CN111774098B - Ethylene oligomerization catalyst system, preparation method and application thereof - Google Patents
Ethylene oligomerization catalyst system, preparation method and application thereof Download PDFInfo
- Publication number
- CN111774098B CN111774098B CN202010703255.XA CN202010703255A CN111774098B CN 111774098 B CN111774098 B CN 111774098B CN 202010703255 A CN202010703255 A CN 202010703255A CN 111774098 B CN111774098 B CN 111774098B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- chromium
- reaction
- phosphine
- ethylene
- 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.)
- Active
Links
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims abstract description 81
- 239000005977 Ethylene Substances 0.000 title claims abstract description 81
- 239000003054 catalyst Substances 0.000 title claims abstract description 59
- 238000006384 oligomerization reaction Methods 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title abstract description 17
- 239000003446 ligand Substances 0.000 claims abstract description 71
- KUXDQQMEFBFTGX-UHFFFAOYSA-N [N].P Chemical compound [N].P KUXDQQMEFBFTGX-UHFFFAOYSA-N 0.000 claims abstract description 44
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims abstract description 20
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims abstract description 18
- 150000001845 chromium compounds Chemical class 0.000 claims abstract description 15
- 229910052751 metal Inorganic materials 0.000 claims abstract description 14
- 239000002184 metal Substances 0.000 claims abstract description 14
- 125000005234 alkyl aluminium group Chemical group 0.000 claims abstract description 12
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims abstract description 11
- -1 4-methylcyclohexyl Chemical group 0.000 claims description 75
- 238000006243 chemical reaction Methods 0.000 claims description 71
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 28
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 28
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 21
- 239000002904 solvent Substances 0.000 claims description 21
- 239000011651 chromium Substances 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 19
- 150000001875 compounds Chemical class 0.000 claims description 18
- 238000001816 cooling Methods 0.000 claims description 17
- 229910052757 nitrogen Inorganic materials 0.000 claims description 14
- 229910052763 palladium Inorganic materials 0.000 claims description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 13
- 239000001257 hydrogen Substances 0.000 claims description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims description 13
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 claims description 12
- 230000035484 reaction time Effects 0.000 claims description 11
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 9
- XEHUIDSUOAGHBW-UHFFFAOYSA-N chromium;pentane-2,4-dione Chemical compound [Cr].CC(=O)CC(C)=O.CC(=O)CC(C)=O.CC(=O)CC(C)=O XEHUIDSUOAGHBW-UHFFFAOYSA-N 0.000 claims description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 150000004703 alkoxides Chemical class 0.000 claims description 8
- 229910052804 chromium Inorganic materials 0.000 claims description 8
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 8
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 8
- WQONPSCCEXUXTQ-UHFFFAOYSA-N 1,2-dibromobenzene Chemical compound BrC1=CC=CC=C1Br WQONPSCCEXUXTQ-UHFFFAOYSA-N 0.000 claims description 6
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 claims description 6
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 5
- CYPYTURSJDMMMP-WVCUSYJESA-N (1e,4e)-1,5-diphenylpenta-1,4-dien-3-one;palladium Chemical compound [Pd].[Pd].C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 CYPYTURSJDMMMP-WVCUSYJESA-N 0.000 claims description 4
- UKSZBOKPHAQOMP-SVLSSHOZSA-N (1e,4e)-1,5-diphenylpenta-1,4-dien-3-one;palladium Chemical compound [Pd].C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 UKSZBOKPHAQOMP-SVLSSHOZSA-N 0.000 claims description 4
- 125000004198 2-fluorophenyl group Chemical group [H]C1=C([H])C(F)=C(*)C([H])=C1[H] 0.000 claims description 4
- 125000004180 3-fluorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C(F)=C1[H] 0.000 claims description 4
- 125000004860 4-ethylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])C([H])([H])[H] 0.000 claims description 4
- 125000001255 4-fluorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1F 0.000 claims description 4
- 125000004861 4-isopropyl phenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 4
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 claims description 4
- 125000000590 4-methylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 4
- 235000010290 biphenyl Nutrition 0.000 claims description 4
- 239000004305 biphenyl Substances 0.000 claims description 4
- YNHIGQDRGKUECZ-UHFFFAOYSA-L bis(triphenylphosphine)palladium(ii) dichloride Chemical compound [Cl-].[Cl-].[Pd+2].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 YNHIGQDRGKUECZ-UHFFFAOYSA-L 0.000 claims description 4
- NXQGGXCHGDYOHB-UHFFFAOYSA-L cyclopenta-1,4-dien-1-yl(diphenyl)phosphane;dichloropalladium;iron(2+) Chemical compound [Fe+2].Cl[Pd]Cl.[CH-]1C=CC(P(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1.[CH-]1C=CC(P(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 NXQGGXCHGDYOHB-UHFFFAOYSA-L 0.000 claims description 4
- 125000001624 naphthyl group Chemical group 0.000 claims description 4
- 125000003261 o-tolyl group Chemical group [H]C1=C([H])C(*)=C(C([H])=C1[H])C([H])([H])[H] 0.000 claims description 4
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims description 4
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 4
- 125000002178 anthracenyl group Chemical group C1(=CC=CC2=CC3=CC=CC=C3C=C12)* 0.000 claims description 3
- 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 3
- WQKGAJDYBZOFSR-UHFFFAOYSA-N potassium;propan-2-olate Chemical compound [K+].CC(C)[O-] WQKGAJDYBZOFSR-UHFFFAOYSA-N 0.000 claims description 3
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 3
- WVSBQYMJNMJHIM-UHFFFAOYSA-N (benzene)chromium tricarbonyl Chemical group [Cr].[O+]#[C-].[O+]#[C-].[O+]#[C-].C1=CC=CC=C1 WVSBQYMJNMJHIM-UHFFFAOYSA-N 0.000 claims description 2
- YVSMQHYREUQGRX-UHFFFAOYSA-N 2-ethyloxaluminane Chemical compound CC[Al]1CCCCO1 YVSMQHYREUQGRX-UHFFFAOYSA-N 0.000 claims description 2
- CMAOLVNGLTWICC-UHFFFAOYSA-N 2-fluoro-5-methylbenzonitrile Chemical compound CC1=CC=C(F)C(C#N)=C1 CMAOLVNGLTWICC-UHFFFAOYSA-N 0.000 claims description 2
- 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 claims description 2
- 229910021555 Chromium Chloride Inorganic materials 0.000 claims description 2
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 claims description 2
- RPBPCPJJHKASGQ-UHFFFAOYSA-K chromium(3+);octanoate Chemical compound [Cr+3].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O.CCCCCCCC([O-])=O RPBPCPJJHKASGQ-UHFFFAOYSA-K 0.000 claims description 2
