CN117624254A - Preparation method of trimethoxy-containing asymmetric alpha-diimine nickel complex - Google Patents
Preparation method of trimethoxy-containing asymmetric alpha-diimine nickel complex Download PDFInfo
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- CN117624254A CN117624254A CN202311577875.3A CN202311577875A CN117624254A CN 117624254 A CN117624254 A CN 117624254A CN 202311577875 A CN202311577875 A CN 202311577875A CN 117624254 A CN117624254 A CN 117624254A
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- nickel complex
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- diimine
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 169
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 66
- 229910000071 diazene Inorganic materials 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- -1 polyethylene Polymers 0.000 claims abstract description 41
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 33
- 239000003054 catalyst Substances 0.000 claims abstract description 26
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000005977 Ethylene Substances 0.000 claims abstract description 24
- 239000004698 Polyethylene Substances 0.000 claims abstract description 21
- 229920000573 polyethylene Polymers 0.000 claims abstract description 20
- 229910052751 metal Inorganic materials 0.000 claims description 28
- 239000002184 metal Substances 0.000 claims description 28
- 125000000217 alkyl group Chemical group 0.000 claims description 24
- 150000001875 compounds Chemical class 0.000 claims description 24
- 229910052739 hydrogen Inorganic materials 0.000 claims description 19
- 125000003118 aryl group Chemical group 0.000 claims description 18
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical group CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 claims description 18
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 claims description 18
- 239000000543 intermediate Substances 0.000 claims description 17
- 125000006376 (C3-C10) cycloalkyl group Chemical group 0.000 claims description 16
- 125000003545 alkoxy group Chemical group 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 13
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 13
- JBXIOAKUBCTDES-UHFFFAOYSA-N 2h-acenaphthylen-1-one Chemical compound C1=CC(C(=O)C2)=C3C2=CC=CC3=C1 JBXIOAKUBCTDES-UHFFFAOYSA-N 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 229910052731 fluorine Inorganic materials 0.000 claims description 10
- 229910052740 iodine Inorganic materials 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 125000004104 aryloxy group Chemical group 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- JGHYBJVUQGTEEB-UHFFFAOYSA-M dimethylalumanylium;chloride Chemical compound C[Al](C)Cl JGHYBJVUQGTEEB-UHFFFAOYSA-M 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 8
- 125000005234 alkyl aluminium group Chemical group 0.000 claims description 8
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 8
- 238000006467 substitution reaction Methods 0.000 claims description 8
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 7
- 238000006555 catalytic reaction Methods 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 229910052736 halogen Inorganic materials 0.000 claims description 5
- 150000002367 halogens Chemical class 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 5
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminum chloride Substances Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- 229910052794 bromium Inorganic materials 0.000 claims description 4
- RAABOESOVLLHRU-UHFFFAOYSA-N diazene Chemical compound N=N RAABOESOVLLHRU-UHFFFAOYSA-N 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- AFPRJLBZLPBTPZ-UHFFFAOYSA-N acenaphthoquinone Chemical compound C1=CC(C(C2=O)=O)=C3C2=CC=CC3=C1 AFPRJLBZLPBTPZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000005456 alcohol based solvent Chemical class 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 230000000536 complexating effect Effects 0.000 claims description 3
- 150000004820 halides Chemical class 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- 239000003426 co-catalyst Substances 0.000 claims 1
- 229920000642 polymer Polymers 0.000 abstract description 30
- 239000003446 ligand Substances 0.000 abstract description 17
- 230000003197 catalytic effect Effects 0.000 abstract description 8
- 230000009471 action Effects 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 4
- 238000009826 distribution Methods 0.000 abstract description 3
- 239000004699 Ultra-high molecular weight polyethylene Substances 0.000 abstract 1
- 229920000785 ultra high molecular weight polyethylene Polymers 0.000 abstract 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 49
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 28
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 24
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 24
- 230000037048 polymerization activity Effects 0.000 description 22
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 21
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- UFFBMTHBGFGIHF-UHFFFAOYSA-N 2,6-dimethylaniline Chemical compound CC1=CC=CC(C)=C1N UFFBMTHBGFGIHF-UHFFFAOYSA-N 0.000 description 16
- 239000002904 solvent Substances 0.000 description 12
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 11
- 238000000921 elemental analysis Methods 0.000 description 11
- 125000004432 carbon atom Chemical group C* 0.000 description 10
- 238000010200 validation analysis Methods 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- 239000003208 petroleum Substances 0.000 description 8
- 101100323029 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) alc-1 gene Proteins 0.000 description 6
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- CWRYPZZKDGJXCA-UHFFFAOYSA-N acenaphthene Chemical compound C1=CC(CC2)=C3C2=CC=CC3=C1 CWRYPZZKDGJXCA-UHFFFAOYSA-N 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 4
- 238000004440 column chromatography Methods 0.000 description 4
- 238000006482 condensation reaction Methods 0.000 description 4
- 238000010828 elution Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 150000002430 hydrocarbons Chemical group 0.000 description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 4
- 229920013716 polyethylene resin Polymers 0.000 description 4
- 239000000741 silica gel Substances 0.000 description 4
- 229910002027 silica gel Inorganic materials 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- HXGDTGSAIMULJN-UHFFFAOYSA-N acetnaphthylene Natural products C1=CC(C=C2)=C3C2=CC=CC3=C1 HXGDTGSAIMULJN-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 125000002619 bicyclic group Chemical group 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 125000002950 monocyclic group Chemical group 0.000 description 2
- 150000002815 nickel Chemical class 0.000 description 2
- 239000012041 precatalyst Substances 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000004809 thin layer chromatography Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 239000001993 wax Substances 0.000 description 2
- 125000005918 1,2-dimethylbutyl group Chemical group 0.000 description 1
- 125000006218 1-ethylbutyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 1
- KWVPRPSXBZNOHS-UHFFFAOYSA-N 2,4,6-Trimethylaniline Chemical compound CC1=CC(C)=C(N)C(C)=C1 KWVPRPSXBZNOHS-UHFFFAOYSA-N 0.000 description 1
- WKBALTUBRZPIPZ-UHFFFAOYSA-N 2,6-di(propan-2-yl)aniline Chemical compound CC(C)C1=CC=CC(C(C)C)=C1N WKBALTUBRZPIPZ-UHFFFAOYSA-N 0.000 description 1
- OIXUMNZGNCAOKY-UHFFFAOYSA-N 2,6-diethyl-4-methylaniline Chemical compound CCC1=CC(C)=CC(CC)=C1N OIXUMNZGNCAOKY-UHFFFAOYSA-N 0.000 description 1
- FOYHNROGBXVLLX-UHFFFAOYSA-N 2,6-diethylaniline Chemical compound CCC1=CC=CC(CC)=C1N FOYHNROGBXVLLX-UHFFFAOYSA-N 0.000 description 1
- 125000006176 2-ethylbutyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(C([H])([H])*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 0.000 description 1
- 125000005916 2-methylpentyl group Chemical group 0.000 description 1
- 125000003542 3-methylbutan-2-yl group Chemical group [H]C([H])([H])C([H])(*)C([H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000005917 3-methylpentyl group Chemical group 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
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 1
- 229910021585 Nickel(II) bromide Inorganic materials 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000002178 anthracenyl group Chemical group C1(=CC=CC2=CC3=CC=CC=C3C=C12)* 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 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
- 125000006547 cyclononyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([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
- 125000004855 decalinyl group Chemical group C1(CCCC2CCCCC12)* 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 125000005046 dihydronaphthyl group Chemical group 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- DZGCGKFAPXFTNM-UHFFFAOYSA-N ethanol;hydron;chloride Chemical compound Cl.CCO DZGCGKFAPXFTNM-UHFFFAOYSA-N 0.000 description 1
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000012761 high-performance material Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002431 hydrogen Chemical group 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 125000003392 indanyl group Chemical group C1(CCC2=CC=CC=C12)* 0.000 description 1
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000012968 metallocene catalyst Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 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
- IPLJNQFXJUCRNH-UHFFFAOYSA-L nickel(2+);dibromide Chemical compound [Ni+2].[Br-].[Br-] IPLJNQFXJUCRNH-UHFFFAOYSA-L 0.000 description 1
- 150000002940 palladium Chemical class 0.000 description 1
- 125000003538 pentan-3-yl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention provides a preparation method of an asymmetric alpha-diimine nickel complex containing trimethoxy. The catalyst has a single catalytic active center, can realize the regulation and control of the molecular weight and branching degree of the polymer by changing the ligand structure and the polymerization condition, and has the advantages of easy preparation, high catalytic activity, low cost, high thermal stability and the like. The preparation method has the advantages of mild condition, short period and simple operation condition. The catalyst was subjected to an ethylene polymerization system study in excess of Me 2 Under the action of AlCl or MMAO promoter, the activity of these catalysts can be up to 2.11X10 7 g PE(mol of cat.) ‑1 h ‑1 And the weight average molecular weight of the obtained polymer was 2.18‑12.64×10 5 g·mol ‑1 The molecular weight distribution fluctuates between 1.43 and 1.80. With the rise of temperature, the branched chain content of every 1000 carbons is between 195 and 205, which shows extremely strong regulation and control performance on the molecular weight of polyethylene, and can be used for preparing ultra-high molecular weight polyethylene.
