CN103044181A - Method for preparing octene-1 by ethylene tetramerization reaction - Google Patents
Method for preparing octene-1 by ethylene tetramerization reaction Download PDFInfo
- Publication number
- CN103044181A CN103044181A CN201110314594XA CN201110314594A CN103044181A CN 103044181 A CN103044181 A CN 103044181A CN 201110314594X A CN201110314594X A CN 201110314594XA CN 201110314594 A CN201110314594 A CN 201110314594A CN 103044181 A CN103044181 A CN 103044181A
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- CN
- China
- Prior art keywords
- benzene
- phenyl
- ortho position
- reaction
- heteroatomic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Links
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 19
- 239000005977 Ethylene Substances 0.000 title abstract description 25
- -1 alkylaluminum compound Chemical class 0.000 claims abstract description 48
- 239000011651 chromium Substances 0.000 claims abstract description 29
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 19
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 16
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 12
- OEOIWYCWCDBOPA-UHFFFAOYSA-N 6-methyl-heptanoic acid Chemical compound CC(C)CCCCC(O)=O OEOIWYCWCDBOPA-UHFFFAOYSA-N 0.000 claims abstract description 4
- 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 abstract description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 42
- 239000003795 chemical substances by application Substances 0.000 claims description 17
- 229910052782 aluminium Inorganic materials 0.000 claims description 11
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 7
- 229910052796 boron Inorganic materials 0.000 claims description 7
- 150000001336 alkenes Chemical class 0.000 claims description 5
- 125000005234 alkyl aluminium group Chemical group 0.000 claims description 5
- 239000004411 aluminium Substances 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 4
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 4
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 4
- 239000004327 boric acid Substances 0.000 claims description 4
- FXCLIEYDXXVEAI-UHFFFAOYSA-N benzene;dichloromethane Chemical compound ClCCl.C1=CC=CC=C1 FXCLIEYDXXVEAI-UHFFFAOYSA-N 0.000 claims description 3
- KTMKRRPZPWUYKK-UHFFFAOYSA-N methylboronic acid Chemical compound CB(O)O KTMKRRPZPWUYKK-UHFFFAOYSA-N 0.000 claims description 3
- 125000003774 valeryl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 150000005826 halohydrocarbons Chemical class 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 34
- 150000001875 compounds Chemical class 0.000 abstract description 14
- 125000005842 heteroatom Chemical group 0.000 abstract description 4
- 239000003607 modifier Substances 0.000 abstract description 2
- 239000004711 α-olefin Substances 0.000 abstract description 2
- WDFAEKROFHJXHQ-UHFFFAOYSA-N 1-chloro-3,4,5-trifluoro-2-methylbenzene Chemical compound FC=1C(=C(C(=C(C=1)Cl)C)F)F WDFAEKROFHJXHQ-UHFFFAOYSA-N 0.000 abstract 2
- MFHPYLFZSCSNST-UHFFFAOYSA-N 1-chloro-2-(trichloromethyl)benzene Chemical compound ClC1=CC=CC=C1C(Cl)(Cl)Cl MFHPYLFZSCSNST-UHFFFAOYSA-N 0.000 abstract 1
- JYLVSNNSOWDQQX-UHFFFAOYSA-N 1-fluoro-2-(trichloromethyl)benzene Chemical compound FC1=CC=CC=C1C(Cl)(Cl)Cl JYLVSNNSOWDQQX-UHFFFAOYSA-N 0.000 abstract 1
- 229910021556 Chromium(III) chloride Inorganic materials 0.000 abstract 1
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 abstract 1
- 239000011636 chromium(III) chloride Substances 0.000 abstract 1
- 230000003993 interaction Effects 0.000 abstract 1
- 238000006384 oligomerization reaction Methods 0.000 description 49
- 238000002360 preparation method Methods 0.000 description 42
- 230000000694 effects Effects 0.000 description 17
- 238000009826 distribution Methods 0.000 description 15
- 239000012190 activator Substances 0.000 description 14
- 239000013543 active substance Substances 0.000 description 14
- RUIZXJNYLMYDLB-UHFFFAOYSA-N [P].C1=CC=CC=C1C1=CC=CC=C1 Chemical group [P].C1=CC=CC=C1C1=CC=CC=C1 RUIZXJNYLMYDLB-UHFFFAOYSA-N 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 12
- MBXXQYJBFRRFCK-UHFFFAOYSA-N benzyl fluoride Chemical compound FCC1=CC=CC=C1 MBXXQYJBFRRFCK-UHFFFAOYSA-N 0.000 description 12
- 150000002736 metal compounds Chemical class 0.000 description 11
- 238000003756 stirring Methods 0.000 description 11
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 9
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 150000002902 organometallic compounds Chemical class 0.000 description 8
- 125000000538 pentafluorophenyl group Chemical group FC1=C(F)C(F)=C(*)C(F)=C1F 0.000 description 8
- 229910052698 phosphorus Inorganic materials 0.000 description 8
- 239000011574 phosphorus Substances 0.000 description 8
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 7
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 6
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 6
- AGEZXYOZHKGVCM-UHFFFAOYSA-N benzyl bromide Chemical compound BrCC1=CC=CC=C1 AGEZXYOZHKGVCM-UHFFFAOYSA-N 0.000 description 6
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 6
- 230000004048 modification Effects 0.000 description 6
- 238000012986 modification Methods 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 5
- 238000006073 displacement reaction Methods 0.000 description 5
