CN114797970B - Ethylene oligomerization modification auxiliary agent and homogeneous catalysis system thereof - Google Patents
Ethylene oligomerization modification auxiliary agent and homogeneous catalysis system thereof Download PDFInfo
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- CN114797970B CN114797970B CN202210449469.8A CN202210449469A CN114797970B CN 114797970 B CN114797970 B CN 114797970B CN 202210449469 A CN202210449469 A CN 202210449469A CN 114797970 B CN114797970 B CN 114797970B
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- oligomerization
- isobutyl
- butyl
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- 238000006384 oligomerization reaction Methods 0.000 title claims abstract description 113
- 230000004048 modification Effects 0.000 title claims abstract description 46
- 238000012986 modification Methods 0.000 title claims abstract description 46
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 239000005977 Ethylene Substances 0.000 title claims abstract description 39
- 238000007172 homogeneous catalysis Methods 0.000 title abstract description 18
- 239000012752 auxiliary agent Substances 0.000 title abstract description 13
- 239000003054 catalyst Substances 0.000 claims abstract description 63
- 239000002904 solvent Substances 0.000 claims abstract description 35
- 150000004696 coordination complex Chemical class 0.000 claims abstract description 4
- -1 siloxane organic compound Chemical class 0.000 claims description 447
- 238000006116 polymerization reaction Methods 0.000 claims description 42
- 238000006243 chemical reaction Methods 0.000 claims description 35
- 239000012456 homogeneous solution Substances 0.000 claims description 30
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 24
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 23
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 22
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 20
- 125000000962 organic group Chemical group 0.000 claims description 20
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 20
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 20
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 claims description 19
- 125000004973 1-butenyl group Chemical group C(=CCC)* 0.000 claims description 18
- 125000006433 1-ethyl cyclopropyl group Chemical group [H]C([H])([H])C([H])([H])C1(*)C([H])([H])C1([H])[H] 0.000 claims description 18
- 125000006432 1-methyl cyclopropyl group Chemical group [H]C([H])([H])C1(*)C([H])([H])C1([H])[H] 0.000 claims description 18
- 125000004974 2-butenyl group Chemical group C(C=CC)* 0.000 claims description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 18
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 18
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 claims description 18
- 125000003860 C1-C20 alkoxy group Chemical group 0.000 claims description 17
- 239000002815 homogeneous catalyst Substances 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 17
- 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 15
- 238000000034 method Methods 0.000 claims description 15
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 14
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 14
- 239000012535 impurity Substances 0.000 claims description 13
- 239000003446 ligand Substances 0.000 claims description 13
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- 125000002723 alicyclic group Chemical group 0.000 claims description 12
- 239000011261 inert gas Substances 0.000 claims description 10
- 230000035484 reaction time Effects 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 229920006395 saturated elastomer Polymers 0.000 claims description 9
- 239000004215 Carbon black (E152) Substances 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 229930195733 hydrocarbon Natural products 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 8
- 125000003545 alkoxy group Chemical group 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 6
- 125000004104 aryloxy group Chemical group 0.000 claims description 6
- 125000004122 cyclic group Chemical group 0.000 claims description 5
- 150000002894 organic compounds Chemical class 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- 239000005662 Paraffin oil Substances 0.000 claims description 4
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 150000001924 cycloalkanes Chemical class 0.000 claims description 4
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 4
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 claims description 3
- 125000005234 alkyl aluminium group Chemical group 0.000 claims description 2
- 125000001997 phenyl group Chemical class [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims 1
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 abstract description 26
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 abstract description 26
- 230000003197 catalytic effect Effects 0.000 abstract description 19
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 abstract description 13
- 239000007790 solid phase Substances 0.000 abstract description 13
- 230000037048 polymerization activity Effects 0.000 abstract description 9
- 150000001336 alkenes Chemical class 0.000 abstract description 5
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 4
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 52
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 34
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 15
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 12
- 238000004458 analytical method Methods 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- 125000004429 atom Chemical group 0.000 description 9
- 239000002184 metal Substances 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 7
- 239000004711 α-olefin Substances 0.000 description 7
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- QNLZIZAQLLYXTC-UHFFFAOYSA-N 1,2-dimethylnaphthalene Chemical compound C1=CC=CC2=C(C)C(C)=CC=C21 QNLZIZAQLLYXTC-UHFFFAOYSA-N 0.000 description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 3
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- KVZJLSYJROEPSQ-UHFFFAOYSA-N 1,2-dimethylcyclohexane Chemical compound CC1CCCCC1C KVZJLSYJROEPSQ-UHFFFAOYSA-N 0.000 description 2
- AFZZYIJIWUTJFO-UHFFFAOYSA-N 1,3-diethylbenzene Chemical compound CCC1=CC=CC(CC)=C1 AFZZYIJIWUTJFO-UHFFFAOYSA-N 0.000 description 2
- WJUNKQFLRQGJAR-UHFFFAOYSA-N 1,3-diethylcyclohexane Chemical compound CCC1CCCC(CC)C1 WJUNKQFLRQGJAR-UHFFFAOYSA-N 0.000 description 2
- QHJMFSMPSZREIF-UHFFFAOYSA-N 1,3-dimethylnaphthalene Chemical compound C1=CC=CC2=CC(C)=CC(C)=C21 QHJMFSMPSZREIF-UHFFFAOYSA-N 0.000 description 2
- KTCNWORLNAKRDZ-UHFFFAOYSA-N 1-butan-2-yl-3-ethylbenzene Chemical compound CCC(C)C1=CC=CC(CC)=C1 KTCNWORLNAKRDZ-UHFFFAOYSA-N 0.000 description 2
- QPUYECUOLPXSFR-UHFFFAOYSA-N 1-methylnaphthalene Chemical compound C1=CC=C2C(C)=CC=CC2=C1 QPUYECUOLPXSFR-UHFFFAOYSA-N 0.000 description 2
- RJTJVVYSTUQWNI-UHFFFAOYSA-N 2-ethylnaphthalene Chemical compound C1=CC=CC2=CC(CC)=CC=C21 RJTJVVYSTUQWNI-UHFFFAOYSA-N 0.000 description 2
- GXDHCNNESPLIKD-UHFFFAOYSA-N 2-methylhexane Chemical compound CCCCC(C)C GXDHCNNESPLIKD-UHFFFAOYSA-N 0.000 description 2
- VLJXXKKOSFGPHI-UHFFFAOYSA-N 3-methylhexane Chemical compound CCCC(C)CC VLJXXKKOSFGPHI-UHFFFAOYSA-N 0.000 description 2
- PFEOZHBOMNWTJB-UHFFFAOYSA-N 3-methylpentane Chemical compound CCC(C)CC PFEOZHBOMNWTJB-UHFFFAOYSA-N 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 150000001555 benzenes Chemical class 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- 230000009849 deactivation Effects 0.000 description 2
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- XPBBUZJBQWWFFJ-UHFFFAOYSA-N fluorosilane Chemical class [SiH3]F XPBBUZJBQWWFFJ-UHFFFAOYSA-N 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical group 0.000 description 2
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 2
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical compound CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methyl-cyclopentane Natural products CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 2
- CRSOQBOWXPBRES-UHFFFAOYSA-N neopentane Chemical compound CC(C)(C)C CRSOQBOWXPBRES-UHFFFAOYSA-N 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- ODLMAHJVESYWTB-UHFFFAOYSA-N propylbenzene Chemical compound CCCC1=CC=CC=C1 ODLMAHJVESYWTB-UHFFFAOYSA-N 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- RUUVWUNHERVOAY-RKDXNWHRSA-N (1r,3r)-1,3-diethylcyclopentane Chemical compound CC[C@@H]1CC[C@@H](CC)C1 RUUVWUNHERVOAY-RKDXNWHRSA-N 0.000 description 1
- GLARPVPCYBPUQZ-UHFFFAOYSA-N 1,2-diethylcycloheptane Chemical compound CCC1CCCCCC1CC GLARPVPCYBPUQZ-UHFFFAOYSA-N 0.000 description 1
- GQDRGBVPGCYTNU-UHFFFAOYSA-N 1,2-diethylcyclohexane Chemical compound CCC1CCCCC1CC GQDRGBVPGCYTNU-UHFFFAOYSA-N 0.000 description 1
- JKMYLSLBFNMSFP-UHFFFAOYSA-N 1,2-diethylcyclopentane Chemical compound CCC1CCCC1CC JKMYLSLBFNMSFP-UHFFFAOYSA-N 0.000 description 1
- UUCHLIAGHZJJER-UHFFFAOYSA-N 1,2-diethylnaphthalene Chemical compound C1=CC=CC2=C(CC)C(CC)=CC=C21 UUCHLIAGHZJJER-UHFFFAOYSA-N 0.000 description 1
- CLYDEJQPKBFLJW-UHFFFAOYSA-N 1,2-dimethylcycloheptane Chemical compound CC1CCCCCC1C CLYDEJQPKBFLJW-UHFFFAOYSA-N 0.000 description 1
- RIRARCHMRDHZAR-UHFFFAOYSA-N 1,2-dimethylcyclopentane Chemical compound CC1CCCC1C RIRARCHMRDHZAR-UHFFFAOYSA-N 0.000 description 1
- ABNVRGNXKSTEOK-UHFFFAOYSA-N 1,2-dipropylcyclohexane Chemical compound CCCC1CCCCC1CCC ABNVRGNXKSTEOK-UHFFFAOYSA-N 0.000 description 1
