CN115260368B - Polymerization method of ethylene-internal olefin-diene copolymer and copolymer obtained by polymerization method - Google Patents
Polymerization method of ethylene-internal olefin-diene copolymer and copolymer obtained by polymerization method Download PDFInfo
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- CN115260368B CN115260368B CN202110480841.7A CN202110480841A CN115260368B CN 115260368 B CN115260368 B CN 115260368B CN 202110480841 A CN202110480841 A CN 202110480841A CN 115260368 B CN115260368 B CN 115260368B
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- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 55
- 238000000034 method Methods 0.000 title claims abstract description 21
- 229920001577 copolymer Polymers 0.000 title claims abstract description 18
- -1 diimine metal complex Chemical class 0.000 claims abstract description 82
- 229910000071 diazene Inorganic materials 0.000 claims abstract description 75
- 150000001336 alkenes Chemical class 0.000 claims abstract description 33
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 29
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000005977 Ethylene Substances 0.000 claims abstract description 23
- 150000001993 dienes Chemical class 0.000 claims abstract description 18
- 230000003197 catalytic effect Effects 0.000 claims abstract description 13
- 125000001424 substituent group Chemical group 0.000 claims description 169
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 88
- 229910052736 halogen Inorganic materials 0.000 claims description 45
- 150000002367 halogens Chemical class 0.000 claims description 45
- 229910052751 metal Inorganic materials 0.000 claims description 38
- 239000002184 metal Substances 0.000 claims description 38
- 229910052739 hydrogen Inorganic materials 0.000 claims description 37
- 239000001257 hydrogen Substances 0.000 claims description 37
- RAABOESOVLLHRU-UHFFFAOYSA-N diazene Chemical compound N=N RAABOESOVLLHRU-UHFFFAOYSA-N 0.000 claims description 36
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 36
- 238000006243 chemical reaction Methods 0.000 claims description 32
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims description 25
- 125000000027 (C1-C10) alkoxy group Chemical group 0.000 claims description 23
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims description 19
- 150000001875 compounds Chemical class 0.000 claims description 18
- 229910052759 nickel Inorganic materials 0.000 claims description 17
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 claims description 16
- 125000004191 (C1-C6) alkoxy group Chemical group 0.000 claims description 14
- 125000006736 (C6-C20) aryl group Chemical group 0.000 claims description 14
- 229910052782 aluminium Inorganic materials 0.000 claims description 12
- 125000003860 C1-C20 alkoxy group Chemical group 0.000 claims description 9
- 125000003358 C2-C20 alkenyl group Chemical group 0.000 claims description 9
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical group [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 8
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 8
- 125000003118 aryl group Chemical group 0.000 claims description 7
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 229910052796 boron Inorganic materials 0.000 claims description 5
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 5
- 229910052794 bromium Chemical group 0.000 claims description 5
- 239000002685 polymerization catalyst Substances 0.000 claims description 5
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical group [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 4
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 239000000460 chlorine Chemical group 0.000 claims description 4
- 125000000000 cycloalkoxy group Chemical group 0.000 claims description 4
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 4
- 229910052763 palladium Chemical group 0.000 claims description 4
- 239000004711 α-olefin Substances 0.000 claims description 4
- 125000006659 (C1-C20) hydrocarbyl group Chemical group 0.000 claims description 3
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 3
- 125000005234 alkyl aluminium group Chemical group 0.000 claims description 3
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- 239000011737 fluorine Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 150000001639 boron compounds Chemical class 0.000 claims description 2
- 125000004122 cyclic group Chemical group 0.000 claims description 2
- 125000001153 fluoro group Chemical group F* 0.000 claims description 2
- 150000002430 hydrocarbons Chemical group 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims 6
- 150000004696 coordination complex Chemical class 0.000 claims 2
- 150000002899 organoaluminium compounds Chemical class 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 20
- 230000000694 effects Effects 0.000 abstract description 8
- 238000007334 copolymerization reaction Methods 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 238000002156 mixing Methods 0.000 abstract description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 54
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 48
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 47
- 229920000642 polymer Polymers 0.000 description 47
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 36
- 239000000243 solution Substances 0.000 description 34
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 33
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 19
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 19
- 238000009826 distribution Methods 0.000 description 19
- 239000012065 filter cake Substances 0.000 description 18
- 230000037048 polymerization activity Effects 0.000 description 18
- 229920000098 polyolefin Polymers 0.000 description 16
- 238000002360 preparation method Methods 0.000 description 14
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 13
- 239000003446 ligand Substances 0.000 description 13
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 13
- 239000003960 organic solvent Substances 0.000 description 12
- NLDGJRWPPOSWLC-UHFFFAOYSA-N deca-1,9-diene Chemical compound C=CCCCCCCC=C NLDGJRWPPOSWLC-UHFFFAOYSA-N 0.000 description 11
- ILPBINAXDRFYPL-UHFFFAOYSA-N 2-octene Chemical compound CCCCCC=CC ILPBINAXDRFYPL-UHFFFAOYSA-N 0.000 description 10
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 10
- 238000010907 mechanical stirring Methods 0.000 description 10
- 229910001220 stainless steel Inorganic materials 0.000 description 10
- 239000010935 stainless steel Substances 0.000 description 10
- 238000000921 elemental analysis Methods 0.000 description 9
- 238000001914 filtration Methods 0.000 description 9
- 238000001556 precipitation Methods 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 238000006386 neutralization reaction Methods 0.000 description 8
- 239000002244 precipitate Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 8
- 238000001291 vacuum drying Methods 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 7
- 239000000178 monomer Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 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 6
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- 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 6
- VOSLXTGMYNYCPW-UHFFFAOYSA-N 1,10-Undecadiene Chemical compound C=CCCCCCCCC=C VOSLXTGMYNYCPW-UHFFFAOYSA-N 0.000 description 5
- JLTDJTHDQAWBAV-UHFFFAOYSA-O dimethyl(phenyl)azanium Chemical compound C[NH+](C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-O 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 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 5
- VHSVJTYBTJCDFL-UHFFFAOYSA-L 1,2-dimethoxyethane;nickel(2+);dibromide Chemical compound Br[Ni]Br.COCCOC VHSVJTYBTJCDFL-UHFFFAOYSA-L 0.000 description 4
- 229910021585 Nickel(II) bromide Inorganic materials 0.000 description 4
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 4
- OCMNCWNTDDVHFK-UHFFFAOYSA-L dichloronickel;1,2-dimethoxyethane Chemical compound Cl[Ni]Cl.COCCOC OCMNCWNTDDVHFK-UHFFFAOYSA-L 0.000 description 4
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 4
- IPLJNQFXJUCRNH-UHFFFAOYSA-L nickel(2+);dibromide Chemical compound [Ni+2].[Br-].[Br-] IPLJNQFXJUCRNH-UHFFFAOYSA-L 0.000 description 4
- VJHGSLHHMIELQD-UHFFFAOYSA-N nona-1,8-diene Chemical compound C=CCCCCCC=C VJHGSLHHMIELQD-UHFFFAOYSA-N 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000002904 solvent 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
- GGQQNYXPYWCUHG-RMTFUQJTSA-N (3e,6e)-deca-3,6-diene Chemical compound CCC\C=C\C\C=C\CC GGQQNYXPYWCUHG-RMTFUQJTSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000012442 inert solvent Substances 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- ZOKYTRIEIDWYSG-PKNBQFBNSA-N (e)-dodec-5-ene Chemical compound CCCCCC\C=C\CCCC ZOKYTRIEIDWYSG-PKNBQFBNSA-N 0.000 description 2
- XWJBRBSPAODJER-UHFFFAOYSA-N 1,7-octadiene Chemical compound C=CCCCCC=C XWJBRBSPAODJER-UHFFFAOYSA-N 0.000 description 2
- RYPKRALMXUUNKS-UHFFFAOYSA-N 2-Hexene Natural products CCCC=CC RYPKRALMXUUNKS-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 125000006374 C2-C10 alkenyl group Chemical group 0.000 description 2
- 125000005865 C2-C10alkynyl group Chemical group 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 125000003302 alkenyloxy group Chemical group 0.000 description 2
- 125000005133 alkynyloxy group Chemical group 0.000 description 2
- 239000000010 aprotic solvent Substances 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 238000012662 bulk polymerization Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 150000008282 halocarbons Chemical class 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-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
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 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
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- 229920006124 polyolefin elastomer Polymers 0.000 description 2
- 239000000126 substance Substances 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
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 2
- AHAREKHAZNPPMI-AATRIKPKSA-N (3e)-hexa-1,3-diene Chemical compound CC\C=C\C=C AHAREKHAZNPPMI-AATRIKPKSA-N 0.000 description 1
- PRBHEGAFLDMLAL-GQCTYLIASA-N (4e)-hexa-1,4-diene Chemical compound C\C=C\CC=C PRBHEGAFLDMLAL-GQCTYLIASA-N 0.000 description 1
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- YCTDZYMMFQCTEO-FNORWQNLSA-N (E)-3-octene Chemical compound CCCC\C=C\CC YCTDZYMMFQCTEO-FNORWQNLSA-N 0.000 description 1
- IRUCBBFNLDIMIK-BQYQJAHWSA-N (e)-oct-4-ene Chemical compound CCC\C=C\CCC IRUCBBFNLDIMIK-BQYQJAHWSA-N 0.000 description 1
- IRUCBBFNLDIMIK-FPLPWBNLSA-N (z)-oct-4-ene Chemical compound CCC\C=C/CCC IRUCBBFNLDIMIK-FPLPWBNLSA-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
- VNQXSTWCDUXYEZ-UHFFFAOYSA-N 1,7,7-trimethylbicyclo[2.2.1]heptane-2,3-dione Chemical compound C1CC2(C)C(=O)C(=O)C1C2(C)C VNQXSTWCDUXYEZ-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- FOYHNROGBXVLLX-UHFFFAOYSA-N 2,6-diethylaniline Chemical compound CCC1=CC=CC(CC)=C1N FOYHNROGBXVLLX-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- ZQDPJFUHLCOCRG-UHFFFAOYSA-N 3-hexene Chemical compound CCC=CCC ZQDPJFUHLCOCRG-UHFFFAOYSA-N 0.000 description 1
