CN109174190B - 用于乙烯选择性齐聚的催化剂体系 - Google Patents
用于乙烯选择性齐聚的催化剂体系 Download PDFInfo
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- CN109174190B CN109174190B CN201811080567.9A CN201811080567A CN109174190B CN 109174190 B CN109174190 B CN 109174190B CN 201811080567 A CN201811080567 A CN 201811080567A CN 109174190 B CN109174190 B CN 109174190B
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- ethylene
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- 238000006384 oligomerization reaction Methods 0.000 title claims abstract description 62
- 239000003054 catalyst Substances 0.000 title claims abstract description 47
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 239000005977 Ethylene Substances 0.000 title claims abstract description 42
- 239000003446 ligand Substances 0.000 claims abstract description 34
- 125000005842 heteroatom Chemical group 0.000 claims abstract description 19
- 150000001875 compounds Chemical class 0.000 claims abstract description 15
- 239000012190 activator Substances 0.000 claims abstract description 12
- 150000003623 transition metal compounds Chemical class 0.000 claims abstract description 10
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 6
- 150000002736 metal compounds Chemical class 0.000 claims abstract description 5
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 4
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 4
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 4
- 125000005843 halogen group Chemical group 0.000 claims abstract description 3
- 125000002950 monocyclic group Chemical group 0.000 claims abstract description 3
- -1 (diphenyl) phosphorus dimethyl tin phosphorus Chemical compound 0.000 claims description 45
- 238000006243 chemical reaction Methods 0.000 claims description 39
- 125000006267 biphenyl group Chemical group 0.000 claims description 25
- 235000010290 biphenyl Nutrition 0.000 claims description 24
- 239000004305 biphenyl Substances 0.000 claims description 24
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 24
- 239000011651 chromium Substances 0.000 claims description 17
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 12
- 238000002360 preparation method Methods 0.000 claims description 11
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 9
- 229910052804 chromium Inorganic materials 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 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 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 4
