CN113402554A - PNSiNP ligand and preparation method thereof, ethylene oligomerization catalyst and application thereof - Google Patents
PNSiNP ligand and preparation method thereof, ethylene oligomerization catalyst and application thereof Download PDFInfo
- Publication number
- CN113402554A CN113402554A CN202110651359.5A CN202110651359A CN113402554A CN 113402554 A CN113402554 A CN 113402554A CN 202110651359 A CN202110651359 A CN 202110651359A CN 113402554 A CN113402554 A CN 113402554A
- Authority
- CN
- China
- Prior art keywords
- ligand
- reaction
- pnsinp
- phenyl
- ethylene
- Prior art date
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- Granted
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- 239000003446 ligand Substances 0.000 title claims abstract description 150
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 239000005977 Ethylene Substances 0.000 title claims abstract description 82
- 238000002360 preparation method Methods 0.000 title claims abstract description 56
- 238000006384 oligomerization reaction Methods 0.000 title claims abstract description 54
- 239000003054 catalyst Substances 0.000 title claims abstract description 31
- 150000003623 transition metal compounds Chemical class 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims description 108
- -1 2, 4-dimethylphenyl Chemical group 0.000 claims description 90
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 60
- 239000002904 solvent Substances 0.000 claims description 55
- KUXDQQMEFBFTGX-UHFFFAOYSA-N [N].P Chemical compound [N].P KUXDQQMEFBFTGX-UHFFFAOYSA-N 0.000 claims description 50
- 239000012295 chemical reaction liquid Substances 0.000 claims description 46
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 45
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 44
- 150000001875 compounds Chemical class 0.000 claims description 38
- 238000003756 stirring Methods 0.000 claims description 38
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 36
- 239000000243 solution Substances 0.000 claims description 35
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 32
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 28
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 27
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical group OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 26
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 22
- 238000004440 column chromatography Methods 0.000 claims description 22
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 claims description 18
- 239000011651 chromium Substances 0.000 claims description 17
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 15
- 229910052782 aluminium Inorganic materials 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- 230000035484 reaction time Effects 0.000 claims description 12
- WSNMPAVSZJSIMT-UHFFFAOYSA-N COc1c(C)c2COC(=O)c2c(O)c1CC(O)C1(C)CCC(=O)O1 Chemical compound COc1c(C)c2COC(=O)c2c(O)c1CC(O)C1(C)CCC(=O)O1 WSNMPAVSZJSIMT-UHFFFAOYSA-N 0.000 claims description 9
- 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 9
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-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 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- 125000002178 anthracenyl group Chemical group C1(=CC=CC2=CC3=CC=CC=C3C=C12)* 0.000 claims description 8
- 239000004305 biphenyl Substances 0.000 claims description 8
- 235000010290 biphenyl Nutrition 0.000 claims description 8
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 8
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 8
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 8
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 8
- 125000001624 naphthyl group Chemical group 0.000 claims description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 8
- LJXQPZWIHJMPQQ-UHFFFAOYSA-N pyrimidin-2-amine Chemical compound NC1=NC=CC=N1 LJXQPZWIHJMPQQ-UHFFFAOYSA-N 0.000 claims description 8
- 229910052723 transition metal Inorganic materials 0.000 claims description 8
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 7
- 229910052804 chromium Inorganic materials 0.000 claims description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- 125000005234 alkyl aluminium group Chemical group 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000000746 purification Methods 0.000 claims description 6
- 150000003624 transition metals Chemical class 0.000 claims description 6
- 125000001255 4-fluorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1F 0.000 claims description 5
- 238000001953 recrystallisation Methods 0.000 claims description 5
- 125000004198 2-fluorophenyl group Chemical group [H]C1=C([H])C(F)=C(*)C([H])=C1[H] 0.000 claims description 4
- 125000004180 3-fluorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C(F)=C1[H] 0.000 claims description 4
- 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
- 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 4
- 125000000590 4-methylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 claims description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 4
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 4
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 125000003261 o-tolyl group Chemical group [H]C1=C([H])C(*)=C(C([H])=C1[H])C([H])([H])[H] 0.000 claims description 4
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 claims description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 150000004696 coordination complex Chemical class 0.000 claims description 3
- YVSMQHYREUQGRX-UHFFFAOYSA-N 2-ethyloxaluminane Chemical compound CC[Al]1CCCCO1 YVSMQHYREUQGRX-UHFFFAOYSA-N 0.000 claims description 2
- 229910021555 Chromium Chloride Inorganic materials 0.000 claims description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- URAPFRVSOJQECJ-UHFFFAOYSA-N benzene chromium Chemical compound [Cr].C1=CC=CC=C1 URAPFRVSOJQECJ-UHFFFAOYSA-N 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
- CYOMBOLDXZUMBU-UHFFFAOYSA-K chromium(3+);oxolane;trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3].C1CCOC1.C1CCOC1.C1CCOC1 CYOMBOLDXZUMBU-UHFFFAOYSA-K 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 claims description 2
- GCPCLEKQVMKXJM-UHFFFAOYSA-N ethoxy(diethyl)alumane Chemical compound CCO[Al](CC)CC GCPCLEKQVMKXJM-UHFFFAOYSA-N 0.000 claims description 2
- UAIZDWNSWGTKFZ-UHFFFAOYSA-L ethylaluminum(2+);dichloride Chemical compound CC[Al](Cl)Cl UAIZDWNSWGTKFZ-UHFFFAOYSA-L 0.000 claims description 2
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 2
- 230000014759 maintenance of location Effects 0.000 claims description 2
- 239000012046 mixed solvent Substances 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 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 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 2
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 claims description 2
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 claims description 2
- LFXVBWRMVZPLFK-UHFFFAOYSA-N trioctylalumane Chemical compound CCCCCCCC[Al](CCCCCCCC)CCCCCCCC LFXVBWRMVZPLFK-UHFFFAOYSA-N 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims description 2
- CMAOLVNGLTWICC-UHFFFAOYSA-N 2-fluoro-5-methylbenzonitrile Chemical compound CC1=CC=C(F)C(C#N)=C1 CMAOLVNGLTWICC-UHFFFAOYSA-N 0.000 claims 1
- 125000002524 organometallic group Chemical group 0.000 claims 1
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 abstract description 44
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 abstract description 43
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 abstract description 24
- 230000000694 effects Effects 0.000 abstract description 21
- 229920000642 polymer Polymers 0.000 abstract description 18
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 239000000047 product Substances 0.000 description 53
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 38
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 34
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 22
- 238000005160 1H NMR spectroscopy Methods 0.000 description 20
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 17
- 238000001816 cooling Methods 0.000 description 14
- 239000000203 mixture Substances 0.000 description 14
- 239000002808 molecular sieve Substances 0.000 description 11
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 238000007599 discharging Methods 0.000 description 10
- 239000005457 ice water Substances 0.000 description 10
- 238000002386 leaching Methods 0.000 description 10
- 238000010828 elution Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- XGRJZXREYAXTGV-UHFFFAOYSA-N chlorodiphenylphosphine Chemical compound C=1C=CC=CC=1P(Cl)C1=CC=CC=C1 XGRJZXREYAXTGV-UHFFFAOYSA-N 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 150000001335 aliphatic alkanes Chemical class 0.000 description 4
- 239000003814 drug Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YUYHCACQLHNZLS-UHFFFAOYSA-N dichloro-cyclohexyl-methylsilane Chemical compound C[Si](Cl)(Cl)C1CCCCC1 YUYHCACQLHNZLS-UHFFFAOYSA-N 0.000 description 3