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 claims description 2
- UAIZDWNSWGTKFZ-UHFFFAOYSA-L ethylaluminum(2+);dichloride Chemical compound CC[Al](Cl)Cl UAIZDWNSWGTKFZ-UHFFFAOYSA-L 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 2
- RPDAUEIUDPHABB-UHFFFAOYSA-N potassium ethoxide Chemical compound [K+].CC[O-] RPDAUEIUDPHABB-UHFFFAOYSA-N 0.000 claims description 2
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 claims description 2
- WBQTXTBONIWRGK-UHFFFAOYSA-N sodium;propan-2-olate Chemical compound [Na+].CC(C)[O-] WBQTXTBONIWRGK-UHFFFAOYSA-N 0.000 claims description 2
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 2
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 claims description 2
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 claims description 2
- LFXVBWRMVZPLFK-UHFFFAOYSA-N trioctylalumane Chemical compound CCCCCCCC[Al](CCCCCCCC)CCCCCCCC LFXVBWRMVZPLFK-UHFFFAOYSA-N 0.000 claims description 2
- OBETXYAYXDNJHR-UHFFFAOYSA-N 2-Ethylhexanoic acid Chemical compound CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 claims 1
- SHZIWNPUGXLXDT-UHFFFAOYSA-N caproic acid ethyl ester Natural products CCCCCC(=O)OCC SHZIWNPUGXLXDT-UHFFFAOYSA-N 0.000 claims 1
- 229920000642 polymer Polymers 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 description 20
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 16
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 15
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 15
- 238000005160 1H NMR spectroscopy Methods 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 238000007599 discharging Methods 0.000 description 10
- 239000005457 ice water Substances 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 7
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- 238000004440 column chromatography Methods 0.000 description 6
- 238000001953 recrystallisation Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000012295 chemical reaction liquid Substances 0.000 description 4
- YTFQUBRFOJIJOZ-UHFFFAOYSA-N chloro-bis(4-methoxyphenyl)phosphane Chemical compound C1=CC(OC)=CC=C1P(Cl)C1=CC=C(OC)C=C1 YTFQUBRFOJIJOZ-UHFFFAOYSA-N 0.000 description 4
- XGRJZXREYAXTGV-UHFFFAOYSA-N chlorodiphenylphosphine Chemical compound C=1C=CC=CC=1P(Cl)C1=CC=CC=C1 XGRJZXREYAXTGV-UHFFFAOYSA-N 0.000 description 4
- 239000003814 drug Substances 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 3
- GHAKVYIBHNIGBD-UHFFFAOYSA-N chloro-(2-fluorophenyl)-phenylphosphane Chemical compound FC1=CC=CC=C1P(Cl)C1=CC=CC=C1 GHAKVYIBHNIGBD-UHFFFAOYSA-N 0.000 description 3
- 239000004711 α-olefin Substances 0.000 description 3
- 239000007983 Tris buffer Substances 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 239000007810 chemical reaction solvent Substances 0.000 description 2
- PNFPTKBGLKZWPC-UHFFFAOYSA-N chloro-(3-fluorophenyl)-phenylphosphane Chemical compound FC1=CC=CC(P(Cl)C=2C=CC=CC=2)=C1 PNFPTKBGLKZWPC-UHFFFAOYSA-N 0.000 description 2
- CBWKFJKGHCCNBC-UHFFFAOYSA-N chloro-(4-fluorophenyl)-phenylphosphane Chemical compound C1=CC(F)=CC=C1P(Cl)C1=CC=CC=C1 CBWKFJKGHCCNBC-UHFFFAOYSA-N 0.000 description 2
- GGLMHXUXAVEHDE-UHFFFAOYSA-N chloro-bis(2,6-dimethylphenyl)phosphane Chemical compound CC1=CC=CC(C)=C1P(Cl)C1=C(C)C=CC=C1C GGLMHXUXAVEHDE-UHFFFAOYSA-N 0.000 description 2
- PEKLJSZEUFVLKO-UHFFFAOYSA-N chloro-bis(2-methoxyphenyl)phosphane Chemical compound COC1=CC=CC=C1P(Cl)C1=CC=CC=C1OC PEKLJSZEUFVLKO-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000004696 coordination complex Chemical class 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- JYLPOJPHFDVWCY-UHFFFAOYSA-K oxolane;trichlorochromium Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3].C1CCOC1 JYLPOJPHFDVWCY-UHFFFAOYSA-K 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 238000004458 analytical method Methods 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
- 230000009286 beneficial effect Effects 0.000 description 1
- VNIXYVYRHPMNGR-UHFFFAOYSA-N bis(4-methylphenyl)phosphane;hydrochloride Chemical compound Cl.C1=CC(C)=CC=C1PC1=CC=C(C)C=C1 VNIXYVYRHPMNGR-UHFFFAOYSA-N 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- BJBXRRHIBSXGLF-UHFFFAOYSA-N chloro-bis(4-methylphenyl)phosphane Chemical compound C1=CC(C)=CC=C1P(Cl)C1=CC=C(C)C=C1 BJBXRRHIBSXGLF-UHFFFAOYSA-N 0.000 description 1
- WBKDDMYJLXVBNI-UHFFFAOYSA-K chromium(3+);2-ethylhexanoate Chemical compound [Cr+3].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O WBKDDMYJLXVBNI-UHFFFAOYSA-K 0.000 description 1
- QXFRPNUEXMUURF-UHFFFAOYSA-N chromium;oxolane Chemical compound [Cr].C1CCOC1 QXFRPNUEXMUURF-UHFFFAOYSA-N 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000006471 dimerization reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000010813 internal standard method Methods 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000005829 trimerization reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
-
- 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
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/645—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having two nitrogen atoms as the only ring hetero atoms
- C07F9/6509—Six-membered rings
- C07F9/650952—Six-membered rings having the nitrogen atoms in the positions 1 and 4
- C07F9/650994—Six-membered rings having the nitrogen atoms in the positions 1 and 4 condensed with carbocyclic rings or carbocyclic ring systems
-
- 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
-
- 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
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Materials Engineering (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention provides an ethylene oligomerization catalyst system, a preparation method and application thereof. The catalyst system comprises a phosphine-nitrogen ligand shown in a formula I, a metal chromium compound and an alkyl aluminum cocatalyst. The molar ratio of the metal chromium compound to the phosphine-nitrogen ligand is 1: (0.8 to 5), preferably 1: (1-2); the molar ratio of the alkyl aluminum cocatalyst to the metal chromium compound is (50-2000): 1, preferably (100-1000): 1. The catalyst system of the invention is used for ethylene oligomerization, which can improve the selectivity of 1-hexene and 1-octene, and has low polymer production amount and excellent industrialization prospect.
Description
Technical Field
The invention relates to a catalyst system, in particular to an ethylene oligomerization catalyst system, a preparation method and application thereof.
Background
Linear alpha-olefins are linear olefins having a C ═ C double bond at the molecular chain end (e.g., 1-butene, 1-hexene, 1-octene, etc.), and are an important chemical raw material, and are used in many fields such as ethylene comonomers, plasticizers, surfactants, and lubricating oil additives. Compared with 1-butene, polyethylene taking 1-hexene and 1-octene as comonomers has higher tearing strength, stress cracking resistance and other excellent performances, and is more and more favored by the market.