- 239000003446 ligand Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- ANRQGKOBLBYXFM-UHFFFAOYSA-M phenylmagnesium bromide Chemical compound Br[Mg]C1=CC=CC=C1 ANRQGKOBLBYXFM-UHFFFAOYSA-M 0.000 description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- 239000005864 Sulphur Substances 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 229940043279 diisopropylamine Drugs 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 150000002894 organic compounds Chemical class 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 229910052726 zirconium Inorganic materials 0.000 description 3
- QQPXXHAEIGVZKQ-UHFFFAOYSA-N 1,3-dichloro-2-(dichloromethyl)benzene Chemical compound ClC(Cl)C1=C(Cl)C=CC=C1Cl QQPXXHAEIGVZKQ-UHFFFAOYSA-N 0.000 description 2
- FNRIGXVAVWLNKH-UHFFFAOYSA-N 1-bromo-3,4-dichloro-2-methylbenzene Chemical compound CC1=C(Br)C=CC(Cl)=C1Cl FNRIGXVAVWLNKH-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- KEVMYFLMMDUPJE-UHFFFAOYSA-N 2,7-dimethyloctane Chemical group CC(C)CCCCC(C)C KEVMYFLMMDUPJE-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- OYJMOLPKBXVNKZ-UHFFFAOYSA-N benzene difluoromethane Chemical compound C(F)F.C1=CC=CC=C1 OYJMOLPKBXVNKZ-UHFFFAOYSA-N 0.000 description 2
- BLJGQRQOVKQVIW-UHFFFAOYSA-N benzene;dibromomethane Chemical compound BrCBr.C1=CC=CC=C1 BLJGQRQOVKQVIW-UHFFFAOYSA-N 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- SSXPEHBFLFUZCU-UHFFFAOYSA-M chloro(diphenyl)stibane Chemical compound C=1C=CC=CC=1[Sb](Cl)C1=CC=CC=C1 SSXPEHBFLFUZCU-UHFFFAOYSA-M 0.000 description 2
- XGRJZXREYAXTGV-UHFFFAOYSA-N chlorodiphenylphosphine Chemical compound C=1C=CC=CC=1P(Cl)C1=CC=CC=C1 XGRJZXREYAXTGV-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- 239000012442 inert solvent Substances 0.000 description 2
- 239000002608 ionic liquid Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 125000005647 linker group Chemical group 0.000 description 2
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 229910052715 tantalum Inorganic materials 0.000 description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 238000005829 trimerization reaction Methods 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 2
- 125000005023 xylyl group Chemical group 0.000 description 2
- UZYYBZNZSSNYSA-UHFFFAOYSA-N 1,2,4-trichloro-3-methylbenzene Chemical compound CC1=C(Cl)C=CC(Cl)=C1Cl UZYYBZNZSSNYSA-UHFFFAOYSA-N 0.000 description 1
- BNDBNWZIQPVJGZ-UHFFFAOYSA-N 1,2-dichloro-4-fluoro-3-methylbenzene Chemical compound CC1=C(F)C=CC(Cl)=C1Cl BNDBNWZIQPVJGZ-UHFFFAOYSA-N 0.000 description 1
- 125000002030 1,2-phenylene group Chemical group [H]C1=C([H])C([*:1])=C([*:2])C([H])=C1[H] 0.000 description 1
- LTFQDRXFSGCPJX-UHFFFAOYSA-N 1-bromo-2-(dichloromethyl)-3-fluorobenzene Chemical compound FC1=C(C(Cl)Cl)C(=CC=C1)Br LTFQDRXFSGCPJX-UHFFFAOYSA-N 0.000 description 1
- WXDJPMREMHJZQA-UHFFFAOYSA-N 1-bromo-3-chloro-2-(dichloromethyl)benzene Chemical compound ClC1=C(C(Cl)Cl)C(=CC=C1)Br WXDJPMREMHJZQA-UHFFFAOYSA-N 0.000 description 1
- XKZQKPRCPNGNFR-UHFFFAOYSA-N 2-(3-hydroxyphenyl)phenol Chemical group OC1=CC=CC(C=2C(=CC=CC=2)O)=C1 XKZQKPRCPNGNFR-UHFFFAOYSA-N 0.000 description 1
- NQFUESPETLDORH-UHFFFAOYSA-N 2-(dichloromethyl)-1,3-difluorobenzene Chemical compound FC1=CC=CC(F)=C1C(Cl)Cl NQFUESPETLDORH-UHFFFAOYSA-N 0.000 description 1
- YVSMQHYREUQGRX-UHFFFAOYSA-N 2-ethyloxaluminane Chemical compound CC[Al]1CCCCO1 YVSMQHYREUQGRX-UHFFFAOYSA-N 0.000 description 1
- MKARNSWMMBGSHX-UHFFFAOYSA-N 3,5-dimethylaniline Chemical compound CC1=CC(C)=CC(N)=C1 MKARNSWMMBGSHX-UHFFFAOYSA-N 0.000 description 1
- JNRLEMMIVRBKJE-UHFFFAOYSA-N 4,4'-Methylenebis(N,N-dimethylaniline) Chemical class C1=CC(N(C)C)=CC=C1CC1=CC=C(N(C)C)C=C1 JNRLEMMIVRBKJE-UHFFFAOYSA-N 0.000 description 1
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- DCERHCFNWRGHLK-UHFFFAOYSA-N C[Si](C)C Chemical compound C[Si](C)C DCERHCFNWRGHLK-UHFFFAOYSA-N 0.000 description 1
- 241000555268 Dendroides Species 0.000 description 1
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- PSDYQSWHANEKRV-UHFFFAOYSA-N [S]N Chemical compound [S]N PSDYQSWHANEKRV-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical group [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical group [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- HVURSIGIEONDKB-UHFFFAOYSA-N benzene;chromium Chemical compound [Cr].C1=CC=CC=C1.C1=CC=CC=C1 HVURSIGIEONDKB-UHFFFAOYSA-N 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical group [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- 150000001639 boron compounds Chemical class 0.000 description 1
- BRTALTYTFFNPAC-UHFFFAOYSA-N boroxin Chemical compound B1OBOBO1 BRTALTYTFFNPAC-UHFFFAOYSA-N 0.000 description 1
- VPCAAUUIFCAFRZ-UHFFFAOYSA-N butylalumane Chemical compound CCCC[AlH2] VPCAAUUIFCAFRZ-UHFFFAOYSA-N 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000008859 change Effects 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
- 230000000052 comparative effect Effects 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- GGSUCNLOZRCGPQ-UHFFFAOYSA-N diethylaniline Chemical compound CCN(CC)C1=CC=CC=C1 GGSUCNLOZRCGPQ-UHFFFAOYSA-N 0.000 description 1
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000001188 haloalkyl group Chemical group 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-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