Description
Technical Field
The invention relates to the technical field of olefin catalysts, in particular to a preparation method of an asymmetric alpha-diimine nickel complex containing trimethoxy.
Background
Polyethylene is one of the synthetic resins with the greatest global yield at present, and ethylene gas as a raw material for preparing the polyethylene is widely existing and has rich production potential. In particular, the demand for polyethylene resins in China has a growing trend year by year, but unfortunately, china still relies heavily on importation to meet this demand. In the process of preparing polyethylene, a plurality of different manufacturing processes, various catalysts and comonomer types are adopted, and the diversity of the factors gives a wide choice for custom production of ethylene homopolymers and copolymers with excellent properties. The polyethylene resin not only has wide application in the traditional industrial field, but also covers a plurality of fields of military, agriculture, medical treatment and the like, and provides an important material foundation for various industries. Therefore, the polyethylene resin is not only one of the props of the modern industry, but also a key component of the economic and technological development of China. While meeting domestic demands, we should actively explore innovative manufacturing technology to reduce dependence on import and improve autonomous capability of China in the field of polyethylene resin industry. This will help to promote our country to occupy a more important place in global competition, while meeting the urgent need for high performance materials in various fields.
Up to now, polyethylene catalysts which have been used in industrialization mainly comprise: ziegler-Natta type catalysts (CN 116410360A (2023); CN115043961A (2022); angew.chem.,1955, 67, 426-427), metallocene catalysts (CN 115003707A (2022); CN114249775A (2022); angew.chem.int.ed.,1980, 19, 390), late transition metal catalysts (CN 105461757A (2014); CN104059180B (2013); J.am.chem.Soc.; 120 (16), 4049-4050) and alpha-diimine type late transition metal catalysts (CN 107698699A (2017), dalton T.; 2022, 51, 14375-14407).
Since 1995, brookhart introduced alpha-nickel diimine and palladium complexes, which have led to extensive research due to their unique properties in polyethylene structure control, and have not been previously applied to ethylene polymerization. Their unique chain growth characteristics distinguish them from metallocene and Ziegler-Natta catalysts because they allow the regulation of the branching and structure of the polyethylene solely by the control of the ethylene feed.
Currently, some olefin research groups have made a series of improvements in the structure of the α -diimine nickel catalysts, greatly increasing the level of activity in ethylene polymerization, and providing finer control over polymer properties such as molecular weight, dispersion and microstructure. However, there are challenges in terms of limited thermal stability and difficulty in controlling under high temperature conditions. Therefore, there is a need to provide a new preparation method of an asymmetric alpha-diimine nickel complex containing trimethoxy, which solves the above technical problems.
Disclosure of Invention
The asymmetric alpha-diimine nickel complex containing trimethoxy provided by the invention comprises the following components: the following formula (I) is an asymmetric alpha-diimine nickel complex containing trimethoxy:
wherein R is 1 Identical or different, each independently selected from H, F, cl, br, I or optionally substituted with one or more R 3 Substituted with the following groups: c (C) 1-6 Alkyl, C 1-6 Alkyloxy, C 3-10 Cycloalkyl, C 3-10 Cycloalkyl oxy, C 6-14 Aryl, C 6-14 An aryloxy group;
R 2 selected from H, halogen, C 1-6 Alkyl or C 1-6 An alkoxy group;
each R 3 Identical or different, each independently selected from H, F, cl, br, I, C 1-6 Alkyl, C 1-6 Alkoxy, C 3-10 Cycloalkyl, C 3-10 Cycloalkyl oxy, C 6-14 Aryl, C 6-14 An aryloxy group.
Preferably, said R 1 The same or different, each independently selected from methyl, ethyl or isopropyl; r is R 2 Selected from hydrogen or methyl.
Preferably, the nickel complex has a structure as shown in formula (I-1), formula (I-2), formula (I-3), formula (I-4) or formula (I-5):
wherein X is the same or different and is each independently selected from Cl and Br;
the complex represented by formula (I) is selected from complexes having the following group definition:
C1：R 1 ＝Me；R 2 ＝H；C2：R 1 ＝Et；R 2 ＝H；C3：R 1 ＝ i Pr；R 2 ＝H；
C4：R 1 ＝Me；R 2 ＝Me；C5：R 1 ＝Et；R 2 ＝Me。
preferably, the following formula (II) is an intermediate of an asymmetric alpha-diimine nickel complex containing trimethoxy:
wherein R is 1 And R is 2 Having the definition as defined in claim 1.
Preferably, the intermediate has a structure represented by formula (II-1), formula (II-2), formula (II-3), formula (II-4) or formula (II-5):
the intermediate represented by formula (II) is selected from intermediates having the following group definition:
L1：R 1 ＝Me；R 2 ＝H；L2：R 1 ＝Et；R 2 ＝H；L3：R 1 ＝i-Pr；R 2 ＝H；
L4：R 1 ＝Me；R 2 ＝Me；L5：R 1 ＝Et；R 2 ＝Me。
preferably, the cocatalyst is selected from one or more of aluminoxane, alkyl aluminum and alkyl aluminum chloride;
the aluminoxane is selected from one or two of Methylaluminoxane (MAO) or triisobutylaluminum Modified Methylaluminoxane (MMAO);
the alkyl aluminum chloride is selected from diethyl aluminum chloride (Et) 2 AlCl), dimethylaluminum chloride (Me) 2 AlCl), aluminum sesquioxide (EASC);
when the catalyst composition further comprises a promoter, the molar ratio of metal Al in the promoter to central metal Ni of the nickel complex shown in formula (I) is (200-3000);
when the cocatalyst is Methylaluminoxane (MAO), the molar ratio of metal Al in the Methylaluminoxane (MAO) to central metal Ni of the nickel complex shown in the formula (I) is (1000-3000);
when the cocatalyst is triisobutylaluminum Modified Methylaluminoxane (MMAO), the molar ratio of metal Al in the triisobutylaluminum Modified Methylaluminoxane (MMAO) to central metal Ni of the complex shown in the formula (I) is (1000-3000);
the cocatalyst is diethylaluminum chloride (Et) 2 AlCl), diethylaluminum chloride (Et) 2 The molar ratio of the metal A1 in AlCl) to the central metal Ni of the nickel complex shown in the formula (I) is (200-1000);
the cocatalyst is dimethylaluminum chloride (Me) 2 AlCl), dimethylaluminum chloride (Me) 2 AlCl) and the nickel complex of formula (I) has a molar ratio of (200-600) to the central metal Ni.
The invention also provides a preparation method of the asymmetric alpha-diimine nickel complex containing trimethoxy, which is characterized by comprising the following steps: reacting (e.g., complexing) the intermediate of claim 3 or 4 with a nickel-containing compound to obtain a nickel complex of formula (I);
the saidThe nickel-containing compound is selected from nickel-containing halides, which may be (DME) NiBr, for example 2 Or NiBr 2 For Example (DME) NiBr 2 ；
The reaction is carried out under anaerobic conditions, for example under protection of an inert gas such as nitrogen; the molar ratio of the nickel-containing compound to the compound shown in the formula (II) is 1:1 to 2; the temperature of the reaction is 30-100 ℃; the reaction time is 8-16 hours; the reaction is carried out in an organic solvent, which may be selected from one or more of halogenated alkanes or alcohol solvents.