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 4
- 150000007522 mineralic acids Chemical class 0.000 claims description 4
- 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
- 238000011065 in-situ storage Methods 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 150000002902 organometallic compounds Chemical class 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- 239000012442 inert solvent Substances 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 229910052715 tantalum Inorganic materials 0.000 claims description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 239000010937 tungsten Substances 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
- RPGWZZNNEUHDAQ-UHFFFAOYSA-N phenylphosphine Chemical class PC1=CC=CC=C1 RPGWZZNNEUHDAQ-UHFFFAOYSA-N 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 10
- 239000004711 α-olefin Substances 0.000 abstract description 8
- 125000003118 aryl group Chemical group 0.000 abstract 1
- 125000003367 polycyclic group Chemical group 0.000 abstract 1
- 239000000047 product Substances 0.000 description 30
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 24
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 22
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 20
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- 238000009826 distribution Methods 0.000 description 14
- 239000007787 solid Substances 0.000 description 12
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 11
- 230000000694 effects Effects 0.000 description 9
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 9
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 150000003613 toluenes Chemical class 0.000 description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 229910021556 Chromium(III) chloride Inorganic materials 0.000 description 6
- 239000004698 Polyethylene Substances 0.000 description 6
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 description 6
- 239000011636 chromium(III) chloride Substances 0.000 description 6
- GPAYUJZHTULNBE-UHFFFAOYSA-N diphenylphosphine Chemical compound C=1C=CC=CC=1PC1=CC=CC=C1 GPAYUJZHTULNBE-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 229920000573 polyethylene Polymers 0.000 description 6
- JPJGNZQDELRZGE-UHFFFAOYSA-N (phenyl-$l^{2}-phosphanyl)benzene Chemical compound C=1C=CC=CC=1[P]C1=CC=CC=C1 JPJGNZQDELRZGE-UHFFFAOYSA-N 0.000 description 4