- IPIWUBVZCIGHAC-UHFFFAOYSA-N dichloro-methyl-propan-2-ylsilane Chemical compound CC(C)[Si](C)(Cl)Cl IPIWUBVZCIGHAC-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000009776 industrial production Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 229920000098 polyolefin Polymers 0.000 description 3
- CAJIIZKPZKCXOG-UHFFFAOYSA-N tert-butyl-dichloro-methylsilane Chemical compound CC(C)(C)[Si](C)(Cl)Cl CAJIIZKPZKCXOG-UHFFFAOYSA-N 0.000 description 3
- 239000004711 α-olefin Substances 0.000 description 3
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 238000006356 dehydrogenation reaction Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methylcyclopentane Chemical compound CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 2
- NFJPEKRRHIYYES-UHFFFAOYSA-N methylidenecyclopentane Chemical compound C=C1CCCC1 NFJPEKRRHIYYES-UHFFFAOYSA-N 0.000 description 2
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 2
- JYLPOJPHFDVWCY-UHFFFAOYSA-K oxolane;trichlorochromium Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3].C1CCOC1 JYLPOJPHFDVWCY-UHFFFAOYSA-K 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- DCBBPHAUPIMNRY-UHFFFAOYSA-N (2-fluorophenyl)-phenylphosphane;hydrochloride Chemical compound Cl.FC1=CC=CC=C1PC1=CC=CC=C1 DCBBPHAUPIMNRY-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- ZJKXBORAOFKUPU-UHFFFAOYSA-N Cl.C1=CC(F)=CC=C1PC1=CC=CC=C1 Chemical compound Cl.C1=CC(F)=CC=C1PC1=CC=CC=C1 ZJKXBORAOFKUPU-UHFFFAOYSA-N 0.000 description 1
- NBNACMLOHNJDJT-UHFFFAOYSA-N Cl.FC1=CC=CC(PC=2C=CC=CC=2)=C1 Chemical compound Cl.FC1=CC=CC(PC=2C=CC=CC=2)=C1 NBNACMLOHNJDJT-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000008037 PVC plasticizer Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- WJNVROGBBUICIR-UHFFFAOYSA-N bis(2-methoxyphenyl)phosphanium;chloride Chemical compound Cl.COC1=CC=CC=C1PC1=CC=CC=C1OC WJNVROGBBUICIR-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
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- GHAKVYIBHNIGBD-UHFFFAOYSA-N chloro-(2-fluorophenyl)-phenylphosphane Chemical compound FC1=CC=CC=C1P(Cl)C1=CC=CC=C1 GHAKVYIBHNIGBD-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 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 1
- 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 1
- 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 1
- 150000001845 chromium compounds Chemical class 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000006071 cream Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
- 238000010813 internal standard method Methods 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000004451 qualitative analysis Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
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- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/645—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having two nitrogen atoms as the only ring hetero atoms
- C07F9/6509—Six-membered rings
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- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1845—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing phosphorus
- B01J31/1875—Phosphinites (R2P(OR), their isomeric phosphine oxides (R3P=O) and RO-substitution derivatives thereof)
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- 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
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Abstract
The invention discloses a PNSiNP ligand and a preparation method thereof, an ethylene oligomerization catalyst and an application thereof, wherein the ligand is shown as a formula I, and the oligomerization catalyst comprises the PNSiNP ligand shown as the formula I and a transition metal compound. The catalytic system can catalyze ethylene oligomerization with high activity, the catalytic activity is as high as 1600000 g/(gCr.h), the polymer generation amount is reduced to be below 0.1 wt%, and the overall selectivity of 1-hexene and 1-octene with high additional values can be more than 88%.
Description
Technical Field
The invention belongs to the technical field of ethylene oligomerization, and particularly relates to a PNSiNP ligand and a preparation method thereof, an ethylene oligomerization catalyst and application thereof.
Background
Linear alpha-olefin is an important chemical raw material and can be used as polyolefin comonomer, PVC plasticizer, surfactant, lubricating oil additive and other fields. The consumption of the comonomer accounts for more than half of the consumption of the alpha-olefin, and the polyolefin products of the 1-octene and the 1-hexene have good mechanical properties and excellent processability, so that the polyolefin products have a large amount of demands in industrial production. The production method of linear alpha-olefin mainly includes ethylene oligomerization process, wax cracking process, alkane dehydrogenation process, coal chemical extraction process, alkane catalytic cracking process, extraction separation method, fatty alcohol dehydrogenation method and the like. The products of different production processes are distributed differently, wherein the product of the ethylene oligomerization process has high linearization degree and good product quality, and is the most important industrial production method.
In recent years, the selective oligomerization of ethylene to produce 1-octene and 1-hexene has received increasing attention. Bollmann et al (J.AM. CHEM. SOC.2004,126,14712-14713), from Sasol corporation, for the first time, have achieved highly selective oligomerization of ethylene to produce 1-octene and 1-hexene. A Cr/PNP/MAO catalytic system is adopted, the catalyst consists of a trivalent chromium precursor and a PNP ligand, MAO is taken as a cocatalyst, toluene or alkane is taken as a solvent, the reaction temperature is 45 ℃, and the ethylene pressure is 4.5 MPa. Octene-1 selectivity 70%, hexene-1 selectivity 13%, catalyst activity about 300kg product/(gCr). Sasol company applies a series of ethylene oligomerization patents CN105263890A, CN104220402A, CN105228973A, CN105228974A, CN101052605A and the like, and realizes the industrial production of 1-octene through ethylene selective tetramerization in 2014.
The ligand framework used in the ethylene selective oligomerization catalyst comprises monodentate N ligands, multidentate PNP, PCCP, PCICP, PNCN and various derived ligands, and the steric hindrance effect and the electron donating effect of the ligands have great influence on the activity and the selectivity. Patents US8609924B2, CN105562096A, CN105562095A, CN105562097A, CN105562099A, CN105566036A, CN105566045A, CN105566037A, CN105566046A, CN104415790A and the like disclose a series of oligomerization catalysts of ligands with different PCCP skeleton structures, wherein the oligomerization activity of the PCCP ligands is similar to that of the PNP ligands of Sasol, but the products have more isoolefins, poor economy and more polymers, which are not favorable for the long-period operation of the device.
On the premise of ensuring the catalytic activity, the product selectivity of the existing catalytic systems such as PNP, PCCP and the like is only about 80 percent, and the space for promotion is still provided. Meanwhile, the P framework structure is influenced by substituents on nitrogen/carbon, the selectivity of the polymer is generally more than 0.2 wt%, and the long-period operation of the device is influenced. In view of the problems of low selectivity and high polymer yield of the conventional ligand structure catalyst, the development of a novel ligand structure catalyst is urgently needed.
Disclosure of Invention
The invention aims to provide a novel PNSiNP ligand and a preparation method thereof.
The invention also aims to provide an ethylene oligomerization catalyst and application thereof in ethylene oligomerization reaction. The catalyst improves the selectivity of 1-hexene and 1-octene in the ethylene oligomerization reaction process, the polymer production is lower, the invention can improve the selectivity of 1-hexene and 1-octene to more than 88 wt%, the polymer production is reduced to less than 0.1 wt%, and the activity is as high as 1600000 g/(gCr.h).
In order to achieve the above purpose, the technical scheme of the invention is as follows:
the invention provides a PNSiNP ligand, which has a structure shown in a formula I:
wherein R is1、R2Each independently selected from aryl and derivatives thereof. R3、R4Each independently selected from methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, ethenyl, propenyl, cyclopentyl, cyclohexyl, phenyl, naphthyl, anthracenyl or biphenyl, preferably from methyl, ethyl, isopropyl, n-butyl, cyclohexyl.
Preferably, R in the PNSiNP ligand shown in the structure of the formula I1，R2Selected from the group consisting of 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-methoxyphenyl, o-methoxyphenyl, 4-ethoxyphenyl, o-ethoxyphenyl, 2-fluorophenyl, 3-fluorophenyl, 4-fluorophenyl, 2- (trimethylsilyl) phenyl, 3- (trimethylsilyl) phenyl, 4- (trimethylsilyl) phenyl, 2- (tri-n-butylsilyl) phenyl, 3- (tri-n-butylsilyl) phenyl or 4- (tri-n-butylsilyl) phenyl.