Preferably, 1) substitution reaction is carried out on acenaphthone shown in formula (III) and aniline shown in formula (IV) to obtain 2-aniline acenaphthone shown in formula (V);
2) Condensing the 2-aniline acenaphthenone shown in the formula (V) obtained in the step 1) with a compound shown in the formula (VI) to obtain a compound shown in the formula (II):
preferably, in step 1), the substitution reaction is carried out under the catalysis of p-toluene sulfonic acid.
The invention also provides a preparation method of the polyethylene, which comprises the following steps: ethylene is polymerized under the action of the catalyst composition described above.
Compared with the related art, the preparation method of the asymmetric alpha-diimine nickel complex containing trimethoxy provided by the invention has the following beneficial effects:
the invention provides a preparation method of an asymmetric alpha-diimine nickel complex containing trimethoxy, which comprises the following steps:
the present invention is an asymmetric alpha-diimine nickel catalyst for ethylene polymerization, for example, a pyridine diimine mononuclear or binuclear nickel complex (New J.chem.,2016,40, 9329 and) was subjected to ethylene polymerization using formula 1, the polymer was detected to be a polyethylene wax having a molecular weight of thousands and a similar branching content, and these nickel complexes of formula 2 all exhibited high activity for ethylene polymerization and produced branched polyethylene waxes of low molecular weight, and the precatalyst now bearing a larger benzonaphthyl substituent exhibited higher activity than its analogue.
In addition, the invention also designs and synthesizes the [ 1-amino-2- (2, 6-diphenyl methyl-3, 4-difluoro aniline) acenaphthene]Nickel (II) bromide complex (formula 3) (Polymer, 2020, 187, 122089) is polymerized to obtain polyethylene with high branching and ultra-high molecular weight (M) w ＝11.42×10 5 gmol -1 Tm=82.6 ℃), with a narrow polydispersity, the mechanical properties of the polyethylene being analyzed by Dynamic Mechanical Analysis (DMA) and monotonic stress strain tests, which show a high tensile strength, a good elastomer recovery (up to 63%) and a highest elongation at break (up to 2592.6%), these findings emphasizing the necessity of further tuning the catalyst, in particular in terms of thermal stability and molecular weight distribution.
Drawings
FIG. 1 shows the molecular structure of C1 provided by the invention;
FIG. 2 shows the molecular structure of C4 provided by the invention;
FIG. 3 is a high temperature 13CNMR spectrum of polyethylene obtained at 30℃according to the invention.
Detailed Description
The invention will be further described with reference to the drawings and embodiments.
Referring to fig. 1-3, fig. 1 shows a molecular structure of C1 according to the present invention; FIG. 2 shows the molecular structure of C4 provided by the invention; FIG. 3 shows the high temperature of the polyethylene obtained at 30℃according to the invention 13 CNMR spectra.
The trimethoxy-containing asymmetric alpha-diimine nickel complex comprises: the following formula (I) is an asymmetric alpha-diimine nickel complex containing trimethoxy:
wherein R is 1 Identical or different, each independently selected from H, F, cl, br, I or optionally substituted with one or more R 3 Substituted with the following groups: c (C) 1-6 Alkyl, C 1-6 Alkyloxy, C 3-10 Cycloalkyl, C 3-10 Cycloalkyl oxy, C 6-14 Aryl, C 6-14 An aryloxy group;
R 2 selected from H, halogen, C 1-6 Alkyl or C 1-6 An alkoxy group;
each R 3 Identical or different, each independently selected from H, F, cl, br, I, C 1-6 Alkyl, C 1-6 Alkoxy, C 3-10 Cycloalkyl, C 3-10 Cycloalkyl oxy, C 6-14 Aryl, C 6-14 An aryloxy group.
Preferably, in formula (I), R 1 Identical or different, each independently selected from H, F, cl, br, I, C 1-6 Alkyl, C 1-6 Alkoxy, C 3-10 Cycloalkyl, C 3-10 Cycloalkoxy radicals C 6-14 Aryl, C 6-14 An aryloxy group;
more preferably, R 1 Identical or different, each independently selected from C 1-6 Alkyl or C 1-6 An alkoxy group; r is R 2 Selected from H or C 1-6 An alkyl group;
also preferably, R 1 Identical or different, each independently selected from C 1-3 An alkyl group; r is R 2 Selected from H or C 1-3 An alkyl group;
still more preferably, R 1 The same or different, each independently selected from methyl, ethyl or isopropyl; r is R 2 Selected from hydrogen or methyl.
Most preferably, the nickel complex has a structure as shown in formula (I-1), formula (I-2), formula (I-3), formula (I-4) or formula (I-5):
wherein X is the same or different and is each independently selected from Cl and Br;
the complex represented by formula (I) is selected from complexes having the following group definition:
C1：R 1 ＝Me；R 2 ＝H；C2：R 1 ＝Et；R 2 ＝H；C3：R 1 ＝ i Pr；R 2 ＝H；
C4：R 1 ＝Me；R 2 ＝Me；C5：R 1 ＝Et；R 2 ＝Me。
preferably, the following formula (II) is an intermediate of an asymmetric alpha-diimine nickel complex containing trimethoxy:
wherein R is 1 Identical or different, each independently selected from H, F, cl, br, I or optionally unsubstituted or substituted with one or more R 3 Substituted with the following groups: c (C) 1-6 Alkyl, C 1-6 Alkoxy, C 3-10 Cycloalkyl, C 3-10 Cycloalkoxy radicals C 6-14 Aryl, C 6-14 An aryloxy group;
R 2 selected from H, halogen, C 1-6 Alkyl or C 1-6 An alkoxy group;
R 3 having the definition as described above.
Preferably, in formula (II), R 1 Identical or different, each independently selected from H, F, cl, br, I, C 1-6 Alkyl, C 1-6 Alkoxy, C 3-10 Cycloalkyl, C 3-10 Cycloalkoxy radicals C 6-14 Aryl, C 6-14 An aryloxy group;
preferably, R 1 Identical or different, each independently selected from C 1-6 Alkyl or C 1-6 An alkoxy group; r is R 2 Selected from H or C 1-6 An alkyl group;
also preferably, R 1 Identical or different, each independently selected from C 1-3 An alkyl group; r is R 2 Selected from H or C 1-3 An alkyl group;
still more preferably, R 1 The same or different, each independently selected from methyl, ethyl or isopropyl; r is R 2 Selected from hydrogen or methyl.
Most preferably, the intermediate has a structure represented by formula (II-1), formula (II-2), formula (II-3), formula (II-4) or formula (II-5):
the intermediate represented by formula (II) is selected from intermediates having the following group definition:
L1：R 1 ＝Me；R 2 ＝H；L2：R 1 ＝Et；R 2 ＝H；L3：R 1 ＝ i Pr；R 2 ＝H；
L4：R 1 ＝Me；R 2 ＝Me；L5：R 1 ＝Et；R 2 ＝Me。
preferably, the present invention also provides a catalyst composition comprising a procatalyst selected from nickel complexes of formula (I) and optionally a cocatalyst selected from one or more of aluminoxanes, alkylaluminums and alkylaluminumchlorides;
according to the invention, the aluminoxane is selected from one or two of Methylaluminoxane (MAO) or triisobutylaluminum Modified Methylaluminoxane (MMAO);
according to the invention, the alkylaluminum chloride is selected from diethylaluminum chloride (Et) 2 AlCl), dimethylaluminum chloride (Me) 2 AlCl), aluminum sesquioxide (EASC);
according to the present invention, when the catalyst composition further comprises a promoter, the molar ratio of metal Al in the promoter to central metal Ni of the nickel complex represented by formula (I) is (200 to 3000), for example, may be 200:1. 300:1. 400: 1. 500:1. 600:1. 1000: 1. 1500: 1. 2000:1 or 2500:1, a step of;
when the cocatalyst is Methylaluminoxane (MAO), the molar ratio of metal Al in Methylaluminoxane (MAO) to central metal Ni of the nickel complex shown in the formula (I) is (1000-3000), and the preferable molar ratio is 1000:1, a step of;
when the cocatalyst is triisobutylaluminum Modified Methylaluminoxane (MMAO), the molar ratio of metal Al in the triisobutylaluminum Modified Methylaluminoxane (MMAO) to central metal Ni of the complex shown in the formula (I) is (1000-3000), and the preferred molar ratio is 1000:1, a step of;
the cocatalyst is diethylaluminum chloride (Et) 2 AlCl), diethylaluminum chloride (Et) 2 The molar ratio of the metal A1 in AlCl) to the central metal Ni of the nickel complex shown in the formula (I) is (200-1000): 1, for example, may be 200:1. 300:1. 400: 1. 500:1 or 600:1, a step of;
the cocatalyst is dimethylaluminum chloride (Me) 2 AlCl), dimethylaluminum chloride (Me) 2 The molar ratio of the metal A1 in AlCl) to the central metal Ni of the nickel complex shown in the formula (I) is (200-600): 1, for example, may be 200:1. 300:1. 400: 1. 500:1 or 600:1.
