CN110092744B - High-thermal-stability tertiary-butyl-containing asymmetric diimine pyridine complex, and preparation method and application thereof - Google Patents
High-thermal-stability tertiary-butyl-containing asymmetric diimine pyridine complex, and preparation method and application thereof Download PDFInfo
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- CN110092744B CN110092744B CN201810085977.6A CN201810085977A CN110092744B CN 110092744 B CN110092744 B CN 110092744B CN 201810085977 A CN201810085977 A CN 201810085977A CN 110092744 B CN110092744 B CN 110092744B
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- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 238000010668 complexation reaction Methods 0.000 title claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 title abstract description 28
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 title abstract description 14
- 229910000071 diazene Inorganic materials 0.000 title abstract description 11
- RAABOESOVLLHRU-UHFFFAOYSA-N diazene Chemical compound N=N RAABOESOVLLHRU-UHFFFAOYSA-N 0.000 title abstract description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 100
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 100
- -1 polyethylene Polymers 0.000 claims abstract description 75
- 238000000034 method Methods 0.000 claims abstract description 54
- 150000001875 compounds Chemical class 0.000 claims abstract description 45
- 239000003054 catalyst Substances 0.000 claims abstract description 34
- 239000003446 ligand Substances 0.000 claims abstract description 32
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000005977 Ethylene Substances 0.000 claims abstract description 29
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 22
- 239000004698 Polyethylene Substances 0.000 claims abstract description 21
- 229920000573 polyethylene Polymers 0.000 claims abstract description 21
- 150000003624 transition metals Chemical class 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims description 34
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 claims description 31
- 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 20
- 229910052751 metal Inorganic materials 0.000 claims description 14
- 239000002184 metal Substances 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 7
- 229910052742 iron Inorganic materials 0.000 claims description 7
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 7
- 238000006467 substitution reaction Methods 0.000 claims description 7
- 238000006555 catalytic reaction Methods 0.000 claims description 6
- 238000006482 condensation reaction Methods 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N N-phenyl amine Natural products NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 4
- 125000005234 alkyl aluminium group Chemical group 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 4
- 150000004820 halides Chemical class 0.000 claims description 4
- 150000001448 anilines Chemical class 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- IDHCQGUWHXGMQW-UHFFFAOYSA-N 1-(2-acetylpyridin-3-yl)ethanone Chemical class CC(=O)C1=CC=CN=C1C(C)=O IDHCQGUWHXGMQW-UHFFFAOYSA-N 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000012453 solvate Substances 0.000 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminum chloride Substances Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000000379 polymerizing effect Effects 0.000 claims 1
- 229920000642 polymer Polymers 0.000 abstract description 70
- 230000003197 catalytic effect Effects 0.000 abstract description 18
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 abstract description 8
- 238000009776 industrial production Methods 0.000 abstract description 3
- 150000002505 iron Chemical class 0.000 abstract description 2
- 229920006351 engineering plastic Polymers 0.000 abstract 1
- 230000007613 environmental effect Effects 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 92
- 230000037048 polymerization activity Effects 0.000 description 50
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 37
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 25
- 125000003118 aryl group Chemical group 0.000 description 16
- 239000002904 solvent Substances 0.000 description 13
- 239000002244 precipitate Substances 0.000 description 12
- 238000010992 reflux Methods 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
- 239000003208 petroleum Substances 0.000 description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 8
- 239000000460 chlorine Substances 0.000 description 8
- 238000004440 column chromatography Methods 0.000 description 8
- 238000002844 melting Methods 0.000 description 8
- 230000008018 melting Effects 0.000 description 8
- 239000012046 mixed solvent Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 238000010200 validation analysis Methods 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 7
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 6
- 125000003545 alkoxy group Chemical group 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000003480 eluent Substances 0.000 description 6
- 150000002430 hydrocarbons Chemical group 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 239000011541 reaction mixture Substances 0.000 description 6
- 239000003039 volatile agent Substances 0.000 description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 5
- 125000004104 aryloxy group Chemical group 0.000 description 5
- 125000000000 cycloalkoxy group Chemical group 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 125000002950 monocyclic group Chemical group 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 239000000725 suspension Substances 0.000 description 5
- 125000006376 (C3-C10) cycloalkyl group Chemical group 0.000 description 4
- QPFMBZIOSGYJDE-ZDOIIHCHSA-N 1,1,2,2-tetrachloroethane Chemical class Cl[13CH](Cl)[13CH](Cl)Cl QPFMBZIOSGYJDE-ZDOIIHCHSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- ZZVUWRFHKOJYTH-UHFFFAOYSA-N diphenhydramine Chemical group C=1C=CC=CC=1C(OCCN(C)C)C1=CC=CC=C1 ZZVUWRFHKOJYTH-UHFFFAOYSA-N 0.000 description 4
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 4
- 238000010907 mechanical stirring Methods 0.000 description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 125000005605 benzo group Chemical group 0.000 description 3
- 238000012790 confirmation Methods 0.000 description 3
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 3
- 125000000753 cycloalkyl group Chemical group 0.000 description 3
- 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 3
- 238000011161 development Methods 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 229940078552 o-xylene Drugs 0.000 description 3
- 229920000098 polyolefin Polymers 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 125000005913 (C3-C6) cycloalkyl group Chemical group 0.000 description 2
- UFFBMTHBGFGIHF-UHFFFAOYSA-N 2,6-dimethylaniline Chemical compound CC1=CC=CC(C)=C1N UFFBMTHBGFGIHF-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 125000005275 alkylenearyl group Chemical group 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 150000005840 aryl radicals Chemical class 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
- 150000001868 cobalt Chemical class 0.000 description 2
- 229910017052 cobalt Chemical group 0.000 description 2
- 239000010941 cobalt Chemical group 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical group [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 2
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 2
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 150000004698 iron complex Chemical class 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 2
- 125000002294 quinazolinyl group Chemical group N1=C(N=CC2=CC=CC=C12)* 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 125000004191 (C1-C6) alkoxy group Chemical group 0.000 description 1
- 125000003161 (C1-C6) alkylene group Chemical group 0.000 description 1
- 125000006552 (C3-C8) cycloalkyl group Chemical group 0.000 description 1
- 125000006704 (C5-C6) cycloalkyl group Chemical group 0.000 description 1
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-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
- BEZVGIHGZPLGBL-UHFFFAOYSA-N 2,6-diacetylpyridine Chemical compound CC(=O)C1=CC=CC(C(C)=O)=N1 BEZVGIHGZPLGBL-UHFFFAOYSA-N 0.000 description 1
- CPRZSOOKYBJCJH-UHFFFAOYSA-N 2,6-dibenzhydryl-4-tert-butylaniline Chemical compound NC=1C(C(C=2C=CC=CC=2)C=2C=CC=CC=2)=CC(C(C)(C)C)=CC=1C(C=1C=CC=CC=1)C1=CC=CC=C1 CPRZSOOKYBJCJH-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
- ICSNLGPSRYBMBD-UHFFFAOYSA-N 2-aminopyridine Chemical compound NC1=CC=CC=N1 ICSNLGPSRYBMBD-UHFFFAOYSA-N 0.000 description 1
- 125000005915 C6-C14 aryl group Chemical group 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-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
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 125000000641 acridinyl group Chemical group C1(=CC=CC2=NC3=CC=CC=C3C=C12)* 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 125000002178 anthracenyl group Chemical group C1(=CC=CC2=CC3=CC=CC=C3C=C12)* 0.000 description 1
- 125000004931 azocinyl group Chemical group N1=C(C=CC=CC=C1)* 0.000 description 1
- 125000003785 benzimidazolyl group Chemical group N1=C(NC2=C1C=CC=C2)* 0.000 description 1
- 125000004603 benzisoxazolyl group Chemical group O1N=C(C2=C1C=CC=C2)* 0.000 description 1
- 125000000499 benzofuranyl group Chemical group O1C(=CC2=C1C=CC=C2)* 0.000 description 1
- 125000004196 benzothienyl group Chemical group S1C(=CC2=C1C=CC=C2)* 0.000 description 1
- 125000003354 benzotriazolyl group Chemical group N1N=NC2=C1C=CC=C2* 0.000 description 1
- 125000004541 benzoxazolyl group Chemical group O1C(=NC2=C1C=CC=C2)* 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
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- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
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- 239000012043 crude product Substances 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
- 230000007123 defense Effects 0.000 description 1
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- 125000005046 dihydronaphthyl group Chemical group 0.000 description 1
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
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- 125000001072 heteroaryl group Chemical group 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
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- 125000002883 imidazolyl group Chemical group 0.000 description 1
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- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
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- KEFOZNJTQPJEOB-UHFFFAOYSA-N pyridine-2,3-diimine Chemical compound N=C1C=CC=NC1=N KEFOZNJTQPJEOB-UHFFFAOYSA-N 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 125000000714 pyrimidinyl group Chemical group 0.000 description 1
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- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
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- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000005329 tetralinyl group Chemical group C1(CCCC2=CC=CC=C12)* 0.000 description 1
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- 238000001291 vacuum drying Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
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Abstract
The invention provides a high-heat-stability transition metal complex containing tert-butyl asymmetric diimine and pyridine for preparing polyethylene wax, and a preparation method and application thereof. The preparation method of the transition metal complex and the intermediate compound thereof has the advantages of mild conditions, short period and simple operation conditions. The complex can be applied to catalysts for ethylene polymerization, has a single catalytic activity center, can realize the regulation and control of polymer molecular weight by changing a ligand structure and polymerization conditions, and has the advantages of low cost, high catalytic activity, outstanding thermal stability and the like. In particular, iron complexes are provided which retain a catalytic activity of 2.82X 10 even at a high temperature of 110 DEG C 6 g·mol –1 (Fe)h –1 The method conforms to the operation temperature of industrial production, so that the method can be used as engineering plastics at higher environmental temperature and has great industrial application potential; in particular the polyethylene obtained has a weight-average molecular weight M w In the range of 5.1 to 7.7 kg/mol ‑1 The product (MMAO, 50-100 ℃) can be used for preparing the polyethylene wax which is urgently needed commercially.
Description
Technical Field
The invention relates to the technical field of polyolefin catalysts, in particular to a high-heat-stability tertiary butyl-containing asymmetric diimine pyridine complex for preparing polyethylene wax, and a preparation method and application thereof.
Background
The polyolefin material is taken as a support product for modern scientific technology and social development, not only meets the requirements of people on daily life in society, but also becomes an indispensable important material in various fields such as advanced science and technology, national defense construction and the like. Among them, polyethylene (PE) is the most productive species among the synthetic resins in the world, has the characteristics of good chemical resistance, high mechanical strength, recoverability, low cost and the like, and plays a very important role in the field of synthesizing olefin materials.
