CN109608507A - Big steric hindrance diimine nickel catalyst and its ligand, preparation method and purposes - Google Patents
Big steric hindrance diimine nickel catalyst and its ligand, preparation method and purposes Download PDFInfo
- Publication number
- CN109608507A CN109608507A CN201910043404.1A CN201910043404A CN109608507A CN 109608507 A CN109608507 A CN 109608507A CN 201910043404 A CN201910043404 A CN 201910043404A CN 109608507 A CN109608507 A CN 109608507A
- Authority
- CN
- China
- Prior art keywords
- formula
- steric hindrance
- diimine
- catalyst
- big steric
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 229910000071 diazene Inorganic materials 0.000 title claims abstract description 41
- RAABOESOVLLHRU-UHFFFAOYSA-N diazene Chemical compound N=N RAABOESOVLLHRU-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title abstract description 14
- 239000003446 ligand Substances 0.000 title abstract description 10
- 229920000098 polyolefin Polymers 0.000 claims abstract description 29
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 26
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 23
- 239000003054 catalyst Substances 0.000 claims abstract description 22
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 19
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 15
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 12
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 11
- 230000003197 catalytic effect Effects 0.000 claims abstract description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 54
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 33
- -1 ethylene, propylene Chemical group 0.000 claims description 32
- 150000001875 compounds Chemical class 0.000 claims description 31
- 238000006243 chemical reaction Methods 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 20
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 17
- 229910052736 halogen Inorganic materials 0.000 claims description 15
- 150000002367 halogens Chemical class 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 11
- 150000001336 alkenes Chemical class 0.000 claims description 10
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 9
- 235000019441 ethanol Nutrition 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims description 6
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 239000003377 acid catalyst Substances 0.000 claims description 6
- 150000007524 organic acids Chemical class 0.000 claims description 6
- 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 5
- 235000019253 formic acid Nutrition 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- 239000012046 mixed solvent Substances 0.000 claims description 5
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 4
- 239000000010 aprotic solvent Substances 0.000 claims description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 4
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 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
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical class ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 3
- 229950005499 carbon tetrachloride Drugs 0.000 claims description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- 239000003208 petroleum Substances 0.000 claims description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- 238000003541 multi-stage reaction Methods 0.000 claims description 2
- 241000790917 Dioxys <bee> Species 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 238000006555 catalytic reaction Methods 0.000 abstract description 8
- 229920000573 polyethylene Polymers 0.000 description 28
- 239000004698 Polyethylene Substances 0.000 description 26
- 230000015572 biosynthetic process Effects 0.000 description 21
- 238000003786 synthesis reaction Methods 0.000 description 21
- IPLJNQFXJUCRNH-UHFFFAOYSA-L nickel(2+);dibromide Chemical compound [Ni+2].[Br-].[Br-] IPLJNQFXJUCRNH-UHFFFAOYSA-L 0.000 description 20
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 19
- 239000005977 Ethylene Substances 0.000 description 19
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 19
- 239000000047 product Substances 0.000 description 19
- QHTBEPXLLPUTBL-UHFFFAOYSA-N butane-2,3-diimine Chemical compound CC(=N)C(C)=N QHTBEPXLLPUTBL-UHFFFAOYSA-N 0.000 description 16
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 14
- 238000000113 differential scanning calorimetry Methods 0.000 description 14
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 229910052763 palladium Inorganic materials 0.000 description 9
- 229940050176 methyl chloride Drugs 0.000 description 8
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- UMMOQCVRSGRAFB-UHFFFAOYSA-N Nc1cc(C(c2ccccc2)c2ccccc2)c(O)c(c1)C(c1ccccc1)c1ccccc1 Chemical compound Nc1cc(C(c2ccccc2)c2ccccc2)c(O)c(c1)C(c1ccccc1)c1ccccc1 UMMOQCVRSGRAFB-UHFFFAOYSA-N 0.000 description 7
- 229910021585 Nickel(II) bromide Inorganic materials 0.000 description 7
- 238000000119 electrospray ionisation mass spectrum Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 7
- MUJIDPITZJWBSW-UHFFFAOYSA-N palladium(2+) Chemical compound [Pd+2] MUJIDPITZJWBSW-UHFFFAOYSA-N 0.000 description 7
- 238000010992 reflux Methods 0.000 description 7
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 6
- 239000003426 co-catalyst Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 241000196324 Embryophyta Species 0.000 description 5
- 239000001273 butane Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000005227 gel permeation chromatography Methods 0.000 description 5
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 5
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- PBKONEOXTCPAFI-UHFFFAOYSA-N 1,2,4-trichlorobenzene Chemical compound ClC1=CC=C(Cl)C(Cl)=C1 PBKONEOXTCPAFI-UHFFFAOYSA-N 0.000 description 4
- 239000007868 Raney catalyst Substances 0.000 description 4
- 229910000564 Raney nickel Inorganic materials 0.000 description 4
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- ZZVUWRFHKOJYTH-UHFFFAOYSA-N diphenhydramine Chemical group C=1C=CC=CC=1C(OCCN(C)C)C1=CC=CC=C1 ZZVUWRFHKOJYTH-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 150000002431 hydrogen Chemical group 0.000 description 4
- 238000001819 mass spectrum Methods 0.000 description 4
- 238000001840 matrix-assisted laser desorption--ionisation time-of-flight mass spectrometry Methods 0.000 description 4
- 239000002808 molecular sieve Substances 0.000 description 4
- 230000008569 process Effects 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
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- 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
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 2
- 125000001118 alkylidene group Chemical group 0.000 description 2
- ILAHWRKJUDSMFH-UHFFFAOYSA-N boron tribromide Chemical compound BrB(Br)Br ILAHWRKJUDSMFH-UHFFFAOYSA-N 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N dimethyl sulfoxide Natural products CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 230000003292 diminished effect Effects 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000002905 metal composite material Substances 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 230000005311 nuclear magnetism Effects 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 239000012265 solid product Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 2
- OPSWAWSNPREEFQ-UHFFFAOYSA-K triphenoxyalumane Chemical group [Al+3].[O-]C1=CC=CC=C1.[O-]C1=CC=CC=C1.[O-]C1=CC=CC=C1 OPSWAWSNPREEFQ-UHFFFAOYSA-K 0.000 description 2
- VYXHVRARDIDEHS-UHFFFAOYSA-N 1,5-cyclooctadiene Chemical compound C1CC=CCCC=C1 VYXHVRARDIDEHS-UHFFFAOYSA-N 0.000 description 1
- 239000004912 1,5-cyclooctadiene Substances 0.000 description 1
- KSEPXCIDQMXYRW-UHFFFAOYSA-N 3-benzhydrylphenol Chemical class OC1=CC=CC(C(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 KSEPXCIDQMXYRW-UHFFFAOYSA-N 0.000 description 1
