CN117983306A - Catalyst containing PCCP ligand for ethylene selective tetramerization and preparation method and application thereof - Google Patents
Catalyst containing PCCP ligand for ethylene selective tetramerization and preparation method and application thereof Download PDFInfo
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- CN117983306A CN117983306A CN202211351203.6A CN202211351203A CN117983306A CN 117983306 A CN117983306 A CN 117983306A CN 202211351203 A CN202211351203 A CN 202211351203A CN 117983306 A CN117983306 A CN 117983306A
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- China
- Prior art keywords
- ligand
- groups
- alkyl
- transition metal
- ethylene
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- 239000003446 ligand Substances 0.000 title claims abstract description 95
- 238000002360 preparation method Methods 0.000 title claims abstract description 59
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 239000005977 Ethylene Substances 0.000 title claims abstract description 57
- 239000003054 catalyst Substances 0.000 title claims abstract description 43
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims abstract description 68
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 44
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims abstract description 34
- 150000003623 transition metal compounds Chemical class 0.000 claims abstract description 33
- 239000012190 activator Substances 0.000 claims abstract description 27
- 125000003118 aryl group Chemical group 0.000 claims abstract description 18
- 125000004122 cyclic group Chemical group 0.000 claims abstract description 15
- 125000005842 heteroatom Chemical group 0.000 claims abstract description 12
- 125000004429 atom Chemical group 0.000 claims abstract description 11
- 239000001257 hydrogen Substances 0.000 claims abstract description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 11
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims abstract description 11
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 10
- 239000000126 substance Substances 0.000 claims abstract description 6
- -1 1, 2-dimethylethyl Chemical group 0.000 claims description 118
- 238000006243 chemical reaction Methods 0.000 claims description 56
- 229910052723 transition metal Inorganic materials 0.000 claims description 22
- 150000001875 compounds Chemical class 0.000 claims description 18
- 239000011651 chromium Substances 0.000 claims description 17
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 16
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 12
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical class C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 claims description 11
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 11
- 150000001336 alkenes Chemical class 0.000 claims description 9
- 239000012442 inert solvent Substances 0.000 claims description 9
- 125000004215 2,4-difluorophenyl group Chemical group [H]C1=C([H])C(*)=C(F)C([H])=C1F 0.000 claims description 8
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- 229910052804 chromium Inorganic materials 0.000 claims description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 8
- 150000003624 transition metals Chemical class 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 6
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 6
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 6
- 238000011065 in-situ storage Methods 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 5
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 5
- 229920002554 vinyl polymer Polymers 0.000 claims description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 239000000460 chlorine Substances 0.000 claims description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- 229910052735 hafnium Inorganic materials 0.000 claims description 3
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 3
- 239000002608 ionic liquid Chemical class 0.000 claims description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 239000011733 molybdenum Substances 0.000 claims description 3
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 238000003786 synthesis reaction Methods 0.000 claims description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 239000010937 tungsten Substances 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims description 3
- 125000004973 1-butenyl group Chemical group C(=CCC)* 0.000 claims description 2
- 125000006039 1-hexenyl group Chemical group 0.000 claims description 2
- 125000006028 1-methyl-2-butenyl group Chemical group 0.000 claims description 2
- 125000006017 1-propenyl group Chemical group 0.000 claims description 2
- 125000004201 2,4-dichlorophenyl group Chemical group [H]C1=C([H])C(*)=C(Cl)C([H])=C1Cl 0.000 claims description 2
- 125000004974 2-butenyl group Chemical group C(C=CC)* 0.000 claims description 2
- 125000004182 2-chlorophenyl group Chemical group [H]C1=C([H])C(Cl)=C(*)C([H])=C1[H] 0.000 claims description 2
- 125000004198 2-fluorophenyl group Chemical group [H]C1=C([H])C(F)=C(*)C([H])=C1[H] 0.000 claims description 2
- 125000006026 2-methyl-1-butenyl group Chemical group 0.000 claims description 2
- 125000005916 2-methylpentyl group Chemical group 0.000 claims description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 2
- 125000000175 2-thienyl group Chemical group S1C([*])=C([H])C([H])=C1[H] 0.000 claims description 2
- 125000004189 3,4-dichlorophenyl group Chemical group [H]C1=C([H])C(Cl)=C(Cl)C([H])=C1* 0.000 claims description 2
- 125000004211 3,5-difluorophenyl group Chemical group [H]C1=C(F)C([H])=C(*)C([H])=C1F 0.000 claims description 2
- 125000004975 3-butenyl group Chemical group C(CC=C)* 0.000 claims description 2
- 125000004180 3-fluorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C(F)=C1[H] 0.000 claims description 2
- 125000005917 3-methylpentyl group Chemical group 0.000 claims description 2
- 125000001541 3-thienyl group Chemical group S1C([H])=C([*])C([H])=C1[H] 0.000 claims description 2
- 125000001255 4-fluorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1F 0.000 claims description 2
- 125000006043 5-hexenyl group Chemical group 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- ZUSWDTWYONAOPH-UHFFFAOYSA-N [2-(trifluoromethyl)phenyl]hydrazine;hydrochloride Chemical group [Cl-].[NH3+]NC1=CC=CC=C1C(F)(F)F ZUSWDTWYONAOPH-UHFFFAOYSA-N 0.000 claims description 2
- 125000002178 anthracenyl group Chemical group C1(=CC=CC2=CC3=CC=CC=C3C=C12)* 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 235000010290 biphenyl Nutrition 0.000 claims description 2
- 239000004305 biphenyl Substances 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 2
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 claims description 2
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims description 2
- 125000005745 ethoxymethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])* 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 claims description 2
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000001624 naphthyl group Chemical group 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 125000003854 p-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Cl 0.000 claims description 2
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 claims description 2
- 125000001844 prenyl group Chemical group [H]C([*])([H])C([H])=C(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- 125000003548 sec-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 239000011593 sulfur Substances 0.000 claims description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 2
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 13
