CN110483587A - Big steric hindrance ketimide Raney nickel and its ligand compound, preparation method and application - Google Patents
Big steric hindrance ketimide Raney nickel and its ligand compound, preparation method and application Download PDFInfo
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- CN110483587A CN110483587A CN201910799077.2A CN201910799077A CN110483587A CN 110483587 A CN110483587 A CN 110483587A CN 201910799077 A CN201910799077 A CN 201910799077A CN 110483587 A CN110483587 A CN 110483587A
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- Prior art keywords
- ketimide
- steric hindrance
- formula
- phenyl
- nickel
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 33
- 239000003446 ligand Substances 0.000 title claims abstract description 28
- 239000007868 Raney catalyst Substances 0.000 title claims description 16
- 229910000564 Raney nickel Inorganic materials 0.000 title claims description 16
- 238000002360 preparation method Methods 0.000 title abstract description 10
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 title 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 107
- -1 polyethylene Polymers 0.000 claims abstract description 50
- 239000003054 catalyst Substances 0.000 claims abstract description 40
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 39
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 23
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 10
- 230000003197 catalytic effect Effects 0.000 claims abstract description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 39
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 33
- YMWUJEATGCHHMB-UHFFFAOYSA-N dichloromethane Natural products ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 29
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 29
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 23
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 21
- 239000000377 silicon dioxide Substances 0.000 claims description 14
- 239000003960 organic solvent Substances 0.000 claims description 13
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- 229910052736 halogen Inorganic materials 0.000 claims description 10
- 150000002367 halogens Chemical class 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 239000003377 acid catalyst Substances 0.000 claims description 6
- 125000003545 alkoxy group Chemical group 0.000 claims description 6
- 125000004429 atom Chemical group 0.000 claims description 6
- 229950005499 carbon tetrachloride Drugs 0.000 claims description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 6
- 150000007524 organic acids Chemical class 0.000 claims description 6
- 239000003208 petroleum Substances 0.000 claims description 6
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 5
- 150000002790 naphthalenes Chemical class 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 4
- 229920000098 polyolefin Polymers 0.000 claims description 4
- MIOPJNTWMNEORI-GMSGAONNSA-N (S)-camphorsulfonic acid Chemical compound C1C[C@@]2(CS(O)(=O)=O)C(=O)C[C@@H]1C2(C)C MIOPJNTWMNEORI-GMSGAONNSA-N 0.000 claims description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical group COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 3
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 3
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 3
- 235000019253 formic acid Nutrition 0.000 claims description 3
- 150000002431 hydrogen Chemical class 0.000 claims description 3
- 238000001802 infusion Methods 0.000 claims description 3
- 150000002815 nickel Chemical class 0.000 claims description 3
- 125000001624 naphthyl group Chemical group 0.000 claims description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims 1
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 claims 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N Nitrogen dioxide Chemical class O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 claims 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 abstract description 22
- 239000005977 Ethylene Substances 0.000 abstract description 22
- 239000004698 Polyethylene Substances 0.000 abstract description 17
- 229920000573 polyethylene Polymers 0.000 abstract description 17
- 230000000694 effects Effects 0.000 abstract description 15
- 238000006555 catalytic reaction Methods 0.000 abstract description 7
- 238000006243 chemical reaction Methods 0.000 description 11
- 239000000047 product Substances 0.000 description 10
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 6
- 239000003426 co-catalyst Substances 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 150000002466 imines Chemical class 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical class CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- 229910052723 transition metal Inorganic materials 0.000 description 4
- 150000003624 transition metals Chemical class 0.000 description 4
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- 239000004705 High-molecular-weight polyethylene Substances 0.000 description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 3
- 229910052681 coesite Inorganic materials 0.000 description 3
- 229910052906 cristobalite Inorganic materials 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 125000001841 imino group Chemical group [H]N=* 0.000 description 3
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 3
- 229910052682 stishovite Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 3
- 229910052905 tridymite Inorganic materials 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- SJBBXFLOLUTGCW-UHFFFAOYSA-N 1,3-bis(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC(C(F)(F)F)=C1 SJBBXFLOLUTGCW-UHFFFAOYSA-N 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 241000854350 Enicospilus group Species 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 125000005594 diketone group Chemical group 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000004809 thin layer chromatography Methods 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- RELMFMZEBKVZJC-UHFFFAOYSA-N 1,2,3-trichlorobenzene Chemical class ClC1=CC=CC(Cl)=C1Cl RELMFMZEBKVZJC-UHFFFAOYSA-N 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical class ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- 238000004701 1H-13C HSQC Methods 0.000 description 1