- 239000003921 oil Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 150000003388 sodium compounds Chemical class 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 238000010671 solid-state reaction Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- LGQXXHMEBUOXRP-UHFFFAOYSA-N tributyl borate Chemical compound CCCCOB(OCCCC)OCCCC LGQXXHMEBUOXRP-UHFFFAOYSA-N 0.000 description 1
- CMHHITPYCHHOGT-UHFFFAOYSA-N tributylborane Chemical compound CCCCB(CCCC)CCCC CMHHITPYCHHOGT-UHFFFAOYSA-N 0.000 description 1
- FAQYAMRNWDIXMY-UHFFFAOYSA-N trichloroborane Chemical compound ClB(Cl)Cl FAQYAMRNWDIXMY-UHFFFAOYSA-N 0.000 description 1
- AJSTXXYNEIHPMD-UHFFFAOYSA-N triethyl borate Chemical compound CCOB(OCC)OCC AJSTXXYNEIHPMD-UHFFFAOYSA-N 0.000 description 1
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-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
- LOFJKBAHPJENQS-UHFFFAOYSA-N tris(oxomethylidene)chromium Chemical compound O=C=[Cr](=C=O)=C=O LOFJKBAHPJENQS-UHFFFAOYSA-N 0.000 description 1
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 description 1
- 125000002221 trityl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1C([*])(C1=C(C(=C(C(=C1[H])[H])[H])[H])[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a method for preparing octene-1 by ethylene tetramerization reaction; the catalyst consists of components , (b), (c) and/or (d) according to the molar ratio of 1: 0.5-100: 0.1-5000: 0-500; the component is 1, 2-bis (N (P (phenyl) 2)2) -benzene, 1, 4-bis (N (P (phenyl)2)2) -benzene or N (CH)2CH2N (P (phenyl)2)2)3(ii) a Component (b) is CrCl3(THF)3Chromium isooctanoate or chromium acetylacetonate; component is the product of the interaction of an alkylaluminum compound or an aluminoxane compound with a modifier containing at least two heteroatoms; the component (d) is ortho trichloromethyl fluorobenzene, ortho trifluoro methyl chlorobenzene, ortho trichloromethyl chlorobenzene, ortho trifluoro methyl chlorobenzene or 2 or 6-dichloro-trichloromethyl benzene; product C8The mass percentage of the linear alpha-olefin is more than 60 percent.
Description
Technical field
The present invention relates to the method that a kind of ethene four poly-reactions prepare octene-1.
Background technology
The senior linear alpha-alkenes such as decylene-1, octene-1 and hexene-1 obtain by ethylene oligomerization reaction.But in the ethylene oligomerization technology of routine, generally can contain multiple high alpha-olefin in the product, meet Schulz-Flory distribution or Poisson and distribute.Disclose a kind of nickel catalyst such as US Patent No. 6184428, it comprises 2-diphenylphosphine phenylformic acid as chelating ligand, as the NiCl of nickel precursor
26H
2O and as the Tetraphenyl sodium borate of catalyst activator.Also disclose in this patent documentation, in the ethylene oligomerization reaction of using this nickel catalyst, the selectivity of octene-1 is 19%.SHOP technique (US 3676523, US 3635937) is used similar catalyst system, and the content of octene-1 accounts for 11% in the oligomerization product.Other typical ethylene oligomerization technique, in the ethylene oligomerization technique such as the Chevron technique (DE1443927) of Gulf Oil Corporation, ethyl corporation (BP/Amoco, US3906053), the content of octene-1 is generally 13～25%.The chromium-based catalysts system is used for ethylene trimerization and prepares hexene-1, has also realized suitability for industrialized production (US5550305), but the content of its principal product hexene-1 is generally all greater than 90%, and the content of octene-1 is (＜3%) seldom.
Fe-series catalyst (J.Am.Chem.Soc., 1998, the 120:7143 of the report such as Brookhart; Chem.Commun.1998,849; WO 99/02472) be used for ethylene oligomerization, the oligomerization product that obtains also is wide distribution, and the content of its octene-1 is lower (＜20%) also.
A lot of patents and bibliographical information have been arranged transition metal and aromatic ring ligand binding is formed for the method for alkene trimerization, four poly-or catalyzer that polymerization is used, such as WO 03/053890A1, WO03/053891, WO 03/054038, WO 04/056479A1, WO 04/056477A1, WO04/056480A1, WO 04/056478A1, US 2005187418A1, WO 05/123884A2 and WO 05/123633A1 etc.Recently the ethene four poly-three-way catalyst systems of report can high selectivity octene-1 (WO 2004/056478A1), and the content of octene-1 reaches 60% in its purpose product.Patent documentation WO 04/056479, US20090118117, US7906681, US7829749, US7511183, US7381857, US7297832 disclose by make ethene four gather to prepare the method for octene-1 with chromium-based catalysts, wherein said chromium-based catalysts contains and has phosphorus and nitrogen as heteroatomic heteroatom ligand, such as (phenyl)
2PN (sec.-propyl) P (phenyl)
2Deng.Patent CN101720253, CN101606605, CN101600722, CN101351424, CN101291734, CN1993180A, CN1741850A and CN1741849A etc. disclose the method that alkene four gathers, described catalyst system all comprises heteroatom ligand, transistion metal compound and promotor, and other described promotor is mainly aluminum alkyls, alkylaluminoxane and boron compound etc.Disclose in above-mentioned ethene four poly-technology and can surpass 70% octene-1 by ethene four being gathered prepare selectivity, wherein said chromium-based catalysts contains and has phosphorus and nitrogen as heteroatomic heteroatom ligand.