The design and development of olefin polymerization catalysts are the key to the development of polyethylene products.
Currently, polyethylene catalysts for industrial production are mainly Ziegler-Natta catalysts, metallocene catalysts and Phillips catalysts. In 1998, brookhart and Gibbson respectively reported a class of iron and cobalt complexes of 2,6-dienaminopyridine (formula 1, A), which can polymerize ethylene with high activity to obtain highly linear polyolefins. Since then, more and more research has been focused on the preparation and modification of late transition metal catalysts, such as the class B and C complexes in formula 1.
The inventor has introduced benzhydryl (formula 1,D, E) into the iron and cobalt complexes of pyridinediimine, and introduced Cl and Me substituent groups at para-position of aromatic imine benzene ring to improve catalytic activity and thermal stability of the catalytic system, and still has higher catalytic activity at 80 ℃ and obtains polyethylene with high molecular weight. (Polymer, 2012,53,1870, chem Comm.,2011,47,3257).
As a novel catalyst system, some fundamental research difficulties and restriction factors for promoting industrialization still exist. For example, the late transition metal complex itself has poor thermal stability, and thus tends to cause a decrease in the activity of the catalyst with an increase in the reaction temperature. Therefore, in addition to the improvement of the catalytic performance of the catalyst and the improvement of the preparation conditions and efficiency, obtaining a catalyst with higher activity and high thermal stability is one of the important matters of research, and is the key to advance the chemical industrialization as soon as possible.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a transition metal complex containing tert-butyl asymmetric imino pyridine shown as the following formula (I):
wherein M is selected from iron or cobalt;
R 1 、R 2 identical or different, each independently selected from H, F, cl, br, I, unsubstituted or optionally substituted by one or more R a Substituted of the following groups: c 1-6 Alkyl or C 1-6 An alkoxy group;
each R 3 、R 4 、R 5 Identical or different, each independently selected from H, F, cl, br, I, unsubstituted or optionally substituted by one or more R b Substituted of the following groups: c 1-6 Alkyl radical, C 1-6 Alkoxy radical, C 3-10 Cycloalkyl radical, C 3-10 Cycloalkyloxy, aryl, aryloxy, C 1-6 An alkylene aryl group;
each X is the same or different and is independently selected from F, cl, br, I;
each R a Identical or different, each independently selected from H, F, cl, br, I, unsubstituted or optionally substituted by one or more R c Substituted C 1-6 Alkyl radical, C 1-6 Alkoxy radical, C 3-10 Cycloalkyl, C 3-10 Cycloalkyloxy, aryl, aryloxy;
each R b Identical or different, each independently selected from H, F, cl, br, I, unsubstituted or optionally substituted by one or more R c Substituted C 1-6 Alkyl radical, C 1-6 Alkoxy radical, C 3-10 Cycloalkyl, C 3-10 Cycloalkyloxy, aryl, aryloxy;
each R c Identical or different, each independently selected from H, F, cl, br, I or the following groups: c 1-6 Alkyl radical, C 1-6 Alkoxy radical, C 3-10 Cycloalkyl, C 3-10 Cycloalkyloxy, aryl, aryloxy.
According to an embodiment of the invention, in formula (I), R 1 、R 2 The same or different, each is independently selected from H, C 1-3 Alkyl, for example selected from H, methyl, ethyl, n-propyl, isopropyl;
according to an embodiment of the present invention, each R 3 、R 4 、R 5 The same or different, each independently selected from H, F, cl, br, I, C 1-3 Alkyl or C 1-3 An alkylene aryl group;
according to an embodiment of the invention, each X, which is the same or different, is independently selected from Cl, br.
By way of example, the complex of formula (I) according to the invention is selected from the group comprising, but not limited to, complexes having the following group definitions:
the complex Fe-1: wherein R is 1 = Me, X is selected from Cl, other groups are H;
the complex Fe-2: wherein R is 1 = Et, X is selected from Cl, the other groups are H;
the complex Fe-3: wherein R is 1 = i-Pr, X is selected from Cl and the other groups are H;
the complex Fe-4: wherein R is 1 ＝Me，R 2 = Me, X is selected from Cl, other groups are H;
the complex Fe-5: wherein R is 1 ＝Et，R 2 = Me, X is selected from Cl, other groups are H;
the present invention also provides a ligand compound represented by the following formula (II):
wherein R is 1 、R 2 、R 3 、R 4 、R 5 Having the definitions as described above.
As an example, the ligand compound represented by formula (II) according to the present invention is selected from the group consisting of, but not limited to, compounds having the following group definitions:
ligand L1: r 1 = Me, other groups are H;
ligand L2: r 1 Et, other groups are H;
ligand L3: r 1 = i-Pr, other groups are H;
ligand L4: r 1 ＝Me，R 2 = Me, other groups are H;
a ligand L5: r is 1 ＝Et，R 2 = Me, other groups are H.
The invention also provides a preparation method of the transition metal complex shown in the formula (I), which comprises the following steps:
reacting a ligand represented by the above formula (II) with a compound MX 2 Carrying out complexation reaction to obtain a complex shown in the formula (I);
wherein M, X has the definition described above.
According to the invention, said compound MX 2 One or more selected from iron or cobalt containing halides, hydrates or other solvates of said halides, e.g. (DME) FeBr 2 、FeCl 2 ·4H 2 O、FeCl 2 Or CoCl 2 ·6H 2 One or more of O.
According to the invention, the reaction is preferably carried out in the absence of oxygen, for example under the protection of an inert gas such as nitrogen.
According to the invention, said compound MX 2 The molar ratio to the compound represented by the formula (II) may be 1:1 to 1.5, preferably 1:1 to 1.3, more preferably 1.
According to the invention, the temperature of the reaction may be between 10 and 35 ℃, such as between 20 and 25 ℃; the reaction time is 4 to 8 hours, preferably 6 to 8 hours.
According to the invention, the reaction can be carried out in an organic solvent, which can be selected from one or more of alcoholic solvents, such as methanol, ethanol, preferably ethanol.
Preferably, the method further comprises purifying the obtained complex shown in the formula (I), wherein the purification method comprises the following steps:
a) The solvent of the compound shown in the formula (I) is pumped by a vacuum pump, and then the compound is dissolved in an organic solvent (such as anhydrous ether) for precipitation;
b) After the precipitation in step a), solid-liquid separation is carried out, and the solid phase is washed by anhydrous ether and dried.
The invention also provides the use of the transition metal complex shown in the formula (I) for catalyzing olefin polymerization, preferably ethylene polymerization.
The present invention also provides a method for preparing the ligand compound represented by the above formula (II), comprising the steps of:
1) R is represented by the formula (III) 4 Substituted diacetylpyridines with R of formula (IV) 5 Carrying out substitution reaction on substituted aniline to obtain a compound shown in a formula (V);
2) Carrying out condensation reaction on the compound shown in the formula (V) obtained in the step 1) and the compound shown in the formula (VI) to obtain a ligand compound shown in the formula (II);
wherein R is 1 、R 2 、R 3 、R 4 、R 5 Having the definitions as described above.
According to the invention, in step 1), the substitution reaction can be carried out under catalysis of p-toluenesulfonic acid.
According to the present invention, in step 1), the substitution reaction may be carried out in an aromatic hydrocarbon solvent, such as toluene, o-xylene, m-xylene, chlorobenzene, etc., preferably in toluene.
According to the present invention, in step 1), the substitution reaction may be performed under heating reflux for 8 to 12 hours, preferably 10 to 12 hours.
According to the invention, in the step 1), the molar charge ratio of the diacetylpyridine represented by the formula (III) to the aniline represented by the formula (IV) is 1-1.5, and is preferably 1:1.
According to the present invention, after the reaction of step 1), the compound represented by formula (V) obtained can be further purified, and the purification method comprises the following steps:
a1 Dissolving the compound of formula (V) obtained in step 1) in dichloromethane;
b1 Carrying out loading and column chromatography by using basic alumina, eluting by using a mixed solvent of petroleum ether and ethyl acetate (the volume ratio of the petroleum ether to the ethyl acetate is 100);
c1 Removing the solvent to obtain a purified compound represented by formula (V).
According to the invention, in step 2), the condensation reaction can be carried out under catalysis of p-toluenesulfonic acid.
According to the invention, in step 2), the condensation reaction can be carried out in an aromatic hydrocarbon solvent, such as toluene, o-xylene, m-xylene, chlorobenzene, etc., preferably in toluene.
According to the present invention, in step 2), the condensation reaction may be performed under heating reflux for 4 to 8 hours, preferably 6 to 8 hours.
According to the invention, in step 2), the molar charge ratio of the compound of formula (V) to the compound of formula (VI) is 1.0 to 1.5, preferably 1.1.
Preferably, the compound represented by formula (II) obtained may be further purified, and the purification method may include the steps of:
a') dissolving the compound of formula (II) obtained in step 2) in dichloromethane;
b') carrying out loading and column chromatography by using basic alumina, eluting by using a mixed solvent of petroleum ether and ethyl acetate (the volume ratio of the petroleum ether to the ethyl acetate is preferably 125);
c') removing the solvent to obtain a purified compound represented by the formula (II).
The invention also provides application of the asymmetric diimine pyridine ligand compound containing tert-butyl and benzhydryl and shown in the formula (II) in preparation of the transition metal complex shown in the formula (I).
The invention also provides a catalyst composition, which is characterized by comprising a main catalyst and an optional cocatalyst, wherein the main catalyst is selected from transition metal complexes shown in a formula (I).
According to the present invention, the cocatalyst may be selected from one or more of aluminoxane, alkylaluminum, and alkylaluminum chloride.
According to the present invention, the aluminoxane may be selected from one or both of Methylaluminoxane (MAO) or triisobutylaluminum-Modified Methylaluminoxane (MMAO).
According to the invention, when the catalyst composition further comprises a cocatalyst, the molar ratio of the metal Al in the cocatalyst to the central metal of the complex represented by formula (I), for example Fe, is (500 to 4000): 1, preferably (1000 to 3300): 1, and can be, for example, 1000.
Preferably, when the cocatalyst is Methylaluminoxane (MAO), the molar ratio of the metal Al in the Methylaluminoxane (MAO) to the central metal of the complex represented by formula (I), for example Fe, is (1000-2500): 1, more preferably the molar ratio is 2000.
Preferably, when the cocatalyst is triisobutylaluminum-Modified Methylaluminoxane (MMAO), the molar ratio of metal Al in triisobutylaluminum-Modified Methylaluminoxane (MMAO) to the central metal of the complex represented by formula (I), for example, fe, is (1000 to 3250): 1, more preferably 2750.
The invention also provides a preparation method of polyethylene, which comprises the following steps: ethylene is polymerized by the catalyst composition.