- MCSXGCZMEPXKIW-UHFFFAOYSA-N 3-hydroxy-4-[(4-methyl-2-nitrophenyl)diazenyl]-N-(3-nitrophenyl)naphthalene-2-carboxamide Chemical compound Cc1ccc(N=Nc2c(O)c(cc3ccccc23)C(=O)Nc2cccc(c2)[N+]([O-])=O)c(c1)[N+]([O-])=O MCSXGCZMEPXKIW-UHFFFAOYSA-N 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
- 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
- LHHPZYHDQNNRAK-UHFFFAOYSA-N 6-ethylundeca-1,10-diene Chemical compound C=CCCCC(CC)CCCC=C LHHPZYHDQNNRAK-UHFFFAOYSA-N 0.000 description 1
- UCKITPBQPGXDHV-UHFFFAOYSA-N 7-methylocta-1,6-diene Chemical compound CC(C)=CCCCC=C UCKITPBQPGXDHV-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- NNWIRQZPEDSHLN-UHFFFAOYSA-N 9-oxodecanal Chemical compound CC(=O)CCCCCCCC=O NNWIRQZPEDSHLN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- 229920000034 Plastomer Polymers 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001350 alkyl halides Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [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
- BFAKENXZKHGIGE-UHFFFAOYSA-N bis(2,3,5,6-tetrafluoro-4-iodophenyl)diazene Chemical compound FC1=C(C(=C(C(=C1F)I)F)F)N=NC1=C(C(=C(C(=C1F)F)I)F)F BFAKENXZKHGIGE-UHFFFAOYSA-N 0.000 description 1
- AZWXAPCAJCYGIA-UHFFFAOYSA-N bis(2-methylpropyl)alumane Chemical compound CC(C)C[AlH]CC(C)C AZWXAPCAJCYGIA-UHFFFAOYSA-N 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
- 229930006711 bornane-2,3-dione Natural products 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000013078 crystal Substances 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
- YKNMBTZOEVIJCM-UHFFFAOYSA-N dec-2-ene Chemical compound CCCCCCCC=CC YKNMBTZOEVIJCM-UHFFFAOYSA-N 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- HJXBDPDUCXORKZ-UHFFFAOYSA-N diethylalumane Chemical compound CC[AlH]CC HJXBDPDUCXORKZ-UHFFFAOYSA-N 0.000 description 1
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 1
- IYPLTVKTLDQUGG-UHFFFAOYSA-N dodeca-1,11-diene Chemical compound C=CCCCCCCCCC=C IYPLTVKTLDQUGG-UHFFFAOYSA-N 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- UAIZDWNSWGTKFZ-UHFFFAOYSA-L ethylaluminum(2+);dichloride Chemical compound CC[Al](Cl)Cl UAIZDWNSWGTKFZ-UHFFFAOYSA-L 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 238000004442 gravimetric analysis Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 1
- 238000002356 laser light scattering Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 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
- 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
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- IRUCBBFNLDIMIK-UHFFFAOYSA-N oct-4-ene Chemical compound CCCC=CCCC IRUCBBFNLDIMIK-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 125000002524 organometallic group Chemical group 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
- 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
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000007363 ring formation reaction Methods 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
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000012916 structural analysis Methods 0.000 description 1
- 239000010689 synthetic lubricating oil Substances 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
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 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
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- ZQDPJFUHLCOCRG-AATRIKPKSA-N trans-3-hexene Chemical compound CC\C=C\CC ZQDPJFUHLCOCRG-AATRIKPKSA-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
- LFXVBWRMVZPLFK-UHFFFAOYSA-N trioctylalumane Chemical compound CCCCCCCC[Al](CCCCCCCC)CCCCCCCC LFXVBWRMVZPLFK-UHFFFAOYSA-N 0.000 description 1
- CNWZYDSEVLFSMS-UHFFFAOYSA-N tripropylalumane Chemical compound CCC[Al](CCC)CCC CNWZYDSEVLFSMS-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
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 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
- C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
- C08F210/18—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers with non-conjugated dienes, e.g. EPT rubbers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2410/00—Features related to the catalyst preparation, the catalyst use or to the deactivation of the catalyst
- C08F2410/03—Multinuclear procatalyst, i.e. containing two or more metals, being different or not
Landscapes
- 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)
- Catalysts (AREA)
Abstract
The invention discloses a polymerization method of an ethylene-internal olefin-diene copolymer and a copolymer obtained by the polymerization method. The copolymerization process comprises copolymerizing ethylene with at least one internal olefin and at least one diene in the presence of a catalytic system comprising a diimine metal complex of the formula (I),
Description
Technical Field
The invention relates to the field of olefin polymerization, in particular to a polymerization method of an ethylene-internal olefin-diene copolymer and the copolymer obtained by the polymerization method.
Background
Polyolefin materials such as polyethylene and polypropylene have become one of the most important products in the chemical industry since the discovery of Ziegler-Natta catalysts in the fifties of the twentieth century, and are widely used in various fields due to their low cost and excellent mechanical properties. However, the nonpolar nature of the polyolefin material limits the application range, so that the functional modification of the polyolefin material is a very popular subject in the field, and the modified polyolefin has improved properties in various aspects such as dyeing property, adhesion, hydrophilicity and the like. The functional modification of the polyolefin material can be obtained by a method of performing post-functionalization on the polymer or directly copolymerizing the polymer with a polar monomer, or a method of copolymerizing the monomer with a reactive group and introducing the functional group in a further reaction.
In 1995, brookhart et al reported the use of an alpha-nickel diimine/palladium complex to catalyze ethylene polymerization (M.Brookhart et al J.am.chem.Soc.1995,117, 6414) and provided a new catalyst system for the preparation of novel polyolefin materials. The nickel diimine/palladium catalyst can catalyze the (co) polymerization of special monomers which are difficult to polymerize in the common method. For example, internal olefin monomers, because of their large steric drag, have cationic metal centers with bulky ligands that are not easily inserted into the double bonds of internal olefins, and only a few documents report the polymerization behavior of internal olefins (Polymer 2017,127,88;Macromol.Rapid Commun. 2016,37,1375-1381;Organometallics 2018,37,1358-1367); similarly, diolefin monomers have low polymerization activity and/or are prone to cyclization reactions (Kohtaro Osakada et al.J.am.chem.Soc.2007,129,7002; macromol.rapid Commun.2008,29,1932; dalton Transactions 2009,8955), and therefore have been reported for few applications.
Therefore, the copolymerization of ethylene, internal olefin and diene is realized, and the non-cyclic copolymer with reactive double bonds is obtained, so that a large amount of cheap internal olefin monomers can be effectively utilized, the raw material cost is greatly reduced, meanwhile, the reactive groups are introduced, a foundation is provided for subsequent functional modification, the reaction efficiency of grafting, crosslinking and the like is greatly improved, the usability of polyolefin is improved, and the application range of products is expanded.
Disclosure of Invention
The invention is widely and intensively studied to prepare a catalytic system containing a novel complex, which can catalyze ethylene, at least one internal olefin and at least one diene to copolymerize with high activity to prepare a supported olefin polymer with double bonds. Compared with commercial polyolefin elastomer and synthetic lubricating oil additive, the invention does not need to separate internal olefin from mixed olefin, thus greatly simplifying the process flow and reducing the production cost; the product has a reactive double bond structure, can be correspondingly modified according to the application requirements of specific fields, and has wider applicability and better performance.
It is an object of the present invention to provide a process for polymerizing an ethylene-internal olefin-diene copolymer by copolymerizing ethylene with at least one internal olefin and at least one diene in the presence of a catalytic system comprising a diimine metal complex of the formula (I),
wherein, the structural general formula of the diimine metal complex is as follows:
in the formula (I), R 1 、R 2 Independently selected from the group consisting of substituted or unsubstituted C1-C30 hydrocarbyl groups; r is R 3 、R 4 Independently selected from hydrogen, halogen, hydroxy, substituted or unsubstituted C1-C30 hydrocarbyl, R 3 、R 4 Optionally mutually looping; r' is selected from C1-C20 hydrocarbon groups containing substituent or not containing substituent; y is selected from group VIA nonmetallic atoms; m is a group VIII metal; x is selected from halogen, C1-C10 alkyl containing substituent or C1-C10 alkoxy containing substituent or no substituent.
According to some embodiments of the diimine metal complexes of the present invention, M is selected from nickel or palladium.
According to some embodiments of the diimine metal complexes of the present invention, Y is selected from O or S.
According to some embodiments of the diimine metal complexes of the present invention, X is selected from the group consisting of halogen, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C1-C10 alkoxy, preferably selected from the group consisting of halogen, substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C1-C6 alkoxy.
According to some embodiments of the diimine metal complexes of the present invention, R' is selected from the group consisting of substituted or unsubstituted C1-C20 alkyl groups, preferably substituted or unsubstituted C1-C10 alkyl groups, more preferably substituted or unsubstituted C1-C6 alkyl groups.
According to some embodiments of the diimine metal complexes of the present invention, R 3 And R is 4 And are the same or different and are each independently selected from hydrogen, halogen, hydroxy, C1-C20 alkyl with or without substituents, C2-C20 alkenyl with or without substituents, C2-C20 alkynyl with or without substituents, C3-C20 cycloalkyl with or without substituents, C1-C20 alkoxy with or without substituents, C2-C20 alkenyloxy with or without substituents, C2-C20 alkynyloxy with or without substituents, C3-C20 cycloalkoxy with or without substituents, C6-C20 aryl with or without substituents, C7-C20 aralkyl with or without substituents, and C7-C20 alkylaryl with or without substituents.