In the traditional production method, products in the ethylene non-selective oligomerization process are in Schulz-Flory distribution, the selectivity of specific components is poor, and corresponding high-purity linear alpha-olefin can be obtained only through a separation process with high energy consumption, which cannot meet the increasing demand of industry on the specific alpha-olefin. In recent years, the research on ethylene selective oligomerization technology has been greatly developed. In 1987, IFP-SABIC company realized the industrialization of the technology for producing 1-butene by ethylene dimerization. In 2003, Phillips company realized the industrial production of 1-hexene by ethylene trimerization in Katalr. In 2014, Sasol corporation in south Africa built the first ethylene tetramerization worldwide production plant for 1-octene and 1-hexene in Louisiana, using Cr/PNP catalyst system.
At present, in ethylene selective oligomerization catalysts, chromium-based catalysts, titanium-based catalysts, tantalum-based catalysts and the like have good performances, wherein the Cr-based catalysts have better activity and selectivity, and are more and more concerned by researchers. Patent publications CN103100421A, CN104511311A, CN102451758B, etc. describe a series of ethylene tetramerization catalysts with different PNP ligands. The performance of the catalysts is mainly influenced by the ligand structure, the steric hindrance effect and the electron donating effect of the ligand have great influence on the activity and the selectivity, and on the premise of ensuring the catalytic activity, the product selectivity is only about 80 percent, and the catalysts still have improved space. Meanwhile, the PNP framework structure is influenced by a substituent on nitrogen, the selectivity of the polymer is generally over 0.2 wt%, and the long-period operation of the device is influenced. In view of the problems of low selectivity and high polymer yield of the current PNP ligand structure catalyst, the development of a novel ligand structure catalyst is urgently needed.
Disclosure of Invention
In order to solve the technical problems, the invention provides an ethylene oligomerization catalyst system, and a preparation method and application thereof. The catalyst ligand is a phosphine phenylenediamine framework, and two nitrogen atoms are connected through two benzene rings to form a stable closed-loop structure, so that the selectivity of 1-hexene and 1-octene in the product can be improved, the generation of polymers is reduced, and the catalyst has an excellent industrial prospect.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
an ethylene oligomerization catalyst system comprises a phosphine-nitrogen ligand shown in a formula I, a metal chromium compound and an alkyl aluminum cocatalyst;
in the formula I, R1、R2、R3、R4Each independently selected from aryl or derivatives thereof;
preferably, in formula I, R1、R2、R3、R4Each independently selected from the group consisting of phenyl, benzyl, biphenyl, naphthyl, anthracenyl, ethenyl, propenyl, cyclohexyl, 4-methylcyclohexyl, 4-ethylcyclohexyl, 4-isopropylcyclohexyl, 2-methylphenyl, 4-methylphenyl, 2, 4-dimethylphenyl, 2, 6-dimethylphenyl, 2-ethylphenyl, 4-ethylphenyl, 2, 4-diethylphenyl, 2, 6-diethylphenyl, 2-isopropylphenyl, 4-isopropylphenyl, 2, 4-diisopropylphenyl, 2, 6-diisopropylphenyl, 2-butylphenyl, 4-butylphenyl, 2, 4-dibutylphenyl, 2, 6-dibutylphenyl, 4-methoxyphenyl, o-methoxyphenyl, 4-ethoxyphenyl, o-ethoxyphenyl, 2-fluorophenyl, 3-fluorophenyl or 4-fluorophenyl.
Further, the molar ratio of the metal chromium compound to the phosphine-nitrogen ligand is 1: (0.8 to 5) may be, for example, 1:0.8, 1:1, 1:1.5, 1:2, 1:3, 1:4, 1:5, etc., preferably 1: (1-2); the molar ratio of the alkylaluminum cocatalyst to the metal chromium compound is (50-2000): 1, and may be, for example, 50:1, 100:1, 200:1, 300:1, 400:1, 500:1, 600:1, 700:1, 800:1, 900:1, 1000:1, 1200:1, 1500:1, 2000:1, and the like, preferably (100-1000): 1.
Further, the metal chromium compound is one or more of organic salt, inorganic salt, coordination complex or organic metal complex of metal chromium, preferably one or more of chromium acetylacetonate, chromium chloride, chromium trichloro-tris (tetrahydrofuran), chromium (III) 2-ethylhexanoate, chromium octanoate, chromium hexacarbonyl, chromium benzenetricarbonyl and chromium diphenyloxide;
preferably, the alkylaluminum cocatalyst is selected from at least one of trimethylaluminum, triethylaluminum, triisobutylaluminum, trioctylaluminum, diethylaluminum monochloride, ethylaluminum dichloride, ethylaluminum sesquichloride, methylaluminoxane, modified methylaluminoxane and ethylaluminoxane, preferably methylaluminoxane and/or modified methylaluminoxane.
The preparation method of the phosphine-nitrogen ligand in the formula I comprises the following steps:
step 1), dissolving o-phenylenediamine and 1, 2-dibromobenzene under anhydrous and anaerobic conditions, and reacting under the action of alkoxide and palladium catalyst to obtain a compound shown as a formula II, wherein the compound is marked as a product A;
further, the alkoxide is selected from one or more of potassium tert-butoxide, sodium tert-butoxide, potassium methoxide, sodium methoxide, potassium ethoxide, sodium ethoxide, potassium isopropoxide and sodium isopropoxide; the palladium catalyst is selected from one or more of [1,1' -bis (diphenylphosphino) ferrocene ] palladium dichloride, tris (dibenzylideneacetone) dipalladium, bis (dibenzylideneacetone) palladium, dichlorobis (triphenylphosphine) palladium and tetrakis (triphenylphosphine) palladium.
Further, the reaction solvent is one or more of toluene, methylcyclohexane, acetonitrile, cyclohexane and n-heptane;
further, the molar ratio of the o-phenylenediamine, the 1, 2-dibromobenzene, the palladium catalyst and the alkoxide is 1 (1 to 2) to 0.01 to 0.5 (1.5 to 3.5), and may be, for example, 1:1:0.01:1.5, 1:1.5:0.1:2, 1:2:0.5:3, 1:1:0.3:3.5, 1:2:0.1:2, 1:1.5:0.5:2.5, and the like.
Further, the reaction in the step 1) is carried out for 10-24 hours under the solvent reflux condition.
After the reaction in the step is finished, the target product can be refined by column chromatography and recrystallization purification methods; the preferable conditions of the column chromatography are that the height-diameter ratio of the chromatographic column is 2-4, the retention time is 1-2 min, and the solvent used for recrystallization is preferably a mixed solvent of ethanol and ethyl acetate.