- 229920000642 polymer Polymers 0.000 abstract description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 40
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 34
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 34
- 239000000203 mixture Substances 0.000 description 27
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 26
- 229910052786 argon Inorganic materials 0.000 description 20
- 238000006384 oligomerization reaction Methods 0.000 description 19
- 239000000047 product Substances 0.000 description 17
- WYURNTSHIVDZCO-UHFFFAOYSA-N tetrahydrofuran Substances C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 14
- 238000005160 1H NMR spectroscopy Methods 0.000 description 13
- 239000000706 filtrate Substances 0.000 description 13
- 239000007787 solid Substances 0.000 description 13
- CAHQGWAXKLQREW-UHFFFAOYSA-N Benzal chloride Chemical compound ClC(Cl)C1=CC=CC=C1 CAHQGWAXKLQREW-UHFFFAOYSA-N 0.000 description 12
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- 230000000694 effects Effects 0.000 description 12
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 11
- 238000006555 catalytic reaction Methods 0.000 description 9
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 6
- 239000003921 oil Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- DLVKAFJXCCATIO-UHFFFAOYSA-N 2-chloro-1,3-dimethyl-1,3,2-diazaphospholidine Chemical compound CN1CCN(C)P1Cl DLVKAFJXCCATIO-UHFFFAOYSA-N 0.000 description 5
- 150000001845 chromium compounds Chemical class 0.000 description 5
- 239000012074 organic phase Substances 0.000 description 5
- 238000002390 rotary evaporation Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 125000001424 substituent group Chemical group 0.000 description 5
- 238000005829 trimerization reaction Methods 0.000 description 5
- 239000004711 α-olefin Substances 0.000 description 5
- YVSMQHYREUQGRX-UHFFFAOYSA-N 2-ethyloxaluminane Chemical compound CC[Al]1CCCCO1 YVSMQHYREUQGRX-UHFFFAOYSA-N 0.000 description 4
- GPAYUJZHTULNBE-UHFFFAOYSA-N diphenylphosphine Chemical compound C=1C=CC=CC=1PC1=CC=CC=C1 GPAYUJZHTULNBE-UHFFFAOYSA-N 0.000 description 4
- VURFVHCLMJOLKN-UHFFFAOYSA-N diphosphane Chemical compound PP VURFVHCLMJOLKN-UHFFFAOYSA-N 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- XYFCBTPGUUZFHI-UHFFFAOYSA-N phosphine group Chemical group P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 4
- 229920006124 polyolefin elastomer Polymers 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 229920001903 high density polyethylene Polymers 0.000 description 3
- 239000004700 high-density polyethylene Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 3
- KVKFRMCSXWQSNT-UHFFFAOYSA-N n,n'-dimethylethane-1,2-diamine Chemical compound CNCCNC KVKFRMCSXWQSNT-UHFFFAOYSA-N 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 3
- 125000002524 organometallic group Chemical group 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- WCFQIFDACWBNJT-UHFFFAOYSA-N $l^{1}-alumanyloxy(2-methylpropyl)aluminum Chemical compound CC(C)C[Al]O[Al] WCFQIFDACWBNJT-UHFFFAOYSA-N 0.000 description 2
- LWNGJAHMBMVCJR-UHFFFAOYSA-N (2,3,4,5,6-pentafluorophenoxy)boronic acid Chemical compound OB(O)OC1=C(F)C(F)=C(F)C(F)=C1F LWNGJAHMBMVCJR-UHFFFAOYSA-N 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- USCSRAJGJYMJFZ-UHFFFAOYSA-N 3-methyl-1-butyne Chemical compound CC(C)C#C USCSRAJGJYMJFZ-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 150000001639 boron compounds Chemical class 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 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 2
- CYOMBOLDXZUMBU-UHFFFAOYSA-K chromium(3+);oxolane;trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3].C1CCOC1.C1CCOC1.C1CCOC1 CYOMBOLDXZUMBU-UHFFFAOYSA-K 0.000 description 2
- MJSNUBOCVAKFIJ-LNTINUHCSA-N chromium;(z)-4-oxoniumylidenepent-2-en-2-olate Chemical compound [Cr].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O MJSNUBOCVAKFIJ-LNTINUHCSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- 238000006471 dimerization reaction Methods 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000010687 lubricating oil Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- UMIPWJGWASORKV-UHFFFAOYSA-N oct-1-yne Chemical compound CCCCCCC#C UMIPWJGWASORKV-UHFFFAOYSA-N 0.000 description 2
- 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 description 2
- 125000004437 phosphorous atom Chemical group 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 238000010898 silica gel chromatography Methods 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 2
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 2
- PSBFBDKLGNQGSR-UHFFFAOYSA-N (2,4-difluorophenyl)phosphane Chemical compound FC1=C(C=CC(=C1)F)P PSBFBDKLGNQGSR-UHFFFAOYSA-N 0.000 description 1
- XIONUQPOXCUMMB-UHFFFAOYSA-N (2-bromophenyl)-diphenylphosphane Chemical compound BrC1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 XIONUQPOXCUMMB-UHFFFAOYSA-N 0.000 description 1
- MGJUWNNLIIIAFX-UHFFFAOYSA-N (2-fluorophenyl)phosphane Chemical compound FC1=CC=CC=C1P MGJUWNNLIIIAFX-UHFFFAOYSA-N 0.000 description 1
- WVSBQYMJNMJHIM-UHFFFAOYSA-N (benzene)chromium tricarbonyl Chemical group [Cr].[O+]#[C-].[O+]#[C-].[O+]#[C-].C1=CC=CC=C1 WVSBQYMJNMJHIM-UHFFFAOYSA-N 0.000 description 1
- QFMZQPDHXULLKC-UHFFFAOYSA-N 1,2-bis(diphenylphosphino)ethane Chemical class C=1C=CC=CC=1P(C=1C=CC=CC=1)CCP(C=1C=CC=CC=1)C1=CC=CC=C1 QFMZQPDHXULLKC-UHFFFAOYSA-N 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910021556 Chromium(III) chloride Inorganic materials 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 229920010126 Linear Low Density Polyethylene (LLDPE) Polymers 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- BAVYZALUXZFZLV-UHFFFAOYSA-O Methylammonium ion Chemical compound [NH3+]C BAVYZALUXZFZLV-UHFFFAOYSA-O 0.000 description 1
- CJKRXEBLWJVYJD-UHFFFAOYSA-N N,N'-diethylethylenediamine Chemical compound CCNCCNCC CJKRXEBLWJVYJD-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000002015 acyclic group Chemical group 0.000 description 1
- 125000005234 alkyl aluminium group Chemical group 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 239000002199 base oil Substances 0.000 description 1
- BRTALTYTFFNPAC-UHFFFAOYSA-N boroxin Chemical compound B1OBOBO1 BRTALTYTFFNPAC-UHFFFAOYSA-N 0.000 description 1
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 1
- 229910000024 caesium carbonate Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- XGRJZXREYAXTGV-UHFFFAOYSA-N chlorodiphenylphosphine Chemical compound C=1C=CC=CC=1P(Cl)C1=CC=CC=C1 XGRJZXREYAXTGV-UHFFFAOYSA-N 0.000 description 1
- BFGKITSFLPAWGI-UHFFFAOYSA-N chromium(3+) Chemical compound [Cr+3] BFGKITSFLPAWGI-UHFFFAOYSA-N 0.000 description 1
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 description 1
- DHXAPNVJPXZTHF-UHFFFAOYSA-K chromium(3+);cyclopentanecarboxylate Chemical compound [Cr+3].[O-]C(=O)C1CCCC1.[O-]C(=O)C1CCCC1.[O-]C(=O)C1CCCC1 DHXAPNVJPXZTHF-UHFFFAOYSA-K 0.000 description 1
- WYYQVWLEPYFFLP-UHFFFAOYSA-K chromium(3+);triacetate Chemical compound [Cr+3].CC([O-])=O.CC([O-])=O.CC([O-])=O WYYQVWLEPYFFLP-UHFFFAOYSA-K 0.000 description 1
- 235000007831 chromium(III) chloride Nutrition 0.000 description 1
- 239000011636 chromium(III) chloride Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- GBRBMTNGQBKBQE-UHFFFAOYSA-L copper;diiodide Chemical compound I[Cu]I GBRBMTNGQBKBQE-UHFFFAOYSA-L 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 150000001923 cyclic compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 125000005265 dialkylamine group Chemical group 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 229920000092 linear low density polyethylene Polymers 0.000 description 1
