CN105732486A - Pyridine imine compound and preparation method thereof, pyridine imine nickel catalyst and preparation method thereof and polyolefin - Google Patents
Pyridine imine compound and preparation method thereof, pyridine imine nickel catalyst and preparation method thereof and polyolefin Download PDFInfo
- Publication number
- CN105732486A CN105732486A CN201610249184.4A CN201610249184A CN105732486A CN 105732486 A CN105732486 A CN 105732486A CN 201610249184 A CN201610249184 A CN 201610249184A CN 105732486 A CN105732486 A CN 105732486A
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- China
- Prior art keywords
- alkyl
- formula
- aryl
- pyridine imine
- pyridine
- Prior art date
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- -1 Pyridine imine compound Chemical class 0.000 title claims abstract description 102
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 title claims abstract description 76
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 title claims abstract description 72
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 229920000098 polyolefin Polymers 0.000 title claims abstract description 25
- 150000002466 imines Chemical class 0.000 title abstract description 5
- 239000003054 catalyst Substances 0.000 claims abstract description 53
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 51
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 49
- 239000001257 hydrogen Substances 0.000 claims abstract description 49
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 37
- 125000003710 aryl alkyl group Chemical group 0.000 claims abstract description 34
- 150000001336 alkenes Chemical class 0.000 claims abstract description 21
- 125000003118 aryl group Chemical group 0.000 claims abstract description 21
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 21
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims abstract description 18
- 230000000694 effects Effects 0.000 claims abstract description 16
- 150000001875 compounds Chemical class 0.000 claims description 50
- 229910052799 carbon Inorganic materials 0.000 claims description 44
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 29
- 239000004698 Polyethylene Substances 0.000 claims description 21
- 229920000573 polyethylene Polymers 0.000 claims description 21
- 125000003545 alkoxy group Chemical group 0.000 claims description 19
- 125000003368 amide group Chemical group 0.000 claims description 19
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 19
- 229910052759 nickel Inorganic materials 0.000 claims description 16
- 229910052736 halogen Inorganic materials 0.000 claims description 14
- 150000002367 halogens Chemical group 0.000 claims description 14
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 14
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 12
- 150000002940 palladium Chemical class 0.000 claims description 10
- 238000006555 catalytic reaction Methods 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 8
- 239000002243 precursor Substances 0.000 claims description 8
- 150000001721 carbon Chemical group 0.000 claims description 6
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 claims description 6
- 230000007062 hydrolysis Effects 0.000 claims description 5
- 238000006460 hydrolysis reaction Methods 0.000 claims description 5
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 4
- 150000002815 nickel Chemical class 0.000 claims description 2
- 125000005184 naphthylamino group Chemical class C1(=CC=CC2=CC=CC=C12)N* 0.000 claims 3
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 claims 2
- 230000026030 halogenation Effects 0.000 claims 1
- 238000005658 halogenation reaction Methods 0.000 claims 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 8
- 239000003446 ligand Substances 0.000 abstract description 6
- 125000004432 carbon atom Chemical group C* 0.000 abstract 2
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 abstract 1
- 125000005245 nitryl group Chemical group [N+](=O)([O-])* 0.000 abstract 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 45
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 44
- 238000006243 chemical reaction Methods 0.000 description 42
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 30
- 150000002431 hydrogen Chemical class 0.000 description 30
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 24
- 239000007787 solid Substances 0.000 description 24
- 238000005481 NMR spectroscopy Methods 0.000 description 23
- JGSLKNWXPRDWBA-UHFFFAOYSA-N 2-methylidene-1h-pyridine Chemical compound C=C1NC=CC=C1 JGSLKNWXPRDWBA-UHFFFAOYSA-N 0.000 description 20
- 239000000243 solution Substances 0.000 description 14
- 239000002585 base Substances 0.000 description 12
- 150000005002 naphthylamines Chemical class 0.000 description 12
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 11
- 239000005977 Ethylene Substances 0.000 description 11
- 239000003960 organic solvent Substances 0.000 description 11
- 229920000642 polymer Polymers 0.000 description 11
- 239000003153 chemical reaction reagent Substances 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 8
- 238000005406 washing Methods 0.000 description 7
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 6
- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
- 239000002841 Lewis acid Substances 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- 230000008901 benefit Effects 0.000 description 6
- 150000007517 lewis acids Chemical class 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 6
- 239000007868 Raney catalyst Substances 0.000 description 5
- 229910000564 Raney nickel Inorganic materials 0.000 description 5
- 239000003513 alkali Substances 0.000 description 5
- 238000001514 detection method Methods 0.000 description 5
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 5
- UFWIBTONFRDIAS-UHFFFAOYSA-N naphthalene-acid Natural products C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 5
- 230000005311 nuclear magnetism Effects 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 229910021585 Nickel(II) bromide Inorganic materials 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 238000010790 dilution Methods 0.000 description 4
- 239000012895 dilution Substances 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000002808 molecular sieve Substances 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- IPLJNQFXJUCRNH-UHFFFAOYSA-L nickel(2+);dibromide Chemical compound [Ni+2].[Br-].[Br-] IPLJNQFXJUCRNH-UHFFFAOYSA-L 0.000 description 4
- 238000001953 recrystallisation Methods 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 4
- 238000010025 steaming Methods 0.000 description 4
- 0 *c1cc(-c2cccc3c2c(N)c(*)cc3*)cc(*=C)c1* Chemical compound *c1cc(-c2cccc3c2c(N)c(*)cc3*)cc(*=C)c1* 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- QILSFLSDHQAZET-UHFFFAOYSA-N diphenylmethanol Chemical compound C=1C=CC=CC=1C(O)C1=CC=CC=C1 QILSFLSDHQAZET-UHFFFAOYSA-N 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 239000000806 elastomer Substances 0.000 description 3
- 125000001841 imino group Chemical group [H]N=* 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000001840 matrix-assisted laser desorption--ionisation time-of-flight mass spectrometry Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000012544 monitoring process Methods 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 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
- 238000001291 vacuum drying Methods 0.000 description 3
- 239000011592 zinc chloride Substances 0.000 description 3
- 235000005074 zinc chloride Nutrition 0.000 description 3
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 2
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- ZRNSSRODJSSVEJ-UHFFFAOYSA-N 2-methylpentacosane Chemical compound CCCCCCCCCCCCCCCCCCCCCCCC(C)C ZRNSSRODJSSVEJ-UHFFFAOYSA-N 0.000 description 2
- CSDQQAQKBAQLLE-UHFFFAOYSA-N 4-(4-chlorophenyl)-4,5,6,7-tetrahydrothieno[3,2-c]pyridine Chemical compound C1=CC(Cl)=CC=C1C1C(C=CS2)=C2CCN1 CSDQQAQKBAQLLE-UHFFFAOYSA-N 0.000 description 2
- 241001614291 Anoplistes Species 0.000 description 2
- 239000004705 High-molecular-weight polyethylene Substances 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000005234 alkyl aluminium group Chemical group 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- RAABOESOVLLHRU-UHFFFAOYSA-N diazene Chemical compound N=N RAABOESOVLLHRU-UHFFFAOYSA-N 0.000 description 2
- 229910000071 diazene Inorganic materials 0.000 description 2
- 230000003292 diminished effect Effects 0.000 description 2
- FUKUFMFMCZIRNT-UHFFFAOYSA-N hydron;methanol;chloride Chemical compound Cl.OC FUKUFMFMCZIRNT-UHFFFAOYSA-N 0.000 description 2
- NBVXSUQYWXRMNV-UHFFFAOYSA-N monofluoromethane Natural products FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 150000003222 pyridines Chemical class 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000010850 salt effect Methods 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 229960001866 silicon dioxide Drugs 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 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
- IYDMICQAKLQHLA-UHFFFAOYSA-N 1-phenylnaphthalene Chemical compound C1=CC=CC=C1C1=CC=CC2=CC=CC=C12 IYDMICQAKLQHLA-UHFFFAOYSA-N 0.000 description 1
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 1
- RUULIZSYTQWKFX-UHFFFAOYSA-N 8-phenylnaphthalen-1-amine Chemical compound C=12C(N)=CC=CC2=CC=CC=1C1=CC=CC=C1 RUULIZSYTQWKFX-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- CSDSSGBPEUDDEE-UHFFFAOYSA-N O=Cc1ncccc1 Chemical compound O=Cc1ncccc1 CSDSSGBPEUDDEE-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 230000010165 autogamy Effects 0.000 description 1
- OFWBDYUSWOSTGT-UHFFFAOYSA-N benzenesulfonic acid;toluene Chemical compound CC1=CC=CC=C1.OS(=O)(=O)C1=CC=CC=C1 OFWBDYUSWOSTGT-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000006392 deoxygenation reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000006471 dimerization reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- XVVLAOSRANDVDB-UHFFFAOYSA-N formic acid Chemical compound OC=O.OC=O XVVLAOSRANDVDB-UHFFFAOYSA-N 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 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
- 238000006384 oligomerization reaction Methods 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 150000004291 polyenes Chemical class 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000003335 steric effect Effects 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 238000010189 synthetic method Methods 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
- 230000007704 transition Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- CRUISIDZTHMGJT-UHFFFAOYSA-L zinc;dichloride;hydrochloride Chemical compound Cl.[Cl-].[Cl-].[Zn+2] CRUISIDZTHMGJT-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—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
- 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
- C07D213/44—Radicals substituted by doubly-bound oxygen, sulfur, or nitrogen atoms, or by two such atoms singly-bound to the same carbon atom
- C07D213/53—Nitrogen atoms
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
-
- 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
- C07F15/045—Nickel compounds without a metal-carbon linkage
-
- 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
-
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- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
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- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
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Abstract
The invention provides a pyridine imine compound and a preparation method thereof, a pyridine imine nickel catalyst and a preparation method thereof and polyolefin. The pyridine imine compound is shown in the formula (I), wherein R1, R2 and R3 are hydrogen or aryl or aryl alkyl respectively and independently; the number of carbon atoms of alkyl in aryl alkyl ranges from 1 to 6; R4, R5 and R6 are hydrogen or C1-C6 alkyl or nitryl or C1-C6 nitryl alkoxy or N,N'-dialkyl amino or trifluoromethyl respectively and independently; the number of carbon atoms of alkyl in N,N'-dialkyl amino ranges from 1 to 6. Compared with the prior art, the pyridine imine compound shown in the formula (I) has a large-steric-hindrance sandwich structure, the pyridine imine nickel catalyst of the structure shown in the formula (II) is formed with the pyridine imine compound as a ligand and also has a large-steric-hindrance sandwich structure, the catalyst has high thermal stability and activity on olefin polymerization, and therefore polyolefin with a controllable degree of branching and a high molecular weight can be generated. (Please see the description for the formula (I) and the formula (II).).