Preferably, the polymerization reaction temperature is 30 ~ 110 ℃, for example can be 30 ℃, 40 ℃,50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃, 110 ℃; the polymerization reaction time is 5-60 min, for example, 5min, 10min, 15min, 30min, 45min, 60min; the polymerization pressure is 0.5 to 10atm, and may be, for example, 1atm, 5atm or 10atm.
According to the present invention, the solvent for the polymerization reaction may be one or more selected from toluene, o-xylene, dichloromethane, ethanol, tetrahydrofuran, hexane, or cyclohexane.
According to the invention, the polymerization is preferably carried out under an ethylene atmosphere.
The invention also provides the use of the above transition metal complex or catalyst composition in the catalysis of olefin polymerization, particularly ethylene polymerization.
Has the advantages that:
1. the invention provides a high-thermal-stability compound containing tert-butyl asymmetric diimine pyridine ligands for preparing polyethylene wax and a transition metal complex thereof. The complex contains an electron-donating substituent tert-butyl group and a bulky substituent benzhydryl group, has a single catalytic activity center, can realize the regulation and control of the molecular weight of a polymer by changing the ligand structure and the polymerization reaction condition, and has the advantages of outstanding thermal stability, high catalytic activity, low cost and the like.
2. The invention provides a preparation method of a high-heat-stability asymmetric diimine pyridine ligand compound containing tert-butyl and benzhydryl and a transition metal complex thereof for preparing polyethylene wax. The preparation processes of the two compounds have the advantages of mild reaction conditions, short period, simple operation conditions and the like.
3. The invention provides a high-thermal-stability asymmetric diimine pyridine ligand compound containing tert-butyl and benzhydryl and application of a transition metal complex thereof. Is prepared from asymmetric diimine gold prepared from intermediateThe metal complex is used as a catalyst for ethylene polymerization reaction. The activity of the iron complex for catalyzing ethylene polymerization can reach 14.08 multiplied by 10 under the condition of 80 ℃ for example 6 g·mol -1 (Fe)·h -1 The weight average molecular weight M of the prepared polyethylene w 2.1 to 318.2kg mol -1 The molecular weight of the polyethylene is greatly regulated and controlled by fluctuation.
4. The method for preparing the polyethylene provided by the invention is simple to operate, has mild reaction conditions, and can be used for preparing highly linear polyethylene. Especially in MMAO cocatalyst at 50-100 deg.C to obtain polyethylene with weight average molecular weight M w In the range of 5.1 to 7.7 kg/mol -1 Can be used for preparing the polyethylene wax which is needed in commerce urgently.
5. In the diimine pyridine complex structure containing bulky benzhydryl substituent groups designed and synthesized by the invention, the aryl imine plane and the coordination plane are basically in vertical positions due to the steric hindrance of the ortho benzhydryl group, and the effective protection can be formed on the metal active center. Therefore, the complex in the invention has higher activity and more stable property.
6. The diimine pyridine transition metal complex containing electron-donating substituent tert-butyl designed and synthesized by the invention can be used for preparing commercially urgently needed polyethylene wax; the high reaction activity and thermal stability of the catalyst are stronger, particularly the iron complex has high catalytic activity and thermal stability, for example, the catalytic activity of the catalyst is 12.01 to 13.08 multiplied by 10 under the condition of MMAO cocatalyst at 50 to 80 DEG C 6 g·mol –1 (Fe)h –1 Small floating, high thermal stability, even at 110 deg.C, the catalytic activity can still be maintained at 2.82X 10 6 g·mol –1 (Fe)h –1 The method meets the operation temperature of industrial production and has a wide application prospect.
Definition and description of terms:
unless defined otherwise, all technical and scientific terms herein have the same meaning as commonly understood by one of ordinary skill in the art to which the claimed subject matter belongs. It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the subject matter of the application. In this application, the use of "or", "or" means "and/or" unless stated otherwise. Furthermore, the term "comprising" as well as other forms, such as "includes," "including," and "containing," are not limiting.
The term "C 1-6 Alkyl "means a straight-chain or branched alkyl group having 1 to 6 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, sec-butyl, pentyl, neopentyl.
The term "C 1-6 Alkoxy "is to be understood as preferably meaning a straight-chain or branched, saturated monovalent hydrocarbon radical of the formula-O-alkyl, where the term" alkyl "has the above-mentioned definition and is, for example, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, pentyloxy, isopentyloxy, hexyloxy or isomers thereof. In particular, "alkoxy" is "C 1-6 Alkoxy group "," C 1-4 Alkoxy group "," C 1-3 Alkoxy ", methoxy, ethoxy or propoxy, preferably methoxy, ethoxy or propoxy. Further preferably "C 1-2 Alkoxy ", in particular methoxy or ethoxy.
The term "C 3-10 Cycloalkyl "is to be understood as preferably meaning a straight-chain or branched, saturated, monovalent, monocyclic hydrocarbon ring which contains, for example, 3, 4, 5, 6, 7 or 8 carbon atoms. C 3-8 Cycloalkyl is, for example, a monocyclic hydrocarbon ring, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl or cycloheptyl. In particular, the cycloalkyl is C 4-6 Cycloalkyl, C 5-6 Cycloalkyl or cyclohexyl. For example, the term "C 3-6 Cycloalkyl "is understood as preferably meaning a saturated monovalent monocyclic hydrocarbon ring which contains, for example, 3, 4, 5 or 6 carbon atoms. Specifically, C 3-6 Cycloalkyl is a monocyclic hydrocarbon ring, such as cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.
The term "C 3-10 Cycloalkyloxy is to be understood as preferably meaning a radical of the formula-O-cycloalkyl in which the term "C" is intended 3-10 Cycloalkyl "has the definition as described above.
The term "aryl" is understood to mean preferably a mono-, bi-or tricyclic hydrocarbon ring having a monovalent aromatic or partially aromatic character of 6 to 20 carbon atoms, preferably "C 6-14 Aryl ". The term "C 6-14 Aryl "is to be understood as preferably meaning a mono-, bi-or tricyclic hydrocarbon ring having a monovalent or partially aromatic character with 6, 7, 8, 9, 10, 11, 12, 13 or 14 carbon atoms (" C 6-14 Aryl group "), in particular a ring having 6 carbon atoms (" C 6 Aryl "), such as phenyl; or biphenyl, or is a ring having 9 carbon atoms ("C 9 Aryl), such as indanyl or indenyl, or a ring having 10 carbon atoms ("C 10 Aryl radicals), such as tetralinyl, dihydronaphthyl or naphthyl, or rings having 13 carbon atoms ("C 13 Aryl radicals), such as the fluorenyl radical, or a ring having 14 carbon atoms ("C) 14 Aryl), such as anthracenyl.
Examples of monocyclic rings of heteroaryl groups include, but are not limited to, thienyl, furyl, pyrrolyl, oxazolyl, thiazolyl, imidazolyl, pyrazolyl, isoxazolyl, isothiazolyl, oxadiazolyl, triazolyl, thiadiazolyl, thia-4H-pyrazolyl and the like and their benzo derivatives, e.g., benzofuranyl, benzothienyl, benzoxazolyl, benzisoxazolyl, benzimidazolyl, benzotriazolyl, indazolyl, indolyl, isoindolyl and the like; or pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, and the like, and benzo derivatives thereof, such as quinolyl, quinazolinyl, isoquinolyl, and the like; or azocinyl, indolizinyl, purinyl and the like and benzo derivatives thereof; or cinnolinyl, phthalazinyl, quinazolinyl, quinoxalinyl, naphthyridinyl, pteridinyl, carbazolyl, acridinyl, phenazinyl, phenothiazinyl, phenoxazinyl, and the like.
The term "aryloxy" is to be understood as preferably meaning a group of the formula-O-aryl or-O-heteroaryl, where the term "aryl" has the abovementioned meaning.
The term "aryl C 1-6 Alkylene "is understood as preferably meaning C 1-6 Radicals in which one substituent of the alkylene group is an aryl group. Wherein, C 1-6 Alkylene means C 1-6 The alkyl group further contains a substitution site, wherein the terms "aryl", "C", and 1-6 alkyl "has the above definition.
Drawings
FIG. 1 is a reaction scheme showing the preparation of intermediates in example 1, ligands in examples 2 to 6, and complexes in examples 7 to 11, according to the present invention.
FIG. 2 is a schematic diagram of the crystal structure of the complex Fe-3 prepared in example 9.
FIG. 3 is a graph of the temperature-increasing nuclear magnetic hydrogen spectrum of the polymer obtained in example 12 i).
FIG. 4 shows the temperature-programmed nuclear magnetic carbon spectrum of the polymer obtained in example 12 i).
FIG. 5 is a chart of temperature-rising nuclear magnetic hydrogen spectra of the polymer obtained in example 17 h).
FIG. 6 shows a temperature-increasing NMR spectrum of the polymer obtained in example 17 h).
Detailed Description
The present invention will be further illustrated with reference to the following specific examples, but the present invention is not limited to the following examples. The method is a conventional method unless otherwise specified. The starting materials are commercially available from the open literature unless otherwise specified.
Both methylaluminoxane (MAO for short) and modified methylaluminoxane (MMAO for short) were obtained from Akzo Nobel of the United states. In examples 12-21 below, al/Fe is defined as the molar ratio of metallic Al in the cocatalyst MAO or MMAO to Fe in the complex.
Example 1 preparation of 2-acetyl-6 (1- (2,6-bis (benzhydryl) -4-tert-butyl-anilino) ethyl) pyridine (IA) of the formula
2,6-diacetylpyridine 3.26g (20 mmol), 2,6-bis (benzhydryl) -4-tert-butyl-aniline 9.63g (20 mmol) were weighed and added into a reaction flask, about 150mL of toluene was added into the reaction flask, then catalytic amount of p-toluenesulfonic acid was added into the reaction system, and a water separator was connected. After stirring at reflux temperature for 12h, the reaction mixture was filtered under heating and all volatiles were evaporated under reduced pressure. Then, the obtained crude product was subjected to column chromatography on basic alumina column, eluted with a mixed solvent of petroleum ether and ethyl acetate as an eluent (100/1), and the solvent was removed to obtain 5.01g of pale yellow powder, i.e., IA, 2-acetyl-6 (1- (2,6-bis (benzhydryl) -4-tert-butyl-anilino) ethyl) pyridine, in yield: 40 percent. Melting point: 212-214 ℃.
The structure confirmation data is as follows:
FTIR(KBr,cm -1 ):3024(w),2957(m),1700(ν(C＝O),s),1650(ν(C＝N),s),1573(w),1493(s),1448(s),1364(s),1413(m),1363(s),1309(w),1237(s),1192(w),1116(s),1077(s),1029(m),997(w),949(m),892(w),867(w),814(m),765(m),739(s).