the invention also provides a preparation method of the asymmetric alpha-diimine nickel complex containing trimethoxy, which is characterized by comprising the following steps: reacting (e.g., complexing) the intermediate of claim 3 or 4 with a nickel-containing compound to obtain a nickel complex of formula (I);
the nickel-containing compound is selected from nickel-containing halides, which may be (DME) NiBr, for example 2 Or NiBr 2 For Example (DME) NiBr 2 ；
The reaction is carried out under anaerobic conditions, for example under protection of an inert gas such as nitrogen; the molar ratio of the nickel-containing compound to the compound shown in the formula (II) is 1:1 to 2; the temperature of the reaction is 30-100 ℃; the reaction time is 8-16 hours; the reaction is carried out in an organic solvent, which may be selected from one or more of halogenated alkanes or alcohol solvents.
According to the invention, the temperature of the reaction is between 30 and 100 ℃, preferably 30 ℃;
according to the invention, the reaction time is 8 to 16 hours, preferably 12 to 16 hours, more preferably 14 to 16 hours;
according to the invention, the reaction is carried out in an organic solvent, which may be selected from one or more of halogenated alkanes or alcoholic solvents, for example from one or both of dichloromethane or ethanol.
Preferably, the resulting nickel complex of formula (i) may be further purified, and the purification method may include the steps of:
a) Pumping the obtained compound shown in the formula (I) into a solvent by using a vacuum pump, and then dissolving the compound in an organic solvent (such as anhydrous diethyl ether);
b) After precipitation, the solid-liquid separation is carried out, and the solid phase is precipitated with anhydrous diethyl ether and dried.
The invention also provides a preparation method of the intermediate shown in the formula (II), which comprises the following steps:
preferably, 1) substitution reaction is carried out on acenaphthone shown in formula (III) and aniline shown in formula (IV) to obtain 2-aniline acenaphthone shown in formula (V);
2) Condensing the 2-aniline acenaphthenone shown in the formula (V) obtained in the step 1) with a compound shown in the formula (VI) to obtain a compound shown in the formula (II):
preferably, in step 1), the substitution reaction is carried out under the catalysis of p-toluene sulfonic acid.
The invention also provides a preparation method of the polyethylene, which comprises the following steps: ethylene is polymerized under the action of the catalyst composition described above.
According to the invention, in step 1), the substitution reaction is carried out in a solvent, such as in a dichloromethane/ethanol solution;
according to the invention, in step 1), the substitution reaction is carried out at room temperature for 24 to 48 hours, preferably 24 to 48 hours;
according to the invention, in step 1), the molar feed ratio of acenaphthodione represented by formula (III) to aniline represented by formula (IV) is 1:1 to 2, more preferably l:1.1;
according to the invention, after the reaction of step 1), the 2-acenaphthenone of formula (V) is obtained and can be further purified. The purification method may comprise the steps of:
a) Dissolving 2-aniline acenaphthenone shown in formula (V) obtained in step 1) in dichloromethane;
b) The support was carried out using silica gel, column chromatography was carried out on a silica gel column using a mixed solvent of petroleum ether and ethyl acetate (the volume ratio of petroleum ether to ethyl acetate was 75: 1) Elution was performed for the eluent, and the elution fraction was detected by thin layer chromatography (developing solvent is petroleum ether and ethyl acetate in a volume ratio of 10:1, collecting a second fraction;
c) The solvent is removed to give the purified 2-acenaphthenone of formula (V), and according to the invention, in step 2), the condensation reaction may be carried out under the catalysis of p-toluene sulfonic acid.
According to the invention, in step 2), the condensation reaction is carried out under the catalysis of p-toluene sulphonic acid;
preferably, in step 2), the condensation reaction is carried out in a solvent, for example in an aromatic solvent, such as toluene:
preferably, in step 2), the condensation reaction is carried out under reflux with heating for 6 to 10 hours, more preferably 8 to 10 hours;
preferably, in step 2), the molar feed ratio of the 2-acenaphthenone represented by formula (V) to the compound represented by formula (VI) is 1:1 to 2, more preferably a molar ratio of 1:1.1.
according to the present invention, the obtained compound represented by the formula (II) may be further purified, and the purification method may include the steps of:
a') dissolving the compound represented by the formula (II) obtained in the step 2 in methylene chloride;
b') carrying out column chromatography by using basic alumina, and carrying out column chromatography by using a mixed solvent of petroleum ether and ethyl acetate (the volume ratio of petroleum ether to ethyl acetate is preferably 100: 1) Eluting the eluting agent, detecting an elution fraction by thin layer chromatography, and collecting a second fraction;
c') removing the solvent to obtain the purified compound represented by the formula (II).
The invention also provides a preparation method of the polyethylene, which comprises the following steps: polymerizing ethylene under the action of the catalyst composition of claim 5;
preferably, the polymerization reaction temperature is 20 to 100 ℃, for example, 30 ℃,40 ℃, 60 ℃, 80 ℃ or 100 ℃;
preferably, the polymerization reaction time is 5-60 min, for example, 5min, 10min, 15min, 30min, 45min or 60min;
preferably, the pressure of the polymerization reaction is 0.5 to 10atm, and may be 1atm, 5atm or 10atm, for example;
preferably, the solvent for the polymerization reaction is selected from one or more of toluene, dichloromethane, ethanol, tetrahydrofuran, hexane or cyclohexane;
preferably, the polymerization is carried out under an ethylene atmosphere.
The invention also provides the use of the methoxy-containing asymmetric alpha-diimine nickel complexes of formula (I) for catalyzing olefin polymerization, preferably ethylene polymerization.
The invention also provides the use of the above catalyst composition for catalyzing olefin polymerization, in particular ethylene polymerization.
The invention also provides application of the intermediate of the asymmetric alpha-diimine nickel complex containing the methoxy group shown in the formula (II), which is used for preparing the asymmetric alpha-diimine nickel complex containing the methoxy group shown in the formula (I).
Definition and interpretation of terms
The term "C 1-6 Alkyl "is understood to mean a linear or branched saturated monovalent hydrocarbon radical having 1,2, 3,4,5 or 6 carbon atoms, for example methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, 2-methylbutyl, 1-ethylpropyl, 1, 2-dimethylpropyl, neopentyl, 1-dimethylpropyl, 4-methylpentyl, 3-methylpentyl, 2-methylpentyl, 1-methylpentyl, 2-ethylbutyl, 1-ethylbutyl, 3-dimethylbutyl 2, 2-dimethylbutyl, 1-dimethylbutyl, 2, 3-dimethylbutylCyclobutyl, 1, 3-dimethylbutyl or 1, 2-dimethylbutyl or isomers thereof. In particular, the radicals have 1,2, 3 or 4 carbon atoms ("C 1-4 Alkyl "), such as methyl, ethyl, propyl, butyl, isopropyl, isobutyl, sec-butyl, tert-butyl, more particularly said groups having 1,2 or 3 carbon atoms (" C 1-3 Alkyl "), such as methyl, ethyl, n-propyl or isopropyl.