Description
Technical field
The invention belongs to catalyst field and field of polymer material preparing technology, particularly relate to pyridine imine compounds
And preparation method thereof, pyridine imine nickel class catalyst and preparation method thereof, polyolefin.
Background technology
The polyolefin character due to its excellence and the price of relative moderate, become in modern society's life is indispensable
A kind of material.At present, the yield of synthesis of polyolefins is the hugest, again due to the particularity of its synthetic method, so for
The research of its core catalyst occupies of paramount importance status.
Scan the history of olefinic polymerization industrial development, we it is found that technical progress invariably with new catalyst
Discovery and the successful exploitation of Technology the most relevant.During olefinic polymerization, catalyst often decides whole
The polymerization behavior of alkene, the particle shape producing polymer and the topological structure of polymer and performance.For olefinic polymerization
The development of catalyst makes the polymerization kind of alkene become more various, and performance is the most superior, has greatly widened the reality of polymer
Border application.
Since Ziegler-Na Ta catalyst is after the 1950's obtains Nobel Prize, development alkene is gathered by people
Close catalyst and pay a lot of effort.First it is found that metallic nickel is suppression for olefinic polymerization, Ziegler is in nineteen fifty-two
Finding in ethylene polymerisation process, the catalyst that the existence of nickel salts can make alkyl aluminum activate can only be by ethylene dimerization, and this is just
It it is famous nickel effect (Adv.Organomet.Chem.1968,61).Research through many decades makes this situation be changed
See, high molecular polyolefine material can be produced, such as now with a lot of catalyst based on nickel: various types of SHOP are catalyzed
Agent demonstrates highly active oligomerization ethylene growth end of the chain alkene or the polyethylene of high molecular
(Angew.Chem.Int.Ed.1978,17,466)(Angew.Chem.Int.Ed.2013,52,12492).Nineteen ninety-five
Brookhart finds diimine nickel catalyst, and this catalyst can be with Highh activity polyethylene, resulting polymers molecular weight up to number
100000 (J.Am.Chem.Soc., 1995,117,6414.), this polymerization catalyst activity and gained molecular weight of polyethylene can be with
Front transition catalyst compares favourably, and this is filled with strong strength energetically to late transition metal catalyzed ethylene polymerization.Grubbs etc. later
Even if people finds that neutral salicylic alidehyde imine Raney nickel can also synthesize high molecular polymerization in the case of adding polarity additive
Thing or copolymer (Science 2000,287,460).Research worker finds that again the sulfonic acid phosphine catalyst of some nickel is permissible recently
The Hi-fax (Organometallics, 2008,27,4821) that polymerizable molecular amount is thousands of.
Finding according to previous studies, High molecular weight polyethylene synthesis generally requires the Raney nickel of big steric hindrance, great majority
In the case of, steric hindrance is the biggest, and the molecular weight of the polyethylene that catalysis obtains is the biggest, the diimine nickel catalyst energy of such as some big steric hindrances
Enough highly active polymerizations are up to hundreds thousand of High molecular weight polyethylenes (J.Am.Chem.Soc.2013,135,16316).But it is right
For pyridine imine Raney nickel, result is the most interesting, improves steric hindrance and can not increase molecular weight of polyethylene, says reduction on the contrary
Molecular weight, a lot of regulation and control are many can not effectively increase molecular weight of polyethylene.
Summary of the invention
In view of this, the technical problem to be solved in the present invention be to provide pyridine imine compounds and preparation method thereof,
Pyridine imine class catalyst and preparation method thereof, polyolefin, this pyridine imine nickel class catalyst can catalyze and synthesize high-molecular-weight poly
Ethylene.
The invention provides a kind of pyridine imine compounds, as shown in formula (I):
Wherein, described R1、R2With R3It is each independently hydrogen, aryl or aryl alkyl；The carbon of alkyl in described aryl alkyl
Atomic number is 1～6；
Described R4、R5With R6It is each independently hydrogen, the alkyl of C1～C6, nitro, the alkoxyl of C1～C6, N, N-dioxane
Base amino or trifluoromethyl；The carbon number of the alkyl in described N, N-dialkyl amido is 1～6.
Preferably, described R1、R2With R3It is each independently hydrogen, aryl or alkyl diaryl；Alkane in described alkyl diaryl
The carbon number of base is 1～3.
Present invention also offers the preparation method of a kind of pyridine imine compounds, including:
Replacement naphthylamine derivative shown in formula (I-1) is reacted with the pyridine carbonyl based compound shown in formula (I-2), obtains formula
(I) the pyridine imine compounds shown in.
Wherein, described R1、R2With R3It is each independently hydrogen, aryl or aryl alkyl；The carbon of alkyl in described aryl alkyl
Atomic number is 1～6；
Described R4、R5With R6It is each independently hydrogen, the alkyl of C1～C6, nitro, the alkoxyl of C1～C6, N, N-dioxane
Base amino or trifluoromethyl；The carbon number of the alkyl in described N, N-dialkyl amido is 1～6.
Preferably, the replacement naphthylamine derivative shown in described formula (I-1) is prepared in accordance with the following methods:
S1) the picolinamide compound shown in formula (A) is deposited with silver salt in palladium salt with the fragrant iodine substituent shown in formula (B)
Heating is reacted under the conditions, obtains the compound shown in formula (C)；
S2) by the compound hydrolysis shown in described formula (C), the compound shown in formula (D) is obtained；
S3) compound shown in described formula (D) is converted into the replacement naphthylamine derivative shown in formula (I-1)；
Wherein, described R2With R3It is each independently hydrogen, aryl or aryl alkyl；In described aryl alkyl, the carbon of alkyl is former
Subnumber is 1～6；
Described R4、R5With R6It is each independently hydrogen, the alkyl of C1～C6, nitro, the alkoxyl of C1～C6, N, N-dioxane
Base amino or trifluoromethyl；The carbon number of the alkyl in described N, N-dialkyl amido is 1～6.