According to some embodiments of the diimine metal complexes of the present invention, in formula (I), R 1 、R 2 Independently selected from the group consisting of substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C6-C20 aryl, preferably R 1 、R 2 Is a group of formula (II):
in the formula (II), R 1 ～R 5 Identical or different, each independently selected from hydrogen, halogen, hydroxy, C1-C20 alkyl with or without substituents, C2-C20 alkenyl with or without substituents, C2-C20 alkynyl with or without substituents, C3-C20 cycloalkyl with or without substituents, C1-C20 alkoxy with or without substituents, C2-C20 alkenyloxy with or without substituents, C2-C20 alkynyloxy with or without substituents, C3-C20 cycloalkoxy with or without substituents, C6-C20 aryl with or without substituents, C7-C20 aralkyl with or without substituents, C7-C20 alkylaryl with or without substituents ；R 1 ～R 5 Optionally mutually ring;
preferably, in formula (II), R 1 ～R 5 Each independently selected from the group consisting of hydrogen, halogen, hydroxy, C1-C10 alkyl with or without substituents, C2-C10 alkenyl with or without substituents, C2-C10 alkynyl with or without substituents, C3-C10 cycloalkyl with or without substituents, C1-C10 alkoxy with or without substituents, C2-C10 alkenyloxy with or without substituents, C2-C10 alkynyloxy with or without substituents, C3-C10 cycloalkoxy with or without substituents, C6-C15 aryl with or without substituents, C7-C15 aralkyl with or without substituents, and C7-C15 alkaryl with or without substituents.
According to some embodiments of the diimine metal complexes of the present invention, the diimine metal complexes have a structure as shown in formula (III):
in the formula (III), R 1 ～R 5 Each independently selected from hydrogen, halogen, hydroxy, C1-C10 alkyl with or without substituents, C3-C10 cycloalkyl with or without substituents, C1-C10 alkoxy with or without substituents, C3-C10 cycloalkoxy with or without substituents, C6-C15 aryl with or without substituents, C7-C15 aralkyl with or without substituents, C7-C15 alkylaryl with or without substituents;
R 3 、R 4 Independently selected from hydrogen, C1-C10 alkyl, halogenated C1-C10 alkyl, C1-C10 alkoxy, halogenated C1-C10 alkoxy, halogen, preferably independently selected from hydrogen, C1-C6 alkyl, halogenated C1-C6 alkyl, C1-C6 alkoxy, halogenated C1-C6 alkoxy, halogen;
m is nickel; y is O; x is selected from fluorine, chlorine and bromine;
r' is selected from C1-C20 alkyl groups with or without substituents, preferably C1-C10 alkyl groups with or without substituents, more preferably C1-C6 alkyl groups with or without substituents.
The diimine metal complexes of formula (I) may be prepared by: bringing a diimine compound represented by the formula (1) into contact with MX n And R' YH are reacted with each other,
in the above formula (1), R 1 、R 2 、R 3 And R is 4 Having the same definition as formula (I); MX (MX) n Wherein M and X have the same definition as the formula (I), n is the number of X satisfying the valence state of M, and n is 1,2 or 3; y and R 'in R' YH have the same definition as in formula (I).
The above reaction is carried out in an organic solvent, preferably the organic solvent is a haloalkane, more preferably the organic solvent is selected from one or more of dichloromethane, chloroform and 1, 2-dichloroethane. The reaction is preferably carried out at a temperature of 15-40 ℃.
The MXn includes nickel halides such as nickel bromide and nickel chloride; and 1, 2-dimethoxyethane nickel halides such as 1, 2-dimethoxyethane nickel bromide and 1, 2-dimethoxyethane nickel chloride.
The related structure and preparation method of the diimine metal complex shown in the formula (I) or the formula (III) can be seen in Chinese patent application CN201911049039.1, and Chinese patent application CN201911049039.1 is fully incorporated into the invention.
According to some embodiments of the diimine metal complexes of the present invention, the diimine metal complexes have a structure as shown in formula (IV):
in the formula (IV), R 5 ～R 7 Independently selected from hydrogen, halogen, hydroxy, substituted or unsubstituted C1-C30 hydrocarbon, R 5 ～R 7 Optionally mutually looping; preferably, R 5 ～R 7 Independently selected from hydrogen, C1-C10 alkyl, halogenated C1-C10 alkyl, C1-C10 alkoxy, halogenated C1-C10 alkoxy, halogen, more preferably from hydrogen, C1-C6 alkyl, halogenated C1-C6 alkyl, C1-C6 alkoxy, halogenated C1-C6 alkoxy, halogen.
In the formula (IV), R 1 、R 2 Identical or different, independently selected from the group consisting of substituted or unsubstituted C1-C30 hydrocarbyl groups; r' is selected from C1-C20 hydrocarbon groups containing substituent or not containing substituent; y is selected from group VIA nonmetallic atoms; m is a group VIII metal; x is selected from halogen, C1-C10 alkyl containing substituent or not and C1-C10 alkoxy containing substituent or not.
According to some embodiments of the diimine metal complexes of the present invention, in formula (IV), R 1 、R 2 Independently selected from the group consisting of substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C6-C20 aryl, preferably R 1 、R 2 Is a group represented by the above formula (II).
According to some embodiments of the diimine metal complexes of the present invention, the diimine metal complexes have a structure as shown in formula (V):
in the formula (V), R 1 ～R 5 The same or different, are independently selected from hydrogen, halogen, substituent-containing or substituent-free C1-C6 alkyl, substituent-containing or substituent-free C1-C6 alkoxy; r is R 5 ～R 10 Independently selected from hydrogen, halogen, C1-C6 alkyl, C1-C6 alkoxy; m is nickel; y is O; x is selected from halogen; r' is selected from C1-C6 alkyl containing substituent or not containing substituent.
The diimine metal complexes of formula (IV) may be prepared by: bringing a diimine compound represented by the formula (2) into contact with MX n And R' YH are reacted with each other,
in the formula (2), R 5 、R 6 、R 7 Has the same definition as formula (IV); r is R 1 And R is 2 Having the same definition as formula (I); MX (MX) n Wherein M and X have the same definition as the formula (I), n is the number of X satisfying the valence state of M, and n is 1, 2 or 3; y and R 'in R' YH have the same definition as in formula (I).
The above reaction to form the diimine metal complex of the formula (IV) is carried out in an organic solvent, preferably the organic solvent is a halogenated alkane, more preferably the organic solvent is one or more selected from dichloromethane, chloroform and 1, 2-dichloroethane. The reaction is preferably carried out at a temperature of 15-40 ℃.
The MXn includes nickel halides such as nickel bromide and nickel chloride; and 1, 2-dimethoxyethane nickel halides such as 1, 2-dimethoxyethane nickel bromide and 1, 2-dimethoxyethane nickel chloride.
The preparation of the diimine compound represented by the formula (2) comprises reacting a diketone compound represented by the formula (2') with R 1 NH 2 And R is 2 NH 2 And (3) reacting to produce the diimine compound shown in the formula (2).
Wherein R is 1 And R is 2 Having the same definition as formula (I); r is R 5 -R 7 Has the same definition as formula (IV).
In the reaction for producing the diimine compound of (2), the catalyst used in the reaction is selected from organic acids such as formic acid, acetic acid and p-toluenesulfonic acid, and the solvent is preferably one or more of methanol, ethanol and acetonitrile.
The related structure and preparation method of the diimine metal complex shown in the formula (IV) or the formula (V) can be seen in Chinese patent application CN201911049899.5, and Chinese patent application CN201911049899.5 is fully incorporated into the invention.
According to some embodiments of the diimine metal complexes of the present invention, the diimine metal complexes have a structure as shown in formula (VI):
wherein R is 5 ～R 8 Identical or different, independently selected from hydrogen, halogen, hydroxy, substituted or unsubstituted C1-C30 hydrocarbyl, R 5 ～R 8 Optionally mutually looping; preferably, R 5 ～R 8 Independently selected from hydrogen, C1-C10 alkyl, halogenated C1-C10 alkyl, C1-C10 alkoxy, halogenated C1-C10 alkoxy, halogen, more preferably from hydrogen, C1-C6 alkyl, halogenated C1-C6 alkyl, C1-C6 alkoxy, halogenated C1-C6 alkoxy, halogen.
In the formula (VI), R 1 、R 2 Identical or different, independently selected from the group consisting of substituted or unsubstituted C1-C30 hydrocarbyl groups; r' is selected from C1-C20 hydrocarbon groups containing substituent or not containing substituent; y is selected from group VIA nonmetallic atoms; m is a group VIII metal; x is selected from halogen, C1-C10 alkyl containing substituent or not and C1-C10 alkoxy containing substituent or not.
According to some embodiments of the diimine metal complexes of the present invention, in formula (VI), R 1 、R 2 Independently selected from the group consisting of substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C6-C20 aryl, preferably R 1 、R 2 Is a group represented by the above formula (II).
According to some embodiments of the diimine metal complexes of the present invention, the diimine metal complexes have a structure as shown in formula (VII):
in the formula (VII), R 1 ～R 11 The same or different, independently selectedFrom hydrogen, halogen, hydroxy, C1-C20 alkyl with or without substituents, C2-C20 alkenyl with or without substituents, C2-C20 alkynyl with or without substituents, C3-C20 cycloalkyl with or without substituents, C1-C20 alkoxy with or without substituents, C2-C20 alkenyloxy with or without substituents, C2-C20 alkynyloxy with or without substituents, C3-C20 cycloalkoxy with or without substituents, C6-C20 aryl with or without substituents, C6-C20 aryloxy with or without substituents, C7-C20 aralkyl with or without substituents, C7-C20 aralkoxy with or without substituents, C7-C20 alkylaryl with or without substituents, and C7-C20 aralkoxy with or without substituents.
Preferably, R 1 ～R 11 Independently selected from the group consisting of hydrogen, halogen, hydroxy, C1-C10 alkyl with or without substituents, C2-C10 alkenyl with or without substituents, C2-C10 alkynyl with or without substituents, C3-C10 cycloalkyl with or without substituents, C1-C10 alkoxy with or without substituents, C2-C10 alkenyloxy with or without substituents, C2-C10 alkynyloxy with or without substituents, C3-C10 cycloalkoxy with or without substituents, C6-C15 aryl with or without substituents, C7-C15 aralkyl with or without substituents, and C7-C15 alkylaryl with or without substituents.