Step 2), dissolving the product A under anhydrous and anaerobic conditions, dropwise adding triethylamine, then adding a compound in the following formula III, and reacting to obtain the phosphine-nitrogen ligand;
wherein R is1、R2Each independently selected from aryl or derivatives thereof;
preferably, R1、R2Each independently selected from phenyl, benzyl, biphenyl, naphthyl, anthryl, ethenyl, and propyleneCyclohexyl, 4-methylcyclohexyl, 4-ethylcyclohexyl, 4-isopropylcyclohexyl, 2-methylphenyl, 4-methylphenyl, 2, 4-dimethylphenyl, 2, 6-dimethylphenyl group, a 2, 6-dimethylphenyl group, 2-ethylphenyl group, 4-ethylphenyl group, 2, 4-diethylphenyl group, 2, 6-diethylphenyl group, 2-isopropylphenyl group, 4-isopropylphenyl group, 2, 4-diisopropylphenyl group, 2, 6-diisopropylphenyl group, 2-butylphenyl group, 4-butylphenyl group, 2, 4-dibutylphenyl group, 2, 6-dibutylphenyl group, 4-methoxyphenyl group, o-methoxyphenyl group, 4-ethoxyphenyl group, o-ethoxyphenyl group, 2-fluorophenyl group, 3-fluorophenyl group or 4-fluorophenyl group.
Further, the reaction solvent is one or more of dichloromethane, acetonitrile, n-hexane and n-heptane.
Furthermore, the molar ratio of the product A to the triethylamine and the compound of formula III is 1 (1.5-3.5): (1.6-3.6), and may be, for example, 1:1.5:1.6, 1:3.5:3.6, 1:2:2, 1:3:2.5, 1:2.5:3, 1:1.5:2, etc.
Preferably, the step 2) is carried out for 9-30 h at-10-30 ℃. For example, at the temperature of-10 to 0 ℃, after the triethylamine and the compound of the formula III are all dripped, the reaction is firstly carried out for 3 to 6 hours, and then the temperature is slowly increased to be below 30 ℃ for continuous reaction for 6 to 24 hours.
After the reaction in the step 2), refining the target product by column chromatography and recrystallization purification; the preferable conditions of the column chromatography are that the height-diameter ratio of the chromatographic column is 2-4, the retention time is 1-2 min, and the solvent used for recrystallization is preferably a mixed solvent of ethanol and ethyl acetate.
An ethylene oligomerization method comprises the following steps: in the presence of the catalyst system, ethylene oligomerization is carried out to prepare 1-hexene and 1-octene.
The ethylene oligomerization method specifically comprises the following steps:
heating a reaction kettle to 110-160 ℃ before reaction, vacuumizing for 1-4 h, performing nitrogen replacement, cooling to room temperature, performing ethylene replacement, adding a solvent and an alkyl aluminum cocatalyst, then adding a metal chromium compound and a phosphine-nitrogen ligand, introducing 0.1-0.7 MPa hydrogen and 2-7 MPa ethylene in sequence to start reaction when the temperature reaches 35-90 ℃, preferably 40-70 ℃, and performing reaction for 10-240 min, preferably 20-100 min. Preferably, the ethylene oligomerization reaction uses the purified alkane as a solvent, and more preferably one or more of methylcyclohexane, toluene, n-hexane, cyclohexane, n-heptane, and n-octane.
Compared with the prior art, the catalyst system has the beneficial effects that the ethylene oligomerization activity can reach more than 900 kg/(gCr.h), and the total selectivity of 1-hexene and 1-octene is more than 85%, so that the production cost can be reduced, and the economic added value is high.
Detailed Description
The present invention is further illustrated by the following specific examples, which are intended to be illustrative of the invention and are not to be construed as limiting the scope of the invention.
The starting materials used in the examples are conventional in the art and the purity specifications used are either analytically or chemically pure. Relevant solvents in the examples molecular sieves were soaked to remove water before use.
Raw material source information:
1, 2-dibromobenzene: 98%, Bailingwei Tech Co Ltd
O-phenylenediamine: 99.5%, Bailingwei Tech Co Ltd
Triethylamine: not less than 99.5% (GC), Shanghai Aladdin Biotechnology Ltd
Diphenyl phosphine chloride: 97% of Alfa Angsa chemical Co Ltd
Potassium tert-butoxide: 97% of Alfa Angsa chemical Co Ltd
[1,1' -bis (diphenylphosphino) ferrocene ] dichloropalladium, 99%, Prodweis technologies Ltd
Chloro (2-fluorophenyl) (phenyl) phosphine: 97%, Shanghai Xinkai medicine science and technology Limited
Chloro (3-fluorophenyl) (phenyl) phosphine: 97%, Shanghai Xinkai medicine science and technology Limited
Chloro (4-fluorophenyl) (phenyl) phosphine: 97%, Shanghai Xinkai medicine science and technology Limited
Chlorobis (2, 6-dimethylphenyl) phosphine: 98% Jiangsu Xinnoco catalyst Co., Ltd
Chlorobis (4-methylphenyl) phosphine: more than 97%, Jiangsu Xinnoco catalyst Co., Ltd
Chlorobis (2-methoxyphenyl) phosphine: 98% of Alfa Sha (China) Chemicals Co., Ltd
Chlorobis (4-methoxyphenyl) phosphine: 98% of Alfa Sha (China) Chemicals Co., Ltd
Ethyl acetate: 99.9%%, Bailingwei science & technology Limited
Ethanol: chemical reagent of analytical pure, national drug group Co Ltd
MMAO-3a (modified methylaluminoxane): 7 wt% Al, n-heptane solvent, Nomoon chemical (Ningbo) Co., Ltd
MAO (methylaluminoxane), 10% strength by weight, toluene solvent, Nomoon chemical (Ningbo) Co., Ltd
iPr-PNP (CAS: 60981-68-20): more than 97%, Jiangsu Xinnoco catalyst Co., Ltd
The activity of the catalyst for oligomerization is qualitatively and quantitatively analyzed by components in the reaction solution, and the conditions of a GC analyzer are as follows:
the instrument model is as follows: shimadzu GC2010
A chromatographic column: DB-5(30m 0.25mm 0.25 μm)
Column temperature procedure: the temperature was first maintained at 35 ℃ for 10min and then raised to 250 ℃ at a rate of 10 ℃/min, and maintained at this temperature for 10 min.
Detector temperature: 300 deg.C
Carrier gas: 1bar
Air: 0.3bar
Gas (H)2)：0.3bar
Product quality analysis was performed using an internal standard method:
in the formula m1Is the mass of a certain product, m is the mass of the internal standard, a1The peak area of the product detected in the gas chromatogram is shown as a peak area of an internal standard substance. k is a correction factor associated with the substance to be measured and the detection condition.
Example 1
Preparation of phosphine-nitrogen ligand:
dissolving 1mol of o-phenylenediamine and 1.1mol of 1, 2-dibromobenzene in 500ml of toluene under anhydrous and anaerobic conditions to obtain a reaction solution I; under the protection of nitrogen, 2.2mol of potassium tert-butoxide and 0.1mol of [1,1' -bis (diphenylphosphino) ferrocene ] palladium dichloride catalyst are added into the reaction liquid I, then the temperature is slowly raised to 105 ℃, reflux stirring reaction is carried out for 16h, the reaction liquid is purified by column chromatography (tetrahydrofuran is used for leaching, the height-diameter ratio is 3), then recrystallization is carried out at 78 ℃ (the solvent is ethanol: ethyl acetate is 6:1), and 0.8mol of the product A is obtained by treatment.