Disclosed ethene four poly-catalyzer and method have one or more lower column defects usually in science and patent documentation up to now: 1. product hexene-1 or octene-1 selectivity are low; 2. product purity low, the high carbon number product of part long-chain arranged; 3. form polymkeric substance, this causes reactor plugs, is difficult to continuous long-term operation; 4. poor catalyst activity, promotor cost are high; 5. severe reaction conditions, need high pressure, cause input, maintenance and energy cost high; 6. responsive to the promotor qualitative change.
Summary of the invention
The object of the present invention is to provide a kind of ethene four poly-reactions to prepare the method for octene-1; The catalyst system of four components that the used catalyzer of present method is comprised of heteroatomic part (a), transistion metal compound (b), organometallic compound activator (c) by containing at least two heteroatomic compound modifier modifications and promotor (d); Catalyst system possesses the performance that highly selective prepares octene-1.
Described a kind of ethene four poly-reactions of the present invention prepare the method for octene-1, ethene four poly-reactions are to carry out in the inert solvent, selectable solvent comprises alkane, aromatic hydrocarbons, halohydrocarbon, alkene, and typical solvent comprises benzene,toluene,xylene, isopropyl benzene, normal heptane, normal hexane, methylcyclohexane, hexanaphthene, 1-hexene, 1-octene, ionic liquid.
The temperature of ethene four poly-reactions is carried out preferred 50 ℃～150 ℃ in 0 ℃～200 ℃.The pressure of ethene four poly-reactions carries out under the pressure of 0.1MPa～20MPa, preferred 1.0MPa～10MPa.The concentration of catalyzer is from 0.01 μ mol metal/L～1000 μ mol metal/L in the reaction system, preferred 0.1 μ mol metal/L～10 μ mol metal/L.
The catalyst composition that is used for ethylene oligomerization is by containing heteroatomic part (a), transistion metal compound (b), the organometallic compound activator (c) by containing at least two heteroatomic compound modified dose of modifications, the catalyst system of three or four components that promotor (d) forms;
The described heteroatomic part (a) that contains is to meet the compound shown in the following general formula (I):
Wherein, group A and D are identical or different, are selected from the group that contains phosphorus, nitrogen, sulphur atom; B is a linking group or single atom, is selected from C, N, P atom; Or be selected from alkyl and derivative, aryl and derivative thereof; R
5Be selected from the alkyl of hydrogen, straight or branched; Or be selected from monocycle and polyaromatic and derivative thereof; Or be selected from halogen atom; R
1, R
2, R
3, R
4Be selected from phenyl, substituted-phenyl and derivative thereof; Describedly contain heteroatomic part (a), or contain two or more structural unit shown in the general formula (I) connects formation by group or chemical bond compounds that meet;
Said transistion metal compound (b) is the compound of chromium, molybdenum, tungsten, titanium, tantalum, vanadium, zirconium, iron, nickel or palladium;
Said organometallic compound activator (c) is alkylaluminium cpd or aluminium alkoxide compound and contains at least two interactional products of heteroatomic properties-correcting agent, or two or more aluminum alkylss or aikyiaiurnirsoxan beta and the interactional product of two or more properties-correcting agent;
It is described that to contain at least two heteroatomic properties-correcting agent are [Ph
3C] [Al{OC (CF
3)
3}
4], Ph
2C (Me) OAlMe
2, B (C
6F5)
3, phenylo boric acid, methyl-boron-dihydroxide, two valeryl two boron, BF
3, BCl
3, BBr
3Or BCl
3
Described promotor (d) is aromatic hydrocarbons or the haloarene compounds that halogenated alkane or a kind of haloalkyl that contains at least an alkyl that is replaced at alpha-position by at least two halogen atoms on aromatic ring replace;
In the described catalyst composition, the component that comprises (a), (b), (c) and mol ratio (d) are (a): (b): (c): (d)=1: 0.5～100: 0.1～5000: 0～500; Four components with (a), (b), (c), (d) form are pre-mixed; Or can join directly that to carry out original position in the reaction system synthetic; Described catalyst component is used for ethylene oligomerization, and reaction is carried out in the inert solvent, can be selected from alkane, aromatic hydrocarbons, alkene, ionic liquid; 0 ℃～200 ℃ of the temperature of reaction, reaction pressure 0.1MPa～20MPa makes the ethylene oligomerization product.
Describe catalyst system in detail and contain following component:
(1) at least a being selected from contained heteroatomic part (a) shown in the general formula (I)
In the formula, group A and D are identical or different, be selected to contain phosphorus, arsenic, antimony, bismuth, nitrogen, sulphur atom group, or single atom; B is a linking group, is selected from alkyl, substituted hydrocarbon radical and contains heteroatomic substituted hydrocarbon radical, and such as methylene radical, dimethylated methylene base, 1,2-ethane, 1,2-phenylene, 1,2-propane, 1, the adjacent diphenol, 1 of 2-, 2-dimethylhydrazine; Or single atom, ion, such as boron, silicon, phosphorus, nitrogen, sulphur.B or do not have makes A be connected chemical bond with D and directly connects; R
5Be selected from alkyl, alkenyl, cycloalkyl, aryl, arylalkyl, alkylaryl or the fused ring aryl of hydrogen, halogen, straight or branched, or contain heteroatomic group, as contain the group of N, siliceous group and their derivative; R
5Preferably sec.-propyl, the tertiary butyl, cyclohexyl, aryl and their derivative.