The term "C 3-10 Cycloalkyl "is understood to mean a saturated monovalent mono-or bicyclic hydrocarbon ring having 3,4,5, 6, 7, 8, 9 or 10 carbon atoms. The C is 3-10 Cycloalkyl may be a monocyclic hydrocarbon group such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl or cyclodecyl, or a bicyclic hydrocarbon group such as a decalin ring.
The term "C 6-14 Aryl "is understood to mean preferably a mono-, bi-or tricyclic hydrocarbon ring (" C ") having a monovalent aromatic or partially aromatic character of 6, 7, 8, 9, 10, 11, 12, 13 or 14 carbon atoms 1-14 Aryl), in particular a ring having 6 carbon atoms ("C) 6 Aryl "), such as phenyl; or biphenyl, or a ring having 9 carbon atoms ("C 9 Aryl "), e.g. indanyl or indenyl, or a ring having 10 carbon atoms (" C 10 Aryl "), such as tetralin, dihydronaphthyl or naphthyl, or a ring having 13 carbon atoms (" C " 3 Aryl "), e.g. fluorenyl, or a ring having 14 carbon atoms (" C) 14 Aryl "), such as anthracenyl.
The term "halogen" includes F, cl, br, I.
The invention has the beneficial effects that:
1. the invention provides a preparation method of an asymmetric alpha-diimine nickel complex containing methoxy. The nickel complex prepared by the invention has a single catalytic active center, and can realize the regulation and control of the molecular weight and branching degree of the polymer by changing the ligand structure and the polymerization condition.
2. The catalyst has the advantages of high catalytic activity, low cost, outstanding thermal stability and the like, and the preparation method has mild conditions, short period and simple operation conditions.
3. The nickel complex can be applied to the catalytic reaction of ethylene polymerization, and the catalytic activity of the nickel complex is as high as 2.11 multiplied by 10 7 g·mol -1 (Ni)·h -1 The catalytic activity thereof is maintained at 1.96×10 even at a high temperature of 90 DEG C 6 g·mol -1 (Ni)·h -1 The operating temperature of industrial production is met, and the prepared polyethylene has weight average molecular weight M w At 2.18-12.64X10 5 g·mol -1 The molecular weight distribution is between 1.43 and 1.80, the regulation performance on the molecular weight of the polyethylene is extremely strong, and the branching degree of the obtained polyethylene is higher.
Example 1
Preparation of 2- (2, 6-bis (benzhydryl) -3,4, 5-trimethoxyaniline) acenaphthenone of formula (V)
A solution of 2, 6-bis (benzhydryl) -3,4, 5-trimethoxyaniline (10.31 g,20 mmol) in methylene chloride (80 ml) and an ethanol solution of acenaphthodione (3.64 g,20 mmol) (200 ml) were mixed together, and then a catalytic amount (20 mol%) of p-toluene sulfonic acid was added to react at room temperature for 24 hours. The solvent was removed and the residue was purified with ethyl acetate and petroleum ether in a volume ratio of 1:75, detecting elution fractions by a thin-layer silica gel plate, wherein the volume ratio of the developing agent of petroleum ether to ethyl acetate is 10:1, collecting a second fraction, and removing the solvent to obtain an orange solid. Yield: 68%.
The structure validation data are as follows:
FT-IR(KBr,cm -1 )：3058(w),2937(w),1731(ν(C＝O)m),
1655(ν(C＝N)m),1600(s),1493(s),1454(m),1327(s),1173(w),1043(m),975(w),829(s).
1 HNMR(600MHz,CDCl 3 ,TMS)：δ3.01(s,6H,2×OCH 3 ),3.91(s,3H,OCH 3 ),5.47(s,2H,2×CH),6.30(t,J＝7.4Hz,2H,Ph-H),6.47(t,J＝7.5Hz,4H,Ph-H),6.73(t,J＝7.8Hz,1H,Ph-H),6.97–7.12(m,11H,Ph-H),7.16(t,J＝7.5Hz,4H,Ph-H),7.46(d,J＝8.4Hz,1H,Ph-H),7.63(t,J＝7.6Hz,1H,Ph-H),7.89(d,J＝8.2Hz,1H,Ph-H),7.97(d,J＝7.0Hz,1H,Ph-H).
13 CNMR(151MHz,CDCl 3 ,TMS)：δ50.6,59.3,120.7,121.2,125.2,125.5,126.6,127.1,127.6,127.7,127.8,128.6,129.5,129.7,129.8,131.7,141.2,142.2,144.7,145.4,146.1,152.1,163.7(C＝N),190.0(C＝O).
elemental analysis: c (C) 47 H 37 NO 4 (679.82) theory: c,83.04; h,5.49; n,2.06. Experimental values: c,82.66; h,5.60; n,2.08.
Example 2
Preparation of 1- (2, 6-dimethylaniline) -2- (2, 6-di (benzhydryl) -3,4, 5-trimethoxyaniline) acenaphthene [ L1 ] of formula (II)]Wherein R is 1 Is methyl, R 2 Is hydrogen.
A solution of 2- (2, 6-bis (benzhydryl) -3,4, 5-trimethoxyaniline) acenaphthenone (1.00 g,1.47 mmol) and 2, 6-dimethylaniline (0.2 g,1.65 mmol) in toluene (50 mL) was heated at reflux for 12h with the addition of a catalytic amount of p-toluene sulfonic acid (20 mol%). The solvent toluene was removed and the residue was purified using ethyl acetate and petroleum ether in a volume ratio of 1:75, and performing alkaline alumina column chromatography. The eluted fractions were checked by thin silica gel plates, the second fraction was collected and the solvent was removed to give an orange solid. Yield: 28%.
The structure validation data are as follows:
FT-IR(KBr,cm -1 )：3024(w),2938(w),1668(ν(C＝N)m),1643(ν(C
＝N)m),1593(s),1456(s),1329(w),1277(w),1112(w),1082(m),936(s),829(s),777(m),698(s).
1 HNMR(600MHz,CDCl 3 ,TMS)：2.2(s,6H,2×CH 3 ),3.0(s,6H,2×OCH 3 ),3.9(s,3H,OCH 3 ),5.7(s,2H,2×CH),6.2(t,J＝7.4Hz,2H,Ph-H),6.4(dt,J＝15.1,7.3Hz,5H,Ph-H),6.7(t,J＝7.8Hz,1H,Ph-H),7.0–7.1(m,13H,Ph-H),7.1–7.2(m,6H,Ph-H),7.3(d,J＝8.3Hz,1H,Ph-H),7.5(d,J＝8.3Hz,1H,Ph-H).
13 CNMR(151MHz,CDCl 3 ,TMS)：14.3,18.3,22.8,25.7,31.7,51.1,59.3,60.9,68.1,121.5,121.5,123.9,124.2,125.0,125.3,125.4,126.8,127.1,127.4,127.7,127.8,128.3,128.5,128.7,128.7,128.7,129.5,130.0,139.8,141.3,144.8,146.0,147.1,149.4,152.2,162.0(C＝N),165.3(C＝N)
elemental analysis: c (C) 55 H 46 N 2 O 3 (782.98) theory: c,84.37; h,5.92; n,3.58. Experimental values: c,84.10; h,6.34; n,3.53.
Example 3
Ligand L2 was prepared as in example 2, except that the same molar amount of 2, 6-diethylaniline was used instead of 2, 6-dimethylaniline. Yield: 26%.
The structure validation data are as follows:
FT-IR(KBr,cm -1 )：3023(w),2936(w),1671(ν(C＝N)m),1645(ν(C
＝N)m),1594(s),1455(s),1329(w),1275(w),1111(w),1082(m),978(s),829(s),778(m),699(s).
1 HNMR(600MHz,CDCl 3 ,TMS)：1.2(t,J＝7.6Hz,6H,2×CH 3 ),2.6(qd,J＝7.7,7.3,5.4Hz,4H,2×CH 2 ),3.0(s,6H,2×OCH 3 ),3.9(s,3H,OCH 3 ),5.7(s,2H,2×CH),6.2(t,J＝7.4Hz,2H,Ph-H),6.4–6.5(m,5H,Ph-H),6.7(t,J＝7.8Hz,1H,Ph-H),7.0(d,J＝7.5Hz,1H,Ph-H),7.1–7.1(m,5H,Ph-H),7.1–7.2(m,6H,Ph-H),7.2(dd,J＝10.2,6.1Hz,7H,Ph-H),7.3(d,J＝8.3Hz,1H,Ph-H),7.6(d,J＝8.2Hz,1H,Ph-H).