Dissolving 100mmol of product A in 200ml of dichloromethane under anhydrous and oxygen-free conditions; and (2) dropwise adding 220mmol of triethylamine into the reaction liquid under stirring at-5 ℃, slowly adding 110mmol of diphenyl phosphine chloride into the reaction liquid, adding 110mmol of diphenyl phosphine chloride after the solution is stable and does not release heat continuously, reacting for 3 hours under stirring, removing the low-temperature constant-temperature reaction bath, and stirring for 12 hours at room temperature. The reaction solution was purified by column chromatography (tetrahydrofuran elution, height to diameter ratio of 2), followed by recrystallization at 78 ℃ (solvent ethanol: ethyl acetate ═ 5:1) to give a phosphine-nitrogen ligand represented by the following formula L1:
nuclear magnetic data for ligand L1 are as follows: 1H NMR (400MHz, CDCl)3)：7.45(m,12H)，7.38(m,8H)，6.56(m,4H)，6.38(m,4H).
Oligomerization of ethylene:
before the reaction, a 300ml reaction kettle is heated to 130 ℃, vacuumized for 3 hours and replaced by nitrogen for three times. After the temperature is cooled to room temperature, the ethylene is replaced twice, 100ml of dehydrated and deoxidized solvent methylcyclohexane and 0.6ml of MMAO-3a are added, then 4.2 mu mol of ligand L1 and 3.5 mu mol of chromium acetylacetonate (Al/Cr is 300) are added, and the reaction is started by sequentially introducing 0.5Mpa of hydrogen and 5MPa of ethylene when the temperature is constant at 45 ℃. The reaction temperature is 45 ℃ and the reaction time is 40 min. After the reaction is finished, closing the ethylene inlet valve, using ice water bath or quickly cooling to below 5 ℃, slowly releasing pressure, and discharging the reactor to obtain the ethylene oligomerization product.
Example 2
Preparation of phosphine-nitrogen ligand:
the phosphine-nitrogen ligand L2 was prepared according to the method in example 1, except for the following raw materials added and the differences in the amounts of the raw materials shown in Table 1:
the palladium catalyst is bis (dibenzylideneacetone) palladium and the compound of formula III is selected from chloro (2-fluorophenyl) (phenyl) phosphine to give a phosphine-nitrogen ligand of formula L2:
nuclear magnetic data for ligand L2 are as follows: 1H NMR (400MHz, CDCl)3)：7.75(m,2H)，7.22～7.45(m，16H)，6.33～6.58(m，8H).
Oligomerization of ethylene:
before reaction, a 500ml reaction kettle is heated to 110 ℃, vacuumized for 4 hours and replaced by nitrogen for three times. After the temperature is cooled to room temperature, the ethylene is replaced twice, 200ml of dehydrated and deoxidized solvent methylcyclohexane and 1.4ml of MMAO-3a (7 wt% Al, n-heptane) are added, then 5 mu mol of ligand L2 and 5 mu mol of tetrahydrofuran chromium chloride (Al/Cr is 500) are added, and the reaction is started by sequentially introducing 0.4MPa hydrogen and 4.5MPa ethylene when the temperature is constant at 60 ℃. The reaction temperature is 60 ℃, and the reaction time is 60 min. After the reaction is finished, closing the ethylene inlet valve, using ice water bath or quickly cooling to below 5 ℃, slowly releasing pressure, and discharging the reactor to obtain the ethylene oligomerization product.
Example 3
Preparation of phosphine-nitrogen ligand:
the phosphine-nitrogen ligand L3 was prepared according to the method in example 1, except for the following raw materials added and the differences in the amounts of the raw materials shown in Table 1:
the palladium catalyst was tetrakis (triphenylphosphine) palladium, the alkoxide was potassium isopropoxide, and the compound of formula III was selected from chloro (3-fluorophenyl) (phenyl) phosphine to give a phosphine-nitrogen ligand of formula L3 below:
nuclear magnetic data for ligand L3 are as follows: 1H NMR (400MHz, CDCl)3)：7.38～7.45(m，12H)，7.15-7.24(m,6H),6.31～6.61(m，8H).
Oligomerization of ethylene:
before reaction, a 500ml reaction kettle is heated to 120 ℃, vacuumized for 2 hours and replaced by nitrogen for three times. After the temperature is cooled to room temperature, the ethylene is replaced twice, 200ml of dehydrated and deoxidized solvent toluene and 0.95ml of MAO are added, then 7 mu mol of ligand L3 and 3.5 mu mol of tetrahydrofuran chromium chloride (Al/Cr is 400) are added, and the reaction is started by introducing 0.3MPa of hydrogen and 4.5MPa of ethylene in sequence when the temperature is constant at 65 ℃. The reaction temperature is 65 ℃ and the reaction time is 60 min. After the reaction is finished, closing the ethylene inlet valve, using ice water bath or quickly cooling to below 5 ℃, slowly releasing pressure, and discharging the reactor to obtain the ethylene oligomerization product.
Example 4
Preparation of phosphine-nitrogen ligand:
the phosphine-nitrogen ligand L4 was prepared according to the method in example 1, except for the following raw materials added and the differences in the amounts of the raw materials shown in Table 1:
the palladium catalyst is dichlorobis (triphenylphosphine) palladium, and the compound shown in the formula III is selected from chloro (4-fluorophenyl) (phenyl) phosphine to obtain a phosphine-nitrogen ligand shown in the following formula L4:
nuclear magnetic data for ligand L4 are as follows: 1H NMR (400MHz, CDCl)3)：7.36～7.45(m，14H)，7.09(m,4H)，6.35～6.49(m，8H).
Oligomerization of ethylene:
before reaction, a 500ml reaction kettle is heated to 140 ℃, vacuumized for 2.5 hours and replaced by nitrogen for three times. After the temperature is cooled to room temperature, the ethylene is replaced twice, 200ml of dehydrated and deoxidized solvent toluene and 1.2ml of MMAO are added, then 5 mu mol of ligand L4 and 3.5 mu mol of chromium acetylacetonate (Al/Cr is 600) are added, and the reaction is started by sequentially introducing 0.5Mpa of hydrogen and 4.5MPa of ethylene when the temperature is constant at 70 ℃. The reaction temperature is 70 ℃, and the reaction time is 80 min. After the reaction is finished, closing the ethylene inlet valve, using ice water bath or quickly cooling to below 5 ℃, slowly releasing pressure, and discharging the reactor to obtain the ethylene oligomerization product.
Example 5
Preparation of phosphine-nitrogen ligand:
the phosphine-nitrogen ligand L5 was prepared according to the method in example 1, except for the following raw materials added and the differences in the amounts of the raw materials shown in Table 1:
the palladium catalyst is tris (dibenzylideneacetone) dipalladium, and the compound shown in the formula III is selected from chlorobis (2, 6-dimethylphenyl) phosphine to obtain a phosphine-nitrogen ligand shown as the following formula L5:
nuclear magnetic data for ligand L5 are as follows: 1H NMR (400MHz, CDCl)3)：7.04～7.43(m，12H)，6.32～6.49(m，8H)，2.34(m，24H).