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- 238000004679 31P NMR spectroscopy Methods 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 4
- 150000001845 chromium compounds Chemical class 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- PSJBWGOXVCPDTJ-UHFFFAOYSA-N diphenylphosphane;potassium Chemical compound [K].C=1C=CC=CC=1PC1=CC=CC=C1 PSJBWGOXVCPDTJ-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000001103 potassium chloride Substances 0.000 description 4
- 235000011164 potassium chloride Nutrition 0.000 description 4
- NTTOTNSKUYCDAV-UHFFFAOYSA-N potassium hydride Chemical compound [KH] NTTOTNSKUYCDAV-UHFFFAOYSA-N 0.000 description 4
- 229910000105 potassium hydride Inorganic materials 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 238000011085 pressure filtration Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- 150000001639 boron compounds Chemical class 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 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 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 229920000642 polymer Polymers 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
- OEOIWYCWCDBOPA-UHFFFAOYSA-N 6-methyl-heptanoic acid Chemical compound CC(C)CCCCC(O)=O OEOIWYCWCDBOPA-UHFFFAOYSA-N 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
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 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
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000005234 alkyl aluminium group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000006555 catalytic reaction Methods 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
- 239000003426 co-catalyst Substances 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- YFAXVVMIXZAKSR-UHFFFAOYSA-L dichloro(diethyl)stannane Chemical compound CC[Sn](Cl)(Cl)CC YFAXVVMIXZAKSR-UHFFFAOYSA-L 0.000 description 1
- PKKGKUDPKRTKLJ-UHFFFAOYSA-L dichloro(dimethyl)stannane Chemical compound C[Sn](C)(Cl)Cl PKKGKUDPKRTKLJ-UHFFFAOYSA-L 0.000 description 1
- ISXUHJXWYNONDI-UHFFFAOYSA-L dichloro(diphenyl)stannane Chemical compound C=1C=CC=CC=1[Sn](Cl)(Cl)C1=CC=CC=C1 ISXUHJXWYNONDI-UHFFFAOYSA-L 0.000 description 1
