CN113372389B - Phosphine-nitrogen ligand, preparation method thereof, ethylene oligomerization ternary catalyst system and application - Google Patents
Phosphine-nitrogen ligand, preparation method thereof, ethylene oligomerization ternary catalyst system and application Download PDFInfo
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- CN113372389B CN113372389B CN202110722509.7A CN202110722509A CN113372389B CN 113372389 B CN113372389 B CN 113372389B CN 202110722509 A CN202110722509 A CN 202110722509A CN 113372389 B CN113372389 B CN 113372389B
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- phosphine
- reaction
- ethylene
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- chromium
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- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims abstract description 101
- 239000005977 Ethylene Substances 0.000 title claims abstract description 101
- 239000003446 ligand Substances 0.000 title claims abstract description 82
- 238000006384 oligomerization reaction Methods 0.000 title claims abstract description 62
- KUXDQQMEFBFTGX-UHFFFAOYSA-N [N].P Chemical compound [N].P KUXDQQMEFBFTGX-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 239000003054 catalyst Substances 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 91
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims abstract description 22
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 22
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims abstract description 18
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000004519 manufacturing process Methods 0.000 claims abstract description 8
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 7
- -1 2,4-dimethylphenyl Chemical group 0.000 claims description 89
- 150000001875 compounds Chemical class 0.000 claims description 42
- 238000000034 method Methods 0.000 claims description 40
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 39
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 32
- 239000002904 solvent Substances 0.000 claims description 30
- 238000001816 cooling Methods 0.000 claims description 21
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 19
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 claims description 18
- XEHUIDSUOAGHBW-UHFFFAOYSA-N chromium;pentane-2,4-dione Chemical compound [Cr].CC(=O)CC(C)=O.CC(=O)CC(C)=O.CC(=O)CC(C)=O XEHUIDSUOAGHBW-UHFFFAOYSA-N 0.000 claims description 17
- 229910052757 nitrogen Inorganic materials 0.000 claims description 16
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 14
- 239000001257 hydrogen Substances 0.000 claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims description 14
- 230000035484 reaction time Effects 0.000 claims description 14
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 13
- 230000008569 process Effects 0.000 claims description 13
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-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
- FVKFHMNJTHKMRX-UHFFFAOYSA-N 3,4,6,7,8,9-hexahydro-2H-pyrimido[1,2-a]pyrimidine Chemical compound C1CCN2CCCNC2=N1 FVKFHMNJTHKMRX-UHFFFAOYSA-N 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 claims description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 7
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 7
- 239000012279 sodium borohydride Substances 0.000 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 6
- 125000004861 4-isopropyl phenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 5
- 229910052804 chromium Inorganic materials 0.000 claims description 5
- 239000011651 chromium Substances 0.000 claims description 5
- 238000004440 column chromatography Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 125000004860 4-ethylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])C([H])([H])[H] 0.000 claims description 4
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 claims description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 claims description 4
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methylcyclopentane Chemical compound CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 claims description 4
- NFJPEKRRHIYYES-UHFFFAOYSA-N methylidenecyclopentane Chemical compound C=C1CCCC1 NFJPEKRRHIYYES-UHFFFAOYSA-N 0.000 claims description 4
- 125000001624 naphthyl group Chemical group 0.000 claims description 4
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 238000001953 recrystallisation Methods 0.000 claims description 4
- 125000004198 2-fluorophenyl group Chemical group [H]C1=C([H])C(F)=C(*)C([H])=C1[H] 0.000 claims description 3
- 125000004180 3-fluorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C(F)=C1[H] 0.000 claims description 3
- 125000000590 4-methylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 claims description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 3
- 125000002178 anthracenyl group Chemical group C1(=CC=CC2=CC3=CC=CC=C3C=C12)* 0.000 claims description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 3
- 235000010290 biphenyl Nutrition 0.000 claims description 3
- 239000004305 biphenyl Substances 0.000 claims description 3
- 230000014759 maintenance of location Effects 0.000 claims description 3
- 125000003261 o-tolyl group Chemical group [H]C1=C([H])C(*)=C(C([H])=C1[H])C([H])([H])[H] 0.000 claims description 3
- 238000000746 purification Methods 0.000 claims description 3
- 238000007670 refining Methods 0.000 claims description 3
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 2
- YVSMQHYREUQGRX-UHFFFAOYSA-N 2-ethyloxaluminane Chemical compound CC[Al]1CCCCO1 YVSMQHYREUQGRX-UHFFFAOYSA-N 0.000 claims description 2
- 125000001255 4-fluorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1F 0.000 claims description 2
- 229910021555 Chromium Chloride Inorganic materials 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- 230000009471 action Effects 0.000 claims description 2
- 239000012298 atmosphere Substances 0.000 claims description 2
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 claims description 2
- WBKDDMYJLXVBNI-UHFFFAOYSA-K chromium(3+);2-ethylhexanoate Chemical compound [Cr+3].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O WBKDDMYJLXVBNI-UHFFFAOYSA-K 0.000 claims description 2
- RPBPCPJJHKASGQ-UHFFFAOYSA-K chromium(3+);octanoate Chemical compound [Cr+3].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O.CCCCCCCC([O-])=O RPBPCPJJHKASGQ-UHFFFAOYSA-K 0.000 claims description 2
- 150000004696 coordination complex Chemical class 0.000 claims description 2
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 claims description 2
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 2
- 239000001282 iso-butane Substances 0.000 claims description 2
- 239000012046 mixed solvent Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims description 2
- 125000002524 organometallic group Chemical group 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 239000003426 co-catalyst Substances 0.000 claims 2
- WVSBQYMJNMJHIM-UHFFFAOYSA-N (benzene)chromium tricarbonyl Chemical group [Cr].[O+]#[C-].[O+]#[C-].[O+]#[C-].C1=CC=CC=C1 WVSBQYMJNMJHIM-UHFFFAOYSA-N 0.000 claims 1
- 125000004199 4-trifluoromethylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C(F)(F)F 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 25
- 229920000642 polymer Polymers 0.000 abstract description 9
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 11
- 238000005259 measurement Methods 0.000 description 11
- 239000007858 starting material Substances 0.000 description 11
- 238000007599 discharging Methods 0.000 description 10
- 239000005457 ice water Substances 0.000 description 10
- 239000000126 substance Substances 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 7
- XGRJZXREYAXTGV-UHFFFAOYSA-N chlorodiphenylphosphine Chemical compound C=1C=CC=CC=1P(Cl)C1=CC=CC=C1 XGRJZXREYAXTGV-UHFFFAOYSA-N 0.000 description 6
- QXFRPNUEXMUURF-UHFFFAOYSA-N chromium;oxolane Chemical compound [Cr].C1CCOC1 QXFRPNUEXMUURF-UHFFFAOYSA-N 0.000 description 6