13 CNMR(151MHz,CDCl 3 ,TMS)：δ13.2,13.3,14.3,14.6,22.8,24.4,24.5,24.7,31.7,51.0,59.3,60.9,118.4,121.5,122.1,124.2,124.2,125.3,125.5,126.1,126.3,126.9,126.9,126.9,127.4,127.7,127.8,127.8,128.3,128.6,128.7,128.7,129.5,130.0,130.9,139.8,141.3,144.8,146.2,147.1,148.4,152.3,162.1,165.2.
elemental analysis: c (C) 57 H 50 N 2 O 3 (811.04) theory: c,84.41; h,6.21; n,3.45. Experimental values: c,84.69; h,6.54; n,3.49.
Example 4
Ligand L3 was prepared as in example 2, except that the same molar amount of 2, 6-diisopropylaniline was used in place of 2, 6-dimethylaniline. Yield: 28%.
The structure validation data are as follows:
FT-IR(KBr,cm -1 )：3024(w),2940(w),1670(ν(C＝N)m),1642(ν
(C＝N)m),1597(s),1455(s),1328(w),1275(w),1113(w),1081(m),937(s),830(s),760(m),699(s).
1 HNMR(600MHz,CDCl 3 ,TMS)：1.0(d,J＝6.8Hz,6H,2×CH 3 ),1.3(d,J＝6.8Hz,6H,2×CH 3 ),3.0(s,6H,2×OCH3),3.1(p,J＝6.9Hz,2H,2×CH),3.9(s,3H,OCH 3 ),5.6(s,2H,2×CH),6.2(t,J＝7.4Hz,2H,Ph-H),6.3–6.4(m,5H,Ph-H),6.6(t,J＝7.8Hz,1H,Ph-H),7.0–7.1(m,4H,Ph-H),7.1(dd,J＝14.9,7.3Hz,7H,Ph-H),7.2–7.2(m,8H,Ph-H),7.3(d,J＝8.3Hz,1H,Ph-H),7.6(d,J＝8.2Hz,1H,Ph-H).
13 CNMR(151MHz,CDCl 3 ,TMS)：δ23.8,24.3,28.7,51.0,59.3,60.9,121.6,122.7,123.7,124.2,124.6,125.3,125.5,126.6,126.9,127.4,127.7,127.9,128.3,128.6,128.6,128.7,129.5,130.0,135.9,139.9,141.3,144.8,146.2,147.1,147.2,152.2,162.5,165.2.
elemental analysis: c (C) 59 H 54 N 2 O 3 (839.09) theory: c,84.45; h,6.49; n,3.34. Experimental values: c,84.40; h,6.53; n,3.51.
Example 5
Ligand L4 was prepared as in example 1, except that the same molar amount of 2,4, 6-trimethylaniline was used in place of 2, 6-dimethylaniline. Yield: 30%.
The structure validation data are as follows:
FT-IR(KBr,cm -1 )：3024(w),2939(w),1656(ν(C＝N)m),1633(ν
(C＝N)m),1593(s),1455(s),1329(w),1274(w),1111(w),1079(m),976(s),828(s),761(m),699(s).
1 HNMR(600MHz,CDCl 3 ,TMS)：2.2(s,6H,2×CH 3 ),2.4(s,3H,CH 3 ),3.0(s,6H,2×OCH 3 ),3.9(s,3H,OCH 3 ),5.6(s,2H,2×CH),6.2(t,J＝7.4Hz,2H,Ph-H),6.4(t,J＝7.6Hz,4H,Ph-H),6.5(d,J＝7.1Hz,1H,Ph-H),6.6–6.7(m,1H,Ph-H),7.0(s,2H,Ph-H),7.0–7.2(m,16H,Ph-H),7.3(d,J＝8.3Hz,1H,Ph-H),7.6(d,J＝8.2Hz,1H,Ph-H).
13 CNMR(151MHz,CDCl 3 .TMS)：δ14.3,18.2,21.1,22.8,31.7,51.1,59.3,60.9,121.5,124.1,124.8,125.3,125.4,126.8,127.1,127.4,127.7,127.8,128.4,128.5,128.7,128.8,129.2,129.6,130.1,133.1,141.3,144.8,146.1,146.9,147.2,152.3,162.1,165.4.
elemental analysis: c (C) 56 H 48 N 2 O 3 (797.01) theory: c,84.39; h,6.07; n,3.51. Experimental values: c,84.20; h,6.42; n,3.50.
Example 6
Ligand L5 was prepared as in example 1, except that the same molar amount of 2, 6-diethyl-4-methylaniline was used instead of 2, 6-dimethylaniline. Yield: 31%.
The structure validation data are as follows:
FT-IR(KBr,cm -1 )：3023(w),2935(w),1660(ν(C＝N)m),1635(ν
(C＝N)m),1595(s),1458(s),1330(w),1274(w),1114(w),1082(m),979(s),829(s),763(m),700(s).
1 HNMR(600MHz,CDCl 3 ,TMS)：1.1(t,J＝7.6Hz,6H,2×CH 3 ),2.4(s,3H,CH 3 ),2.5(dt,J＝14.7,7.5Hz,2H,CH 2 ),2.7(dq,J＝15.1,7.6Hz,2H,CH 2 ),3.0(s,6H,2×OCH 3 ),3.9(s,3H,OCH 3 ),5.7(s,2H,2×CH),6.2–6.3(m,2H,Ph-H),6.4(t,J＝7.7Hz,4H,Ph-H),6.5–6.6(m,1H,Ph-H),6.7(dd,J＝8.3,7.2Hz,1H,Ph-H),7.0–7.2(m,14H,Ph-H),7.2–7.3(m,4H,Ph-H),7.3(d,J＝8.3Hz,1H,Ph-H),7.6(d,J＝8.2Hz,1H,Ph-H).
13 CNMR(151MHz,CDCl 3 ,TMS)：δ13.4,14.3,14.7,20.8,21.4,24.5,24.7,51.0,59.3,60.9,121.5,121.6,122.1,124.1,125.3,125.5,126.2,126.8,126.9,126.9,127.1,127.4,127.6,127.7,127.8,128.1,128.4,128.4,128.5,128.6,128.7,128.8,129.1,129.5,129.6,130.0,130.7,133.3,139.1,139.8,141.3,144.7,145.9,146.2,147.2,152.2,162.2,165.2.
elemental analysis: c (C) 58 H 52 N 2 O 3 (825.07) theory: c,84.43; h,6.35; n,3.40. Experimental values: c,84.10; h,6.35; n,3.53.
Example 7
Preparing [1- (2, 6-dimethylaniline) -2- (2, 6-di (benzhydryl) -3,4, 5-trimethoxyaniline) acenaphthene ] nickel (II) [ complex C1] shown in the formula (I), wherein R1 is methyl, R2 is hydrogen, and X is bromine.
At room temperature, (DME) NiBr 2 (0.062 g,0.20 mmol) and 1- (2, 6-dimethylaniline) -2- (2, 6-di (benzhydryl) -3,4, 5-trimethoxyaniline) acenaphthylene (0.16 g,0.20 mmol) prepared in example 2 were mixed and dissolved in methylene chloride, stirred under nitrogen for 24 hours, after methylene chloride was removed under reduced pressure, diethyl ether was added to precipitate a red solid, and the mixture was filtered, washed with diethyl ether and dried to obtain a dark red solid. Yield: 93%.
The structural characterization data are as follows:
FT-IR(KBr,cm -1 )：3024(w),2942(w),1643(ν(C＝N)m),1617(ν
(C＝N)m),1583(s),1494(s),1460(w),1295(w),1113(w),1044(m),979(s),830(s),766(m),700(s).
elemental analysis: c (C) 55 H 46 Br 2 N 2 NiO 3 (1001.49) theory: c,65.96; h,4.63; n,2.80. Experimental values: c,65.70; h,4.61; n,2.85.