Present invention also offers a kind of pyridine imine nickel class catalyst, as shown in formula (II):
Wherein, described R1、R2With R3It is each independently hydrogen, aryl or aryl alkyl；The carbon of alkyl in described aryl alkyl
Atomic number is 1～6；
Described R4、R5With R6It is each independently hydrogen, the alkyl of C1～C6, nitro, the alkoxyl of C1～C6, N, N-dioxane
Base amino or trifluoromethyl；The carbon number of the alkyl in described N, N-dialkyl amido is 1～6；
Described X is halogen.
Present invention also offers the preparation method of a kind of pyridine imine nickel class catalyst, including:
Pyridine imine compounds shown in formula (I) is reacted with wrapping halogen-containing nickel precursor compound, obtains formula (II)
Shown pyridine imine nickel class catalyst；
Wherein, described R1、R2With R3It is each independently hydrogen, aryl or aryl alkyl；The carbon of alkyl in described aryl alkyl
Atomic number is 1～6；
Described R4、R5With R6It is each independently hydrogen, the alkyl of C1～C6, nitro, the alkoxyl of C1～C6, N, N-dioxane
Base amino or trifluoromethyl；The carbon number of the alkyl in described N, N-dialkyl amido is 1～6；
Described X is halogen.
Preferably, described bag halogen-containing nickel precursor compound is the glycol dimethyl ether coordination compound of nickel halogenide.
Present invention also offers a kind of polyolefin, pyridine imine nickel class catalyst obtain with promoter catalysis in olefine polymerization
Arrive.
Preferably, described alkene is low-carbon alkene；The methyl number that 1000 methylene that described polyolefin has are corresponding is
20～80；The molecular weight of described polyethylene is 20000～1000000g/mol, and fusing point is from amorphous state to 110 DEG C；
Described alkene is high-carbon straight chain terminal olefine；The methyl number that 1000 methylene that described polyolefin has are corresponding is 20
～70, molecular weight is 10000～30000g/mol, and fusing point is from amorphous state to 100 DEG C.
Present invention also offers a kind of polyolefinic preparation method, including:
Under pyridine imine nickel class catalyst is the catalyst effect with promoter, alkene is carried out polyreaction,
To polyolefin.
The invention provides a kind of pyridine imine compounds and preparation method thereof, pyridine imine nickel class catalyst and system thereof
Preparation Method, polyolefin, shown in described pyridine compounds and their such as formula (I), wherein, described R1、R2With R3It is each independently
Hydrogen, aryl or aryl alkyl；In described aryl alkyl, the carbon number of alkyl is 1～6；Described R4、R5With R6It is each independently
Hydrogen, the alkyl of C1～C6, nitro, the alkoxyl of C1～C6, N, N-dialkyl amido or trifluoromethyl；Described N, N-dialkyl amino
The carbon number of the alkyl in base is 1～6.Compared with prior art, the pyridine imine compounds shown in formula (I) has big position
Resistance sandwich structure, defines with it for part and has the pyridine imine nickel class catalyst of formula (II) structure and also have big steric hindrance three
Mingzhi's structure, this type of catalyst has the highest heat stability and an activity for the polymerization of alkene, thus can produce have controlled
The degree of branching and the higher polyolefin of molecular weight.
Experiment shows, polyolefin prepared by the present invention is the elastomer of the various degree of branching, and the degree of branching is that 1000 carbon are branched
Degree is 20～80.
Accompanying drawing explanation
Fig. 1 shows the monocrystalline knot of the big steric hindrance sandwich pyridine imine compounds of 3 preparations according to embodiments of the present invention
Structure schematic diagram, the 1st and the 2nd nitrogen-atoms during wherein N1 and N2 represents this ligand structure respectively；C1, C2 and C7 represent this part
The 1st, 2 and 7 carbon atom in structure, in this ligand structure, remaining carbon atom does not marks (all hydrogen atoms on figure here
Do not show) yet；
Fig. 2 is the polyethylene hydrogen nuclear magnetic resonance spectrogram of the embodiment of the present invention 9 preparation, and nuclear-magnetism detection uses Bruker
400MHz nuclear magnetic resonance analyser；
Fig. 3 is the polyethylene hydrogen nuclear magnetic resonance spectrogram of the embodiment of the present invention 10 preparation, and nuclear-magnetism detection uses Bruker
400MHz nuclear magnetic resonance analyser；
Fig. 4 is the polyethylene core magnetic resonance carbon spectrogram of the embodiment of the present invention 10 preparation, and nuclear-magnetism detection uses Bruker
400MHz nuclear magnetic resonance analyser.
Detailed description of the invention
Below in conjunction with the embodiment of the present invention, the technical scheme in the embodiment of the present invention is clearly and completely described,
Obviously, described embodiment is only a part of embodiment of the present invention rather than whole embodiments.Based in the present invention
Embodiment, the every other embodiment that those of ordinary skill in the art are obtained under not making creative work premise, all
Belong to the scope of protection of the invention.
The invention provides a kind of pyridine imine compounds, as shown in formula (I):
Wherein, described R1、R2With R3It is each independently hydrogen, aryl or aryl alkyl, preferably hydrogen, unsubstituted aryl
Or aryl alkyl, more preferably hydrogen, the aryl of unsubstituted C5～C10 or alkyl diaryl, it is further preferably hydrogen, phenyl or two virtues
Ylmethyl；In described aryl alkyl, the carbon number of alkyl is 1～6, preferably 1～4, more preferably 1～3, be further preferably 1～
2, most preferably 1.
Described R4、R5With R6It is each independently hydrogen, the alkyl of C1～C6, nitro, the alkoxyl of C1～C6, N, N-dioxane
Base amino or trifluoromethyl, preferably hydrogen, the alkyl of C1～C4, nitro, the alkoxyl of C1～C4, N, N-dialkyl amido or three
Methyl fluoride, more preferably hydrogen, the alkyl of C1～C2, nitro, the alkoxyl of C1～C2, N, N-dialkyl amido or trifluoromethyl；
The carbon number of the alkyl in described N, N-dialkyl amido is 1～6, preferably 1～4, more preferably 1～2, is further preferably 1.
In some embodiments that the present invention provides, described pyridine imine compounds is preferably as shown in formula (1)；At this
In some embodiments of bright offer, described pyridine imine compounds is preferably as shown in formula (2)；Some provided in the present invention are real
Executing in example, described pyridine imine compounds is preferably as shown in formula (3).
Present invention also offers the preparation method of a kind of above-mentioned pyridine imine compounds, including:
Replacement naphthylamine derivative shown in formula (I-1) is reacted with the pyridine carbonyl based compound shown in formula (I-2), obtains formula
(I) the pyridine imine compounds shown in.
Wherein, described R1、R2With R3It is each independently hydrogen, aryl or aryl alkyl；The carbon of alkyl in described aryl alkyl
Atomic number is 1～6；
Described R4、R5With R6It is each independently hydrogen, the alkyl of C1～C6, nitro, the alkoxyl of C1～C6, N, N-dioxane
Base amino or trifluoromethyl；The carbon number of the alkyl in described N, N-dialkyl amido is 1～6.
Wherein, described R1、R2、R3、R4、R5With R6The most same as above, do not repeat them here.
In the present invention, the replacement naphthylamine derivative shown in described formula (I-1) is prepared the most in accordance with the following methods:
S1) the picolinamide compound shown in formula (A) is deposited with silver salt in palladium salt with the fragrant iodine substituent shown in formula (B)
Heating is reacted under the conditions, obtains the compound shown in formula (C)；
S2) by the compound hydrolysis shown in described formula (C), the compound shown in formula (D) is obtained；
S3) compound shown in described formula (D) is converted into the replacement naphthylamine derivative shown in formula (I-1)；
Picolinamide compound shown in formula (A) is existed with silver salt in palladium salt with the fragrant iodine substituent shown in formula (B)
Under conditions of heat and react, obtain the compound shown in formula (C).Wherein, described palladium salt is well known to those skilled in the art
Palladium salt, there is no special restriction, the present invention is preferably the one in Palladous chloride., palladium and tetra-triphenylphosphine palladium or
Multiple；The silver salt that described silver salt is well known to those skilled in the art, there is no special restriction, is preferably acetic acid in the present invention
Silver；The temperature of described reaction is preferably 120 DEG C～160 DEG C；The time of described reaction be preferably 12～36h, more preferably 15～
30h, is further preferably 20～25h.