R
1, R
2, R
3, R
4Be phenmethyl, phenyl, tolyl, xylyl, 2,4,6-trimethylphenyl, 3,5-dimethylbenzene methyl, two phenyl, naphthyl, anthryl, methoxyl group, oxyethyl group, phenoxy group, tolyloxy, dimethylamino, the first and second amino, sulfur phenenyl, pyridyl, sulphur ethyl, sulphur phenoxy group, trimethyl silicon based, methyl, ethyl, vinyl, propyl group, butyl, propenyl, proyl, cyclopentyl, cyclohexyl, ferrocenyl, tetrahydrofuran base etc.Preferred R
1, R
2, R
3, R
4Be phenyl, substituted-phenyl, xylyl, two phenyl, naphthyl, sulfur phenenyl and ethyl.
(2) a kind of transistion metal compound (b)
Selectable transistion metal compound has the compound of chromium, molybdenum, tungsten, titanium, tantalum, vanadium, zirconium, iron, nickel, palladium etc.Preferably chromium, zirconium, titanium compound, best is chromium cpd.Selectable chromium cpd comprises general formula CrR
n mThose shown compounds, R in the formula
nBe organic negative ion or neutral molecule, R
nIn usually contain 1～10 carbon atom, n is 0～6 integer, the valence state of chromium is 0～6 valency.Concrete R
nGroup is as being organism or its group that contains carboxyl, beta-diketon base and alkyl.Consider that from the angle that is easy to dissolve with easy handling chromium cpd preferably comprises chromium acetate, isocaprylic acid chromium, n-caprylic acid chromium, chromium acetylacetonate, diisoamyl diene chromium, dibenzene-chromium, CrCl
3(THF)
3, (phenyl) tricarbonyl chromium, Chromium hexacarbonyl a kind of and or multiple mixture.Best chromium cpd is CrCl
3(THF)
3, isocaprylic acid chromium, chromium acetylacetonate.
(3) a kind of organometallic compound promoting agent (c)
Selectable organometallic compound activator (c) is alkylaluminium cpd or aluminium alkoxide compound and contains at least two interactional products of heteroatomic properties-correcting agent, also can be two or more aluminum alkylss or aikyiaiurnirsoxan beta and the interactional product of two or more properties-correcting agent; Particularly be selected from various trialkylaluminiums and aluminium alkoxide compound, such as aikyiaiurnirsoxan beta of triethyl aluminum, triisobutyl aluminium, three n-butylaluminum, tri-n-hexyl aluminum, tri-n-octylaluminium, methylaluminoxane, ethylaluminoxane, isobutyl aluminium alkoxide and modification etc.Or use aluminum alkyl halide, alkyl aluminum hydride or alkylaluminium sesquichloride, such as AlEt
2Cl and Al
2Et
3Cl
3, or with above-mentioned one or more aluminum alkylss of mentioning or the mixture of aikyiaiurnirsoxan beta.At least contain two heteroatomic properties-correcting agent such as Tetrafluoroboric acid etherate, a tetrafluoro borate, hexafluoro antimonate, boroxin, three (pentafluorophenyl group) boron, the tri butyl boron hydrochlorate, tributyl borate, boric acid three isopropyl junket, trityl four (pentafluorophenyl group) borate, 3,5-dimethylphenyl ammonium four (pentafluorophenyl group) borate, diethyl phenyl ammonium four (pentafluorophenyl group) borate, methyldiphenyl base ammonium four (pentafluorophenyl group) borate, ethyl phenylbenzene ammonium four (pentafluorophenyl group) borate, [Ph
3C] [Al{OC (CF
3)
3}
4], Ph
2C (Me) OAlMe
2, phenylo boric acid, methyl-boron-dihydroxide, two valeryl two boron, BF
3, BCl
3, BBr
3Or BCl
3
(4) a kind of promotor (d)
Promotor can be added or not add in the catalyzer of the present invention, but the activity of catalyzer and the selectivity of purpose product octene-1 can be improved after adding promotor.Preferred promotor of using comprises halogen-containing organic compound, but is not limited to following compounds:
Three fluoro methylbenzene, three chloro methylbenzene, three bromo methylbenzene, ortho position three fluoro methyl fluoride benzene, ortho position three chloro methyl fluoride benzene, ortho position three bromo methyl fluoride benzene, ortho position two fluoro methyl fluoride benzene, ortho position dichloro-methyl fluorobenzene, ortho position two bromo methyl chloride benzene, ortho position three fluoro methyl chloride benzene, ortho position three chloro methyl chloride benzene, ortho position three bromo methyl chloride benzene, ortho position two fluoro methyl chloride benzene, ortho position dichloro-methyl chlorobenzene, ortho position two bromo methyl chloride benzene, ortho position three fluoro monobromomethane benzene, ortho position three chloro monobromomethane benzene, ortho position three bromo monobromomethane benzene, ortho position dichloro-methyl bromobenzene, ortho position dichloro-methyl bromobenzene, ortho position two bromo monobromomethane benzene, 2,6-dichloro three fluoro methylbenzene, 2,6-dichloro three chloro methylbenzene, 2,6-dichloro three bromo methylbenzene, 2,6-dichloro two fluoro methylbenzene, 2,6-dichloro benzal chloride, 2,6-dichloro two bromo methylbenzene, 2,6-difluoro two fluoro methylbenzene, 2,6-difluoro three chloro methylbenzene, 2,6-difluoro three bromo methylbenzene, 2,6-difluoro benzal chloride, 2,5-difluoro two bromo methylbenzene, 2,6-dibromo three fluoro methylbenzene, 2,6-dibromo three chloro methylbenzene, 2,6-dibromo two fluoro methylbenzene, 2, the 6-Dibromo-dichloro is for methylbenzene, 2-fluoro-6-chloro-three fluoro methylbenzene, 2-fluoro-6-chloro-three chloro methylbenzene, 2-chloro-6-chloro-benzal chloride, 2-fluoro-6-chloro-two fluoro methylbenzene, 2-fluoro-6-chloro-three bromo methylbenzene, 2-fluoro-6-bromo-three fluoro methylbenzene, 2-chloro-6-bromo-three chloro methylbenzene, 2-chloro-6-bromo-two fluoro methylbenzene, 2-chloro-6-bromo-benzal chloride, 2-chloro-6-bromo-three fluoro methylbenzene, 2-chloro-6-bromo-three chloro methylbenzene, 2-fluoro-6-bromo-two fluoro methylbenzene, 2-fluoro-6-bromo-benzal chloride, wherein more effective promotor is: ortho position three chloro methyl fluoride benzene, ortho position three fluoro methyl chloride benzene, ortho position three chloro methyl chloride benzene, ortho position three fluoro methyl chloride benzene, 2,6-, two chloro-trichlorines are for methylbenzene.