The invention also provides a preparation method of the ligand, which comprises the following steps:
dissolving 2-aminopyrimidine in a solvent A under anhydrous and anaerobic conditions to obtain a reaction solution I;
and (2) dropwise adding triethylamine into the reaction liquid I under stirring at-10-0 ℃, continuously adding a compound shown as a structure II into the reaction liquid I, reacting for 3-6h under stirring, continuously reacting for 6-24h under stirring at room temperature, and purifying the reaction liquid to obtain a product I, namely the phosphine-nitrogen ligand. The compound of formula II has the following structure:
wherein R is1、R2Each independently selected from the group consisting of 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-methoxyphenyl, o-methoxyphenyl, 4-ethoxyphenyl, o-ethoxyphenyl, 2-fluorophenyl, 3-fluorophenyl, 4-fluorophenyl, 2- (trimethylsilyl) phenyl, o-methoxyphenyl, 4-fluorophenyl, and mixtures thereof, 3- (trimethylsilyl) phenyl group, 4- (trimethylsilyl) phenyl group, 2- (tri-n-butylsilyl) phenyl group, 3- (tri-n-butylsilyl) phenyl group, 4- (tri-n-butylsilyl) phenyl group.
Dissolving a phosphine-nitrogen ligand in a solvent A under anhydrous and anaerobic conditions to obtain a reaction solution II;
dropwise adding n-butyllithium into the reaction liquid II under stirring at the temperature of between 80 ℃ below zero and 70 ℃ below zero, continuously adding the compound shown in the structure of the formula III and the catalyst, slowly heating to room temperature, continuously reacting for 36 to 72 hours under stirring, and purifying the reaction liquid to obtain a product II, namely the PNSiNP ligand.
The compound of formula III has the structure shown below:
R3、R4each independently selected from methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, ethenyl, propenyl, cyclopentyl, cyclohexyl, phenyl, naphthyl, anthracenyl or biphenyl, preferably from methyl, ethyl, isopropyl, n-butyl, cyclohexyl.
In the preparation method of the ligand, the solvent A is selected from one or more of toluene, methylcyclohexane, dichloromethane, acetonitrile, cyclohexane, n-hexane and n-heptane. The molar ratio of the 2-aminopyrimidine to the triethylamine is 1: 1-1: 3, preferably 1: 2.2; the molar ratio of the 2-aminopyrimidine to the compound shown in the formula II is 1: 1-1: 3, preferably 1: 2.2. wherein solvent A is used in excess.
In the preparation method of the ligand, the catalyst is selected from trifluoroacetic acid. Preferably, the molar ratio of the compound shown in the structure of the formula III to the phosphine-nitrogen ligand is 1: 2-1: 3, and the molar ratio of the n-butyllithium to the compound shown in the structure of the formula III is 1.5: 1-2.5: 1; the molar ratio of the catalyst to the compound represented by the structure of formula III is 0.08: 1-0.12: 1.
The purification treatment comprises the steps of carrying out column chromatography purification on the reaction liquid to obtain a target product and carrying out recrystallization on the target product, wherein the height-diameter ratio of a chromatographic column used for the column chromatography purification is 2-4, the retention time is 1-3min, and a solvent used for the recrystallization is a mixed solvent of ethanol and ethyl acetate.
The invention provides an ethylene oligomerization catalyst, which comprises a transition metal complex and an alkyl aluminum cocatalyst, wherein the transition metal complex comprises a transition metal compound and a PNSiNP ligand.
The transition metal compound is one or more than two of compounds of chromium, molybdenum, cobalt, titanium, vanadium, zirconium, nickel and palladium, preferably compounds of chromium, zirconium and nickel, and the transition metal compound comprises organic salt, inorganic salt, coordination complex or organic metal complex of transition metal, preferably one or more than two of chromium acetylacetonate, chromium chloride, chromium tris (tetrahydrofuran) trichloride, chromium (III) 2-ethylhexanoate, chromium (III) octanoate, chromium hexacarbonyl and chromium (benzene) tricarbonyl.
The alkyl aluminum cocatalyst disclosed by the invention is selected from one or more than two of trimethylaluminum, triethylaluminum, triisobutylaluminum, diethyl aluminum ethoxide, diethyl aluminum monochloride, ethyl aluminum dichloride, aluminum sesquiethyl chloride, trioctylaluminum, Methylaluminoxane (MAO), Modified Methylaluminoxane (MMAO) or ethylaluminoxane.
In the catalyst, the molar ratio of the transition metal compound to the PNSiNP ligand is 1: 1-3, preferably 1: 1-2; the molar ratio of aluminum alkyl cocatalyst to transition metal compound is from 50 to 2000:1, preferably from 90 to 800:1, in terms of the molar ratio of aluminum element to transition metal element.
The invention also provides the application of the catalyst, which is used for ethylene oligomerization.
In some preferred embodiments of the present invention, the ethylene oligomerization process comprises: heating the reaction kettle to 160 ℃ for 110-160 ℃ before reaction, vacuumizing for 1-4h, replacing by nitrogen, cooling to room temperature, replacing ethylene, adding a solvent B and an alkyl aluminum cocatalyst, then adding a transition metal compound and a PNSiNP ligand, and introducing 0-0.8MPa hydrogen and 2MPa-7MPa ethylene in sequence to start reaction after the temperature reaches the reaction temperature, wherein the reaction temperature is 35-90 ℃, preferably 40-70 ℃, and the reaction time is 10-240 min, preferably 20-100 min.
The catalyst composition is applied to ethylene oligomerization, the ethylene oligomerization reaction solvent B is one or more than 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, and the solvent B is used in excess.
In a more specific embodiment, the polymerization process of the catalyst composition of the present invention is as follows: polymerization was carried out in a 300mL autoclave, and the purified alkane was used as solvent C. Before the reaction, the reaction kettle is heated to 130 ℃, vacuumized for 1-3h, and replaced by nitrogen for three times. Cooling to room temperature, replacing ethylene twice, adding 150ml of dehydrated and deoxidized solvent C and quantitative alkyl aluminum cocatalyst, then adding a metal chromium compound and a PNSiNP ligand, and introducing 0.2-0.7MPa hydrogen and 2MPa-7MPa ethylene in sequence to start reaction when the temperature is constant near the reaction temperature. The reaction temperature is 35-90 ℃, preferably 40-70 ℃, and the reaction time is 10min-240min, preferably 20min-100 min. After the reaction is finished, closing the ethylene inlet valve, rapidly cooling by using ice water bath or liquid nitrogen, slowly releasing pressure, and discharging the kettle to obtain an ethylene oligomerization product.
Compared with the prior art, the ethylene oligomerization catalyst system has the activity for ethylene oligomerization of over 1600000 g/(gCr.h), the total selectivity of 1-hexene and 1-octene of 90 percent and the PE selectivity of less than 0.05 percent by weight, can reduce the production cost and has high economic added value.
Detailed Description
The following specific examples are merely illustrative of the present invention, but these examples are only part of the present invention and do not limit the application of the present invention in other fields.
The starting materials used in the examples are conventional in the art and the purity specifications used are either analytically or chemically pure.