- CTRHCENQKGMZLE-UHFFFAOYSA-L dipropyltin(2+);dichloride Chemical compound CCC[Sn](Cl)(Cl)CCC CTRHCENQKGMZLE-UHFFFAOYSA-L 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000000686 essence Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- NXPHGHWWQRMDIA-UHFFFAOYSA-M magnesium;carbanide;bromide Chemical compound [CH3-].[Mg+2].[Br-] NXPHGHWWQRMDIA-UHFFFAOYSA-M 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- DVSDBMFJEQPWNO-UHFFFAOYSA-N methyllithium Chemical compound C[Li] DVSDBMFJEQPWNO-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 239000010689 synthetic lubricating oil Substances 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- LGQXXHMEBUOXRP-UHFFFAOYSA-N tributyl borate Chemical compound CCCCOB(OCCCC)OCCCC LGQXXHMEBUOXRP-UHFFFAOYSA-N 0.000 description 1
- SQBBHCOIQXKPHL-UHFFFAOYSA-N tributylalumane Chemical compound CCCC[Al](CCCC)CCCC SQBBHCOIQXKPHL-UHFFFAOYSA-N 0.000 description 1
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 1
- LALRXNPLTWZJIJ-UHFFFAOYSA-N triethylborane Chemical compound CCB(CC)CC LALRXNPLTWZJIJ-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
- 238000005829 trimerization reaction Methods 0.000 description 1
- LFXVBWRMVZPLFK-UHFFFAOYSA-N trioctylalumane Chemical compound CCCCCCCC[Al](CCCCCCCC)CCCCCCCC LFXVBWRMVZPLFK-UHFFFAOYSA-N 0.000 description 1
- OBAJXDYVZBHCGT-UHFFFAOYSA-N tris(pentafluorophenyl)borane Chemical compound FC1=C(F)C(F)=C(F)C(F)=C1B(C=1C(=C(F)C(F)=C(F)C=1F)F)C1=C(F)C(F)=C(F)C(F)=C1F OBAJXDYVZBHCGT-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
- B01J31/18—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)
-
- 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
- C07C2/14—Catalytic processes with inorganic acids; with salts or anhydrides of acids
- C07C2/20—Acids of halogen; Salts thereof ; Complexes thereof with organic compounds
- C07C2/22—Metal halides; Complexes thereof with organic compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/20—Olefin oligomerisation or telomerisation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/60—Complexes comprising metals of Group VI (VIA or VIB) as the central metal
- B01J2531/62—Chromium
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- C07C2531/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- C07C2531/22—Organic complexes
Abstract
Description
技术领域
本发明属于催化领域,涉及乙烯选择性齐聚反应,尤其是一种用于乙烯选择性齐聚的催化剂体系。
技术背景
众所周知,辛烯-1、已烯-1等线性α-烯烃是重要的化工产品和中间体,广泛应用于聚乙烯共聚单体、增塑剂醇、香精香料、合成润滑油及油品添加剂等领域。辛烯-1、已烯-1用做聚乙烯的共聚单体可明显改善聚乙烯的密度,提高其抗撕裂强度和拉伸强度等机械性能。用做生产增塑剂醇的原料时,可以使聚乙烯制品的低温柔软性、加工性、室外耐候性更好,尤其适用于制造电缆电线、汽车配件或装饰件等。