Oligomerization of ethylene:
before the reaction, a 500ml reaction kettle is heated to 140 ℃, vacuumized for 1.5h and replaced by nitrogen for three times. Cooling to room temperature, replacing ethylene twice, adding 200ml dehydrated and deoxidized solvent cyclohexane and 0.4ml MMAO, then adding 5.5 μmol ligand L5 and 3.5 μmol chromium acetylacetonate (Al/Cr is 200), and introducing 0.5MPa hydrogen and 4.5MPa ethylene in sequence to start reaction when the temperature is constant at 50 ℃. The reaction temperature is 50 ℃, and the reaction time is 50 min. After the reaction is finished, closing the ethylene inlet valve, using ice water bath or quickly cooling to below 5 ℃, slowly releasing pressure, and discharging the reactor to obtain the ethylene oligomerization product.
Example 6
Preparation of phosphine-nitrogen ligand:
the phosphine-nitrogen ligand L6 was prepared according to the method in example 1, except for the following raw materials added and the differences in the amounts of the raw materials shown in Table 1:
the alkoxide is sodium methoxide and the compound of formula III is selected from bis (4-methylphenyl) phosphine chloride to give a phosphine-nitrogen ligand of formula L6:
nuclear magnetic data for ligand L6 are as follows: 1H NMR (400MHz, CDCl)3)：7.23～7.26(m，16H)，6.34～6.59(m，8H)，2.34(m，12H).
Oligomerization of ethylene:
before reaction, a 500ml reaction kettle is heated to 120 ℃, vacuumized for 3 hours and replaced by nitrogen for three times. After the temperature is cooled to room temperature, the ethylene is replaced twice, 200ml of dehydrated and deoxidized solvent methylcyclohexane and 1.6ml of MMAO are added, then 5.5 mu mol of ligand L6 and 3.5 mu mol of trichloro-tris (tetrahydrofuran) chromium (Al/Cr ═ 800) are added, and the reaction is started by sequentially introducing 0.5Mpa of hydrogen and 4.5MPa of ethylene when the temperature is constant at 60 ℃. The reaction temperature is 60 ℃, and the reaction time is 60 min. After the reaction is finished, closing the ethylene inlet valve, using ice water bath or quickly cooling to below 5 ℃, slowly releasing pressure, and discharging the reactor to obtain the ethylene oligomerization product.
Example 7
Preparation of phosphine-nitrogen ligand:
the phosphine-nitrogen ligand L7 was prepared according to the method in example 1, except for the following raw materials added and the differences in the amounts of the raw materials shown in Table 1:
the palladium catalyst is tris (dibenzylideneacetone) dipalladium and the compound shown in the formula III is selected from chlorobis (2-methoxyphenyl) phosphine to obtain a phosphine-nitrogen ligand shown in the following formula L7:
nuclear magnetic data for ligand L7 are as follows: 1H NMR (400MHz, CDCl)3)：7.27～7.34(m，8H)，6.99～7.01(m，8H)，6.31～6.60(m，8H)，3.83(m，12H).
Oligomerization of ethylene:
before reaction, a 500ml reaction kettle is heated to 135 ℃, vacuumized for 3 hours and replaced by nitrogen for three times. Cooling to room temperature, replacing ethylene twice, adding 200ml of dehydrated and deoxidized solvent methylcyclohexane and 1.2ml of MMAO, then adding 4 mu mol of ligand L7 and 3.5 mu mol of chromium acetylacetonate (Al/Cr is 600), and introducing 0.5Mpa of hydrogen and 4.5MPa of ethylene in sequence to start reaction when the temperature is constant at 50 ℃. The reaction temperature is 50 ℃, and the reaction time is 60 min. After the reaction is finished, closing the ethylene inlet valve, using ice water bath or quickly cooling to below 5 ℃, slowly releasing pressure, and discharging the reactor to obtain the ethylene oligomerization product.
Example 8
Preparation of phosphine-nitrogen ligand:
the phosphine-nitrogen ligand L8 was prepared according to the method in example 1, except for the following raw materials added and the differences in the amounts of the raw materials shown in Table 1:
the palladium catalyst is bis (dibenzylideneacetone) palladium, and the compound shown in the formula III is selected from chlorobis (4-methoxyphenyl) phosphine to obtain a phosphine-nitrogen ligand shown in the following formula L8:
nuclear magnetic data for ligand L8 are as follows: 1H NMR (400MHz, CDCl)3)：7.27(m,8H)，6.99(m，8H)，6.38～6.56(m，8H)，3.83(m，12H).
Oligomerization of ethylene:
before the reaction, a 500ml reaction kettle is heated to 155 ℃, vacuumized for 2 hours and replaced by nitrogen for three times. Cooling to room temperature, replacing ethylene twice, adding 200ml of dehydrated and deoxidized solvent methylcyclohexane and 1ml of MMAO, then adding 5.7 mu mol of ligand L8 and 3.5 mu mol of chromium acetylacetonate (Al/Cr is 500), and introducing 0.5Mpa hydrogen and 4.5MPa ethylene in sequence to start reaction when the temperature is constant at 50 ℃. The reaction temperature is 50 ℃, and the reaction time is 60 min. After the reaction is finished, closing the ethylene inlet valve, using ice water bath or quickly cooling to below 5 ℃, slowly releasing pressure, and discharging the reactor to obtain the ethylene oligomerization product.
Example 9
Preparation of phosphine-nitrogen ligand:
the phosphine-nitrogen ligand L9 was prepared according to the method in example 1, except for the following raw materials added and the differences in the amounts of the raw materials shown in Table 1:
the palladium catalyst was dichlorobis (triphenylphosphine) palladium, and the compound of formula III was selected from chlorobis (4-methoxyphenyl) phosphine and chloro (2-fluorophenyl) (phenyl) phosphine (molar ratio 1: 1) to give a phosphine-nitrogen ligand of formula L9 below:
nuclear magnetic data for ligand L9 are as follows: 1H NMR (400MHz, CDCl)3)：7.27～7.36(m，8H)，6.99～7.09(m，8H)，6.30～6.48(m，8H)，3.83(m，6H).
Oligomerization of ethylene:
before reaction, a 500ml reaction kettle is heated to 120 ℃, vacuumized for 3 hours and replaced by nitrogen for three times. Cooling to room temperature, replacing ethylene twice, adding 200ml of dehydrated and deoxidized solvent methylcyclohexane and 1ml of MMAO, then adding 5.8 mu mol of ligand L9 and 3.5 mu mol of chromium acetylacetonate (Al/Cr is 500), and introducing 0.5Mpa hydrogen and 4.5MPa ethylene in sequence to start reaction when the temperature is constant at 50 ℃. The reaction temperature is 50 ℃, and the reaction time is 60 min. After the reaction is finished, closing the ethylene inlet valve, using ice water bath or quickly cooling to below 5 ℃, slowly releasing pressure, and discharging the reactor to obtain the ethylene oligomerization product.