- DMNMTOCJARNNNH-UHFFFAOYSA-N 1,2-dipropylcyclopentane Chemical compound CCCC1CCCC1CCC DMNMTOCJARNNNH-UHFFFAOYSA-N 0.000 description 1
- GTSQJWPYFMLHCU-UHFFFAOYSA-N 1,3-diethylcycloheptane Chemical compound CCC1CCCCC(CC)C1 GTSQJWPYFMLHCU-UHFFFAOYSA-N 0.000 description 1
- MJFZQQIJTPPNTK-UHFFFAOYSA-N 1,3-diethylnaphthalene Chemical compound C1=CC=CC2=CC(CC)=CC(CC)=C21 MJFZQQIJTPPNTK-UHFFFAOYSA-N 0.000 description 1
- PTWXFJWKUMXFLI-UHFFFAOYSA-N 1,3-dimethylcycloheptane Chemical compound CC1CCCCC(C)C1 PTWXFJWKUMXFLI-UHFFFAOYSA-N 0.000 description 1
- XAZKFISIRYLAEE-UHFFFAOYSA-N 1,3-dimethylcyclopentane Chemical compound CC1CCC(C)C1 XAZKFISIRYLAEE-UHFFFAOYSA-N 0.000 description 1
- HBEFNVDTQZBZBF-UHFFFAOYSA-N 1,3-dipropylcyclopentane Chemical compound CCCC1CCC(CCC)C1 HBEFNVDTQZBZBF-UHFFFAOYSA-N 0.000 description 1
- HYFLWBNQFMXCPA-UHFFFAOYSA-N 1-ethyl-2-methylbenzene Chemical compound CCC1=CC=CC=C1C HYFLWBNQFMXCPA-UHFFFAOYSA-N 0.000 description 1
- ZMXIYERNXPIYFR-UHFFFAOYSA-N 1-ethylnaphthalene Chemical compound C1=CC=C2C(CC)=CC=CC2=C1 ZMXIYERNXPIYFR-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- IFTRQJLVEBNKJK-UHFFFAOYSA-N Ethylcyclopentane Chemical compound CCC1CCCC1 IFTRQJLVEBNKJK-UHFFFAOYSA-N 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- SHOVVTSKTTYFGP-UHFFFAOYSA-L butylaluminum(2+);dichloride Chemical compound CCCC[Al](Cl)Cl SHOVVTSKTTYFGP-UHFFFAOYSA-L 0.000 description 1
- OCKPCBLVNKHBMX-UHFFFAOYSA-N butylbenzene Chemical compound CCCCC1=CC=CC=C1 OCKPCBLVNKHBMX-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229910000071 diazene Inorganic materials 0.000 description 1
- VJRUISVXILMZSL-UHFFFAOYSA-M dibutylalumanylium;chloride Chemical compound CCCC[Al](Cl)CCCC VJRUISVXILMZSL-UHFFFAOYSA-M 0.000 description 1
- RFUDQCRVCDXBGK-UHFFFAOYSA-L dichloro(propyl)alumane Chemical compound [Cl-].[Cl-].CCC[Al+2] RFUDQCRVCDXBGK-UHFFFAOYSA-L 0.000 description 1
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 1
- JGHYBJVUQGTEEB-UHFFFAOYSA-M dimethylalumanylium;chloride Chemical compound C[Al](C)Cl JGHYBJVUQGTEEB-UHFFFAOYSA-M 0.000 description 1
- QRQUTSPLBBZERR-UHFFFAOYSA-M dioctylalumanylium;chloride Chemical compound CCCCCCCC[Al](Cl)CCCCCCCC QRQUTSPLBBZERR-UHFFFAOYSA-M 0.000 description 1
- ZMXPNWBFRPIZFV-UHFFFAOYSA-M dipropylalumanylium;chloride Chemical compound [Cl-].CCC[Al+]CCC ZMXPNWBFRPIZFV-UHFFFAOYSA-M 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- UAIZDWNSWGTKFZ-UHFFFAOYSA-L ethylaluminum(2+);dichloride Chemical compound CC[Al](Cl)Cl UAIZDWNSWGTKFZ-UHFFFAOYSA-L 0.000 description 1
- ITZHTNFXLDFAPB-UHFFFAOYSA-N ethylcycloheptane Chemical compound CCC1CCCCCC1 ITZHTNFXLDFAPB-UHFFFAOYSA-N 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 238000010813 internal standard method Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- YSTQWZZQKCCBAY-UHFFFAOYSA-L methylaluminum(2+);dichloride Chemical compound C[Al](Cl)Cl YSTQWZZQKCCBAY-UHFFFAOYSA-L 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methylcycloheptane Chemical compound CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- RBLGTYCOUOIUNY-UHFFFAOYSA-L octylaluminum(2+);dichloride Chemical compound CCCCCCCC[Al](Cl)Cl RBLGTYCOUOIUNY-UHFFFAOYSA-L 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- CJZNZUMUPIJOMM-UHFFFAOYSA-N propylcycloheptane Chemical compound CCCC1CCCCCC1 CJZNZUMUPIJOMM-UHFFFAOYSA-N 0.000 description 1
- DEDZSLCZHWTGOR-UHFFFAOYSA-N propylcyclohexane Chemical compound CCCC1CCCCC1 DEDZSLCZHWTGOR-UHFFFAOYSA-N 0.000 description 1
- KDIAMAVWIJYWHN-UHFFFAOYSA-N propylcyclopentane Chemical compound CCCC1CCCC1 KDIAMAVWIJYWHN-UHFFFAOYSA-N 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000013341 scale-up Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- SQBBHCOIQXKPHL-UHFFFAOYSA-N tributylalumane Chemical compound CCCC[Al](CCCC)CCCC SQBBHCOIQXKPHL-UHFFFAOYSA-N 0.000 description 1
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 1
- 238000005829 trimerization reaction Methods 0.000 description 1
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 1
- LFXVBWRMVZPLFK-UHFFFAOYSA-N trioctylalumane Chemical compound CCCCCCCC[Al](CCCCCCCC)CCCCCCCC LFXVBWRMVZPLFK-UHFFFAOYSA-N 0.000 description 1
- CNWZYDSEVLFSMS-UHFFFAOYSA-N tripropylalumane Chemical compound CCC[Al](CCC)CCC CNWZYDSEVLFSMS-UHFFFAOYSA-N 0.000 description 1
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0272—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255
- B01J31/0274—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255 containing silicon
-
- 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
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
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Abstract
The invention discloses an ethylene oligomerization modified auxiliary agent and an olefin oligomerization homogeneous catalysis system thereof, wherein the catalysis system comprises: the component A is a main catalyst component; the component B is a cocatalyst component; the component C is a solvent component, and the component D is an oligomerization modification auxiliary component. The oligomerization modifying adjunct component D may be present in coordination complex or supramolecular assembly or covalent bond with the procatalyst component A. The oligomerization modification auxiliary component D can obviously improve the polymerization activity and high-temperature stability of a catalytic system, simultaneously improve the product selectivity and the total yield of 1-hexene and 1-octene, and reduce the content of solid-phase products represented by oligomerization products. In particular, the oligomerization modification auxiliary component D can also obviously reduce the consumption of the cocatalyst, and has higher technical economy.
Description
Technical Field
The technology relates to the field of olefin polymerization reaction and catalysts, in particular to an ethylene oligomerization modified auxiliary agent and a homogeneous catalysis system for olefin oligomerization. The catalyst system is especially suitable for olefin oligomerization, has excellent polymerization activity in oligomerization, can obviously improve the total yield of 1-hexene and 1-octene, simultaneously obviously reduces the content of solid phase products, and improves the selectivity of 1-hexene and 1-octene. In particular, the amount of cocatalyst is also significantly reduced due to the addition of the oligomerization modification auxiliary.
Background
The linear alpha-olefin refers to linear olefins with double bonds at the terminal of molecules and more than C4, and is an important petrochemical raw material with huge demand. Wherein C is 4 ～C 24 The linear alpha-olefin of (C) has wide application in the preparation of low-density polyethylene, high-grade detergent, higher alcohol, higher PAO lubricating oil, surfactant, oil additive and other fields. At present, ethylene oligomerization processes are producing linear alpha-olefins, especially C 4 ～C 24 The most dominant and promising approach to linear alpha-olefins.
Chinese patent CN201610124178.6 discloses a Cr-based catalyst using a molar ratio of promoter methylaluminoxane to Cr-based catalyst of up to 20-1500:1. Literature alpha-diimine nickel chloride/MAO catalyzed ethylene oligomerization [ J ]]Daqing oil institute report, 2003 (04): 36-38+119 reports a MAO cocatalyst catalyzed nickel-based catalyst system with polymerization activity up to 6X 10 5 g/(mol Ni h), the selectivity of alpha-olefin can reach 82.96%, and the addition amount of MAO is 100-800 times of that of the catalyst. Therefore, the ethylene oligomerization catalyst system has the problems of large MAO consumption, low activity and low selectivity of the reaction system. Because MAO structure is complicated, production technology difficulty is big, MMAO's production is monopolized by foreign company completely, only few companies such as Albemarle and Akzo Nobel produce internationally, so its market price is high. The industrial use amount of MMAO is large, the production cost is high, and the MMAO becomes an important factor for restricting the development of ethylene oligomerization in China; in addition, the catalyst system has more oligomers, isomers and solid-phase products in the oligomerization process, and is easy to block pipelines in the material conveying process, so that unnecessary shutdown and maintenance are caused. In addition, the presence of oligomers, isomers, solid phase products also adds energy and cost to the subsequent product separation. Therefore, the byproducts also become a major obstacle to the industrialization of the oligomerization reaction of the catalyst.
In summary, the current field of ethylene oligomerization for preparing linear alpha-olefins has the following disadvantages in terms of catalysts: (1) The activity of the catalyst is low, so that the impurity and ash content in the product are high, and the quality of the final product is affected; (2) Yields and selectivities of 1-hexene and 1-octene (i.e., ethylene trimerization and tetramerization) are low; (3) The consumption of the cocatalyst is mostly expensive methylaluminoxane or modified methylaluminoxane, and the consumption is extremely large, so that the cost is high, the ash content of the cocatalyst in the product is higher, and the economical efficiency of the product is reduced; (4) The solid phase products in the products are more, which can cause the phenomenon of reactor sticking or pipeline blockage.