- 239000012295 chemical reaction liquid Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000004711 α-olefin Substances 0.000 description 5
- 238000007792 addition Methods 0.000 description 3
- GHAKVYIBHNIGBD-UHFFFAOYSA-N chloro-(2-fluorophenyl)-phenylphosphane Chemical compound FC1=CC=CC=C1P(Cl)C1=CC=CC=C1 GHAKVYIBHNIGBD-UHFFFAOYSA-N 0.000 description 3
- PNFPTKBGLKZWPC-UHFFFAOYSA-N chloro-(3-fluorophenyl)-phenylphosphane Chemical compound FC1=CC=CC(P(Cl)C=2C=CC=CC=2)=C1 PNFPTKBGLKZWPC-UHFFFAOYSA-N 0.000 description 3
- CBWKFJKGHCCNBC-UHFFFAOYSA-N chloro-(4-fluorophenyl)-phenylphosphane Chemical compound C1=CC(F)=CC=C1P(Cl)C1=CC=CC=C1 CBWKFJKGHCCNBC-UHFFFAOYSA-N 0.000 description 3
- PEKLJSZEUFVLKO-UHFFFAOYSA-N chloro-bis(2-methoxyphenyl)phosphane Chemical compound COC1=CC=CC=C1P(Cl)C1=CC=CC=C1OC PEKLJSZEUFVLKO-UHFFFAOYSA-N 0.000 description 3
- YTFQUBRFOJIJOZ-UHFFFAOYSA-N chloro-bis(4-methoxyphenyl)phosphane Chemical compound C1=CC(OC)=CC=C1P(Cl)C1=CC=C(OC)C=C1 YTFQUBRFOJIJOZ-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical group [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 230000002159 abnormal effect Effects 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- BJBXRRHIBSXGLF-UHFFFAOYSA-N chloro-bis(4-methylphenyl)phosphane Chemical compound C1=CC(C)=CC=C1P(Cl)C1=CC=C(C)C=C1 BJBXRRHIBSXGLF-UHFFFAOYSA-N 0.000 description 2
- PBLUOOURLNAOAJ-UHFFFAOYSA-N chloro-bis[4-(trifluoromethyl)phenyl]phosphane Chemical compound C1=CC(C(F)(F)F)=CC=C1P(Cl)C1=CC=C(C(F)(F)F)C=C1 PBLUOOURLNAOAJ-UHFFFAOYSA-N 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 125000002306 tributylsilyl group Chemical group C(CCC)[Si](CCCC)(CCCC)* 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000009566 Mao-to Substances 0.000 description 1
- ZUSWDTWYONAOPH-UHFFFAOYSA-N [2-(trifluoromethyl)phenyl]hydrazine;hydrochloride Chemical group [Cl-].[NH3+]NC1=CC=CC=C1C(F)(F)F ZUSWDTWYONAOPH-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000005234 alkyl aluminium group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- URAPFRVSOJQECJ-UHFFFAOYSA-N benzene chromium Chemical compound [Cr].C1=CC=CC=C1 URAPFRVSOJQECJ-UHFFFAOYSA-N 0.000 description 1
- VNIXYVYRHPMNGR-UHFFFAOYSA-N bis(4-methylphenyl)phosphane;hydrochloride Chemical compound Cl.C1=CC(C)=CC=C1PC1=CC=C(C)C=C1 VNIXYVYRHPMNGR-UHFFFAOYSA-N 0.000 description 1
- LWGHHAWTVLRZGE-UHFFFAOYSA-N bis[4-(trifluoromethyl)phenyl]phosphane;hydrochloride Chemical compound Cl.C1=CC(C(F)(F)F)=CC=C1PC1=CC=C(C(F)(F)F)C=C1 LWGHHAWTVLRZGE-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001844 chromium Chemical class 0.000 description 1
- CYOMBOLDXZUMBU-UHFFFAOYSA-K chromium(3+);oxolane;trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3].C1CCOC1.C1CCOC1.C1CCOC1 CYOMBOLDXZUMBU-UHFFFAOYSA-K 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000006713 insertion reaction Methods 0.000 description 1
- 238000010813 internal standard method Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000010689 synthetic lubricating oil Substances 0.000 description 1
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 description 1
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- NHXVNEDMKGDNPR-UHFFFAOYSA-N zinc;pentane-2,4-dione Chemical group [Zn+2].CC(=O)[CH-]C(C)=O.CC(=O)[CH-]C(C)=O NHXVNEDMKGDNPR-UHFFFAOYSA-N 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
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6561—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom containing systems of two or more relevant hetero rings condensed among themselves or condensed with a common carbocyclic ring or ring system, with or without other non-condensed hetero rings
-
- 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
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
- B01J31/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
- B01J31/143—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron of aluminium
-
- 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
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/2247—At least one oxygen and one phosphorous atom present as complexing atoms in an at least bidentate or bridging ligand
-
- B01J35/19—
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
- C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
- C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
- C07C2/08—Catalytic processes
- C07C2/26—Catalytic processes with hydrides or organic compounds
- C07C2/32—Catalytic processes with hydrides or organic compounds as complexes, e.g. acetyl-acetonates
-
- 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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/20—Olefin oligomerisation or telomerisation
-
- 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
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- B01J2531/62—Chromium
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Abstract
The invention provides a phosphine-nitrogen ligand, a preparation method thereof, an ethylene oligomerization three-way catalyst system and application. The phosphine-nitrogen ligand has a structure shown in a formula I, has high stability, high catalyst activity and high product selectivity, and improves the tolerance temperature of the catalyst. The three-way catalyst system comprises a phosphine-nitrogen ligand shown in a formula I, a chromium metal compound and an alkyl aluminoxane cocatalyst. The catalyst is used for ethylene oligomerization, can realize reaction at higher temperature, reduces the generation of polymers, has the beneficial effects that the activity can reach more than 1500 kg/(gCr.h), and the total selectivity of 1-hexene and 1-octene is more than 90 percent, can reduce the production cost, and has high economic added value.
Description
Technical Field
The invention relates to a three-way catalyst system, in particular to a phosphine-nitrogen ligand, a preparation method thereof, an ethylene oligomerization catalyst system and application.
Background
Linear alpha-olefins are understood to mean C with a double bond at the end of the molecule 4 The linear olefin is an important raw material in petrochemical industry, and can be used as a comonomer, a synthetic intermediate of a surfactant, alcohol for a plasticizer, synthetic lubricating oil, an oil additive and other fields. The polyethylene comonomer is the most abundant in the alpha-olefin consumption. Among them, polyethylene produced by using 1-hexene and 1-octene as comonomers has better tear resistance and impact resistance, and is receiving more and more attention from the market.
At present, linear alpha-olefin products are mostly derived from ethylene oligomerization processes. Products in the ethylene oligomerization process are distributed in Poisson, specific components are poor in selectivity, specific high-purity linear alpha-olefin can be obtained only through a rectification separation process with high energy consumption, and the production cost is relatively high. The selective oligomerization of ethylene to produce 1-hexene, 1-octene and other high-grade linear alpha-olefins has the advantages of simple process, low investment, high atom utilization rate and the like, and is a research hotspot of academia.
WO2004/056478 by Sasol discloses an ethylene tetramerization catalyst system composed of chromium acetylacetonate, PNP ligand and MAO, and the selectivity of 1-octene can reach 70%. On the basis of the research of Sasol company, patent CN105562090A, CN105562101A, CN105562102A, CN107282128A, CN105562103A, CN105562100A, CN105498840A, CN105562095A, CN107282125A and the like disclose a series of tetramerization catalysts containing different ligand compounds, which have high catalytic activity, but the selectivity of target products, namely 1-hexene and 1-octene, is basically below 85 wt%. Patent CN101605605B discloses a catalyst containing PCCP skeleton structure ligand, which can be used for preparing 1-octene by ethylene tetramerization, but the polymer content is higher.