- 239000004707 linear low-density polyethylene Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- PYLWMHQQBFSUBP-UHFFFAOYSA-N monofluorobenzene Chemical compound FC1=CC=CC=C1 PYLWMHQQBFSUBP-UHFFFAOYSA-N 0.000 description 1
- MAJFLEHNBOUSIY-UHFFFAOYSA-N n-[chloro(dimethylamino)phosphanyl]-n-methylmethanamine Chemical group CN(C)P(Cl)N(C)C MAJFLEHNBOUSIY-UHFFFAOYSA-N 0.000 description 1
- CHKWHTPECBLEBR-UHFFFAOYSA-N n-methyl-n'-propylethane-1,2-diamine Chemical compound CCCNCCNC CHKWHTPECBLEBR-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 150000002891 organic anions Chemical class 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- PAYRUJLWNCNPSJ-UHFFFAOYSA-O phenylazanium Chemical compound [NH3+]C1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-O 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- SQBBHCOIQXKPHL-UHFFFAOYSA-N tributylalumane Chemical compound CCCC[Al](CCCC)CCCC SQBBHCOIQXKPHL-UHFFFAOYSA-N 0.000 description 1
- LALRXNPLTWZJIJ-UHFFFAOYSA-N triethylborane Chemical compound CCB(CC)CC LALRXNPLTWZJIJ-UHFFFAOYSA-N 0.000 description 1
- FQMMZTDQJFUYSA-UHFFFAOYSA-N triheptylalumane Chemical compound CCCCCCC[Al](CCCCCCC)CCCCCCC FQMMZTDQJFUYSA-UHFFFAOYSA-N 0.000 description 1
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 1
- JOJQVUCWSDRWJE-UHFFFAOYSA-N tripentylalumane Chemical compound CCCCC[Al](CCCCC)CCCCC JOJQVUCWSDRWJE-UHFFFAOYSA-N 0.000 description 1
- MXSVLWZRHLXFKH-UHFFFAOYSA-N triphenylborane Chemical compound C1=CC=CC=C1B(C=1C=CC=CC=1)C1=CC=CC=C1 MXSVLWZRHLXFKH-UHFFFAOYSA-N 0.000 description 1
- CNWZYDSEVLFSMS-UHFFFAOYSA-N tripropylalumane Chemical compound CCC[Al](CCC)CCC CNWZYDSEVLFSMS-UHFFFAOYSA-N 0.000 description 1
- OBAJXDYVZBHCGT-UHFFFAOYSA-N tris(pentafluorophenyl)borane Chemical compound FC1=C(F)C(F)=C(F)C(F)=C1B(C=1C(=C(F)C(F)=C(F)C=1F)F)C1=C(F)C(F)=C(F)C(F)=C1F OBAJXDYVZBHCGT-UHFFFAOYSA-N 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a catalyst containing PCCP ligand for ethylene selective tetramerization, and a preparation method and application thereof, wherein the catalyst comprises ligand, transition metal compound and activator, wherein the chemical structural formula of the ligand is shown as the following formula (I): Wherein the groups R 1 and R 2 are each independently selected from hydrogen, alkyl, heteroatom-containing alkyl, alkenyl or aromatic groups; or R 1 and R 2 are linked to form a cyclic structure containing 5 to 10 atoms; the groups R 3 to R 8 are each independently selected from hydrogen, alkyl, heteroatom-containing alkyl, alkenyl or aromatic groups; or R 1 and R 2 are linked to form a cyclic structure containing 5 to 10 atoms. Compared with the prior art, the invention improves the catalytic activity and the selectivity of 1-octene, reduces the cyclic C6 content and has low polymer content.
Description
Technical Field
The invention relates to the technical field of ethylene oligomerization, in particular to a catalyst containing PCCP ligand for ethylene selective tetramerization, a preparation method and application thereof.
Background
Linear alpha-olefin (LAO) is used as an important chemical raw material, can be used for preparing lubricating oil, surfactant, detergent and the like, has extremely high economic application value, wherein 1-hexene and 1-octene are synthesized into polyolefin elastomer (POE) and High Density Polyethylene (HDPE), and the amount of comonomer in the Linear Low Density Polyethylene (LLDPE) is more than 20 percent, the comonomer content in the HDPE is 1-2 percent, and the comonomer content in the LLDPE is generally 8-10 percent. Ethylene oligomerization is an important method for producing linear alpha-olefin, and compared with the traditional methods such as a wax cracking process, an extraction separation method, a fatty alcohol dehydrogenation method, olefin dimerization and disproportionation, an internal olefin isomerization method and the like, the ethylene oligomerization method has the advantages of high linearization degree, narrow polymerization degree distribution, low separation cost and great comprehensive advantages, and is widely applied to industrial production.
The traditional ethylene oligomerization catalysis mainly uses metallic titanium, zirconium, iron and other catalysis systems, and the catalysis systems mainly follow Cossee-Arlman mechanisms, namely ethylene molecules are coordinated and inserted into the metal center of the catalyst, and as ethylene molecules are continuously inserted, the linear chain of a metal alkyl chain grows, and the linear alpha-olefin of the product is normally distributed, and needs to be further separated and purified according to actual requirements in industrial application. The ethylene high-selectivity oligomerization mainly follows a metal cyclization mechanism, so that the produced alpha-olefin is in Schulz-Flory distribution, and the product at the peak has higher content, and the method provides an important path for producing the alpha-olefin with specific carbon number. In recent years, the increasing demand for 1-hexene and 1-octene has made ethylene selective oligomerization a hot spot for research in industry and academia.
At present, reports of high-selectivity oligomerization of ethylene mainly focus on three aspects of dimerization, trimerization and tetramerization for preparing 1-butene, 1-hexene and 1-octene. In these catalytic systems, minor changes in the catalyst structure have a great influence on the product distribution, while regulation of the catalyst structure depends on the framework and substituents of the ligand. In recent years, research in this area has focused on developing novel efficient ligands and exploring the mechanism of ethylene selective oligomerization catalysis, with some important achievements. In 2002, british Petroleum reported that Cr/Ar 2PN(R)PAr2 (Ar is ortho methoxy substituted aryl) system was used for the selective preparation of 1-hexene (Chemical Communication,2002,858). In 2003, phillips Petroleum realized ethylene trimerization industrialization (US 5523507) by utilizing the developed Phillips chromium trimerization catalyst, and realized industrialized production of 1-hexene by sequentially adopting similar catalytic systems for medium petrifaction (Yanshan) and medium petroleum (Daqing) in China. In China, autonomous industrial production of 1-octene prepared by high-activity and high-selectivity tetramerization of ethylene cannot be realized at present, and the 1-octene can be used for producing fields of high-quality Polyethylene (PE), polyolefin elastomer (POE), lubricating oil base oil (PAO), plasticizer, surfactant and the like. 1-octene has higher economic value than 1-hexene. In 2002, british Petroleum reported that PNP ligands with the structure of PAr 2N(R)PAr2 (Ar is ortho methoxy substituted aryl) were used for chromium catalyzed high selectivity ethylene trimerization to 1-hexene with selectivity up to 91.5% (chem. Commun.2002,8,858-859). In 2004, sasol company successfully achieved ethylene tetramerization with up to 67.5% 1-octene selectivity using the PNP ligand/chromium catalyst system described above (J. Am. Chem. Soc.2004,126,45, 14712-14713). In the ethylene tetramerization catalytic reaction, ethylene trimerization still occurs, and the product still contains 11.9% of 1-hexene. Therefore, the total selectivity of 1-hexene and 1-octene with high economic value is not high, only 79.4 percent, still needs to be improved, and the polymer content is more than 1 percent, and when continuous reaction is carried out, the phenomena of polymer wall hanging, stirring paddle winding and the like easily occur, thus influencing the continuous operation of industrial devices.