By the compound hydrolysis shown in described formula (C), obtain the compound shown in formula (D)；Described hydrolysis is preferably in alkalescence
Under the conditions of carry out；The alkaline condition that described alkalescence condition is well known to those skilled in the art, there is no special restriction, this
Bright for ethanolic sodium hydroxide solution.
Above-mentioned course of reaction is as follows:
Compound shown in described formula (D) is converted into the replacement naphthylamine derivative shown in formula (I-1), in the present invention this
Step can be realized by following two method:
Method one, works as R2With R3During for aryl alkyl: under lewis acid effect, by the compound shown in described formula (D) with
Compound mixing shown in formula (E), reacting by heating, obtain the replacement naphthylamine derivative shown in formula (I-1), reaction scheme is as follows:
Wherein, described R7With R8For aryl alkyl group in addition to alkyl；Described n is 1～6, and preferably 1～4 are more excellent
Elect 1～3 as, be further preferably 1～2, most preferably 1.
The lewis acid that described lewis acid is well known to those skilled in the art, there is no special restriction, the present invention
In be preferably one or more in lithium perchlorate, zinc chloride hydrochloric acid complex and p-methyl benzenesulfonic acid；Described lewis acid with
The ratio of the compound shown in described formula (D) is preferably (0.5～2) mg:1mmol.
Under lewis acid effect, the compound shown in described formula (D) is mixed with the compound shown in formula (E), heating
Reaction；The temperature of described reaction is preferably 80 DEG C～160 DEG C, and more preferably 100 DEG C～160 DEG C are further preferably 120 DEG C～160
℃；The time of described reaction is preferably 0.5～24h, and more preferably 0.5～10h, be further preferably 0.5～5h, most preferably 0.5
～2h；In the present invention, it is preferred to first mixed with the compound shown in formula (E) by the compound shown in formula (D), it is heated to reaction temperature
Degree, then adds lewis acid.
After reaction terminates, preferably it is purified post processing；The described method processed after purification is that those skilled in the art are ripe
The method known, there is no special restriction, after preferably reaction terminates in the present invention, is cooled to room temperature, is dissolved in organic solvent, water
Washing, be dried, after filtration, concentrate, again with methanol solution washs, and obtains the replacement naphthylamine derivative shown in formula (I-1)；Described organic
The organic solvent that solvent is well known to those skilled in the art, there is no special restriction, is preferably dichloromethane in the present invention.
Method two: the compound shown in described formula (D) is reacted with brominated reagent, obtains the compound shown in formula (F)；So
After under the effect of palladium salt and alkali, the compound shown in described formula (F) is reacted with the compound shown in formula (G), obtains formula (I-
1) the replacement naphthylamine derivative shown in, reaction scheme is as follows:
Wherein, described R9For hydrogen, the alkyl of C1～C6, nitro, the alkoxyl of C1～C6, N, N-dialkyl amido or trifluoro
Methyl.
Compound shown in formula (D) is reacted with brominated reagent, obtains the compound shown in formula (F).Described brominated reagent
The brominated reagent being well known to those skilled in the art；Described reaction is carried out the most in organic solvent；Described organic solvent
The organic solvent being well known to those skilled in the art, there is no special restriction, is preferably in toluene and ethanol in the present invention
One or more.
Then under the palladium salt effect with alkali, by anti-with the compound shown in formula (G) for the compound shown in described formula (F)
Should, obtain the replacement naphthylamine derivative shown in formula (I-1).Described palladium salt is preferably Palladous chloride., palladium and tetra-triphenylphosphine palladium
In one or more；The alkali that described alkali is well known to those skilled in the art, there is no special restriction, in the present invention preferably
For sodium carbonate；It is anti-that compound shown in described formula (F) and the compound shown in formula (G) carry out condensation under the palladium salt effect with alkali
Should；The temperature of described reaction is preferably 100 DEG C～140 DEG C；The described response time be preferably 12～24h, more preferably 12～
20h, is further preferably 12～15h.
Replacement naphthylamine derivative shown in formula (I-1) is reacted with the pyridine carbonyl based compound shown in formula (I-2)；At this
In bright, this reaction is carried out the most in organic solvent, and the organic solvent that described organic solvent is well known to those skilled in the art is i.e.
Can, there is no special restriction, the present invention is preferably toluene and one or more in ethanol；Further, this reaction further preferably exists
Carry out under middle acid condition；When reaction condition is acid, it is preferably added to toluene benzenesulfonic acid.The temperature of described reaction is preferably
100 DEG C～140 DEG C, more preferably carry out under conditions of backflow；The time of described reaction is preferably 12～24h, more preferably 14
～24h, it is further preferably 18～24h.
After reaction terminates, it is preferably added to methanol dilution, after filtration, recrystallization, obtain the pyridine imine class shown in formula (I)
Compound.Solvent used by described recrystallization is preferably dichloromethane and normal hexane.
Present invention also offers a kind of pyridine imine nickel class catalyst, as shown in formula (II):
Wherein, described R1、R2With R3It is each independently hydrogen, aryl or aryl alkyl, preferably hydrogen, unsubstituted aryl
Or aryl alkyl, more preferably hydrogen, the aryl of unsubstituted C5～C10 or alkyl diaryl, it is further preferably hydrogen, phenyl or two virtues
Ylmethyl；In described aryl alkyl, the carbon number of alkyl is 1～6, preferably 1～4, more preferably 1～3, be further preferably 1～
2, most preferably 1.
Described R4、R5With R6It is each independently hydrogen, the alkyl of C1～C6, nitro, the alkoxyl of C1～C6, N, N-dioxane
Base amino or trifluoromethyl, preferably hydrogen, the alkyl of C1～C4, nitro, the alkoxyl of C1～C4, N, N-dialkyl amido or three
Methyl fluoride, more preferably hydrogen, the alkyl of C1～C2, nitro, the alkoxyl of C1～C2, N, N-dialkyl amido or trifluoromethyl；
The carbon number of the alkyl in described N, N-dialkyl amido is 1～6, preferably 1～4, more preferably 1～2, is further preferably 1.
Described X is halogen, preferably Cl or Br, more preferably Br.
In some embodiments that the present invention provides, described pyridine imine nickel class catalyst is preferably as shown in formula (4)；At this
In some embodiments that invention provides, described pyridine imine nickel class catalyst is preferably as shown in formula (5)；The present invention provide another
In some embodiments, described pyridine imine nickel class catalyst is preferably as shown in formula (6).
Present invention also offers the preparation method of a kind of above-mentioned pyridine imine nickel class catalyst, including: shown in formula (I)
Pyridine imine compounds reacts with wrapping halogen-containing nickel precursor compound, obtains the pyridine imine nickel class catalysis shown in formula (II)
Agent.
Wherein, described bag halogen-containing nickel precursor compound is preferably the glycol dimethyl ether coordination compound of nickel halogenide, at this
Invention can be designated as DMENiX2, wherein DME is expressed as glycol dimethyl ether, and X is halogen；In the present invention, halogen is comprised described in
Nickel precursor compound be more preferably DMENiCl2Or DMENiBr2。
Pyridine imine compounds shown in formula (I) is reacted with wrapping halogen-containing nickel precursor compound.Should in the present invention
Reaction is carried out the most in organic solvent；The organic solvent that described organic solvent is well known to those skilled in the art, there is no
Special restriction, is preferably dichloromethane in the present invention；Described reaction is carried out the most at ambient temperature.
After reaction terminates, preferably wash with ether, obtain the pyridine imine nickel class catalyst shown in formula (II) after drying.
Present invention also offers a kind of polyolefin, above-mentioned pyridine imine nickel class catalyst gather with promoter catalyzed alkene
Conjunction obtains.
The promoter that wherein said promoter is well known to those skilled in the art, there is no special restriction, this
Invention is preferably alkyl aluminum class promoter, more preferably MAO and one or more in diethyl aluminum chloride.
When described alkene is low-carbon alkene, during such as one or more in ethylene, propylene and butylene, the polyene that polymerization obtains
The methyl number that 1000 methylene that hydrocarbon has are corresponding is 20～80, preferably 25～75, more preferably 25～71, then
It is preferably 35～70, most preferably 45～70；The molecular weight of described polyethylene is 20000～1000000g/mol, preferably
It is 20000～500000g/mol, is further preferably 20000～200000g/mol, be further preferably 50000～200000g/mol；Institute
Stating fusing point from amorphous state to 110 DEG C, preferably 20 DEG C～110 DEG C, be further preferably 20 DEG C～80 DEG C.