- WKBALTUBRZPIPZ-UHFFFAOYSA-N 2,6-di(propan-2-yl)aniline Chemical compound CC(C)C1=CC=CC(C(C)C)=C1N WKBALTUBRZPIPZ-UHFFFAOYSA-N 0.000 description 1
- KLSLBUSXWBJMEC-UHFFFAOYSA-N 4-Propylphenol Chemical compound CCCC1=CC=C(O)C=C1 KLSLBUSXWBJMEC-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000004699 Ultra-high molecular weight polyethylene Substances 0.000 description 1
- HFKJQIJFRMRSKM-UHFFFAOYSA-N [3,5-bis(trifluoromethyl)phenoxy]boronic acid Chemical class OB(O)OC1=CC(C(F)(F)F)=CC(C(F)(F)F)=C1 HFKJQIJFRMRSKM-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 125000005234 alkyl aluminium group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000003796 beauty Effects 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000006392 deoxygenation reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- RAABOESOVLLHRU-UHFFFAOYSA-N diazene Chemical compound N=N RAABOESOVLLHRU-UHFFFAOYSA-N 0.000 description 1
- 229910000071 diazene Inorganic materials 0.000 description 1
- URSLCTBXQMKCFE-UHFFFAOYSA-N dihydrogenborate Chemical compound OB(O)[O-] URSLCTBXQMKCFE-UHFFFAOYSA-N 0.000 description 1
- 230000003292 diminished effect Effects 0.000 description 1
- 125000005982 diphenylmethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003292 glue Substances 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
- 229920001519 homopolymer Polymers 0.000 description 1
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- VIKNJXKGJWUCNN-XGXHKTLJSA-N norethisterone Chemical compound O=C1CC[C@@H]2[C@H]3CC[C@](C)([C@](CC4)(O)C#C)[C@@H]4[C@@H]3CCC2=C1 VIKNJXKGJWUCNN-XGXHKTLJSA-N 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- LVLZXBIWQHFREA-UHFFFAOYSA-N phenol;phosphane Chemical compound [PH4+].[O-]C1=CC=CC=C1 LVLZXBIWQHFREA-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 229920002627 poly(phosphazenes) Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 125000004213 tert-butoxy group Chemical group [H]C([H])([H])C(O*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 229920000785 ultra high molecular weight polyethylene Polymers 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C251/02—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups
- C07C251/04—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups having carbon atoms of imino groups bound to hydrogen atoms or to acyclic carbon atoms
- C07C251/10—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups having carbon atoms of imino groups bound to hydrogen atoms or to acyclic carbon atoms to carbon atoms of an unsaturated carbon skeleton
- C07C251/16—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups having carbon atoms of imino groups bound to hydrogen atoms or to acyclic carbon atoms to carbon atoms of an unsaturated carbon skeleton containing six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/04—Nickel compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/02—Ethene
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to the big steric hindrance ketimide nickel complex and its loaded catalyst, ligand compound, preparation method and application of a kind of formula (I), wherein R1, Ar and BAF‑As defined herein.Big steric hindrance ketimide nickel complex of the invention can be used as catalyst in catalysis low-carbon alkene such as ethylene polymerization, and having high catalytic activity, (activity is up to 8 × 106g·mol‑1·h‑1) and high thermal stability, can obtaining high molecular weight, (number-average molecular weight is up to 1.59 × 106G/mol polyethylene).
Description
Technical field
The present invention relates to catalytic fields and synthesis polyphosphazene polymer olefin material field, more particularly to big steric hindrance ketimide nickel to urge
Agent and its ligand compound, preparation method and application.
Background technique
Since more than halfth century, late transition metal catalysis in olefine polymerization has attracted very big interest.Out-phase olefinic polymerization is urged
Agent considers the form that can control product due to it from industrial point of view, avoids the dirt of reactor, has continuous production
Ability obtained everybody more concerns and preference.It is as one " poison " that metallic nickel, which enters this field,.Ziegler and
His colleague demonstrates famous " nickel effect ", and alkyl aluminum makes ethylene be fully converted to 1- butylene in the presence of nickel salt.
This discovery becomes the starting point of Ziegler catalyst development.Now, it is reported there are many metallic nickel and generates High molecular weight polyethylene.
It is exactly to illustrate diimine nickel to prepare High molecular weight polyethylene in mono- important work of nineteen ninety-five Brookhart, activity
It matches in excellence or beauty in Former transition metal catalyst.Salicylic alidehyde imine Raney nickel is developed in Grubbs in 2000 and his colleague and has shown this
A field another kind significant progress.The catalyst of SHOP type is commercially used for synthetic linear alpha-olefin.Suitable knot
Structure modification, such catalyst can produce High molecular weight polyethylene.For example, the Raney nickel of some phosphine phenol ligand structures
There is good property for vinyl polymerization and ethylene and acrylic ester copolymerization.
Although nearest research interest focuses on the relevant ligand of phosphine, but the unique property such as it is readily synthesized due to having
Imine derivative ligand is still attracting system.Moreover, Phosphine ligands contain it is easy to oxidize, potential spontaneous combustion and toxicity etc. lack
Point.It is interesting that literature survey shows that the Raney nickel containing phosphine generally produces the polyethylene of line style in ethylene polymerisation process.Phase
Instead, it is mostly based on N^N and N^O system Raney nickel and generates different branched polyethylenes.Industrially, in order to improve polyethylene
Processability and some other property, branching is usually introduced by ethylene and alpha-olefin copolymer.