1 H NMR(400MHz,CDCl 3 .TMS):δ8.14(d,J＝8.0Hz,1H,Py-H m ),8.07(d,J＝7.6Hz,1H,Py-H m ),7.85(t,J＝7.6Hz,1H,Py-H p ),7.25-7.15(m,12H,aryl-H),7.01(t,J＝8.0Hz,8H,aryl-H),6.89(s,2H,aryl-H),5.26(s,2H,CHPh 2 ),2.67(s,3H,O＝CCH 3 ),1.11(m,9H,C(CH 3 ) 3 ),1.10(m,3H,N＝CCH 3 ).
13 C NMR(100MHz,CDCl 3 .TMS):δ200.3,169.1,155.5,152.2,145.7,145.0,143.7,142.8,137.0,131.4,129.8,129.4,128.2,127.9,126.1,126.0,125.1,124.6,122.2,52.4,34.3,31.3,25.6,16.7.
elemental analysis: c 45 H 42 N 2 Theoretical O (626.84): c,86.22; h,6.75; n,4.47. Experimental values: c,86.23; h,6.98; and N,4.29.
Example 2 preparation of 2- (1- (2,6-bis (benzhydryl) -4-tert-butyl-anilino) ethyl) -6 (1- (2,6-dimethyl-anilino) ethyl) pyridine of the formula (ligand L1)
2.00g (3.19 mmol) of 2-acetyl-6 (1- (2,6-bis (benzhydryl) -4-tert-butyl-anilino) ethyl) pyridine and 0.42g (3.50 mmol) of 2,6-dimethylaniline were weighed into a reaction flask, about 50mL of toluene solvent was added, heating and stirring were performed under reflux, half an hour later, catalytic equivalent of p-toluenesulfonic acid was added into the reaction flask, and the reaction mixture was heated under reflux for 6h. Cool to room temperature and evaporate volatiles in vacuo. Next, the obtained crude residual solid was subjected to column chromatography on basic alumina column (125 (v/v) and eluted with a mixed solvent of petroleum ether and ethyl acetate as eluent) to remove the solvent, and 0.60g of a pale yellow powder was obtained, i.e., L1,2- (1- (2,6-bis (benzhydryl) -4-tert-butyl-anilino) ethyl) -6 (1- (2,6-dimethyl-anilino) ethyl) pyridine, yield: 45 percent. Melting point: 142-144 ℃.
The structure validation data is as follows:
FTIR(KBr,cm -1 ):3026(w),2957(w),1645(ν(C＝N),s),1570(w),1494(m),1451(m),1365(s),1326(w),1296(w),1245(s),1207(m),1124(m),1030(m),914(w),820(m),763(s).
1 H NMR(400MHz,CDCl 3 .TMS):δ8.39(d,J＝7.6Hz,1H,Py-H m ),8.04(d,J＝7.6Hz,1H,Py-H m ),7.82(t,J＝8.0Hz,1H,Py-H p ),7.25–7.07(m,15H,aryl-H),7.03(t,J＝7.2Hz,8H,aryl-H),6.90(s,2H,aryl-H),5.30(s,2H,CHPh 2 ),2.12(s,3H,N＝CCH 3 ),2.06(s,6H,2×CH 3 ),1.14(s,3H,N＝CCH 3 ),1.11(s,9H,C(CH 3 ) 3 ).
13 C NMR(100MHz,CDCl 3 .TMS):δ169.7,167.4,155.2,154.9,148.8,145.8,144.8,143.8,142.9,136.6,131.4,129.8,129.4,128.2,127.9,127.9,126.0,125.9,125.4,125.0,123.0,122.3,121.8,52.3,34.3,31.3,18.0,17.0,16.4.
elemental analysis: c 53 H 51 N 3 (730.01) theoretical: c,87.20; h,7.04; n,5.76. Experimental values: c,87.04; h,7.15; n,5.58.
Example 3 preparation of 2- (1- (2,6-bis (benzhydryl) -4-tert-butyl-anilino) ethyl) -6 (1- (2,6-diethyl-anilino) ethyl) pyridine of the formula (ligand L2)
2.00g (3.19 mmol) of 2-acetyl-6 (1- (2,6-bis (benzhydryl) -4-tert-butyl-phenylimino) ethyl) pyridine and 0.52g (3.50 mmol) of 2,6-diethylaniline were weighed into a reaction flask, about 50mL of toluene solvent was added, heating and stirring were performed under reflux, half an hour later, catalytic equivalent of p-toluenesulfonic acid was added to the reaction flask, and the reaction mixture was heated under reflux for 6h. Cool to room temperature and evaporate volatiles in vacuo. Then, the obtained crude residual solid was subjected to column chromatography on basic alumina column (125 (v/v) and eluted with a mixed solvent of petroleum ether and ethyl acetate as an eluent) to remove the solvent, and 1.02g of a pale yellow powder, i.e., L2,2- (1- (2,6-bis (benzhydryl) -4-tert-butyl-anilino) ethyl) -6 (1- (2,6-diethyl-anilino) ethyl) pyridine was obtained in a yield of 42%. Melting point: 138-140 ℃.
The structure validation data is as follows:
FTIR(KBr,cm -1 ):3027(w),2960(w),1638(ν(C＝N),s),1566(w),1494(w),1447(s),1365(s),1320(w),1294(w),1237(s),1191(m),1117(s),1029(w),865(w),823(m),761(s).
1 H NMR(400MHz,CDCl 3 .TMS):δ8.38(d,J＝7.6Hz,1H,Py-H m ),8.04(d,J＝7.6Hz,1H,Py-H m ),7.82(t,J＝8.0Hz,1H,Py-H p ),7.26–7.22(m,5H,aryl-H),7.19–7.11(m,10H,aryl-H),7.03(t,J＝6.8Hz,8H,aryl-H),6.90(s,2H,aryl-H),5.30(s,2H,CHPh 2 ),2.48–2.31(s,4H,2×CH 2 ),2.13(s,3H,N＝CCH 3 ),1.18–1.14(m,9H,2×CH 3 ,N＝CCH 3 ),1.11(s,9H,C(CH 3 ) 3 ).
13 C NMR(100MHz,CDCl 3 .TMS):δ169.58,167.05,155.13,154.86,147.77,145.84,144.73,143.79,142.89,136.52,131.36,131.13,129.79,129.37,128.11,127.85,125.94,125.87,125.85,124.98,123.20,122.19,121.74,53.32,52.26,34.21,31.28,24.51,16.85,16.70,13.66.
elemental analysis: c 55 H 55 N 3 .Et 2 O+H 2 Theoretical value of O (850.20): c,83.35; h,7.94; n,4.94. Experimental values: c,83.42; h,7.14; and N,5.15.
Example 4 preparation of 2- (1- (2,6-bis (benzhydryl) -4-tert-butyl-anilino) ethyl) -6 (1- (2,6-diisopropyl-anilino) ethyl) pyridine of the formula (ligand L3)
2.00g (3.19 mmol) of 2-acetyl-6 (1- (2,6-bis (benzhydryl) -4-tert-butyl-anilino) ethyl) pyridine and 0.62g (3.50 mmol) of 2,6-diisopropylaniline were weighed into a reaction flask, about 50mL of toluene solvent was added, heating and stirring were performed under reflux, half an hour later, catalytic equivalent of p-toluenesulfonic acid was added to the reaction flask, and the reaction mixture was heated under reflux for 6 hours. Cool to room temperature and evaporate volatiles in vacuo. Next, the obtained crude residual solid was subjected to column chromatography on basic alumina column (125 (v/v) and eluted with a mixed solvent of petroleum ether and ethyl acetate as eluent) to remove the solvent, and 1.00g of a pale yellow powder, i.e., L3,2- (1- (2,6-bis (benzhydryl) -4-tert-butyl-anilino) ethyl) -6 (1- (2,6-diisopropyl-anilino) ethyl) pyridine was obtained, in yield: 40 percent. Melting point: 204-206 ℃.
The structure validation data is as follows:
FTIR(KBr,cm -1 ):3061(w),2960(s),1650(ν(C＝N),s),1570(w),1494(m),1450(s),1363(s),1326(m),1294(m),1241(s),1190(s),1123(s),1079(m),1033(m),817(m),764(m).
1 H NMR(400MHz,CDCl 3 .TMS):δ8.38(d,J＝7.6Hz,1H,Py-H m ),8.04(d,J＝7.2Hz,1H,Py-H m ),7.83(t,J＝8.0Hz,1H,Py-H p ),7.26–7.08(m,15H,aryl-H),7.03(t,J＝7.2Hz,8H,aryl-H),6.90(s,2H,aryl-H),5.31(s,2H,CHPh 2 ),2.84–2.73(m,2H,CHMe 2 ),2.15(s,3H,N＝CCH 3 ),1.19(s,6H,2×CH 3 ),1.17(s,9H,2×CH 3 ,N＝CCH 3 ),1.11(s,9H,C(CH 3 ) 3 ).
13 C NMR(100MHz,CDCl 3 .TMS):δ169.7,167.2,155.2,154.9,146.5,145.9,144.8,143.8,142.9,136.6,135.8,131.4,129.8,129.4,128.2,128.0,126.0,125.9,125.0,123.5,123.0,122.2,121.8,52.3,34.3,31.3,28.3,23.2,23.0,17.1,16.9.
elemental analysis: c 57 H 59 N 3 (786.12) theoretical: c,87.09; h,7.57; n,5.35. Experimental values: c,87.16; h,7.67; n,5.32.
Example 5 preparation of 2- (1- (2,6-bis (benzhydryl) -4-tert-butyl-anilino) ethyl) -6 (1- (m-trimethylanilino) ethyl) pyridine of the formula
2.00g (3.19 mmol) of 2-acetyl-6 (1- (2,6-bis (benzhydryl) -4-tert-butyl-anilino) ethyl) pyridine and 0.48g (3.50 mmol) of 2,4,6-m-trimethylaniline were weighed into a reaction flask, about 50mL of toluene solvent was added, heating and stirring were performed under reflux, half an hour later, catalytic equivalent of p-toluenesulfonic acid was added to the reaction flask, and the reaction mixture was heated under reflux for 6 hours. Cool to room temperature and evaporate volatiles in vacuo. Next, the obtained crude residual solid was subjected to column chromatography on basic alumina column (125 (v/v) with a mixed solvent of petroleum ether and ethyl acetate as eluent) to elute, and the solvent was removed to obtain 0.71g of pale yellow powder, i.e., L4,2- (1- (2,6-bis (benzhydryl) -4-tert-butyl-anilino) ethyl) -6 (1- (m-trimethylanilino) ethyl) pyridine, yield: 30 percent. Melting point: 146-148 ℃.