The diimine metal complexes of formula (VI) may be prepared by: bringing a diimine compound represented by the formula (3) into contact with MX n And R' YH are reacted with each other,
in the formula (3), R 1 And R is 2 Has the same definition as formula (I), R 5 -R 8 Having the same definition as formula (VI); MX (MX) n Wherein M and X have the same meanings as those of formula (I), n is a number satisfying the valence of MN is 1,2 or 3; y and R 'in R' YH have the same definition as in formula (I).
The above reaction to form the diimine metal complex of the formula (VI) is carried out in an organic solvent, preferably the organic solvent is a halogenated alkane, more preferably the organic solvent is one or more selected from dichloromethane, chloroform and 1, 2-dichloroethane. The reaction is preferably carried out at a temperature of 15-40 ℃.
The MXn includes nickel halides such as nickel bromide and nickel chloride; and 1, 2-dimethoxyethane nickel halides such as 1, 2-dimethoxyethane nickel bromide and 1, 2-dimethoxyethane nickel chloride.
The preparation of the diimine compound represented by the formula (3) comprises reacting a diketone compound represented by the formula (3') with R 1 NH 2 And R is 2 NH 2 And (3) reacting to produce the diimine compound represented by the formula (3).
In the above reaction for producing the diimine compound represented by the formula (3), the reaction is carried out in the presence of an aluminum alkyl and an aprotic solvent, preferably one or more of toluene, benzene and xylene. The alkyl aluminum compound is a C1-C6 alkyl aluminum compound such as trimethylaluminum, triethylaluminum, tripropylaluminum, etc., preferably trimethylaluminum.
The related structure and preparation method of the diimine metal complexes shown in the formula (VI) or the formula (VII) can be seen in Chinese patent application CN201911048975.0, and the whole Chinese patent application CN201911048975.0 is incorporated into the invention.
According to some embodiments of the diimine metal complexes of the present invention, the diimine metal complexes have a structure as shown in formula (VIII):
wherein,,R 21 ～R 24 independently selected from hydrogen, halogen, hydroxy, substituted or unsubstituted C1-C20 hydrocarbyl, substituted or unsubstituted C1-C20 hydrocarbyloxy, R 21 ～R 24 Optionally interconnected to form a ring or ring system; preferably, R 21 ～R 24 Each independently selected from the group consisting of hydrogen, halogen, C1-C20 alkyl with or without substituents, C2-C20 alkenyl with or without substituents, C2-C20 alkynyl with or without substituents, C1-C20 alkoxy with or without substituents, C2-C20 alkenyloxy with or without substituents, C2-C20 alkynyloxy with or without substituents, C6-C20 aryl with or without substituents, C6-C20 aryloxy with or without substituents, C7-C20 aralkyl with or without substituents, C7-C20 aralkoxy with or without substituents, C7-C20 alkaryl with or without substituents, and C7-C20 alkaryloxy with or without substituents.
In the formula (VIII), R 1 、R 2 Identical or different, independently selected from the group consisting of substituted or unsubstituted C1-C30 hydrocarbyl groups; r' is selected from C1-C20 hydrocarbon groups containing substituent or not containing substituent; y is selected from group VIA nonmetallic atoms; m is a group VIII metal; x is selected from halogen, C1-C10 alkyl containing substituent or not and C1-C10 alkoxy containing substituent or not.
According to some embodiments of the diimine metal complexes of the present invention, in formula (VIII), R 1 、R 2 Independently selected from substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C6-C20 aryl, preferably R 1 、R 2 Is a group represented by the above formula (II).
According to some embodiments of the diimine metal complexes of the present invention, the diimine metal complexes have a structure as shown in formula (IX):
in the formula (IX), R 1 ～R 10 Independently selected from the group consisting of hydrogen, halogen, hydroxy, C1-C20 alkyl with or without substituents, C2-C20 alkenyl with or without substituents, C2-C20 alkynyl with or without substituents, C3-C20 cycloalkyl with or without substituents, C1-C20 alkoxy with or without substituents, C2-C20 alkenyloxy with or without substituents, C2-C20 alkynyloxy with or without substituents, C3-C20 cycloalkoxy with or without substituents, C6-C20 aryl with or without substituents, C6-C20 aryloxy with or without substituents, C7-C20 aralkyl with or without substituents, C7-C20 aralkoxy with or without substituents, C7-C20 alkylaryl with or without substituents, and C7-C20 aryloxy with or without substituents.
The diimine metal complex shown in the formula (VIII) is prepared by the following steps: bringing a diimine compound represented by the formula (4) into contact with MX n And R' YH are reacted with each other,
in the formula (4), R 1 And R is 2 Having the same definition as formula (I); r is R 21 ～R 24 Having the same definition as formula (VIII); MX (MX) n Wherein M and X have the same definition as the formula (I), n is the number of X satisfying the valence state of M, and n is 1,2 or 3; y and R 'in R' YH have the same definition as in formula (I).
The above reaction to form the diimine metal complex of the formula (VIII) is carried out in an organic solvent, preferably the organic solvent is a halogenated alkane, more preferably the organic solvent is one or more selected from the group consisting of methylene chloride, chloroform and 1, 2-dichloroethane. The reaction is preferably carried out at a temperature of 15-40 ℃.
The MXn includes nickel halides such as nickel bromide and nickel chloride; and 1, 2-dimethoxyethane nickel halides such as 1, 2-dimethoxyethane nickel bromide and 1, 2-dimethoxyethane nickel chloride.
The preparation of the diimine compound represented by the formula (4) comprises reacting a diketone compound represented by the formula (4') with R 1 NH 2 And R is 2 NH 2 And (3) reacting to produce the diimine compound shown in the formula (4).
In the above reaction for producing the diimine compound represented by the formula (4), the reaction is carried out in the presence of p-toluenesulfonic acid and an aprotic solvent, preferably one or more of toluene, benzene and xylene.
The related structure and preparation method of the diimine metal complexes represented by the above formula (VIII) or formula (IX) can be seen in Chinese patent CN201911049898.0, and Chinese patent CN201911049898.0 is fully incorporated herein.
In the above technical scheme, preferably, the substituent is selected from 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, halogenated C1-C6 alkoxy.
In some embodiments, the C1-C6 alkyl is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, isopentyl, n-hexyl, isohexyl, 3-dimethylbutyl, and the like.
In some embodiments, the C1-C6 alkoxy is selected from methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, n-pentoxy, isopentoxy, n-hexoxy, isohexoxy, 3-dimethylbutoxy, and the like.
In the above technical solution, preferably, the halogen is selected from fluorine, chlorine, bromine and iodine.
The catalytic system preferably comprises a procatalyst diimine metal complex and a cocatalyst, the cocatalyst being an agent which promotes the catalytic reaction, the cocatalyst being selected from organoaluminum compounds and/or organoboron compounds; wherein the organic aluminum compound is preferably at least one of alkyl aluminoxane, alkyl aluminum and alkyl aluminum halide, and the organic boron compound is preferably at least one of aromatic boron and borate.
The organoaluminum compound is selected from alkyl aluminoxanes or of the formula AlR n X 1 3-n An organoaluminum compound (aluminum alkyl or aluminum alkyl halide). AlR of the formula n X 1 3-n Wherein R is a H, C1-C20 hydrocarbyl or C1-C20 hydrocarbyloxy group, preferably C1-C20 alkyl, C1-C20 alkoxy, C7-C20 aralkyl or C6-C20 aryl group; x is X 1 Halogen, preferably chlorine or bromine; 0<n≤3。
According to some embodiments of the invention, specific examples of the organoaluminum compound include, but are not limited to: trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, trioctylaluminum, diethylaluminum monohydride, diisobutylaluminum monohydride, diethylaluminum monochloride, diisobutylaluminum monochloride, sesquiethylaluminum chloride, ethylaluminum dichloride, methylaluminoxane (MAO), modified Methylaluminoxane (MMAO).
According to some embodiments of the invention, the organoboron compound is selected from an aromatic boron and/or borate. The arylboron is preferably substituted or unsubstituted phenylboron, more preferably tris (pentafluorophenyl) borane. The borates are preferably N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate and/or trityl methyl tetrakis (pentafluorophenyl) borate.
According to some embodiments of the invention, when the cocatalyst is an organoaluminum compound, the molar ratio of aluminum in the organoaluminum compound to M in the procatalyst diimine metal complex is (10-10 7 ) 1, e.g., 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 in between, preferably (10-100000): 1, more preferablySelected from (100-10000): 1.
When the cocatalysts are organoboron compounds and organoaluminum compounds, the molar ratio of boron in the cocatalysts to M in the procatalysts diimine metal complex is (0.1-1000) 1, e.g., 0.1:1, 0.2:1, 0.5:1, 1:1, 2:1, 3:1, 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; the molar ratio of aluminum in the organic aluminum compound to M in the main catalyst diimine metal complex is (10-10) 5 ) 1, e.g., 10:1, 20:1, 50:1, 100:1, 200:1, 300:1, 400:1, 500:1, 600:1, 700:1, 800:1, 1000:1, 2000:1, 3000:1, 5000:1, 10000:1, 100000:1 and any value therebetween, preferably (10-5000): 1, more preferably (10-1000): 1.
The amount of the main catalyst diimine metal complex is not particularly limited and may be adjusted according to the specific conditions.
Wherein the internal olefin is preferably selected from non-alpha olefins having 4 to 20 carbon atoms, specific examples include, but are not limited to: 2-hexene, 3-hexene, 2-octene, 3-octene, 4-octene, 2-decene, 5-dodecene, etc.
Wherein the diolefin is preferably selected from diolefins having 4 to 20 carbon atoms, specific examples include, but are not limited to: 1, 3-butadiene, 2-methyl-1, 3-butadiene, 1, 3-pentadiene, 1, 3-hexadiene, 1, 4-hexadiene, 1, 7-octadiene, 7-methyl-1, 6-octadiene, 1, 8-nonadiene, 1, 9-decadiene, 1, 10-undecadiene, 6-ethyl-1, 10-undecadiene, 1, 11-dodecadiene, and the like.