Raw material source information:
2-aminopyrimidine: 99%, Bailingwei Tech Co Ltd
Triethylamine: not less than 99.5% (GC), Shanghai Aladdin Biotechnology Ltd
Diphenyl phosphine chloride: 97% of Alfa Angsa chemical Co Ltd
Dichlorodimethylsilane: 98.5% (GC), Shanghai Aladdin Biotechnology Ltd
Tert-butylmethyldichlorosilane: 95% Shanghai Aladdin Biotechnology Ltd
Isopropyl methyl dichlorosilane: 96% Shanghai Aladdin Biotechnology Ltd
Cyclohexyl methyl dichlorosilane: 95% Shanghai Aladdin Biotechnology Ltd
N-butyl lithium: 15% Hexane solution (1.6mol), Shanghai Aladdin Biotech Co., Ltd
Chloro (2-fluorophenyl) (phenyl) phosphine: 97%, Shanghai Xinkai medicine science and technology Limited
Chloro (3-fluorophenyl) (phenyl) phosphine: 97%, Shanghai Xinkai medicine science and technology Limited
Chloro (4-fluorophenyl) (phenyl) phosphine: 97%, Shanghai Xinkai medicine science and technology Limited
Chlorobis (4-methylphenyl) phosphine: more than 97%, Shanghai Aladdin Biotechnology Ltd
Chlorobis (4-methoxyphenyl) phosphine: 98% of Alfa Sha (China) Chemicals Co., Ltd
4- (trimethylsilyl) phenylphosphonium chloride: 97% Jiangsu Xinnoco catalyst Co., Ltd
4- (tri-n-butylsilyl) phenyl phosphine chloride: 97% Jiangsu Xinnoco catalyst Co., Ltd
Ethyl acetate: 99.9% by Bailingwei Tech Co Ltd
Ethanol: chemical reagent of analytical pure, national drug group Co Ltd
MMAO-3 a: the molar concentration of Al was 1.75mol/L (7 wt% Al, n-heptane solvent), Jiangsu Xinnoco catalyst Co., Ltd
MAO Al molar concentration 1.5mol/L (10 wt% AL, toluene solvent), Jiangsu Xinnaoko catalyst Co., Ltd
The Al/M of the oligomerization reaction is the molar ratio of the aluminum alkyl to the metal center.
The oligomerization catalyst activity is defined as the mass of 1-octene and 1-hexene produced per gram of metal per hour. The mass of 1-octene and 1-hexene was determined by qualitative and quantitative analysis of each component in the reaction solution using the following conditions for the GC analyzer:
the instrument model is as follows: shimadzu GC2010
A chromatographic column: DB-5(30m 0.25mm 0.25 μm)
Column temperature procedure: the temperature was first maintained at 35 ℃ for 10min and then raised to 250 ℃ at a rate of 10 ℃/min, and maintained at this temperature for 10 min.
Detector temperature: 300 deg.C
Carrier gas: 1bar
Air: 0.3bar
Fuel gas (H2): 0.3bar
The sample quality analysis was performed using an internal standard method. The following should be mentioned:
wherein m1 is the mass of a certain product, m is the mass of an internal standard substance, a1 is the peak area of the product detected in a gas chromatogram, and a is the peak area of the internal standard substance. k is a correction factor associated with the substance to be measured and the detection condition.
Example 1
Preparation of PNSiNP ligand: the relevant solvent is soaked by a molecular sieve for removing water before use.
Preparation of phosphine-nitrogen ligand: dissolving 100mmol of 2-aminopyrimidine in 200ml of dichloromethane under anhydrous and anaerobic conditions to obtain a reaction solution I; and (2) dropwise adding 220mmol of triethylamine into the reaction liquid I under stirring at-5 ℃, slowly adding 110mmol of a compound (diphenyl phosphine chloride) shown as the structure II into the reaction liquid I, adding the rest 110mmol of diphenyl phosphine chloride when the solution is stable and does not release heat continuously, reacting for 3 hours under stirring, removing the low-temperature constant-temperature reaction bath, and stirring for 12 hours at room temperature. Purifying the reaction liquid by using column chromatography (tetrahydrofuran is used for leaching, the height-diameter ratio is 2), then recrystallizing at 78 ℃ (the solvent is ethanol: ethyl acetate: 5:1), and treating the reaction liquid to obtain a product I, namely the phosphine-nitrogen ligand La，LaThe structure of the compound (A) is shown as follows:
the above ligand (L)a) The nuclear magnetic data for (c) are as follows:1H NMR(400MHz，CDCl3)：8.45(s，2H)，7.38～7.45(m，20H)，6.93(s，1H)
preparation of PNSiNP ligand: 50mmol of phosphine-nitrogen ligand L under anhydrous and oxygen-free conditionsaDissolving the mixture in 180ml of dichloromethane to obtain a reaction solution II; 40mmol of n-butyllithium was added dropwise to the reaction solution II under stirring at-78 deg.C, 20mmol of the compound represented by the formula III (dichlorodimethylsilane) and 2.5mmol of trifluoroacetic acid were further added thereto, the temperature was slowly raised to room temperature, and the reaction was continued for 50 hours under stirring. Purifying the reaction liquid by using column chromatography (tetrahydrofuran is used for leaching, the height-diameter ratio is 2), then recrystallizing at 78 ℃ (the solvent is ethanol: ethyl acetate: 5:1), and treating the reaction liquid to obtain a product, namely the PNSiNP ligand L1, wherein the structure of L1 is shown as the following formula:
the nuclear magnetic data for the above ligand (L1) are as follows:1H NMR(400MHz，CDCl3)：8.47(s，4H)，7.36～7.48(m，40H)，0.14(s，6H)
oligomerization of ethylene:
before reaction, a 300ml reaction kettle is heated to 150 ℃, vacuumized for 3 hours and replaced by nitrogen for three times. After the temperature is cooled to room temperature, ethylene is replaced twice, 100ml of dehydrated and deoxidized solvent methylcyclohexane and 1ml of MMAO-3a (7 wt% Al, n-heptane) (Al/Cr molar ratio is 500) are added, then 4.2 mu mol of PNSiNP ligand L1 and 3.5 mu mol of chromium acetylacetonate are added, and after the temperature is kept constant at 45 ℃, 0.5Mpa hydrogen and 5MPa ethylene are sequentially introduced to start the reaction. The reaction temperature is 45 ℃ and the reaction time is 60 min. 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, for an activity of 1623kg/gCr.h, a selectivity of (1-hexene + 1-octene) of 88.6 wt% and a polymer selectivity of 0.09 wt%.
Example 2
Preparation of PNSiNP ligand: the relevant solvent is soaked by a molecular sieve for removing water before use.
Preparation of phosphine-nitrogen ligand: the preparation is as in example 1, giving the phosphine-nitrogen ligand La。
Preparation of PNSiNP ligand: 60mmol of phosphine-nitrogen ligand L under the anhydrous and oxygen-free conditionsaDissolving the mixture in 180ml of dichloromethane to obtain a reaction solution II; at-78 ℃, 50mmol of n-butyllithium is dropwise added into the reaction liquid II under stirring, 20mmol of the compound (isopropyl methyl dichlorosilane) shown in the formula III structure and 2.4mmol of trifluoroacetic acid are continuously added into the reaction liquid II, then the temperature is slowly raised to the room temperature, and the reaction is continuously carried out for 70 hours under stirring. Purifying the reaction liquid by using column chromatography (tetrahydrofuran is used for leaching, the height-diameter ratio is 2), then recrystallizing at 75 ℃ (the solvent is ethanol: ethyl acetate: 5:1), and treating the reaction liquid to obtain a product, namely the PNSiNP ligand L2, wherein the structure of L2 is shown as the following formula:
the nuclear magnetic data for the above ligand (L2) are as follows:1H NMR(400MHz，CDCl3)：8.42(s，4H)，7.35～7.49(m，40H)，0.92～1.78(m，7H)，0.14(s，3H)
oligomerization of ethylene:
before the reaction, a 500ml reaction kettle is heated to 160 ℃, vacuumized for 1.5h and replaced by nitrogen for three times. After the temperature is cooled to room temperature, the ethylene is replaced twice, 200ml of dehydrated and deoxidized solvent methylcyclohexane and 1.4ml (Al/Cr ═ 612) of MMAO-3a (7 wt% Al, n-heptane) are added, then 4.8 mu mol of PNSiNP ligand L2 and 4 mu mol of tetrahydrofuran chromium chloride are added, and the reaction is started by sequentially introducing 0.4MPa hydrogen and 4.5MPa ethylene when the temperature is constant at 55 ℃. The reaction temperature is 55 ℃, and the reaction time is 40 min. 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 for an activity of 2278kg/gCr. h, a selectivity for (1-hexene + 1-octene) of 89.7 wt% and a polymer selectivity of 0.07 wt%.