The structure confirmation data is as follows:
FTIR(KBr,cm -1 ):3026(w),2960(w),1650(ν(C＝N),s),1573(w),1494(w),1450(m),1364(s),1325(w),1296(w),1245(m),1219(s),1150(w),1123(s),1079(s),1030(m),855(m),822(m),768(m).
1 H NMR(400MHz,CDCl 3 .TMS):δ8.39(d,J＝7.6Hz,1H,Py-H m ),8.04(d,J＝7.2Hz,1H,Py-H m ),7.81(t,J＝7.6Hz,1H,Py-H p ),7.26–7.13(m,12H,aryl-H),7.03(t,J＝6.8Hz,8H,aryl-H),6.90(s,4H,aryl-H),5.31(s,2H,CHPh 2 ),2.31(s,3H,CH 3 ),2.12(s,3H,N＝CCH 3 ),2.03(s,6H,2×CH 3 ),1.16(s,3H,N＝CCH 3 ),1.11(s,9H,C(CH 3 ) 3 ).
13 C NMR(100MHz,CDCl 3 .TMS):δ169.6,167.5,155.1,155.0,146.2,145.8,144.7,143.8,142.9,136.5,132.1,131.4,131.3,129.8,129.4,129.3,128.5,128.1,127.9,126.0,126.0,125.9,125.2,125.0,122.2,121.8,52.3,34.2,31.3,20.7,17.8,16.3.
elemental analysis: c 54 H 53 N 3 (744.04) theoretical: c,87.17; h,7.18; n,5.65. Experimental values: c,87.03; h,7.62; and N,5.30.
Example 6 preparation of 2- (1- (2,6-bis (benzhydryl) -4-tert-butyl-anilino) ethyl) -6 (1- (2,6-diethyl-4-methyl-anilino) ethyl) pyridine of the formula (ligand L5)
2.00g (3.19 mmol) of 2-acetyl-6 (1- (2,6-bis (benzhydryl) -4-tert-butyl-anilino) ethyl) pyridine and 0.57g (3.50 mmol) of 2,6-diethyl-4-methylaniline were weighed into a reaction flask, about 50mL of toluene solvent was added, the mixture was heated under stirring and refluxed, half an hour later, catalytic equivalent of p-toluenesulfonic acid was added to the reaction flask, and the reaction mixture was heated under reflux for 6 hours. Cool to room temperature and evaporate volatiles in vacuo. Next, the obtained crude residual solid was subjected to column chromatography on basic alumina column (125 (v/v) and eluted with a mixed solvent of petroleum ether and ethyl acetate as eluent) to remove the solvent, and 0.86g of a pale yellow powder was obtained as L5,2- (1- (2,6-bis (benzhydryl) -4-tert-butyl-anilino) ethyl) -6 (1- (2,6-diethyl-4-methyl-anilino) ethyl) pyridine, yield: 35 percent. Melting point: 176-178 ℃.
The structure confirmation data is as follows:
FTIR(KBr,cm -1 ):3028(w),2961(m),1640(ν(C＝N),s),1568(m),1494(m),1451(s),1362(s),1322(w),1294(w),1242(m),1209(w),1117(s),1077(s),1030(m),862(m),825(m),766(m),740(s).
1 H NMR(400MHz,CDCl 3 .TMS):δ8.39(d,J＝8.0Hz,1H,Py-H m ),8.04(d,J＝7.6Hz,1H,Py-H m ),7.81(t,J＝8.0Hz,1H,Py-H p ),7.26–7.13(m,12H,aryl-H),7.03(t,J＝7.2Hz,8H,aryl-H),6.94(s,2H,aryl-H),6.91(s,2H,aryl-H),5.31(s,2H,CHPh 2 ),2.45–2.25(m,7H,2×CH 2 ,CH 3 ),2.13(s,3H,N＝CCH 3 ),1.17–1.13(m,9H,2×CH 3 ,N＝CCH 3 ),1.11(s,9H,C(CH 3 ) 3 ).
13 C NMR(100MHz,CDCl 3 .TMS):δ169.6,167.2,155.1,155.0,145.8,145.2,144.7,143.8,142.9,136.5,132.3,131.4,131.0,129.8,129.4,128.1,127.8,126.6,125.9,125.9,125.0,122.1,121.7,52.2,34.2,31.2,24.5,20.9,16.9,16.6,13.8.
elemental analysis: c 56 H 57 N 3 (772.09) theoretical: c,87.12; h,7.44; n,5.44. Experimental values: c,87.13; h,7.49; n,5.41.
EXAMPLE 7 preparation of 2- (1- (2,6-bis (benzhydryl) -4-tert-butyl-anilino) ethyl) -6 (1- (2,6-dimethyl-anilino) ethyl) pyridine Fe complex (Fe-1)
161mg (0.22 mmol) of 2- (1- (2,6-bis (benzhydryl) -4-tert-butyl-anilino) ethyl) -6 (1- (2,6-dimethyl-anilino) ethyl) pyridine (L1) and 39.8mg (0.20 mmol) of FeCl 2 ·4H 2 O, dissolved in 10mL of freshly distilled ethanol under nitrogen. The color of the solution rapidly turned blue, forming a precipitate. The suspension was stirred at room temperature for 8h to ensure adequate reaction. The precipitate was collected by filtration and washed with copious amounts of diethyl ether (3X 5 mL). 158mg of blue powder were obtained, namely Fe-1, yield: 92 percent.
The structure validation data is as follows:
FTIR(KBr；cm -1 ):3027(w),2961(m),1604(ν(C＝N),w),1582(s),1494(m),1470(m),1446(m),1370(s),1264(s),1209(s),1030(m),810(m),773(s),742(m),700(s).
1 H NMR(600MHz,CDCl 3 ,TMS):δ78.42(s,1H,Py-H m ),78.03(s,1H,Py-H m ),67.64(s,1H,Py-H p ),14.93(s,2H,aryl-H m ),13.71(s,2H,aryl-H m ),9.19(s.6H,2×CH 3 ),7.05(s,4H,aryl-H),6.77(s,2H,aryl-H),5.47(s,4H,aryl-H),4.98(s,2H,aryl-H),4.92(s,4H,aryl-H),2.66(s,9H,C(CH 3 ) 3 ),-3.16(s,4H,aryl-H),-11.44(s,2H,CHPh 2 ),-13.46(s,1H,aryl-H),-23.49(s,N＝CCH 3 ),-44.35(s,N＝CCH 3 ).
elemental analysis: c 53 H 51 N 3 FeCl 2 .Et 2 Theoretical value of O (904.84): c,73.01; h,6.57; n,4.64. Experimental values: c,73.36; h,6.05; and N,4.72.
EXAMPLE 8 preparation of 2- (1- (2,6-bis (benzhydryl) -4-tert-butyl-anilino) ethyl) -6 (1- (2,6-diethyl-anilino) ethyl) pyridine Fe complex (Fe-2)
167mg (0.22 mmol) of 2- (1- (2,6-bis (benzhydryl) -4-tert-butyl-anilino) ethyl) -6 (1- (2,6-diethyl-anilino) ethyl) pyridine (L2) and 39.8mg (0.20 mmol) of FeCl 2 ·4H 2 O, dissolved in 10mL of freshly distilled ethanol under a nitrogen atmosphere. The color of the solution rapidly turned blue, forming a precipitate. The suspension was stirred at room temperature for 8h to ensure adequate reaction. The precipitate was collected by filtration and washed with copious amounts of diethyl ether (3X 5 mL). 170mg of blue powder were obtained, namely Fe-2, yield: 96 percent.
The structure validation data is as follows:
FTIR(KBr；cm -1 ):3026(w),2966(m),1602(ν(C＝N),w),1577(m),1495(w),1447(s),1373(s),1314(w),1266(s),1205(s),1112(m),1079(w),1029(s),807(s),769(m),741(s),700(s).
1 H NMR(600MHz,CDCl 3 ,TMS):δ78.13(s,1H,Py-H m ),77.46(s,1H,Py-H m ),72.03(s,1H,Py-H p ),14.74(s,2H,aryl-H m ),14.07(s,2H,aryl-H m ),7.15(s,4H,aryl-H),6.75(s,2H,aryl-H),5.95(s,4H,aryl-H),4.90(s,2H,aryl-H),4.78(s,4H,aryl-H),3.85(s,4H,2×CH 2 ),2.81(s,9H,C(CH 3 ) 3 ),-4.02(s,4H,aryl-H),-4.49(s,6H,2×CH 3 ),-12.55(s,1H,aryl-H p ),-14.60(s,2H,CHPh 2 ),-29.35(s,N＝CCH 3 ),-41.59(s,N＝CCH 3 ).
elemental analysis: c 55 H 55 N 3 FeCl 2 .Et 2 Theoretical value of O (932.89): c,73.39; h,6.81; n,4.50. Experimental values: c,73.97; h,6.30; and N,4.59.
EXAMPLE 9 preparation of 2- (1- (2,6-bis (benzhydryl) -4-tert-butyl-anilino) ethyl) -6 (1- (2,6-diisopropyl-anilino) ethyl) pyridine Fe complex (Fe-3)
173mg (0.22 mmol) of 2- (1- (2,6-bis (benzhydryl) -4-tert-butyl-anilino) ethyl) -6 (1- (2,6-diisopropyl-anilino) ethyl) pyridine (L3) and 39.8mg (0.20 mmol) of FeCl 2 ·4H 2 O, dissolved in 10mL of freshly distilled ethanol under nitrogen. The color of the solution rapidly turned blue, forming a precipitate. The suspension was stirred at room temperature for 8h to ensure adequate reaction. The precipitate was collected by filtration and washed with copious amounts of diethyl ether (3X 5 mL). 122mg of blue powder was obtained, namely Fe-3, yield: 67%.
A schematic diagram of the Fe-3 crystal structure is shown in FIG. 2.
As can be seen from the figure, the central metal Fe of the complex Fe-3 is respectively connected with three nitrogen atoms N1, N2 and N3 and two chlorine atoms Cl1 and Cl2 in a penta-coordination mode, and is in a twisted tetragonal pyramid structure. Wherein three nitrogen atoms form a tetragonal pyramid base with the Cl1 atom, and Cl2 occupies the tetragonal pyramid apex. Due to steric effect, the distance between Fe atom and the conic vertex Cl2 atom is about
The distances between the atoms of the substrate and the Fe atom are N (1) -Fe (1), N (3) -Fe (1), N (2) -Fe (1) and Cl (1) -Fe (1) in sequence
And &>
In addition to this, the present invention is,the imine group is almost on the same plane with the pyridine ring, the plane of 2,6-bis (benzhydryl) -4-tert-butyl-phenyl on one side is almost vertical to the cone bottom plane skeleton, the torsion angle is 83.8 degrees, and the torsion angle between the plane of aryl ring on the other side and the cone bottom plane skeleton is smaller and is 73.5 degrees.