The performance of the ethylene oligomerization catalyst disclosed at present is mainly influenced by a ligand structure, the steric hindrance effect and the electron donating effect of the ligand have great influence on the activity and the selectivity, the product selectivity is basically below 85wt%, the polymer selectivity is generally above 0.2wt%, the tolerance temperature of the catalyst is generally less than 60 ℃, the production stability is poor when the conditions of abnormal temperature, high temperature fluctuation and the like occur, and the long-period operation of the device is very unfavorable. Therefore, the development of a novel ligand structure catalyst is of great significance to the development of ethylene tetramerization industrialization.
Disclosure of Invention
In order to solve the technical problems, the invention provides an ethylene oligomerization three-way catalyst system and a preparation method and application thereof.
The PNNNP ligand adopts a ring structure, and the six-membered ring has better stability and higher temperature tolerance compared with an open structure. The three closed-loop structures formed by nitrogen and carbon and the complex structure formed by the metal chromium salt have larger steric hindrance, the ethylene molecules are subjected to insertion reaction to not easily generate a structure with more than nine-membered rings, the selectivity of 1-hexene and 1-octene in the product is higher and can reach more than 90%, the polymer selectivity is low, and the polymer has excellent industrial prospect.
In order to realize the purpose, the technical scheme adopted by the invention is as follows:
in one aspect, the invention provides a phosphine-nitrogen ligand, the structure of which is shown in formula I:
in the formula I, R 1 、R 2 Each independently selected from alkyl, aryl or derivatives thereof, R 1 、R 2 May be the same or different;
preferably, in formula I, R 1 、R 2 Each independently selected from phenyl, benzyl, biphenyl, naphthyl, anthracenyl, ethenyl, propenyl, cyclohexyl, 4-methylcyclohexyl, 4-ethylcyclohexyl, 4-isopropylcyclohexyl, 2-methylphenyl, 4-methylphenyl, 2,4-dimethylphenyl, 2,6-dimethylphenyl, 2-ethylphenyl, 4-ethylphenyl, 2,4-diethylphenyl, 2,6-diethylphenyl, 2-isopropylphenyl, 4-isopropylphenyl, 2,4-diisopropylphenyl, 2,6-diisopropylphenyl, 2-butylphenyl, 4-butylphenyl, 2,4-dibutylphenyl, 2,6-dibutylphenyl, 4-methoxyphenyl, o-methoxyphenyl, 4-ethoxyphenyl, o-ethoxyphenyl, 2- (trimethylsilanyl) phenyl, 3- (trimethylalkyl) phenyl, 4- (trimethylsilanyl) phenyl, 2-fluorophenyl, 3-fluorophenyl, 4- (trifluoromethylphenyl) phenyl, tri-n-butylsilyl, 3- (trifluoromethylphenyl) 5364-trifluoromethylphenyl, tri (n-butylsilyl) phenyl, 3- (trifluoromethylphenyl) phenyl, 4- (trifluoromethylphenyl) 5364-butylsilyl, 3- (trifluoromethylphenyl) phenyl).
More preferably, the phosphine-nitrogen ligand of formula I has any one of the structures shown in formulas L1-L10 below:
the invention also provides a preparation method of the phosphine-nitrogen ligand shown in the formula I, which comprises the following steps:
1) Dissolving a compound 1,5,7-triazabicyclo (4.4.0) dec-5-ene in methanol under the atmosphere of nitrogen, and reacting for 1-5 h at 10-35 ℃ under the action of sodium borohydride to obtain a compound shown in a formula II;
2) Dissolving a compound shown as a formula II in a solvent A under anhydrous and anaerobic conditions, adding triethylamine and a compound shown as a formula III, and reacting to obtain a phosphine-nitrogen ligand shown as a formula I;
in the formula III, R 1 、R 2 Same as in formula I, i.e. R 1 、R 2 Each independently selected from alkyl, aryl or derivatives thereof;
preferably, R 1 、R 2 Each independently selected from the group consisting of phenyl, benzyl, biphenyl, naphthyl, anthracenyl, ethenyl, propenyl, cyclohexyl, 4-methylcyclohexyl, 4-ethylcyclohexyl, 4-isopropylcyclohexyl, 2-methylphenyl, 4-methylphenyl, 2,4-dimethylphenyl, 2,6-dimethylphenyl, 2-ethylphenyl, 4-ethylphenyl, 2,4-diethylphenyl, 2,6-diethylphenyl, 2-isopropylphenyl, 4-isopropylphenyl, 2,4-diisopropylphenyl, 2,6-diisopropylphenyl, 2-butylphenyl, naphthyl, 4-methylcyclohexyl, 4-ethylcyclohexyl, 4-isopropylphenyl, 4-ethylphenyl, 2-ethylphenyl, 4-isopropylphenyl, 2-ethylphenyl, 2-isopropylphenyl, and 2-isopropylphenyl 4-butylphenyl, 2,4-dibutylphenyl, 2,6-dibutylphenyl, 4-methoxyphenyl, o-methoxyphenyl, 4-ethoxyphenyl, o-ethoxyphenyl, 2- (trimethylsilanyl) phenyl, 3- (trimethylsilanyl) phenyl, 4- (trimethylsilanyl) phenyl, 2-fluorophenyl, 3-fluorophenyl, 4-fluorophenyl, 2- (trifluoromethyl) phenyl, 3- (trifluoromethyl) phenyl, 4- (trifluoromethyl) phenyl, 3,5-bis (trifluoromethyl) phenyl, 2- (tri-n-butylsilyl) phenyl, 3- (tri-n-butylsilyl) phenylA group, 4- (tri-n-butylsilyl) phenyl;
more preferably, the compound of formula III is selected from diphenyl phosphonium chloride, chlorobis [4- (trifluoromethyl) phenyl ] phosphine, chloro (2-fluorophenyl) (phenyl) phosphine, chloro (3-fluorophenyl) (phenyl) phosphine, chloro (4-fluorophenyl) (phenyl) phosphine, chlorobis (4-methylphenyl) phosphine, chlorobis (2-methoxyphenyl) phosphine, chlorobis (4-methoxyphenyl) phosphine, 4- (trimethylsilanyl) phenyl phosphonium chloride, 4- (tri-n-butylsilyl) phenyl phosphonium chloride.
Further, in step 1), the molar ratio of 1,5,7-triazabicyclo (4.4.0) dec-5-ene to sodium borohydride is 1.9 to 5, preferably 1:1 to 3, and for example, 1;
the concentration of 1,5,7-triazabicyclo (4.4.0) deca-5-ene dissolved in methanol is 0.1-5 mol/L;
further, in the step 1), the reaction temperature is preferably 15-25 ℃, and the reaction time is preferably 1-3 h;
further, in the step 1), after the reaction is completed, a drying post-treatment process is further included, and preferably, the spin-drying condition is 30-50 ℃ under the condition of vacuum pump suction pressure.
In step 2), the molar ratio of the compound represented by formula II to the triethylamine and the compound represented by formula III is 1 (1.5 to 3.5) (2.2 to 3.6), and for example, 1.
Further, in the step 2), the solvent A is selected from any one or a combination of at least two of dichloromethane, acetonitrile, n-hexane, n-heptane and toluene, preferably dichloromethane and/or acetonitrile;
preferably, the concentration of the compound shown in the formula II dissolved in the solvent A is 0.1-2 mol/L.
Further, in the step 2), the triethylamine is continuously added, preferably dropwise added, wherein the dropwise adding time is preferably 0.5-3 hours, and more preferably 0.8-1.5 hours;
preferably, when the triethylamine addition is completed, the compound shown in the formula III is added; the diphenyl phosphine chloride can release a large amount of heat in the feeding process, and more preferably, the compound shown in the formula III is added in a plurality of times in sections, and the temperature of the system is controlled within the range of-5 ℃ in the feeding process.