In view of the above problems, the inventors have studied. By introducing an oligomerization modification auxiliary agent into the system, a more suitable and efficient catalyst system is preferred, the consumption of a cocatalyst is reduced, meanwhile, the wall sticking and pipeline blockage of a reactor can be prevented, the frequency of stopping and cleaning a kettle is reduced, the product quality is improved, a target product is produced more effectively and economically, and the problems that the selectivity of the linear alpha-olefin (1-hexene and 1-octene) is lower and the oligomer, the isomer and the solid-phase product are more are solved.
Disclosure of Invention
In view of the above shortcomings of the prior art, one of the purposes of the present invention is to provide an ethylene oligomerization modifying additive. The ethylene oligomerization modification auxiliary agent is one or more selected from siloxane organic compounds, silazane organic compounds, ether compounds and fluorosilane compounds, the main structure of the ethylene oligomerization modification auxiliary agent is one or more selected from cage-shaped, semi-cage-shaped and star-shaped structures, and the organic groups in the molecular chain of the ethylene oligomerization modification auxiliary agent are selected from C 1 -C 20 Aliphatic hydrocarbon radicals, C 1 -C 20 Alkoxy, C 1 -C 20 Alicyclic group, C 1 -C 20 Alicyclic alkoxy group, C 1 -C 20 Aryloxy or C of (2) 1 -C 20 One or more of the aromatic hydrocarbon groups of (a).
The introduction of the oligomerization modification auxiliary agent can play a role in stabilizing the active center of the main catalyst, and the introduction of the oligomerization modification auxiliary agent can increase the steric hindrance of the ligand structure, further prevent the attack of small molecules and long-chain molecules of impurities on the active center and inhibit the deactivation reaction. The long chain molecules are difficult to coordinate and insert with the active center, so that the content of the oligomer and the high polymer is obviously reduced, and the phenomena of reactor wall sticking, pipeline blockage and the like which are easy to occur in the subsequent industrial application stage are reduced.
It is another object of the present invention to provide a homogeneous catalytic system for oligomerization of ethylene which allows to significantly reduce the amount of expensive cocatalysts. After the oligomerization modification auxiliary agent is introduced, the consumption of the cocatalyst can be reduced by 20-90%, and the method has outstanding technical economy.
According to one aspect of the invention, the invention provides a homogeneous catalytic system for oligomerization of ethylene, comprising the following components: a main catalyst component A; a cocatalyst component B; a solvent component C and an oligomerization modification auxiliary component D; wherein the oligomerization modification auxiliary component D is one or more selected from siloxane organic compounds, silazane organic compounds, ether compounds and fluorosilane compounds, the main structure of the oligomerization modification auxiliary component D is one or more selected from cage-shaped, semi-cage-shaped and star-shaped structures, and the organic groups in the molecular chain of the oligomerization modification auxiliary component D are selected from C 1 -C 20 Aliphatic hydrocarbon radicals, C 1 -C 20 Alkoxy, C 1 -C 20 Alicyclic group, C 1 -C 20 Alicyclic alkoxy group, C 1 -C 20 Aryloxy or C of (2) 1 -C 20 One or more of the aromatic hydrocarbon groups of (a).
As a preferred scheme of the invention, the configuration method of the homogeneous catalysis system is as follows: the oligomerization modification auxiliary component D is dissolved in the solvent component C to form a homogeneous solution, the homogeneous solution is kept in a continuous stirring state for at least 30min, a certain amount of main catalyst component A is added into the homogeneous solution and dissolved, the main catalyst component A and the oligomerization modification auxiliary component D exist in a coordination complex or supermolecule assembly or covalent bond form in a certain proportion, the homogeneous solution component needs to be continuously stirred for at least 100min, the configuration operation is operated in an inert gas environment, and the obtained homogeneous catalyst system S is reserved for oligomerization for later use.
As a preferred scheme of the invention, the ethylene oligomerization step based on the homogeneous catalysis system is as follows: the oligomerization reaction kettle is baked for at least 120min under the vacuum and at least 100 ℃, high-purity nitrogen or argon is used for switching for 3 times at least during the period, when the reaction kettle is reduced to a reaction temperature T, a proper amount of polymerization solvent E is added, a certain amount of cocatalyst component B is added and stirred for at least 5min to remove impurities in the reaction kettle, then a certain amount of configured homogeneous catalysis system S is added, ethylene is immediately introduced to start oligomerization reaction, the polymerization pressure is P, and after the reaction time T, a polymerization product is discharged and analyzed.
As a preferable scheme of the invention, the addition of the oligomerization modification auxiliary component D can obviously improve the catalytic activity of the main catalyst by at least 10%, the total yield of 1-hexene and 1-octene is improved by 1-20%, the selectivity of 1-hexene in the C6 component is improved by 0.5-10%, and the selectivity of 1-octene in the C8 component is improved by 0.5-10%.
As a preferred embodiment of the present invention, the oligomerization modifying auxiliary component D may be one or more of the following siloxane-based organic compound general formulae (I), (II), (III):
x, y, z are integers from 0 to 20;
m is C or Si;
R 1 ，R 2 and R is 3 Is an organic group of the same or different structure, which may be present simultaneously or not (i.e. may be H atom), and is selected from the group consisting of C1-C20 aliphatic hydrocarbon group, C1-C20 alkoxy group, C1-C20 alicyclic group, C1-C20 aryloxy group or C1-C20 aromatic hydrocarbon group, preferably methyl, ethyl, propyl, isopropyl, 1-butyl, 2-butyl, 1-isobutyl, 2-isobutyl, propenyl, 1-butenyl, 2-butenyl, 1-methylpropenyl, cyclopropyl, 1-methylcyclopropyl, 2-methylcyclopropyl, 1-ethylcyclopropyl, 2-ethylcyclopropyl, 1-propylcyclopropyl, cyclobutyl, 1-methylcyclobutyl, 2-methylcyclobutyl, 1-ethylcyclobutyl, 2-ethylcyclobutyl, 1-propylcyclobutyl, 2-propylcyclopentyl, cyclopentyl, 1-methylcyclopentyl, 2-ethylcyclopentyl, 1-ethylcyclopentyl, 2-ethylcyclopentyl, hexylcyclopentyl, 2-propylcyclopentyl, and 2-propylcyclopentyl At least one of a group, 1-methylcyclohexyl, 2-methylcyclohexyl, 1-ethylcyclohexyl, 2-ethylcyclohexyl, 1-propylcyclohexyl, 2-propylcyclohexyl; r is R 4 ，R 5 And R is 6 Is an organic group of the same or different structure, which may be present simultaneously or not (i.e., may be an H atom), selected from the group consisting of a C1-C20 aliphatic hydrocarbon group, a C1-C20 alkoxy group, a C1-C20 alicyclic alkoxy group, a C1-C20 aryloxy group, and a C1-C20 aromatic hydrocarbon group, preferably at least one of methyl, ethyl, propyl, isopropyl, 1-butyl, 2-butyl, 1-isobutyl, 2-isobutyl, propenyl, 1-butenyl, 2-butenyl, 1-methylpropenyl, cyclopropyl, 1-methylcyclopropyl, 2-methylcyclopropyl, 1-ethylcyclopropyl, 2-ethylcyclopropyl, 1-propylcyclopropyl, cyclobutyl, 1-methylcyclobutyl, 2-methylcyclobutyl, 1-ethylcyclobutyl, 2-ethylcyclobutyl, 1-propylcyclobutyl, 2-propylcyclobutyl, cyclopentyl, 1-methylcyclopentyl, 2-methylcyclopentyl, 1-ethylcyclopentyl, 2-ethylcyclopentyl, 1-propylcyclopentyl, 2-propylcyclopentyl, cyclohexyl, 1-methylcyclohexyl, 2-methylcyclohexyl, 1-ethylcyclohexyl, 2-ethylcyclohexyl, 1-propylcyclohexyl, 2-propylcyclohexyl; r is R 7 ，R 8 And R is 9 Is an organic group of the same or different structure, which may be present simultaneously or not (i.e. may be H atom), and is selected from the group consisting of C1-C20 aliphatic hydrocarbon group, C1-C20 alkoxy group, C1-C20 alicyclic group, C1-C20 aryloxy group or C1-C20 aromatic hydrocarbon group, preferably methyl, ethyl, propyl, isopropyl, 1-butyl, 2-butyl, 1-isobutyl, 2-isobutyl, propenyl, 1-butenyl, 2-butenyl, 1-methylpropenyl, cyclopropyl, 1-methylcyclopropyl, 2-methylcyclopropyl, 1-ethylcyclopropyl, 2-ethylcyclopropyl, 1-propylcyclopropyl, cyclobutyl, 1-methylcyclobutyl, 2-methylcyclobutyl, 1-ethylcyclobutyl, 2-ethylcyclobutyl, 1-propylcyclobutyl, 2-propylcyclopentyl, cyclopentyl, 1-methylcyclopentyl, 2-ethylcyclopentyl, 1-ethylcyclohexyl, 2-methylcyclohexyl, 1-methylcyclohexylAt least one of a group, a 2-ethylcyclohexyl group, a 1-propylcyclohexyl group and a 2-propylcyclohexyl group.