目前工业上生产辛烯-1、已烯-1等线性α-烯烃的方法主要有石蜡裂解、烷烃脱氢、醇脱水和乙烯齐聚等方法,据统计乙烯齐聚是目前生产线性α-烯烃的主要方法。传统的乙烯齐聚技术得到的齐聚产物的碳数分布符合Schulz-Flory分布,这种分布使齐聚产物中辛烯-1、己烯-1的含量不可能太高。例如US6184428公开了一种镍催化剂,采用硼化合物为助催化剂,可以催化乙烯齐聚得到线性α-烯烃的混合物,其中辛烯-1的含量占19%。SHOP工艺(US3676523、US3635937)使用相似的催化体系,齐聚产物中辛烯-1的含量占11%。其它典型的乙烯齐聚工艺,如海湾石油公司的Chevron工艺(DE1443927)、乙基公司(BP/Amoco,US3906053)的乙烯齐聚工艺中,辛烯-1的含量一般为13~25%。铬系催化剂体系用于乙烯三聚制备己烯-1,也已经实现工业化生产(US5550305),但其主产物己烯-1的含量一般都大于90%,辛烯-1的含量很少(<3%)。Brookhart等报道的铁系催化剂(J.Am.Chem.Soc.,1998,120:7143;Chem.Commun.1998,849;WO 99/02472)用于乙烯齐聚,得到的齐聚产物也呈宽分布,其辛烯-1的含量也较低(<20%)。最近报道的乙烯四聚三元催化剂体系可以高选择性合成辛烯-1(WO2004/056478A1、US2006/0229480、US 2006/0173226、CN107282132A、CN107282123A、CN107282127A、CN107282131A、CN107282130A等),其目的产物中辛烯-1的含量达到60%。
综上所述,乙烯选择性齐聚催化体系中活性中心的结构和中心金属是控制乙烯齐聚产物选择性的关键,也是近年来乙烯选择性齐聚领域研究开发的热点。对于乙烯选择性齐聚催化剂来说,所涉及的中心金属主要有铬、钛等。金属络合物配体的结构是影响催化剂性能的关键,因此进行配体结构的创新设计也是高选择性齐聚催化体系开发的关键。
发明内容
本发明的目的在于弥补现有技术中存在的不足之处,提供一种包含杂原子的配体a、过渡金属化合物b和有机金属化合物活化剂c三个组份的催化体系、催化体系的制备及用于乙烯齐聚,特别是高选择性制备辛烯-1、己烯-1,具有催化活性高、辛烯-1+己烯-1选择性高、催化剂寿命长、副产物聚乙烯少等优点,可以保证生产装置的长周期运行。
本发明的目的可以通过如下技术方案来实现:
一种用于乙烯选择性齐聚的催化体系,包含一种含杂原子的配体a、一种过渡金属化合物b和一种有机金属化合物活化剂c、所述的含杂原子的配体a是符合下列通式(I)所示的化合物:
其中,R1、R2、R3、R4可以选自苯基、取代苯基及其衍生物。R5、R6可以选自直链或支链的烷基、单环及多环芳基及其衍生物;也可以选自卤素原子;
优选的,含杂原子的配体a为(二苯基)磷二甲基锡磷(二苯基)、(二苯基)磷二乙基锡磷(二苯基)、(二苯基)磷二丙基锡磷(二苯基)、(二苯基)磷二丁基锡磷(二苯基)、(二苯基)磷二苯基锡磷(二苯基)、(二苯基)磷二环己基锡磷(二苯基)、(二苯基)磷二苯基锡磷(二苯基)、(二邻甲苯基)磷二甲基锡磷(二邻甲苯基)、(二邻氟苯基)磷二甲基锡磷(二邻氟苯基)、(二对氟苯基)磷二甲基锡磷(二对氟苯基)。
含杂原子的配体a的合成可以通过如下方法进行:首先由二取代的二卤化锡和二苯基膦氢或取代二苯基膦氢或二苯衍生物膦氢进行反应得到含有杂原子的配体a。
反应方程式如下:
所述的含杂原子的配体a,也可以是含两个或多个符合通式(I)所示结构单元通过基团或化学键连接起来形成的新化合物;如得到桥连、树枝状及星形的化合物,也可以是结合于高分子链上形成的高分子化的聚合物。
所述的过渡金属化合物b是铬、钼、钨、钛、钽、钒、锆、铁、镍、钯的化合物;优选的是铬、锆、钛化合物,最佳的是铬化合物。可选择的铬化合物包括通式CrRn m所示的那些化合物,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基团如为含羧基、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、(苯基)三羰基铬、六羰基铬的一种及或多种的混合物。最好的铬化合物为CrCl3(THF)3、异辛酸铬、乙酰丙酮铬。
所述的有机金属化合物活化剂c是烷基铝化合物、铝氧烷化合物、有机硼化合物、有机盐、无机酸或无机盐,也可以是它们中的一种或几种的混合物;具体而言选自各种三烷基铝及铝氧烷化合物,如三乙基铝、三异丁基铝、三正丁基铝、三正已基铝、三正辛基铝、甲基铝氧烷、乙基铝氧烷、异丁基铝氧烷及改性的铝氧烷等。也可以使用烷基铝卤化物、烷基铝氢化物或烷基铝倍半氯化物,如AlEt2Cl和A12Et3C13,也可以是与上述提及的一种或多种烷基铝或铝氧烷的混合物。有机盐类活化剂如甲基锂、甲基溴化镁等;无机酸及无机盐类活化剂如四氟硼酸醚合物、四氟硼酸盐、六氟锑酸盐等。有机硼化合物包括环硼氧烷、硼氢化钠、三乙基硼烷、三(五氟苯基)硼、三丁基硼酸盐等。
所述的催化剂中,包含的组分a、b和c的摩尔比为a:b:c=1:0.5~100:0.1~5000;含杂原子的配体a与过渡金属化合物b的摩尔比可以为1:0.5~100。催化剂中含杂原子的配体a与有机金属化合物活化剂c的摩尔比1:0.1~1:5000,最好为1:1~1000:1,更优选地为1:1~200:1。
所述的杂原子的配体a、过渡金属化合物b、金属有机活化剂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。这里所述的反应可以是上述杂原子的配体、过渡金属化合物、金属有机活化剂的一种、两种、三种及四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。