Further, in the step 2), the reaction is carried out at the temperature of-10-30 ℃, preferably-10-25 ℃; the reaction time is 9 to 30 hours, preferably 12 to 24 hours.
Preferably, the reaction is carried out in stages, and as a preferred scheme, the method is as follows: firstly reacting for 3-6 h at-10-0 ℃, then heating to 10-25 ℃ and continuing to react for 6-24 h;
preferably, the rate of temperature rise is 1 to 3 ℃/min.
Further, in the step 2), after the reaction is finished, post-treatment processes such as refining and purification are also included;
as a preferable scheme, for example, the target product can be purified by column chromatography and recrystallization purification; the preferable conditions of the column chromatography are that the height-diameter ratio of the chromatographic column is 2-4, the retention time is 1-2 min, the solvent used for recrystallization is preferably a mixed solvent of ethanol and ethyl acetate, and the mixing volume ratio is 1:0.05 to 1.
On the other hand, the invention provides an ethylene oligomerization three-way catalyst system which comprises phosphine-nitrogen ligand shown in formula I, chromium metal compound and alkyl aluminoxane cocatalyst.
Further, the molar ratio of the chromium metal compound to the phosphine-nitrogen ligand is 1: (1 to 4.5) may be, for example, 1:1, 1.5, 1:2, 1:3, 1:4, 1: (1-2);
the molar ratio of the alkylaluminoxane cocatalyst to the chromium metal compound is (50 to 1800): 1, and may be, for example, 50.
Further, the chromium metal compound is selected from an organic salt, an inorganic salt, a coordination complex or an organometallic complex of chromium, preferably any one of or a combination of at least two of chromium acetylacetonate, chromium chloride, chromium tris (tetrahydrofuran) trichloride, chromium (III) 2-ethylhexanoate, chromium (III) octanoate, chromium hexacarbonyl and chromium (benzene) tricarbonyl.
Further, the alkylaluminoxane cocatalyst is selected from C1-C4 alkyl aluminoxane cocatalysts, preferably any one or a combination of at least two of methylaluminoxane, modified methylaluminoxane and ethylaluminoxane, and more preferably methylaluminoxane and/or modified methylaluminoxane.
In another aspect, the invention also provides an ethylene oligomerization method, which comprises the step of carrying out ethylene oligomerization reaction in the presence of the three-way catalyst system to prepare 1-hexene and 1-octene.
As a preferable scheme, the ethylene oligomerization method comprises the following steps:
heating a reaction kettle to 110-160 ℃ before reaction, vacuumizing for 2-6 h, performing nitrogen replacement, cooling to 10-40 ℃, performing ethylene replacement, adding a solvent B and an alkylaluminoxane cocatalyst, then adding a chromium metal compound and a phosphine-nitrogen ligand shown in a formula I, introducing 0.1-0.8 MPa of hydrogen and 2-10 MPa of ethylene in sequence to start reaction when the temperature reaches 35-120 ℃, preferably 40-70 ℃, and performing reaction for 5-240 min, preferably 10-100 min.
The three-way catalyst system is applied to ethylene oligomerization reaction, and the solvent B is selected from any one or the combination of at least two of n-butane, isobutane, n-pentane, cyclopentane, methylcyclopentane, methylene cyclopentane, n-hexane, cyclohexane, methylcyclohexane, n-heptane, n-octane, n-nonane, benzene, toluene and xylene;
preferably, the molar concentration of the catalyst in the solvent B is 5 to 50 [ mu ] mol/L based on the chromium metal compound therein.
In a more specific embodiment, the ethylene oligomerization method specifically comprises the following steps:
the polymerization was carried out in a 300mL autoclave using solvent B having a purity of 99.5% or more. Before the reaction, the reaction kettle is heated to 130 ℃, vacuumized for 2-3 hours and replaced by nitrogen for three times. Cooling to 10-40 deg.c, replacing with ethylene, adding solvent B and alkyl aluminoxane cocatalyst, adding chromium metal compound and phosphine-nitrogen ligand of the formula I, introducing hydrogen of 0.1-0.8 MPa and ethylene of 2-10 MPa for reaction at 35-120 deg.c, preferably 40-90 deg.c for 5-240 min, preferably 10-100 min.
Compared with the prior art, the invention has the beneficial effects that:
the invention designs a PNNNP type ethylene oligomerization catalyst ligand with a triazo-bicyclic structure, which has high stability, high catalyst activity and high product selectivity, improves the tolerant temperature of the catalyst, can realize reaction at higher temperature, can also maintain stable high activity and high selectivity even if the temperature is abnormal and fluctuates at high temperature, and reduces the generation of polymers. When the ternary catalyst system is used for ethylene oligomerization, the activity can reach more than 1500 kg/(gCr.h), the selectivity of the polymer is obviously reduced, the total selectivity of 1-hexene and 1-octene is more than 90%, the production cost can be reduced, and the economic added value is high.
Detailed Description
The present invention is further illustrated by the following specific examples, which are intended to be illustrative of the invention and are not to be construed as limiting the scope of the invention.
The starting materials used in the examples are, unless otherwise specified, conventional starting materials commercially available in the art, and the purity specifications used are either analytically or chemically pure. Relevant solvents in the examples molecular sieves were soaked to remove water before use.
Source information of main raw materials:
1,5,7-triazabicyclo (4.4.0) dec-5-ene: 98%, shanghai TCI chemicals, ltd;
triethylamine: not less than 99.5% (GC), shanghai Aladdin Biotechnology Limited;
diphenyl phosphine chloride: 97%, alfa Angsa (China) Chemicals, inc.;
methanol: 99.5%, beijing Bailingwei science and technology Limited;
sodium borohydride: 98%, shanghai Aladdin Biotechnology, inc.;
dichloromethane: 99.5%, shanghai Aladdin Biotechnology, inc.;
acetonitrile: 99.5%, beijing Bailingwei science and technology Limited;
chloro-bis [4- (trifluoromethyl) phenyl ] phosphine: 97%, sahn chemical technology (China) Inc.;
chloro (2-fluorophenyl) (phenyl) phosphine: 97%, shanghai Xinkai pharmaceutical science and technology Limited;
chloro (3-fluorophenyl) (phenyl) phosphine: 97%, shanghai Xinkai pharmaceutical science and technology Limited;
chloro (4-fluorophenyl) (phenyl) phosphine: 97%, shanghai Xinkai pharmaceutical science and technology Limited;
chlorobis (4-methylphenyl) phosphine: more than 97%, jiangsu Xinnoco catalyst Co., ltd;
chlorobis (2-methoxyphenyl) phosphine: 98%, alfa aesar (china) chemicals ltd;
chlorobis (4-methoxyphenyl) phosphine: 98%, alfa aesar (china) chemicals ltd;
4- (trimethylsilanyl) phenylphosphine chloride: 97%, jiangsu Xinnoco catalyst, inc.;
4- (tri-n-butylsilyl) phenyl phosphine chloride: 97%, jiangsu Xinnoco catalyst Co., ltd;
ethyl acetate: 99.9%%, welibos technologies ltd;
ethanol: analytical purity, chemical reagents of national drug group limited;
MMAO-3a (modified methylaluminoxane): concentration 7wt% of Al, n-heptane solvent, nomon chemical (Ningbo) Co., ltd;
MAO (methylaluminoxane), 10% strength by weight, toluene solvent, nomoon chemical (Ningbo) Ltd;
iPr-PNP (CAS: 60981-68-20): more than 97%, jiangsu Xinnoco catalyst Co.