The structure validation data is as follows:
FTIR(KBr；cm -1 ):3024(w),2960(m),1605(ν(C＝N),w),1576(m),1494(m),1447(s),1368(s),1321(w),1270(s),1201(m),1103(m),1030(s),937(m),807(m),767(s),743(s),700(s).
1 H NMR(600MHz,CDCl 3 ,TMS):δ81.83(s,1H,Py-H m ),79.39(s,1H,Py-H m ),76.53(s,1H,Py-H p ),14.03(s,4H,aryl-H m ),7.32(s,4H,aryl-H),6.89(s,2H,aryl-H),6.18(s,4H,aryl-H),4.66(s,2H,aryl-H),4.52(s,4H,aryl-H),2.85(s,9H,C(CH 3 ) 3 ),-4.21(s,6H,2×CH 3 ),-5.12(s,4H,aryl-H),-6.40(s,6H,2×CH 3 ),-12.22(s,1H,aryl-H p ),-15.28(s,2H,CHPh 2 ),-17.61(s,2H,2×CH),-35.04(s,N＝CCH 3 ),-42.42(s,N＝CCH 3 ).
elemental analysis: c 57 H 59 N 3 FeCl 2 (912.87) theoretical: c,75.00; h,6.51; n,4.60. Experimental values: c,74.06; h,6.52; n,4.37.
EXAMPLE 10 preparation of Fe complex of 2- (1- (2,6-bis (benzhydryl) -4-tert-butyl-anilino) ethyl) -6 (1- (m-trimethylanilino) ethyl) pyridine (Fe-4)
164mg (0.22 mmol) of 2- (1- (2,6-bis (benzhydryl) -4-tert-butyl-anilino) ethyl) -6 (1- (m-trimethylanilino) ethyl) pyridine (L4) and 39.8mg (0.20 mmol) of FeCl 2 ·4H 2 O, dissolved in 10mL of freshly distilled ethanol under a nitrogen atmosphere. The color of the solution rapidly turned blue, forming a precipitate. The suspension was stirred at room temperature for 8h to ensure adequate reaction. The precipitate was collected by filtration and washed with copious amounts of diethyl ether (3X 5 mL). 155mg of blue powder were obtained, namely Fe-4, yield: 89 percent.
The structure validation data is as follows:
FTIR(KBr；cm -1 ):3024(w),2960(m),1607(ν(C＝N),w),1579(m),1475(w),1449(s),1370(s),1264(s),1218(w),1195(s),1078(m),1031(s),861(s),812(m),769(m),744(s),704(s).
1 H NMR(600MHz,CDCl 3 ,TMS):δ77.31(s,2H,Py-H m ),70.06(s,1H,Py-H p ),23.08(s,3H,CH 3 ),14.06(s,2H,aryl-H m ),13.91(s,2H,aryl-H m ),9.51(s,6H,2×CH 3 ),7.12(s,4H,aryl-H),6.83(s,2H,aryl-H),5.73(s,4H,aryl-H),4.87(s,2H,aryl-H),4.81(s,4H,aryl-H),2.69(s,9H,C(CH 3 ) 3 ),-3.24(s,4H,aryl-H),-10.80(s,2H,CHPh 2 ),-25.77(s,N＝CCH 3 ),-43.31(s,N＝CCH 3 ).
elemental analysis: c 54 H 53 N 3 FeCl 2 (870.78) theoretical: c,74.48; h,6.14; n,4.83. Experimental values: c,73.18; h,6.06; and N,4.63.
EXAMPLE 11 preparation of 2- (1- (2,6-bis (benzhydryl) -4-tert-butyl-anilino) ethyl) -6 (1- (2,6-diethyl-4-methyl-anilino) ethyl) pyridine Fe complex (Fe-5)
170mg (0.22 mmol) of 2- (1- (2,6-bis (benzhydryl) -4-tert-butyl-anilino) ethyl) -6 (1- (2,6-diethyl-4-methyl-anilino) ethyl) pyridine (L5) and 39.8mg (0.20 mmol) of FeCl 2 ·4H 2 O, dissolved in 10mL of freshly distilled ethanol under a nitrogen atmosphere. The color of the solution rapidly turned blue, forming a precipitate. The suspension was stirred at room temperature for 8h to ensure adequate reaction. The precipitate was collected by filtration and washed with copious amounts of diethyl ether (3X 5 mL). 160mg of blue powder were obtained, namely Fe-5, yield: 89 percent.
The structure validation data is as follows:
FTIR(KBr；cm -1 ):3029(w),2963(s),1605(ν(C＝N),w),1582(m),1495(m),1449(s),1425(w),1369(s),1264(s),1214(m),1075(m),1033(s),860(s),808(m),770(m),745(s),704(s).
1 H NMR(600MHz,CDCl 3 ,TMS):δ78.26(s,1H,Py-H m ),76.79(s,1H,Py-H m ),76.32(s,1H,Py-H p ),23.07(s,3H,CH 3 ),14.26(s,2H,aryl-H m ),13.75(s,2H,aryl-H m ),7.26(s,4H,aryl-H),6.85(s,2H,aryl-H),6.19(s,4H,aryl-H),4.74(s,2H,aryl-H),4.65(s,4H,aryl-H),4.32(s,2H,CH 2 ),3.82(s,2H,CH 2 ),2.92(s,9H,C(CH 3 ) 3 ),-4.20(s,4H,aryl-H),-4.94(s,6H,2×CH 3 ),-14.23(s,2H,CHPh 2 ),-31.98(s,N＝CCH 3 ),-41.22(s,N＝CCH 3 ).
elemental analysis: c 56 H 57 N 3 FeCl 2 (898.84) theoretical: c,74.83; h,6.39; n,4.68. Experimental values: c,74.06; h,6.36; n,4.53.
Example 12. Co-catalysis of ethylene polymerization under high pressure with Complex Fe-1 and cocatalyst MAO:
a) 30mL of a toluene solution of the catalyst Fe-1 (2. Mu. Mol) were injected under an ethylene atmosphere into a 250mL stainless steel autoclave equipped with mechanical stirring, followed by the addition of 30mL of toluene, the addition of the desired amount of 2.1mL of cocatalyst MAO (1.46 mol/L in toluene) and the further addition of toluene to bring the total volume of the reaction to 100mL. At this time Al/Fe = 2000. Mechanical stirring is started, 400 rpm is maintained, and when the polymerization temperature reaches 30 ℃, ethylene is charged into the reaction kettle, and the polymerization reaction starts. The polymerization was carried out for 30min with stirring while maintaining the ethylene pressure of 10atm at 30 ℃. Neutralizing the reaction solution with 10% hydrochloric acid acidified ethanol solution to obtain polymer precipitate, washing with ethanol for several times, vacuum drying at 50 deg.C to constant weight, weighing to obtain 2.12g polymer, polymerization activity: 2.12X 10 6 g/mol(Fe)h -1 Polymerization molecular weight M w ＝318.2kg mol -1 (M w Mass average molecular weight of the polymer, obtained by GPC measurement), polymer T m ＝134.2℃(T m Melting temperature of polymer, obtained by DSC test).
b) Basically, the method a) in the embodiment is different: the polymerization temperature was 40 ℃. Polymerization Activity: 5.07X 10 6 g/mol(Fe)h -1 Polymerization molecular weight M w ＝179.4kg mol -1 Of a polymer T m ＝132.3℃。
c) Basically, the method a) in the embodiment is different: the polymerization temperature was 50DEG C. Polymerization Activity: 5.70X 10 6 g/mol(Fe)h -1 Polymerization molecular weight M w ＝114.1kg mol -1 Of polymers T m ＝132.0℃。
d) Basically, the method a) in the embodiment is different: the polymerization temperature was 60 ℃. Polymerization Activity: 7.39X 10 6 g/mol(Fe)h -1 Polymeric molecular weight M w ＝111.6kg mol -1 Of polymers T m ＝133.1℃。
e) Basically the same as the method a) in the embodiment: the polymerization temperature was 70 ℃. Polymerization Activity: 8.01X 10 6 g/mol(Fe)h -1 Polymerization molecular weight M w ＝63.9kg mol -1 Of a polymer T m ＝131.3℃。
f) Basically, the method a) in the embodiment is different: the polymerization temperature was 80 ℃. Polymerization Activity: 12.88X 10 6 g/mol(Fe)h -1 Polymerization molecular weight M w ＝23.2kg mol -1 Of polymers T m ＝131.3℃。
g) Basically the same as the method a) in the embodiment: the polymerization temperature was 90 ℃. Polymerization Activity: 12.39X 10 6 g/mol(Fe)h -1 Polymerization molecular weight M w ＝15.8kg mol -1 Of a polymer T m ＝131.2℃。
h) Basically, the method a) in the embodiment is different: the polymerization temperature was 100 ℃. Polymerization Activity: 7.79X 10 6 g/mol(Fe)h -1 Polymerization molecular weight M w ＝14.9kg mol -1 Of a polymer T m ＝130.5℃。
i) Basically, the method a) in the embodiment is different: the polymerization temperature was 110 ℃. Polymerization Activity: 2.82X 10 6 g/mol(Fe)h -1 Polymerization molecular weight M w ＝8.5kg mol -1 Of polymers T m ＝128.7℃。
The polymer obtained, 100mg, was dissolved in 3ml of deuterated 1,1,2,2-tetrachloroethane and tested at 135 deg.C 1 H data, as shown in fig. 3. The signals accumulated 100 times, resulting in two sets of multiple signal peaks at shifts of 5.90 (ppm) and 5.00 (ppm), evidenced by vinyl groups (-CH =)CH 2 )。
The polymer obtained, 100mg, was dissolved in 3ml of deuterated 1,1,2,2-tetrachloroethane and tested at 135 deg.C 13 C data, as shown in fig. 4. The signal was accumulated 6000 times, resulting in two sets of signal peaks at shifts 114.4 (ppm) and 139.6 (ppm), indicating ethylene end groups of long polyethylene chains, demonstrating that the resulting polymer is a highly linear polyethylene.