The Raney nickel of these nitrogen systems generates the ability of branched polyethylene from industrial angle using ethylene as unique raw material
Very attractive from the point of view of degree, extensive research is also being done really by E.I.Du Pont Company.WO02/059165A2, which is disclosed, utilizes 2,6- bis-
Isopropyl aniline and 3,4- acetyl butyryl react to prepare ligand L 6, and by the ligand L 6 and allyl nickel chloride and four (3,5- bis-
(trifluoromethyl) phenyl) to prepare catalyst 6, the reaction mechanism mechanism of reaction is as follows for Boratex reaction:
However, such catalyst 6 very low (activity of catalyzed ethylene polymerization at room temperature of activity in ethylene polymerization
Only 6.4 × 104g·mol-1·h-1), and not high enough (number-average molecular weight is less than the molecular weight of resulting polyethylene product
80000)。
In addition, the supported of Former transition metal catalyst has been widely studied, there are some systems by Successful commercial
Change, however, in contrast, load of seldom research about late transition metal catalyst.In research once in a while, one is homogeneously urged
Agent is carried on solid carrier the generation for leading to the crowded and some side reaction of serious steric hindrance, and catalysis all can greatly be caused to be lived
Property reduce.Moreover, because existing bisperfluorobutanesulfoneimide catalyst is characteristic disclosed in single-component catalyst and space, it is expected that directly negative
It is loaded on carrier.Unfortunately, although due to the catalyst cationic characteristic, these catalyst are for such as silica
Carrier shows very low adsorptivity.And in existing load study, the silica supports used are needed with some aluminium
Co-catalyst such as methylaluminoxane pre-processes, to enhance metallic catalyst for the adsorptivity of silica supports.In addition, also needing
A large amount of co-catalyst is wanted to realize the high activity of catalyst.
In consideration of it, this field needs to urge for obtaining the novel of more high catalytic activity of the Alathon of higher molecular weight
Agent.In addition, such catalyst can be preferably directly loaded on silica supports for industrial application, catalysis
It does not need to add co-catalyst when vinyl polymerization yet.
Summary of the invention
The purpose of the present invention is to provide a kind of novel nickel catalysts or nickel catalyst carried, are being used for C2-C6Low-carbon
Thermal stability with higher and catalytic activity in the homopolymerization of alkene, and resulting polymer has higher molecule
Amount.The object of the invention is also to provide ligand compounds of such Raney nickel and its preparation method and application.
This application provides a kind of big steric hindrance ketimide nickel complexes of formula (I):
Wherein
R1Selected from C1-C6Alkyl, phenyl or substituted phenyl, the substituted phenyl are selected from OH, halogen by one or more
Element, nitro, C1-C6Alkyl and C1-C6Substituent group in alkoxy replaces；
The group of Ar expression (101):
In formula (101), R2、R3And R8It is independently from each other hydrogen, C1-C6Alkyl, halogen, nitro, methoxyl group or phenyl；
And R4、R5、R6And R7It is independently from each other phenyl, substituted phenyl, naphthalene or substituted naphthalene, the substituted phenyl
Or the naphthalene replaced is selected from OH, halogen, nitro, C by one or more1-C6Alkyl and C1-C6Substituent group in alkoxy replaces；
SymbolThe group of expression (101) and the tie point of the N atom in formula (I)；
BAF- indicates four (3,5- bis- (trifluoromethyl) phenyl) borate anions, and
SymbolIndicate the allyl for being connected to Ni atom.
In preferred embodiments, R4、R5、R6And R7It is independently from each other phenyl or naphthyl；Preferably, R2、R3And R8
It is independently from each other hydrogen or C1-C6Alkyl.
On the other hand, the present invention provides a kind of big steric hindrance Raney nickel of support type, comprising: is loaded to by infusion process
Above-mentioned big steric hindrance ketimide nickel complex on carrier.Preferably, the carrier is selected from silica, anhydrous magnesium chloride and three
One of Al 2 O is a variety of.
On the other hand, the present invention provides a kind of ketimide ligand compound of formula (II):
Wherein, R1It is as defined above with Ar.
On the other hand, the present invention provides a kind of method for preparing above-mentioned big steric hindrance ketimide nickel complex, described
Method includes: the ketimide ligand compound and allyl nickel salt and four (3,5- bis- (trifluoromethyl) benzene for making above-mentioned formula (II)
Base) borate reacts in organic solvent, wherein the organic solvent is selected from tetrahydrofuran, petroleum ether, toluene, benzene, dichloro
Methane, tetrachloromethane, Isosorbide-5-Nitrae-dioxane and 1, one of 2- dichloroethanes or a variety of.
On the other hand, the present invention provides a kind of method of ketimide ligand compound for preparing above-mentioned formula (II),
The described method includes:
In the presence of organic acid catalyst, 60~150 DEG C at a temperature of, formula Ar-NH2Novel arylamine compound and formulaDione compounds react 12~72h in organic solvent, wherein R1It is as defined above with Ar.