The catalyst system composed of the main catalyst and the cocatalyst can realize the direct copolymerization of ethylene, at least one internal olefin and at least one diene to prepare the branched polyethylene with double bond structure.
Wherein the branched polyolefin refers to a branched polyolefin having a methyl group number of 20 to 150 per 1000 methylene groups in the polymer chain.
The branched polyolefin structure is composed of 13 Molecular weight as measured by C NMR and high temperature GPCThe actual molecular weight measured by high-temperature laser light scattering is compared and determined.
The above reaction may be carried out in an inert solvent, preferably alkanes, aromatic hydrocarbons and halogenated hydrocarbons, or may be carried out directly in olefins as bulk polymerization. Among them, the inert solvent is preferably a saturated hydrocarbon of C5-C20, such as hexane, heptane; halogenated hydrocarbons such as methylene chloride, 1, 2-dichloroethane, 1, 2-tetrachloroethane; aromatic hydrocarbons such as toluene, xylene.
The time for contacting the olefin with the diimine metal complex and the organoaluminum compound in the optional inert solvent may be from 0.5 to 72 hours, as desired; the polymerization temperature is-50 to 200 ℃, preferably 30 to 100 ℃, for example 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃, etc.; the polymerization pressure is 0.1 to 5.0MPa, preferably 0.1 to 2.0MPa, for example, 1.0MPa, 2.0MPa, 3.0MPa, 4.0MPa, 5.0MPa, etc.
By adjusting the structure of the catalyst, the catalyst system can efficiently catalyze ethylene, at least one internal olefin and at least one diene to prepare the branched polyethylene with a double bond structure.
Internal olefins in the present invention refer to olefins in which the double bond is not terminal, and the internal olefin of one olefin may be a mixture of isomers or a single internal olefin. For example, butenes, which may be 1 to C4, cis 2 to C4, trans 2 to C4 and isobutene, may also be mixtures of one or more isomers. The catalyst structure and the composition of the mixed olefins have a certain influence on the structure and the properties of the polymer product.
The catalytic system consisting of the above-described procatalyst diimine metal complexes together with a cocatalyst allows for the preparation of branched polyolefins by polymerization of at least one C4-C20 internal olefin and optionally a C2-C20 terminal olefin monomer. The branched polyolefin refers to a branched polyolefin having a methyl group number of 20 to 150 per 1000 methylene groups in the polymer chain.
The catalyst disclosed by the invention can be applied to various process equipment which is used in the industry at present. The method can be used under homogeneous phase conditions, or can be used under heterogeneous phase conditions after being loaded with an organic carrier or an inorganic carrier.
In the present invention, a representative preparation method comprises the steps of:
(a) The complex of the invention is used as a polymerization catalyst to polymerize mixed olefin at the temperature of-50-200 ℃ and the pressure variation range (0.1-5.0 MPa), thereby forming the branched polymer.
Preferably, a cocatalyst is also present in this step; more preferably, the cocatalyst is selected from the following components: an alkyl aluminum reagent and/or an organoboron reagent.
In another preferred embodiment, step (a) is performed in a solvent selected from the group consisting of: toluene, hexane, methylene chloride, 1, 2-dichloroethane, tetrahydrofuran or without solvent, bulk polymerization.
It is a second object of the present invention to provide an ethylene-internal olefin-diene copolymer obtained by the polymerization process.
Compared with the prior art, the invention has the main advantages that:
(a) The novel catalyst system is utilized to realize the catalytic mixing of olefin and diene copolymer with high activity for the first time, expensive higher alpha-olefin is not needed, and a complex separation process flow in the production of the higher alpha-olefin can be avoided, so that the high-efficiency and high-performance utilization of large chemical products is realized, and the raw material cost is greatly reduced.
(b) The diene is utilized to introduce a reaction group, so that the product can be directly modified according to different requirements to obtain different functional grafted products, and compared with the direct grafting modification by using free radicals, the structure is more uniform, and the side reaction is less; the diene in the mixed olefin can be directly utilized as a comonomer, so that the raw material cost is reduced.
(c) The molecular weight and the melting point of the reactive branched olefin polymer can be controlled in a wider range, and the reactive branched olefin polymer can be used in the fields of processing aids, polyolefin elastomers, plastomers and the like.
The application will be further illustrated with reference to specific examples. It is to be understood that these examples are merely illustrative of the present application and are not intended to limit the scope of the present application. The experimental procedures, which do not address the specific conditions in the examples below, are generally carried out under conventional conditions or under conditions recommended by the manufacturer.
The symbols used in the different formulae or formulae in the present application are, for example, R 1 ～R 8 、R 21 ～R 24 、R 1 ～R 11 R', X, M, Y and the like have the same meanings as defined in the general formulae or the structural formulae unless otherwise specified.
In the present application, C1-C20 alkyl refers to C1-C20 straight chain alkyl or C3-C20 branched chain alkyl, 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, n-decyl.
Examples of C3-C20 cycloalkyl groups include, but are not limited to: cyclopropyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, 4-ethylcyclohexyl, 4-n-propylcyclohexyl, 4-n-butylcyclohexyl.
Examples of C6-C20 aryl groups include, but are not limited to: phenyl, 4-methylphenyl, 4-ethylphenyl, dimethylphenyl, vinylphenyl.
C2-C20 alkenyl refers to C1-C20 straight chain alkenyl or C3-C20 branched alkenyl, including but not limited to: vinyl, allyl, butenyl.
Examples of C7-C20 aralkyl groups include, but are not limited to: phenylmethyl, phenylethyl, phenyl-n-propyl, phenylisopropyl, phenyl-n-butyl, and phenyl-t-butyl.
Examples of C7-C20 alkylaryl groups include, but are not limited to: tolyl, ethylphenyl, n-propylphenyl, isopropylphenyl, n-butylphenyl, and tert-butylphenyl.
Detailed Description
The present invention will be described in detail with reference to the following examples, but it should be understood that the examples are only illustrative of the present invention and are not intended to limit the scope of the present invention in any way. All reasonable variations and combinations that are included within the scope of the inventive concept fall within the scope of the present invention.
The raw materials used in examples and comparative examples, if not particularly limited, are all as disclosed in the prior art, and are, for example, available directly or prepared according to the preparation methods disclosed in the prior art.
The analytical characterization instrument used in the present invention is as follows:
1. nuclear magnetic resonance apparatus: bruker DMX 300 (300 MHz) with tetramethyl silicon (TMS) as an internal standard.
2. Molecular weight and molecular weight distribution PDI of polymer (pdi=mw/Mn): the measurement was carried out at 150℃using a PL-GPC220 chromatograph in the presence of trichlorobenzene as a solvent (wherein the standard sample is PS and the flow rate is 1.0mL/min, and the column is 3 XPlgel 10um M1×ED-B300×7.5 nm).
3. Complex structural analysis: single crystal test analysis was performed using a Rigaku RAXIS Rapid IP diffractometer.
4. The activity measurement method comprises the following steps: gravimetric analysis. The activity is expressed as polymer weight (g). Times.60/(nickel (mol). Times.reaction time (min)).
Example 1
Complex A-Ni 1 Is prepared from the following steps:
will contain 0.277g (0.9 mmol) (DME) NiBr 2 Is slowly added dropwise to an ethanol solution (10 mL) containing 0.175g (0.6 mmol) of ligand A-L 1 To the dichloromethane solution (10 mL) of (2) was stirred at room temperature for 6: 6 h, and dehydrated ether was added for precipitation. Filtering to obtain a filter cake, washing the filter cake with anhydrous diethyl ether, and vacuum drying to obtain yellow powdery solid A-Ni 1 . Yield: 70.2%. Elemental analysis (C) 44 H 58 Br 6 N 4 Ni 3 O 2 ): c,39.72; h,4.39; n,4.21; experimental values (%): c,39.38; h,4.60; n,3.96.
Continuously drying 1L stainless steel polymerization kettle with mechanical stirring at 130deg.C for 2 hr, vacuumizing while it is hot, and using N 2 The air was replaced 3 times. 380mL of hexane, 30mL of 2-octene, 1mL of 1, 9-decanedione and 5.0mL of MAO (1.53 mol/L toluene solution) were added to the polymerization system, together with 3.3mg (2.5. Mu. Mol) of complex A-Ni 1 Ethylene pressure of 10atm was maintained at 60℃and the reaction was stirred for 30min. Finally, the mixture was neutralized with an ethanol solution acidified with 10wt% hydrochloric acid to obtain a polymer. Molecular weight M of the resulting Polymer w ＝13.3×10 4 Molecular weight distribution pdi=3.6, polymerization activity=2.8x10 6 gPE/mol[Ni]h, the proportion of carbon-carbon double bonds in the polymer is 0.34mol percent.
Example 2
This example differs from example 1 in that, in the polymerization step, 30mL of trans-4-octene, 2mL of 1, 9-decadiene, and the resulting polymer had a molecular weight M w ＝14.5×10 4 Molecular weight distribution pdi=3.8, polymerization activity=1.9×10 6 gPE/mol[Ni]h, the proportion of carbon-carbon double bonds in the polymer is 0.56mol%.
Example 3
Complex A-Ni 2 Is prepared from
Will contain 0.277g (0.9 mmol) (DME) NiBr 2 Is slowly added dropwise to an ethanol solution (10 mL) containing 0.272g (0.6 mmol) of ligand A-L 2 In methylene chloride (10 mL). The color of the solution immediately changed to dark red and a large amount of precipitate was formed. Stirring at room temperature for 6h, adding anhydrous diethyl ether for precipitation. Filtering to obtain a filter cake, washing the filter cake with anhydrous diethyl ether, and vacuum drying to obtain brownish red powdery solid A-Ni 2 . The yield was 74.1%. Elemental analysis (C) 64 H 62 Br 6 F 4 N 4 Ni 3 O 2 ): c,46.57; h,3.79; n,3.39; experimental values (%): c,46.72; h,3.97; n,3.48.