R 1 ，R 2 ，R 3 ，R 4 ，R 5 ，R 6 ，R 7 And R is 8 Is an organic group of the same or different structure, which may be present simultaneously or not (i.e., may be an H atom), selected from the group consisting of a C1-C20 aliphatic hydrocarbon group, a C1-C20 alkoxy group, a C1-C20 alicyclic alkoxy group, a C1-C20 aryloxy group, and a C1-C20 aromatic hydrocarbon group, preferably at least one of methyl, ethyl, propyl, isopropyl, 1-butyl, 2-butyl, 1-isobutyl, 2-isobutyl, propenyl, 1-butenyl, 2-butenyl, 1-methylpropenyl, cyclopropyl, 1-methylcyclopropyl, 2-methylcyclopropyl, 1-ethylcyclopropyl, 2-ethylcyclopropyl, 1-propylcyclopropyl, cyclobutyl, 1-methylcyclobutyl, 2-methylcyclobutyl, 1-ethylcyclobutyl, 2-ethylcyclobutyl, 1-propylcyclobutyl, 2-propylcyclobutyl, cyclopentyl, 1-methylcyclopentyl, 2-methylcyclopentyl, 1-ethylcyclopentyl, 2-ethylcyclopentyl, 1-propylcyclopentyl, 2-propylcyclopentyl, cyclohexyl, 1-methylcyclohexyl, 2-methylcyclohexyl, 1-ethylcyclohexyl, 2-ethylcyclohexyl, 1-propylcyclohexyl and 2-propylcyclohexyl.
n is an integer.
The oligomerization modification auxiliary component D can also be one of the following general formulas (IV), (V) and (VI) of silazane organic compounds:
n is an integer of 0 to 30.
R 1 ，R 2 And R is 3 Is an organic group of the same or different structure, which may be present simultaneously or not (i.e., may be an H atom), selected from the group consisting of a C1-C20 aliphatic hydrocarbon group, a C1-C20 alkoxy group, a C1-C20 alicyclic alkoxy group, a C1-C20 aryloxy group, and a C1-C20 aromatic hydrocarbon group, preferably at least one of methyl, ethyl, propyl, isopropyl, 1-butyl, 2-butyl, 1-isobutyl, 2-isobutyl, propenyl, 1-butenyl, 2-butenyl, 1-methylpropenyl, cyclopropyl, 1-methylcyclopropyl, 2-methylcyclopropyl, 1-ethylcyclopropyl, 2-ethylcyclopropyl, 1-propylcyclopropyl, cyclobutyl, 1-methylcyclobutyl, 2-methylcyclobutyl, 1-ethylcyclobutyl, 2-ethylcyclobutyl, 1-propylcyclobutyl, 2-propylcyclobutyl, cyclopentyl, 1-methylcyclopentyl, 2-methylcyclopentyl, 1-ethylcyclopentyl, 2-ethylcyclopentyl, 1-propylcyclopentyl, 2-propylcyclopentyl, cyclohexyl, 1-methylcyclohexyl, 2-methylcyclohexyl, 1-ethylcyclohexyl, 2-ethylcyclohexyl, 1-propylcyclohexyl and 2-propylcyclohexyl.
m and n are integers from 0 to 20.
R 1 ，R 2 And R is 3 Is an organic group of the same or different structure, which may be present simultaneously or not (i.e., may be an H atom), and is selected from the group consisting of a C1-C20 aliphatic hydrocarbon group, a C1-C20 alkoxy group, a C1-C20 alicyclic alkoxy group, a C1-C20 aryloxy group, and a C1-C20 aromatic hydrocarbon group. R is R 2 Is an organic radical which may or may not be present simultaneously and is selected from the group consisting of C1-C20 aliphatic hydrocarbon radicals, C1-C20 alkoxy radicals, C1-C20 alicyclic alkoxy radicals, C1-C20 aryloxy radicals and C1-C20 aromatic hydrocarbon radicals, preferably methyl, ethyl, propyl, isopropyl, 1-butyl, 2-butyl, 1-isobutyl, 2-isobutyl, propenyl, 1-butenyl, 2-butenyl, 1-methylpropenyl, cyclopropyl, 1-methylcyclopropyl, 2-methylcyclopropyl, 1-ethylcyclopropyl, 2-ethylcyclopropyl, 1-propylAt least one of cyclopropyl, 2-propylcyclopropyl, cyclobutyl, 1-methylcyclobutyl, 2-methylcyclobutyl, 1-ethylcyclobutyl, 2-ethylcyclobutyl, 1-propylcyclobutyl, 2-propylcyclobutyl, cyclopentyl, 1-methylcyclopentyl, 2-methylcyclopentyl, 1-ethylcyclopentyl, 2-ethylcyclopentyl, 1-propylcyclopentyl, 2-propylcyclopentyl, cyclohexyl, 1-methylcyclohexyl, 2-methylcyclohexyl, 1-ethylcyclohexyl, 2-ethylcyclohexyl, 1-propylcyclohexyl and 2-propylcyclohexyl.
X is F, cl or Br.
R 1 Selected from the group consisting of C1-C20 aliphatic hydrocarbon radicals, C1-C20 alkoxy radicals, C1-C20 alicyclic alkoxy radicals, C1-C20 aryloxy radicals, and C1-C20 aromatic hydrocarbon radicals. R is R 2 ，R 3 And R is 4 Is an organic group of the same or different structure, which may be present simultaneously or not (i.e., may be an H atom), selected from the group consisting of a C1-C20 aliphatic hydrocarbon group, a C1-C20 alkoxy group, a C1-C20 alicyclic alkoxy group, a C1-C20 aryloxy group, and a C1-C20 aromatic hydrocarbon group; r is R 5 ，R 6 And R is 7 Is an organic group of the same or different structure, which may be present simultaneously or not (i.e., may be an H atom), selected from the group consisting of a C1-C20 aliphatic hydrocarbon group, a C1-C20 alkoxy group, a C1-C20 alicyclic alkoxy group, a C1-C20 aryloxy group, and a C1-C20 aromatic hydrocarbon group; r is R 8 ，R 9 And R is 10 Is an organic group of the same or different structure, which may be present simultaneously or not (i.e. may be H atom), selected from the group consisting of C1-C20 aliphatic hydrocarbon group, C1-C20 alkoxy group, C1-C20 alicyclic alkoxy group, C1-C20 aryloxy group or C1-C20 aromatic hydrocarbon group, preferably methyl, ethyl, propyl, isopropyl, 1-butyl, 2-butyl, 1-isobutyl, 2-isobutyl, propenyl, 1-butenyl, 2-butenyl, 1-methylpropenyl, cyclopropyl, 1-methylcyclopropyl, 2-methylcyclopropyl, 1-ethylcyclopropyl, 2-ethylcyclopropyl, 1-propylcyclopropyl, 2-propylcyclopropyl At least one of cyclobutyl, 1-methylcyclobutyl, 2-methylcyclobutyl, 1-ethylcyclobutyl, 2-ethylcyclobutyl, 1-propylcyclobutyl, 2-propylcyclobutyl, cyclopentyl, 1-methylcyclopentyl, 2-methylcyclopentyl, 1-ethylcyclopentyl, 2-ethylcyclopentyl, 1-propylcyclopentyl, 2-propylcyclopentyl, cyclohexyl, 1-methylcyclohexyl, 2-methylcyclohexyl, 1-ethylcyclohexyl, 2-ethylcyclohexyl, 1-propylcyclohexyl and 2-propylcyclohexyl.
In the method of the invention, the main catalyst component A is one or more of Fe (II), fe (III), co (II), co (VI), ni (II), pd (II), cr (VI), ti (IV) and Ti (III) series catalysts.
The main catalyst component A is formed by coordinating the ligand with corresponding Fe (II), fe (III), co (II), co (VI), ni (II), pd (II), cr (VI), ti (IV) and Ti (III) according to the following structure:
MCl x ，
m is at least one of Fe (II), fe (III), co (II), co (VI), ni (II), pd (II), cr (VI), ti (IV) and Ti (III);
R 1 、R 2 h, C of a shape of H, C 1 -C 20 Preferably at least one of H, methyl, ethyl, propyl, 1-butyl, 2-butyl, 1-isobutyl, 2-isobutyl; r is R 3 Is selected from C 1 -C 20 Aliphatic hydrocarbon radicals, C 1 -C 20 Alkoxy, C 1 -C 20 Alicyclic group, C 1 -C 20 Alicyclic alkoxy group, C 1 -C 20 Aryloxy or C of (2) 1 -C 20 Preferably methyl, ethyl, propyl, isopropyl, 1-butyl, 2-butyl, 1-isobutyl, 2-isobutyl, propenyl, 1-butenyl, 2-butenyl, 1-methylpropenyl, cyclopropyl, 1-methylcyclopropyl, 2-methylcyclopropyl, 1-ethylcyclopropyl, 2-ethylcyclopropyl, 1-propylcyclopropyl, 2-propylcyclopropyl, cyclobutyl, 1-methylcyclobutyl, 2-methylcyclobutyl, 1-ethylcyclobutyl, 2-ethylcyclobutyl,At least one of 1-propylcyclobutyl, 2-propylcyclobutyl, cyclopentyl, 1-methylcyclopentyl, 2-methylcyclopentyl, 1-ethylcyclopentyl, 2-ethylcyclopentyl, 1-propylcyclopentyl, 2-propylcyclopentyl, cyclohexyl, 1-methylcyclohexyl, 2-methylcyclohexyl, 1-ethylcyclohexyl, 2-ethylcyclohexyl, 1-propylcyclohexyl and 2-propylcyclohexyl.
The main catalyst component A can also be a main catalyst formed by central atoms of Fe (II), fe (III), co (II), co (VI), ni (II), pd (II), cr (VI), ti (IV) and Ti (VI) and ligands with the following formulas.
R is selected from C 1 -C 20 Aliphatic hydrocarbon radicals, C 1 -C 20 Alkoxy, C 1 -C 20 Alicyclic group, C 1 -C 20 Alicyclic alkoxy group, C 1 -C 20 Aryloxy or C of (2) 1 -C 20 Preferably at least one of methyl, ethyl, propyl, isopropyl, 1-butyl, 2-butyl, 1-isobutyl, 2-isobutyl, propenyl, 1-butenyl, 2-butenyl, 1-methylpropenyl, cyclopropyl, 1-methylcyclopropyl, 2-methylcyclopropyl, 1-ethylcyclopropyl, 2-ethylcyclopropyl, 1-propylcyclopropyl, cyclobutyl, 1-methylcyclobutyl, 2-methylcyclobutyl, 1-ethylcyclobutyl, 2-ethylcyclobutyl, 1-propylcyclobutyl, 2-propylcyclobutyl, cyclopentyl, 1-methylcyclopentyl, 2-methylcyclopentyl, 1-ethylcyclopentyl, 2-ethylcyclopentyl, 1-propylcyclopentyl, 2-propylcyclopentyl, cyclohexyl, 1-methylcyclohexyl, 2-methylcyclohexyl, 1-ethylcyclohexyl, 2-ethylcyclohexyl, 1-propylcyclohexyl, 2-propylcyclohexyl.