In preferred embodiments, the organic acid catalyst is selected from formic acid, acetic acid, p-methyl benzenesulfonic acid or camphorsulfonic acid；
The organic solvent is to be selected from tetrahydrofuran, petroleum ether, toluene, benzene, methylene chloride, tetrachloromethane, Isosorbide-5-Nitrae-dioxane and 1,
One of 2- dichloroethanes is a variety of.
On the other hand, the present invention provides a kind of method for preparing polyolefin compound, which comprises in use
The big steric hindrance ketimide nickel complex stated is as catalyst to C2-C6Low-carbon alkene carries out catalytic polymerization.
On the other hand, the present invention provides a kind of method for preparing polyolefin compound, which comprises in use
The big steric hindrance Raney nickel of the support type stated is to C2-C6Low-carbon alkene carries out catalytic polymerization.
In preferred embodiments, the polymerization reaction 20~100 DEG C at a temperature of carry out.
This application provides a kind of novel ketimide nickel complex and its be supported on it is nickel catalyst carried on carrier, lead to
Crossing the Ar substituent group for connecting the N atom in its ligand with imines and carrying out particular design is with significantly bigger steric hindrance knot
Thus structure provides big steric hindrance in the side of metal nickle atom.Such big steric hindrance structure is in catalysis low-carbon alkene
Ni metal center can be effectively protected in polymerization reaction, so that the thermal stability and chemistry that improve nickel complex as catalyst are living
Property.
Further, since connection p-hydroxybenzene is designed on the carbonyl of ketimide, so that resulting nickel complex is easy
Ground adsorb and be supported on silica etc. carrier on, form the loaded catalyst with high activity and thermal stability,
Simultaneously it is not necessary to the typically required co-catalyst used.
In addition, utilizing the nickel catalyst carried polyethylene number-average molecular weight come catalyzed ethylene polymerization, obtained of the invention
It is relatively higher, thus can be used to prepare ultra-high molecular weight polyethylene.Moreover, by nickel catalyst carried being urged using of the invention
The polyethylene for changing preparation is graininess, thus there is no common polyethylene products due to cluster for obtained polyethylene polymer
Viscous kettle problem caused by aggregation, therefore of the invention nickel catalyst carried it is more applicable for large-scale industrial production.
Specific embodiment
For existing ketimide Raney nickel in the prior art, activity is very low and resulting in ethylene polymerization
The not high problem of the molecular weight of polyethylene product, by deeply and widely research, the present inventor unexpectedly send out
It is existing, it is designed by structure again, is set on the aromatic substituent being connect with the N atom of imines in ketimide ligand compound
Counting, there is the aryl of greater room steric hindrance to replace structure, and the significant of approximate semi-surrounding is thus provided around active metal nickle atom
Bigger steric hindrance structure, such big steric hindrance structure can be effectively protected in Ni metal in the polymerization reaction of catalysis ethylene
The heart, while connection p-hydroxybenzene is designed on the carbonyl of ketimide, so as to improve nickel complex as catalyst
Thermal stability and chemical activity, while using such big steric hindrance ketimide nickel complex as catalyst, the ethylene of acquisition is equal
Polymers can have higher molecular weight.
In addition, the present invention is also unexpectedly found that under study for action, using having hydroxy functional group designed by the present invention
Big steric hindrance ketimide nickel complex, such nickel complex can easily be carried on the carrier of silica etc.
On, to form the support type out-phase Raney nickel with high activity.In addition, utilizing supported catalyst provided by the present invention
Agent can also be avoided using co-catalyst.
Based on this discovery, the present invention designs first and provides a kind of ketimide ligand compound of lower formula (II):
Wherein
R1Selected from C1-C6Alkyl, phenyl or substituted phenyl, the substituted phenyl are selected from OH, halogen by one or more
Element, nitro, C1-C6Alkyl and C1-C6Substituent group in alkoxy replaces；
The group of Ar expression (101):
In formula (101), R2、R3And R8It is independently from each other hydrogen, C1-C6Alkyl, halogen, nitro, methoxyl group or phenyl；
Preferably, R2、R3And R8It is independently from each other hydrogen or C1-C6Alkyl；R4、R5、R6And R7It is independently from each other phenyl, replaces
Phenyl, naphthalene or substituted naphthalene, the substituted phenyl or substituted naphthalene are selected from OH, halogen, nitre by one or more
Base, C1-C6Alkyl and C1-C6Substituent group in alkoxy replaces；Preferably, R4、R5、R6And R7Be independently from each other phenyl or
Naphthalene；And symbolThe group of expression (101) and the tie point of the N atom in formula (I).
As used in this article, C1-C6Alkyl indicates the linear or branched alkyl group group containing 1~6 carbon atom, in fact
Example is methyl, ethyl, propyl, butyl, amyl, hexyl and its isomeric form, preferably methyl, ethyl or tert-butyl.