In 2010, korean SK energy company developed a series of dimethyl-substituted DPPE type ligands with chiral framework for catalyzing ethylene selective tetramer (Organometallics, 2010,29,5805), 1-octene selectivity up to 59.2%, activity up to 1790 kg/(g Cr/h), but still 0.7% polymer formation. In 2013, zhang et al designed and synthesized a series of vinyl bridged bisphosphine ligands containing bisphenylphosphine groups (-PPh 2), ph 2P(R)C＝C(H)PPh2, which catalyzed ethylene selective oligomerization, showed good ethylene oligomerization catalytic activity (ACS CATALYSIS,2013,3,2311), when R was tert-butyl, the activity reached 4238 kg/(g Cr/h), the overall selectivity of 1-hexene and 1-octene with high added value could reach 79.1%, but the 1-octene content was only 33.1%. In 2019, korean SK energy company introduces fluorine atom (CATALYSIS COMMUNICATIONS,2019,121,15) at ortho position of-PPh 2 part in Ph 2P(R)C＝C(H)PPh2 biphosphine ligand, so that the activity of the system is improved, the content of cyclic C 6 in the product is reduced, the total selectivity of 1-hexene and 1-octene is improved (up to 90%), but the introduction of F atom leads to about 15% reduction of 1-octene content. In 2020, duPhos ligand was used by Dow corporation to catalyze ethylene selective oligomerization (Organometallics, 2020,39,976) with 1-octene selectivities of up to 66.4% and activities of up to 1070 kg/(gCr/h), but with higher polymer content (2.0%). In 2022, jiang et al replaced one of the diarylphosphine fragments of Ar 2P(R)NPAr2 ligand with an acyclic bis (dialkylamine) phosphine fragment (Applied Organometallic Chemistry,2022; 36:e6454.) to give Ar 2P(R)NP(NR2)2 ligand for catalyzing ethylene selective oligomerization with an activity up to 1596kg/g Cr/h, with a combined selectivity of 1-hexene and 1-octene up to 86%, where the selectivity of 1-octene is only 22.78%. In the same year Britovsek et al introduce a cyclodiphosphine nitrogen fragment into Ar 2P(R)NPAr2 ligand to replace two diaryl phosphine fragments in Ar 2P(R)NPAr2 ligand (CATALYSIS SCIENCE & Technology,2022,12,4544) for catalyzing ethylene selective oligomerization, the comprehensive selectivity of 96% of 1-hexene and 1-octene can be realized, but the activity can only reach 26.44kg/g Cr/h at maximum.
Disclosure of Invention
The invention aims to overcome at least one of the defects in the prior art and provide an ethylene selective tetramerization catalyst containing PCCP ligand, which has the advantages of improved catalytic activity and 1-octene selectivity, reduced cyclic C 6 content and low polymer content, and a preparation method and application thereof.
The aim of the invention can be achieved by the following technical scheme:
In order to further improve the selectivity of 1-octene and the activity of the catalytic system, the invention creatively introduces a diamine phosphine fragment and a cyclodiphosphine nitrogen alkane fragment with adjustable steric hindrance into a vinyl bridged diphosphine ligand (Ph 2P(R)C＝C(H)PPh2). By introducing the cyclodiphosphine nitrogen fragments and changing the substituents on the N atom and the P atom, the invention successfully improves the 1-octene selectivity of the catalytic system to 70.2 percent, improves the total selectivity of 1-hexene and 1-octene to 96.1 percent, and has the activity up to 5650kg/g Cr/h, and the specific scheme is as follows:
A catalyst for ethylene selective tetramerization containing PCCP ligand, which comprises ligand, transition metal compound and activator, wherein the chemical structural formula of the ligand is shown as the following formula (I):
In the method, in the process of the invention,
The groups R 1 and R 2 are each independently selected from hydrogen, alkyl, heteroatom-containing alkyl, alkenyl or aromatic groups; or R 1 and R 2 are linked to form a cyclic structure containing 5 to 10 atoms; in other words, R 1 and R 2 are optionally linked together, wherein the optional features of the bond are represented by dashed lines; when R 1、R2 are taken together, a cyclic structure containing 5 to 10 atoms may be formed;
The groups R 3 to R 8 are each independently selected from hydrogen, alkyl, heteroatom-containing alkyl, alkenyl or aromatic groups; or R 7 and R 8 are linked to form a cyclic structure containing 5 to 10 atoms. In other words, R 7 and R 8 are optionally linked together, wherein the optional features of the bond are represented by dashed lines; when R 7、R8 are linked together, a cyclic structure containing 5 to 10 atoms may be formed.
Further, the alkyl is C 1-C50 alkyl, specifically including methyl, ethyl, n-propyl, isopropyl, n-butyl, 1-methylpropyl, 2-methylpropyl, 1, 2-dimethylethyl, n-pentyl, 1-methylbutyl, 2-dimethylpropyl, cyclopentyl, n-hexyl, 2-methylpentyl, 3-methylpentyl, 1-dimethylpropyl, n-heptyl, cycloheptyl, n-octyl, n-decyl, 2-methylcyclopentyl or 2, 6-dimethylcyclohexyl;
The heteroatom-containing alkyl is C 1-C50 alkyl, and the heteroatom specifically comprises oxygen, sulfur, silicon, halogen (including fluorine and chlorine) and nitrogen atoms, and specifically comprises methoxy, ethoxy, propoxy, isopropoxy, butoxy, 1-methoxyethyl, ethoxymethyl, isopropoxymethyl, 1-isopropoxyethyl, methoxyethoxymethyl, methoxypropoxymethyl, methylthio, ethylthio, propylthio, isopropylthio, butylthio, trimethylsilyl, trifluoromethyl, 2-chlorocyclopentyl, methylamino, ethylamino, propylamino and isopropylamino;
The alkenyl is C 1-C50 alkenyl, which specifically comprises vinyl, allyl, 1-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-2-butenyl, 2-methyl-1-butenyl, 3-methyl-2-butenyl, cyclopentadienyl, 1-hexenyl, 5-hexenyl, 2-methylcyclohexenyl, 2, 6-dimethylcyclohexenyl, 3-cyclohexenyl or 2-methyl-2-cyclohexenyl;
The aromatic group is aryl of C 4-C50 and derivatives thereof, specifically included are phenyl, 4-fluorophenyl, 2-fluorophenyl, 3-fluorophenyl, 2-chlorophenyl, 4-chlorophenyl, 2- (trifluoromethyl) phenyl, 2, 4-di (trifluoromethyl) phenyl, 2, 6-difluorophenyl, 2, 5-difluorophenyl, 2, 4-difluorophenyl, 2, 3-difluorophenyl, 3, 4-difluorophenyl, 3, 5-difluorophenyl, 2, 6-dichlorophenyl, 2, 5-dichlorophenyl, 2, 4-dichlorophenyl, 2, 3-dichlorophenyl, 3, 4-dichlorophenyl, 3, 5-dichlorophenyl, 2-fluoro-4-chlorophenyl, 2,4, 6-trifluorophenyl, 4-methylphenyl, 2-ethylphenyl, 3-ethylphenyl 2, 4-dimethylphenyl, 2, 4-diisopropylphenyl, 2, 4-di-tert-butylphenyl, 2, 6-dimethylphenyl, 2, 6-diisopropylphenyl, 3, 5-dimethylphenyl, 3, 5-di-tert-butylphenyl, 2,4, 6-trimethylphenyl, naphthyl, anthracenyl, biphenyl, 2-thienyl, 3-thienyl, 5-fluoro-2-thienyl, 2-fluoro-3-thienyl, 2, 5-difluoro-3-thienyl, 2-fluoro-1-naphthyl, 7-fluoro-1-naphthyl, 8-fluoro-1-naphthyl, 7-chloro-1-naphthyl, 8-fluoro-1-anthracenyl, 9-fluoro-1-anthracenyl, 10-fluoro-1-anthryl, 8-chloro-1-anthryl or 2, 8-difluoro-1-naphthyl.