In the method of the invention, the cocatalyst component B is one or more of alkyl aluminum, alkyl aluminoxane, modified alkyl aluminoxane and organic boride, wherein the organic group is one or more of saturated or unsaturated linear chain, branched chain or cyclic chain.
AlR is the general formula of aluminum alkyls n X 3-n Wherein R is C 1 -C 20 The alkyl is saturated or unsaturated straight chain, branched chain or cyclic chain, X is halogen, n is more than or equal to 0 and less than or equal to 3; preferably at least one of trimethylaluminum, dimethylaluminum chloride, methylaluminum dichloride, triethylaluminum, diethylaluminum chloride, ethylaluminum dichloride, tripropylaluminum, dipropylaluminum chloride, monopropylaluminum dichloride, tributylaluminum, dibutylaluminum chloride, monobutylaluminum dichloride, trioctylaluminum chloride, dioctylaluminum chloride and monooctylaluminum dichloride. Alkyl aluminoxanes have the general formula Al (OR) n Wherein R is C 1 -C 20 The alkyl is saturated or unsaturated straight chain, branched chain or cyclic chain, and n is more than or equal to 1 and less than or equal to 20.R is preferably at least one selected from the group consisting of methyl, ethyl, propyl, isopropyl, 1-butyl, 2-butyl, 1-isobutyl, 2-isobutyl, propenyl, 1-butenyl, 2-butenyl, 1-methylpropenyl, cyclopropyl, 1-methylcyclopropyl, 2-methylcyclopropyl, 1-ethylcyclopropyl, 2-ethylcyclopropyl, cyclobutyl, 1-methylcyclobutyl, 2-methylcyclobutyl, 1-ethylcyclobutyl, 2-ethylcyclobutyl, 1-propylcyclobutyl, 2-propylcyclobutyl, cyclopentyl, 1-methylcyclopentyl, 2-methylcyclopentyl, 1-ethylcyclopentyl, 2-ethylcyclopentyl, 1-propylcyclopentyl, 2-propylcyclopentyl, cyclohexyl, 1-methylcyclohexyl, 2-methylcyclohexyl, 1-ethylcyclohexyl, 2-ethylcyclohexyl, 1-propylcyclohexyl and 2-propylcyclohexyl. The organoboride comprises B (C 6 X 5 ) 3 、BR n X 3-n And the like, wherein X is halogen, R is C 1 -C 20 The alkyl is a saturated or unsaturated straight chain, branched chain or cyclic chain; r is preferably methyl, ethyl, propyl, isopropyl, 1-butyl, 2-butyl, 1-isobutyl, 2-isobutyl, propenyl, 1-butenyl, 2-butenyl, 1-methylpropenyl, cyclopropyl, 1-methylcyclopropyl, 2-methylcyclopropyl, 1-ethylcyclopropyl, 2-ethylcyclopropyl, 1-propylcyclopropyl, 2-propylcyclopropyl, cyclobutyl, 1-methylcyclobutyl, 2-methylcyclobutyl, 1-ethylcyclobutyl, 2-ethylcyclobutyl, 1-propylcyclobutyl, 2-propylcyclobutylAt least one of a group, a cyclopentyl group, a 1-methylcyclopentyl group, a 2-methylcyclopentyl group, a 1-ethylcyclopentyl group, a 2-ethylcyclopentyl group, a 1-propylcyclopentyl group, a 2-propylcyclopentyl group, a cyclohexyl group, a 1-methylcyclohexyl group, a 2-methylcyclohexyl group, a 1-ethylcyclohexyl group, a 2-ethylcyclohexyl group, a 1-propylcyclohexyl group, and a 2-propylcyclohexyl group.
In the process of the present invention, the solvent component C is selected from one or more of alkanes, cycloalkanes, benzenes, wherein the alkane solvent is C 5 -C 30 Saturated alkane, C 5 -C 30 Alicyclic hydrocarbon, C 5 -C 30 Aromatic hydrocarbon, C 5 -C 30 One or more of saturated heterocyclic hydrocarbon and paraffin oil. The benzene solvent is selected from one or more of benzene, toluene, ethylbenzene, xylene, propylbenzene and isopropylbenzene.
In the method of the invention, the concentration of the oligomerization modification auxiliary component D in the solvent component C in the homogeneous catalysis system S is 0.05-100mmol/L, the concentration of the main catalyst component A in the solvent component C is 1-1000mmol/L, and the molar ratio of the oligomerization modification auxiliary component D to the main catalyst component A is 1:100-100:1.
In the process of the present invention, the polymerization solvent E is selected from one or more of alkanes, cycloalkanes, benzenes, wherein the alkane solvent is C 5 -C 30 Saturated alkane, C 5 -C 30 Alicyclic hydrocarbon, C 5 -C 30 Aromatic hydrocarbon, C 5 -C 30 One or more of saturated heterocyclic hydrocarbon and paraffin oil. The solvent component C and the polymerization solvent E may be the same component or may be different components.
Component C the alkane solvent and polymerization solvent E are selected from n-pentane, isopentane, neopentane, n-hexane, 2-pentane, 3-pentane, n-hexane, 2-methylpentane, 3-methylpentane, n-heptane, 2-methylhexane, 3-methylhexane, cyclopentane, 1-methylcyclopentane, 1, 2-dimethylcyclopentane, 1, 3-dimethylcyclopentane, 1-ethylcyclopentane, 1, 2-diethylcyclopentane, 1, 3-diethylcyclopentane, 1-propylcyclopentane, 1, 2-dipropylcyclopentane, 1, 3-dipropylcyclopentane, cyclohexane, 1-methylcyclohexane, 1, 2-dimethylcyclohexane, 1, 3-dimethylcyclohexane 1-ethylcyclohexane, 1, 2-diethylcyclohexane, 1, 3-diethylcyclohexane, 1-propylcyclohexane, 1, 2-dipropylcyclohexane, 1, 3-diethylcyclohexane, cycloheptane, 1-methylcycloheptane, 1, 2-dimethylcycloheptane, 1, 3-dimethylcycloheptane, 1-ethylcycloheptane, 1, 2-diethylcycloheptane, 1, 3-diethylcycloheptane, 1-propylcycloheptane, 1, 2-dipropylcycloheptane, 1, 3-dipropylcycloheptane, benzene, toluene, 1, 2-methylbenzene, 1, 3-dimethylbenzene, 1, 2-ethylbenzene, 1, 3-diethylbenzene, ethylbenzene, 1, 2-methylethylbenzene, 1, 3-diethylethylbenzene, 1, 2-ethylethylbenzene, 1, 3-diethylethylbenzene, decalin, 1-methylnaphthalene, dimethylnaphthalene, 1-ethylnaphthalene, 2-ethylnaphthalene, 1, 2-dimethylnaphthalene, 1, 3-dimethylnaphthalene, 1, 2-diethylnaphthalene, 1, 3-diethylnaphthalene, C-diethyl naphthalene, C-3-diethylnaphthalene 10 -C 20 At least one of the linear alkanes.
In the process of the present invention, the molar ratio of the procatalyst component A to the cocatalyst component B is 1:1-1:2000, preferably 1:2-1:200.
in the process of the invention, the polymerization temperature is selected from the range from 0 to 250 ℃, preferably from 30 to 150 ℃, the polymerization pressure is selected from the range from 0 to 20MPa, preferably from 0.5 to 10MPa, and the activity of the catalyst after the addition of the oligomerization modifying auxiliary component D to the catalyst system is up to 1X 10 7 g/(mol mh), the total selectivity of 1-hexene and 1-octene is over 90%, the content of solid phase product is lower than 0.3%, the selectivity of 1-hexene in C6 product is up to 95%, and the selectivity of 1-octene in C8 product is up to 99%.
Compared with the prior art, the beneficial effects of the application are as follows:
on one hand, the oligomerization modification auxiliary component D adopted by the invention is added into a homogeneous solution formed by the main catalyst component A and the solvent component C, and the oligomerization modification auxiliary component D and the main catalyst component A exist in a coordination complex or supermolecule assembly or covalent bond form in a certain proportion. The introduction of the oligomerization modification auxiliary agent can play a role in stabilizing the active center of the main catalyst, and the introduction of the oligomerization modification auxiliary agent can increase the steric hindrance of the ligand structure, further prevent the attack of small molecules and long-chain molecules of impurities on the active center and inhibit the deactivation reaction. The gain effect thus obtained is that the homogeneous catalytic system S has a significantly improved thermal stability and polymerization activity, which is improved by at least 10% compared to a catalytic system not modified by the oligomerization modification auxiliary component D, and the temperature resistance is improved by at least 5 ℃.
On the other hand, the introduction of the oligomerization modification auxiliary component D increases the steric hindrance around the active center, inhibits the coordination insertion behavior of long-chain molecules and the active center, and obviously reduces the content of ethylene polymerized oligomer and high polymer, and the content of solid-phase products is lower than 0.3%. The reduction of the content of the solid-phase polymerization product can avoid the phenomena of reactor wall sticking, pipeline blockage and the like which are easy to occur in the subsequent industrial application stage, and lighten the difficulty of industrial application.
In yet another aspect, in terms of product selectivity, the homogeneous catalytic system S described herein provides a total selectivity of 1-hexene to 1-octene in the oligomerization of ethylene of over 90%, with 1-hexene selectivity in the C6 product being up to 95% and 1-octene selectivity in the C8 product being up to 99%. It follows that this homogeneous catalytic system exhibits a selectivity profile with significant advantages.