As used in this article, C1-C6Alcoxyl basis representation passes through the above-mentioned C of oxygen atom (O) connection1-C6Alkyl, the example
It is methoxyl group, ethyoxyl, propoxyl group, tert-butoxy etc..
As used in this article, halogen includes fluorine, chlorine, bromine and iodine, preferably chlorine or bromine.
In the present invention, on the basis of being designed to connection p-hydroxybenzene on the carbonyl of ketimide, by formula (II)
Ketimide ligand compound substituent R1It is further designed, especially substituent A r is specifically designed, In with Ar
It is at least introduced in its specific structure formula (101) indicated and is independently from each other phenyl, substituted phenyl, naphthalene or substituted naphthalene
The big steric group R of four of base4、R5、R6And R7, so that the ligand compound forms approximate semi-enclosed cage structure.This
So that when the ligand compound and active metal Ni atom cooperatively form complex, it can be in active metal Ni atom side shape
At big steric hindrance, so that when such complex is applied to the polymerization reaction of catalysis ethylene as catalyst, it can
It is effectively protected Ni metal center, it is living as the thermal stability and chemistry of catalyst so as to improve resulting nickel complex
Property.Moreover, because connection p-hydroxybenzene is designed on the carbonyl of ketimide, so that resulting nickel complex easily adsorbs
And on the carrier for being supported on silica etc., easily form the loaded catalyst with high activity and thermal stability,
Simultaneously it is not necessary to the typically required co-catalyst used.
The preparation method of the ketimide ligand compound of above-mentioned formula (II) provided by the invention is not particularly limited, example
It can be such as made by the following method: in the presence of organic acid catalyst, at 60~150 DEG C, preferably 80 DEG C -100 DEG C of temperature
Under degree, formula Ar-NH2Novel arylamine compound and formulaDione compounds or keto-aldehyde compound in organic solvent
12~72h of middle reaction, wherein R1It is as defined above with Ar.Preferably, it is reacted under the conditions of temperature rising reflux.Preferably, it uses
Organic acid catalyst can be selected from formic acid, acetic acid, p-methyl benzenesulfonic acid or camphorsulfonic acid.Preferably, the organic solvent used can be with
In tetrahydrofuran, petroleum ether, toluene, benzene, methylene chloride, tetrachloromethane, Isosorbide-5-Nitrae-dioxane and 1,2- dichloroethanes
It is one or more, for example, toluene.Preferably, in the reaction, it can use such as anhydrous magnesium sulfate and remove the water that dereaction generates.
Preferably, the molar ratio of amine and the aldehyde is 1: (0.1~10)；In a particular embodiment, formula Ar-NH2Novel arylamine compound
With formulaDione compounds or keto-aldehyde compound molar ratio be 1: (0.1~10), more preferably 1: (1~
5)。
As used in this article, to those skilled in the art, in above-mentioned novel arylamine compound, expression
(101) the Ar substituent group of structure can be easily based on for example substituted or unsubstituted benzene of most basic raw material or naphthalene chemical combination
Object obtains corresponding structure using routine techniques well known in the art, and is connected on the N atom of amine and obtains corresponding aryl
Amine compounds.Moreover, the benzene that above-mentioned dione compounds can use the commercially available corresponding diketone in this field and contraposition replaces
Phenolic compounds obtains corresponding dione compounds as raw material, by popular response well known in the art.
In the present invention, it is preferred to which the ketimide ligand compound of above-mentioned formula (II) may, for example, be following formula (II1)
Compound:
Wherein Ph indicates phenyl (i.e. group C6H5-)。
Based on the ketimide ligand compound of above-mentioned formula (II), the present invention provides a kind of big steric hindrance ketimides of formula (I)
Nickel complex:
Wherein, substituent R1There is identical meanings defined above, BAF with Ar-Indicate four (3,5- bis- (trifluoromethyl) benzene
Base) borate anion, and symbolIndicate the allyl (CH for being connected to Ni atom2=CH-CH2-)。
Such big steric hindrance ketimide nickel complex can be for example prepared by the following method: make the ketone of above-mentioned formula (II)
Imine ligand compound and allyl nickel salt such as allyl nickel chloride and four (3,5- bis- (trifluoromethyl) phenyl) borates such as four
(3,5- bis- (trifluoromethyl) phenyl) Boratex reacts in organic solvent, wherein organic solvent can for selected from tetrahydrofuran,
Petroleum ether, toluene, benzene, methylene chloride, tetrachloromethane, Isosorbide-5-Nitrae-dioxane and 1, one of 2- dichloroethanes or a variety of, example
For example methylene chloride.Preferably, in the reaction, the ligand compound and allyl nickel salt of formula (II) and four (3,5- bis- (trifluoros
Methyl) phenyl) borate can be reacted with the molar ratio for being such as, but not limited to 1: 1: 1.Such reaction for example can be
It carries out at room temperature, the reaction time for example can be 10~20 hours.