Example 8
Complex C2 was prepared as in example 7, except that the same molar amount of ligand L2 prepared in example 3 was used to replace the ligand L1 prepared in example 2. Yield: 92%.
The structure validation data are as follows:
FT-IR(KBr,cm -1 )：3025(w),2940(w),1641(m),1619(m),1582(s),1494(s),1460(w),1294(w),1112(w),1045(m),978(s),829(s),762(m),700(s).
elemental analysis: c (C) 59 H 56 Br 2 N 2 NiO 3 (1029.54) theory: c,66.50; h,4.90; n,2.72. Experimental values: c,66.10; h,4.65; n,2.86.
Example 9
Complex C3 was prepared as in example 7, except that ligand L1 was prepared by substituting the same molar amount of ligand L3 prepared in example 4 for ligand L1 prepared in example 2. Yield: 90%.
The structure validation data are as follows:
FT-IR(KBr,cm -1 )：3025(w),2943(w),1640(m),1616(m),1581(s),1494(s),1461(w),1292(w),1111(w),1044(m),979(s),830(s),761(m),700(s).
elemental analysis: c (C) 61 H 60 Br 2 N 2 NiO 3 (1057.59) theory: c,67.01; h,5.15; n,2.65. Experimental values: c,66.53; h,4.79; n,2.80.
Example 10
Complex C4 was prepared as in example 7, except that ligand L1 was prepared by substituting the same molar amount of ligand L4 prepared in example 5 for ligand L2. Yield: 89%.
The structure validation data are as follows:
FT-IR(KBr,cm -1 )：3024(w),2942(w),1643(m),1619(m),1582(s),1494(s),1461(w),1291(w),1112(w),1044(m),979(s),829(s),762(m),699(s).
elemental analysis: c (C) 58 H 54 Br 2 N 2 NiO 3 (1015.51) theory: c,66.23; h,4.76; n,2.76. Experimental values: c,66.09; h,4.68; n,2.83.
Example 11
Complex C5 was prepared as in example 7, except that ligand L1 was prepared by substituting the same molar amount of ligand L5 prepared in example 6 for ligand L2. Yield: 92%.
The structure validation data are as follows:
FT-IR(KBr,cm -1 )：3025(w),2940(w),1640(m),1617(m),1583(s),1494(s),1460(w),1294(w),1114(w),1045(m),979(s),829(s),762(m),699(s).
elemental analysis: c (C) 58 H 52 Br 2 N 2 NiO 3 (1043.57) theory: c,66.76; h,5.02; n,2.68. Experimental values: c,66.87; h,5.10; n,3.01.
Example 12
By means of the complexes C1 and Me 2 Ethylene polymerization under AlCl promoter pressure:
a) Ethylene polymerization was carried out in a 250mL stainless steel reactor. In the process of vacuumizingAfter nitrogen is backfilled twice, ethylene is backfilled once again, so that the reaction kettle is maintained in an ethylene atmosphere. When the temperature of the reaction kettle was stabilized at 30 ℃, the pre-catalyst C1 (2. Mu. Mol) was dissolved in 20mL of toluene, 0.9mL of cocatalyst Me 2 AlCl (0.9M/n-heptane solution, al: ni=400) was added continuously with toluene to make the total volume of the reaction solution 100mL. Ethylene gas was continuously introduced to maintain the ethylene pressure at 10atm, and reacted at 30℃for 30 minutes. The ethylene gas inlet was stopped at the end of the reaction time and the remaining gas was discharged from the reactor vessel, after which the polyethylene obtained was quenched in 10% ethanol hydrochloride and the polymer was pumped down and weighed at room temperature.
Polymerization activity: 7.11×10 6 g·mol -1 (Ni)·h -1 Tm=82.1 ℃ (Tm is the melting temperature of the polymer, obtained by DSC testing), molecular weight M of the polymer w ＝5.80×10 5 g·mol -1 Pdi=1.58 (Mw is the weight average molecular weight of the polymerization, measured by high temperature GPC).
b) Substantially identical to a), the difference is that: cocatalyst Me was used in an amount of 0.45mL 2 AlC1 (0.9M/n-heptane solution) to let Al/ni=200: 1. polymerization activity: 4.92×10 6 g·mol -1 (Ni)·h -1 Polymer tm=70.1 ℃, mw=7.48×10 5 g·mol -1 ,PDI＝1.62。
c) Substantially identical to a), the difference is that: cocatalyst Me was used in an amount of 0.68mL 2 AlC1 (0.9M/n-heptane solution) to let Al/ni=300: 1. polymerization activity: 5.46×10 6 g·mol -1 (Ni)·h -1 Polymer tm=75.4 ℃, mw=7.21×10 5 g·mol -1 ,PDI＝1.58。
d) Substantially identical to a), the difference is that: cocatalyst Me was used in an amount of 0.79mL 2 AlC1 (0.9M/n-heptane solution) to let Al/ni=350: 1. polymerization activity: 6.17X10 6 g·mol -1 (Ni)·h -1 Polymer tm=73.6 ℃, mw=6.50×10 5 g·mol -1 ,PDI＝1.65。
e) Substantially identical to a), the difference is that: cocatalyst Me was used in an amount of 1.01mL 2 AlC1 (0.9M/n-heptane solution)) And Al/ni=450: 1. polymerization activity: 6.21×10 6 g·mol -1 (Ni)·h -1 Polymer tm=75.2 ℃, mw=5.49×10 5 g·mol -1 ,PDI＝1.57。
f) Substantially identical to a), the difference is that: cocatalyst Me was used in an amount of 1.13mL 2 AlC1 (0.9M/n-heptane solution) to let Al/ni=500: 1. polymerization activity: 5.73X10 6 g·mol -1 (Ni)·h -1 Polymer tm=73.8 ℃, mw=5.47×10 5 g·mol -1 ,PDI＝1.53。
g) Substantially identical to a), the difference is that: cocatalyst Me was used in an amount of 1.36mL 2 AlC1 (0.9M/n-heptane solution) to let Al/ni=600: 1. polymerization activity: 5.11X10.times.10 6 g·mol -1 (Ni)·h -1 Polymer tm=71.9 ℃, mw=4.86×10 5 g·mol -1 ,PDI＝1.71。
h) Substantially identical to a), the difference is that: the polymerization temperature was 40 ℃. Polymerization activity: 6.83×10 6 g·mol -1 (Ni)·h -1 Polymer tm=71.6 ℃, mw=5.50×10 5 g·mol -1 ,PDI＝1.70。
i) Substantially identical to a), the difference is that: the polymerization temperature was 60 ℃. Polymerization activity: 6.02X10 6 g·mol -1 (Ni)·h -1 Polymer tm=69.4 ℃, mw=3.86×10 5 g·mol -1 ,PDI＝1.64。
j) Substantially identical to a), the difference is that: the polymerization temperature was 80 ℃. Polymerization activity: 3.42×10 6 g·mol -1 (Ni)·h -1 Polymer tm=70.6 ℃, mw=2.35×10 5 g·mol -1 ,PDI＝1.77。
j) Substantially identical to a), the difference is that: the polymerization temperature was 90 ℃. Polymerization activity: 1.96×10 6 g·mol -1 (Ni)·h -1 Polymer tm=68.3 ℃, mw=2.18×10 5 g·mol -1 ,PDI＝1.80。
k) Substantially identical to a), the difference is that: the polymerization time was 5min. Polymerization activity: 21.06X10 6 g·mol -1 (Ni)·h -1 Polymer tm=72.6 ℃, mw=4.48×10 5 g·mol -1 ,PDI＝1.49。
l) is substantially identical to a), with the difference that: the polymerization time was 10min. Polymerization activity: 13.59X10 6 g·mol -1 (Ni)·h -1 Polymer tm=76.3 ℃, mw=6.71×10 5 g·mol -1 ,PDI＝1.48。
m) is substantially identical to a), with the difference that: the polymerization time was 15min. Polymerization activity: 10.26×10 6 g·mol -1 (Ni)·h -1 Polymer tm=78.4 ℃, mw=5.79×10 5 g·mol -1 ,PDI＝1.42。
n) is substantially identical to a), with the difference that: the polymerization time was 45min. Polymerization activity: 6.67×10 6 g·mol -1 (Ni)·h -1 Polymer tm=78.3 ℃, mw=7.91×10 5 g·mol -1 ,PDI＝1.69。
o) is substantially identical to a), with the difference that: the polymerization time was 60min. Polymerization activity: 6.36×10 6 g·mol -1 (Ni)·h -1 Polymer tm=79.2 ℃, mw=8.21×10 5 g·mol -1 ,PDI＝1.66。
p) is substantially identical to a), with the difference that: the polymerization pressure was 1atm. Polymerization activity: 2.21×10 6 g·mol -1 (Ni)·h -1 Polymer tm=71.6 ℃, mw=4.83×10 5 g·mol -1 ,PDI＝1.48。
q) is substantially identical to a), with the difference that: the polymerization pressure was 5atm. Polymerization activity: 4.22×10 6 g·mol -1 (Ni)·h -1 Polymer tm=70.3 ℃, mw=5.47×10 5 g·mol -1 ,PDI＝1.48。
r) is substantially identical to a), with the difference that: the main catalyst is C2. Polymerization activity: 7.92×10 6 g·mol -1 (Ni)·h -1 Polymer tm=77.5 ℃, mw=11.00×10 5 g·mol -1 ,PDI＝1.43。
s) are substantially identical to a), with the difference that: the main catalyst is C3. Polymerization activity: 8.21×10 6 g·mol -1 (Ni)·h -1 Polymer tm=78.4 ℃, mw=12.64×10 5 g·mol -1 ,PDI＝1.59。
t) is substantially identical to a), with the difference that: the main catalyst is C4. Polymerization activity: 6.39X10 6 g·mol -1 (Ni)·h -1 Polymer tm=75.3 ℃, mw=8.63×10 5 g·mol -1 ,PDI＝1.65。
u) is substantially identical to a), with the difference that: the main catalyst is C5. Polymerization activity: 7.51X10 6 g·mol -1 (Ni)·h -1 Polymer tm=70.9 ℃, mw=9.63×10 5 g·mol -1 ,PDI＝1.59。
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
The foregoing description is only illustrative of the present invention and is not intended to limit the scope of the invention, and all equivalent structures or equivalent processes or direct or indirect application in other related technical fields are included in the scope of the present invention.