On the other hand, most of the traditional ethylene oligomerization reactions use high-priced methylaluminoxane or modified methylaluminoxane cocatalysts, the addition amount of the cocatalysts is extremely high, and the ratio of [ Al ]/[ M ] is about 1000-2000 times, so that the high-priced aluminoxane cocatalysts limit the industrial application of the ethylene oligomerization catalyst. The homogeneous catalysis system S modified by the oligomerization modification auxiliary component D can obviously reduce the addition amount of cocatalyst methylaluminoxane or modified methylaluminoxane, the [ Al ]/[ M ] ratio can be reduced to 1-100, and the gain effect is mainly attributed to the oligomerization modification auxiliary component D which can obviously reduce the activation energy required by the activation of the main catalyst.
Finally, in the oligomerization modification auxiliary component and the homogeneous catalysis system thereof, the optimization of the catalytic reaction performance and the product performance can be realized through the change of polymerization reaction conditions (such as temperature, pressure, time, cocatalyst addition amount and the like).
Drawings
FIG. 1 polymerization activity curves of example 1 and comparative example 1.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to examples. The following examples are only illustrative of the present invention and should not be construed as limiting the scope of the invention. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used in the examples were conventional products commercially available without the manufacturer's knowledge.
FIG. 1 is a graph showing the polymerization activity of ethylene oligomerization in example 1 and comparative example 1 of the present invention;
the catalytic activity of the ethylene oligomerization reaction is quantitatively analyzed by each component in the reaction product, the liquid phase component is analyzed by an internal standard method and gas chromatography, and the solid phase product is analyzed by a weighing method.
Example 1:
the oligomerization modifying auxiliary component D is shown in the left of the following figure, wherein M is Si, x=y=z=5, r 1 、R 2 、R 3 、R 4 、R 5 、R 6 Is isopropyl, R 7 、R 8 、R 9 Is n-butyl; the ligand structure of the main catalyst component A is shown in the right of the following figure, the central metal atom is Co (II), R 1 、R 2 、R 3 Is isopropyl.
Homogeneous catalytic system S configuration: adding 0.1mmol of oligomerization modification auxiliary component D shown in the figure into 1L of toluene solution to form a homogeneous solution, keeping the homogeneous solution in a continuous stirring state for at least 30min, adding 5mmol of main catalyst component A into the homogeneous solution to dissolve, and continuously stirring for at least 120min, wherein the configuration operation is operated under an inert gas environment, and the obtained homogeneous catalyst system S is reserved for oligomerization.
1L oligomerization reaction kettle is baked for at least 120min under vacuum and 150 ℃, high-purity nitrogen is used for switching for 3 times at least during the period, after the reaction kettle is cooled to the reaction temperature of 65 ℃, 300mL of polymerization solvent toluene is added, 100 mu mol of cocatalyst component methylaluminoxane is added, the mixture is stirred for at least 5min to remove impurities in the reaction kettle, then 3 mu mol of configured homogeneous catalysis system S (3 mu mol calculated by the content of main catalyst component A) is added, ethylene is introduced immediately to start oligomerization reaction, the polymerization pressure is 1.5MPa, and after the reaction time is 30min, the polymerization product is discharged and analyzed. The results of the product analysis are shown in Table 1.
Example 2:
the oligomerization modifying auxiliary component D is shown in the left of the following figure, wherein M is Si, x=y=z=12, r 1 、R 2 、R 3 、R 4 、R 5 、R 6 Is isopropyl, R 7 、R 8 、R 9 Is isobutyl; the ligand structure of the main catalyst component A is shown in the right of the following figure, the central metal atom is Cr (VI), and R is isopropyl.
Homogeneous catalytic system S configuration: 50mmol of oligomerization modification auxiliary component D shown in the figure is added into 1L of normal hexane solution to form a homogeneous solution, the homogeneous solution is kept in a continuous stirring state for at least 30min, 5mmol of main catalyst component A is added into the homogeneous solution and dissolved, stirring is continued for at least 120min, the configuration operation is operated under an inert gas environment, and the obtained homogeneous catalyst system S is reserved for oligomerization.
1L oligomerization reaction kettle is baked for at least 120min under vacuum and 150 ℃, high-purity argon is used for at least 3 times during the baking, the reaction kettle is cooled to the reaction temperature of 85 ℃, 300mL of polymerization solvent toluene is added, 120 mu mol of cocatalyst component methylaluminoxane is added, the mixture is stirred for at least 5min to remove impurities in the reaction kettle, then 10 mu mol of configured homogeneous catalysis system S (10 mu mol calculated by the content of main catalyst component A) is added, ethylene is introduced immediately to start oligomerization reaction, the polymerization pressure is 2.5MPa, and after the reaction time is 80min, the polymerization product is discharged and analyzed. The results of the product analysis are shown in Table 1.
Example 3:
the oligomerization modifying auxiliary component D is shown in the left side of the following graph, wherein R 1 、R 2 、R 3 、R 4 Is hydroxy, R 5 、R 6 、R 7 、R 8 Is n-butyl; the ligand structure of the main catalyst component A is shown in the right of the following figure, wherein the central metal atom is Fe (III), and R is isobutyl.
Homogeneous catalytic system S configuration: 80mmol of oligomerization modification auxiliary component D shown in the figure is added into 1L of toluene solution to form a homogeneous solution, the homogeneous solution is kept in a continuous stirring state for at least 30min, 500mmol of main catalyst component A is added into the homogeneous solution and dissolved, stirring is continued for at least 120min, the preparation operation is operated under an inert gas environment, and the obtained homogeneous catalyst system S is reserved for oligomerization.
1L oligomerization reaction kettle is baked for at least 120min under vacuum and 150 ℃, high-purity nitrogen is used for switching for 3 times at least during the period, 350mL of polymerization solvent n-heptane is added after the reaction kettle is cooled to the reaction temperature of 75 ℃, 600 mu mol of cocatalyst component modified methylaluminoxane is added, the impurities in the reaction kettle are removed by stirring for at least 5min, 5 mu mol of configured homogeneous catalysis system S (calculated as the content of main catalyst component A is 5 mu mol) is added, ethylene is immediately introduced to start oligomerization reaction, the polymerization pressure is 6.0MPa, and after the reaction time is 30min, the polymerization product is discharged and analyzed. The results of the product analysis are shown in Table 1.
Example 4:
the oligomerization modifying adjunct component D is shown in the left of the following figure, where n=15; the ligand structure of the main catalyst component A is shown in the right of the following figure, wherein the central metal atom is Ni (II), and R is n-butyl.
Homogeneous catalytic system S configuration: adding 2mmol of oligomerization modification auxiliary component D shown in the figure into 1L of n-heptane solution to form a homogeneous solution, keeping the homogeneous solution in a continuous stirring state for at least 30min, adding 50mmol of main catalyst component A into the homogeneous solution, dissolving, and continuously stirring for at least 200min, wherein the configuration operation is operated under an inert gas environment, and the obtained homogeneous catalyst system S is reserved for oligomerization.
1L oligomerization reaction kettle is baked for at least 120min under vacuum and 160 ℃, high-purity nitrogen is used for switching for 3 times at least during the period, 450mL of polymerization solvent n-heptane is added after the reaction kettle is cooled to the reaction temperature of 45 ℃, 200 mu mol of cocatalyst component modified methylaluminoxane is added, the mixture is stirred for at least 5min to remove impurities in the reaction kettle, 5 mu mol of configured homogeneous catalysis system S (calculated as the content of main catalyst component A is 5 mu mol) is added, ethylene is immediately introduced to start oligomerization reaction, the polymerization pressure is 4.0MPa, and after the reaction time is 50min, the polymerization product is discharged and analyzed. The results of the product analysis are shown in Table 1.
Example 5:
the oligomerization modifying auxiliary component D is shown in the left of the following figure, wherein n=15, r 1 、R 2 、R 3 Is ethyl; the ligand structure of the main catalyst component A is shown in the right of the following figure, wherein the central metal atom is Ni (II), and R is n-hexyl.
Homogeneous catalytic system S configuration: 20mmol of oligomerization modification auxiliary component D shown in the figure is added into 1L of toluene solution to form a homogeneous solution, the homogeneous solution is kept in a continuous stirring state for at least 30min, 100mmol of main catalyst component A is added into the homogeneous solution and dissolved, stirring is continued for at least 200min, the configuration operation is operated under an inert gas environment, and the obtained homogeneous catalyst system S is reserved for oligomerization.
1L oligomerization reaction kettle is baked for at least 120min under vacuum and 160 ℃, high-purity nitrogen is used for switching for 3 times at least during the period, 450mL of polymerization solvent dimethylbenzene is added into the reaction kettle, 240 mu mol of cocatalyst component modified methylaluminoxane is added into the reaction kettle, the mixture is stirred for at least 5min to remove impurities in the reaction kettle, 6 mu mol of configured homogeneous catalysis system S (calculated as the content of main catalyst component A is 6 mu mol) is added into the reaction kettle, ethylene is introduced into the reaction kettle to start oligomerization reaction, the polymerization pressure is 3.0MPa, and after the reaction time is 60min, the polymerization product is discharged and analyzed. The results of the product analysis are shown in Table 1.
Example 6:
the oligomerization modifying adjunct component D is shown in the left of the following figure, where m=n= 9,R 1 、R 2 、R 3 Is ethyl; the ligand structure of the main catalyst component A is shown in the right of the figure, the central metal atom is Co (VI), R 1 、R 2 、R 3 Is isopropyl.
Homogeneous catalytic system S configuration: 80mmol of oligomerization modification auxiliary component D shown in the figure is added into 1L of toluene solution to form a homogeneous solution, the homogeneous solution is kept in a continuous stirring state for at least 30min, 800mmol of main catalyst component A is added into the homogeneous solution and dissolved, stirring is continued for at least 100min, the configuration operation is operated under an inert gas environment, and the obtained homogeneous catalyst system S is reserved for oligomerization.