In the present invention, it is preferred to which the big steric hindrance ketimide nickel complex of above-mentioned formula (I) can have such as following formula
(I1) structure；
Wherein BAF-WithAs defined above, and Ph indicates phenyl (i.e. group C6H5-)。
Big steric hindrance ketimide nickel complex based on above-mentioned formula (I), the present invention also provides a kind of big steric hindrance nickel of support type
Big steric hindrance ketimide nickel complex can be loaded or be adsorbed onto carrier for example, by the common infusion process in this field by catalyst
Above obtain.For example, by stirring big steric hindrance ketimide nickel complex and carrier in organic solvent such as toluene with uniform
Mixing, then filtration drying can be obtained nickel catalyst carried.Preferably, the carrier used can be selected from silica,
One of anhydrous magnesium chloride and aluminum oxide are a variety of.Dissociate since big steric hindrance ketimide nickel complex of the invention has
Hydroxyl can be easy to be adsorbed on the carrier of such as silica.
In a specific embodiment, nickel catalyst carried (the Ni-OH@SiO that the present invention obtains2) can indicate such as
Under:
The above-mentioned big steric hindrance ketimide nickel complex of the present invention can be used as catalyst or the big steric hindrance nickel of above-mentioned support type
Catalyst may be used to prepare C2-C6The homopolymer of low-carbon alkene such as ethylene.Preferably, above-mentioned polymerization reaction is at 20~100 DEG C
At a temperature of carry out.
Embodiment
For a further understanding of the present invention, the preferred embodiment of the invention is described below with reference to embodiment, still
It should be appreciated that these descriptions are only further explanation the features and advantages of the present invention, rather than limiting the scope of the invention.
The synthesis of complex and polymerization process are carried out under anhydrous and oxygen-free in following embodiment, the object of all sensitivities
Matter is stored in glove box, and for all solvents all by stringent dry water removal, ethylene gas passes through water removal deoxygenation pillar purifying.No
It illustrates, is directly used after all raw material purchases.
Silica gel post separation uses the silica gel of 200-300 mesh；Nuclear-magnetism detection Bruker 400MHz nuclear magnetic resonance spectrometer；Elemental analysis
It is measured by China Science & Technology University's physics and chemistry center；Molecular weight and molecualr weight distribution is measured by high temperature GPC；Mass spectrum Thermo
LTQ Orbitrap XL (ESI+) or P-SIMS-Gly of Bruker DaltonicsInc (EI+) measurement.
Embodiment 1:2- ((2,6- bis- (di-p-tolyl methyl) -4- aminomethyl phenyls) imino group) -1- (4- hydroxy phenyl)
Propyl- 1- ketone (II1) preparation
Under nitrogen protection, in 250 milliliters of round-bottomed flasks for being equipped with reflux condensate device, magnetic stirring apparatus and oil bath
In, by bis- (the diphenyl methyl) -4- methylanilines of 2,6- (1758 milligrams, 4 mMs), 1- (4- hydroxy phenyl) propane -1,2-
The solution of diketone (328 milligrams, 2 mMs) and p-methyl benzenesulfonic acid (20 milligrams) in toluene (20 milliliters) stirs 12 at 80 DEG C
Hour, it is monitored and is reacted by thin-layer chromatography (TLC).After showing a primary product point on chromatographic sheet, terminate anti-
It answers.The reaction is cooled to room temperature, Precipitation yellow solids, and are isolated by filtration to obtain yellow solid (585 milligrams, receive
Rate 50%).Products therefrom is tested and analyzed, title compound is as a result turned out to be.
1H NMR (400MHz, CDCl3) δ 7.52 (br, 2H), 7.35-6.75 (m, 20H), 6.66 (br, 2H), 6.45 (br,
2H), 5.29 (s, 2H, CHPh2), 2.13 (s, 3H, aryl-CH3), 1.15 (s, 3H, N=CMe).
13C NMR (100MHz, [D6] DMSO) δ 189.82 (s, COCH3), 170.44 (s), 162.52 (s), 144.26
(s), 143.07 (s), 142.63 (s), 133.24 (s), 131.76 (s), 131.03 (s), 129.52 (s), 129.21 (s),
128.75 (s), 128.53 (s), 128.35 (s), 126.49 (s), 126.38 (s), 125.45 (s), 115.11 (s), 51.17
(s, CHPh2), 21.02 (s), 17.40 (s).
HRMS (m/z): theoretical value C42H36O2N:[M+H]+586.2741；Measured value: 5702742.
Embodiment 2:2- ((2,6- bis- (di-p-tolyl methyl) -4- aminomethyl phenyls) imino group) -1- (4- hydroxy phenyl)
The preparation of propyl- 1- ketone nickel complex (catalyst n i-OH)
In glove box, in 20 milliliters of vials, by 2- ((2,6- bis- (di-p-tolyl methyl) -4- aminomethyl phenyls)
Imino group) -1- (4- hydroxy phenyl) propyl- 1- ketone (293 milligrams, 0.5 mM), allyl nickel chloride (67.5 milligrams, 0.5 milli
Mole) and four (3,5- bis- (trifluoromethyl) phenyl) Boratexes (443 milligrams, 0.5 mM) mixture in methylene chloride (15
Milliliter) in solution be stirred at room temperature 12 hours.Gained mixture diatomite is filtered and evaporated, red solid is obtained
(619 milligrams, yield 80%).Products therefrom is tested and analyzed, title compound is as a result turned out to be.