When described alkene is high-carbon straight chain terminal olefine, during such as 1-decene, 1000 Asias that the polyolefin that polymerization obtains has
The methyl number that methyl is corresponding is 20～70, preferably 30～60, more preferably 30～50, is further preferably 30～40；
Molecular weight is 10000～30000g/mol, preferably 15000～25000g/mol, is further preferably 20000～25000g/mol；
Described fusing point is from amorphous state to 100 DEG C, and preferably 20 DEG C～110 DEG C, be further preferably 50 DEG C～100 DEG C.
Present invention also offers a kind of polyolefinic preparation method, be included in above-mentioned pyridine imine nickel class catalyst for catalysis
Alkene, with under the effect of promoter, is carried out polyreaction, obtains polyolefin by agent.
The pressure of described alkene is preferably 1～10 atmospheric pressure；The temperature of described polyreaction is preferably 20 DEG C～80 DEG C,
More preferably 20 DEG C～60 DEG C, be further preferably 20 DEG C～40 DEG C.
The pyridine imine compounds shown in formula (I) that the present invention provides has big steric hindrance sandwich structure, with it for joining
Body defines to be had the pyridine imine nickel class catalyst of formula (II) structure and also has big steric hindrance sandwich structure, this type of catalyst pair
Polymerization in alkene has the highest heat stability and activity, thus can produce and have the controlled degree of branching and higher the gathering of molecular weight
Alkene.
In order to further illustrate the present invention, the pyridine imine compounds that the present invention provided below in conjunction with embodiment and
Preparation method, pyridine imine class catalyst and preparation method thereof, polyolefin are described in detail.
Reagent used in following example is commercially available.
The synthesis of coordination compound, polymerization process is all to carry out under anhydrous and oxygen-free, and the material of all sensitivities leaves glove box in
In, all solvents all pass through strict being dried and remove water, and ethylene gas is by except water deoxygenation pillar purification, being not particularly illustrated, all
Raw material buy after directly use.
Silicagel column separates with the silica gel of 200-300 mesh, nuclear-magnetism detection Bruker 400MHz nuclear-magnetism instrument.Elementary analysis by
China Science & Technology University's physics and chemistry center measures.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+) measures.Single crystal X diffraction
Analyze and use Oxford Diffraction Gemini S Ultra CCD single crystal diffraction instrument, Cu K α
Room temperature radiates.The reagent raw material used in embodiment, is the most all purchased from Aldrich (analytical pure), and
And without specializing, be all unprocessed direct use.
Dichloromethane (AR, dichloromethane), Beijing Chemical Plant,At N after molecular sieve is predrying2Add under protection
Enter calcium hydride backflow, with front steaming；
Toluene (AR, toluene), Beijing Chemical Plant,At N after molecular sieve is predrying2Protection lower addition metallic sodium returns
Stream, with front steaming；
Hexamethylene (AR, cyclohexane), Beijing Chemical Plant,At N after molecular sieve is predrying2Metal is added under protection
Sodium refluxes, with front steaming；
O-dichlorohenzene (AR, o-dichlorobenzene), Beijing Chemical Plant,After molecular sieve is predrying under N2 protects
Add calcium hydride backflow, with front steaming；
Formic acid (formic acid), AR (88%), Beijing Chemical Plant, directly use；
Ethylene (ethylene), polymer grade, unprocessed direct use；High-purity N2
(high-purity nitrogen), unprocessed direct use；
Ethanol (ethanol), analytical pure, Tianjin reagent two factory, directly use；
Methanol (methanol), industrial goods, Tianjin reagent two factory, directly use；
Hydrochloric acid-methanol solution (hydrochloric acid-methanol solution), 2%, autogamy；
All solvents are analytical reagent, unprocessed direct use.
Embodiment 1:2,4-bis-(benzhydryl)-8-phenyl-1-naphthylamine
8-phenyl-1-naphthylamine 20 mMs and benzhydrol 40 mMs, heating is added in the pressure flask of 150 milliliters
To 120 degree, adding the concentrated hydrochloric acid solution 10 mMs of anhydrous zinc chloride, reaction is bubbled, is heated to 160 degree；160
After degree reaction half an hour, stopped reaction, it is cooled to room temperature, is dissolved in 200 milliliters of dichloromethane solutions, with 3 water taking advantage of 100 milliliters
Washing, anhydrous magnesium sulfate is dried.Filter, be concentrated into 20 milliliters, in product, add the methanol of 200 milliliters, take advantage of 100 milliliters with 3
Methanol washing, obtaining white powder solid is 2,4-bis-(benzhydryl)-8-phenyl-1-naphthylamine, vacuum drying, obtain solid
10.49g, productivity is 95%, and purity is more than 99%.
Nuclear magnetic resonance, NMR 2 to obtaining in embodiment 1,4-bis-(benzhydryl)-8-phenyl-1-naphthylamine are utilized to be analyzed,
Obtain result1H NMR(400MHz,CDCl3): δ 7.94 (d, J=7.8Hz, 1H, Ar-H), 7.49 6.75 (m, 27H, Ar-H),
6.40(s,1H,Ar-H),6.09(s,1H,CHPh2),5.51(s,1H,CHPh2),3.74(s,2H,N-H)；13C NMR
(101MHz,CDCl3):δ144.27,143.75,142.56,139.14,138.53,132.74,131.20,129.52,
129.43,129.36,128.90,128.51,128.38,128.29,127.53,126.53,126.10,124.69,124.51,
123.74,122.00,53.41(CHPh2),52.26(CHPh2)。
To 2 obtained in embodiment 1, the molecular weight of 4-bis-(benzhydryl)-8-phenyl-1-naphthylamine is analyzed, and obtains
Result HRMS (m/z): calcd for C42H33N:[M+H]+552.2686,found:552.2671。
Embodiment 2:2,4-bis-(benzhydryl)-8-p-methylphenyl-naphthalidine
8-p-methylphenyl-naphthalidine 20 mMs and benzhydrol 40 mmoles is added in the pressure flask of 150 milliliters
You, be heated to 120 degree, adds the concentrated hydrochloric acid solution 10 mMs of anhydrous zinc chloride, and reaction is bubbled, is heated to 160
Degree, after 160 degree of reaction half an hours, stopped reaction, it is cooled to room temperature, is dissolved in 200 milliliters of dichloromethane solutions.100 are taken advantage of with 3
The water washing of milliliter, anhydrous magnesium sulfate is dried.Filter, be concentrated into 20 milliliters, in product, add the methanol of 200 milliliters, take advantage of with 3
The methanol washing of 100 milliliters, obtaining white powder solid is 2,4-bis-(benzhydryl)-8-p-methylphenyl-naphthalidine, vacuum
Being dried, obtain solid 10.75g, productivity is 95%, and purity is more than 99%.
Utilize nuclear magnetic resonance, NMR that 2,4-bis-(the benzhydryl)-8-p-methylphenyl-naphthalidine obtained in embodiment 2 is carried out
Analyze, obtain result1H NMR(400MHz,CDCl3): δ 7.92 (d, J=8.3Hz, 1H, Ar-H), 7.36 7.01 (m, 18H,
Ar-H), 6.93 (dd, J=21.7,6.4Hz, 8H, Ar-H), 6.37 (s, 1H, Ar-H), 6.08 (s, 1H, CHPh2),5.48(s,
1H,CHPh2),3.69(s,2H,N-H),2.34(s,3H,CH3)；13C NMR(101MHz,CDCl3):δ144.18,142.51,
140.80,139.87,138.46,136.95,132.56,131.00,129.34,129.23,129.05,128.80,128.75,
128.61,128.31,128.09,126.31,125.88,124.35,124.28,122.79,121.80,53.22(CHPh2),
52.10(CHPh2),21.14(CH3)。
The molecular weight of 2,4-bis-(the benzhydryl)-8-p-methylphenyl-naphthalidine obtained in embodiment 2 is carried out point
Analysis, obtains result HRMS (m/z): calcd for C43H35N:[M+H]+566.2842,found:566.2825。
Embodiment 3:2,4-bis-(benzhydryl)-8-is to phenyl-naphthalidine
8-is added to phenyl-naphthalidine 20 mMs and benzhydrol 40 mmoles in the pressure flask of 150 milliliters
You, be heated to 120 degree, adds the concentrated hydrochloric acid solution 10 mMs of anhydrous zinc chloride, and reaction is bubbled, is heated to 160
Degree.After 160 degree of reaction half an hours, stopped reaction, it is cooled to room temperature, is dissolved in 200 milliliters of dichloromethane solutions, takes advantage of 100 with 3
The water washing of milliliter, anhydrous magnesium sulfate is dried.Filter, be concentrated into 20 milliliters, in product, add the methanol of 200 milliliters, take advantage of with 3
The methanol washing of 100 milliliters, obtaining white powder solid is 2, and 4-bis-(benzhydryl)-8-is to phenyl-naphthalidine, vacuum
Being dried, obtain solid 12.06g, productivity is 96%, and purity is more than 99%.