j) Basically, the method f) in the present embodiment is different: 1.1mL of cocatalyst MAO (1.46 mol/L in toluene) Al/Fe =1000:1. polymerization Activity: 2.11X 10 6 g/mol(Fe)h -1 Polymeric molecular weight M w ＝135.5kg mol -1 Of polymers T m ＝133.5℃。
k) Basically, the method f) in the present embodiment is different: 1.5mL of cocatalyst MAO (1.46 mol/L in toluene) Al/Fe =1500:1. polymerization Activity: 7.50X 10 6 g/mol(Fe)h -1 Polymerization molecular weight M w ＝52.0kg mol -1 Of a polymer T m ＝132.2℃。
l) is substantially the same as method f) in this example, except that: 1.8mL of cocatalyst MAO (1.46 mol/L in toluene) Al/Fe =1750:1. polymerization Activity: 8.27X 10 6 g/mol(Fe)h -1 Polymerization molecular weight M w ＝29.0kg mol -1 Of a polymer T m ＝131.4℃。
m) is substantially the same as method f) in the present example, except that: 2.4mL of cocatalyst MAO (1.46 mol/L in toluene) so that Al/Fe =2250:1. polymerization Activity: 11.12X 10 6 g/mol(Fe)h -1 Polymerization molecular weight M w ＝13.3kg mol -1 Of a polymer T m ＝129.6℃。
n) is substantially the same as method f) in this example, except that: 2.6mL of cocatalyst MAO (1.46 mol/L in toluene) Al/Fe =2500:1. polymerization Activity: 10.85X 10 6 g/mol(Fe)h -1 Polymeric molecular weight M w ＝11.2kg mol -1 Of polymers T m ＝130.3℃。
o) is substantially the same as method f) in this example, except that: the polymerization time was 5min. Polymerization Activity:26.51×10 6 g/mol(Fe)h -1 polymeric molecular weight M w ＝5.0kg mol -1 Of polymers T m ＝127.8℃。
p) is substantially the same as method f) in this example, except that: the polymerization time was 10min. Polymerization Activity: 26.10 × 10 6 g/mol(Fe)h -1 Polymerization molecular weight M w ＝9.8kg mol -1 Of polymers T m ＝129.3℃。
q) is essentially the same as method f) in this example, except that: the polymerization time was 15min. Polymerization Activity: 20.36X 10 6 g/mol(Fe)h -1 Polymeric molecular weight M w ＝12.9kg mol -1 Of polymers T m ＝130.1℃。
r) is substantially the same as method f) in the present example, except that: the polymerization time was 45min. Polymerization Activity: 9.08X 10 6 g/mol(Fe)h -1 Polymeric molecular weight M w ＝38.8kg mol -1 Of a polymer T m ＝130.5℃。
s) is substantially the same as method f) in this example, except that: the polymerization time was 60min. Polymerization Activity: 7.63X 10 6 g/mol(Fe)h -1 Polymeric molecular weight M w ＝46.6kg mol -1 Of a polymer T m ＝131.2℃。
t) is substantially the same as method f) in this example, except that: the polymerization pressure was 1atm. Polymerization Activity: 0.60X 10 6 g/mol(Fe)h -1 Polymerization molecular weight M w ＝1.7kg mol -1 Of polymers T m ＝118.6℃。
u) is substantially the same as method f) in the present example, except that: the polymerization pressure was 5atm. Polymerization Activity: 8.02X 10 6 g/mol(Fe)h -1 Polymeric molecular weight M w ＝12.0kg mol -1 Of a polymer T m ＝129.6℃。
Example 13. Ethylene polymerization under pressure using the complex Fe-2 in combination with MAO:
essentially the same as example 12 f), except that: the main catalyst is Fe-2. Polymerization Activity: 13.87X 10 6 g/mol(Fe)h -1 Polymerization molecular weight M w ＝13.9kg mol -1 Of polymers T m ＝130.3℃。
Example 14. Ethylene polymerization under pressure using the complex Fe-3 in combination with MAO:
essentially the same as example 12 f), except that: the main catalyst is Fe-3. Polymerization Activity: 2.55X 10 6 g/mol(Fe)h -1 Polymerization molecular weight M w ＝33.4kg mol -1 Of a polymer T m ＝131.6℃。
Example 15. Ethylene polymerization under pressure with the combination of the complexes Fe-4 and MAO:
essentially the same as example 12 f), except that: the main catalyst is Fe-4. Polymerization Activity: 11.61X 10 6 g/mol(Fe)h -1 Polymerization molecular weight M w ＝18.8kg mol -1 Of a polymer T m ＝132.1℃。
Example 16. Ethylene polymerization under pressure using the complex Fe-5 in combination with MAO:
essentially the same as example 12 f), except that: the main catalyst is Fe-5. Polymerization Activity: 10.26X 10 6 g/mol(Fe)h -1 Polymerization molecular weight M w ＝17.3kg mol -1 Of a polymer T m ＝130.6℃。
Example 17. Ethylene polymerization under pressure with the combination of complexes Fe-1 and MMAO:
a) 30mL of a toluene solution of the catalyst Fe-1 (2.0. Mu. Mol) was injected under an ethylene atmosphere into a 250mL stainless steel autoclave equipped with mechanical stirring, followed by addition of 30mL of toluene, addition of 1.5mL of the cocatalyst MMAO (2.0 mol/L in toluene) in the required amount, and further addition of toluene so that the total volume of the reaction solution became 100mL. At this time Al/Fe = 2000. Mechanical stirring was started and maintained at 400 rpm, and when the polymerization temperature reached 30 ℃, ethylene was charged into the reactor and the polymerization started. The polymerization was carried out for 30min with stirring while maintaining the ethylene pressure of 10atm at 30 ℃. Neutralizing the reaction solution with 10% hydrochloric acid acidified ethanol solution to obtain polymer precipitate, washing with ethanol for several times, drying at 50 deg.C under vacuum to constant weight, weighing to obtain 1.50g polymer, polymerization activity: 1.50X 10 6 g/mol(Fe)h -1 Polymerization molecular weight M w ＝12.6kg mol -1 (M w Mass average molecular weight of the polymer, obtained by GPC measurement), polymer T m ＝126.7℃(T m Melting temperature of the polymer, obtained by DSC test).
b) Basically, the method a) in the embodiment is different: the polymerization temperature was 40 ℃. Polymerization Activity: 8.90X 10 6 g/mol(Fe)h -1 Polymeric molecular weight M w ＝9.0kg mol -1 Of polymers T m ＝123.7℃。
c) Basically the same as the method a) in the embodiment: the polymerization temperature was 50 ℃. Polymerization Activity: 12.01X 10 6 g/mol(Fe)h -1 Polymerization molecular weight M w ＝7.7kg mol -1 Of a polymer T m ＝128.9℃。
d) Basically the same as the method a) in the embodiment: the polymerization temperature was 60 ℃. Polymerization Activity: 12.39X 10 6 g/mol(Fe)h -1 Polymerization molecular weight M w ＝7.7kg mol -1 Of polymers T m ＝128.4℃。
e) Basically the same as the method a) in the embodiment: the polymerization temperature was 70 ℃. Polymerization Activity: 12.84X 10 6 g/mol(Fe)h -1 Polymeric molecular weight M w ＝7.3kg mol -1 Of polymers T m ＝129.1℃。
f) Basically, the method a) in the embodiment is different: the polymerization temperature was 80 ℃. Polymerization Activity: 13.08X 10 6 g/mol(Fe)h -1 Polymerization molecular weight M w ＝7.2kg mol -1 Of a polymer T m ＝130.4℃。
g) Basically, the method a) in the embodiment is different: the polymerization temperature was 90 ℃. Polymerization Activity: 5.28X 10 6 g/mol(Fe)h -1 Polymerization molecular weight M w ＝3.4kg mol -1 Of a polymer T m ＝124.8℃。
h) Basically, the method a) in the embodiment is different: the polymerization temperature was 100 ℃. Polymerization Activity: 2.97X 10 6 g/mol(Fe)h -1 Polymerization molecular weight M w ＝2.1kg mol -1 Of a polymer T m ＝119.8℃。
The polymer obtained, 100mg, was dissolved in 3ml of deuterated 1,1,2,2-tetrachloroethane and tested at 135 deg.C 1 H data, as shown in fig. 5. The signals are accumulated 100 times.
The polymer obtained, 100mg, was dissolved in 3ml of deuterated 1,1,2,2-tetrachloroethane and tested at 135 deg.C 13 C data, as shown in fig. 6. The signal accumulates 6000 times.