1H NMR (400MHz, CDCl3) δ 7.78-7.50 (m, 10H), 7.37 (s, 4H), 7.24 (t, J=7.3Hz, 4H),
7.18 (d, J=6.7Hz, 2H), 7.08 (s, 6H), 6.94 (s, 4H), 6.87 (s, 3H), 6.76 (s, 2H), 6.67 (d, J=
8.6Hz, 2H), 5.68 (s, 1H), 5.40-4.95 (m, 3H), 2.12 (s, 3H, aryl-CH3), 1.02 (s, 3H, N=CMe).
13C NMR (100MHz, CDCl3) δ 195.40 (s), 176.51 (s), 165.68 (s), 142.02 (s), 140.56
(s), 140.41 (s), 138.44 (s), 135.55 (s), 133.76 (s), 129.87 (s), 129.50 (s), 129.44 (s),
129.34 (s), 127.84 (s), 127.64 (s), 125.02 (s), 119.46 (s, allyls), 117.45 (s), 53.17 (s),
21.50 (s, aryl-CH3), 20.50 (s, N=CMe).
1H-13C HSQC relevance (CDCl3): 119.46 (s, allyl)/5.40-4.95 (m, 3H), 21.50 (s, virtues
Base-CH3)/2.12 (s, 3H, aryl-CH3), 20.50 (s, N=CMe)/1.02 (s, 3H, N=CMe).
Elemental analysis: theoretical value C77H52BF24NNiO2: C, 59.72；H, 3.38；Measured value: C, 59.86；H, 3.25.
Embodiment 3: nickel catalyst carried (Ni-OH@SiO2) preparation
In Muffle furnace, by as the silica of carrier (be purchased from Grace-Dai Weixun company, model 955) 600
It roasts 6 hours, is stored in spare in glove box at DEG C.
Under conditions of nitrogen protection, in glove box, in 20 milliliters of vials, by 100 milligrams of loads produced above
Catalyst n i-OH obtained is dissolved in 1 milliliter of toluene in body silica and 1 micromole's embodiment 2, and is stirred at room temperature
It mixes 6 hours.Then it by the way that solid product is obtained by filtration, and is washed twice with toluene (15 milliliters), finally by vacuum drying, i.e.,
It can be obtained required nickel catalyst carried.
Application examples 1-11: composition catalyst (Ni-OH) and loaded catalyst (Ni-OH@SiO2) catalyzed ethylene polymerization
Application
In glove box, under nitrogen atmosphere, (filled into 350 milliliters of autoclaves with magnetic stirring apparatus, oil bath heating
Set and thermometer) 28 milliliters of toluene or 30 milliliters of normal heptanes is added.By reactor be connected to high pressure line and to pipeline into
Row vacuumizes, and is heated to reactor temperature shown in the following table 1 (20 DEG C, 50 DEG C, 80 DEG C or 100 DEG C) using oil bath, heat preservation 15
Minute.Then the composition catalyst (Ni-OH) or loaded catalyst (Ni-OH@being dissolved in 2 milliliters of methylene chloride is added
SiO2) (1 micromole), close valve.Adjusting ethylene pressure is reaction 3 minutes after atmospheric pressure shown in the following table 1；Stop reaction.
Reaction kettle is opened, ethyl alcohol (50 milliliters) is added thereto with precipitation solid, is filtered under diminished pressure, (50 DEG C) drying of vacuum oven obtain
White solid.The results are shown in Table 1.
Table 1: Raney nickel is catalyzed ethylene homoaResult
aEthylene homo condition: catalyst=1 is micro- to rub；Toluene=28 milliliter, methylene chloride=2 milliliter, ethylene=8 atmosphere
Pressure, time=3 minute；
bActivity=107g·mol-1·h-1；It as known in the art, is the quality using polyethylene divided by catalyst
Amount of substance, then obtained divided by the reaction time；
cMolecular weight determination is that polystyrene is used to measure as solvent at 150 DEG C as standard trichloro-benzenes by GPC；；
dEvery 1000 carbon degrees of branching are by nuclear magnetic resonance hydrogen spectruming determining；
eFusing point is measured with differential scanning calorimeter；
fTime=30 minute；
gNormal heptane=30 milliliter, time=30 minute.