乙烯选择性齐聚反应主要在隋性溶剂中进行。可选择的溶剂包括烷烃、芳烃、卤代烃、烯烃等。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。
乙烯选择性齐聚反应的温度可在0℃~200℃内进行,优选50℃~150℃。乙烯选择性齐聚反应的压力可在0.1MPa~20MPa的压力下进行,优选1.0MPa~10MPa。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。
本发明的优点和有益效果:
本发明的催化剂体系用于乙烯选择性齐聚,与现有技术相比具有如下优点:催化剂活性高、目的产物辛烯-1+己烯的选择性高、催化剂合成简单、成本低、催化剂寿命长等特点,产物中C6~C8线性α-烯烃的质量百分含量>90%,C8线性α-烯烃的质量百分含量>60%。
具体实施方式
下面列举实施例对本发明加以进一步说明,而不是用来限制本发明的范围。
实施例1
1、制备(二苯基)磷二甲基锡磷(二苯基)配体(C26H26SnP2)
向经过N2充分置换的反应瓶中加入0.20g(5.00mmol)氢化钾和30mL四氢呋喃,在搅拌的状态下滴加0.76mL(5.00mmol)二苯基膦氢,随时将反应中产生的氢气导出反应体系。反应4h后,将溶液过滤抽干得到橘红色的固体二苯基膦钾。用10mL正己烷洗涤固体三次后,向固体中重新加入30mL正己烷,在搅拌过程中加入0.4943g(2.25mmol)二甲基二氯化锡,混合物在65℃加热条件下搅拌12h,反应完全后经氮气压滤除去氯化钾沉淀。将溶液真空抽干,正己烷重结晶,得到白色粉末状配体,产率70%。
表征结果:1H NMR(δ,ppm,CDCl3,TMS):0.90~0.91(t,6H,CH3),7.24~7.35(m,20H,Ar–H);13C NMR(δ,ppm,CDCl3):-10.1~-10.7,127.82~128.70,133.91~134.72;31PNMR(δ,ppm,CDCl3):-56.35。
2、催化剂的制备
在经N2充分置换的带搅拌的100mL反应器中加入经脱水处理的甲苯(10mL),1.4mol/L的MAO(甲基铝氧烷)甲苯溶液(7.0mL,9.9mmol),(二苯基)磷二甲基锡磷(二苯基)配体(34mg)(66μmol),CrCl3·(THF)3(12mg,33μmol),室温反应5min后备用。
3、乙烯齐聚
500mL的高压釜加热到抽真空2小时,经氮气置换数次后充入乙烯,降温到预定温度,加入经脱水处理的甲苯(200mL)及上述催化剂。在40℃、4.4MPa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。得到齐聚产物21.3g,催化剂活性为1.29×106g齐聚物/mol Cr.h。齐聚产物的分布见表1。
实施例2
1、制备(二苯基)磷二乙基锡磷(二苯基)配体(C28H30SnP2)
向经过N2充分置换的反应瓶中加入0.20g(5.00mmol)氢化钾和30mL四氢呋喃,在搅拌的状态下滴加0.76mL(5.00mmol)二苯基膦氢,随时将反应中产生的氢气导出反应体系。反应4h后,将溶液过滤抽干得到橘红色的固体二苯基膦钾。用10mL正己烷洗涤固体三次后,向固体中重新加入30mL正己烷,在搅拌过程中加入0.5574g(2.25mmol)二乙基二氯化锡,混合物在65℃加热条件下搅拌12h,反应完全后经氮气压滤除去氯化钾沉淀。将溶液真空抽干,正己烷重结晶,得到白色粉末状配体,产率70%。表征结果:1H NMR(δ,ppm,CDCl3,TMS):0.90~0.91(t,6H,CH3),1.40~1.50(t,4H,CH2),7.24~7.35(m,20H,Ar–H);13C NMR(δ,ppm,CDCl3):-6.8~-6.7,15.1~15.3,127.82~128.70,133.91~134.72;31P NMR(δ,ppm,CDCl3):-56.35。
2、催化剂的制备
在经N2充分置换的带搅拌的100mL反应器中加入经脱水处理的甲苯(10mL),1.4mol/L的MAO(甲基铝氧烷)甲苯溶液(7.0mL,9.9mmol),(二苯基)磷二甲基锡磷(二苯基)配体(36.11mg)(66μmol),CrCl3·(THF)3(12mg,33μmol),室温反应5min后备用。
3、乙烯齐聚
500mL的高压釜加热到抽真空2小时,经氮气置换数次后充入乙烯,降温到预定温度,加入经脱水处理的甲苯(200mL)及上述催化剂。在40℃、4.4MPa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。得到齐聚产物27.6g,催化剂活性为1.67×106g齐聚物/mol Cr.h。齐聚产物的分布见表1。
实施例3
同实施例1。不同之处在于(二苯基)磷二甲基锡磷(二苯基)配体的加入量为(17mg)(33μmol)。得到齐聚产物35.1g,催化剂活性为2.13×106g齐聚物/mol Cr.h。齐聚产物的分布见表1。
实施例4
1、制备(二苯基)磷二丙基锡磷(二苯基)配体(C30H34SnP2)
向经过N2充分置换的反应瓶中加入0.20g(5.00mmol)氢化钾和30mL四氢呋喃,在搅拌的状态下滴加0.76mL(5.00mmol)二苯基膦氢,随时将反应中产生的氢气导出反应体系。反应4h后,将溶液过滤抽干得到橘红色的固体二苯基膦钾。用10mL正己烷洗涤固体三次后,向固体中重新加入30mL正己烷,在搅拌过程中加入0.6205g(2.25mmol)二丙基二氯化锡,混合物在65℃加热条件下搅拌12h,反应完全后经氮气压滤除去氯化钾沉淀。将溶液真空抽干,正己烷重结晶,得到白色粉末状配体,产率53%。