Utilize nuclear magnetic resonance, NMR that phenyl-naphthalidine is carried out by 2,4-bis-(the benzhydryl)-8-obtained in embodiment 3
Analyze, obtain result1H NMR(400MHz,CDCl3) δ 7.90 (d, J=8.5Hz, 1H, Ar-H), 7.64 7.53 (m, 4H, Ar-
H), 7.47 7.34 (m, 4H, Ar-H), 7.33 7.20 (m, 2H, Ar-H), 7.10 (m, 13H, Ar-H), 6.89 (dd, J=
24.3,6.3Hz,8H,Ar-H),6.30(s,1H,Ar-H),6.01(s,1H,CHPh2),5.38(s,1H,CHPh2),3.66(s,
2H,N-H)；13C NMR(101MHz,CDCl3)δ145.47,143.87,141.58,141.13,141.13,139.57,
133.90,132.57,131.12,130.80,130.70,130.35,130.12,129.83,129.61,129.01,128.40,
128.15,127.86,127.44,125.82,124.31,122.93,54.51(CHPh2),53.56(CHPh2)。
The molecular weight of phenyl-naphthalidine is carried out by 2,4-bis-(the benzhydryl)-8-obtained in embodiment 3 point
Analysis, obtains result HRMS (m/z): calcd for C48H37N:[M+H]+628.2999,found:628.2994。
Embodiment 4:2-(2,4-bis-(benzhydryl)-8-phenylnaphthalene imino group) methylene pyridine (3)
The pyridine aldehydes of 30 mMs, the 2 of 10 mMs, 4-bis-(benzhydryl)-8-phenyl-1-naphthylamine and catalytic amount right
Toluenesulfonic acid 10 milligrams is the reflux in toluene 24 hours of 150 milliliters.Point board monitoring reaction terminates, and reaction dissolvent has been threaded to yellow
Solid separates out.Add 300 ml methanol dilutions, be filtrated to get yellow solid, dichloromethane and normal hexane and be recrystallized to give pure
Product, for 2-(2,4-bis-(benzhydryl)-8-phenylnaphthalene imino group) methylene pyridine, vacuum drying, obtains solid 5.00g, produces
Rate is 78%, and purity is more than 99%.
Utilize nuclear magnetic resonance, NMR 2-(2,4-bis-(the benzhydryl)-8-phenylnaphthalene imino group) methylene to obtaining in embodiment 4
Yl pyridines is analyzed, and obtains result1H NMR(400MHz,CDCl3): δ 8.40 (d, J=4.6Hz, 1H ,-N=C-H), 8.03
(d, J=8.5Hz, 1H, Ar-H), 7.57 7.41 (m, 2H, Ar-H), 7.35 (t, J=7.8Hz, 1H, Ar-H), 7.24 7.11
(m, 11H, Ar-H), 7.08 6.90 (m, 12H, Ar-H), 6.82 (m, 4H, Ar-H), 6.71 (s, 1H, Ar-H), 6.66 (t, J=
7.3Hz,1H,Ar-H),6.22(s,1H,CHPh2),5.59(s,1H,CHPh2)；13C NMR(101MHz,CDCl3):δ164.08
(N=CH), 153.85,148.65,146.61,145.12,143.86,143.76,139.87,135.57,135.38,
132.48,130.66,130.01,129.53,129.39,129.23,129.02,128.34,128.01,127.61,126.27,
125.94,125.33,124.97,124.68,124.50,123.95,121.31,53.47(CHPh2),51.63(CHPh2)。
Molecule to 2-(2,4-bis-(the benzhydryl)-8-phenylnaphthalene imino group) methylene pyridine obtained in embodiment 4
Amount is analyzed, and obtains result HRMS (m/z): calcd for C48H36N2:[M+H]+641.2951,found:641.2950。
Embodiment 5:2-(2,4-bis-(benzhydryl)-8-p-methylphenyl naphthalene imino group) methylene pyridine (2)
The pyridine aldehydes of 30 mMs, the 2 of 10 mMs, 4-bis-(benzhydryl)-8-p-methylphenyl-naphthalidine and catalysis
The p-methyl benzenesulfonic acid 10 milligrams of amount is the reflux in toluene 24 hours of 150 milliliters.Point board monitoring reaction terminates, and reaction dissolvent is threaded to
Yellow solid is had to separate out.Add 300 ml methanol dilutions, be filtrated to get yellow solid, dichloromethane and normal hexane recrystallization and obtain
To pure product, for 2-(2,4-bis-(benzhydryl)-8-p-methylphenyl naphthalene imino group) methylene pyridine (L2), vacuum is done
Dry, obtain solid 5.70g, productivity is 87%, and purity is more than 99%.
Utilize nuclear magnetic resonance, NMR 2-(2,4-bis-(the benzhydryl)-8-p-methylphenyl naphthalene imido to obtaining in embodiment 5
Base) methylene pyridine is analyzed, and obtains result1H NMR(400MHz,CDCl3): δ 8.44 (d, J=4.5Hz, 1H ,-N=C-
H), 8.02 (d, J=8.4Hz, 1H, Ar-H), 7.61 7.46 (m, 2H, Ar-H), 7.39 7.32 (m, 1H, Ar-H), 7.29
7.11(m,9H,Ar-H),7.07–6.96(m,12H,Ar-H),6.87–6.74(m,6H,Ar-H),6.69(s,1H,Ar-H),
6.21(s,1H,CHPh2),5.58(s,1H,CHPh2),1.91(s,3H,CH3)；13C NMR(101MHz,CDCl3):δ163.76
(N=CH), 153.92,148.75,146.57,143.84,143.73,142.18,139.81,135.48,135.22,
135.18,132.42,130.54,129.82,129.51,129.37,129.21,128.86,128.38,128.32,128.19,
127.99,126.25,125.91,124.98,124.54,124.49,123.80,121.33,53.42(CHPh2),51.57
(CHPh2),20.82(CH3)。
To 2-(2,4-bis-(the benzhydryl)-8-p-methylphenyl naphthalene imino group) methylene pyridine obtained in embodiment 5
Molecular weight be analyzed, obtain result HRMS (m/z): calcd for C49H38N2:[M+H]+655.3108,found:
655.3098。
Embodiment 6:2-(2,4-bis-(benzhydryl)-8-is to phenyl naphthalene imino group) methylene pyridine (3)
The pyridine aldehydes of 30 mMs, the 2 of 10 mMs, 4-bis-(benzhydryl)-8-is to phenyl-naphthalidine and catalysis
The p-methyl benzenesulfonic acid 10 milligrams of amount is the reflux in toluene 24 hours of 150 milliliters.Point board monitoring reaction terminates, and reaction dissolvent is threaded to
Yellow solid is had to separate out.Add 300 ml methanol dilutions, be filtrated to get yellow solid, dichloromethane and normal hexane recrystallization and obtain
It is 2-(2,4-bis-(benzhydryl)-8-is to phenyl naphthalene imino group) methylene pyridine to pure product, vacuum drying, must consolidate
Body 5.45g, productivity is 76%, and purity is more than 99%.