1L oligomerization reaction kettle is baked for at least 120min under vacuum and 160 ℃, high-purity nitrogen or argon is used for switching for 3 times at least during the period, after the reaction kettle is cooled to the reaction temperature of 35 ℃, 450mL of polymerization solvent n-hexane is added, 200 mu mol of cocatalyst component modified methylaluminoxane is added, the mixture is stirred for at least 5min to remove impurities in the reaction kettle, 2 mu mol of configured homogeneous catalysis system S (2 mu mol calculated by the content of the main catalyst component A) is added, ethylene is immediately introduced to start oligomerization reaction, the polymerization pressure is 6.0MPa, and after the reaction time is 75min, the polymerization product is discharged and subjected to product analysis. The results of the product analysis are shown in Table 1.
Comparative example 1:
ligand structure of main catalyst component AAs shown in the following figure, the central metal atom is Co (II), R 1 、R 2 、R 3 Is isopropyl.
Homogeneous catalytic system configuration: 5mmol of the main catalyst component A is added into 1L of toluene solution to form a homogeneous solution, the homogeneous solution is kept in a continuous stirring state for at least 30min, the preparation operation is operated under an inert gas environment, and the obtained homogeneous catalyst solution is reserved for oligomerization.
And (3) baking the 1L oligomerization reaction kettle for at least 120min under the vacuum and 150 ℃ environment, switching for 3 times by using high-purity nitrogen or argon at least during the period, cooling the reaction kettle to the reaction temperature of 65 ℃, adding 300mL of polymerization solvent toluene, adding 100 mu mol of cocatalyst component methylaluminoxane, stirring for at least 5min to remove impurities in the reaction kettle, adding 3 mu mol of configured homogeneous catalysis system, introducing ethylene to start oligomerization reaction, and discharging a polymerization product and analyzing the product after the reaction time is 30min under the polymerization pressure of 1.5 MPa. The results of the product analysis are shown in Table 1.
Comparative example 2:
the ligand structure of the main catalyst component A is shown in the following figure, wherein the central metal atom is Fe (III), and R is isobutyl.
Homogeneous catalytic system S configuration: 500mmol of the main catalyst component A is added into 1L of toluene solution to form a homogeneous solution, the solution is continuously stirred for at least 30min, the preparation operation is operated under the inert gas environment, and the obtained homogeneous catalyst solution is reserved for oligomerization.
1L oligomerization reaction kettle is baked for at least 120min under vacuum and 150 ℃, high-purity nitrogen or argon is used for switching for 3 times at least during the period, the reaction kettle is cooled to the reaction temperature of 75 ℃, 350mL of polymerization solvent n-heptane is added, 600 mu mol of cocatalyst component modified methylaluminoxane is added, the mixture is stirred for at least 5min to remove impurities in the reaction kettle, then 5 mu mol of configured homogeneous catalysis system is added, ethylene is introduced to start oligomerization reaction, the polymerization pressure is 6.0MPa, and after the reaction time is 30min, the polymerization product is discharged and analyzed. The results of the product analysis are shown in Table 1.
Table 1 summary of the results of the analysis of the products of the examples and comparative examples
As is clear from the analytical characterization results of the ethylene oligomerization products prepared in examples 1-6 and comparative examples 1-2, the polymerization activities of the catalytic systems used in examples 1-6 were higher than 1X 10 7 g/(mol mh) is much higher than the polymerization activity of the catalytic system used in comparative examples 1-2 (FIG. 1 is a comparison of the polymerization activities of example 1 and comparative example 1). In the product, the total selectivity yield of 1-hexene and 1-octene in examples 1-6 was over 90%, up to 91.2%, much higher than 84.6% and 82.7% in comparative examples 1-2. In addition, the selectivity of 1-hexene in the C6 product was as high as 95.6%, which is far higher than 92.4% and 91.9% in comparative examples 1-2. The selectivity of 1-octene in the C8 product was as high as 99.3%, much higher than 95.1% and 94.3% in comparative examples 1-2. The solid phase products in examples 1-6 were less than 0.3wt% of the total product, whereas the solid phase products in comparative examples 1-2 were 0.63wt% and 0.71wt% of the total product, and the relatively low solid phase product ratios in examples 1-6 were beneficial for reducing the occurrence of reactor sticking and pipe plugging phenomena and for industrial scale-up continuous operation.
It should be noted that the above-described embodiments are only for explaining the present invention and do not constitute any limitation of the present invention. The invention has been described with reference to exemplary embodiments, but it is understood that the words which have been used are words of description and illustration, rather than words of limitation. Modifications may be made to the invention as defined in the appended claims, and the invention may be modified without departing from the scope and spirit of the invention. Although the invention is described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, as the invention extends to all other means and applications which perform the same function.
Claims (5)
1. The homogeneous catalyst for oligomerization of ethylene is characterized by comprising the following components: a main catalyst component A; a cocatalyst component B; a solvent component C and an oligomerization modification auxiliary component D; the main structure of the oligomerization modification auxiliary component D is one or more of cage-shaped, semi-cage-shaped and star-shaped structures,
the oligomerization modification auxiliary component D is one or more of the following siloxane organic compound general formulas (I), (II) and (III): or is one of the following general formulas (IV), (V) and (VI) of silazane organic compounds:
x, y, z are integers from 0 to 20;
m is C or Si;
R 1 ，R 2 and R is 3 Is an organic group of the same or different structure selected from at least one of H atom, methyl group, ethyl group, propyl group, isopropyl group, 1-butyl group, 2-butyl group, 1-isobutyl group, 2-isobutyl group, propenyl group, 1-butenyl group, 2-butenyl group, 1-methylpropenyl group, cyclopropyl group, 1-methylcyclopropyl group, 2-methylcyclopropyl group, 1-ethylcyclopropyl group, 2-propylcyclopropyl group, cyclobutyl group, 1-methylcyclobutyl group, 2-methylcyclobutyl group, 1-ethylcyclobutyl group, 2-ethylcyclobutyl group, 1-propylcyclobutyl group, 2-propylcyclobutyl group, cyclopentyl group, 1-methylcyclopentyl group, 2-methylcyclopentyl group, 1-ethylcyclopentyl group, 2-ethylcyclopentyl group, 1-propylcyclopentyl group, 2-propylcyclopentyl group, cyclohexyl group, 1-methylcyclohexyl group, 2-methylcyclohexyl group, 1-ethylcyclohexyl group, 2-ethylcyclohexyl group, 1-propylcyclohexyl group, 2-propylcyclohexyl group;
R 4 ，R 5 And R is 6 Is an organic group with the same structure or different structures and is selected from H atoms,At least one of methyl, ethyl, propyl, isopropyl, 1-butyl, 2-butyl, 1-isobutyl, 2-isobutyl, propenyl, 1-butenyl, 2-butenyl, 1-methylpropenyl, cyclopropyl, 1-methylcyclopropyl, 2-methylcyclopropyl, 1-ethylcyclopropyl, 2-ethylcyclopropyl, 1-propylcyclopropyl, cyclobutyl, 1-methylcyclobutyl, 2-methylcyclobutyl, 1-ethylcyclobutyl, 2-ethylcyclobutyl, 1-propylcyclobutyl, 2-propylcyclobutyl, cyclopentyl, 1-methylcyclopentyl, 2-methylcyclopentyl, 1-ethylcyclopentyl, 2-ethylcyclopentyl, 1-propylcyclopentyl, 2-propylcyclopentyl, cyclohexyl, 1-methylcyclohexyl, 2-methylcyclohexyl, 1-ethylcyclohexyl, 2-ethylcyclohexyl, 1-propylcyclohexyl, 2-propylcyclohexyl;
R 7 ，R 8 and R is 9 At least one selected from the group consisting of H atom, methyl group, ethyl group, propyl group, isopropyl group, 1-butyl group, 2-butyl group, 1-isobutyl group, 2-isobutyl group, propenyl group, 1-butenyl group, 2-butenyl group, 1-methylpropenyl group, cyclopropyl group, 1-methylcyclopropyl group, 2-methylcyclopropyl group, 1-ethylcyclopropyl group, 1-propylcyclopropyl group, cyclobutyl group, 1-methylcyclobutyl group, 2-methylcyclobutyl group, 1-ethylcyclobutyl group, 2-ethylcyclobutyl group, 1-propylcyclobutyl group, 2-propylcyclobutyl group, cyclopentyl group, 1-methylcyclopentyl group, 2-methylcyclopentyl group, 1-ethylcyclopentyl group, 2-ethylcyclopentyl group, 1-propylcyclopentyl group, cyclohexyl group, 1-methylcyclohexyl group, 2-methylcyclohexyl group, 1-ethylcyclohexyl group, 2-ethylcyclohexyl group, 1-propylcyclohexyl group and 2-propylcyclohexyl group;