Further, the groups R 1 and R 2 are selected from hydrogen, alkyl or aromatic groups; the alkyl group comprises octyl, isopropyl or tertiary butyl, and the aromatic group comprises phenyl;
The groups R 3 and R 4 are selected from phenyl or substituted phenyl; the substituted phenyl comprises substituted phenyl 2-fluorophenyl or 2, 4-difluorophenyl;
The groups R 5 and R 6 are selected from alkyl; the alkyl group comprises methyl, ethyl or propyl;
the groups R 7 and R 8 are selected from alkyl groups, including in particular methyl groups, or R 7 and R 8 are linked together to form a cyclodiphosphino nitrogen group.
Further, the alkyl groups in the groups R 1 and R 2 are tert-butyl groups; the substituted phenyl groups in the groups R 3 and R 4 are 2, 4-difluorophenyl groups; the alkyl groups in the radicals R 5 and R 6 are propyl groups; the groups R 7 and R 8 are joined together to form a cyclodiphosphino nitrogen group.
Further, the transition metal in the transition metal compound is selected from iron, cobalt, nickel, copper, titanium, vanadium, chromium, manganese, molybdenum, tungsten, nickel, palladium, zirconium or hafnium; the transition metal in the catalyst system of the present invention may be a transition metal compound commonly used in the art, and a metal atom in the transition metal compound is a metal active center, which plays an important role in the catalytic process. More preferably, the transition metal of the transition metal compound is selected from chromium, and in particular, the corresponding transition metal compound may be any chromium compound that enables the selective oligomerization of ethylene. Alternative chromium compounds include those of the general formula CrR n wherein R n is an organic anion or neutral molecule, R n generally contains 1 to 20 carbon atoms, n is an integer from 0 to 6, and Cr has a valence of 0 to 6. The specific R n group is an organic matter containing carboxyl, beta-dicarbonyl and hydrocarbon groups or other groups. From the viewpoint of ease of dissolution and handling, preferred chromium compounds include one of chromium trichloride-tris (tetrahydrofuran) complex, (benzene) chromium tricarbonyl, chromium (III) octoate, chromium hexacarbonyl, chromium (III) acetylacetonate, chromium (III) cyclopentanoate, chromium (III) 2-ethylhexanoate, chromium (III) acetate, chromium (III) 2, 6-tetramethylheptanedione, and chromium (III) chloride. Preferably, the chromium compound is selected from chromium trichloride-tris (tetrahydrofuran) complex, chromium (III) acetylacetonate, chromium (III) 2-ethylhexanoate.
The activator comprises an alkyl aluminum compound, an aluminoxane compound or an organoboron compound; the activator in the catalyst system of the present invention acts as an activator in the catalyst system. Activators useful in the present invention may be any compound that when mixed with a ligand and a transition metal compound forms an active catalyst. The activators may be used alone or in combination. Further, the activator comprises one or a mixture of several of alkyl aluminum compound, aluminoxane compound, organic boron compound, inorganic acid or inorganic salt.
Specifically, the activator may be an alkylaluminum compound, which may be various trialkylaluminums such as trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum, tri-n-butylaluminum, tri-n-pentylaluminum or tri-n-heptylaluminum; the alkylaluminum compound may also be an alkylaluminum halide, alkylaluminum hydride or alkylaluminum sesquichloride, such as diethylaluminum chloride (AlEt 2 Cl) and triethylaluminum chloride (Al 2Et3Cl3).
Specifically, the activator may be an aluminoxane compound, which can be generally prepared by mixing water with an alkylaluminum compound (e.g., trimethylaluminum). The aluminoxane oligomer compound prepared may be a linear compound, a cyclic compound, a cage compound, or a mixture thereof. Suitable aluminoxane compounds can be selected from Methylaluminoxane (MAO), ethylaluminoxane (EAO), isobutylaluminoxane (i BAO), modified Methylaluminoxane (MMAO), and volatile removed methylaluminoxane (DMAO), among others.
Specifically, suitable boron compounds may include boroxine, triethylborane, triphenylborane, tris (pentafluorophenyl) borane, methylammonium tetrakis (pentafluorophenyl) borate, anilinium tetrakis (pentafluorophenyl) borate, and the like. The organoboron compound may be used in a form of a mixture with the organoaluminum compound.
Preferably, the activator may be selected from Methylaluminoxane (MAO), ethylaluminoxane (EAO), isobutylaluminoxane (i BAO) and Modified Methylaluminoxane (MMAO).
The molar ratio of the ligand to the transition metal element in the transition metal compound is (0.1-100): 1; preferably (0.1-20): 1, more preferably (0.5-4): 1; the molar ratio of the activator to the transition metal element in the transition metal compound is (1-10000): 1, preferably (1-5000): 1, more preferably (300-000): 1, and finally preferably (400-700): 1.
Further, the aluminoxane compound specifically comprises a modified methylaluminoxane MMAO-3A; the molar ratio of the ligand to the transition metal element in the transition metal compound is 1:1; the mole ratio of the activator to the transition metal element in the transition metal compound is (400-700): 1.
Further, the molar ratio of the activator to the transition metal element in the transition metal compound is (600-700): 1.
A process for preparing a catalyst for the selective tetramerization of ethylene containing PCCP ligand as described above, which process comprises: the ligand, the transition metal compound and the activator are pre-mixed or directly added into a reaction system for in-situ synthesis, thus obtaining the catalyst containing PCCP ligand for ethylene selective tetramerization.
In some embodiments, the ligand of formula (I), the transition metal compound, and the activator may be mixed simultaneously or in any order in the presence or absence of a solvent to provide an active catalyst. The mixing of the catalyst components can be carried out at 0-300 c and the presence of the olefin during the mixing of the catalyst components generally shows a protective effect, providing improved catalytic performance. Further, the mixing of the catalyst components may be performed at a temperature in the range of about 15-100 ℃.
In some embodiments, the detachable metal-ligand complex may be prepared in situ from the transition metal compound and the ligand of formula (I). The metal-ligand complex is then added to the reaction medium. Alternatively, the chromium compound and the ligand may be separately added to the reactor, thereby preparing the chromium-ligand complex in situ. In situ preparation of the complex means that the complex is prepared in the medium in which the catalytic reaction takes place and finally the activator is added.
Use of a catalyst for the selective tetramerisation of ethylene containing PCCP ligands as described above, for the selective tetramerisation of ethylene to 1-octene, the reaction being carried out in an inert solvent at a temperature of from 0 to 250 ℃ and at a pressure of from 10 to 40000psig, the concentration of transition metal in the transition metal compound in the inert solvent being from 0.01 to 10000 μmol/L, preferably from 0.05 to 200 μmol/L, more preferably from 0.1 to 10 μmol/L.