A1L stainless steel polymerizer equipped with mechanical stirring was dried continuously at 130℃for 2hrs, evacuated while hot and then N-well dried 2 The air was replaced 3 times. 380mL of hexane, 30mL of 2-octene, 2mL of 1, 8-nonadiene, 1.0mL (1.0 mol/L of heptane) of trimethylaluminum, 12.8mg (25.0. Mu. Mol) of tris (pentafluorophenyl) borane, 20.0mg (25.0. Mu. Mol) of N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, and 4.1 mg (2) were added.5. Mu. Mol) of complex A-Ni 2 . Ethylene pressure of 10atm was maintained at 60℃and the reaction was vigorously stirred for 30min. Neutralization with 10wt% hydrochloric acid acidified ethanol solution, the resulting polymer molecular weight M w ＝5.7×10 4 Molecular weight distribution pdi=3.9, polymerization activity=2.0×10 6 gPE/mol[Ni]h, the proportion of carbon-carbon double bonds in the polymer is 0.55mol percent.
Example 4
Complex B-Ni 1 Is prepared from the following steps:
Will contain 0.277g (0.9 mmol) (DME) NiBr 2 Is slowly added dropwise to an ethanol solution (10 mL) containing 0.249g (0.6 mmol) of ligand B-L 1 In methylene chloride (10 mL). The color of the solution immediately changed to dark red and a large amount of precipitate was formed. Stirring at room temperature for 6h, adding anhydrous diethyl ether for precipitation. Filtering to obtain a filter cake, washing the filter cake with anhydrous diethyl ether, and vacuum drying to obtain a brownish red powdery solid B-Ni 1 . The yield was 78.6%. Elemental analysis (C) 64 H 66 Br 6 N 4 Ni 3 O 2 ): c,48.69; h,4.21; n,3.55; experimental values (%): c, 48.54; h,4.47; n,3.21.
A1L stainless steel polymerizer equipped with mechanical stirring was dried continuously at 130℃for 2hrs, evacuated while hot and then N-well dried 2 The air was replaced 3 times. 420mL of hexane, 30mL of 2-octene, 2mL of 1, 9-decadiene and 5.0mL of MAO (1.53 mol/L in toluene) were added, followed by 4.0mg (2.5. Mu. Mol) of complex B-Ni 1 Ethylene pressure of 10atm was maintained at 60℃and the reaction was vigorously stirred for 30min. Neutralization with 10wt% hydrochloric acid in ethanol, the resulting polymer having a molecular weight M w ＝4.7×10 4 Molecular weight distribution pdi=2.5, polymerization activity=3.6x10 6 gPE/mol[Ni]h, the proportion of carbon-carbon double bonds in the polymer is 0.86mol percent.
Example 5
This example differs from example 4 in that 30mL of the reverse reaction was added during the polymerization step -3-octene, 2ml of 1, 9-decadiene, molecular weight M of the polymer obtained w ＝4.9×10 4 Molecular weight distribution pdi=2.5, polymerization activity=4.2×10 6 gPE/mol[Ni]h, the proportion of carbon-carbon double bonds in the polymer is 0.84mol%.
Example 6
This example differs from example 4 in that, in the polymerization step, 30mL of cis-4-octene, 2mL of 1, 9-decadiene, and the resulting polymer had a molecular weight M w ＝3.5×10 4 Molecular weight distribution pdi=2.7, polymerization activity=3.3×10 6 gPE/mol[Ni]h, the proportion of carbon-carbon double bonds in the polymer is 0.72mol%.
Example 7
This example differs from example 4 in that in the polymerization step, 4mL of 1, 9-decadiene was added, the ethylene pressure of 5atm was maintained, and the resulting polymer molecular weight M w ＝1.5×10 4 Molecular weight distribution pdi=3.1, polymerization activity=1.0×10 6 gPE/mol[Ni]h, the proportion of carbon-carbon double bonds in the polymer is 2.78mol%.
Example 8
This example differs from example 4 in that in the polymerization step, 4mL of 1, 10-undecadiene was added, the ethylene pressure of 5atm was maintained, and the resulting polymer molecular weight M w ＝1.9×10 4 Molecular weight distribution pdi=2.7, polymerization activity=1.1×10 6 gPE/mol[Ni]h, the proportion of carbon-carbon double bonds in the polymer is 2.97mol%.
Example 9
Complex B-Ni 2 Is prepared from the following steps:
will contain 0.277g (0.9 mmol) (DME) NiBr 2 Is slowly added dropwise to an ethanol solution (10 mL) containing 0.233g (0.6 mmol) of ligand B-L 2 In methylene chloride (10 mL). The color of the solution immediately changed to dark red and a large amount of precipitate was formed. Stirring at room temperature for 6h, adding anhydrous diethyl ether for precipitation. Filtering to obtain filter cake, and using anhydrous diethyl etherWashing the filter cake, and vacuum drying to obtain brownish red powdery solid B-Ni 2 . Yield rate: 78.2%. Elemental analysis (C) 60 H 58 Br 6 N 4 Ni 3 O 2 ): c,47.33; h,3.84; n,3.68; experimental values (%): c,47.38; h,4.00; n,3.46.
Continuously drying 1L stainless steel polymerization kettle with mechanical stirring at 130deg.C for 6 hr, vacuumizing while it is hot, and using N 2 The air was replaced 3 times. 380mL of hexane, 30mL of 2-octene, 2mL of 1, 9-decanediene, and 1.0mL (1.0 mol/L of heptane solution) of trimethylaluminum, 12.8mg (25.0. Mu. Mol) of tris (pentafluorophenyl) borane, 20.0mg (25.0. Mu. Mol) of N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate were added to the polymerization system, along with 3.8mg (2.5. Mu. Mol) of complex B-Ni 2 Ethylene pressure of 10atm was maintained at 60℃and the reaction was stirred for 30min. Finally neutralizing with 10wt% hydrochloric acid acidified ethanol solution to obtain polymer with molecular weight M w ＝8.4×10 4 Molecular weight distribution pdi=4.5, polymerization activity=6.1×10 6 gPE/mol[Ni]h, the proportion of carbon-carbon double bonds in the polymer is 0.39mol%.
Example 10
Complex B-Ni 3 Is prepared from the following steps:
will contain 0.277g (0.9 mmol) (DME) NiBr 2 Is slowly added dropwise to an ethanol solution (10 mL) containing 0.389g (0.6 mmol) of ligand B-L 3 In methylene chloride (10 mL). The color of the solution immediately changed to dark red and a large amount of precipitate was formed. Stirring at room temperature for 6h, adding anhydrous diethyl ether for precipitation. Filtering to obtain a filter cake, washing the filter cake with anhydrous diethyl ether, and vacuum drying to obtain a brownish red powdery solid B-Ni 3 . The yield was 74.1%. Elemental analysis (C) 52 H 34 Br 14 N 4 Ni 3 O 2 ): c,30.59; h,1.68; n,2.74; experimental values (%): c, 30.72; h,1.97; n,2.48.
A1L stainless steel polymerizer equipped with mechanical stirring was connected at 130 ℃Drying for 2hrs, evacuating while hot and applying N 2 The air was replaced 3 times. 380mL of hexane, 30mL of 2-octene, 2mL of 1, 10-undecadiene, and 1.0mL (1.0 mol/L of heptane) of trimethylaluminum, 12.8mg (25.0. Mu. Mol) of tris (pentafluorophenyl) borane, 20.0mg (25.0. Mu. Mol) of N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, and 5.1mg (2.5. Mu. Mol) of complex B-Ni were added 3 . The reaction was vigorously stirred at 60℃for 30min while maintaining an ethylene pressure of 10 atm. Neutralization with 10wt% hydrochloric acid acidified ethanol solution, the resulting polymer molecular weight M w ＝9.6×10 4 Molecular weight distribution pdi=4.7, polymerization activity=3.9×10 6 gPE/mol[Ni]h, the proportion of carbon-carbon double bonds in the polymer is 0.43mol%.
Example 11
Complex C-Ni 1 Preparation of (R in the structural formula (III)) 1 、R 3 Is ethyl, R 2 、R 4 -R 7 、R 10 Is hydrogen, R 8 、R 9 And R is 11 Methyl, R' is ethyl, M is nickel, Y is oxygen, and X is bromine
Under the protection of nitrogen, 2, 6-diethylaniline (2.0 ml,12 mmol) is dissolved in 20ml toluene, and then 12ml (1.0M, 12 mmol) of trimethylaluminum is dripped at normal temperature, the reaction is refluxed for 2 hours, the system is cooled to room temperature, camphorquinone (0.831 g,5 mmol) is added, and the system is refluxed for 6 hours. Neutralizing the reaction product with sodium hydroxide aqueous solution, extracting with dichloromethane, drying, and column chromatography to obtain yellow ligand C-L 1 The yield was 69.2%. 1 H-NMR(CDCl 3 ): δ6.94-6.92(m,6H,C Ar -CH 3 ),2.56-2.51(m,4H,C Ar -CH 3 ),2.36-2.31(m,4H,C Ar -CH 3 ), 1.82-1.78(m,4H,CH 2 ),1.54(m,1H),1.24-1.18(m,12H),1.09(s,3H,CH 3 ),0.94(m, 6H,CH 3 )。
Will contain 0.277g (0.9 mmol) (DME) NiBr 2 Is slowly added dropwise to an ethanol solution containing 0.258 g (0.6 mmol) of ligand C-L 1 Is in methylene chloride solution. The color of the solution immediately changed to dark red and a large amount of precipitate was formed. Stirring at room temperature for 6h, adding anhydrous diethyl ether for precipitation. Filtering to obtain a filter cake, washing the filter cake with anhydrous ethyl ether, and vacuum dryingObtaining brownish red powdery solid C-Ni 1 . Yield: 78.2%. Elemental analysis (C) 64 H 90 Br 6 N 4 Ni 3 O 2 ): c,47.96; h,5.66; n,3.50; experimental values (%): c,47.48; h,6.00; n,3.26.