Example 10
Preparation of phosphine-nitrogen ligand:
the phosphine-nitrogen ligand L10 was prepared according to the method in example 1, except for the following raw materials added and the differences in the amounts of the raw materials shown in Table 1:
the palladium catalyst is tetrakis (triphenylphosphine) palladium, and the compound shown in the formula III is selected from chlorobis (4-methoxyphenyl) phosphine and diphenyl phosphonium chloride (molar ratio is 1: 1), so that a phosphine-nitrogen ligand shown in the following formula L10 is obtained:
nuclear magnetic data for ligand L10 are as follows: 1H NMR (400MHz, CDCl)3)：7.38～7.45(m，10H)，6.99～7.27(m，8H)，6.29～6.50(m，8H)，3.83(m，6H).
Oligomerization of ethylene:
before the reaction, a 500ml reaction kettle is heated to 160 ℃, vacuumized for 3 hours and replaced by nitrogen for three times. Cooling to room temperature, replacing ethylene twice, adding 200ml of dehydrated and deoxidized solvent methylcyclohexane and 0.8ml of MMAO, then adding 3.8 mu mol of ligand L10 and 3.5 mu mol of chromium acetylacetonate (Al/Cr is 400), and introducing 0.5Mpa hydrogen and 4.5MPa ethylene in sequence to start reaction when the temperature is constant at 50 ℃. The reaction temperature is 50 ℃, and the reaction time is 60 min. After the reaction is finished, closing the ethylene inlet valve, using ice water bath or quickly cooling to below 5 ℃, slowly releasing pressure, and discharging the reactor to obtain the ethylene oligomerization product.
Comparative example 1
All conditions of the ethylene oligomerization experiment were the same as in example one except that the phosphine-nitrogen ligand used was a commercially available catalyst, iPr-PNP.
TABLE 1 raw material molar ratio and reaction conditions for the preparation of phosphine-nitrogen ligands in the examples
The products were analyzed by GC and tested for catalyst activity and product selectivity in the examples and comparative examples, with the results shown in table 2:
TABLE 2 catalyst activity and product Selectivity in the examples
The results in Table 2 show that the ethylene oligomerization activity can reach 900 kg/(gCr. h), the selectivity of 1-hexene and 1-octene can reach more than 85 wt%, and the polymer selectivity can be as low as less than 0.1 wt%, which are superior to iPr-PNP ligand reported in literature, and have good industrial application prospect.
The above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, several modifications and additions can be made without departing from the method of the present invention, and these modifications and additions should also be regarded as the protection scope of the present invention.
Claims (18)
1. An ethylene oligomerization catalyst is characterized by comprising a phosphine-nitrogen ligand shown in a formula I, a metal chromium compound and an alkyl aluminum cocatalyst;
in the formula I, R1、R2、R3、R4Each independently selected from aryl;
the molar ratio of the metal chromium compound to the phosphine-nitrogen ligand is 1: (0.8-5); the molar ratio of the alkyl aluminum cocatalyst to the metal chromium compound is (50-2000): 1.
2. The catalyst of claim 1, wherein in formula I, R is1、R2、R3、R4Each independently selected from the group consisting of phenyl, benzyl, biphenyl, naphthyl, anthracenyl, ethenyl, propenyl, cyclohexyl, 4-methylcyclohexyl, 4-ethylcyclohexyl, 4-isopropylcyclohexyl, 2-methylphenyl, 4-methylphenyl, 2, 4-dimethylphenyl, 2, 6-dimethylphenyl, 2-ethylphenyl, 4-ethylphenyl, 2, 4-diethylphenyl, 2, 6-diethylphenyl, 2-isopropylphenyl, 4-isopropylphenyl, 2, 4-diisopropylphenyl, 2, 6-diisopropylphenyl, 2-butylphenyl, 4-butylphenyl, 2, 4-dibutylphenyl, 2, 6-dibutylphenyl, 4-methoxyphenyl, o-methoxyphenyl, 4-ethoxyphenyl, o-ethoxyphenyl, 2-fluorophenyl, 3-fluorophenyl or 4-fluorophenyl.
3. The catalyst of claim 1, wherein the molar ratio of the metallic chromium compound to the phosphine-nitrogen ligand is from 1: (1-2); the molar ratio of the alkyl aluminum cocatalyst to the metal chromium compound is (100-1000): 1.
4. The catalyst of claim 1, wherein the metallic chromium compound is one or more of an organic salt and an inorganic salt of metallic chromium.
5. The catalyst of claim 4, wherein the chromium metal compound is one or more of chromium acetylacetonate, chromium chloride, chromium trichlorotris (tetrahydrofuran), chromium III 2-ethylhexanoate, chromium octanoate, chromium hexacarbonyl, chromium benzenetricarbonyl, and chromium diphenyloxide.
6. The catalyst of claim 4 wherein the alkylaluminum cocatalyst is selected from at least one of trimethylaluminum, triethylaluminum, triisobutylaluminum, trioctylaluminum, diethylaluminum monochloride, ethylaluminum dichloride, ethylaluminum sesquichloride, methylaluminoxane, modified methylaluminoxane, ethylaluminoxane.
7. The catalyst of claim 6, wherein the alkylaluminum cocatalyst is selected from methylaluminoxane and/or modified methylaluminoxane.
8. The catalyst according to any one of claims 1 to 7, wherein the phosphine-nitrogen ligand in the formula I is prepared by a method comprising the following steps:
1) dissolving o-phenylenediamine and 1, 2-dibromobenzene under anhydrous and anaerobic conditions, and reacting under the action of alkoxide and palladium catalyst to obtain a compound shown as a formula II, wherein the compound is marked as a product A;
2) under the anhydrous and anaerobic condition, dissolving the product A, dropwise adding triethylamine, then adding a compound in the following formula III, and reacting to obtain the phosphine-nitrogen ligand;
wherein R is1、R2Each independently selected from aryl groups.
9. The catalyst of claim 8, wherein R is1、R2Each independently selected from the group consisting of phenyl, benzyl, biphenyl, naphthyl, anthracenyl, ethenyl, propenyl, cyclohexyl, 4-methylcyclohexyl, 4-ethylcyclohexyl, 4-isopropylcyclohexyl, 2-methylphenyl, 4-methylphenyl, 2, 4-dimethylphenyl, 2, 6-dimethylphenyl, 2-ethylphenyl, 4-ethylphenyl, 2, 4-diethylphenyl, 2, 6-diethylphenyl, 2-isopropylphenyl, 4-isopropylphenyl, 2, 4-diisopropylphenyl, 2, 6-diisopropylphenyl, 2-butylphenyl, 4-butylphenyl, 2, 4-dibutylphenyl, 2, 6-dibutylphenyl, 4-methoxyphenyl, o-methoxyphenyl, 4-ethoxyphenyl, o-ethoxyphenyl, 2-fluorophenyl, 3-fluorophenyl or 4-fluorophenyl.
10. The catalyst according to claim 8, wherein in step 1), the alkoxide is selected from one or more of potassium tert-butoxide, sodium tert-butoxide, potassium methoxide, sodium methoxide, potassium ethoxide, sodium ethoxide, potassium isopropoxide, and sodium isopropoxide.