The activity of the catalyst for oligomerization is qualitatively and quantitatively analyzed by components in the reaction solution, and the conditions of a GC analyzer are as follows:
the instrument model is as follows: shimadzu GC2010; and (3) chromatographic column: DB-5 (30m 0.25mm 0.25 μm);
column temperature procedure: maintaining at 35 deg.C for 10min, heating to 250 deg.C at a speed of 10 deg.C/min, and maintaining at the temperature for 10min;
detector temperature: 300 ℃; carrier gas: 1bar; air: 0.3bar; gas (H) 2 )：0.3bar。
Product quality analysis was performed using an internal standard method:
in the formula m 1 Is the mass of a certain product, m is the mass of the internal standard, a 1 The peak area of the product detected in the gas chromatogram is shown as a peak area of an internal standard substance. k is a correction factor associated with the substance to be measured and the detection condition.
The nuclear magnetic instrument adopts Agilent 400 MNMR, and the used solvent is deuterated chloroform.
Example 1
Preparation of phosphine-nitrogen ligand:
1) Under the nitrogen atmosphere, 1mol (139.2 g) of 1,5,7-triazabicyclo (4.4.0) dec-5-ene is dissolved in 800ml methanol, 1mol (37.8 g) of sodium borohydride is added, reaction is carried out for 3h at 25 ℃, and then 0.95mol (138.7 g) of a compound shown in formula II is obtained by spin-drying at 30-50 ℃ under the condition of vacuum pump negative pressure:
the nuclear magnetic data for the compound of formula II is as follows:
1H NMR(400MHz，CDCl 3 )：2.29-2.63(m,8H)，1.91(s,2H)，1.48-1.55(m,4H).
2) Dissolving 100mmol (13.9 g) of the compound shown in the formula II in 200ml of dichloromethane under anhydrous and oxygen-free conditions; at the temperature of minus 5 ℃, 220mmol (22.3 g) of triethylamine is dripped into the reaction liquid under stirring, 110mmol (24.3 g) of diphenyl phosphine chloride is slowly added into the reaction liquid, the temperature of the system is controlled at 0 ℃ in the process of charging the diphenyl phosphine chloride, heat release is not continued, 110mmol (24.3 g) of diphenyl phosphine chloride is added into the reaction liquid, the reaction liquid is stirred at the temperature of 0 ℃ for carrying out first-stage low-temperature reaction, the low-temperature constant-temperature reaction bath is removed after 3h, and then the reaction liquid is stirred at the temperature of 25 ℃ for carrying out second-stage reaction for 12 h. Purifying the reaction solution by using column chromatography (tetrahydrofuran elution, height-diameter ratio of 2, retention time of 1-2 min), and then recrystallizing at 78 ℃ (the solvent is ethanol: ethyl acetate = 5:1) to obtain the phosphine-nitrogen ligand shown as the following formula L1:
nuclear magnetic data for ligand L1 are as follows: 1H NMR (400MHz, CDCl) 3 )：7.38-7.45(m,20H)，4.89(s,1H)，2.31-2.60(m,8H)，1.50-1.52(m,4H).
Oligomerization of ethylene:
before reaction, a 300ml reaction kettle is heated to 120 ℃, vacuumized for 3 hours and replaced by nitrogen for three times. When the temperature is cooled to 35 ℃, ethylene is replaced twice, 100ml of dehydrated and deoxidized solvent methylcyclohexane and 0.8ml (1.4 mmol) of MMAO-3a are added, then 4.2 mu mol of phosphine-nitrogen ligand L1 and 3.5 mu mol of chromium acetylacetonate (the molar ratio of MMAO-3a to chromium acetylacetonate is 400 1) are added, and when the temperature is constant at 50 ℃, 0.5Mpa hydrogen and 4.5MPa ethylene are sequentially introduced to start reaction. The reaction temperature is 50 ℃, and the reaction time is 60min. After the reaction is finished, closing the ethylene inlet valve, using ice water bath or quickly cooling to below 5 ℃, slowly releasing pressure, and discharging the reactor to obtain the ethylene oligomerization product. The product was analyzed by GC and the results of the catalyst activity and selectivity measurements are shown in Table 2.
Example 2
Preparation of phosphine-nitrogen ligand:
phosphine-nitrogen ligand L2 was prepared according to the procedure of example 1, except that the compound of formula III was added in different amounts, and that the molar ratios of the starting materials and the reaction conditions shown in Table 1 were different: the compound of formula III is selected from chloro (2-fluorophenyl) (phenyl) phosphine to provide a phosphine-nitrogen ligand of formula L2:
nuclear magnetic data for ligand L2 are as follows: 1H NMR (400MHz, CDCl) 3 )：7.22-7.75(m,18H)，4.92(s,1H)，2.33～2.65(m，8H)，1.49～1.58(m，4H).
Oligomerization of ethylene:
before the reaction, a 500ml reaction kettle is heated to 120 ℃, vacuumized for 4 hours and replaced by nitrogen for three times. Cooling to 35 ℃, replacing ethylene twice, adding 200ml of dehydrated and deoxidized solvent methylcyclohexane and 0.96ml (1.75 mmol) of MMAO-3a, then adding 3.85 mu mol of ligand L2 and 3.5 mu mol of trichlorotris (tetrahydrofuran) chromium (the molar ratio of MMAO-3a to trichlorotris (tetrahydrofuran) chromium is 500, and introducing 0.4Mpa hydrogen and 4.5MPa ethylene in sequence to start reaction when the temperature is constant at 65 ℃. The reaction temperature is 65 ℃ and the reaction time is 30min. After the reaction is finished, closing the ethylene inlet valve, using ice water bath or quickly cooling to below 5 ℃, slowly releasing pressure, and discharging the reactor to obtain the ethylene oligomerization product. The product was analyzed by GC and the results of the catalyst activity and selectivity measurements are shown in Table 2.
Example 3
Preparation of phosphine-nitrogen ligand:
phosphine-nitrogen ligand L3 was prepared according to the procedure of example 1, except that the compound of formula III was added in a different manner, and that the molar ratios of the starting materials and the reaction conditions shown in Table 1 were different: the compound of formula III is selected from chloro (3-fluorophenyl) (phenyl) phosphine to provide a phosphine-nitrogen ligand of formula L3 below:
nuclear magnetic data for ligand L3 are as follows: 1H NMR (400MHz, CDCl) 3 )：7.15-7.45(m,18H)，4.88(s,1H)，2.33～2.65(m，8H)，1.49～1.58(m，4H).
Oligomerization of ethylene:
before the reaction, a 500ml reaction kettle is heated to 120 ℃, vacuumized for 2 hours and replaced by nitrogen for three times. After the temperature is cooled to 35 ℃, ethylene is replaced twice, 200ml of dehydrated and deoxidized solvent toluene and 1.14ml (1.75 mmol) of MAO are added, then 5.25 mu mol of ligand L3 and 3.5 mu mol of trichlorotris (tetrahydrofuran) chromium are added, the molar ratio of MAO to trichlorotris (tetrahydrofuran) chromium is 500, and the reaction is started by sequentially introducing 0.4Mpa of hydrogen and 4.5MPa of ethylene when the temperature is constant at 60 ℃. The reaction temperature is 70 ℃, and the reaction time is 60min. After the reaction is finished, closing the ethylene inlet valve, using ice water bath or quickly cooling to below 5 ℃, slowly releasing pressure, and discharging the reactor to obtain the ethylene oligomerization product. The product was analyzed by GC and the results of the catalyst activity and selectivity measurements are shown in Table 2.