Containing the synthetic of heteroatomic part (a) can carry out by the following method: at first by PCl
3And Diisopropylamine (PCl
3With the mol ratio of Diisopropylamine be 1: 2～1: 10) react and obtain product N, N-di-isopropyl phosphorus dichloride acid amides (A1).Magnesium powder and bromobenzene (mol ratio of magnesium powder and bromobenzene is 10: 1～1: 1) react and obtain lattice reagent phenyl-magnesium-bromide (A2).A1 and A2 react the product that obtains and react with dry HCl gas and obtain diphenyl antimony chloride base phosphorus (A3).A3 and aminated compounds react and obtain containing heteroatomic part (a).
Containing heteroatomic part (a) in the catalyzer can be from 1: 0.5～100 with the mol ratio of transistion metal compound (b).
The mol ratio 1: 0.1～1: 5000 that contains heteroatomic part (a) and organometallic compound activator (c) in the catalyzer is preferably from 1: 1～1: 1000, more preferably from 1: 1～1: 100.
Containing heteroatomic part (a) in the catalyzer can be from 1: 0～1: 500 with the mol ratio of promotor.
(I) the heteroatomic part described in, also can be one or more such as the unit of (I) formula structure, combine by group, chemical bond or Intermolecular Forces etc.As obtain the compound of bridging, dendroid and star, also can be the polymkeric substance that is incorporated into the high molecular that forms on the macromolecular chain.More typically but be not of the present invention be used to limiting, such as the two (N (P (phenyl) of 1,2-
2)
2)-benzene, Isosorbide-5-Nitrae-two (N (P (phenyl)
2)
2)-benzene, N (CH
2CH
2N (P (phenyl)
2)
2)
3Deng.
The reactive mode of the heteroatomic part (I), transistion metal compound, metal organic activator and organic compound promotor, can pass through liquid phase reaction, as under the effect of solvent, reacting selectable solvent such as toluene, benzene and its derivative etc.; Also can pass through solid state reaction; Also can generate catalyzer by in the oligomerisation reaction process, carrying out reaction in－situ.Reaction described here can be the reaction between a kind of, two kinds, three kinds and the four kinds of compounds of above-mentioned heteroatomic part, transistion metal compound, metal organic activator and organic compound promotor.The process of this reaction also is ageing (pre-complexing) process of catalyzer.
The preparation of catalyzer is containing heteroatomic part (a), transistion metal compound (b), being pre-mixed through containing at least two heteroatomic compound modified organometallic compound activators (c), promotor (d); Also can be containing heteroatomic part (a), transistion metal compound (b), joining directly through containing at least two heteroatomic compound modified organometallic compound activators (c), promotor (d) that to carry out original position in the reaction system synthetic;
Four-way catalyst system of the present invention is used for ethylene oligomerization, particularly ethene four is poly-, compared with prior art has following advantage: the characteristics such as the promotor consumption is few, catalyst activity is high, purpose product octene-1 selectivity high, catalyzer is synthetic simply, cost is low, catalyst life is long, C in the product
6～C
8The quality percentage composition of linear alpha-alkene＞90%, C
8The quality percentage composition of linear alpha-alkene＞60%.
Embodiment
The below enumerates 10 embodiment and 1 Comparative Examples, and the present invention is further specified.
Embodiment 1
1, preparation (phenylbenzene) phosphorus nitrogen (sec.-propyl) phosphorus (phenylbenzene) part (C
27H
27NP
2)
(1) preparation N, N-di-isopropyl dichlor-phosphoryl amine
Through N
2Add the toluene (100mL) through processed in the 250mL reactor that fully band of displacement stirs, add PCl
3(21.87mL, 0.25mol), and cool to-20 ℃.Add lentamente while stirring Diisopropylamine (70mL, 0.5mol) under the room temperature, stir and rise to room temperature after 3 hours and continued again to react 2 hours, then filter, dry product 38.1g (0.19mol, 74%).
(2) preparation phenyl-magnesium-bromide lattice reagent
Through N
2Add through the THF of processed (100mL) in the 250mL reactor that fully band of displacement stirs, magnesium powder (9.11g, 0.375mol), the ice bath cooling also slowly drips bromobenzene (11.775g, 0.075mol).After 2 hours, reflux continues reaction and obtained lattice reagent in 2 hours.
(3) preparation diphenyl phosphorus chloride
Through N
2Add through the THF of processed (100mL) in the 250mL reactor that fully band of displacement stirs, add N, N-di-isopropyl phosphorus dichloride acid amides (6.64mL, 36mmol), be cooled to 0 ℃, slowly add phenyl-magnesium-bromide lattice reagent (6.52g, 36mmol).Rose to room temperature reaction 12 hours.Then reaction mixture dilutes with hexanaphthene, and with dry HCl gas sparging 1 hour, filters, and drying obtains diphenyl antimony chloride base phosphorus.
(4) preparation (phenylbenzene) phosphorus nitrogen (sec.-propyl) phosphorus (phenylbenzene)
Through N
2Add the methylene dichloride (20mL) through processed in the 100mL reactor that fully band of displacement stirs, triethylamine (3.75mL), diphenyl phosphorus chloride (1.326mL, 7.2mol), be cooled to 0 ℃, slowly add Isopropylamine (0.28mL, 3.6mol).Rise to room temperature behind the stirring reaction 30min and continue reaction 12 hours.Filtration, drying obtain product (0.87g, 56.6%).