Example 3
Preparation of PNSiNP ligand: the relevant solvent is soaked by a molecular sieve for removing water before use.
Preparation of phosphine-nitrogen ligand: the preparation is as in example 1, giving the phosphine-nitrogen ligand La。
Preparation of PNSiNP ligand: under the anhydrous and oxygen-free conditions, 40mmol of phosphine-nitrogen ligand LaDissolving the mixture in 180ml of dichloromethane to obtain a reaction solution II; and (3) dropwise adding 40mmol of n-butyllithium into the reaction liquid II under stirring at-78 ℃, continuously adding 20mmol of the compound (tert-butylmethyldichlorosilane) shown in the formula III structure and 2.2mmol of trifluoroacetic acid, slowly heating to room temperature, and continuously reacting for 40 hours under stirring. Purifying the reaction liquid by using column chromatography (tetrahydrofuran is used for leaching, the height-diameter ratio is 2), then recrystallizing at 73 ℃ (the solvent is ethanol: ethyl acetate: 5:1), and treating the reaction liquid to obtain a product, namely the PNSiNP ligand L3, wherein the structure of L3 is shown as the following formula:
the nuclear magnetic data for the above ligand (L3) are as follows:1H NMR(400MHz，CDCl3)：8.48(s，4H)，7.36～7.50(m，40H)，0.98(s，9H)，0.14(s，3H)
oligomerization of ethylene:
before reaction, a 500ml reaction kettle is heated to 120 ℃, vacuumized for 2 hours and replaced by nitrogen for three times. After cooling to room temperature, the ethylene was replaced twice, 200ml of toluene as a dehydrated deoxygenated solvent and 0.93ml of (Al/Cr ═ 400) MAO (10 wt%, toluene) were added, then 4.2. mu. mol of PNSiNP ligand L3 and 3.5. mu. mol of tetrahydrofuran chromium chloride were added, and the reaction was started by introducing 0.3MPa of hydrogen and 4.5MPa of ethylene in this order while keeping the temperature constant at 60 ℃. The reaction temperature is 60 ℃, and the reaction time is 45 min. 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, activity 1551kg/gCr. h, (1-hexene + 1-octene) selectivity 91.5 wt%, polymer selectivity 0.05 wt%.
Example 4
Preparation of PNSiNP ligand: the relevant solvent is soaked by a molecular sieve for removing water before use.
Preparation of phosphine-nitrogen ligand: the preparation is as in example 1, giving the phosphine-nitrogen ligand La。
Preparation of PNSiNP ligand: under the anhydrous and oxygen-free conditions, 45mmol of phosphine-nitrogen ligand LaDissolving the mixture in 180ml of dichloromethane to obtain a reaction solution II; at-78 ℃, 34mmol of n-butyllithium is dropwise added into the reaction liquid II under stirring, 20mmol of the compound (cyclohexylmethyldichlorosilane) shown in the formula III structure and 2.2mmol of trifluoroacetic acid are continuously added into the reaction liquid II, then the temperature is slowly raised to the room temperature, and the reaction is continuously carried out for 60 hours under stirring. Purifying the reaction liquid by using column chromatography (tetrahydrofuran is used for leaching, the height-diameter ratio is 2), then recrystallizing at 70 ℃ (the solvent is ethanol: ethyl acetate: 5:1), and treating the reaction liquid to obtain a product, namely the PNSiNP ligand L4, wherein the structure of L4 is shown as the following formula:
the nuclear magnetic data for the above ligand (L4) are as follows:1H NMR(400MHz，CDCl3)：8.46(s，4H)，7.35～7.49(m，40H)，1.30～1.60(m，11H)，0.13(s，3H)
oligomerization of ethylene:
before the reaction, a 500ml reaction kettle is heated to 160 ℃, vacuumized for 2.5 hours and replaced by nitrogen for three times. After the temperature is cooled to room temperature, the ethylene is replaced twice, 200ml of dehydrated and deoxidized solvent toluene and 1.2ml of (Al/Cr ═ 600) MMAO-3a (7 wt% Al, n-heptane) are added, then 4.2 mu mol of PNSiNP ligand L4 and 3.5 mu mol of chromium acetylacetonate are added, and the reaction is started by sequentially introducing 0.5Mpa of hydrogen and 4.5MPa of ethylene when the temperature is constant at 45 ℃. The reaction temperature is 45 ℃ and the reaction time is 25 min. 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, the activity was 1977kg/gCr. h, the (1-hexene + 1-octene) selectivity was 89.8 wt%, the polymer selectivity was 0.08 wt%.
Example 5
Preparation of PNSiNP ligand: the relevant solvent is soaked by a molecular sieve for removing water before use.
Preparation of phosphine-nitrogen ligand: phosphine-nitrogen ligand LbThe preparation method of (3) is as in example 1. With the difference that the compound of structure II added is (2-fluorophenyl) (phenyl) phosphonium chloride; 220mmol of triethylamine is added dropwise to the first reaction solution under stirring at 0 ℃. Phosphine-nitrogen ligand LbThe structure of (a) is as follows:
the above ligand (L)b) The nuclear magnetic data for (c) are as follows:1H NMR(400MHz，CDCl3)：8.45(s，2H)，7.22～7.75(m，18H)，6.93(s，1H)
preparation of PNSiNP ligand: under the anhydrous and anaerobic conditions, 42mmol of phosphine-nitrogen ligand LbDissolving the mixture in 180ml of dichloromethane to obtain a reaction solution II; at-78 ℃, 36mmol of n-butyllithium is dropwise added into the reaction liquid II under stirring, 20mmol of the compound (dichlorodimethylsilane) shown in the formula III structure and 2.0mmol of trifluoroacetic acid are continuously added into the reaction liquid II, then the temperature is slowly raised to the room temperature, and the reaction is continuously carried out for 65 hours under stirring. Purifying the reaction liquid by using column chromatography (tetrahydrofuran is used for leaching, and the height-diameter ratio is 2.5), then recrystallizing at 78 ℃ (the solvent is ethanol: ethyl acetate: 5:1), and treating the reaction liquid to obtain a product, namely the PNSiNP ligand L5, wherein the structure of L5 is shown as the following formula:
the nuclear magnetic data for the above ligand (L5) are as follows:1H NMR(400MHz，CDCl3)：8.45(s，4H)，7.21～7.73(m，36H)，0.15(s，6H)
oligomerization of ethylene:
before reaction, a 500ml reaction kettle is heated to 120 ℃, vacuumized for 4 hours and replaced by nitrogen for three times. After the temperature is cooled to room temperature, the ethylene is replaced twice, 200ml of dehydrated and deoxidized solvent cyclohexane and 0.4ml of (Al/Cr ═ 200) MMAO (7 wt% Al, n-heptane) are added, then 4.2 mu mol of phosphine-nitrogen-silicon ligand L5 and 3.5 mu mol of chromium acetylacetonate are added, and after the temperature is kept constant at 55 ℃, 0.5MPa of hydrogen and 4.5MPa of ethylene are sequentially introduced to start the reaction. The reaction temperature is 55 ℃, and the reaction time is 50 min. 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 for an activity of 1952kg/gCr. h, a selectivity for (1-hexene + 1-octene) of 88.8 wt% and a polymer selectivity of 0.07 wt%.
Example 6
Preparation of PNSiNP ligand: the relevant solvent is soaked by a molecular sieve for removing water before use.
Preparation of phosphine-nitrogen ligand: phosphine-nitrogen ligand LcThe preparation method of (3) is as in example 1. With the difference that the compound of structure II added is (3-fluorophenyl) (phenyl) phosphonium chloride; and dropwise adding 220mmol of triethylamine into the reaction liquid I under stirring at-10 ℃. Phosphine-nitrogen ligand LcThe structure of (a) is as follows:
the above ligand (L)c) The nuclear magnetic data for (c) are as follows:1H NMR(400MHz，CDCl3)：8.45(s，2H)，7.15～7.45(m，18H)，6.93(s，1H)
preparation of PNSiNP ligand: under the anhydrous and anaerobic conditions, 46mmol of phosphine-nitrogen ligand LcDissolving the mixture in 180ml of dichloromethane to obtain a reaction solution II; and (3) dropwise adding 38mmol of n-butyllithium into the reaction liquid II under stirring at-78 ℃, continuously adding 20mmol of the compound (tert-butylmethyldichlorosilane) shown in the formula III structure and 1.8mmol of trifluoroacetic acid, slowly heating to room temperature, and continuously reacting for 55 hours under stirring. Purifying the reaction solution by column chromatography (tetrahydrofuran elution with an aspect ratio of 2.5), and then purifyingRecrystallizing at 75 deg.C (solvent is ethanol: ethyl acetate: 5:1), and treating the reaction solution to obtain the product, i.e. PNSiNP ligand L6, L6 has the following structure:
the nuclear magnetic data for the above ligand (L6) are as follows:1H NMR(400MHz，CDCl3)：8.48(s，4H)，7.21～7.45(m，36H)，0.99(s，9H)，0.13(s，3H)
oligomerization of ethylene:
before reaction, a 500ml reaction kettle is heated to 120 ℃, vacuumized for 5 hours and replaced by nitrogen for three times. After the temperature is cooled to room temperature, the ethylene is replaced twice, 200ml of dehydrated and deoxidized solvent methylcyclohexane and 1.6ml of (Al/Cr ═ 800) MMAO-3a (7 wt% Al, n-heptane) are added, then 4.2 mu mol of phosphine-nitrogen ligand L6 and 3.5 mu mol of chromium acetylacetonate are added, and after the temperature is constant at 60 ℃, 0.5Mpa of hydrogen and 4.5MPa of ethylene are sequentially introduced to start the reaction. The reaction temperature is 60 ℃, and the reaction time is 20 min. 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 for an activity of 1833kg/gCr. h, a selectivity for (1-hexene + 1-octene) of 89.7 wt% and a polymer selectivity of 0.11 wt%.
Example 7
Preparation of PNSiNP ligand: the relevant solvent is soaked by a molecular sieve for removing water before use.
Preparation of phosphine-nitrogen ligand: phosphine-nitrogen ligand LdThe preparation method of (3) is as in example 1. With the difference that the compound of structure II added is (4-fluorophenyl) (phenyl) phosphonium chloride, the reaction solution containing product one is purified using column chromatography (tetrahydrofuran rinse with an aspect ratio of 2.5) and then recrystallized at 75 ℃ (solvent ethanol: ethyl acetate ═ 5:1), phosphine-nitrogen ligand LdThe structure of (a) is as follows:
the nuclear magnetic data of the above ligand (Ld) are as follows: 1H NMR (400MHz, CDCl 3): 8.45(s, 2H), 7.09-7.45 (m, 18H), 6.93(s, 1H)
Preparation of PNSiNP ligand: under the anhydrous and oxygen-free conditions, 48mmol of phosphine-nitrogen ligand LdDissolving the mixture in 180ml of dichloromethane to obtain a reaction solution II; dropwise adding 32mmol of n-butyl lithium into the reaction liquid II under stirring at-78 ℃, continuously adding 20mmol of a compound ((cyclohexylmethyldichlorosilane) shown in the formula III structure and 2.2mmol of trifluoroacetic acid, slowly heating to room temperature, continuously reacting for 58h under stirring, purifying the reaction liquid by using column chromatography (tetrahydrofuran is used for leaching, the height-diameter ratio is 2.5), then recrystallizing at 72 ℃ (the solvent is ethanol: ethyl acetate is 5:1), and treating the reaction liquid to obtain a product, namely the PNSiNP ligand L7, wherein the structure of L7 is shown as the following formula:
the nuclear magnetic data for the above ligand (L7) are as follows:1H NMR(400MHz，CDCl3)：8.49(s，4H)，7.09～7.48(m，36H)，1.29～1.62(m，11H)，0.15(s，3H)
oligomerization of ethylene:
before the reaction, a 500ml reaction kettle is heated to 125 ℃, vacuumized for 3.5 hours and replaced by nitrogen for three times. After the temperature is cooled to room temperature, the ethylene is replaced twice, 200ml of dehydrated and deoxidized solvent methylcyclohexane and 1.2ml of (Al/Cr ═ 600) MMAO-3a (7 wt% Al, n-heptane) are added, then 4.2 mu mol of phosphine-nitrogen ligand L7 and 3.5 mu mol of chromium acetylacetonate are added, and after the temperature is kept constant at 55 ℃, 0.5MPa of hydrogen and 4.5MPa of ethylene are sequentially introduced to start the reaction. The reaction temperature is 55 ℃, and the reaction time is 60 min. 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 had an activity of 2170kg/gCr. h, a selectivity for (1-hexene + 1-octene) of 88.9 wt% and a polymer selectivity of 0.13 wt%.
Example 8
Preparation of PNSiNP ligand: the relevant solvent is soaked by a molecular sieve for removing water before use.
Preparation of phosphine-nitrogen ligand: phosphine-nitrogen ligand LeThe preparation of (1) was carried out as in example 1, with the difference that the compound of the structure II added was bis (4-methylphenyl) phosphonium chloride, the reaction solution containing the first product was purified using column chromatography (tetrahydrofuran elution, height to diameter ratio of 2.5), and then recrystallized at 72 ℃ (ethanol: ethyl acetate ═ 5:1) in the solvent, phosphine-nitrogen ligand LeThe structure of (a) is as follows:
the above ligand (L)e) The nuclear magnetic data for (c) are as follows:1H NMR(400MHz，CDCl3)：8.45(s，2H)，7.23～7.26(m，16H)，6.93(s，1H)，2.34(s，12H)
preparation of PNSiNP ligand: under the anhydrous and oxygen-free conditions, 44mmol of phosphine-nitrogen ligand LeDissolving the mixture in 180ml of dichloromethane to obtain a reaction solution II; 30mmol of n-butyllithium was added dropwise to the reaction solution II under stirring at-78 deg.C, 20mmol of the compound represented by the formula III (dichlorodimethylsilane) and 2.4mmol of trifluoroacetic acid were further added thereto, the temperature was slowly raised to room temperature, and the reaction was continued for 69 hours under stirring. Purifying the reaction liquid by using column chromatography (tetrahydrofuran is used for leaching, and the height-diameter ratio is 2.5), then recrystallizing at 70 ℃ (the solvent is ethanol: ethyl acetate: 5:1), and treating the reaction liquid to obtain a product, namely the PNSiNP ligand L8, wherein the structure of L8 is shown as the following formula:
the nuclear magnetic data for the above ligand (L8) are as follows:1H NMR(400MHz，CDCl3)：8.42(s，4H)，7.21～7.27(m，32H)，2.33(s，24H)，0.16(s，6H)
oligomerization of ethylene:
before the reaction, a 500ml reaction kettle is heated to 155 ℃, vacuumized for 2 hours and replaced by nitrogen for three times. After the temperature is cooled to room temperature, the ethylene is replaced twice, 200ml of dehydrated and deoxidized solvent methylcyclohexane and 1.2ml of (Al/Cr ═ 600) MMAO-3a (7 wt% Al, n-heptane) are added, then 4.2 mu mol of phosphine-nitrogen ligand L8 and 3.5 mu mol of chromium acetylacetonate are added, and after the temperature is kept constant at 50 ℃, 0.5Mpa of hydrogen and 4.5MPa of ethylene are sequentially introduced to start the reaction. The reaction temperature is 50 ℃, and the reaction time is 60 min. 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 for an activity of 1933kg/gCr. h, a selectivity for (1-hexene + 1-octene) of 89.1 wt% and a polymer selectivity of 0.09 wt%.
Example 9
Preparation of PNSiNP ligand: the relevant solvent is soaked by a molecular sieve for removing water before use.
Preparation of phosphine-nitrogen ligand: phosphine-nitrogen ligand LfThe preparation method of (3) is as in example 1. With the difference that the compound shown in structure II is bis (2-methoxyphenyl) phosphine chloride; the reaction solution containing the first product was purified using column chromatography (tetrahydrofuran elution with an aspect ratio of 2.5), followed by recrystallization at 70 ℃ (solvent ethanol: ethyl acetate ═ 5:1), phosphine-nitrogen ligand LfThe structure of (a) is as follows:
the above ligand (L)f) The nuclear magnetic data for (c) are as follows:1H NMR(400MHz，CDCl3)：8.45(s，2H)，6.99～7.34(m，16H)，6.93(s，1H)，3.83(s，12H)
preparation of PNSiNP ligand: under the anhydrous and anaerobic conditions, 42mmol of phosphine-nitrogen ligand LfDissolving the mixture in 180ml of dichloromethane to obtain a reaction solution II; 32mmol of n-butyllithium was added dropwise to the reaction solution II under stirring at-78 deg.C, 20mmol of the compound represented by the formula III (dichlorodimethylsilane) and 2.2mmol of trifluoroacetic acid were further added thereto, the temperature was slowly raised to room temperature, and the reaction was continued for 68 hours under stirring. The reaction solution was purified using column chromatography (tetrahydrofuran elution,aspect ratio of 2.5), and then recrystallized at 78 deg.c (solvent is ethanol: ethyl acetate 8:1), and treating the reaction solution to obtain a product, namely the PNSiNP ligand L9, wherein the structure of L9 is shown as the following formula:
the nuclear magnetic data for the above ligand (L9) are as follows:1H NMR(400MHz，CDCl3)：8.40(s，4H)，6.99～7.27(m，32H)，3.83(s，24H)，0.15(s，6H)
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. After the temperature is cooled to room temperature, the ethylene is replaced twice, 200ml of dehydrated and deoxidized solvent methylcyclohexane and 1.4ml of (Al/Cr ═ 700) MMAO-3a (7 wt% Al, n-heptane) are added, then 4.2 mu mol of phosphine-nitrogen ligand L10 and 3.5 mu mol of chromium acetylacetonate are added, and after the temperature is constant at 53 ℃, 0.5Mpa of hydrogen and 4.5MPa of ethylene are sequentially introduced to start the reaction. The reaction temperature is 53 ℃, and the reaction time is 60 min. 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 for activity 1362kg/gCr. h, (1-hexene + 1-octene) selectivity 88.5 wt%, polymer selectivity 0.06 wt%.
Example 10
Preparation of PNSiNP ligand: the related solvent is soaked in a sieve for removing water before use.
Preparation of phosphine-nitrogen ligand: phosphine-nitrogen ligand LgThe preparation of (1) is as in example 1, except that the compound of structure II is 4- (trimethylsilyl) phenylphosphine chloride is added, the reaction solution containing the first product is purified using column chromatography (tetrahydrofuran elution, aspect ratio of 2.5), and then recrystallized at 70 ℃ (solvent ethanol: ethyl acetate ═ 8:1), phosphine-nitrogen ligand LgThe structure of (a) is as follows:
the above ligand (L)g) The nuclear magnetic data for (c) are as follows:1H NMR(400MHz，CDCl3)：8.45(s，2H)，7.36～7.40(m，16H)，6.93(s，1H)，0.25(s，36H)
preparation of PNSiNP ligand: under the anhydrous and oxygen-free conditions, 44mmol of phosphine-nitrogen ligand LgDissolving the mixture in 180ml of dichloromethane to obtain a reaction solution II; at-78 ℃, 34mmol of n-butyllithium is dropwise added into the reaction liquid II under stirring, 20mmol of the compound (isopropyl methyl dichlorosilane) shown in the formula III structure and 2.2mmol of trifluoroacetic acid are continuously added into the reaction liquid II, then the temperature is slowly raised to the room temperature, and the reaction is continuously carried out for 45 hours under stirring. Purifying the reaction liquid by using column chromatography (tetrahydrofuran is used for leaching, and the height-diameter ratio is 2.5), then recrystallizing at 75 ℃ (the solvent is ethanol: ethyl acetate: 8:1), and treating the reaction liquid to obtain a product, namely the PNSiNP ligand L10, wherein the structure of L10 is shown as the following formula:
the nuclear magnetic data for the above ligand (L10) are as follows:1H NMR(400MHz，CDCl3)：8.49(s，4H)，7.36～7.40(m，32H)，0.92～1.78(m，7H)，0.25(s，72H)，0.13～0.5(s，3H)
oligomerization of ethylene: the oligomerization process was as in example 1.
The product was analyzed by GC for an activity of 1939kg/gCr. h, a selectivity for (1-hexene + 1-octene) of 89.5 wt% and a polymer selectivity of 0.08 wt%.
Example 11
Preparation of PNSiNP ligand: the relevant solvent is soaked by a molecular sieve for removing water before use.
Preparation of phosphine-nitrogen ligand: phosphine-nitrogen ligand LhThe preparation of (1) is as in example 1, with the difference that the compound of the formula II added is 4- (tri-n-butylsilyl) phenylphosphine chloride, the reaction solution containing the first product is purified by column chromatography (tetrahydrofuran elution, aspect ratio of 2.5), and then recrystallized at 70 ℃ (solvent ethanol: acetic acid)Ethyl ester 10:1), phosphine-nitrogen ligand LhThe structure of (a) is as follows:
the above ligand (L)h) The nuclear magnetic data for (c) are as follows:1H NMR(400MHz，CDCl3)：8.45(s，2H)，7.36～7.40(m，16H)，6.93(s，1H)，0.90-1.45(m，108H)
preparation of PNSiNP ligand: under the anhydrous and anaerobic conditions, 46mmol of phosphine-nitrogen ligand LhDissolving the mixture in 180ml of dichloromethane to obtain a reaction solution II; 30mmol of n-butyllithium was added dropwise to the reaction solution II under stirring at-78 deg.C, 20mmol of the compound represented by the formula III (dichlorodimethylsilane) and 2.4mmol of trifluoroacetic acid were further added thereto, the temperature was slowly raised to room temperature, and the reaction was continued for 71 hours under stirring. Purifying the reaction liquid by using column chromatography (tetrahydrofuran is used for leaching, and the height-diameter ratio is 2.5), then recrystallizing at 70 ℃ (the solvent is ethanol: ethyl acetate: 8:1), and treating the reaction liquid to obtain a product, namely the PNSiNP ligand L11, wherein the structure of L11 is shown as the following formula:
the nuclear magnetic data for the above ligand (L11) are as follows:1H NMR(400MHz，CDCl3)：8.51(m，4H)，7.31～7.39(m，32H)，0.90～1.45(m，216H)，0.15(s，6H)
oligomerization of ethylene: the oligomerization process was as in example 1.
The product was analyzed by GC, with an activity of 2625kg/gCr. h, a selectivity of (1-hexene + 1-octene) of 91.7 wt% and a polymer selectivity of 0.06 wt%.
Comparative example 1:
ligand LISynthesis ofiPr-PNP)
Adding 200mL of dichloromethane (treated by a molecular sieve) into a reaction bottle under anhydrous and oxygen-free conditions, then adding 220mmol of triethylamine (anhydrous) and 100mmol of isopropylamine (under the cooling of a low-temperature constant-temperature reaction bath, firstly slowly adding about 110mmol of diphenyl phosphine chloride, when the solution is stable and does not release heat violently, adding the rest 110mmol of diphenyl phosphine chloride, removing the low-temperature constant-temperature reaction bath, and stirring at room temperature for 12 hours.
After the reaction was completed, the solvent in the reaction flask was removed by using a rotary evaporator to obtain a cream yellow solid. The remaining solid product was dissolved in an appropriate amount of the mixed solution (ethanol: ethyl acetate ═ 5: 1). Performing column chromatography with neutral alumina column with length of about 10cm, eluting with ethanol, removing insoluble substances and unreacted phosphorus compounds, removing solvent from the obtained liquid with rotary evaporator, and further drying with vacuum pump to obtain white solid target ligand.1H NMR(400MHz，CDCl3)：7.24～7.35(m，20H)，3.68～3.80(m，1H),1.14(d，6H)
Oligomerization of ethylene: the oligomerization process was as in example 1.
The product was analyzed by GC, activity 780kg/gCr. h, (1-hexene + 1-octene) selectivity 63.5 wt%, polymer selectivity 0.5 wt%.
Claims (12)
1. A PNSiNP ligand has a structure shown in a formula I:
wherein R is1、R2Each independently selected from aryl and derivatives thereof; r3、R4Each independently selected from methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, ethenyl, propenyl, cyclopentyl, cyclohexyl, phenyl, naphthyl, anthracenyl or biphenyl, preferably from methyl, ethyl, isopropyl, n-butyl, cyclohexyl.
2. The PNSiNP ligand of claim 1, wherein the formula I junction isR in the PNSiNP ligand shown in the structure1、R2Selected from the group consisting of 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-methoxyphenyl, o-methoxyphenyl, 4-ethoxyphenyl, o-ethoxyphenyl, 2-fluorophenyl, 3-fluorophenyl, 4-fluorophenyl, 2- (trimethylsilyl) phenyl, 3- (trimethylsilyl) phenyl group, 4- (trimethylsilyl) phenyl group, 2- (tri-n-butylsilyl) phenyl group, 3- (tri-n-butylsilyl) phenyl group, 4- (tri-n-butylsilyl) phenyl group.
3. A process for the preparation of a ligand according to claim 1 or 2, characterized in that it comprises the following steps:
dissolving 2-aminopyrimidine in a solvent A under anhydrous and anaerobic conditions to obtain a reaction solution I;
adding triethylamine into the reaction liquid I under stirring at the temperature of minus 10-0 ℃, continuously adding a compound shown as a structure II into the reaction liquid I, continuously stirring for reacting for 3-6h, continuously stirring for reacting for 6-24h at room temperature, and purifying the reaction liquid to obtain a product I, namely the phosphine-nitrogen ligand; the compound of formula II has the following structure:
wherein R is1、R2Each independently selected from the group consisting of 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-dibutylphenyl4-methoxyphenyl, o-methoxyphenyl, 4-ethoxyphenyl, o-ethoxyphenyl, 2-fluorophenyl, 3-fluorophenyl, 4-fluorophenyl, 2- (trimethylsilyl) phenyl, 3- (trimethylsilyl) phenyl, 4- (trimethylsilyl) phenyl, 2- (tri-n-butylsilyl) phenyl, 3- (tri-n-butylsilyl) phenyl, or 4- (tri-n-butylsilyl) phenyl;
dissolving a phosphine-nitrogen ligand in a solvent A under anhydrous and anaerobic conditions to obtain a reaction solution II;
adding n-butyllithium into the reaction liquid II under stirring at the temperature of between 80 ℃ below zero and 70 ℃ below zero, continuously adding the compound shown in the structure of the formula III and the catalyst into the reaction liquid II, slowly heating to room temperature, continuously reacting for 36 to 72 hours under stirring, and purifying the reaction liquid to obtain a product II, namely the PNSiNP ligand; the compound of formula III has the structure shown below:
R3、R4each independently selected from methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, ethenyl, propenyl, cyclopentyl, cyclohexyl, phenyl, naphthyl, anthracenyl or biphenyl, preferably from methyl, ethyl, isopropyl, n-butyl, cyclohexyl.
4. The ligand preparation method according to claim 3, wherein the molar ratio of the 2-aminopyrimidine to triethylamine is 1: 1-1: 3, and/or the molar ratio of the 2-aminopyrimidine to the compound shown in formula II is 1: 1-1: 3; and/or the solvent A is selected from one or more of toluene, methylcyclohexane, dichloromethane, acetonitrile, cyclohexane, n-hexane and n-heptane.
5. Ligand preparation process according to claim 3 or 4, characterized in that the catalyst is selected from trifluoroacetic acid; and/or the molar ratio of the compound shown in the structure of the formula III to the phosphine-nitrogen ligand is 1: 2-1: 3, and the molar ratio of the n-butyllithium to the compound shown in the structure of the formula III is 1.5: 1-2.5: 1; the molar ratio of the catalyst to the compound shown in the structure of the formula III is 0.08: 1-0.12: 1.
6. The ligand preparation method according to any one of claims 3 to 5, wherein the purification treatment comprises subjecting the reaction solution to column chromatography purification to obtain a target product and subjecting the target product to recrystallization, the column chromatography purification uses a column height-diameter ratio of 2 to 4 and a retention time of 1 to 3min, and the recrystallization uses a mixed solvent of ethanol and ethyl acetate as a solvent.
7. An ethylene oligomerization catalyst is characterized by comprising a transition metal complex and an aluminum alkyl cocatalyst, wherein the transition metal complex comprises a transition metal compound and a PNSiNP ligand, and the PNSiNP ligand is the ligand of any one of claims 1-2 or the ligand prepared by the preparation method of any one of claims 3-6.
8. The catalyst according to claim 7, wherein the transition metal compound is selected from one or more of compounds of chromium, molybdenum, cobalt, titanium, vanadium, zirconium, nickel and palladium, preferably compounds of chromium, zirconium and nickel, and the transition metal compound comprises an organic salt, an inorganic salt, a coordination complex or an organometallic complex of a transition metal, more preferably one or more of chromium acetylacetonate, chromium chloride, chromium tris (tetrahydrofuran) trichloride, chromium (III) 2-ethylhexanoate, chromium (III) octanoate, chromium hexacarbonyl, chromium (benzene) tricarbonyl.
9. The catalyst of any one of claims 6-8, wherein the alkylaluminum cocatalyst is selected from one or more of trimethylaluminum, triethylaluminum, triisobutylaluminum, diethylethoxyaluminum, diethylaluminum monochloride, ethylaluminum dichloride, ethylaluminum sesquichloride, trioctylaluminum, Methylaluminoxane (MAO), Modified Methylaluminoxane (MMAO) or ethylaluminoxane.
10. The catalyst of any one of claims 6-9, wherein the molar ratio of transition metal compound to PNSiNP ligand is 1: 1-3, preferably 1: 1-2; the molar ratio of aluminum alkyl cocatalyst to transition metal compound is 50-2000:1, preferably 90-800:1, based on the molar ratio of aluminum element to transition metal element.
11. Use of a catalyst according to any one of claims 6 to 10 for the oligomerization of ethylene.
12. The application of the method as claimed in claim 11, wherein the reaction kettle is heated to 110-160 ℃ before reaction, vacuumized for 1-4h, replaced by nitrogen, cooled to room temperature, replaced by ethylene, the solvent B and the alkyl aluminum cocatalyst are added, then the transition metal compound and the PNSiNP ligand are added, and after the temperature reaches the reaction temperature, the reaction is started by sequentially introducing 0-0.8MPa hydrogen and 2MPa-7MPa ethylene, wherein the reaction temperature is 35-90 ℃, preferably 40-70 ℃, and the reaction time is 10-240 min, preferably 20-100 min.
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