The inert solvent comprises one or more of alkane, substituted alkane, aromatic hydrocarbon, substituted aromatic hydrocarbon, alkene, substituted alkene or ionic liquid. Typical solvents include, but are not limited to, benzene, toluene, xylene, cumene, chlorobenzene, dichlorobenzene, fluorobenzene, n-heptane, n-hexane, methylcyclohexane, cyclohexane, 1-hexene, 1-octene, and the like, with toluene, methylcyclohexane being preferred.
Further, the reaction temperature is 30-70 ℃, preferably 50-70 ℃, and the pressure is 550-650psig. In another aspect, the temperature of the reaction is from 0 to 150deg.C, preferably from 5 to 125deg.C, more preferably from 10 to 100deg.C, even more preferably from 20 to 75deg.C, and even more preferably from 20 to 50deg.C, and the reaction pressure is from 20 to 40000psig, preferably from 150 to 1000psig, more preferably from 200 to 1000psig, and even more preferably from 400 to 700psig.
Compared with the prior art, the invention has the following advantages:
In order to further improve the selectivity of 1-octene and the activity of the catalytic system, the invention creatively introduces a sterically-hindered adjustable diamine phosphine fragment and a cyclodiphosphine nitrogen fragment into a vinyl bridged biphosphine ligand. By introducing the cyclodiphosphine nitrogen fragments and changing the substituents on the N atom and the P atom, the invention successfully improves the 1-octene selectivity of the catalytic system to 70.2 percent, improves the total selectivity of 1-hexene and 1-octene to 96.1 percent, can effectively improve the selectivity of 1-octene while reducing the cyclic C 6, and has the activity of 5650kg/g Cr/h at most. The reduced steric hindrance when the substituents on the phosphine are linked together, as compared to acyclic phosphines, is advantageous for increasing the catalytic activity and selectivity of 1-octene.
Detailed Description
The following describes in detail the examples of the present invention, which are implemented on the premise of the technical solution of the present invention, and detailed embodiments and specific operation procedures are given, but the scope of protection of the present invention is not limited to the following examples. The term "mass% is not specifically defined but may be regarded as mass%.
A catalyst for ethylene selective tetramerization containing PCCP ligand and a preparation method and application thereof, wherein the preparation method is as follows: the ligand, the transition metal compound and the activator are pre-mixed or directly added into a reaction system for in-situ synthesis, thus obtaining the catalyst containing PCCP ligand for ethylene selective tetramerization. The catalyst is used for ethylene selective tetramerization reaction to generate 1-octene, the reaction is carried out in an inert solvent, the reaction temperature is 0-250 ℃, the reaction pressure is 10-40000psig, and the concentration of transition metal in the transition metal compound in the inert solvent is 0.01-10000 mu mol/L; the inert solvent comprises one or more of alkane, substituted alkane, aromatic hydrocarbon, substituted aromatic hydrocarbon, alkene, substituted alkene or ionic liquid. In some embodiments, the temperature of the reaction is 30-70 ℃, preferably 50-70 ℃, and the pressure is 550-650psig.
Wherein the chemical structural formula of the ligand is shown as the following formula (I):
In the method, in the process of the invention,
The groups R 1 and R 2 are each independently selected from hydrogen, alkyl, heteroatom-containing alkyl, alkenyl or aromatic groups; or R 1 and R 2 are linked to form a cyclic structure containing 5 to 10 atoms; for example, the groups R 1 and R 2 are selected from hydrogen, alkyl or aromatic groups; the alkyl group comprises octyl, isopropyl or tertiary butyl, and the aromatic group comprises phenyl;
The groups R 3 to R 8 are each independently selected from hydrogen, alkyl, heteroatom-containing alkyl, alkenyl or aromatic groups; or R 1 and R 2 are linked to form a cyclic structure containing 5 to 10 atoms. For example, the groups R 3 and R 4 are selected from phenyl or substituted phenyl; the substituted phenyl comprises substituted phenyl 2-fluorophenyl or 2, 4-difluorophenyl; the groups R 5 and R 6 are selected from alkyl; the alkyl group comprises methyl, ethyl or propyl; the groups R 7 and R 8 are selected from alkyl groups, including in particular methyl groups, or R 7 and R 8 are linked together to form a cyclodiphosphino nitrogen group.
In some embodiments, the alkyl groups in groups R 1 and R 2 are t-butyl; the substituted phenyl groups in the groups R 3 and R 4 are 2, 4-difluorophenyl groups; the alkyl groups in the radicals R 5 and R 6 are propyl groups; the groups R 7 and R 8 are joined together to form a cyclodiphosphino nitrogen group.
The transition metal in the transition metal compound is selected from iron, cobalt, nickel, copper, titanium, vanadium, chromium, manganese, molybdenum, tungsten, nickel, palladium, zirconium or hafnium; the activator comprises an alkyl aluminum compound, an aluminoxane compound or an organoboron compound; the molar ratio of the ligand to the transition metal element in the transition metal compound is (0.1-100): 1; the mole ratio of the activator to the transition metal element in the transition metal compound is (1-10000): 1. In some embodiments, the aluminoxane compound specifically comprises a modified methylaluminoxane MMAO-3A; the molar ratio of the ligand to the transition metal element in the transition metal compound is 1:1; the mole ratio of the activator to the transition metal element in the transition metal compound is (400-700): 1, preferably (600-700): 1.
Example 1
The preparation of complex 1 is as follows:
(1) Preparation of 2-chloro-1, 3-dimethyl-1, 3, 2-diazaphospholane
N, N' -dimethylethylenediamine (0.2203 g,25 mmol) was mixed with triethylamine (4 mL,28.75 mmol) and redistilled dichloromethane (3.8 mL) at room temperature in a 25mL argon filled Schlenk flask to give mixture 1. PCl 3 (3.4332 g,25 mmol) was mixed with redistilled dichloromethane (6.3 mL) at room temperature in a 25mL argon filled Schlenk flask to give mixture 2. Triethylamine (4 mL,28.75 mmol) was mixed with redistilled dichloromethane (2.5 mL) in a 25mL argon filled Schlenk flask at room temperature to give mixture 3. Mixture 1 and mixture 2 were simultaneously added drop wise to a 100mL Schlenk flask filled with argon and with redistilled dichloromethane (10 mL) at-40 ℃. The temperature was raised to-30℃and mixture 3 was added dropwise. The reaction system was allowed to warm to room temperature and reacted for 2h. The solvent was removed by rotary evaporation, extracted 3 times with 100mL of diethyl ether, and the organic phase was separated. The solvent was removed by rotary evaporation to give a crude product, which was purified by separation using a silica gel column to give a white powder (3.4364 g, 90.1%).