2, preparation modified active agent
At-78 ℃, under the vigorous stirring, with microsyringe 0.81mL redistilled water (45mmol) slowly is added drop-wise to and contains 6.84mL (50mmol) AlEt
3Toluene (50mL) solution in, after dropwising, make system naturally return to room temperature, continue reaction 12h, namely obtain the toluene solution of EAO.Be added dropwise to the toluene solution 50mL of pentafluorophenyl group boron (10mmol) in the mentioned solution, dropwise rear room temperature and kept 6 hours, obtain the activator of modification.
3, the preparation of catalyzer
Through N
2Add the toluene (10mL) through processed in the 100mL reactor that fully band of displacement stirs, toluene solution (the 20mL of the modified active agent of step 2 preparation, 10mmol), (phenylbenzene) phosphorus nitrogen (sec.-propyl) phosphorus (phenylbenzene) is (67.8 μ mol) (29mg), CrCl
3(THF)
3(12mg, 33 μ mol), for subsequent use behind the room temperature reaction 5min.
4, ethylene oligomerization
The autoclave of 500mL is heated to and vacuumizes 2 hours, is filled with ethene through nitrogen replacement for several times, cools to preset temperature, adds hexanaphthene (200mL) and above-mentioned catalyzer through processed.Carrying out oligomerisation reaction under 45 ℃, the pressure of 5.0MPa, with ice bath cooling, release, is 10% acidifying ethanol termination reaction with massfraction behind the reaction 30min.Obtain oligomerization product 40.75g, catalyst activity is 2.47 * 10
6G oligopolymer/mol Cr.h.The distribution of oligomerization product sees Table 1.
Embodiment 2
1, preparation (phenylbenzene) phosphorus nitrogen (sec.-propyl) phosphorus (phenylbenzene) part (C
27H
27NP
2) with embodiment 1.
2, preparation modified active agent
At-78 ℃, under the vigorous stirring, with microsyringe 0.81mL redistilled water (45mmol) slowly is added drop-wise to and contains 6.84mL (50mmol) AlEt
3Toluene (50mL) solution in, after dropwising, make system naturally return to room temperature, continue reaction 12h, namely obtain the toluene solution of EAO.In mentioned solution, be added dropwise to [Ph
3C] [Al (OC (CF
3)
3)
4] (10mmol) toluene solution 50mL, dropwise rear room temperature and kept 6 hours, obtain the activator of modification.
3, the preparation of catalyzer
With embodiment 1.The modified active agent that adds is modified active agent prepared in the present embodiment.
4, ethylene oligomerization
With embodiment 1.Obtain oligomerization product 6.38g, catalyst activity is 3.87 * 10
5G oligopolymer/mol Cr.h.The distribution of oligomerization product sees Table 1.
Embodiment 3
1, preparation (phenylbenzene) phosphorus nitrogen (sec.-propyl) phosphorus (phenylbenzene) part (C
27H
27NP
2) with embodiment 1.
2, preparation modified active agent
With embodiment 1.Difference is that two the heteroatomic properties-correcting agent that contain at least that add are the Tetrafluoroboric acid sodium compound.
3, the preparation of catalyzer
With embodiment 1.
4, ethylene oligomerization
With embodiment 1.Obtain oligomerization product 8.5g, catalyst activity is 5.15 * 10
5G oligopolymer/molCr.h.The distribution of oligomerization product sees Table 1.
Embodiment 4
Embodiment 2
1, preparation (phenylbenzene) phosphorus nitrogen (sec.-propyl) phosphorus (phenylbenzene) part (C
27H
27NP
2) with embodiment 1.
2, preparation modified active agent
With embodiment 1.Difference is that two the heteroatomic properties-correcting agent that contain at least that add are the boroxin compound.
3, the preparation of catalyzer
With embodiment 1.
4, ethylene oligomerization
With embodiment 1.Obtain oligomerization product 28.31g, catalyst activity is 1.72 * 10
6G oligopolymer/mol Cr.h.The distribution of oligomerization product sees Table 1.
Embodiment 5
1, preparation (phenylbenzene) phosphorus nitrogen (sec.-propyl) phosphorus (phenylbenzene) part (C
27H
27NP
2) with embodiment 1.
2, preparation modified active agent
With embodiment 1.Difference is that two the heteroatomic properties-correcting agent that contain at least that add are boron trichloride.
3, the preparation of catalyzer
With embodiment 1.
4, ethylene oligomerization
With embodiment 1.Obtain oligomerization product 59.68g, catalyst activity is 3.62 * 10
6G oligopolymer/mol Cr.h.The distribution of oligomerization product sees Table 1.
Embodiment 6
1, preparation (phenylbenzene) phosphorus nitrogen (sec.-propyl) phosphorus (phenylbenzene) part (C
27H
27NP
2) with embodiment 1.
2, preparation modified active agent
With embodiment 1.Difference is that two the heteroatomic properties-correcting agent that contain at least that add are boron trifluoride.
3, the preparation of catalyzer
With embodiment 1.
4, ethylene oligomerization
With embodiment 1.Obtain oligomerization product 65.98g, catalyst activity is 4.0 * 10
6G oligopolymer/mol Cr.h.The distribution of oligomerization product sees Table 1.
Embodiment 7
1, preparation (phenylbenzene) phosphorus nitrogen (sec.-propyl) phosphorus (phenylbenzene) part (C
27H
27NP
2) with embodiment 1.
2, preparation modified active agent
With embodiment 1.Difference is that two the heteroatomic properties-correcting agent that contain at least that add are triethyl borate.
3, the preparation of catalyzer
With embodiment 1.