i) Basically, the method f) in the present embodiment is different: 0.8mL of cocatalyst MMAO (2.0 mol/L in toluene) resulted in Al/Fe =1000:1. polymerization Activity: 2.11X 10 6 g/mol(Fe)h -1 Polymerization molecular weight M w ＝41.6kg mol -1 Of a polymer T m ＝129.4℃。
j) Basically, the method f) in the present embodiment is different: 1.1mL of cocatalyst MMAO (2.0 mol/L in toluene) resulted in Al/Fe =1500:1. polymerization Activity: 10.36X 10 6 g/mol(Fe)h -1 Polymeric molecular weight M w ＝22.3kg mol -1 Of a polymer T m ＝131.2℃。
k) Basically the same as the method f) in the embodiment: 1.9mL of cocatalyst MMAO (2.0 mol/L in toluene) resulted in Al/Fe =2500:1. polymerization Activity: 13.68X 10 6 g/mol(Fe)h -1 Polymerization molecular weight M w ＝7.1kg mol -1 Of a polymer T m ＝129.2℃。
l) is substantially the same as method f) in the present example, except that: 2.1mL of cocatalyst MMAO (2.0 mol/L in toluene) resulted in Al/Fe =2750:1. polymerization Activity: 14.08X 10 6 g/mol(Fe)h -1 Polymerization molecular weight M w ＝6.7kg mol -1 Of a polymer T m ＝129.0℃。
m) is substantially the same as method f) in this example, except that: 2.2mL of cocatalyst MMAO (2.0 mol/L in toluene) resulted in Al/Fe =3000:1. polymerization Activity: 11.21X 10 6 g/mol(Fe)h -1 Polymeric molecular weight M w ＝5.2kg mol -1 Of a polymer T m ＝127.8℃。
m) is substantially the same as method f) in this example, except that: 2.4mL of cocatalyst MMAO (2.0 mol)L in toluene) Al/Fe =3250:1. polymerization Activity: 9.47X 10 6 g/mol(Fe)h -1 Polymerization molecular weight M w ＝4.3kg mol -1 Of a polymer T m ＝126.7℃。
n) is substantially the same as method l) in this example, except that: the polymerization time was 5min. Polymerization Activity: 35.06 × 10 6 g/mol(Fe)h -1 Polymerization molecular weight M w ＝3.2kg mol -1 Of a polymer T m ＝125.8℃。
o) is substantially the same as method l) in this example, except that: the polymerization time was 10min. Polymerization Activity: 21.12X 10 6 g/mol(Fe)h -1 Polymerization molecular weight M w ＝3.6kg mol -1 Of polymers T m ＝124.9℃。
p) is substantially the same as method l) in this example, except that: the polymerization time was 15min. Polymerization Activity: 15.32X 10 6 g/mol(Fe)h -1 Polymerization molecular weight M w ＝4.2kg mol -1 Of a polymer T m ＝126.5℃。
q) is essentially the same as method l) in this example, except that: the polymerization time was 45min. Polymerization Activity: 9.86X 10 6 g/mol(Fe)h -1 Polymerization molecular weight M w ＝6.8kg mol -1 Of a polymer T m ＝128.1℃。
r) is substantially the same as method l) in this example, except that: the polymerization time was 60min. Polymerization Activity: 7.54X 10 6 g/mol(Fe)h -1 Polymerization molecular weight M w ＝9.3kg mol -1 Of polymers T m ＝129.0℃。
s) is essentially the same as method l) in this example, except that: the polymerization pressure was 1atm. Polymerization Activity: 0.7X 10 6 g/mol(Fe)h -1 Polymeric molecular weight M w ＝0.6kg mol -1 Of a polymer T m ＝125.1℃。
t) is substantially the same as method l) in this example, except that: the polymerization pressure was 5atm. Polymerization Activity: 8.10X 10 6 g/mol(Fe)h -1 Polymeric molecular weight M w ＝4.2kg mol -1 Of polymers T m ＝125.2℃。
Example 18. Polymerization of ethylene under pressure using the combination of complexes Fe-2 and MMAO:
essentially the same as example 17 l), with the difference that: cocatalyst MMAO (2.0 mol/L in toluene) with a main catalyst of Fe-2,2.1ml such that Al/Fe =2750:1. polymerization Activity: 10.74X 10 6 g/mol(Fe)h -1 Polymerization molecular weight M w ＝6.6kg mol -1 Of a polymer T m ＝127.6℃。
Example 19. Polymerization of ethylene under pressure using the combination of complexes Fe-3 and MMAO:
essentially the same as example 17 l), with the difference that: cocatalyst MMAO (2.0 mol/L in toluene) with a main catalyst of Fe-3,2.1ml makes Al/Fe =2750:1. polymerization Activity: 6.12X 10 6 g/mol(Fe)h -1 Polymerization molecular weight M w ＝6.0kg mol -1 Of a polymer T m ＝127.5℃。
Example 20. Polymerization of ethylene under pressure with the combination of complexes Fe-4 and MMAO:
essentially the same as example 17 l), except that: cocatalyst MMAO (2.0 mol/L in toluene) with a main catalyst of Fe-4,2.1ml such that Al/Fe =2750:1. polymerization Activity: 11.50X 10 6 g/mol(Fe)h -1 Polymerization molecular weight M w ＝5.6kg mol -1 Of a polymer T m ＝127.8℃。
Example 21. Polymerization of ethylene under pressure using the combination of complexes Fe-5 and MMAO:
essentially the same as example 17 l), except that: cocatalyst MMAO (2.0 mol/L in toluene) with a main catalyst of Fe-5,2.1ml such that Al/Fe =2750:1. polymerization Activity: 9.52X 10 6 g/mol(Fe)h -1 Polymerization molecular weight M w ＝5.1kg mol -1 Of a polymer T m ＝127.8℃。
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, or improvement made without departing from the spirit and principle of the present invention shall fall within the protection scope of the present invention.
Claims (18)
1. A transition metal complex represented by the following formula (I):
wherein M is selected from iron;
each R 1 、R 2 Are the same or different and are each independently selected from H or C 1-6 An alkyl group;
R 3 、R 4 、R 5 is selected from H; x is the same and is selected from Cl and Br.
2. The transition metal complex according to claim 1, wherein in the formula (I), R is 1 、R 2 The same or different, each is independently selected from H, C 1-3 An alkyl group.
3. The transition metal complex according to claim 1, wherein in the formula (I), R is 1 、R 2 The same or different, each is independently selected from H, methyl, ethyl, n-propyl, isopropyl;
x is selected from Cl and Br.
4. The transition metal complex of any one of claims 1 to 3, wherein the complex of formula (I) is selected from complexes having the following group definitions:
the complex Fe-1: wherein R is 1 = Me, X is selected from Cl, other groups are H;
the complex Fe-2: wherein R is 1 = Et, X is Cl, other groups are H;
the complex Fe-3: wherein R is 1 = i-Pr, X is selected from Cl and the other groups are H;
the complex Fe-4: wherein R is 1 ＝Me，R 2 = Me, X is selected from Cl, other groups are H;
the complex Fe-5: wherein R is 1 ＝Et，R 2 = Me, X is selected from Cl and the other groups are H.
5. A ligand compound represented by the following formula (II):
wherein R is 1 、R 2 、R 3 、R 4 、R 5 Having the definitions set out in any one of claims 1 to 3.
6. Ligand compound according to claim 5, characterized in that it is selected from compounds having the following group definitions:
ligand L1: r 1 = Me, other groups are H;
ligand L2: r 1 Et, other groups are H;
ligand L3: r 1 = i-Pr, other groups are H;
ligand L4: r 1 ＝Me，R 2 = Me, other groups are H;
a ligand L5: r 1 ＝Et，R 2 = Me, other groups are H.
7. The process for preparing a ligand compound according to claim 5 or 6, comprising the steps of:
1) R is represented by the formula (III) 4 Substituted diacetylpyridines with R of formula (IV) 5 Carrying out substitution reaction on substituted aniline to obtain a compound shown as a formula (V);
2) Carrying out condensation reaction on the benzene compound shown in the formula (V) obtained in the step 1) and the compound shown in the formula (VI) to obtain a ligand compound shown in the formula (II);
wherein R is 1 、R 2 、R 3 、R 4 、R 5 Having the definitions set forth in any one of claims 1-3;
in the step 1), the substitution reaction is carried out under the catalysis of p-toluenesulfonic acid;
in step 1), R shown as the formula (III) 4 Substituted diacetyl pyridine and R shown as formula (IV) 5 Moles of substituted anilines the feeding ratio is 1-1.5;
in step 2), the condensation reaction is carried out under the catalysis of p-toluenesulfonic acid;
in the step 2), the molar charge ratio of the compound shown in the formula (V) to the compound shown in the formula (VI) is 1:1-1.5.
8. Use of the ligand compound according to claim 5 or 6 for the preparation of a transition metal complex of formula (I) according to any one of claims 1 to 4.
9. A process for producing a transition metal complex as claimed in any one of claims 1 to 4, which comprises the steps of:
reacting the ligand compound of claim 5 or 6 with compound MX 2 Carrying out complexation reaction to obtain a complex shown in the formula (I);
wherein M, X has the definition set forth in any of claims 1-4;
said compound MX 2 One or more selected from the group consisting of an iron-containing halide, a hydrate of the halide, or other solvate;
the reaction is carried out under the condition of no oxygen;
said compound MX 2 The molar ratio of the compound to the compound shown in the formula (II) is 1:1-2.
10. The method of claim 9, wherein said compound MX is 2 Selected from (DME) FeBr 2 、FeCl 2 ·4H 2 O or FeCl 2 One or more of (a);
the reaction is carried out under the protection of nitrogen.
11. Use of a transition metal complex according to any one of claims 1 to 4 for catalysing the polymerisation of ethylene.
12. A catalyst composition comprising a procatalyst and optionally a cocatalyst, wherein the procatalyst is selected from the group consisting of the transition metal complexes of any of claims 1-4;
the cocatalyst is selected from one or more of aluminoxane, alkyl aluminum and alkyl aluminum chloride.
13. The catalyst composition of claim 12, wherein the aluminoxane is selected from one or both of Methylaluminoxane (MAO) or triisobutylaluminum-Modified Methylaluminoxane (MMAO).
14. The catalyst composition of claim 12, wherein the molar ratio of the metal Al in the cocatalyst to the central metal Fe of the complex of formula (I) is (500-4000): 1.
15. The catalyst composition of claim 14, wherein when the cocatalyst is Methylaluminoxane (MAO), the molar ratio of the metal Al in Methylaluminoxane (MAO) to the central metal Fe of the complex of formula (I) is (1000-2500: 1;
when the cocatalyst is triisobutyl aluminum Modified Methylaluminoxane (MMAO), the molar ratio of metal Al in the triisobutyl aluminum Modified Methylaluminoxane (MMAO) to the central metal Fe of the complex shown in the formula (I) is (1000-3250): 1.
16. Use of the catalyst composition of any one of claims 12-15 for catalyzing the polymerization of ethylene.
17. A method of preparing polyethylene, comprising: polymerizing ethylene with the catalyst composition of any one of claims 12-15.
18. The method of claim 17, wherein the temperature of the polymerization reaction is 30 to 140 ℃; the time of the polymerization reaction is 5-60 min; the pressure of the polymerization reaction is 0.5-10 atm;
the polymerization reaction is carried out under an ethylene atmosphere.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101370778A (en) * | 2006-01-13 | 2009-02-18 | 巴塞尔聚烯烃股份有限公司 | Process for the preparation of unsymmetric bis(imino) compounds |
| CN102464677A (en) * | 2010-11-17 | 2012-05-23 | 中国科学院化学研究所 | Asymmetric diimine pyridine iron or cobalt complex catalyst, and preparation method and application thereof |
| CN108794545A (en) * | 2017-04-28 | 2018-11-13 | 中国科学院化学研究所 | It is used to prepare the alpha-nickel diimine compound of asymmetry containing tertiary butyl, the Preparation method and use of ultra-high molecular weight polyethylene elastomer |
-
2018
- 2018-01-29 CN CN201810085977.6A patent/CN110092744B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101370778A (en) * | 2006-01-13 | 2009-02-18 | 巴塞尔聚烯烃股份有限公司 | Process for the preparation of unsymmetric bis(imino) compounds |
| CN102464677A (en) * | 2010-11-17 | 2012-05-23 | 中国科学院化学研究所 | Asymmetric diimine pyridine iron or cobalt complex catalyst, and preparation method and application thereof |
| CN108794545A (en) * | 2017-04-28 | 2018-11-13 | 中国科学院化学研究所 | It is used to prepare the alpha-nickel diimine compound of asymmetry containing tertiary butyl, the Preparation method and use of ultra-high molecular weight polyethylene elastomer |
Non-Patent Citations (2)
| Title |
|---|
| 2-[1-(2,6-Dibenzhydryl-4-chlorophenylimino)ethyl]-6-[1-(arylimino)ethyl]pyridyliron(II) dichlorides: Synthesis, characterization and ethylenepolymerization behavior;Xiaoping Cao et al.;《Polymer》;20120303;第53卷;第1870-1880-页 * |
| Access to highly active and thermally stable iron procatalysts using bulky 2-[1-(2,6-dibenzhydryl-4-methylphenylimino)ethyl]-6-[1-(arylimino)ethyl]pyridine ligands;Jiangang Yu et al.;《Chem. Commun.》;20110131;第47卷;第3257-3259页 * |
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