(2) Preparation of ligand L 1
A solution of 3, 3-dimethylbutyyne (0.9306 g,11 mmol) in THF (15 mL) was added to a Schlenk flask filled with argon. 4.4mL of a 2.5mol/L hexane solution (11 mmol) of n-butyllithium was added dropwise in an ice-water bath, and stirred at this temperature for 30min. 2-chloro-1, 3-dimethyl-1, 3, 2-diazaphospholane (1.526 g,10 mmol) was added dropwise. The mixture was allowed to warm to room temperature and stirred for 1h. Water (20 mL) was added to quench the residual n-butyllithium, and the mixture was extracted with diethyl ether and n-hexane to separate an organic phase. The solvent was removed by rotary evaporation and further separated by means of silica gel column chromatography. The solvent was removed by rotary evaporation to give an intermediate product. To a Schlenk flask filled with argon, copper iodide (1.9 mg, 0.010mmol), cesium carbonate (0.016 g,0.050 mmol), and DMF (3.0 mL), intermediate (0.0763 mg,0.50 mmol) and diphenylphosphine (0.0984 g,0.52 mmol) were added sequentially with stirring. The mixture was reacted at 90℃for 4h. Cooled to room temperature. Diatomaceous earth was added to the mixture, and filtered. Distilling the filtrate under reduced pressure, separating by silica gel column chromatography, and removing solvent by rotary evaporation to obtain white oily product L1(0.1636mg,85.1％).1H NMR(400MHz,CDCl3)δ1.01-1.03(s,9H),2.42-2.44(m,4H),2.65-2.67(m,4H),5.0-5.02(s,1H),7.14-7.16(m,4H),7.41-7.43(m,6H).
(3) Preparation of Complex 1
In a dry and argon filled Schlenk reaction tube, ligand L 1 (0.1922 g,0.5 mmol) and CrCl 3(THF)3 (183.3 mg,0.5 mmol) were added and redistilled dichlorotoluene (10 mL) was added and stirred at room temperature for 2h. After completion of the reaction, the mixture was filtered, and the filtrate was dried by suction to give a solid which was washed with n-hexane (5 mL. Times.3) and dried by suction to give 0.2770g (0.46 mmol, 90.1%) of a blue powder.
Example 2
The preparation of complex 2 is as follows:
(1) Preparation of ligand L 2
Preparation of reference ligand L 1 Using N, N '-diethyl ethylenediamine (0.2906 g,25 mmol) instead of N, N' -dimethyl ethylenediamine gives the product as a colourless oil L2(0.0850g,82.4％).1H NMR(400MHz,CDCl3)δ1.01-1.03(s,9H),1.06-1.08(m,6H),2.65-2.69(m,4H),2.96-2.98(m,4H),5.05-5.1(s,1H),7.15-7.17(m,4H),7.40-7.42(m,6H).
(2) Preparation of Complex 2
In a dry and argon filled Schlenk reaction tube, ligand L 2 (0.2063 g,0.5 mmol) and CrCl 3(THF)3 (183.3 mg,0.5 mmol) were added and redistilled dichlorotoluene (10 mL) was added and stirred at room temperature for 2h. After completion of the reaction, the mixture was filtered, and the filtrate was dried by suction to give a solid which was washed with n-hexane (5 mL. Times.3) and dried by suction to give 0.2771g (0.43 mmol, 86.2%) of a blue powder.
Example 3
The preparation of complex 3 is as follows:
(1) Preparation of ligand L 3
Preparation of reference ligand L 1 Using N-methyl-N '-propylethylenediamine (4.5155 g,25 mmol) instead of N, N' -dimethylethylenediamine gives the product as a colourless oil L3(0.0766g,84.8％).1H NMR(400MHz,CDCl3)δ0.87-0.89(s,3H),1.01-1.04(s,9H),1.43-1.46(m,2H),2.43-2.45(m,3H),2.52-2.54(m,2H),2.65-2.68(m,4H),5.1-5.12(s,1H),7.13-7.16(m,4H),7.41-7.45(m,6H).
(2) Preparation of Complex 3
In a dry and argon filled Schlenk reaction tube, ligand L 3 (0.2063 g,0.5 mmol) and CrCl 3(THF)3 (0.1833 g,0.5 mmol) were added, and redistilled dichlorotoluene (10 mL) was added and stirred at room temperature for 2h. After completion of the reaction, the mixture was filtered, and the filtrate was dried by suction to give a solid which was washed with n-hexane (5 mL. Times.3) and dried by suction to give 0.2827g (0.43 mmol, 87.9%) of a blue powder.
Example 4
The preparation of complex 4 is as follows:
(1) Preparation of ligand L 4
Preparation of reference ligand L 1 Using bis (2-fluoro) phenylphosphine (0.1155 g,0.52 mmol) instead of diphenylphosphine, a blue oily product was obtained L4(0.1818g,86.5％).1H NMR(400MHz,CDCl3)δ1.01-1.03(s,9H),2.43-2.45(s,6H),2.64-2.67(m,4H),5.0-5.03(s,1H),7.13-7.15(m,2H),7.19-7.2(m,4H),7.60-7.63(m,2H).
(2) Preparation of Complex 4
In a dry and argon filled Schlenk reaction tube, ligand L 4 (0.2102 g,0.5 mmol) and CrCl 3(THF)3 (0.1833 g,0.5 mmol) were added and redistilled dichlorotoluene (10 mL) was added and stirred at room temperature for 2h. After completion of the reaction, the mixture was filtered, and the filtrate was dried by suction to give a solid which was washed with n-hexane (5 mL. Times.3) and dried by suction to give 0.2978g (0.46 mmol, 91.5%) of a bluish-green powder.
Example 5
The preparation of complex 5 is as follows:
(1) Preparation of ligand L 5
Preparation of reference ligand L 1 Using bis (2, 4-difluoro) phenylphosphine (0.1342 g,0.52 mmol) instead of diphenylphosphine, a yellow powder product was obtained L5(0.1869g,81.9％).1H NMR(400MHz,CDCl3)δ1.01-1.03(s,9H),2.43-2.45(m,6H),2.67-2.7(m,4H),5.03-5.05(s,1H),6.75-6.77(m,4H),7.02-7.05(m,2H),7.11-7.13(m,2H).
(2) Preparation of Complex 5
In a dry and argon filled Schlenk reaction tube, ligand L 5 (0.2282 g,0.5 mmol) and CrCl 3(THF)3 (0.1833 g,0.5 mmol) were added, and redistilled dichlorotoluene (10 mL) was added and stirred at room temperature for 2h. After completion of the reaction, the mixture was filtered, and the filtrate was dried to give a solid which was washed with n-hexane (5 mL. Times.3), and dried to give 0.3053g (0.44 mmol, 88.9%) of a blue powder.
Example 6
The preparation of complex 6 is as follows:
(1) Preparation of ligand L 6
Preparation of reference ligand L 1 Using 1-octyne (1.2122 g,11 mmol) instead of 3, 3-dimethylbutyyne gives a blue powder product L6(0.1807g,87.6％).1H NMR(400MHz,CDCl3)δ0.86-0.89(m,3H),1.29-1.31(m,6H),1.34-1.35(m,2H),1.94-1.96(m,2H),2.43-2.45(s,6H),2.67-2.68(m,4H),4.98-5.02(m,1H),7.15-7.18(m,4H),7.41-7.43(m,6H).
(2) Preparation of Complex 6
In a dry and argon filled Schlenk reaction tube, ligand L 6 (0.2063 g,0.5 mmol) and CrCl 3(THF)3 (0.1833 g,0.5 mmol) were added, and redistilled dichlorotoluene (10 mL) was added and stirred at room temperature for 2h. After completion of the reaction, the mixture was filtered, and the filtrate was dried by suction to give a solid which was washed with n-hexane (5 mL. Times.3), and dried by suction to give 0.2900g (0.45 mmol, 90.2%) of a bluish-green powder.