(2,4-bis-(benzhydryl)-8-is to phenyl naphthalene imido to the 2-obtained in embodiment 6 to utilize nuclear magnetic resonance, NMR
Base) methylene pyridine is analyzed, and obtains result1H NMR(400MHz,CDCl3): δ 8.36 (d, J=3.5Hz, 1H ,-N=C-
H), 8.05 (d, J=8.3Hz, 1H, Ar-H), 7.48 (d, J=7.7Hz, 1H, Ar-H), 7.40 7.09 (m, 20H, Ar-H),
7.10–6.94(m,11H,Ar-H),6.82(m,4H,Ar-H),6.73(s,1H,Ar-H),6.23(s,1H,CHPh2),5.60
(s,1H,CHPh2)；13C NMR(101MHz,CDCl3): δ 163.08 (N=CH), 152.83,147.72,145.56,143.18,
142.77,142.66,139.68,138.37,137.45,134.55,134.40,131.44,129.63,128.85,128.46,
128.32,128.28,127.34,127.27,126.94,125.91,125.83,125.29,125.20,124.88,123.94,
123.58,123.48,122.97,119.95,52.39(CHPh2),50.57(CHPh2)。
To 2-(2,4-bis-(benzhydryl)-8-is to the phenyl naphthalene imino group) methylene pyridine obtained in embodiment 6
Molecular weight be analyzed, obtain result HRMS (m/z): calcd for C4H40N2:[M+H]+717.3264,found:
717.3261。
Embodiment 7:2-(2,4-bis-(benzhydryl)-8-phenylnaphthalene imino group) methylene pyridine Nickel Bromide (II-1)
1,0.5 mM of (DME) NiBr of ligand L of 0.53 mM is added in the Schlenk flask of 50 milliliters2With 20
Milliliter dichloromethane.Red reactant mixture is stirred at room temperature one day, stops stirring and can separate out red brown solid.Filter, with 8
The ether of milliliter washs three times, is vacuum dried 12 hours, obtains solid 2-(2,4-bis-(benzhydryl)-8-phenylnaphthalene imido
Base) methylene pyridine Nickel Bromide 412mg, productivity is 96%, and purity is more than 99%.
To 2-(2,4-bis-(benzhydryl)-8-phenylnaphthalene imino group) the methylene pyridine dibrominated obtained in embodiment 7
Nickel carries out elementary analysis, obtains result Anal.Calcd for C48H36Br2N2Ni:C,67.09；H,4.22；N,
3.26.Found:C,66.71；H,4.40；N,3.26.
To 2-(2,4-bis-(benzhydryl)-8-phenylnaphthalene imino group) the methylene pyridine dibrominated obtained in embodiment 7
Nickel is analyzed, and obtains result: MALDI-TOF:m/z 777.0658 [M-Br]+；779.1352[M–Br+2H]+。
Embodiment 8:2-(2,4-bis-(benzhydryl)-8-p-methylphenyl naphthalene imino group) methylene pyridine Nickel Bromide
(II-2)
2,0.5 mM of (DME) NiBr of ligand L of 0.53 mM is added in the Schlenk flask of 50 milliliters2With 20
Milliliter dichloromethane.Red reactant mixture is stirred at room temperature one day, stops stirring and can separate out red brown solid.Filter, with 8
The ether of milliliter washs three times, is vacuum dried 12 hours.Obtain solid 2-(2,4-bis-(benzhydryl)-8-p-methylphenyl
Naphthalene imino group) methylene pyridine Nickel Bromide 415mg, productivity is 95%, and purity is more than 99%.
To 2-(2,4-bis-(the benzhydryl)-8-p-methylphenyl naphthalene imino group) methylene pyridine obtained in embodiment 8
Nickel Bromide carries out elementary analysis, obtains result Anal.Calcd for C49H38Br2N2Ni:C,67.39；H,4.39；N,
3.21.Found:C,66.90；H,4.51；N,3.17.
To 2-(2,4-bis-(the benzhydryl)-8-p-methylphenyl naphthalene imino group) methylene pyridine obtained in embodiment 8
Nickel Bromide is analyzed, and obtains result MALDI-TOF:m/z 791.0581 [M-Br]+；793.1018[M–Br+2H]+。
Embodiment 9:2-(2,4-bis-(benzhydryl)-8-is to phenyl naphthalene imino group) methylene pyridine Nickel Bromide
(II-3)
3,0.5 mM of (DME) NiBr of ligand L of 0.53 mM is added in the Schlenk flask of 50 milliliters2With 20
Milliliter dichloromethane.Red reactant mixture is stirred at room temperature one day, stops stirring and can separate out red brown solid.Filter, with 8
The ether of milliliter washs three times, is vacuum dried 12 hours, and (2,4-bis-(benzhydryl)-8-is to phenyl to obtain solid 2-
Naphthalene imino group) methylene pyridine Nickel Bromide 430mg, productivity is 92%, and purity is more than 99%.
Utilize nuclear magnetic resonance, NMR that the polyethylene obtained in embodiment 9 is analyzed, obtain its hydrogen nuclear magnetic resonance spectrogram, such as figure
Shown in 2.
To 2-(2,4-bis-(benzhydryl)-8-is to the phenyl naphthalene imino group) methylene pyridine obtained in embodiment 9
Nickel Bromide carries out elementary analysis, obtains result Anal.Calcd for C52H340Br2N2Ni.CH2Cl2:C,64.74；H,
4.15；N,2.75.
To 2-(2,4-bis-(benzhydryl)-8-is to the phenyl naphthalene imino group) methylene pyridine obtained in embodiment 9
Nickel Bromide is analyzed, and obtains result Found:C, and 64.35；H,4.43；N,2.71.MALDI-TOF:m/z 853.0963
[M-Br]+；855.1408[M–Br+2H]+。
Embodiment 10: the application of catalyzed ethylene polymerization
In glove box, under nitrogen atmosphere, to 350mL autoclave (with magnetic stirring apparatus, oil bath heater and temperature
Degree meter) the toluene of middle addition 48mL, 116 milligrams of MAO (MAO).Then liquid nitrogen freezing evacuation, is filled with ethylene past
Return three times, reaction temperature be adjusted to 20 DEG C, and inject wherein by 1.7mg embodiment 8 preparation Raney nickel be dissolved in 2 milli
Rise the solution in chloroform.Close valve, after regulation ethylene pressure is 9 atmospheric pressure, react 30 minutes.Stopped reaction, opens reaction
Still, is added thereto to the methanolic HCl solution of 5% (volume ratio) to precipitate solid, and filtration under diminished pressure obtains this solid, and with pure
Methanol washs three times, and air is dried, and obtains 0.76 gram of polyethylene elastomer, and 1000 Asias that this branched polyethylene has
The methyl number that methyl is corresponding is 49, molecular weight 141000g/mol, and fusing point is 71 DEG C.
Utilize nuclear magnetic resonance, NMR that the polyethylene obtained in embodiment 10 is analyzed, obtain its hydrogen nuclear magnetic resonance spectrogram, as
Shown in Fig. 3；Obtain its carbon-13 nmr spectra figure, as shown in Figure 4.From the figure 3, it may be seen that gained polyethylene has the higher degree of branching.
Embodiment 11: be catalyzed the application of long end of the chain alkene polymerization
In glove box, under nitrogen atmosphere, in the Schlenk flask of 50 milliliters, 2.2 milliliters 0.9 mole every liter is added
Diethyl aluminum chloride, in 8.7 milligrams of embodiments 8, the Raney nickel of preparation is dissolved in the solution in 2 milliliters of chloroforms, 3.79 milliliters of last of the ten Heavenly stems
Alkene, 12 milliliters of toluene, room temperature reaction 3 hours.It is added thereto to the methanolic HCl solution of 5% (volume ratio) to precipitate solid,
Filtration under diminished pressure obtains this solid, and washs three times with pure methanol, and air is dried, and obtains 0.43 gram of polyethylene elastomer, and
The methyl number that 1000 methylene that this branched polymer has are corresponding is 32, and molecular weight 21000g/mol, fusing point is 89
℃.Fig. 3 and 4 respectively illustrates the nucleus magnetic hydrogen spectrum of the polymer of 8 preparations according to embodiments of the present invention from which it can be seen that gained
Polymer branching degree is relatively low, and the linearity is higher.
Additionally, table 1 shows different steric effect catalyst prepared by embodiment of the present invention polymerization at different temperatures
Effect.
The vinyl polymerization a of table 1 pyridine imine nickel class catalyst
Note:aCondition: 2 mMs of catalyst, 1000 equivalent promoters, 5mL chloroform, 45mL toluene, 8 atmospheric pressure ethylene,
30min；bActivity (Act.)=105g/(molNi·h)；cMolecular weight uses polystyrene to pass through GPC at trichloro-benzenes as standard
As solvent 150 DEG C of mensurationdThe side chain number of every 1000 carbon of B=, by nuclear magnetic resonance hydrogen spectruming determining；eBy Differential Scanning Calorimeter
Measure；fIt is polymerized two hours；gNo detection；hLess than 25 degree.