4, ethylene oligomerization
With embodiment 1.Obtain oligomerization product 8.40g, catalyst activity is 5.0 * 10
5G oligopolymer/molCr.h.The distribution of oligomerization product sees Table 1.
Embodiment 8
1, preparation (phenylbenzene) phosphorus nitrogen (sec.-propyl) phosphorus (phenylbenzene) part (C
27H
27NP
2) with embodiment 1.
2, preparation promoting agent
With embodiment 1.Difference is not add to contain at least two heteroatomic properties-correcting agent.Activator directly uses EAO.
3, the preparation of catalyzer
With embodiment 1.
4, ethylene oligomerization
With embodiment 1.Obtain oligomerization product 6.14g, catalyst activity is 3.72 * 10
5G oligopolymer/mol Cr.h.The distribution of oligomerization product sees Table 1.
Embodiment 9
1, preparation (phenylbenzene) phosphorus nitrogen (sec.-propyl) phosphorus (phenylbenzene) part (C
27H
27NP
2) with embodiment 1.
2, preparation modified active agent
At-78 ℃, under the vigorous stirring, with microsyringe 0.81mL redistilled water (45mmol) slowly is added drop-wise to and contains 6.84mL (50mmol) AlEt
3Toluene (50mL) solution in, after dropwising, make system naturally return to room temperature, continue reaction 12h, namely obtain the toluene solution of EAO.After being added dropwise to the methylaluminoxane of 50mmol in the mentioned solution, drip the toluene solution 50mL of pentafluorophenyl group boron (10mmol), dropwise rear room temperature and kept 6 hours, obtain the activator of modification.
3, the preparation of catalyzer
With embodiment 1.
4, ethylene oligomerization
With embodiment 1.Obtain oligomerization product 119.46g, catalyst activity is 7.24 * 10
6G oligopolymer/mol Cr.h.The distribution of oligomerization product sees Table 1.
Embodiment 10
1, preparation (phenylbenzene) phosphorus nitrogen (sec.-propyl) phosphorus (phenylbenzene) part (C
27H
27NP
2) with embodiment 1.
2, preparation modified active agent
With embodiment 10, difference is that the amount of the MAO that adds is 10mmol.
3, the preparation of catalyzer
With embodiment 1.
4, ethylene oligomerization
With embodiment 1.Obtain oligomerization product 82.67g, catalyst activity is 5.01 * 10
6G oligopolymer/mol Cr.h.The distribution of oligomerization product sees Table 1.
Embodiment 11
1, preparation (phenylbenzene) phosphorus nitrogen (sec.-propyl) phosphorus (phenylbenzene) part (C
27H
27NP
2) with embodiment 1.
2, preparation modified active agent
With embodiment 1.
3, the preparation of catalyzer
With embodiment 1.Difference is to add (d) component tetrachloroethane 0.2mmol.
4, ethylene oligomerization
With embodiment 1.Obtain oligomerization product 45.30g, catalyst activity is 2.75 * 10
6G oligopolymer/mol Cr.h.The distribution of oligomerization product sees Table 1.
Embodiment 12
1, preparation (phenylbenzene) phosphorus nitrogen (sec.-propyl) phosphorus (phenylbenzene) part (C
27H
27NP
2) with embodiment 1.
2, preparation modified active agent
With embodiment 1.
3, the preparation of catalyzer
With embodiment 1.Difference is to add (d) component tetrachloroethane 0.5mmol.
4, ethylene oligomerization
With embodiment 1.Obtain oligomerization product 22.31g, catalyst activity is 1.35 * 10
6G oligopolymer/mol Cr.h.The distribution of oligomerization product sees Table 1.
The contrast of table 1 oligomerization product carbon number distribution
aRefer to C
6Middle 1-C
6 =Percentage composition.
bRefer to C
8Middle 1-C
8 =Percentage composition.
The experiment condition of table 2 embodiment 1～10 and catalyst activity
Claims (1)
1. an ethene four gathers the methods that reaction prepares octene-1, it is characterized in that:
Ethene four poly-reactions are to carry out in alkane, aromatic hydrocarbons, halohydrocarbon or alkene solvent;
Temperature of reaction is 0 ℃～200 ℃, and reaction pressure is 0.1MPa～20Mpa, and the concentration of catalyzer is from 0.01 μ mol metal/L～1000 μ mol metal/L;
Catalyzer 1: 0.5 in molar ratio～100: 0.1～5000: 0～500 forms by component (a), (b), (c) and/or (d);
Described component (a) is the two (N (P (phenyl) of 1,2-
2)
2)-benzene, Isosorbide-5-Nitrae-two (N (P (phenyl)
2)
2)-benzene or N (CH
2CH
2N (P (phenyl)
2)
2)
3
Described component (b) is CrCl
3(THF)
3, isocaprylic acid chromium or chromium acetylacetonate;
Described component (c) is alkylaluminium cpd or aluminium alkoxide compound and contains at least two interactional products of heteroatomic properties-correcting agent, or two or more aluminum alkylss or aikyiaiurnirsoxan beta and the interactional product of two or more properties-correcting agent;
It is described that to contain two heteroatomic properties-correcting agent are [Ph
3C] [Al{OC (CF
3)
3}
4], Ph
2C (Me) OAlMe
2, B (C
6F5)
3, phenylo boric acid, methyl-boron-dihydroxide, two valeryl two boron, BF
3, BCl
3, BBr
3Or BCl
3
Described component (d) be ortho position three chloro methyl fluoride benzene, ortho position three fluoro methyl chloride benzene, ortho position three chloro methyl chloride benzene, ortho position three fluoro methyl chloride benzene 2 or 6-two chloro-trichlorines for methylbenzene.
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| US20150298110A1 (en) * | 2012-11-15 | 2015-10-22 | Lg Chem, Ltd | Ligand compound, organic chromium compound, catalyst system for ethylene oligomerization, preparation method thereof, and ethylene oligomerization method using the same |
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