11. The catalyst according to claim 10, wherein in step 1), the palladium catalyst is selected from one or more of [1,1' -bis (diphenylphosphino) ferrocene ] dichloropalladium, tris (dibenzylideneacetone) dipalladium, bis (dibenzylideneacetone) palladium, dichlorobis (triphenylphosphine) palladium and tetrakis (triphenylphosphine) palladium.
12. The catalyst of claim 8, wherein the reaction in step 1) is carried out for 10-24 h under the reflux condition of the solvent.
13. The catalyst of claim 12, wherein the reaction in step 2) is carried out at-10 to 30 ℃ for 9 to 30 hours.
14. The catalyst of claim 12, wherein in the step 1), the molar ratio of o-phenylenediamine, 1, 2-dibromobenzene, palladium catalyst and alkoxide is 1 (1-2): (0.01-0.5): 1.5-3.5 respectively.
15. The catalyst of claim 14, wherein in the step 2), the molar ratio of the product A to the triethylamine and the compound of formula III is 1 (1.5-3.5) to (1.6-3.6).
16. A process for the oligomerization of ethylene to produce 1-hexene and 1-octene in the presence of a catalyst as claimed in any one of claims 1 to 15.
17. The ethylene oligomerization method of claim 16, comprising the steps of:
heating a reaction kettle to 110-160 ℃ before reaction, vacuumizing for 1-4 h, performing nitrogen replacement, cooling to room temperature, performing ethylene replacement, adding a solvent and an alkyl aluminum cocatalyst, adding a metal chromium compound and a phosphine-nitrogen ligand, introducing 0.1-0.7 MPa hydrogen and 2-7 MPa ethylene in sequence to start reaction after the temperature reaches 35-90 ℃, and reacting for 10-240 min.
18. The ethylene oligomerization method according to claim 17, wherein after the temperature reaches 40-70 ℃, 0.1-0.7 MPa of hydrogen and 2-7 MPa of ethylene are sequentially introduced for reaction, and the reaction time is 20-100 min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010703255.XA CN111774098B (en) | 2020-07-21 | 2020-07-21 | Ethylene oligomerization catalyst system, preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010703255.XA CN111774098B (en) | 2020-07-21 | 2020-07-21 | Ethylene oligomerization catalyst system, preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111774098A CN111774098A (en) | 2020-10-16 |
| CN111774098B true CN111774098B (en) | 2022-04-22 |
Family
ID=72763674
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010703255.XA Active CN111774098B (en) | 2020-07-21 | 2020-07-21 | Ethylene oligomerization catalyst system, preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111774098B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113354683B (en) * | 2021-06-21 | 2023-05-30 | 万华化学集团股份有限公司 | Biphosphine ligand, preparation method and application thereof |
| CN113372389B (en) * | 2021-06-29 | 2023-03-03 | 万华化学集团股份有限公司 | Phosphine-nitrogen ligand, preparation method thereof, ethylene oligomerization ternary catalyst system and application |
| CN114920866B (en) * | 2022-05-23 | 2023-07-14 | 万华化学集团股份有限公司 | Preparation method of polyolefin thermoplastic elastomer |
| CN114988980B (en) * | 2022-06-15 | 2023-05-30 | 万华化学集团股份有限公司 | Method for producing 1-octene by high-activity oligomerization of ethylene |
| CN114956939B (en) * | 2022-07-01 | 2024-02-02 | 万华化学集团股份有限公司 | Ethylene oligomerization regulation and control method |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101274290B (en) * | 2007-03-30 | 2011-04-20 | 中国石油天然气股份有限公司 | Late transition metal catalyst and preparation method and application thereof |
| CA2747501C (en) * | 2011-07-26 | 2018-01-23 | Nova Chemicals Corporation | "bulk" ethylene oligomerization |
| CN104511311B (en) * | 2013-09-30 | 2017-07-07 | 华东理工大学 | A kind of ethylene trimer of high selectivity, four poly- catalyst systems and its application method |
| CN106853378B (en) * | 2015-12-08 | 2019-11-12 | 中国科学院大连化学物理研究所 | The ternary catalyst systems of the ligand of structural framework containing PNN and its application |
| CN106853379B (en) * | 2015-12-08 | 2020-01-07 | 中国科学院大连化学物理研究所 | Three-way catalyst system and application thereof in selective oligomerization of ethylene |
| CN108097322B (en) * | 2017-12-11 | 2020-11-06 | 天津科技大学 | Catalyst system for selective oligomerization of ethylene and ethylene oligomerization reaction method |
-
2020
- 2020-07-21 CN CN202010703255.XA patent/CN111774098B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN111774098A (en) | 2020-10-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111774098B (en) | Ethylene oligomerization catalyst system, preparation method and application thereof | |
| CN113372389B (en) | Phosphine-nitrogen ligand, preparation method thereof, ethylene oligomerization ternary catalyst system and application | |
| RU2541528C2 (en) | Highly active and highly selective catalyst of ethylene oligomerisation and method of obtaining hexene or octene with application of said catalyst | |
| CN107282126B (en) | Ethylene tetramerization catalyst composition and application thereof | |
| KR20170045736A (en) | Ligand based chromium catalyst and application in catalyzing ethylene oligomerization | |
| CN111349116B (en) | Bipyridine structure ligand, preparation method thereof, catalytic system based on bipyridine structure and application of catalytic system in ethylene oligomerization | |
| CN111349115B (en) | PNNP structural ligand, preparation method thereof, ethylene oligomerization catalyst system and application thereof | |
| CN114789067B (en) | Ethylene selective oligomerization catalyst composition and preparation method thereof | |
| CN109331880B (en) | Phosphine nitrogen coordination type metal catalyst and application thereof | |
| CN112916046B (en) | Three-way catalyst system and application thereof in ethylene oligomerization reaction | |
| KR20190063840A (en) | Process for preparing oligomer using olefin | |
| CN112473738B (en) | Ethylene oligomerization catalyst system and preparation method and application thereof | |
| CN111774097B (en) | Ethylene oligomerization catalyst system and application thereof | |
| CN114315905B (en) | Preparation of PCPN ligand, ethylene oligomerization catalyst and application thereof | |
| CN113402554B (en) | PNSiNP ligand and preparation method thereof, ethylene oligomerization catalyst and application thereof | |
| CN111715299B (en) | Boron salt complex catalyst, preparation method and application thereof in ethylene oligomerization | |
| EP3689844A1 (en) | Method for olefin oligomerization | |
| CN114160199B (en) | Catalytic system for selectively trimerizing and tetramerizing ethylene and application thereof | |
| CN110801864B (en) | Ethylene tetramerization catalyst composition and application thereof | |
| CN105457679B (en) | A kind of ethylene oligomerization carbon monoxide-olefin polymeric and its application | |
| CN114011469A (en) | Catalyst composition for ethylene oligomerization | |
| CN116899622A (en) | High-selectivity catalyst for ethylene oligomerization and application thereof | |
| CN114933613B (en) | Preparation of PNNP ligand, ethylene oligomerization catalyst and application thereof | |
| CN109956978B (en) | Phenanthrenequinone-based asymmetric alpha-diimine nickel catalyst and preparation method and application thereof | |
| CN114797989B (en) | Supported catalyst and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |