CN113019461B - 一种乙烯选择性齐聚的催化剂体系、反应方法及其应用 - Google Patents
一种乙烯选择性齐聚的催化剂体系、反应方法及其应用 Download PDFInfo
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- CN113019461B CN113019461B CN202110284855.1A CN202110284855A CN113019461B CN 113019461 B CN113019461 B CN 113019461B CN 202110284855 A CN202110284855 A CN 202110284855A CN 113019461 B CN113019461 B CN 113019461B
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- ethylene
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- 239000003054 catalyst Substances 0.000 title claims abstract description 63
- 238000006384 oligomerization reaction Methods 0.000 title claims abstract description 50
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 239000005977 Ethylene Substances 0.000 title claims abstract description 37
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title claims abstract description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 33
- 125000003118 aryl group Chemical group 0.000 claims abstract description 29
- 239000003446 ligand Substances 0.000 claims abstract description 27
- 150000003623 transition metal compounds Chemical class 0.000 claims abstract description 27
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 20
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 5
- 239000001257 hydrogen Substances 0.000 claims abstract description 5
- 150000002736 metal compounds Chemical group 0.000 claims abstract description 5
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims abstract description 4
- 150000001875 compounds Chemical class 0.000 claims description 26
- 239000012190 activator Substances 0.000 claims description 21
- -1 alkyl aluminum compound Chemical class 0.000 claims description 21
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 12
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 11
- 239000011651 chromium Substances 0.000 claims description 11
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 claims description 11
- 229910052804 chromium Inorganic materials 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 9
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 8
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 7
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 6
- 239000012442 inert solvent Substances 0.000 claims description 6
- 230000003213 activating effect Effects 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 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 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
- 239000002608 ionic liquid Substances 0.000 claims description 4
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims description 3
- 125000006736 (C6-C20) aryl group Chemical group 0.000 claims description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 3
- 150000001336 alkenes Chemical class 0.000 claims description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 239000011733 molybdenum Substances 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 229910052715 tantalum Inorganic materials 0.000 claims description 3
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 239000010937 tungsten Substances 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- 239000000047 product Substances 0.000 abstract description 28
- 239000004711 α-olefin Substances 0.000 abstract description 12
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- 239000006227 byproduct Substances 0.000 abstract description 4
- 125000003367 polycyclic group Chemical group 0.000 abstract description 4
- 238000007172 homogeneous catalysis Methods 0.000 abstract description 2
- 229920000642 polymer Polymers 0.000 abstract 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 abstract 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 36
- 230000000694 effects Effects 0.000 description 18
- 239000000243 solution Substances 0.000 description 13
- 238000002360 preparation method Methods 0.000 description 11
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 description 10
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 10
- MZRVEZGGRBJDDB-UHFFFAOYSA-N n-Butyllithium Substances [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 8
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 8
- 238000001816 cooling Methods 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 4
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229910021556 Chromium(III) chloride Inorganic materials 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical group [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 description 4
- 239000011636 chromium(III) chloride Substances 0.000 description 4
- 239000003814 drug Substances 0.000 description 4
- 229940079593 drug Drugs 0.000 description 4
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methylcyclopentane Chemical compound CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 4
- NFJPEKRRHIYYES-UHFFFAOYSA-N methylidenecyclopentane Chemical compound C=C1CCCC1 NFJPEKRRHIYYES-UHFFFAOYSA-N 0.000 description 4
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- NEKMZTAFXAXHNI-UHFFFAOYSA-N (2-bromophenyl)-methyl-phenylphosphane Chemical compound CP(c1ccccc1)c1ccccc1Br NEKMZTAFXAXHNI-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910021554 Chromium(II) chloride Inorganic materials 0.000 description 2
- 125000005234 alkyl aluminium group Chemical group 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 150000001845 chromium compounds Chemical class 0.000 description 2
- XBWRJSSJWDOUSJ-UHFFFAOYSA-L chromium(ii) chloride Chemical compound Cl[Cr]Cl XBWRJSSJWDOUSJ-UHFFFAOYSA-L 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- 229940069096 dodecene Drugs 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 2
- 159000000002 lithium salts Chemical class 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 230000005311 nuclear magnetism Effects 0.000 description 2
- 125000002524 organometallic group Chemical group 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005829 trimerization reaction Methods 0.000 description 2
- WCFQIFDACWBNJT-UHFFFAOYSA-N $l^{1}-alumanyloxy(2-methylpropyl)aluminum Chemical compound CC(C)C[Al]O[Al] WCFQIFDACWBNJT-UHFFFAOYSA-N 0.000 description 1
- WQONPSCCEXUXTQ-UHFFFAOYSA-N 1,2-dibromobenzene Chemical compound BrC1=CC=CC=C1Br WQONPSCCEXUXTQ-UHFFFAOYSA-N 0.000 description 1
- YVSMQHYREUQGRX-UHFFFAOYSA-N 2-ethyloxaluminane Chemical compound CC[Al]1CCCCO1 YVSMQHYREUQGRX-UHFFFAOYSA-N 0.000 description 1
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 description 1
- FZTHAJKHQAMAJM-UHFFFAOYSA-N C1(=CC=CC=C1)OC1=CC=CC=C1.[Cr] Chemical compound C1(=CC=CC=C1)OC1=CC=CC=C1.[Cr] FZTHAJKHQAMAJM-UHFFFAOYSA-N 0.000 description 1
- 229910021581 Cobalt(III) chloride Inorganic materials 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- VURFVHCLMJOLKN-UHFFFAOYSA-N Diphosphine Natural products PP VURFVHCLMJOLKN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910021585 Nickel(II) bromide Inorganic materials 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000005922 Phosphane Substances 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- GYVCVTQHUUFHPO-UHFFFAOYSA-N [Cr]C1=CC=CC=C1 Chemical compound [Cr]C1=CC=CC=C1 GYVCVTQHUUFHPO-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000002199 base oil Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- XGRJZXREYAXTGV-UHFFFAOYSA-N chlorodiphenylphosphine Chemical compound C=1C=CC=CC=1P(Cl)C1=CC=CC=C1 XGRJZXREYAXTGV-UHFFFAOYSA-N 0.000 description 1
- FRBFQWMZETVGKX-UHFFFAOYSA-K chromium(3+);6-methylheptanoate Chemical compound [Cr+3].CC(C)CCCCC([O-])=O.CC(C)CCCCC([O-])=O.CC(C)CCCCC([O-])=O FRBFQWMZETVGKX-UHFFFAOYSA-K 0.000 description 1
- RPBPCPJJHKASGQ-UHFFFAOYSA-K chromium(3+);octanoate Chemical compound [Cr+3].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O.CCCCCCCC([O-])=O RPBPCPJJHKASGQ-UHFFFAOYSA-K 0.000 description 1
- WYYQVWLEPYFFLP-UHFFFAOYSA-K chromium(3+);triacetate Chemical compound [Cr+3].CC([O-])=O.CC([O-])=O.CC([O-])=O WYYQVWLEPYFFLP-UHFFFAOYSA-K 0.000 description 1
- 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 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- DILRJUIACXKSQE-UHFFFAOYSA-N n',n'-dimethylethane-1,2-diamine Chemical compound CN(C)CCN DILRJUIACXKSQE-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- 229910000064 phosphane Inorganic materials 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- SQBBHCOIQXKPHL-UHFFFAOYSA-N tributylalumane Chemical compound CCCC[Al](CCCC)CCCC SQBBHCOIQXKPHL-UHFFFAOYSA-N 0.000 description 1
- ORYGRKHDLWYTKX-UHFFFAOYSA-N trihexylalumane Chemical compound CCCCCC[Al](CCCCCC)CCCCCC ORYGRKHDLWYTKX-UHFFFAOYSA-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
- LFXVBWRMVZPLFK-UHFFFAOYSA-N trioctylalumane Chemical compound CCCCCCCC[Al](CCCCCCCC)CCCCCCCC LFXVBWRMVZPLFK-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- 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
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
- B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
- B01J31/2409—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring with more than one complexing phosphine-P atom
-
- 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
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
- B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
- B01J31/2419—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising P as ring member
- B01J31/2423—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising P as ring member comprising aliphatic or saturated rings
-
- 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
- C07C2/36—Catalytic processes with hydrides or organic compounds as phosphines, arsines, stilbines or bismuthines
-
- 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 Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/50—Organo-phosphines
- C07F9/5022—Aromatic phosphines (P-C aromatic linkage)
-
- 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 Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/50—Organo-phosphines
- C07F9/505—Preparation; Separation; Purification; Stabilisation
- C07F9/5063—Preparation; Separation; Purification; Stabilisation from compounds having the structure P-H or P-Heteroatom, in which one or more of such bonds are converted into P-C bonds
- C07F9/5072—Preparation; Separation; Purification; Stabilisation from compounds having the structure P-H or P-Heteroatom, in which one or more of such bonds are converted into P-C bonds from starting materials having the structure P-H
-
- 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 Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
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Abstract
本发明提供了一种乙烯选择性齐聚的催化剂体系、反应方法及其应用,属于均相催化技术领域。该催化剂体系包括:配体a;过渡金属化合物b,过渡金属化合物b为IVB~VIII族的金属化合物;其中,配体a的结构通式如式(I)所示:R1和R2可以相同或不同,分别独立选自烷基、芳基或芳基的衍生物,但R1和R2至少有一个为芳基或芳基的衍生物;R4、R5与N、P、N不成环,或R4、R5与N、P、N形成多元环;R3~R10可以相同或不同,分别独立选自氢、烷基或芳基。本发明的催化剂体系主要用于乙烯选择性齐聚,具有催化活性高、产物线性α‑烯烃选择性高、1‑丁烯含量少、C6~C8线性α‑烯烃选择性高、聚合物副产物少的特点。
Description
技术领域
本发明属于均相催化技术领域,具体涉及一种乙烯选择性齐聚的催化剂体系、反应方法及其应用。
背景技术
随着全球经济的不断发展和对聚烯烃材料、润滑油基础油高性能化的要求,1-己烯、 1-辛烯、1-癸烯和1-十二烯等高级线性α-烯烃在高性能聚烯烃、高端合成润滑油等领域的应用不断增加,其需求量持续增长。乙烯齐聚法是生产高纯度1-己烯、1-辛烯、1-癸烯和1-十二烯等高级线性α-烯烃的主要方法之一,一般包括非选择性乙烯齐聚和选择性乙烯齐聚。
对于非选择性乙烯齐聚技术,一些新型配体配位的金属铬基均相催化剂被报道用于合成碳数分布较宽的线性α-烯烃。如Sasol公司Overett等人曾报道PCP骨架配体的铬催化剂体系用于催化乙烯非选择性齐聚,产品组成遵循Schulz-Flory分布(α=0.55)(J.Mol.Catal.A:Chem,2008,283,114)。Gambarotta等人曾报道吡啶骨架配体衍生的N,P配位的铬催化剂,在甲基铝氧烷活化下催化乙烯齐聚,但其产物分布有别于Schulz-Flory分布, C6-C8的质量分数达到55%-72%,线性率较高(Organometallics,2013,32,7107;2014,33,1602)。随后,Danopoulos等人报道类似结构的铬基催化剂在甲基铝氧烷活化下催化乙烯齐聚,产物中C6-C8的质量分数达到66%(Organometallics,2016,35,4044)。
对于乙烯选择性齐聚,催化剂体系的活性和目的产物的选择性是评价该技术先进性的关键,而催化剂体系中配体的结构对乙烯齐聚产物碳数的调控具有重要的作用。2004年南非Sasol公司的研究人员在Wass教授开发的乙烯三聚双膦胺(PNP)配体(Chem.Commun.,2002,858~859)的基础上进行了较小的改动,即使原催化体系由乙烯三聚变成乙烯四聚。随后国际上许多化学公司和科学家进行跟踪研究,其中,韩国SK能源公司CN201880057196.4、CN201780043063.7、CN201380014632.7、CN201080003564.0、CN200880002464.9、CN200780100280.1设计合成的手性的PCCP型配体,与Cr和MAO 组成催化体系用于乙烯四聚,具有较高的催化活性和较长时间的稳定性。但该类催化体系中副产物甲基环戊烷和亚甲基环戊烷含量较高,C6~C8线性α-烯烃总选择性偏低。
发明内容
本发明旨在通过精细调节催化剂配体取代基的电子性能和空间位阻,提出催化活性高、C6~C8线性α-烯烃总选择性高的乙烯选择性齐聚催化剂体系。
本发明提出一种乙烯选择性齐聚的催化剂体系,包括:
配体a;
过渡金属化合物b,过渡金属化合物b为IVB~VIII族的金属化合物;
活化剂c,活化剂c为含有IIIA族金属的化合物;
其中,配体a的结构通式如式(I)所示:
R1和R2可以相同或不同,分别独立选自烷基、芳基或芳基的衍生物,但R1和R2至少有一个为芳基或芳基的衍生物;
R4、R5与N、P、N不成环,或R4、R5与N、P、N形成多元环;
R3~R10可以相同或不同,分别独立选自氢、烷基或芳基。
进一步地,烷基为C1-C10的烷基;优选的,烷基选自甲基、乙基、正丙基、异丙基、环戊基、环己基。
进一步地,芳基为C6-C20的芳基及其衍生物;优选的,芳基选自苯基、取代苯基。
进一步地,过渡金属化合物b为铬、钼、钨、钴、钛、钽、钒、锆、铁、镍或钯的化合物。
进一步地,活化剂c为烷基铝化合物、烷基铝氧烷化合物中的一种或两种以上的混合物;其中烷基铝氧烷化合物包括去除挥发性组分的烷基铝氧烷化合物。
进一步地,活化剂c为烷基铝化合物与去除挥发性组分的烷基铝氧烷化合物的混合物,其中,烷基铝化合物为三乙基铝,铝氧烷化合物为去除挥发性组分的甲基铝氧烷。
进一步地,配体a、过渡金属化合物b、活化剂c的摩尔比为1:0.5~100:0.1~5000。
本发明还提出一种乙烯选择性齐聚的反应方法,包括上述任一催化剂体系存在下进行的乙烯齐聚反应。
进一步地,反应在惰性溶剂中进行,惰性溶剂为烷烃、芳烃、烯烃或离子液体中的一种或两种以上混合;反应的温度为0℃~200℃;反应的压力为0.1MPa~50MPa。
本发明还提出上述任一催化剂体系在乙烯选择性齐聚中的应用。
本发明具有以下优势:
本发明催化剂体系催化活性高,目的产物C6~C8线性α-烯烃总选择性高,且1-己烯、 1-辛烯的总选择性高,副产物甲基环戊烷、亚甲基环戊烷的选择性低。
具体实施方式
下面将结合本发明的实施例,对本发明实施例中的技术方案进行清楚、完整地描述,显然,所描述的实施例仅仅是本发明一部分实施例,而不是全部的实施例。在不冲突的情况下,本发明中的实施例及实施例中的特征可以相互组合。
下面对本发明的催化剂体系进行说明。
需要指出,文中“C6~C8线性α-烯烃总选择性”是指C6~C8线性α-烯烃的总量在总产物(所有线性α-烯烃以及副产物)中所占的比例。
本发明一实施例提出一种乙烯选择性齐聚的催化剂体系,其特征在于,包括:
配体a;
过渡金属化合物b,所述过渡金属化合物b为IVB~VIII族的金属化合物;
活化剂c,活化剂c为含有IIIA族金属的化合物;
其中,配体a的结构通式如式(I)所示:
R1和R2可以相同或不同,分别独立选自烷基、芳基或芳基的衍生物,但R1和R2至少有一个为芳基或芳基的衍生物;
R4、R5与N、P、N不成环,或R4、R5与N、P、N形成多元环;
R3~R10可以相同或不同,分别独立选自氢、烷基或芳基。
本发明实施例提供的一种用于乙烯选择性齐聚的催化剂体系,包括配体a、过渡金属化合物b以及活化剂c。其中,配体a结构通式如式(I)所示含有磷原子和氮原子的配体;过渡金属化合物b为IVB~VIII族的金属化合物,为中心金属原子;活化剂c为含有IIIA 族金属的化合物。
本发明一实施例中,所述多元环为五元以上的环状结构,例如,所述多元环可以为五元环,六元环,七元环等。
本发明一实施例中,烷基为C1-C10的烷基。优选的,烷基选自甲基、乙基、正丙基、异丙基、环戊基、环己基。更优选的,烷基选自甲基、乙基、正丙基等。
本发明一实施例中,芳基为C6-C20的芳基及其衍生物。优选的,芳基选自苯基、取代苯基。更优选的,芳基选自苯基、4-甲基苯基、4-甲氧基苯基等。芳基衍生物选自萘基、取代萘基和芴基等。
本发明一实施例中,过渡金属化合物b为铬、钼、钨、钴、钛、钽、钒、锆、铁、镍或钯的化合物。优选的,过渡金属化合物b为CrCl3(THF)3、CrCl2(THF)2、CoCl3、NiBr2中的一种。更优选的,过渡金属化合物b为含铬的过渡金属化合物。可选择的铬化合物包括通式CrRn所示的化合物,式中Rn为有机阴性离子或中性分子,Rn中通常含有1~10 个碳原子,n为0~6的整数,铬的价态为0~6价。具体的Rn基团为含羧基、β-二酮基及烃基的有机物或其基团。从易于溶解和易于操作的角度考虑,更适宜的铬化合物包括醋酸铬、异辛酸铬、正辛酸铬、乙酰丙酮铬、二异戊二烯铬、二苯铬、CrCl3(THF)3、CrCl2(THF)2、(苯基)三羰基铬、六羰基铬的一种。
进一步地,活化剂c为烷基铝化合物、烷基铝氧烷化合物中的一种或两种以上的混合物;其中,烷基铝氧烷化合物包括去除挥发性组分的烷基铝氧烷化合物。
具体而言,活化剂c可以为含有IIIA族金属的化合物。如烷基铝化合物、烷基铝氧烷化合物。烷基铝化合物可以为各种三烷基铝,如三乙基铝(TEAL)、三异丁基铝、三正丁基铝、三正已基铝或三正辛基铝;烷基铝化合物也可以为烷基铝卤化物、烷基铝氢化物或烷基铝倍半氯化物,如一氯二乙基铝(AlEt2Cl)和三氯三乙基二铝(A12Et3Cl3);烷基铝氧烷化合物可以选自甲基铝氧烷(MAO)、乙基铝氧烷、异丁基铝氧烷、改性的铝氧烷和去除挥发性组分的甲基铝氧烷DMAO等。优选的,活化剂c可以为烷基铝化合物与去除挥发性组分的烷基铝氧烷的混合物,其中,烷基铝化合物为TEAL,烷基铝氧烷化合物为DMAO。优选的,TEAL与DMAO的摩尔比为0.01~100,优选0.1~10。
在本发明中,TEAL烷基化能力相对偏弱,更能适应本发明提出的催化剂体系;同时DMAO能够屏蔽掉甲苯等挥发性组分对催化剂络合过程的影响,从而提高催化剂体系的活性,二者混合可进一步降低活化剂的用量。
进一步地,配体a、过渡金属化合物b、活化剂c的摩尔比为1:0.5~100:0.1~5000。
进一步地,配体a、过渡金属化合物b、活化剂c的摩尔比为1:0.5~100:0.1~200。
进一步地,过渡金属化合物b和活化剂c的摩尔比为1:1~500。
进一步地,过渡金属化合物b和活化剂c的摩尔比为1:1~200。
下面对本发明催化剂体系制备方法做进一步说明。
本发明一实施例中,配体a的制备方法可以包括如下步骤:
(1)制备Ph2PPhBr
取一定量的1,2-二溴苯,加入少量的正己烷放到冰箱中冷却10-20min备用。取一定量的n-BuLi,加入少量的正己烷放冰箱中冷却10-20min,然后将上述两种药品取出,将n-BuLi缓慢滴加入上述备用溶液中,搅拌反应约30min后,将少量正己烷稀释后的Ph2PCl滴加进去,搅拌过夜。反应完全之后用砂芯漏斗过滤掉锂盐,溶液减压蒸馏除去溶剂,得无色油状产品Ph2PPhBr。
(2)制备Ph2PPhP(NR3R4)(NR5R6)
取一定量的Ph2PPhBr加入适量的正己烷放冰箱中备用。取一定量的n-BuLi,加入少量的正己烷放冰箱中冷却10-20min,然后将上述两种药品取出,将n-BuLi缓慢滴加入上述备用溶液中,搅拌反应约30min后,将少量正己烷稀释后的ClP(NR3R4)(NR5R6)滴加进去,搅拌过夜。反应完全之后用砂芯漏斗过滤掉锂盐,溶液减压蒸馏除去溶剂,得无色或黄色油状物,然后再加入适量正己烷搅拌,充分混合后放进冰箱进行重结晶。过夜,过滤掉正己烷溶剂,真空干燥,产品为白色或浅黄色固体粉末。
本发明一实施例中,催化剂体系的制备方法可以包括如下步骤:
将组分a、b、c预先混合或直接加入到反应体系中进行原位合成。也就是说,催化剂的制备是把配体a、过渡金属化合物b、活化剂c预先混合;也可以把配体a、过渡金属化合物b、活化剂c直接加入到反应体系中进行原位合成;
含式(I)的配体a、过渡金属化合物b及活化剂c的反应方式,可以通过液相反应,如在溶剂的作用下进行反应,可选择的溶剂如甲苯、苯及其衍生物等;也可以通过固相反应;也可以通过在齐聚反应过程中进行原位反应生成催化剂。这里的反应可以是上述的配体、过渡金属化合物及金属有机活化剂的一种、两种及三种化合物之间的反应。这个反应的过程也是催化剂的陈化(预络合)过程。
下面对本发明催化剂体系在乙烯齐聚反应的方法进一步说明。
本发明还提供了一种乙烯齐聚反应方法,包括上述催化剂体系存在下进行的乙烯齐聚反应。
本发明一实施例中,反应在惰性溶剂中进行,惰性溶剂为烷烃、芳烃、烯烃或离子液体中的一种或两种以上。典型的溶剂包括,但不限于苯、甲苯、二甲苯、异丙苯、正庚烷、正己烷、甲基环己烷、环己烷、1-己烯、1-辛烯、离子液体等,优选甲基环己烷。
本发明一实施例中,反应的温度0℃~200℃。优选45℃~100℃。
本发明一实施例中,乙烯齐聚反应的压力可在0.1MPa~50MPa的压力下进行,优选1.0MPa~10MPa。
本发明一实施例中,反应体系中催化剂的浓度可以从0.01μmol金属/L~1000μmol金属/L,优选0.1μmol金属/L~10μmol金属/L。需要指出,此处金属为过渡金属化合物b中的过渡金属。
以下结合具体实例进一步阐明本发明的内容,但本发明的内容不仅仅局限于下面的实施例。
实施例1
1、N,N,N',N'-四甲基-1-(2-(甲基(苯基)膦基)苯基)-膦二胺(L1)的制备:
取(2-溴苯基)(甲基)(苯基)膦(1.71g,5mmol)加入适量正己烷放冰箱中备用,取一定量的n-BuLi(0.32g,5mmol),加入少量的正己烷放冰箱中冷却10-20min,然后将上述两种药品取出,将n-BuLi缓慢滴加入上述备用溶液中,搅拌反应约30min。取1-氯 -N,N,N',N'-四甲基膦二胺(0.77g,5mmol)加入适量正己烷放进冰箱,15-20min后,取出上述溶液,将1-氯-N,N,N',N'-四甲基膦二胺缓慢地加入上述混合溶液中,搅拌过夜,然后过滤真空干燥,得黄色油状物,然后再加入适量正己烷搅拌,充分混合后放进冰箱进行重结晶。过夜,过滤掉正己烷溶剂,真空干燥,产品为白色固体粉末。
实验所得产物均通过核磁验证结构正确。
2、催化剂的制备
在经N2充分置换的带搅拌的100mL反应器中加入未经脱水处理的甲基环己烷(20mL), N,N,N',N'-四甲基-1-(2-(甲基(苯基)膦基)苯基)-膦二胺(L1)(1.20mg)(3.15μmol), CrCl3·(THF)3(1.12mg,3μmol),室温反应5min后备用。
3、乙烯齐聚反应
100mL的低压釜抽真空20min,经氮气置换数次后充入乙烯,升温到预定温度,加入未经脱水处理的甲基环己烷(20mL)、0.87mL(1.22mmol)的MAO及上述催化剂。在30℃、1MPa的压力下进行齐聚反应,反应30min后用冰浴降温、卸压,用质量分数为10%的酸化乙醇终止反应。齐聚产物的分布见表1、实验条件及催化剂活性见表2。
实施例2
同实施例1。不同之处在于R3、R4为乙基、R5、R6为乙基。齐聚产物的分布见表1、实验条件及催化剂活性见表2。
实施例3
同实施例1。不同之处在于R3、R4甲基、R5、R6为乙基。齐聚产物的分布见表1、实验条件及催化剂活性见表2。
实施例4
同实施例1。不同之处在于R3、R4为正丙基、R5、R6为正丙基。齐聚产物的分布见表1、实验条件及催化剂活性见表2。
实施例5
同实施例1。不同之处在于R3、R4为异丙基、R5、R6为异丙基。齐聚产物的分布见表1、实验条件及催化剂活性见表2。