Claims (10)
1. An asymmetric alpha-diimine nickel complex containing trimethoxy, which is characterized in that the asymmetric alpha-diimine nickel complex containing trimethoxy is shown in the following formula (I):
wherein R is 1 Identical or different, each independently selected from H, F, cl, br, I or optionally substituted with one or more R 3 Substituted with the following groups: c (C) 1-6 Alkyl, C 1-6 Alkyloxy, C 3-10 Cycloalkyl, C 3-10 Cycloalkyl oxy, C 6-14 Aryl, C 6-14 An aryloxy group;
R 2 selected from H, halogen, C 1-6 Alkyl or C 1-6 An alkoxy group;
each R 3 Identical or different, each independently selected from H, F, cl, br, I, C 1-6 Alkyl, C 1-6 Alkoxy radicalRadical, C 3-10 Cycloalkyl, C 3-10 Cycloalkyl oxy, C 6-14 Aryl, C 6-14 An aryloxy group.
2. The trimethoxy-containing asymmetric alpha-nickel diimine complex of claim 1, wherein R 1 The same or different, each independently selected from methyl, ethyl or isopropyl; r is R 2 Selected from hydrogen or methyl.
3. The trimethoxy-containing asymmetric α -diimine nickel complex of claim 1, wherein the nickel complex has a structure according to formula (I-1), formula (I-2), formula (I-3), formula (I-4) or formula (I-5):
wherein X is the same or different and is each independently selected from Cl and Br;
the complex represented by formula (I) is selected from complexes having the following group definition:
C 1：R 1 ＝Me；R 2 ＝H；C2：R 1 ＝Et；R 2 ＝H；C3：R 1 ＝ i Pr；R 2 ＝H；
C4：R 1 ＝Me；R 2 ＝Me；C5：R 1 ＝Et；R 2 ＝Me。
4. the trimethoxy-containing asymmetric α -diimine nickel complex according to claim 1, wherein the following formula (ii) is an intermediate of the trimethoxy-containing asymmetric α -diimine nickel complex:
wherein R is 1 And R is 2 Having the definition as defined in claim 1.
5. The trimethoxy-containing asymmetric α -diimine nickel complex according to claim 1, wherein the intermediate has a structure represented by formula (ii-1), formula (ii-2), formula (ii-3), formula (ii-4) or formula (ii-5):
the intermediate represented by formula (II) is selected from intermediates having the following group definition:
L1：R 1 ＝Me；R 2 ＝H；L2：R 1 ＝Et；R 2 ＝H；L3：R 1 ＝ i Pr；R 2 ＝H；
L4：R 1 ＝Me；R 2 ＝Me；L5：R 1 ＝Et；R 2 ＝Me。
6. the trimethoxy-containing asymmetric α -nickel diimine complex according to any one of claims 1 or 2, wherein said co-catalyst is selected from one or more of aluminoxane, alkyl aluminum and alkyl aluminum chloride;
the aluminoxane is selected from one or two of Methylaluminoxane (MAO) or triisobutylaluminum Modified Methylaluminoxane (MMAO);
the alkyl aluminum chloride is selected from diethyl aluminum chloride (Et) 2 AlCl), dimethylaluminum chloride (Me) 2 AlCl), aluminum sesquioxide (EASC);
when the catalyst composition further comprises a promoter, the molar ratio of metal Al in the promoter to central metal Ni of the nickel complex shown in formula (I) is (200-3000);
when the cocatalyst is Methylaluminoxane (MAO), the molar ratio of metal Al in the Methylaluminoxane (MAO) to central metal Ni of the nickel complex shown in the formula (I) is (1000-3000);
when the cocatalyst is triisobutylaluminum Modified Methylaluminoxane (MMAO), the molar ratio of metal Al in the triisobutylaluminum Modified Methylaluminoxane (MMAO) to central metal Ni of the complex shown in the formula (I) is (1000-3000);
the cocatalyst is diethylaluminum chloride (Et) 2 AlCl), diethylaluminum chloride (Et) 2 The molar ratio of the metal A1 in AlCl) to the central metal Ni of the nickel complex shown in the formula (I) is (200-1000);
the cocatalyst is dimethylaluminum chloride (Me) 2 AlCl), dimethylaluminum chloride (Me) 2 AlCl) and the nickel complex of formula (I) has a molar ratio of (200-600) to the central metal Ni.
7. The method for producing an asymmetric α -diimine nickel trimethoxy-containing complex according to any one of claims 1 to 6, comprising the steps of: reacting (e.g., complexing) the intermediate of claim 3 or 4 with a nickel-containing compound to obtain a nickel complex of formula (I);
the nickel-containing compound is selected from nickel-containing halides, which may be (DME) NiBr, for example 2 Or NiBr 2 For Example (DME) NiBr 2 ；
The reaction is carried out under anaerobic conditions, for example under protection of an inert gas such as nitrogen; the molar ratio of the nickel-containing compound to the compound shown in the formula (II) is 1:1 to 2; the temperature of the reaction is 30-100 ℃; the reaction time is 8-16 hours; the reaction is carried out in an organic solvent, which may be selected from one or more of halogenated alkanes or alcohol solvents.
8. The method for preparing an asymmetric alpha-diimine nickel complex containing trimethoxy according to claim 7, wherein 1) substitution reaction is carried out on acenaphthodione represented by formula (III) and aniline represented by formula (IV) to obtain 2-aniline acenaphthone represented by formula (V);
2) Condensing the 2-aniline acenaphthenone shown in the formula (V) obtained in the step 1) with a compound shown in the formula (VI) to obtain a compound shown in the formula (II):
9. the method for preparing an asymmetric α -diimine nickel complex containing trimethoxy according to claim 7, wherein the substitution reaction is performed under the catalysis of p-toluenesulfonic acid in step 1).
10. A process for the preparation of polyethylene comprising: the polymerization of ethylene by the catalyst composition of claim 5.
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