑料有限公司 | Regulate the catalyzer that molecular weight ethylene polymer distributes |
| CN1268521A (en) * | 1999-03-30 | 2000-10-04 | 中国石油化工集团公司北京化工研究院 | High-activity catalyst for olefin polymerization, preparation method thereof and application of catalyst |
| CN1334276A (en) * | 2000-07-19 | 2002-02-06 | 杨明生 | Linear polyethylene catalyst of gas-phase fluidized-bed method and its preparing process |
| CN109694436A (en) * | 2017-10-24 | 2019-04-30 | 中国石油化工股份有限公司 | A kind of alkene-alkene alkoxide polymer and preparation method thereof |
-
2020
- 2020-06-05 CN CN202010506189.7A patent/CN113754813A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1044282A (en) * | 1988-12-30 | 1990-08-01 | 联合碳化化学品及塑料有限公司 | Regulate the catalyzer that molecular weight ethylene polymer distributes |
| CN1268521A (en) * | 1999-03-30 | 2000-10-04 | 中国石油化工集团公司北京化工研究院 | High-activity catalyst for olefin polymerization, preparation method thereof and application of catalyst |
| CN1334276A (en) * | 2000-07-19 | 2002-02-06 | 杨明生 | Linear polyethylene catalyst of gas-phase fluidized-bed method and its preparing process |
| CN109694436A (en) * | 2017-10-24 | 2019-04-30 | 中国石油化工股份有限公司 | A kind of alkene-alkene alkoxide polymer and preparation method thereof |
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