Example 4
Preparation of phosphine-nitrogen ligand:
phosphine-nitrogen ligand L4 was prepared according to the procedure of example 1, except that the compound of formula III was added in different amounts, and that the molar ratios of the starting materials and the reaction conditions shown in Table 1 were different: the compound of formula III is selected from chloro (4-fluorophenyl) (phenyl) phosphine to provide a phosphine-nitrogen ligand of formula L4 below:
nuclear magnetic data for ligand L4 are as follows: 1H NMR (400MHz, CDCl) 3 ): 7.09-7.42 (m, 18H), 4.93 (s, 1H), 2.31-2.60 (m, 8H), 1.51-1.53 (m, 4H) ethylene oligomerization:
before the reaction, a 500ml reaction kettle is heated to 130 ℃, vacuumized for 2 hours and replaced by nitrogen for three times. Cooling to 35 ℃, replacing ethylene twice, adding 200ml of dehydrated and deoxidized solvent toluene and 1.2ml (2.1 mmol) of MMAO-3a, then adding 5 mu mol of ligand L4 and 3.5 mu mol of chromium acetylacetonate (the molar ratio of MMAO-3a to chromium acetylacetonate is 600: 1), and introducing 0.5Mpa hydrogen and 4.8MPa ethylene in sequence to start reaction when the temperature is constant at 100 ℃. The reaction temperature is 100 ℃, and the reaction time is 70min. After the reaction is finished, closing the ethylene inlet valve, using ice water bath or quickly cooling to below 5 ℃, slowly releasing pressure, and discharging the kettle to obtain the ethylene oligomerization product. The product was analyzed by GC and the results of the catalyst activity and selectivity measurements are shown in Table 2.
Example 5
Preparation of phosphine-nitrogen ligand:
phosphine-nitrogen ligand L5 was prepared according to the procedure of example 1, except that the compound of formula III was added in a different manner, and that the molar ratios of the starting materials and the reaction conditions shown in Table 1 were different: the compound of formula III is selected from bis [4- (trifluoromethyl) phenyl ] phosphine chloride to provide a phosphine-nitrogen ligand of formula L5:
nuclear magnetic data for ligand L5 are as follows: 1H NMR (400MHz, CDCl) 3 ): 7.31-7.62 (m, 18H), 4.91 (s, 1H), 2.29-2.59 (m, 8H), 1.47-1.54 (m, 4H) ethylene oligomerization:
before the reaction, a 500ml reaction kettle is heated to 145 ℃, vacuumized for 2.5 hours and replaced by nitrogen for three times. Cooling to 35 ℃, replacing ethylene twice, adding 200ml of dehydrated and deoxidized solvent cyclohexane and 0.4ml (0.7 mmol) of MMAO-3a, then adding 5.1 mu mol of ligand L5 and 3.5 mu mol of chromium acetylacetonate (the molar ratio of MMAO-3a to chromium acetylacetonate is 200: 1), and introducing 0.5Mpa hydrogen and 4.5MPa ethylene in sequence to start reaction when the temperature is constant at 50 ℃. The reaction temperature is 50 ℃, and the reaction time is 48min. After the reaction is finished, closing the ethylene inlet valve, using ice water bath or quickly cooling to below 5 ℃, slowly releasing pressure, and discharging the reactor to obtain the ethylene oligomerization product. The product was analyzed by GC and the results of the catalyst activity and selectivity measurements are shown in Table 2.
Example 6
Preparation of phosphine-nitrogen ligand:
phosphine-nitrogen ligand L6 was prepared according to the procedure of example 1, except that the compound represented by formula III was added differently, and the molar ratios of the starting materials and the reaction conditions shown in Table 1 were different: the compound of formula III is selected from bis (4-methylphenyl) phosphine chloride to provide a phosphine-nitrogen ligand of formula L6:
nuclear magnetic data for ligand L6 are as follows: 1H NMR (400MHz, CDCl) 3 ): 7.21-7.26 (m, 18H), 4.85 (s, 1H), 2.25-2.58 (m, 20H), 1.45-1.52 (m, 4H) ethylene oligomerization:
before reaction, a 500ml reaction kettle is heated to 120 ℃, vacuumized for 3 hours and replaced by nitrogen for three times. Cooling to 35 ℃, replacing ethylene twice, adding 200ml of dehydrated and deoxidized solvent methylcyclohexane and 1.4ml (2.45 mmol) of MMAO-3a, then adding 7 mu mol of ligand L6 and 3.5 mu mol of trichlorotris (tetrahydrofuran) chromium (the molar ratio of MMAO-3a to trichlorotris (tetrahydrofuran) chromium is 700), and introducing 0.5Mpa hydrogen and 5.0MPa ethylene in sequence to start reaction when the temperature is constant at 80 ℃. The reaction temperature is 80 ℃, and the reaction time is 60min. After the reaction is finished, closing the ethylene inlet valve, using ice water bath or quickly cooling to below 5 ℃, slowly releasing pressure, and discharging the reactor to obtain the ethylene oligomerization product. The product was analyzed by GC and the results of the catalyst activity and selectivity measurements are shown in Table 2.
Example 7
Preparation of phosphine-nitrogen ligand:
phosphine-nitrogen ligand L7 was prepared according to the procedure of example 1, except that the compound of formula III was added in a different manner, and that the molar ratios of the starting materials and the reaction conditions shown in Table 1 were different: the compound of formula III is selected from chlorobis (2-methoxyphenyl) phosphine to provide a phosphine-nitrogen ligand of formula L7:
nuclear magnetic data for ligand L7 are as follows: 1H NMR (400MHz, CDCl) 3 )：6.99-7.34(m,18H)，4.89(s,1H)，3.83(s，12H)，2.33～2.67(m，8H)，1.51～1.55(m，4H).
Oligomerization of ethylene:
before reaction, a 300ml reaction kettle is heated to 155 ℃, vacuumized for 3 hours and replaced by nitrogen for three times. Cooling to 35 ℃, replacing ethylene twice, adding 100ml of dehydrated and deoxidized solvent methylcyclohexane and 0.7ml (1.23 mmol) of MMAO-3a, then adding 2.2 mu mol of ligand L7 and 1.75 mu mol of chromium acetylacetonate (the molar ratio of MMAO-3a to chromium acetylacetonate is 700: 1), and introducing 0.5Mpa hydrogen and 4.5MPa ethylene in sequence to start reaction when the temperature is constant at 50 ℃. The reaction temperature is 50 ℃, and the reaction time is 55min. After the reaction is finished, closing the ethylene inlet valve, using ice water bath or quickly cooling to below 5 ℃, slowly releasing pressure, and discharging the reactor to obtain the ethylene oligomerization product. The product was analyzed by GC and the results of the catalyst activity and selectivity measurements are shown in Table 2.
Example 8
Preparation of phosphine-nitrogen ligand:
phosphine-nitrogen ligand L8 was prepared according to the procedure of example 1, except that the compound of formula III was added in a different manner, and that the molar ratios of the starting materials and the reaction conditions shown in Table 1 were different: the compound of formula III is selected from chlorobis (4-methoxyphenyl) phosphine to provide a phosphine-nitrogen ligand of formula L8:
nuclear magnetic data for ligand L8 are as follows: 1H NMR (400MHz, CDCl) 3 )：6.95-7.27(m,16H)，4.77(s,1H)，3.79(s，12H)，2.29～2.58(m，8H)，1.48～1.53(m，4H).