A1L stainless steel polymerizer equipped with mechanical stirring was dried continuously at 130℃for 6hrs, evacuated while hot and N-terminally heated 2 The air was replaced 3 times. 500ml of hexane, 30ml of 2-octene, 2ml of 1, 9-decadiene and 5.0ml of Methylaluminoxane (MAO) (1.53 mol/l in toluene) were added, 4.0mg (2.5. Mu. Mol) of complex C-Ni was added 1 . The reaction was vigorously stirred at 60℃for 30min while maintaining an ethylene pressure of 10 atm. Neutralization with 5% hydrochloric acid acidified ethanol solution, the resulting polymer molecular weight M w ＝8.3×10 4 Molecular weight distribution pdi=3.2, polymerization activity=3.9×10 6 gPE/mol[Ni]h, the proportion of carbon-carbon double bonds in the polymer is 0.15 mol percent.
Example 12
A1L stainless steel polymerizer equipped with mechanical stirring was dried continuously at 130℃for 2hrs, evacuated while hot and then N-well dried 2 The air was replaced 3 times. 440mL of hexane, 30mL of 2-octene, 2mL of 1, 10-undecadiene, 1.0mL (1.0 mol/L of heptane) of trimethylaluminum, 12.8mg (25.0. Mu. Mol) of tris (pentafluorophenyl) borane, 20.0mg (25.0. Mu. Mol) of N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, and 4.0. 4.0mg (2.5. Mu. Mol) of complex C-Ni were added 1 . Ethylene pressure of 10atm was maintained at 60℃and the reaction was vigorously stirred for 30min. Neutralization with 5% hydrochloric acid acidified ethanol solution, the resulting polymer molecular weight M w ＝8.5×10 4 Molecular weight distribution pdi=3.9, polymerization activity=4.4×10 6 gPE/mol[Ni]h, the proportion of carbon-carbon double bonds in the polymer is 0.17mol percent.
Example 13
This example differs from example 11 in that, in the polymerization step, 30mL of trans-3-hexene, 2mL of 1, 9-decadiene, was added to give a polymer having a molecular weight M w ＝8.8×10 4 Molecular weight distribution pdi=3.8, polymerization activity=3.4×10 6 gPE/mol[Ni]h, the proportion of carbon-carbon double bonds in the polymer is 0.14mol%.
Example 14
Ligand D-L 1 Reference patent CN106397264 (structural formula D-L) 1 R in (B) 1 ＝R 3 ＝R 4 ＝R 6 ＝ Et，R 2 、R 5 、R 7 -R 10 Is hydrogen, R 21 Is tert-butyl, R 22 Hydrogen).
Complex D-Ni 1 Preparation of (in the formula (IX) R 1 、R 3 、R 4 、R 6 Is ethyl, R 2 、R 5 、 R 7 -R 10 、R 22 Is hydrogen, R 21 Tertiary butyl, and R' is ethyl, M is nickel, Y is O, X is Br):
will contain 0.277g (0.9 mmol) (DME) NiBr 2 Is slowly added dropwise to an ethanol solution containing 0.365g (0.6 mmol) of ligand D-L 1 Is in methylene chloride solution. The color of the solution immediately changed to dark red and a large amount of precipitate was formed. Stirring at room temperature for 6h, adding anhydrous diethyl ether for precipitation. Filtering to obtain a filter cake, washing the filter cake with anhydrous diethyl ether, and vacuum drying to obtain brownish red powdery solid D-Ni 1 . The yield was 82.0%. Elemental analysis (C) 92 H 114 Br 6 N 4 Ni 3 O 2 ): c,56.28; h,5.85; n,2.85; experimental values (%): c,56.43; h,6.12; n, 3.08.
Continuously drying 1L stainless steel polymerization kettle with mechanical stirring at 130deg.C for 2 hr, vacuumizing while it is hot, and using N 2 The air was replaced 3 times. 460mL of hexane, 10mL of 2-octene, 1mL of 1, 9-decadiene, 5.0mL of Methylaluminoxane (MAO) (1.53 mol/L in toluene) and 4.9mg (2.5. Mu. Mol) of the complex D-Ni were added 1 . The reaction was vigorously stirred at 60℃for 30min while maintaining an ethylene pressure of 10 atm. Neutralization with 5vt% hydrochloric acid acidified ethanol solution, the resulting polymer molecular weight M w ＝53.1×10 4 Molecular weight distribution pdi=3.6, polymerization activity=1.55×10 6 gPE/mol[Ni]h, the proportion of carbon-carbon double bonds in the polymer is 0.07mol%.
Example 15
Catalyst D-Ni of this example 2 With catalyst D-Ni of example 15 1 Is distinguished in that: r' is isobutyl.
Complex D-Ni 2 Preparation of (in the formula (IX) R 1 、R 3 、R 4 、R 6 Is ethyl, R 2 、R 5 、 R 7 -R 10 、R 22 Is hydrogen, R 21 T-butyl, and R' is isobutyl, M is nickel, Y is O, X is Br):
will contain 0.277g (0.9 mmol) (DME) NiBr 2 Slowly added dropwise to a solution of 2-methyl-1-propanol containing 0.365g (0.6 mmol) of ligand D-L 1 Is in methylene chloride solution. The color of the solution immediately changed to a deep red color, and a large amount of precipitate was formed. Stirring at room temperature for 6h, adding anhydrous diethyl ether for precipitation. Filtering to obtain a filter cake, washing the filter cake with anhydrous diethyl ether, and vacuum drying to obtain brownish red powdery solid D-Ni 2 . The yield was 83.0%. Elemental analysis (C) 96 H 122 Br 6 N 4 Ni 3 O 2 ): c,57.09; h,6.09; n,2.77; experimental values (%): c,57.24; h, 6.32; n,3.04.
Continuously drying 1L stainless steel polymerization kettle with mechanical stirring at 130deg.C for 2 hr, vacuumizing while it is hot, and using N 2 The air was replaced 3 times. 460mL of hexane, 10mL of 5-dodecene, 1mL of 1, 9-decadiene, and 5.0mL of Methylaluminoxane (MAO) (1.53 mol/L in toluene) were added, and 5.0mg (2.5. Mu. Mol) of the complex D-Ni was added 2 . The reaction was vigorously stirred at 60℃for 30min while maintaining an ethylene pressure of 10 atm. Neutralization with 5vt% hydrochloric acid acidified ethanol solution, the resulting polymer molecular weight M w ＝43.1×10 4 Molecular weight distribution pdi=3.5, polymerization activity=1.17×10 6 gPE/mol[Ni]h, the proportion of carbon-carbon double bonds in the polymer is 0.10 mol percent.
Example 16
Complex D-Ni 3 (Complex of formula IXB wherein R 1 ＝R 3 ＝R 4 ＝R 6 ＝iPr，R 2 ＝R 5 ＝R 7 - R 10 ＝R 31 ＝R 32 =h, R' =et, m=ni, y=o, x=br):
ligand D-L 3 Reference patent CN201510462932.2
Complex D-Ni 3 Is prepared from the following steps:
will contain 0.277g (0.9 mmol) (DME) NiBr 2 Is slowly added dropwise to an ethanol solution containing 0.392g (0.6 mmol) of ligand D-L 3 Is in methylene chloride solution. The color of the solution immediately changed to dark red and a large amount of precipitate was formed. Stirring at room temperature for 6h, adding anhydrous diethyl ether for precipitation. Filtering to obtain a filter cake, washing the filter cake with anhydrous diethyl ether, and vacuum drying to obtain brownish red powdery solid D-Ni 3 . The yield was 84.3%. Elemental analysis (C) 100 H 106 Br 6 N 4 Ni 3 O 2 ): c,58.55; h,5.21; n,2.73; experimental values (%): c,58.72; h,4.97; n, 3.11.
Continuously drying 1L stainless steel polymerization kettle with mechanical stirring at 130deg.C for 2 hr, vacuumizing while it is hot, and using N 2 The air was replaced 3 times. 460mL of hexane, 10mL of 2-octene, 1mL of 1, 10-undecadiene, and 5.0mL of Methylaluminoxane (MAO) (1.53 mol/L in toluene) were added, and 5.0mg (2.5. Mu. Mol) of the complex D-Ni was added 3 . The reaction was vigorously stirred at 60℃for 30min while maintaining an ethylene pressure of 10 atm. Neutralization with 5vt% hydrochloric acid acidified ethanol solution, the resulting polymer molecular weight M w ＝56.1×10 4 Molecular weight distribution pdi=4.2, polymerization activity=1.73×10 6 gPE/mol[Ni]h, the proportion of carbon-carbon double bonds in the polymer is 0.07 mol%.
Comparative example 1
This comparative example differs from example 1 in that during the polymerization step 1.6mg (2.5. Mu. Mol) of comparative catalyst A (having the structure of formula A') was added, the resulting polymer having a molecular weight M w ＝8.5×10 4 Molecular weight distribution PDIPolymerization activity=0.34×10 =2.8 6 gPE/mol[Ni]h, the proportion of carbon-carbon double bonds in the polymer is 0.06 mol percent.
Comparative example 2
This comparative example differs from example 1 in that 1.3mg (2.5. Mu. Mol) of comparative catalyst B (whose structure is shown in formula B') was added to give a polymer having a molecular weight M w ＝10.5×10 4 Molecular weight distribution pdi=2.8, polymerization activity=0.14×10 6 gPE/mol[Ni]h, the proportion of carbon-carbon double bonds in the polymer is 0.05mol percent.
It can be seen that the catalyst system still maintains high catalytic activity when catalyzing the polymerization of ethylene-internal olefin-diene, and is more than 10 6 g/mol[Ni]h, the internal alkene and the diene do not show obvious effect of poisoning active centers, the activity is obviously improved compared with that of the traditional nickel diimine catalyst in the comparative example, and the obtained polymer has higher carbon-carbon double bond content.