- 101100493710 Caenorhabditis elegans bath-40 gene Proteins 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 229910021543 Nickel dioxide Inorganic materials 0.000 description 1
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- OFHWXXPQDHVYLN-UHFFFAOYSA-N [3,5-bis(trifluoromethyl)phenoxy]boronic acid;sodium Chemical compound [Na].OB(O)OC1=CC(C(F)(F)F)=CC(C(F)(F)F)=C1 OFHWXXPQDHVYLN-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 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
- 238000007707 calorimetry Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 230000017858 demethylation Effects 0.000 description 1
- 238000010520 demethylation reaction Methods 0.000 description 1
- 238000006392 deoxygenation reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000004069 differentiation Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 125000000219 ethylidene group Chemical group [H]C(=[*])C([H])([H])[H] 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000000499 gel 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
- 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
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 208000021760 high fever Diseases 0.000 description 1
- 239000004700 high-density polyethylene Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 229920004889 linear high-density polyethylene Polymers 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- LGZXYFMMLRYXLK-UHFFFAOYSA-N mercury(2+);sulfide Chemical compound [S-2].[Hg+2] LGZXYFMMLRYXLK-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 239000000178 monomer Substances 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
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000010025 steaming Methods 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
- 238000012360 testing method Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
-
- 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
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C249/00—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C249/02—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of compounds containing imino groups
-
- 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
- C07C251/06—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 a saturated carbon skeleton
- C07C251/08—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 a saturated carbon skeleton being acyclic
-
- C—CHEMISTRY; METALLURGY
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Abstract
The present invention relates to the big steric hindrance diimine nickel complex and its ligand, preparation method and purposes of a kind of hydroxyl substituent group of formula (I), R therein1~R4It is as defined herein with X.Big steric hindrance diimine nickel complex of the invention can be used as catalyst in catalysis low-carbon alkene polymerization reaction, with high catalytic activity and high thermal stability, and it can obtain that molecular weight is 800000g/mol or more, the degree of branching is the corresponding methyl number of every 1000 carbon atoms is 30-60 and fusing point is 110 DEG C or more branched polyolefin.
Description
Technical field
The present invention relates to high molecular materials and catalyst field, and in particular to a kind of big steric hindrance diimine nickel catalyst and its
Ligand, preparation method and purposes.
Background technique
Polyolefin has cheap cost of material, excellent physics and chemical property, becomes indispensable in today's society
Macromolecule resin material.In olefin polymerization, catalyst decides the knot of the kinetic characteristics of olefin polymerization, polymer
Structure and performance and morphology etc..The development of olefin polymerization catalysis, so that the type of polyolefin products is more
It is abundant, performance more differentiation, to promote the development of entire polyolefin field.
Late transition metal catalyst occupies important position in field of olefin polymerisation.Developing new catalyst is to realize high property
The key of energy polyolefine material.By M.Brookhart in later period the 1990s (J.Am.Chem.Soc., 1995,117,
6414.) diimine nickel and palladium catalyst of (J.Am.Chem.Soc., 1996,118,11664.) discovery can use ethylene
There is the polyolefine material of different topology structure as synthesis under conditions of unique raw material, while ethylene and many can also be catalyzed
The copolymerization of polar monomer generates functionalized branched polyolefin (ACSCatal.2016,6,428.).Recently, Long et al. has found
Condition of nickel (II) complex that the big steric hindrance diimide ligand of benzhydril substituent containing ortho position substitution is formed at 100 DEG C
Under can catalyzed ethylene polymerization, and show very high thermal stability and activity, which is suitable for industrial gas phase
Vinyl polymerization (80-100 DEG C).However, being only capable of obtaining low melting point under 80-100 DEG C of polymerization temperature using above-mentioned Raney nickel
The polyethylene of (less than 40 DEG C), thus limit the polyethylene product use scope (J.Am.Chem.Soc.2013,135,
16316.)。
CN105152970A discloses a kind of big steric hindrance diimine palladium catalyst and its ligand, can be catalyzed such as ethylene
Polymerization reaction generates the low hemicrystalline polyethylene of the degree of branching.However, the hemicrystalline polyethylene obtained by the palladium catalyst
Molecular weight highest only about 640000g/mol and only about 100 DEG C of peak melting point, and the degree of branching of resulting polymers is lower than every
Corresponding 30 methyl numbers of 1000 carbon atoms.
Be conducive to improve the heat resistance of polyolefin such as polyethylene in view of high-melting-point, high molecular weight is able to ascend polyethylene
Mechanical property, the performance that the presence of branched structure can make polythene material that there are some linear polyethylenes not have are for example excellent
Flexibility, gas permeability etc..Therefore, there is still a need for exploitation new catalysts for this field, and it can be used to prepare to have significantly more
High molecular weight is for example, at least in 800000g/mol or more and fusing point is at least poly- in 110 DEG C or more the higher branchings of the degree of branching simultaneously
Alkene.
Summary of the invention
In view of above-mentioned, the object of the present invention is to provide a kind of new catalysts, can prepare macromolecule using the catalyst
Amount is at least in 800000g/mol or more and fusing point is at least in 110 DEG C or more while the higher branched polyolefin of the degree of branching.
For this purpose, in one aspect, the present invention provides a kind of big steric hindrance diimine nickels of the hydroxyl substituent group of formula (I) to match
Object is closed,
Wherein
R1And R2It is hydrogen, C independently of one another1-C6Alkyl, halogen or halogenated C1-C6Alkyl；
R3And R4It is hydrogen, C independently of one another1-C6Alkyl, halogen or halogenated C1-C6Alkyl or R3And R4It is in connection
Carbon atom be formed together C2-C4Alkylidene or halogenated C2-C4Alkylidene；And
Each X is independently halogen.
On the other hand, the present invention provides a kind of midbody compound of the hydroxyl substituent group of formula (II),
Wherein R1、R2、R3And R4As defined above, and the midbody compound be used to prepare above-mentioned formula (I) containing hydroxyl
The big steric hindrance diimine nickel complex of base substituent group.
On the other hand, it is sub- that the present invention provides the big steric hindrances of a kind of hydroxyl substituent group for preparing above-mentioned formula (I) two
The method of amine nickel complex, which comprises
In organic solvent, make the midbody compound and formula Ni (GDME) X of above-mentioned formula (II)2Nickel composite reaction,
Wherein GDME indicates glycol dimethyl ether, and X is as defined above.
On the other hand, the present invention provides the method that one kind is used to prepare above-mentioned formula (II) compound, the methods
Include:
In the presence of organic acid catalyst, 50~80 DEG C at a temperature of, the dione compounds of formula (A) and formula (B's)
Compound the in the mixed solvent of proton solvent and aprotic solvent react 12~for 24 hours；It then raises temperature under counterflow condition and continues
Reacting 24~72h, it is preferred to use anhydrous magnesium sulfate removes the water that dereaction generates, so that formula (II) compound is formed,
Wherein R1、R2、R3And R4As defined above.
In a preferred embodiment, the organic acid catalyst is selected from formic acid, acetic acid, p-methyl benzenesulfonic acid or camphor
Sulfonic acid；The proton solvent is selected from methanol, ethyl alcohol, normal propyl alcohol, isopropanol, the tert-butyl alcohol, n-butanol or sec-butyl alcohol；It is described non-proton
Solvent is selected from tetrahydrofuran, petroleum ether, toluene, benzene, methylene chloride, tetrachloromethane, ether, Isosorbide-5-Nitrae-dioxane or 1,2- dichloro
Ethane.
On the other hand, the present invention provides a kind of methods for preparing branched polyolefin compound, which comprises
Use the big steric hindrance diimine nickel complex of formula as described above (I) as catalyst to C2-C8Low-carbon alkene carries out
Catalytic polymerization,
The wherein fusing point of the molecular weight and 110 DEG C of the branched polyolefin compound with 800000g/mol or more or more.
In a preferred embodiment, the method also includes using methylaluminoxane as co-catalyst.
In a preferred embodiment, the C2-C8Low-carbon alkene is selected from ethylene, propylene, 1- butylene, 1- hexene or 1-
Octene.
In a preferred embodiment, point of the branched polyolefin compound with 800000~1600000g/mol
Son amount and 110~130 DEG C of fusing point.
In a preferred embodiment, the degree of branching that the branched polyolefin compound has is every 1000 carbon atoms
Corresponding methyl number is 30-60.
The present invention introduces band by introducing hydroxyl substituent in the contraposition of the big steric hindrance ligand aniline structure of diimine simultaneously
The nickel metal composite for having double halogens to replace, providing a kind of novel has " diimine nickel/hydroxyl substituent " difunctional knot
The big steric hindrance diimine nickel catalyst of structure.In the catalyst, diimine nickel can under the action of co-catalyst methylaluminoxane
To generate the nickel activated centre of the ability with catalysis in olefine polymerization, while hydroxyl substituent is in co-catalyst methylaluminoxane
Aluminium phenolate substituent group can be generated under effect, generate strong In frared spectra, cause nickel that can generate in catalyzed ethylene polymerization molten
The higher but still polyethylene with higher branch degree of point.
Big steric hindrance diimine nickel catalyst of the invention catalysis low-carbon alkene polymerization reaction in have high catalytic activity and
High thermal stability, and can unexpectedly obtain molecular weight be 800000g/mol or more and fusing point be 110 DEG C or more simultaneously
The high branched polyolefin of the degree of branching.Particularly, by utilizing big steric hindrance diimine nickel catalyst of the invention, molecule can be obtained
Amount is 800000-1600000g/mol, fusing point is 110~130 DEG C and the degree of branching is the corresponding methyl number of every 1000 carbon atoms
For 30-60 branched polyolefins.
The high-melting-point of the polymer of acquisition is conducive to improve its heat resistance, and high molecular weight is conducive to promote its mechanical property
Can, while the property that the presence of branched structure can make the polythene material that there are some linear high density polyethylene (HDPE)s not have
It can such as better flexibility, gas permeability.In addition, big steric hindrance diimine nickel catalyst of the invention can use through simple mistake
The midbody compound that Cheng Hecheng is obtained is made, and is easy preparation and is produced on a large scale.
Detailed description of the invention
Fig. 1 is 2,6- bis- (benzhydryl) -4-aminophenol of 1 synthesis according to embodiments of the present invention1H NMR spectra.
Fig. 2 is 2,6- bis- (benzhydryl) -4-aminophenol of 1 synthesis according to embodiments of the present invention13C NMR spectra.
Fig. 3 is 2,6- bis- (benzhydryl) -4-aminophenol electrospray ionisation-of 1 synthesis according to embodiments of the present invention
Mass spectrum (ESI-MS) spectrogram.
Fig. 4 is the N of 2 synthesis according to embodiments of the present invention, N- bis- (2,6- benzhydryl -4- hydroxy phenyl) butane -2,3-
Diimine1H NMR spectra.
Fig. 5 is the N of 2 synthesis according to embodiments of the present invention, N- bis- (2,6- benzhydryl -4- hydroxy phenyl) butane -2,3-
Diimine13C NMR spectra.
Fig. 6 is the N of 2 synthesis according to embodiments of the present invention, N- bis- (2,6- benzhydryl -4- hydroxy phenyl) butane -2,3-
The ESI-MS spectrogram of diimine.
Fig. 7 is the N, N- bis- (2,6- benzhydryl -4- hydroxy phenyl) butane -2,3- of 3 synthesis according to embodiments of the present invention
Diimine closes flight time mass spectrum (MALDI-TOF-MS) spectrogram of Nickel Bromide (II).
Fig. 8 is the polyethylene product of 4 preparation according to embodiments of the present invention1H NMR spectra.
Fig. 9 is differential scanning calorimetry (DSC) figure of the polyethylene product of 4 preparation according to embodiments of the present invention.
Figure 10 is the DSC figure of the polyethylene product of 5 preparation according to embodiments of the present invention.
The DSC figure of the polyethylene product of Figure 11 6 preparation according to embodiments of the present invention.
Figure 12 is the DSC figure of the polyethylene product of 7 preparation according to embodiments of the present invention.
Figure 13 is the N, N- bis- (2,6- benzhydryl -4- hydroxy phenyl) butane -2,3- that comparative example 1 synthesizes according to the present invention
Diimine closes methyl chloride palladium (II's)1H NMR spectra
Figure 14 is the N synthesized according to comparative example 1, N- bis- (2,6- benzhydryl -4- hydroxy phenyl) butane -2,3- diimine
Close methyl chloride palladium (II)13C NMR spectra
Figure 15 is the DSC figure of the polyethylene product prepared according to comparative example 2.
Specific embodiment
It tests and furthers investigate more extensively by the present inventor, it was unexpectedly found that: when in the big position of diimine
When hindering introducing hydroxyl substituent in the contraposition of ligand aniline structure while introducing the nickel metal composite with double halogens substitutions, institute
The big steric hindrance diimine nickel catalyst obtained not only has high catalytic activity and high fever steady in catalysis low-carbon alkene polymerization reaction
It is qualitative, and can improve significantly gained polyolefin product molecular weight (for 800000g/mol or more) and fusing point (be 110
DEG C or more), while polyolefin obtained is that the degree of branching is higher (the corresponding methyl number of every 1000 carbon atoms is 30-60)
Branched polyolefin.
Especially, when the co-catalyst of big steric hindrance diimine nickel catalyst and such as methylaluminoxane (MAO) of the invention
When being used together, it can be ensured that the molecular weight of branched polyolefin obtained is 800000-1600000g/mol, fusing point 110
~130 DEG C and the degree of branching are that the corresponding methyl number of every 1000 carbon atoms is 30-60.It is not intended to be limited to especially theory, according to
Letter, on the one hand this is because hydroxyl (Hammett constant σPIt=- 0.37) is than such as methoxyl group (σP=-0.27) more supplied for electronic
Substituent group (see, for example, Chem.Rev., 1991,91,165)；On the other hand, in big steric hindrance diimine nickel provided by the invention
In catalyst system, the hydroxyl substituent of contraposition can react with co-catalyst MAO, and form aluminium phenolate structure, and by
In the difference of the Pauling electronegativity of O element and Al element be 1.93 (are greater than 1.7) so that being formed by aluminium phenolate structure
O-Al key is ionic bond, thus forms the negative oxygen ion substituent group O of strong supplied for electronic-(σP=-0.81).Therefore, when herein
When introducing contraposition hydroxyl substituent on the aniline structure of the big steric hindrance diimide ligand, it will in diimine nickel obtained
Strong In frared spectra is generated in catalyst, such strong In frared spectra significantly improves the diimine nickel catalyst in alkene such as second
The molecular weight and fusing point of polyethylene product obtained in alkene polymerization, and the present invention is formd based on this discovery.
As a result, the present invention provides the big steric hindrance diimine nickel complex of the hydroxyl substituent group of formula (I),
Wherein
Hydroxyl substituent is in the contraposition of the nitrogen-atoms on benzene ring structure；
R1And R2It is hydrogen, C independently of one another1-C6Alkyl, halogen or halogenated C1-C6Alkyl；
R3And R4It is hydrogen, C independently of one another1-C6Alkyl, halogen or halogenated C1-C6Alkyl or R3And R4It is in connection
Carbon atom be formed together C2-C4Alkylidene or halogenated C2-C4Alkylidene；And
Each X is independently halogen.
As used in this article, C1-C6The example of alkyl include methyl, ethyl, propyl and its isomeric form, butyl and its
Isomeric form, amyl and its isomeric form, hexyl and its isomeric form, preferably methyl, ethyl or tert-butyl.
As used in this article, halogen includes fluorine, chlorine, bromine and iodine, preferably chlorine or bromine.
As used in this article, halogenated C1-C6Alkyl refers to above-mentioned C1-C6Alkyl, the wherein C1-C6In alkyl at least
One hydrogen atom is optionally substituted by halogen.
As used in this article, C2-C4The example of alkylidene includes ethylidene, 1,3- propylidene and 1,4- butylidene；And
Halogenated C2-C4Alkylidene refers to above-mentioned C2-C4Alkylidene, the wherein C2-C4At least one hydrogen atom in alkylidene is by halogen
Replace.
Preferably, in formula (I), R1And R2It is hydrogen or alkyl independently of one another.
Preferably, in formula (I), R3And R4It is C independently of one another1-C6Alkyl or halogenated C1-C6Alkyl.
In the present invention, the big steric hindrance diimine nickel complex of formula (I) can be via the midbody compound system of formula (II)
It is standby:
Wherein R1、R2、R3And R4As defined above,
Such as in organic solvent such as toluene, make the midbody compound and formula Ni (GDME) X of above-mentioned formula (II)2Nickel it is multiple
Closing object (such as glycol dimethyl ether closes Nickel Bromide (II)) reaction can be obtained the Raney nickel of formula (I), and wherein GDME is indicated
Glycol dimethyl ether, each X independently are halogen such as chlorine or bromine.
In the present invention, the compound of above-mentioned formula (II) can be synthesized by following approach, such as in organic acid catalyst
In the presence of, 50~80 DEG C at a temperature of, the dione compounds of formula (A) and the compound of formula (B) are in proton solvent and non-matter
The in the mixed solvent reaction 12 of sub- solvent~for 24 hours；24~the 72h that then raises temperature under counterflow condition that the reaction was continued, it is preferred to use
Anhydrous magnesium sulfate removes the water that dereaction generates, so that formula (II) compound is formed,
Wherein R1、R2、R3And R4As defined above.
Preferably, the organic acid catalyst used can be selected from formic acid, acetic acid, p-methyl benzenesulfonic acid or camphorsulfonic acid etc.,
More preferably formic acid or 4- toluenesulfonic acid.
Preferably, the proton solvent used can selected from methanol, ethyl alcohol, normal propyl alcohol, isopropanol, the tert-butyl alcohol, n-butanol or
Sec-butyl alcohol etc., more preferably ethyl alcohol.
Preferably, the aprotic solvent used can be selected from tetrahydrofuran, petroleum ether, toluene, benzene, methylene chloride, tetrachloro
Methane, ether, Isosorbide-5-Nitrae-dioxane or 1,2- dichloroethanes etc., more preferably toluene or chlorobenzene.
The big steric hindrance diimine nickel complex of formula (I) provided by the invention may be used as catalyst, and it is poly- to be used to prepare branching
Olefin(e) compound, such as catalytic polymer C2-C8Low-carbon alkene.Preferably, co-catalyst such as methyl is added in catalysis reaction
Aikyiaiurnirsoxan beta etc..By utilizing big steric hindrance diimine nickel catalyst of the invention, the branched polyolefin compound of acquisition has
The fusing point of the molecular weight of 800000g/mol or more and 110 DEG C or more.Preferably, the branched polyolefin compound of acquisition has
The molecular weight of 800000~1600000g/mol and 110~130 DEG C of fusing point.It is highly preferred that the branched polyolefin chemical combination obtained
The degree of branching that object has is that the corresponding methyl number of every 1000 carbon atoms is 30-60.
Preferably, the C used2-C8Low-carbon alkene can be selected from ethylene, propylene, 1- butylene, 1- hexene or 1- octene, more excellent
It is selected as ethylene or propylene.It is further preferred that the pressure of ethylene or propylene is 1-10 atmosphere in above-mentioned catalytic polymerization
Pressure, reaction time are 10~60min.
It should be understood that within the scope of the invention, above-mentioned each technical characteristic of the invention and have in below (eg embodiment)
It can be combined with each other between each technical characteristic of body description, to form a new or preferred technical solution.As space is limited, exist
This is no longer repeated one by one.
Embodiment
Particular content of the invention has been illustrated in following embodiments, and the data provided include the synthesis of ligand, metallization
Synthesis, the alkene such as vinyl polymerization or copolymerization process of object are closed, the wherein synthesis of complex, polymerization process is all in anhydrous and oxygen-free
The substance of lower progress, all sensitivities is stored in glove box, and all solvents are all by stringent dry water removal, and ethylene gas is by removing
The purifying of water deoxygenation pillar.It is not particularly illustrated, all raw materials directly use after buying.
Nuclear-magnetism detection Bruker 400MHz nuclear-magnetism instrument；Elemental analysis is surveyed by China Science & Technology University's physics and chemistry center
It is fixed；Molecular weight and molecualr weight distribution is measured by high temperature GPC；Mass spectrum is measured with Thermo LTQ Orbitrap XL；Fusing point is used
TA Instruments DSC Q20 is measured by differential scanning calorimetry (DSC)；Product yields are to be dried in vacuo 12 at 50 DEG C
Gained is weighed after hour；Activity is calculated according to following formula: the activity=polyethylene production/(amount of the substance of catalyst × poly-
Close the time used), active unit 105G (mol Ni or Pd)-1·h-1。
Methylene chloride (AR), Beijing Chemical Plant,In N after molecular sieve predrying2Protection is lower to be added calcium hydride reflux, uses
Before steam；
Toluene (AR), Beijing Chemical Plant,In N after molecular sieve predrying2Protection is lower to be added sodium metal reflux, with preceding steaming
Out；
Hexamethylene (AR), Beijing Chemical Plant,In N after molecular sieve predrying2Protection is lower to be added sodium metal reflux, before
It steams；
O-dichlorohenzene (AR), Beijing Chemical Plant,Calcium hydride reflux is added under N2 protection after molecular sieve predrying, uses
Before steam；
Formic acid, AR (88%), Beijing Chemical Plant directly use；
Ethylene, polymer grade, unprocessed direct use；
High-purity N2, unprocessed direct use；
Ethyl alcohol analyzes pure, two factory of Tianjin reagent, directly uses；
Methanol, industrial goods, two factory of Tianjin reagent directly use；
2,6- bis- (benzhydryl) -4- metoxyphenols, are prepared by literature method
(Angew.Chem.Int.Ed.2015,54,9948.).
If not otherwise specified, other reagent raw material such as methylaluminoxane (MAO) used in the following embodiment etc. are all
It is all unprocessed direct use without specializing purchased from Aldrich (analysis is pure).
The synthesis of embodiment 1:2,6- bis- (benzhydryl) -4-aminophenol
At room temperature, in the eggplant-shape bottle of 500mL (being equipped with thermometer, dropping funel, reflux condenser and blender),
After (the benzhydryl) -4- metoxyphenol of 2,6- bis- (10mmol) is dissolved in 80mL methylene chloride, resulting solution is used into ice
Salt bath is cooled to -10 DEG C, and methylene chloride (25mL) solution of demethylation reagent Boron tribromide (25mmol) is then slowly added dropwise.
After stirring 1h at -10 DEG C, continue to be stirred to react 4h at room temperature.Then, reaction solution is cooled to -10 DEG C, then slowly dripped
Add 20mL water.After 12h is stirred at room temperature in obtained mixing liquid, it is extracted with dichloromethane three times and merges obtained dichloro
Dichloromethane.By this dichloromethane solution with after the dry 2h of 20g anhydrous sodium sulfate, then filtering removes organic in vacuum distillation
Solvent, and resulting solid product is dissolved in 50mL methylene chloride, 200mL n-hexane is then added, is filtered after stirring 1h.It will
Obtained Light brown solid drying at room temperature 12h under vacuum conditions, thus 2,6- bis- (benzhydryl) -4-aminophenol (produces
Amount: 4.3g, yield: 98%).
Fig. 1 is 2,6- bis- (benzhydryl) -4-aminophenol of 1 synthesis according to embodiments of the present invention1H NMR spectra；
Fig. 2 is 2,6- bis- (benzhydryl) -4-aminophenol of 1 synthesis according to embodiments of the present invention13C NMR spectra；Fig. 3 is basis
2,6- bis- (benzhydryl) -4-aminophenol electrospray ionisation-mass spectrum (ESI-MS) spectrogram that the embodiment of the present invention 1 synthesizes.
1H NMR(CDCl3, 400MHz): δ (ppm) 7.23-7.12 (m, 12H, aryl-H), 7.03 (d, J=8Hz, 4H, virtues
Base-H), 6.96 (d, J=8Hz, 4H, aryl-H), 6.34 (s, 2H, aryl-H), 5.12 (s, 2H, CHPh2)。13C NMR(d6-
DMSO,100MHz):δ(ppm)149.56,143.20,136.39,129.69,129.42,128.86,126.99,116.47,
50.39。ESI-MS(m/z):442.2154[M+H]+。
The synthesis of embodiment 2:N, N- bis- (2,6- benzhydryl -4- hydroxy phenyl) butane -2,3- diimine
At room temperature, in the eggplant-shape bottle of 500mL (being equipped with thermometer, dropping funel, reflux condenser and blender),
By the 2,6- bis- (benzhydryl) obtained in embodiment 1-4-aminophenol (20mmol), 2,3- diacetyl (10mmol) and 4- first
Base benzene sulfonic acid (0.5mmol) is dissolved in the in the mixed solvent being made of 100mL toluene and 100mL ethyl alcohol.Pass through oil bath heating to 75
DEG C, after being stirred to react 36h, it is warming up to back flow reaction 72h, and condensation reaction generation is removed using anhydrous magnesium sulfate (3g)
Water.A mainly point can be found with methylene chloride and methanol 5:1 contact plate, indicate that reaction is over.It is gone by rotary evaporation
Except solvent, resulting product is dissolved in methylene chloride (50mL), n-hexane (200mL) then is added, and stir mistake after 1h
Filter.By obtained Light brown solid drying at room temperature 12h under vacuum conditions, N, (2, the 6- benzhydryl -4- hydroxy benzenes of N- bis- are obtained
Base) butane -2,3- diimine (yield: 8.5g, yield: 91%).
Fig. 4 is the N, N- bis- (2,6- benzhydryl -4- hydroxy phenyl) butane -2,3- of 2 synthesis according to embodiments of the present invention
Diimine1H NMR spectra；Fig. 5 is the N of 2 the synthesis according to embodiments of the present invention, (2,6- benzhydryl -4- hydroxy benzenes of N- bis-
Base) butane -2,3- diimine13C NMR spectra；Fig. 6 is the N of 2 synthesis according to embodiments of the present invention, (the 2,6- hexichol first of N- bis-
Base -4- hydroxy phenyl) butane -2,3- diimine ESI-MS spectrogram.
1H NMR(CDCl3, 400MHz): δ (ppm) 7.25-7.14 (m, 26H, aryl-H), 7.04 (d, J=8Hz, 4H, virtues
Base-H), 6.96 (d, J=8Hz, 4H, aryl-H), 6.47 (s, 4H, aryl-H), 5.25 (s, 4H, CHPh2),1.13(s,6H,N
=CMe).13C NMR(CDCl3, 100MHz): δ (ppm) 170.65 (N=CMe), 151.59,143.30,142.55,141.90,
129.64,129.38,128.67,128.43,128.15,126.50,126.22,115.57,51.63(CHPh2),16.67(N
=CMe).Yield 93% (8.7g).ESI-MS(m/z):933.4384[M+H]+。
(2,6- benzhydryl -4- hydroxy phenyl) butane -2,3- diimine of embodiment 3:N, N- bis- closes Nickel Bromide (II)
Synthesis
At room temperature, in the eggplant-shape bottle of 50mL (being equipped with thermometer, dropping funel, reflux condenser and blender),
The N that will be obtained in embodiment 2, N- bis- (2,6- benzhydryl -4- hydroxy phenyl) butane -2,3- diimine (1mmol), ethylene glycol
After dimethyl ether closes Nickel Bromide (II) (1mmol) and the mixing of 20mL methylene chloride, magnetic agitation reacts 36h.Then 100mL is added
N-hexane, and filtered after stirring 1h.By obtained dark brown solid drying at room temperature 12h under vacuum conditions, N, N- bis- (2,6- are obtained
Benzhydryl -4- hydroxy phenyl) butane -2,3- diimine conjunction Nickel Bromide (II) (yield: 1.1g, yield: 93%).
Fig. 7 is the N, N- bis- (2,6- benzhydryl -4- hydroxy phenyl) butane -2,3- of 3 synthesis according to embodiments of the present invention
Diimine closes flight time mass spectrum (MALDI-TOF-MS) figure of Nickel Bromide (II).MALDI-TOF-MS(m/z):988.1507
[M–2Br–2H]+。C68H56Br2N2NiO2Theoretical value: C, 70.92；H, 4.90；N, 2.43；Experiment value: C, 70.89；H, 4.93；N,
2.41。
In addition, the identical program according to above-described embodiment 1~3, the present invention has also synthesized formula (I) chemical combination in following table 1
Object:
Table 1:
Embodiment 4: big steric hindrance diimine nickel catalyst is used for the application of catalyzed ethylene polymerization
In glove box, under nitrogen atmosphere, to 350mL autoclave (with magnetic stirring apparatus, oil bath heating device and
Thermometer) middle addition 50mL toluene and the aluminium atom containing 0.6mmol methylaluminoxane (MAO).Then, reaction vessel is connected
It is connected to high pressure pipeline and pipeline is vacuumized.Reaction vessel is heated to 100 DEG C using oil bath, keeps the temperature 15min.Pass through
Syringe is dissolved in the N obtained by embodiment 3 in 2mL methylene chloride, N- bis- (2,6- benzhydryl -4- hydroxy phenyl) fourth
Alkane -2,3- diimine closes Nickel Bromide (II) (1mg) and is injected into reaction system.Valve is closed, adjusting ethylene pressure is 8MPa
Afterwards, 30min is reacted.Stop reaction, open reaction kettle, ethyl alcohol is added thereto and is then filtered under diminished pressure with precipitation solid, and true
It is dried in empty drying box at 60 DEG C, thus obtains the polyethylene product as white solid of 0.8g.Fig. 8 is according to the present embodiment
The polyethylene product of 4 preparations1H NMR spectra；Fig. 9 is that the differential of the polyethylene product of 4 preparation according to embodiments of the present invention is swept
Retouch calorimetry (DSC) figure.As a result, as shown in the serial number 1 of the following table 2, the number-average molecular weight of the polyethylene of acquisition is
1045000g/mol, fusing point is 120 DEG C, and it is 44 that the degree of branching, which is the corresponding methyl number of every 1000 carbon atoms,.
Embodiment 5~7: the application of catalyzed ethylene polymerization under the conditions of differential responses
With process same as Example 4, the differential responses condition that is only respectively shown in using serial number 2~4 in the following table 2 into
Row reaction, reaction result is referring to table 2.Figure 10 is the DSC figure of the polyethylene product of 5 preparation according to embodiments of the present invention；Figure 11 root
According to the DSC figure of polyethylene product prepared by the embodiment of the present invention 6；Figure 12 is that the polyethylene of 7 preparation according to embodiments of the present invention produces
The DSC of object schemes.
Table 2: the nickel in embodiment 3 cooperates in different polymerizing conditionsaLower catalysis ethylene homo
aPolymerizing condition: nickel complex=1 μm ol, methylaluminoxane=0.6mmol, toluene=50mL, methylene chloride=
2mL, ethylene partial pressure is strong=8bar, the reaction time=30min；bActive unit: 106g·(mol Ni)-1·h-1；cMolecular weight and
The measurement of molecular weight polydispersity coefficient is to use polystyrene as standard sample by gel permeation chromatography (GPC), with 1,2,4- tri-
Chlorobenzene is that solvent measures at 150 DEG C；dThe degree of branching is by nuclear magnetic resonance hydrogen spectruming determining；eFusing point is surveyed with differential scanning calorimetry (DSC)
It is fixed.
Other embodiments: the application of different Raney nickel catalyzed ethylene polymerizations of the invention is used
With process same as Example 4, only matched using other big steric hindrance diimine nickels of the formula (I) synthesized in table 1
It closes object to be reacted as catalyst, obtains that molecular weight is 800000g/mol or more, the degree of branching is every 1000 carbon atoms
The branched polyolefin that corresponding methyl number is 30-60 and fusing point is 110 DEG C or more.
(2,6- benzhydryl -4- hydroxy phenyl) butane -2,3- diimine of comparative example 1:N, N- bis- closes methyl chloride palladium
(II) synthesis
With program same as Example 3, at room temperature, by N, N- bis- (2,6- benzhydryl -4- hydroxy phenyl) butane -
2,3- diimine (1mmol), 1,5- cyclo-octadiene stir after closing methyl chloride palladium (II) (1mmol) and the mixing of 20mL methylene chloride
React 72h.100mL n-hexane is added, is filtered after stirring 1h.By the obtained Orange red solid silicon of the silica gel of 200-300 mesh
Rubber column gel column separation, uses the mixed solvent of methylene chloride and methanol 20:1 as mobile phase.Obtain Chinese red solid product N, N- bis-
(2,6- benzhydryl -4- hydroxy phenyl) butane -2,3- diimine conjunction methyl chloride palladium (II) (yield: 0.62g, yield:
72%).Figure 13 is the N synthesized according to this comparative example 1, N- bis- (2,6- benzhydryl -4- hydroxy phenyl) butane -2,3- diimine
Close methyl chloride palladium (II)1H NMR spectra；Figure 14 is the N synthesized according to comparative example 1, (2, the 6- benzhydryl -4- hydroxyls of N- bis-
Base phenyl) butane -2,3- diimine conjunction methyl chloride palladium (II)13C NMR spectra.
1H NMR(CDCl3, 400MHz): δ (ppm) 7.45 (d, J=8Hz, 4H, aryl-H), 7.33 (d, J=8Hz, 4H,
Aryl-H), 7.25-7.04 (m, 34H, aryl-H), 6.69 (s, 2H, aryl-H), 6.45 (s, 2H, aryl-H), 5.95 (s,
2H, CHPh2), 5.70 (s, 2H, CHPh2), 0.68 (s, 3H, Pd-Me), 0.36 (s, 3H, N=CMe), 0.14 (s, 3H, N=
CMe)。13C NMR(CDCl3, 100MHz): δ (ppm) 178.23 (N=CMe), 173.62 (N=CMe), 154.06,153.22,
143.60,142.17,142.04,141.93,136.80,136.73,136.42,135.91,130.09,129.86,129.82,
129.62,128.73,128.67,128.57,128.28,126.99,126.72,126.60,126.49,116.44,116.32,
51.74(CHPh2),51.44(CHPh2), 20.30 (N=CMe), 19.30 (N=CMe), 5.93 (Pd-Me).MALDI-TOF-MS
(m/z):1036.0029[M–Me–Cl–2H]+,1070.9928[M–Me–2H]+。C69H59ClN2O2Pd: theoretical value C, 76.02；H,
5.46；N,2.57；Experiment value: C, 76.09；H,5.43；N,2.55.
Comparative example 2: the application of palladium complex catalyst vinyl polymerization
With program same as Example 4, in glove box, under nitrogen atmosphere, (magnetic force is had to 350mL autoclave
Agitating device, oil bath heating device and thermometer) middle addition 50mL toluene and four (3,5- bis trifluoromethyl phenyl) boric acid
Sodium (6 μm of ol).Reaction vessel is connected to high pressure line and pipeline is vacuumized.Reaction vessel is heated to using oil bath
40 DEG C, keep the temperature 15min.The N obtained in comparative example 1 in 2mL methylene chloride, bis- (2,6- of N- are dissolved in by syringe
Benzhydryl -4- hydroxy phenyl) butane -2,3- diimine close methyl chloride palladium (II) (5 μm of ol) injection reaction system in.It closes
Valve adjusts ethylene pressure to react 15min after 8MPa.Stop reaction, open reaction kettle, ethyl alcohol is added thereto to precipitate
Solid is filtered under diminished pressure, and vacuum oven dries the polyethylene product for obtaining 1.72g as white solid.Figure 15 is according to comparison
The DSC figure of polyethylene product prepared by example 2.As a result, the number of gained polyethylene is divided equally as shown in the serial number 1 of the following table 3
Son amount is 639000g/mol, and fusing point is 95 DEG C, and it is 26 that the degree of branching, which is the corresponding methyl number of every 1000 carbon atoms,.
Comparative example 3~6: the application of catalyzed ethylene polymerization under the conditions of differential responses
With process identical with comparative example 2, the differential responses condition that is only respectively shown in using the serial number 2~4 in the following table 3
It is reacted, reaction result is referring to table 3.
Table 3: the palladium complex in comparative example 1 is in different polymerizing conditionsaLower catalysis ethylene homo
aPolymerizing condition: palladium complex=5 μm ol (3,5- bis trifluoromethyl phenyl) Boratex (6 μm of ol), toluene=
50mL, methylene chloride=2mL, ethylene partial pressure is strong=8bar, the reaction time=15min.bActive unit: 105g·(mol Pd
)-1·h-1。cThe measurement of molecular weight and molecular weight polydispersity coefficient is to use polystyrene as standard by gel permeation chromatography (GPC)
Sample is that solvent measures at 150 DEG C with 1,2,4- trichloro-benzenes.dThe degree of branching is by nuclear magnetic resonance hydrogen spectruming determining.E fusing point differential
Scanning calorimetry (DSC) measurement.
By sub- using novel big steric hindrance two provided by the invention it can be seen from the result of above embodiments and comparative example
Amine Raney nickel, can obtain that molecular weight is 800000-1600000g/mol, fusing point is 110~130 DEG C and the degree of branching is every
The branched polyolefin that the corresponding methyl number of 1000 carbon atoms is 30-60.On the contrary, can be seen that from the result of comparative example 1-6
Only because the metal species of catalyst are different, the molecular weight (highest of the obtained polyolefin of the palladium catalyst of comparative example 1 is used
It is only about 640000) all significant lower with fusing point (being below 100 DEG C), i.e., it cannot obtain required effect of the invention.
Above to the present invention have been described in detail, but the invention is not limited to specific embodiment parties described herein
Formula.It will be appreciated by those skilled in the art that in the case without departing from the scope of the present invention, other changes and deformation can be made.This hair
Bright range is defined by the following claims.
Claims (10)
1. a kind of big steric hindrance diimine nickel complex of the hydroxyl substituent group of formula (I):
Wherein
R1And R2It is hydrogen, C independently of one another1-C6Alkyl, halogen or halogenated C1-C6Alkyl；
R3And R4It is hydrogen, C independently of one another1-C6Alkyl, halogen or halogenated C1-C6Alkyl or R3And R4It is formed together C2-C4It is sub-
Alkyl or halogenated C2-C4Alkylidene；And
Each X is independently halogen.
2. a kind of midbody compound of the hydroxyl substituent group of formula (II):
Wherein R1、R2、R3And R4As defined in claim 1, and the midbody compound is used to prepare and is wanted according to right
The big steric hindrance diimine nickel complex of the hydroxyl substituent group of formula described in asking 1 (I).
3. a kind of big steric hindrance diimine nickel complex for the hydroxyl substituent group for preparing formula according to claim 1 (I)
Method, which comprises
In organic solvent, make the midbody compound and formula containing hydroxyl substituent of formula as claimed in claim 2 (II)
Ni(GDME)X2Nickel composite reaction, wherein GDME indicates glycol dimethyl ether, and X is as defined in claim 1.
4. the method that one kind is used to prepare the midbody compound of formula according to claim 2 (II), which comprises
In the presence of organic acid catalyst, 50~80 DEG C at a temperature of, the chemical combination of the dione compounds of formula (A) and formula (B)
Object the in the mixed solvent of proton solvent and aprotic solvent react 12~for 24 hours；Then raise temperature under counterflow condition that the reaction was continued
24~72h, it is preferred to use anhydrous magnesium sulfate removes the water that dereaction generates, so that the midbody compound of formula (II) is formed,
Wherein R1、R2、R3And R4As defined in claim 1.
5. according to the method described in claim 4, it is characterized in that, the organic acid catalyst is selected from formic acid, acetic acid, to methyl
Benzene sulfonic acid or camphorsulfonic acid；The proton solvent is selected from methanol, ethyl alcohol, normal propyl alcohol, isopropanol, the tert-butyl alcohol, n-butanol or Zhong Ding
Alcohol；The aprotic solvent is selected from tetrahydrofuran, petroleum ether, toluene, benzene, methylene chloride, tetrachloromethane, ether, 1,4- dioxy
Six rings or 1,2- dichloroethanes.
6. a kind of method for preparing branched polyolefin compound, which comprises
Use the big steric hindrance diimine nickel complex of the hydroxyl substituent group of formula as described in claim 1 (I) as catalyst
To C2-C8Low-carbon alkene carries out catalytic polymerization,
The wherein fusing point of the molecular weight and 110 DEG C of the branched polyolefin compound with 800000g/mol or more or more.
7. according to the method described in claim 6, it is characterized in that, the method also includes using methylaluminoxane to urge as helping
Agent.
8. according to the method described in claim 6, it is characterized in that, the C2-C8Low-carbon alkene is selected from ethylene, propylene, 1- fourth
Alkene, 1- hexene or 1- octene.
9. according to the method described in claim 6, it is characterized in that, the branched polyolefin compound have 800000~
The molecular weight of 1600000g/mol and 110~130 DEG C of fusing point.
10. according to the method described in claim 6, it is characterized in that, the degree of branching of the branched polyolefin compound is every
The corresponding methyl number of 1000 carbon atoms is 30-60.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110483587A (en) * | 2019-08-27 | 2019-11-22 | 中国科学技术大学 | Big steric hindrance ketimide Raney nickel and its ligand compound, preparation method and application |
| CN111362838A (en) * | 2020-04-14 | 2020-07-03 | 中国科学技术大学 | Urea group-containing diimine palladium catalyst, ligand thereof and application thereof in olefin polymerization |
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| CN112745361A (en) * | 2019-10-31 | 2021-05-04 | 中国石油化工股份有限公司 | Diimine complex and preparation method and application thereof |
| CN113233994A (en) * | 2021-04-30 | 2021-08-10 | 河北工业大学 | Alpha-diimine compound with multiple hydroxyl groups, complex, load and application thereof |
| CN114014961A (en) * | 2021-11-03 | 2022-02-08 | 大连理工大学 | Large steric hindrance ortho-benzene bridge bimetal alpha-diimine catalyst, preparation method and application |
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| CN115073506A (en) * | 2022-07-05 | 2022-09-20 | 中国科学技术大学 | Supported alpha-diimine nickel catalyst and preparation and application of ligand thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040132936A1 (en) * | 2003-01-03 | 2004-07-08 | Tagge Christopher D. | Transition metal complexes in the controlled synthesis of polyolefins substituted with functional groups |
| CN105152970A (en) * | 2015-06-25 | 2015-12-16 | 中国科学技术大学 | Diimine palladium catalyst with great steric hindrance, and ligand, preparation method and application thereof |
| CN105968027A (en) * | 2016-06-13 | 2016-09-28 | 中国科学技术大学 | Asymmetric diimine palladium catalyst and ligand, preparation method and application thereof |
| CN107698699A (en) * | 2017-09-27 | 2018-02-16 | 常州大学 | For being catalyzed the α diimine nickels containing contraposition benzhydryl substitution of ethene and 2 hexene oligomerizations（Ⅱ）Complex |
| CN108794545A (en) * | 2017-04-28 | 2018-11-13 | 中国科学院化学研究所 | It is used to prepare the alpha-nickel diimine compound of asymmetry containing tertiary butyl, the Preparation method and use of ultra-high molecular weight polyethylene elastomer |
-
2019
- 2019-01-17 CN CN201910043404.1A patent/CN109608507B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040132936A1 (en) * | 2003-01-03 | 2004-07-08 | Tagge Christopher D. | Transition metal complexes in the controlled synthesis of polyolefins substituted with functional groups |
| CN105152970A (en) * | 2015-06-25 | 2015-12-16 | 中国科学技术大学 | Diimine palladium catalyst with great steric hindrance, and ligand, preparation method and application thereof |
| CN105968027A (en) * | 2016-06-13 | 2016-09-28 | 中国科学技术大学 | Asymmetric diimine palladium catalyst and ligand, preparation method and application thereof |
| CN108794545A (en) * | 2017-04-28 | 2018-11-13 | 中国科学院化学研究所 | It is used to prepare the alpha-nickel diimine compound of asymmetry containing tertiary butyl, the Preparation method and use of ultra-high molecular weight polyethylene elastomer |
| CN107698699A (en) * | 2017-09-27 | 2018-02-16 | 常州大学 | For being catalyzed the α diimine nickels containing contraposition benzhydryl substitution of ethene and 2 hexene oligomerizations（Ⅱ）Complex |
Non-Patent Citations (3)
| Title |
|---|
| JINLONG SUN等，: "Ligand steric effects on a-diimine nickel catalyzed ethylene and 1-hexene polymerization", 《RSC ADV.》 * |
| JUNG-HUA LEE等，: "Ethylene Polymerization Catalyzed by Diimine-Palladium(II) Complexes", 《JOURNAL OF THE CHINESE CHEMICAL SOCIETY》 * |
| SHENGYU DAI等，: "Highly Robust Palladium(II) a-Diimine Catalysts for Slow-Chain-", 《ANGEW. CHEM. INT. ED.》 * |
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