Catalyst II-1～II-3 energy in the presence of promoter MAO or diethyl aluminum chloride as shown in Table 1
Enough highly active polyethylene.By the investigation of catalyst II-1 temperature is found, catalysis activity and the molecular weight of gained polyethylene
Reducing along with temperature raises, the gained polyethylene degree of branching raises along with temperature and raises.Catalyst system and catalyzing is when 5 degree, and some make
The conclusion of people's excitement occurs in that, the activity of catalyst improves 2 times, and the molecular weight of polymer brings up to 440,000.5 degree of longer times
The reaction result resulting polymers number-average molecular weight of such as 2 hours can be up to million.The degree of branching of polymer is big simultaneously
Width reduces, and fusing point significantly raises.When promoter changes diethyl aluminum chloride into, catalysis activity improves 5～10 times, molecular weight
Also decrease with fusing point.When making promoter with diethyl aluminum chloride, catalyst system and catalyzing can keep the highest work under 80 degree
Property.
Claims (10)
1. a pyridine imine compounds, as shown in formula (I):
Wherein, described R1、R2With R3It is each independently hydrogen, aryl or aryl alkyl；The carbon atom of alkyl in described aryl alkyl
Number is 1～6；
Described R4、R5With R6It is each independently hydrogen, the alkyl of C1～C6, nitro, the alkoxyl of C1～C6, N, N-dialkyl amino
Base or trifluoromethyl；The carbon number of the alkyl in described N, N-dialkyl amido is 1～6.
Pyridine imine compounds the most according to claim 1, it is characterised in that described R1、R2With R3It is each independently
Hydrogen, aryl or alkyl diaryl；In described alkyl diaryl, the carbon number of alkyl is 1～3.
3. the preparation method of a pyridine imine compounds, it is characterised in that including:
Replacement naphthylamine derivative shown in formula (I-1) is reacted with the pyridine carbonyl based compound shown in formula (I-2), obtains formula (I)
Shown pyridine imine compounds；
Wherein, described R1、R2With R3It is each independently hydrogen, aryl or aryl alkyl；The carbon atom of alkyl in described aryl alkyl
Number is 1～6；
Described R4、R5With R6It is each independently hydrogen, the alkyl of C1～C6, nitro, the alkoxyl of C1～C6, N, N-dialkyl amino
Base or trifluoromethyl；The carbon number of the alkyl in described N, N-dialkyl amido is 1～6.
Preparation method the most according to claim 3, it is characterised in that the replacement naphthylamine derivative shown in described formula (I-1)
It is prepared in accordance with the following methods:
S1) the picolinamide compound shown in formula (A) and the fragrant iodine substituent shown in formula (B) are existed at palladium salt and silver salt
Under the conditions of heat and react, obtain the compound shown in formula (C)；
S2) by the compound hydrolysis shown in described formula (C), the compound shown in formula (D) is obtained；
S3) compound shown in described formula (D) is converted into the replacement naphthylamine derivative shown in formula (I-1)；
Wherein, described R2With R3It is each independently hydrogen, aryl or aryl alkyl；The carbon number of alkyl in described aryl alkyl
It is 1～6；
Described R4、R5With R6It is each independently hydrogen, the alkyl of C1～C6, nitro, the alkoxyl of C1～C6, N, N-dialkyl amino
Base or trifluoromethyl；The carbon number of the alkyl in described N, N-dialkyl amido is 1～6.
5. a pyridine imine nickel class catalyst, as shown in formula (II):
Wherein, described R1、R2With R3It is each independently hydrogen, aryl or aryl alkyl；The carbon atom of alkyl in described aryl alkyl
Number is 1～6；
Described R4、R5With R6It is each independently hydrogen, the alkyl of C1～C6, nitro, the alkoxyl of C1～C6, N, N-dialkyl amino
Base or trifluoromethyl；The carbon number of the alkyl in described N, N-dialkyl amido is 1～6；
Described X is halogen.
6. the preparation method of a pyridine imine nickel class catalyst, it is characterised in that including:
Pyridine imine compounds shown in formula (I) is reacted with wrapping halogen-containing nickel precursor compound, obtains shown in formula (II)
Pyridine imine nickel class catalyst；
Wherein, described R1、R2With R3It is each independently hydrogen, aryl or aryl alkyl；The carbon atom of alkyl in described aryl alkyl
Number is 1～6；
Described R4、R5With R6It is each independently hydrogen, the alkyl of C1～C6, nitro, the alkoxyl of C1～C6, N, N-dialkyl amino
Base or trifluoromethyl；The carbon number of the alkyl in described N, N-dialkyl amido is 1～6；
Described X is halogen.
7. according to the preparation method shown in claim 6, it is characterised in that described bag halogen-containing nickel precursor compound is halogenation
The glycol dimethyl ether coordination compound of nickel.
8. a polyolefin, it is characterised in that by the pyridine imine nickel class catalyst described in claim 5 or claim 6～7
Pyridine imine nickel class catalyst prepared by any one obtains with promoter catalysis in olefine polymerization.
Polyolefin the most according to claim 8, it is characterised in that described alkene is low-carbon alkene；Described polyolefin has
Methyl number corresponding to 1000 methylene be 20～80；The molecular weight of described polyethylene is 20000～1000000g/mol,
And fusing point is from amorphous state to 110 DEG C；
Described alkene is high-carbon straight chain terminal olefine；The methyl number that 1000 methylene that described polyolefin has are corresponding is 20～70
Individual, molecular weight is 10000～30000g/mol, and fusing point is from amorphous state to 100 DEG C.
10. a polyolefinic preparation method, it is characterised in that including:
At the pyridine imine nickel class catalyst described in claim 5 or the pyridine imine prepared by claim 6～7 any one
Nickel class catalyst is under the effect of catalyst and promoter, alkene is carried out polyreaction, obtains polyolefin.
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Cited By (5)
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| CN107474077A (en) * | 2017-07-03 | 2017-12-15 | 中国科学技术大学 | A kind of α diimine palladium compound catalyst containing ferrocene group and its preparation method and application |
| CN108822237A (en) * | 2018-07-03 | 2018-11-16 | 常州大学 | A kind of pyridine imine palladium（Ⅱ）The method that catalyst preparation and catalysis ethylene prepare oily phase oligomer |
| WO2019205309A1 (en) * | 2018-04-28 | 2019-10-31 | 中国科学院青岛生物能源与过程研究所 | Pyridine imine iron or cobalt metal complex catalyst, preparation method therefor, and application thereof |
| CN111233755A (en) * | 2020-01-16 | 2020-06-05 | 安徽大学 | Pyridine imine ligand, pyridine imine palladium complex based on pyridine imine ligand and catalytic application of pyridine imine palladium complex |
| CN114685702A (en) * | 2022-04-07 | 2022-07-01 | 中国科学院青岛生物能源与过程研究所 | Method for preparing poly-conjugated diene by using pyridine imine iron catalyst and application of poly-conjugated diene |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107474077A (en) * | 2017-07-03 | 2017-12-15 | 中国科学技术大学 | A kind of α diimine palladium compound catalyst containing ferrocene group and its preparation method and application |
| CN107474077B (en) * | 2017-07-03 | 2019-08-27 | 中国科学技术大学 | A kind of α diimine palladium compound catalyst and its preparation method and application containing ferrocene group |
| WO2019205309A1 (en) * | 2018-04-28 | 2019-10-31 | 中国科学院青岛生物能源与过程研究所 | Pyridine imine iron or cobalt metal complex catalyst, preparation method therefor, and application thereof |
| CN108822237A (en) * | 2018-07-03 | 2018-11-16 | 常州大学 | A kind of pyridine imine palladium（Ⅱ）The method that catalyst preparation and catalysis ethylene prepare oily phase oligomer |
| CN111233755A (en) * | 2020-01-16 | 2020-06-05 | 安徽大学 | Pyridine imine ligand, pyridine imine palladium complex based on pyridine imine ligand and catalytic application of pyridine imine palladium complex |
| CN114685702A (en) * | 2022-04-07 | 2022-07-01 | 中国科学院青岛生物能源与过程研究所 | Method for preparing poly-conjugated diene by using pyridine imine iron catalyst and application of poly-conjugated diene |
| CN114685702B (en) * | 2022-04-07 | 2023-08-18 | 中国科学院青岛生物能源与过程研究所 | Method for preparing poly-conjugated diene by using pyridine imine iron catalyst and application of poly-conjugated diene |
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