Claims (22)
1. A process for the polymerization of ethylene-internal olefin-diene copolymers by copolymerizing ethylene with at least one internal olefin and at least one diene in the presence of a catalytic system comprising a diimine metal complex of formula (III),
（III），
R 3 、R 4 independently selected from hydrogen, C1-C10 alkyl, halogenated C1-C10 alkyl, C1-C10 alkoxy, halogenated C1-C10 alkoxy, halogen; r' is selected from C1-C20 hydrocarbon groups containing substituent or not containing substituent; y is selected from O or S; m is selected from nickel or palladium; x is selected from halogen, containingA substituted or unsubstituted C1-C10 hydrocarbon group, a substituted or unsubstituted C1-C10 hydrocarbyloxy group; r is R 1 ～R 5 Each independently selected from the group consisting of hydrogen, halogen, hydroxy, C1-C10 alkyl with or without substituents, C3-C10 cycloalkyl with or without substituents, C1-C10 alkoxy with or without substituents, C3-C10 cycloalkoxy with or without substituents, C6-C15 aryl with or without substituents, C7-C15 aralkyl with or without substituents, and C7-C15 alkylaryl with or without substituents.
2. The polymerization process according to claim 1, wherein,
m is nickel; y is O; x is selected from fluorine, chlorine and bromine; r' is selected from C1-C20 alkyl containing substituent or not containing substituent.
3. The polymerization process according to any one of claims 1 to 2, characterized in that the diimine metal complexes are prepared by the following steps: bringing a diimine compound represented by the formula (1) into contact with MX n And R' YH are reacted with each other,
（1），
（II），
in the formula (1), R 1 、R 2 Is a group represented by the formula (II), R 1 ～R 5 Has the same definition as formula (III), R 3 And R is 4 Having the same definition as formula (III); MX (MX) n Wherein M and X have the same meanings as those of formula (III), n is the number of X satisfying the valence state of M, and n is 1, 2 or 3; y and R 'in R' YH have the same definition as in formula (III).
4. A process for the polymerization of ethylene-internal olefin-diene copolymers by copolymerizing ethylene with at least one internal olefin and at least one diene in the presence of a catalytic system comprising a diimine metal complex of formula (IV):
（IV），
in the formula (IV), R 1 、R 2 Is a group of the formula (II) having the same definition as in formula (III), R 5 ～R 7 Independently selected from hydrogen, halogen, hydroxy, substituted or unsubstituted C1-C30 hydrocarbyl, R 5 ～R 7 Optionally mutually looped.
5. The polymerization process according to claim 4, wherein,
R 5 ～R 7 independently selected from hydrogen, C1-C10 alkyl, halogenated C1-C10 alkyl, C1-C10 alkoxy, halogenated C1-C10 alkoxy, halogen.
6. The polymerization process of claim 4 wherein said diimine metal complex has the structure of formula (V):
（V），
in the formula (V), R 1 ～R 5 Independently selected from hydrogen, halogen, substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C1-C6 alkoxy; r is R 5 ～R 10 Independently selected from hydrogen, halogen, C1-C6 alkyl, C1-C6 alkoxy; m is nickel; y is O; x is selected from halogen; r' is selected from C1-C6 alkyl containing substituent or not containing substituent.
7. The polymerization process according to any one of claims 4 to 6, characterized in that the diimine metal complexes are prepared by: bringing a diimine compound represented by the formula (2) into contact with MX n And R' YHThe reaction is carried out and the reaction is carried out,
（2），
in the formula (2), R 5 、R 6 、R 7 Has the same definition as formula (IV); r is R 1 And R is 2 Is a group of formula (II) having the same definition as formula (III); MX (MX) n Wherein M and X have the same meanings as those of formula (III), n is the number of X satisfying the valence state of M, and n is 1, 2 or 3; y and R 'in R' YH have the same definition as in formula (III).
8. A process for the polymerization of ethylene-internal olefin-diene copolymers by copolymerizing ethylene with at least one internal olefin and at least one diene in the presence of a catalytic system comprising a diimine metal complex of formula (IV):
（VI），
wherein R is 1 、R 2 Is a group of the formula (II) having the same definition as in formula (III), R 5 ～R 8 Independently selected from hydrogen, halogen, hydroxy, substituted or unsubstituted C1-C30 hydrocarbyl, R 5 ～R 8 Optionally mutually looped.
9. The polymerization process of claim 8, wherein,
R 5 ～R 8 independently selected from hydrogen, C1-C10 alkyl, halogenated C1-C10 alkyl, C1-C10 alkoxy, halogenated C1-C10 alkoxy, halogen.
10. The polymerization process of claim 8 wherein the diimine metal complex has a structure according to formula (VII):
（VII），
in the formula (VII), R 1 ～R 11 Independently selected from the group consisting of hydrogen, halogen, hydroxy, C1-C20 alkyl with or without substituents, C2-C20 alkenyl with or without substituents, C2-C20 alkynyl with or without substituents, C3-C20 cycloalkyl with or without substituents, C1-C20 alkoxy with or without substituents, C2-C20 alkenyloxy with or without substituents, C2-C20 alkynyloxy with or without substituents, C3-C20 cycloalkoxy with or without substituents, C6-C20 aryl with or without substituents, C6-C20 aryloxy with or without substituents, C7-C20 aralkyl with or without substituents, C7-C20 aralkoxy with or without substituents, C7-C20 alkylaryl with or without substituents, and C7-C20 aryloxy with or without substituents.
11. The polymerization process according to any one of claims 8 to 10, characterized in that the diimine metal complexes are prepared by the following steps: bringing a diimine compound represented by the formula (3) into contact with MX n And R' YH are reacted with each other,
（3），
in the formula (3), R 5 ～R 8 Having the same definition as formula (VI); r is R 1 And R is 2 Is a group of formula (II) having the same definition as formula (III); MX (MX) n Wherein M and X have the same meanings as those of formula (III), n is the number of X satisfying the valence state of M, and n is 1, 2 or 3; y and R 'in R' YH have the same definition as in formula (III).
12. A process for the polymerization of ethylene-internal olefin-diene copolymers by copolymerizing ethylene with at least one internal olefin and at least one diene in the presence of a catalytic system comprising a diimine metal complex of formula (VIII):
（VIII），
wherein R is 1 、R 2 Is a group of the formula (II) having the same definition as in formula (III), R 21 ～R 24 Independently selected from hydrogen, halogen, hydroxy, substituted or unsubstituted C1-C20 hydrocarbyl, substituted or unsubstituted C1-C20 hydrocarbyloxy, R 21 ～R 24 Optionally interconnected to form a ring or ring system.
13. The polymerization process of claim 12, wherein the polymerization catalyst is,
R 21 ～R 24 Each independently selected from the group consisting of hydrogen, halogen, C1-C20 alkyl with or without substituents, C2-C20 alkenyl with or without substituents, C2-C20 alkynyl with or without substituents, C1-C20 alkoxy with or without substituents, C2-C20 alkenyloxy with or without substituents, C2-C20 alkynyloxy with or without substituents, C6-C20 aryl with or without substituents, C6-C20 aryloxy with or without substituents, C7-C20 aralkyl with or without substituents, C7-C20 aralkoxy with or without substituents, C7-C20 alkaryl with or without substituents, and C7-C20 alkaryloxy with or without substituents.
14. The polymerization process of claim 12 wherein the diimine metal complex has a structure according to formula (IX):
（IX），
wherein R is 1 ～R 10 Independently selected from hydrogen, halogen, hydroxy, substituted or unsubstituted C1-C20Alkyl, C2-C20 alkenyl with or without substituents, C2-C20 alkynyl with or without substituents, C3-C20 cycloalkyl with or without substituents, C1-C20 alkoxy with or without substituents, C2-C20 alkenyloxy with or without substituents, C2-C20 alkynyloxy with or without substituents, C3-C20 cycloalkoxy with or without substituents, C6-C20 aryl with or without substituents, C6-C20 aryloxy with or without substituents, C7-C20 aralkyl with or without substituents, C7-C20 aralkoxy with or without substituents, C7-C20 alkylaryl with or without substituents, C7-C20 alkaryloxy with or without substituents.
15. The polymerization process according to any one of claims 12 to 14, characterized in that the diimine metal complexes are prepared by the following steps: bringing a diimine compound represented by the formula (4) into contact with MX n And R' YH are reacted with each other,
（4）
in the formula (4), R 21 ～R 24 Having the same definition as formula (VIII); r is R 1 And R is 2 Is a group of formula (II) having the same definition as formula (III); MX (MX) n Wherein M and X have the same meanings as those of formula (III), n is the number of X satisfying the valence state of M, and n is 1, 2 or 3; y and R 'in R' YH have the same definition as in formula (III).
16. The polymerization process of claim 1, 4, 8 or 12, wherein,
the catalytic system comprises a cocatalyst selected from an organoaluminium compound and/or an organoboron compound.
17. The polymerization process of claim 16, wherein the polymerization catalyst is,
the organic aluminum compound is selected from at least one of alkyl aluminoxane, alkyl aluminum and alkyl aluminum halide, and the organic boron compound is selected from aromatic boron and/or borate.
18. The polymerization process of claim 16, wherein the polymerization catalyst is,
when the cocatalyst is an organoaluminum compound, the molar ratio of aluminum in the organoaluminum compound to M in the aminimide metal complex is (10-10) 7 ）：1；
When the cocatalyst is an organoboron compound and an organoaluminum compound, the molar ratio of boron in the organoboron compound to M in the aminimide metal complex is (0.1-1000): 1, wherein the molar ratio of aluminum in the organic aluminum compound to M in the amino imine metal complex is (10-10) 5 ）：1。
19. The polymerization process of claim 1, 4, 8 or 12, wherein,
the internal olefin is selected from non-alpha-olefins with 4-20 carbon atoms; and/or the number of the groups of groups,
the diene is selected from the group consisting of dienes having from 4 to 20 carbon atoms.
20. The polymerization process of claim 1, 4, 8 or 12, wherein,
the polymerization temperature is-50-200 ℃.
21. The polymerization process of claim 20, wherein the polymerization catalyst is,
the polymerization temperature is 30-100 ℃.
22. An ethylene-internal olefin-diene copolymer obtained by the polymerization process of claim 1, 4, 8 or 12.
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