It can be seen from the above by using big steric hindrance ketimide nickel complex provided by the invention as catalyst,
There is very high thermal stability and activity for the homopolymerization polymerization reaction of ethylene, the macromolecule with certain degree of branching can be obtained
The polyethylene of amount.For example, activity is up to 1.6 × 10 in the case where individual complex is as catalyst7g·mol-1·
h-1；The number-average molecular weight of polyethylene product is up to 1.04 × 106g/mol；And fusing point is up to 124.6 DEG C.And it is urged in support type
In the case where agent, activity is up to 8.0 × 106g·mol-1·h-1；The number-average molecular weight of polyethylene product up to 1.59 ×
106g/mol；Fusing point is up to 131.9 DEG C.
In addition, it is noted that although it is nickel catalyst carried compared to unsupported Raney nickel activity relatively
It is low, but since the problem of polymer product glues kettle is not present using nickel catalyst carried obtained polyethylene polymer,
It is thus of the invention nickel catalyst carried to be more applicable for large-scale industrial production；Moreover, being catalyzed using load-type nickel
The molecular weight of polyethylene that agent catalyzed ethylene polymerization obtains is relatively higher.
The foregoing description of the disclosed embodiments enables those skilled in the art to implement or use the present invention.
Various modifications to these embodiments will be readily apparent to those skilled in the art, as defined herein
General Principle can be realized in other embodiments without departing from the spirit or scope of the present invention.Therefore, of the invention
It is not intended to be limited to the embodiments shown herein, and is to fit to and the principles and novel features disclosed herein phase one
The widest scope of cause.
Claims (10)
1. a kind of big steric hindrance ketimide nickel complex of formula (I):
Wherein
R1Selected from C1-C6Alkyl, phenyl or substituted phenyl, the substituted phenyl by one or more selected from OH, halogen,
Nitro, C1-C6Alkyl and C1-C6Substituent group in alkoxy replaces；
The group of Ar expression (101):
In formula (101), R2、R3And R8It is independently from each other hydrogen, C1-C6Alkyl, halogen, nitro, methoxyl group or phenyl；And
R4、R5、R6And R7It is independently from each other phenyl, substituted phenyl, naphthalene or substituted naphthalene, the substituted phenyl or takes
The naphthalene in generation is selected from OH, halogen, nitro, C by one or more1-C6Alkyl and C1-C6Substituent group in alkoxy replaces；SymbolThe group of expression (101) and the tie point of the N atom in formula (I)；
BAF-Indicate four (3,5- bis- (trifluoromethyl) phenyl) borate anions, and
SymbolIndicate the allyl for being connected to Ni atom.
2. big steric hindrance ketimide nickel complex according to claim 1, which is characterized in that R4、R5、R6And R7Independently of one another
Selected from phenyl or naphthyl；Preferably, R2、R3And R8It is independently from each other hydrogen or C1-C6Alkyl.
3. a kind of big steric hindrance Raney nickel of support type, comprising: by infusion process load on carrier according to claim 1 in -2
Described in any item big steric hindrance ketimide nickel complexes；Preferably, the carrier is selected from silica, anhydrous magnesium chloride and three
One of Al 2 O is a variety of.
4. a kind of ketimide ligand compound of formula (II):
Wherein, R1It is defined with any one of Ar such as claim 1-2.
5. a kind of method for preparing big steric hindrance ketimide nickel complex according to claim 1, which comprises make as
The ketimide ligand compound and allyl nickel salt and four (3,5- bis- (trifluoromethyl) phenyl) of formula (II) as claimed in claim 4
Borate reacts in organic solvent, wherein the organic solvent is selected from tetrahydrofuran, petroleum ether, toluene, benzene, dichloromethane
Alkane, tetrachloromethane, Isosorbide-5-Nitrae-dioxane and 1, one of 2- dichloroethanes or a variety of.
6. a kind of method for the ketimide ligand compound for preparing formula according to claim 4 (II), which comprises
In the presence of organic acid catalyst, 60~150 DEG C at a temperature of, formula Ar-NH2Novel arylamine compound and formulaDione compounds react 12~72h in organic solvent, wherein R1With it is any in Ar such as claim 1-2
Defined in.
7. according to the method described in claim 6, it is characterized in that, the organic acid catalyst is selected from formic acid, acetic acid, to toluene
Sulfonic acid or camphorsulfonic acid；The organic solvent is to be selected from tetrahydrofuran, petroleum ether, toluene, benzene, methylene chloride, tetrachloromethane, 1,
4- dioxane and 1, one of 2- dichloroethanes or a variety of.
8. a kind of method for preparing polyolefin compound, which comprises
Use according to claim 1 big steric hindrance ketimide nickel complex described in any one of -2 as catalyst to C2-C6Low-carbon
Alkene carries out catalytic polymerization.
9. a kind of method for preparing polyolefin compound, which comprises
Using the big steric hindrance Raney nickel of support type according to claim 3 to C2-C6Low-carbon alkene carries out catalytic polymerization.
10. method according to claim 8 or claim 9, which is characterized in that the polymerization reaction 20~100 DEG C at a temperature of
It carries out.
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| CN201910799077.2A CN110483587B (en) | 2019-08-27 | 2019-08-27 | Large steric hindrance ketimine nickel catalyst and ligand compound, preparation method and application thereof |
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