表征结果:1HNMR(δ,ppm,CDCl3,TMS):0.96~0.97(t,6H,CH3),1.30~1.50(t,8H,CH2),7.24~7.35(m,20H,Ar–H);13C NMR(δ,ppm,CDCl3):2.7~3.0,18.5~18.6,127.82~128.70,133.91~134.72;31PNMR(δ,ppm,CDCl3):-56.47。
2、催化剂的制备
在经N2充分置换的带搅拌的100mL反应器中加入经脱水处理的甲苯(10mL),1.4mol/L的MAO(甲基铝氧烷)甲苯溶液(7.0mL,9.9mmol),(二苯基)磷二甲基锡磷(二苯基)配体(37.97mg)(66μmol),CrCl3·(THF)3(12mg,33μmol),室温反应5min后备用。
3、乙烯齐聚
500mL的高压釜加热到抽真空2小时,经氮气置换数次后充入乙烯,降温到预定温度,加入经脱水处理的甲苯(200mL)及上述催化剂。在40℃、4.4MPa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。得到齐聚产物39.5g,催化剂活性为2.6×106g齐聚物/mol Cr.h。齐聚产物的分布见表1。
实施例5
1、制备(二苯基)磷二苯基锡磷(二苯基)配体(C30H34SnP2)
向经过N2充分置换的反应瓶中加入0.20g(5.00mmol)氢化钾和30mL四氢呋喃,在搅拌的状态下滴加0.76mL(5.00mmol)二苯基膦氢,随时将反应中产生的氢气导出反应体系。反应4h后,将溶液过滤抽干得到橘红色的固体二苯基膦钾。用10mL正己烷洗涤固体三次后,向固体中重新加入30mL正己烷,在搅拌过程中加入0.7736g(2.25mmol)二苯基二氯化锡,混合物在65℃加热条件下搅拌12h,反应完全后经氮气压滤除去氯化钾沉淀。将溶液真空抽干,正己烷重结晶,得到白色粉末状配体,产率47%。
表征结果:1H NMR(δ,ppm,CDCl3,TMS):7.24~7.35(m,30H,Ar–H);13C NMR(δ,ppm,CDCl3):128.82~129.70,132.91~133.22,137.55~137.56;31PNMR(δ,ppm,CDCl3):-53.32。
2、催化剂的制备
在经N2充分置换的带搅拌的100mL反应器中加入经脱水处理的甲苯(10mL),1.4mol/L的MAO(甲基铝氧烷)甲苯溶液(7.0mL,9.9mmol),(二苯基)磷二甲基锡磷(二苯基)配体(42.46mg)(66μmol),CrCl3·(THF)3(12mg,33μmol),室温反应5min后备用。
3、乙烯齐聚
500mL的高压釜加热到抽真空2小时,经氮气置换数次后充入乙烯,降温到预定温度,加入经脱水处理的甲苯(200mL)及上述催化剂。在40℃、4.4MPa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。得到齐聚产物19.8g,催化剂活性为1.2×106g齐聚物/mol Cr.h。齐聚产物的分布见表1。
实施例6
同实施例1。不同之处在于a、b、c三种催化组份在聚合过程中原位合成。得到齐聚产物21.8g,催化剂活性为1.32×106g齐聚物/mol Cr.h。齐聚产物的分布见表1。
实施例7
同实施例1。不同之处在于反应压力为6.0MPa。得到齐聚产物49.2g,催化剂活性为2.98×106g齐聚物/mol Cr.h。齐聚产物的分布见表1。齐聚产物的分布见表1。
实施例8
同实施例1。不同之处在于反应温度为80℃。得到齐聚产物26.8g,催化剂活性为1.67×106g齐聚物/mol Cr.h。齐聚产物的分布见表1。
表1齐聚产物碳数分布对比
a是指C6中1-C6 =的百分含量。b是指C8中1-C8 =的百分含量。
Claims (8)
2.根据权利要求1所述的用于乙烯选择性齐聚的催化剂体系,其特征在于:所述的含杂原子的配体a为(二苯基)磷二甲基锡磷(二苯基)、(二苯基)磷二乙基锡磷(二苯基)、(二苯基)磷二丙基锡磷(二苯基)、(二苯基)磷二丁基锡磷(二苯基)、(二苯基)磷二苯基锡磷(二苯基)、(二苯基)磷二环己基锡磷(二苯基)、(二苯基)磷二苯基锡磷(二苯基)、(二邻甲苯基)磷二甲基锡磷(二邻甲苯基)、(二邻氟苯基)磷二甲基锡磷(二邻氟苯基)、(二对氟苯基)磷二甲基锡磷(二对氟苯基)。
3.根据权利要求1或2所述的用于乙烯选择性齐聚的催化剂体系,其特征在于:所述的含杂原子的配体a是含两个或多个符合通式I所示结构单元通过基团或化学键连接起来形成的新化合物。
4.根据权利要求1或2所述的用于乙烯选择性齐聚的催化剂体系,其特征在于:所述的过渡金属化合物b是铬、钼、钨、钛、钽、钒、锆、铁、镍、钯的化合物。
5.根据权利要求1或2所述的用于乙烯选择性齐聚的催化剂体系,其特征在于:所述的有机金属化合物活化剂c是烷基铝化合物、铝氧烷化合物、无机酸、无机盐的一种或几种的混合物。
6.根据权利要求1或2所述的用于乙烯选择性齐聚的催化剂体系,其特征在于:含杂原子的配体a、过渡金属化合物b、有机金属化合物活化剂c的摩尔比为a:b:c=1:0.5~100:0.1~5000。
7.根据权利要求1或2所述的用于乙烯选择性齐聚的催化剂体系,其特征在于:制备方法是将a、b、c三组份预先混合反应合成;或直接加入到反应体系中进行原位合成。
8.根据权利要求1或2所述的用于乙烯选择性齐聚的催化剂体系,其特征在于:乙烯选择性齐聚反应在隋性溶剂中进行,反应温度0℃~200℃,反应压力0.1MPa~20MPa。
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