R 1 ，R 2 ，R 3 ，R 4 ，R 5 ，R 6 ，R 7 And R is 8 Is an organic group of the same or different structure selected from H atom, methyl, ethyl, propyl, isopropyl, 1-butyl, 2-butyl, 1-isobutyl, 2-isobutyl, propenyl, 1-butenyl, 2-butenyl, 1-methylAt least one of an allyl group, a cyclopropyl group, a 1-methylcyclopropyl group, a 2-methylcyclopropyl group, a 1-ethylcyclopropyl group, a 2-ethylcyclopropyl group, a 1-propylcyclopropyl group, a 2-propylcyclopropyl group, a cyclobutyl group, a 1-methylcyclobutyl group, a 2-methylcyclobutyl group, a 1-ethylcyclobutyl group, a 2-propylcyclobutyl group, a cyclopentyl group, a 1-methylcyclopentyl group, a 2-methylcyclopentyl group, a 1-ethylcyclopentyl group, a 2-ethylcyclopentyl group, a 1-propylcyclopentyl group, a 2-propylcyclopentyl group, a cyclohexyl group, a 1-methylcyclohexyl group, a 2-methylcyclohexyl group, a 1-ethylcyclohexyl group, a 2-ethylcyclohexyl group, a 1-propylcyclohexyl group, a 2-propylcyclohexyl group;
n is an integer, and n is not 0;
n is an integer from 0 to 30, and n is not 0;
R 1 ，R 2 and R is 3 Is an organic group of the same or different structure selected from at least one of H atom, methyl group, ethyl group, propyl group, isopropyl group, 1-butyl group, 2-butyl group, 1-isobutyl group, 2-isobutyl group, propenyl group, 1-butenyl group, 2-butenyl group, 1-methylpropenyl group, cyclopropyl group, 1-methylcyclopropyl group, 2-methylcyclopropyl group, 1-ethylcyclopropyl group, 2-propylcyclopropyl group, cyclobutyl group, 1-methylcyclobutyl group, 2-methylcyclobutyl group, 1-ethylcyclobutyl group, 2-ethylcyclobutyl group, 1-propylcyclobutyl group, 2-propylcyclobutyl group, cyclopentyl group, 1-methylcyclopentyl group, 2-methylcyclopentyl group, 1-ethylcyclopentyl group, 2-ethylcyclopentyl group, 1-propylcyclopentyl group, 2-propylcyclopentyl group, cyclohexyl group, 1-methylcyclohexyl group, 2-methylcyclohexyl group, 1-ethylcyclohexyl group, 2-ethylcyclohexyl group, 1-propylcyclohexyl group, 2-propylcyclohexyl group;
m and n are integers of 0-20, and neither m nor n is 0;
R 1 ，R 2 and R is 3 Is an organic group having the same or different structure and is selected from at least one of methyl, ethyl, propyl, isopropyl, 1-butyl, 2-butyl, 1-isobutyl, 2-isobutyl, propenyl, 1-butenyl, 2-butenyl, 1-methylpropenyl, cyclopropyl, 1-methylcyclopropyl, 2-methylcyclopropyl, 1-ethylcyclopropyl, 2-ethylcyclopropyl, 1-propylcyclopropyl, 2-propylcyclopropyl, cyclobutyl, 1-methylcyclobutyl, 2-methylcyclobutyl, 1-ethylcyclobutyl, 2-ethylcyclobutyl, 1-propylcyclobutyl, 2-propylcyclobutyl, cyclopentyl, 1-methylcyclopentyl, 2-methylcyclopentyl, 1-ethylcyclopentyl, 2-ethylcyclopentyl, 1-propylcyclopentyl, 2-propylcyclohexyl, 1-methylcyclohexyl, 2-methylcyclohexyl, 1-ethylcyclohexyl, 2-ethylcyclohexyl, 1-propylcyclohexyl, 2-propylcyclohexyl;
x is F, cl or Br;
R 1 selected from the group consisting of C1-C20 aliphatic hydrocarbon radicals, C1-C20 alkoxy radicals, C1-C20 alicyclic alkoxy radicals, C1-C20 aryloxy radicals, and C1-C20 aromatic hydrocarbon radicals; r is R 2 ，R 3 And R is 4 Is an organic group of the same or different structure selected from the group consisting of C1-C20 aliphatic hydrocarbon groups, C1-C20 alkoxy groups, C1-C20 alicyclic alkoxy groups, C1-C20 aryloxy groups, and C1-C20 aromatic hydrocarbon groups; r is R 5 ，R 6 And R is 7 Is an organic group of the same or different structure selected from the group consisting of C1-C20 aliphatic hydrocarbon groups, C1-C20 alkoxy groups, C1-C20 alicyclic alkoxy groups, C1-C20 aryloxy groups, and C1-C20 aromatic hydrocarbon groups; r is R 8 ，R 9 And R is 10 Selected from methyl, ethyl, propyl, isopropyl, 1-butyl, 2-butyl, 1-fluviographAt least one of isobutyl, 2-isobutyl, propenyl, 1-butenyl, 2-butenyl, 1-methylpropenyl, cyclopropyl, 1-methylcyclopropyl, 2-methylcyclopropyl, 1-ethylcyclopropyl, 2-ethylcyclopropyl, 1-propylcyclopropyl, 2-propylcyclopropyl, cyclobutyl, 1-methylcyclobutyl, 2-methylcyclobutyl, 1-ethylcyclobutyl, 2-ethylcyclobutyl, 1-propylcyclobutyl, 2-propylcyclobutyl, cyclopentyl, 1-methylcyclopentyl, 2-methylcyclopentyl, 1-ethylcyclopentyl, 2-ethylcyclopentyl, 1-propylcyclopentyl, 2-propylcyclopentyl, cyclohexyl, 1-methylcyclohexyl, 2-methylcyclohexyl, 1-ethylcyclohexyl, 2-ethylcyclohexyl, 1-propylcyclohexyl, 2-propylcyclohexyl;
the molar ratio of the oligomerization modification auxiliary component D to the main catalyst component A is 1:100-100:1; the molar ratio of the main catalyst component A to the cocatalyst component B is 1:1-1:2000;
The preparation method of the homogeneous catalyst comprises the following steps: the oligomerization modification auxiliary component D is dissolved in the solvent component C to form a homogeneous solution, the homogeneous solution is kept in a continuous stirring state for at least 30min, a certain amount of main catalyst component A is added into the homogeneous solution and dissolved, the main catalyst component A and the oligomerization modification auxiliary component D exist in a coordination complex or supermolecule assembly or covalent bond form in a certain proportion, the homogeneous solution component needs to be continuously stirred for at least 100min, the configuration operation is operated in an inert gas environment, and the obtained homogeneous catalyst S is reserved for oligomerization for later use;
the main catalyst component A is one or more of bivalent Fe, trivalent Fe, bivalent Co, tetravalent Co, bivalent Ni, bivalent Pd, tetravalent Cr, tetravalent Ti and trivalent Ti series catalysts;
the main catalyst component A is formed by coordination of the following structural ligands with corresponding bivalent Fe, trivalent Fe, bivalent Co, tetravalent Co, bivalent Ni, bivalent Pd, tetravalent Cr, tetravalent Ti and trivalent Ti:
R 1 、R 2 is H, methyl, ethyl,At least one of propyl, 1-butyl, 2-butyl, 1-isobutyl, 2-isobutyl; r is R 3 Selected from C 1 -C 20 Aliphatic hydrocarbon radicals, C 1 -C 20 Alkoxy, C 1 -C 20 Alicyclic group, C 1 -C 20 Alicyclic alkoxy group, C 1 -C 20 Aryloxy or C of (2) 1 -C 20 M is at least one of bivalent Fe, trivalent Fe, bivalent Co, tetravalent Co, bivalent Ni, bivalent Pd, tetravalent Cr, tetravalent Ti and trivalent Ti;
or,
r is selected from C 1 -C 20 Aliphatic hydrocarbon radicals, C 1 -C 20 Alkoxy, C 1 -C 20 Alicyclic group, C 1 -C 20 Alicyclic alkoxy group, C 1 -C 20 Aryloxy or C of (2) 1 -C 20 Aromatic hydrocarbon groups of (a);
the cocatalyst component B is one or more of alkyl aluminum, alkyl aluminoxane, modified alkyl aluminoxane and organic boride, wherein the organic group is one or more of saturated or unsaturated linear chain, branched chain or cyclic chain.
2. The homogeneous catalyst for oligomerization of ethylene according to claim 1, wherein the solvent component C is one or more selected from the group consisting of alkanes, cycloalkanes, and benzenes, and wherein the alkane solvent is C 5 -C 30 Saturated alkane, C 5 -C 30 Alicyclic hydrocarbon, C 5 -C 30 Aromatic hydrocarbon, C 5 -C 30 One or more of saturated heterocyclic hydrocarbon and paraffin oil.
3. Homogeneous catalyst for oligomerization of ethylene according to claim 1, characterized in that the concentration of the oligomerization modification auxiliary component D in the solvent component C in the homogeneous catalyst S is 0.05-100mmol/L and the concentration of the main catalyst component a in the solvent component C is 1-1000mmol/L.
4. An ethylene oligomerization method based on the homogeneous catalyst for ethylene oligomerization according to claim 1, which is characterized in that an oligomerization reaction kettle is baked for at least 120min under vacuum and above 100 ℃, high-purity nitrogen or argon is used for switching for 3 times at least during the period, when the reaction kettle is reduced to a reaction temperature T, a proper amount of polymerization solvent E is added, a proper amount of cocatalyst component B is added and stirred for at least 5min to remove impurities in the reaction kettle, then a proper amount of configured homogeneous catalyst S is added, ethylene is immediately introduced to start oligomerization reaction, the polymerization pressure is P, and after the reaction time T, a polymerization product is discharged; the polymerization temperature is selected from 30-150 ℃, and the polymerization pressure is selected from 0.5-10MPa.
5. The process according to claim 4, wherein the polymerization solvent E is selected from one or more of alkanes, cycloalkanes, benzenes, wherein the alkane solvent is C 5 -C 30 Saturated alkane, C 5 -C 30 Alicyclic hydrocarbon, C 5 -C 30 Aromatic hydrocarbon, C 5 -C 30 One or more of saturated heterocyclic hydrocarbon and paraffin oil; the solvent component C and the polymerization solvent E may be the same component or may be different components.
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Inventor after: Chen Yuming Inventor after: Yao Wei Inventor after: Li Wei Inventor after: Tao Gan Inventor after: Zhang Xinpeng Inventor after: Wang Jingdai Inventor after: Yang Yongrong Inventor before: Chen Yuming Inventor before: Li Wei Inventor before: Yao Wei Inventor before: Tao Gan Inventor before: Zhang Xinpeng Inventor before: Wang Jingdai Inventor before: Yang Yongrong |