实施例6
同实施例1。不同之处在于R3、R4为环戊基、R5、R6为甲基。齐聚产物的分布见表 1、实验条件及催化剂活性见表2。
实施例7
同实施例1。不同之处在于R3、R4为环己基、R5、R6为正丙基。齐聚产物的分布见表1、实验条件及催化剂活性见表2。
实施例8
同实施例1。不同之处在于R3、R4为苯基、R5、R6为苯基。齐聚产物的分布见表1、实验条件及催化剂活性见表2。
实施例9
同实施例1。不同之处在于反应温度为50℃。齐聚产物的分布见表1,实验条件及催化剂活性见表2。
实施例10
同实施例1。不同之处在于反应温度为70℃。齐聚产物的分布见表1、实验条件及催化剂活性见表2。
实施例11
同实施例9。不同之处在于反应温度为90℃。齐聚产物的分布见表1,实验条件及催化剂活性见表2。
实施例12
同实施例11。不同之处在于MAO的加入量为0.58mL(0.81mmol)。齐聚产物的分布见表1,实验条件及催化剂活性见表2。
实施例13
同实施例1。不同之处在乙烯齐聚反应是在1.0L的不锈钢反应釜中进行,甲基环己烷的加入量为200mL,反应压力为6.0MPa,其中氢气分压为0.5MPa。齐聚产物的分布见表1,实验条件及催化剂活性见表2。
实施例14
同实施例1。不同之处在于,反应压力为3.0MPa。齐聚产物的分布见表1,实验条件及催化剂活性见表2。
实施例15
2-(2-(二苯基膦基)苯基)-1,3-二甲基-1,3,2-二氮磷烷的制备
氯-1,3-二甲基-1,3,2-二氮磷的制备
将N,N-二甲基乙二胺(12.10mL,113.4mmol)和三乙胺(11.14ml,78mmol)的二氯甲烷溶液20mL和三氯化磷(11.88ml,136mmol)的二氯甲烷溶液20mL同时加入到 -40℃的60mL的二氯甲烷中。将溶液升温至-30℃,加入三乙胺(11.14ml,78mmol)。然后将溶液缓慢升至室温,保持2h。去除溶剂,并用乙醚(3×100ml)提取残渣。将乙醚馏分组合在一起,并在减压下除去溶剂,以获得所需产品,从中蒸馏出所需产品。
2-(2-(二苯基膦基)苯基)-1,3-二甲基-1,3,2-二氮磷烷的制备:
取(2-溴苯基)(甲基)(苯基)膦(1.71g,5mmol)加入适量正己烷放冰箱中备用,取一定量的n-BuLi(0.32g,5mmol),加入少量的正己烷放冰箱中冷却10-20min,然后将上述两种药品取出,将n-BuLi缓慢滴加入上述备用溶液中,搅拌反应约30min。取氯-1,3-二甲基-1,3,2-二氮磷(0.76g,5mmol)加入适量正己烷放进冰箱,15-20min后,取出上述溶液,将氯-1,3-二甲基-1,3,2-二氮磷缓慢地加入上述混合溶液中,搅拌过夜,然后过滤真空干燥,得黄色油状物,然后再加入适量正己烷搅拌,充分混合后放进冰箱进行重结晶。过夜,过滤掉正己烷溶剂,真空干燥,产品为白色固体粉末。
实验所得产物均通过核磁验证结构正确。
2、催化剂的制备
在经N2充分置换的带搅拌的100mL反应器中加入未经脱水处理的甲基环己烷(20mL), N,N,N',N'-四甲基-1-(2-(甲基(苯基)膦基)苯基)-膦二胺(L1)(1.20mg)(3.15μmol), CrCl3·(THF)3(1.12mg,3μmol),室温反应5min后备用。
3、乙烯齐聚反应
100mL的低压釜抽真空20min,经氮气置换数次后充入乙烯,升温到预定温度,加入未经脱水处理的甲基环己烷(20mL)、0.87mL(1.22mmol)的MAO及上述催化剂。在30℃、1MPa的压力下进行齐聚反应,反应30min后用冰浴降温、卸压,用质量分数为10%的酸化乙醇终止反应。齐聚产物的分布见表1、实验条件及催化剂活性见表2。
对比例1
同实施例1。不同之处在于,配体的结构不同,如下式所示:
齐聚产物的分布见表1、实验条件及催化剂活性见表2。
Claims (12)
2.按照权利要求1所述的催化剂,其特征在于,
所述烷基为C1-C10的烷基。
3.按照权利要求2所述的催化剂,其特征在于,
所述烷基选自甲基、乙基、正丙基、异丙基、环戊基、环己基。
4.按照权利要求1所述的催化剂,其特征在于,
所述芳基为C6-C20的芳基。
5.按照权利要求4所述的催化剂,其特征在于,
所述芳基为苯基。
6.按照权利要求1所述的催化剂,其特征在于,
所述芳基的衍生物为取代苯基。
7.按照权利要求1所述的催化剂,其特征在于,
所述过渡金属化合物b为铬、钼、钨、钴、钛、钽、钒、锆、铁、镍或钯的化合物。
8.按照权利要求1所述的催化剂,其特征在于,
所述活化剂c为烷基铝化合物、烷基铝氧烷化合物中的一种或两种以上的混合物;其中所述烷基铝氧烷化合物包括去除挥发性组分的烷基铝氧烷化合物。
9.按照权利要求1或8所述的催化剂,其特征在于,
所述活化剂c为烷基铝化合物与去除挥发性组分的烷基铝氧烷化合物的混合物,其中,所述烷基铝化合物为三乙基铝,所述铝氧烷化合物为去除挥发性组分的甲基铝氧烷。
10.按照权利要求1所述的催化剂,其特征在于,
所述配体a、所述过渡金属化合物b、所述活化剂c的摩尔比为1:0.5~100:0.1~5000。
11.一种乙烯选择性齐聚的反应方法,其特征在于,
包括权利要求1-10任一项所述的催化剂存在下进行的乙烯齐聚反应。
12.按照权利要求11所述的方法,其特征在于,
反应在惰性溶剂中进行,所述惰性溶剂为烷烃、芳烃、烯烃或离子液体中的一种或两种以上混合;
反应的温度为0℃~200℃;
反应的压力为0.1MPa~50MPa。
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