Oligomerization of ethylene:
before the reaction, a 500ml reaction kettle is heated to 160 ℃, vacuumized for 3 hours and replaced by nitrogen for three times. Cooling to 35 ℃, replacing ethylene twice, adding 200ml of dehydrated and deoxidized solvent methylcyclohexane and 0.8ml (1.4 mmol) of MMAO-3a, then adding 5.5 mu mol of ligand L8 and 3.5 mu mol of chromium acetylacetonate (the molar ratio of MMAO-3a to chromium acetylacetonate is 400 1), and introducing 0.5Mpa hydrogen and 4.5MPa ethylene in sequence to start reaction when the temperature is constant at 35 ℃. The reaction temperature is 35 ℃, and the reaction time is 50min. After the reaction is finished, closing the ethylene inlet valve, using ice water bath or quickly cooling to below 5 ℃, slowly releasing pressure, and discharging the reactor to obtain the ethylene oligomerization product. The product was analyzed by GC and the results of the catalyst activity and selectivity measurements are shown in Table 2.
Example 9
Preparation of phosphine-nitrogen ligand:
phosphine-nitrogen ligand L9 was prepared according to the procedure of example 1, except that the compound represented by formula III was added differently, and the molar ratios of the starting materials and the reaction conditions shown in Table 1 were different: the compound shown in the formula III is 4- (trimethylsilyl) phenyl phosphine chloride to obtain a phosphine-nitrogen ligand shown in the following formula L9:
nuclear magnetic data for ligand L9 are as follows: 1H NMR (400MHz, CDCl) 3 )：7.33-7.40(m,16H)，4.95(s,1H)，2.33～2.63(m，8H)，1.51～1.58(m，4H),0.25(s，36H).
Oligomerization of ethylene:
before reaction, a 500ml reaction kettle is heated to 125 ℃, vacuumized for 3 hours and replaced by nitrogen for three times. Cooling to 35 ℃, replacing ethylene twice, adding 200ml of dehydrated and deoxidized solvent methylcyclohexane and 1ml (1.75 mmol) of MMAO-3a, then adding 6.0 mu mol of ligand L9 and 3.5 mu mol of chromium acetylacetonate (the molar ratio of MMAO-3a to chromium acetylacetonate is 500: 1), and introducing 0.5Mpa hydrogen and 4.5MPa ethylene in sequence to start reaction when the temperature is constant at 90 ℃. The reaction temperature is 90 ℃, and the reaction time is 60min. After the reaction is finished, closing the ethylene inlet valve, using ice water bath or quickly cooling to below 5 ℃, slowly releasing pressure, and discharging the reactor to obtain the ethylene oligomerization product. The product was analyzed by GC and the results of the catalyst activity and selectivity measurements are shown in Table 2.
Example 10
Preparation of phosphine-nitrogen ligand:
a phosphine-nitrogen ligand L10 was prepared as in example 1, except that the compound of formula III was charged differently, and that the molar ratios of the starting materials and the reaction conditions shown in Table 1 were different: the compound shown in the formula III is 4- (tri-n-butylsilyl) phenyl phosphine chloride to obtain a phosphine-nitrogen ligand shown in a formula L10 as follows:
nuclear magnetic data for ligand L10 are as follows: 1H NMR (400MHz, CDCl) 3 )：7.31-7.46(m,16H)，4.83(s,1H)，2.28～2.59(m，8H)，1.49～1.55(m，4H),0.90～1.40(m，108H).
Oligomerization of ethylene:
before the reaction, a 500ml reaction kettle is heated to 160 ℃, vacuumized for 2 hours and replaced by nitrogen for three times. Cooling to 35 ℃, replacing ethylene twice, adding 200ml of dehydrated and deoxidized solvent methylcyclohexane and 1ml (1.75 mmol) of MMAO-3a, then adding 4.1 mu mol of ligand L10 and 3.5 mu mol of chromium acetylacetonate (the molar ratio of MMAO-3a to chromium acetylacetonate is 500: 1), and introducing 0.5Mpa hydrogen and 4.5MPa ethylene in sequence to start reaction when the temperature is constant at 50 ℃. The reaction temperature is 50 ℃, and the reaction time is 60min. After the reaction is finished, closing the ethylene inlet valve, using ice water bath or quickly cooling to below 5 ℃, slowly releasing pressure, and discharging the reactor to obtain the ethylene oligomerization product. The product was analyzed by GC and the results of the catalyst activity and selectivity measurements are shown in Table 2.
Comparative example 1
Reference example 1 oligomerization of ethylene: all conditions of the ethylene oligomerization experiment were the same as in example 1 except that the phosphine-nitrogen ligand used was a commercially available catalyst iPr-PNP. The product was analyzed by GC and the results of the catalyst activity and selectivity measurements are shown in Table 2.
Comparative example 2
Reference example 1 ethylene oligomerization: all conditions of the ethylene oligomerization experiment were the same as in example 1 except that the alkylaluminum cocatalyst MMAO-3a was replaced with an equimolar amount of triisobutylaluminum. The products were analyzed by GC and found to be only 36 kg/(gCr. H) active, very low in selectivity and with a large amount of polymer formed.
Comparative example 3
Reference example 1 ethylene oligomerization: all conditions of the ethylene oligomerization experiment were the same as in example 1, except that the transition metal compound chromium acetylacetonate was replaced with zinc acetylacetonate in an equimolar amount, and the product was analyzed by GC, and it was found that the catalyst was inactive and the reaction did not proceed normally.
TABLE 1 EXAMPLES 1-10 raw material molar ratios and reaction conditions for the preparation of phosphine-nitrogen ligands
The products were analyzed by GC and tested for catalyst activity and product selectivity in the examples and comparative examples, with the results shown in table 2:
TABLE 2 catalyst Activity and product Selectivity
The results in Table 2 show that the ethylene oligomerization activity can reach more than 1500 kg/(gCr.h), the selectivity of 1-hexene and 1-octene can reach more than 90wt%, and the polymer selectivity can be as low as less than 0.2wt% by adopting the catalytic system of the ligand in the invention, so that the catalyst has good industrial application prospect.
Example 11
All the conditions for ethylene oligomerization were the same as in example 1, except that the oligomerization reaction temperature was increased to 100 ℃ and 120 ℃, and the catalyst activity, conversion rate, and product selectivity in example 1 and comparative example 1 were measured, and the results are shown in table 3:
TABLE 3 high temperature activity and product selectivity of the catalyst
The above description is only a preferred embodiment of the present invention, and it should be noted that, for a person skilled in the art, several modifications and additions can be made without departing from the method of the present invention, and these modifications and additions should also be considered as the protection scope of the present invention.
Claims (25)
1. A phosphine-nitrogen ligand has a structure shown in formula I:
in the formula I, R 1 、R 2 Each independently selected from phenyl, benzyl, biphenyl, naphthyl, anthracenyl, 2-methylphenyl, 4-methylphenyl, 2,4-dimethylphenyl, 2,6-dimethylphenyl, 2-ethylphenyl, 4-ethylphenyl, 2,4-diethylphenyl, 2,6-diethylphenyl, 2-isopropylphenyl, 4-isopropylphenyl, 2,4-diisopropylphenyl, 2,6-diisopropylphenyl, 2-butylphenyl, 4-butylphenyl, 2,4-dibutylphenyl, 2,6-dibutylphenyl, 4-propanilMethoxyphenyl, o-methoxyphenyl, 4-ethoxyphenyl, o-ethoxyphenyl, 2-trimethylsilylphenyl, 3-trimethylsilylphenyl, 4-trimethylsilylphenyl, 2-fluorophenyl, 3-fluorophenyl, 4-fluorophenyl, 2-trifluoromethylphenyl, 3-trifluoromethylphenyl, 4-trifluoromethylphenyl, 3,5-bis (trifluoromethyl) phenyl, 2-tri-n-butylsilylphenyl, 3-tri-n-butylsilylphenyl, 4-tri-n-butylsilylphenyl.
2. The phosphine-nitrogen ligand according to claim 1, having any one of the structures represented by the following formulae L1 to L10:
3. a method for preparing a phosphine-nitrogen ligand as defined in claim 1 or 2, comprising the steps of:
1) Dissolving a compound 1,5,7-triazabicyclo (4.4.0) dec-5-ene in methanol under the atmosphere of nitrogen, and reacting for 1-5 h at 10-35 ℃ under the action of sodium borohydride to obtain a compound shown in a formula II;
2) Dissolving a compound shown as a formula II in a solvent A under anhydrous and anaerobic conditions, adding triethylamine and a compound shown as a formula III, and reacting to obtain a phosphine-nitrogen ligand shown as a formula I;
in the formula III, R 1 、R 2 The same as in formula I.
4. The production method according to claim 3, characterized in that: in the step 1), the molar ratio of 1,5,7-triazabicyclo (4.4.0) dec-5-ene to sodium borohydride is 1.9-5;
the 1,5,7-triazabicyclo (4.4.0) dec-5-ene is dissolved in methanol at the concentration of 0.1-5 mol/L;
the reaction temperature is 15-25 ℃, and the reaction time is 1-3 h.
5. The method of claim 4, wherein: the molar ratio of 1,5,7-triazabicyclo (4.4.0) dec-5-ene to sodium borohydride is 1:1-3.
6. The production method according to claim 3, characterized in that: in the step 2), the mol ratio of the compound shown in the formula II to the triethylamine and the compound shown in the formula III is 1 (1.5-3.5) to 2.2-3.6;
the solvent A is selected from any one or combination of at least two of dichloromethane, acetonitrile, normal hexane, normal heptane and toluene;
the concentration of the compound shown in the formula II dissolved in the solvent A is 0.1-2 mol/L;
the triethylamine is continuously fed;
the reaction is carried out at the temperature of-10 to 30 ℃ for 9 to 30 hours;
and after the reaction is finished, the method also comprises a refining and purifying post-treatment process.
7. The method of claim 6, wherein: the molar ratio of the compound shown in the formula II to the triethylamine and the compound shown in the formula III is 1 (1.9-2.9) to 2.2-3.
8. The method of claim 6, wherein: the triethylamine is added dropwise for 0.5 to 3 hours;
when the triethylamine addition is complete, the compound of formula III is added.
9. The method for producing according to claim 8, characterized in that: the dripping time of the triethylamine is 0.8 to 1.5 hours.
10. The method of claim 8, wherein: the compound shown in the formula III is added for a plurality of times in a segmented manner, and the temperature of the system is controlled within the range of-5 to 5 ℃ in the charging process.
11. The method of claim 6, wherein: the reaction is carried out in sections, the reaction is carried out for 3 to 6 hours at the temperature of between 10 ℃ below zero and 0 ℃, and then the temperature is increased to between 10 and 25 ℃ for continuous reaction for 6 to 24 hours; the heating rate is 1-3 ℃/min.
12. The method of claim 6, wherein: in the refining and purifying post-treatment process, the target product is refined by column chromatography and recrystallization purification methods.
13. The method of manufacturing according to claim 12, wherein: the column chromatography conditions are that the height-diameter ratio of the chromatographic column is 2-4, the retention time is 1-2 min, the solvent used for recrystallization is a mixed solvent of ethanol and ethyl acetate, and the mixing volume ratio is 1:0.05 to 1.
14. A three-way catalyst system for ethylene oligomerization, comprising the phosphine-nitrogen ligand of claim 1 or 2, a chromium metal compound, and an alkylaluminoxane cocatalyst.
15. The ethylene oligomerization three-way catalyst system of claim 14, wherein the molar ratio of the chromium metal compound to the phosphine-nitrogen ligand is from 1: (1-4.5);
the molar ratio of the alkyl aluminoxane cocatalyst to the chromium metal compound is (50-1800): 1.
16. The ethylene oligomerization three-way catalyst system of claim 15, wherein the molar ratio of the chromium metal compound to the phosphine-nitrogen ligand is from 1: (1-2);
the molar ratio of the alkyl aluminoxane cocatalyst to the chromium metal compound is (100-1000): 1.
17. The ethylene oligomerization three-way catalyst system of claim 14, wherein the chromium metal compound is selected from an organic salt, an inorganic salt, a coordination complex, or an organometallic complex of chromium.
18. The three-way catalyst system for ethylene oligomerization according to claim 17, wherein the chromium metal compound is selected from any one of chromium acetylacetonate, chromium chloride, chromium trichlorotris (tetrahydrofuran), chromium (III) 2-ethylhexanoate, chromium (III) octanoate, chromium hexacarbonyl, chromium benzenetricarbonyl, or a combination of at least two thereof.
19. The three-way catalyst system for ethylene oligomerization according to claim 14, wherein the alkylalumoxane co-catalyst is selected from the group consisting of C1-C4 alkyl alumoxane co-catalysts.
20. The three-way catalyst system for ethylene oligomerization according to claim 19, wherein the alkylaluminoxane cocatalyst is selected from any one of methylaluminoxane, modified methylaluminoxane, and ethylaluminoxane, or a combination of at least two thereof.
21. A method for ethylene oligomerization, which is characterized in that the method comprises the step of carrying out ethylene oligomerization reaction in the presence of the ethylene oligomerization three-way catalyst system as described in any one of claims 14 to 20 to prepare 1-hexene and 1-octene.
22. A process for oligomerization of ethylene according to claim 21, characterized by the steps of:
heating the reaction kettle to 110-160 ℃, vacuumizing for 2-6 h, adopting nitrogen for replacement, cooling to 10-40 ℃, adopting ethylene for replacement, firstly adding a solvent B and an alkylaluminoxane cocatalyst, then adding a chromium metal compound and a phosphine-nitrogen ligand shown in a formula I, and after the temperature reaches 35-120 ℃, sequentially introducing 0.1-0.8 MPa hydrogen and 2-10 MPa ethylene to start reaction for 5-240 min.
23. The ethylene oligomerization method according to claim 22, wherein hydrogen and ethylene are sequentially introduced to start reaction after the temperature reaches 40 to 70 ℃;
the reaction time is 10-100 min.
24. A method for oligomerization of ethylene according to claim 22, characterized in that the solvent B is selected from one or a combination of at least two of n-butane, isobutane, n-pentane, cyclopentane, methylcyclopentane, methylenecyclopentane, n-hexane, cyclohexane, methylcyclohexane, n-heptane, n-octane, n-nonane, benzene, toluene, xylene.
25. A process for oligomerization of ethylene according to claim 22, characterized in that the molar concentration of the catalyst in the solvent B is 5 to 50 μmol/L based on the chromium metal compound therein.
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