Example 7
The preparation of complex 7 is as follows:
(1) Preparation of ligand L 7
Preparation of reference ligand L 2 Using 1-octyne (1.2122 g,11 mmol) instead of 3, 3-dimethylbutyyne gives the product as a blue oil L7(0.1897g,86.1％).1H NMR(400MHz,CDCl3)δ0.86-0.88(m,3H),1.01-1.05(m,6H),1.29-1.31(m,6H),1.34-1.37(m,2H),1.96-2.0(m,2H),2.64-2.67(m,4H),2.96-2.98(m,4H),5.0-5.02(s,1H),7.15-7.18(m,4H),7.41-7.43(m,6H).
(2) Preparation of Complex 7
In a dry and argon filled Schlenk reaction tube, ligand L 7 (0.2203 g,0.5 mmol) and CrCl 3(THF)3 (0.1833 g,0.5 mmol) were added, and redistilled dichlorotoluene (10 mL) was added and stirred at room temperature for 2h. After completion of the reaction, the mixture was filtered, and the filtrate was dried to give a solid which was washed with n-hexane (5 mL. Times.3), and dried to give 0.2768g (0.41 mmol, 82.5%) of a blue powder.
Example 8
The preparation of complex 8 is as follows:
(1) Preparation of ligand L 8
Preparation of reference ligand L 1 Using 3-methyl-1-butyne (0.7493 g,11 mmol) instead of 3, 3-dimethylbutyyne gives a blue powder product L8(0.1658g,89.5％).1H NMR(400MHz,CDCl3)δ0.86(m,6H),2.38-2.4(m,1H),2.43-2.45(m,6H),2.67-2.69(m,4H),5.01-5.06(s,1H),7.13-7.15(m,4H),7.41-7.43(m,6H).
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(2) Preparation of Complex 8
In a dry and argon filled Schlenk reaction tube, ligand L 8 (0.1852 g,0.5 mmol) and CrCl 3(THF)3 (0.1833 g,0.5 mmol) were added, and redistilled dichlorotoluene (10 mL) was added and stirred at room temperature for 2h. After completion of the reaction, the mixture was filtered, and the filtrate was dried to give a solid which was washed with n-hexane (5 mL. Times.3) and dried to give 0.2581g (0.43 mmol, 85.9%) of a blue powder.
Example 9
The preparation of complex 1 is as follows:
(1) Preparation of ligand L 9
Preparation of reference ligand L 2 Using 3-methyl-1-butyne (0.7493 g,11 mmol) instead of 3, 3-dimethylbutyyne gives the product as a yellow oil L9(0.1771g,88.9％).1H NMR(400MHz,CDCl3)δ0.86-0.89(m,6H),1.0-1.03(m,6H),2.38-2.4(m,1H),2.67-2.69(m,4H),2.94-2.98(m,4H),5.02-5.05(s,1H),7.15-7.18(m,4H),7.41-7.45(m,6H).
(2) Preparation of Complex 9
In a dry and argon filled Schlenk reaction tube, ligand L 9 (0.1992 g,0.5 mmol) and CrCl 3(THF)3 (0.1833 g,0.5 mmol) were added, and redistilled dichlorotoluene (10 mL) was added and stirred at room temperature for 2h. After completion of the reaction, the mixture was filtered, and the filtrate was dried to give a solid which was washed with n-hexane (5 mL. Times.3), and dried to give 0.2531g (0.40 mmol, 80.5%) of a blue powder.
Example 10
The preparation of complex 10 is as follows:
(1) Preparation of ligand L 10
In a Schlenk reaction tube which was dried and filled with argon, 2-bromophenyl diphenylphosphine (1.0235 g,3 mmol) was added and then dissolved by adding 30mL of THF. To this was added dropwise 1.2mL of a 2.5mol/L hexane solution (3 mmol) of n-butyllithium at-78 ℃. 2-chloro-1, 3-dimethyl-1, 3, 2-diazaphospholane (0.4578 g,3 mmol) was added dropwise with stirring at-78deg.C for 30 min. The reaction system was allowed to warm to room temperature and reacted for 2h. 5mL of water was added to quench the reaction residue of n-butyllithium, and the mixture was separated. The organic phase was washed with saturated sodium chloride solution (10 mL. Times.3) and separated. The organic phase was dried by adding anhydrous magnesium sulfate. Filtering, rotary evaporating to remove solvent to obtain crude product, and separating and purifying with silica gel column to obtain colorless oily product L10(0.9865g,86.9％).1H NMR(400MHz,CDCl3)δ2.43-2.47(m,6H),2.65-2.68(m,4H),7.15-7.17(m,6H),7.44-7.47(m,8H).
(2) Preparation of Complex 10
In a dry and argon filled Schlenk reaction tube, ligand L 10 (0.1892 g,0.5 mmol) and CrCl 3(THF)3 (0.1833 g,0.5 mmol) were added, and redistilled dichlorotoluene (10 mL) was added and stirred at room temperature for 2h. After completion of the reaction, the mixture was filtered, and the filtrate was dried to give a solid which was washed with n-hexane (5 mL. Times.3), and dried to give 0.2521g (0.41 mmol, 82.8%) of a bluish-green powder.
Example 11
The preparation of complex 11 is as follows:
(1) Preparation of ligand L 11
Preparation of reference ligand L 1, 2-chloro-1, 3-dimethyl-1, 3, 2-diazaphospholane was replaced with bis (dimethylamino) chlorophosphine (1.5480 g,10 mmol) to give the product as a colourless powder L11(0.1606g,81.3％).1H NMR(400MHz,CDCl3)δ0.99-1.03(s,9H),2.45-2.47(s,12H),5.01-5.04(s,1H),7.14-7.16(m,4H),7.43-7.47(m,6H).
(2) Preparation of Complex 11
In a dry and argon filled Schlenk reaction tube, ligand L 11 (0.1923 g,0.5 mmol) and CrCl 3(THF)3 (0.1833 g,0.5 mmol) were added and redistilled dichlorotoluene (10 mL) was added and stirred at room temperature for 2h. After completion of the reaction, the mixture was filtered, and the filtrate was dried to give a solid which was washed with n-hexane (5 mL. Times.3) and dried to give 0.2605g (0.43 mmol, 85.1%) of a blue powder.
Example 12
The preparation of complex 12 is as follows:
(1) Preparation of ligand L 12
Preparation of reference ligand L 1 Using diphenylphosphine chloride (2.2064 g,10 mmol) in place of 2-chloro-1, 3-dimethyl-1, 3, 2-diazaphospholane (1.526 g,10 mmol) gives the product as a colourless oil L12(0.1955g,86.4％).1H NMR(400MHz,CDCl3)δ1H NMR(400MHz,CDCl3)δ1.05-1.08(s,9H),5.09–5.13(s,1H),7.12-7.15(m,8H),7.43-7.47(m,12H).
(2) Preparation of Complex 12
In a dry and argon filled Schlenk reaction tube, ligand L 12 (0.3415 g,0.5 mmol) and CrCl 3(THF)3 (0.1833 g,0.5 mmol) were added, and redistilled dichlorotoluene (10 mL) was added and stirred at room temperature for 2h. After completion of the reaction, the mixture was filtered, and the filtrate was dried to give a solid which was washed with n-hexane (5 mL. Times.3) and dried to give 0.3029g (0.44 mmol, 88.7%) of a blue powder.
Example 13
A catalyst for ethylene selective tetramerization containing PCCP ligand and its preparation method and application, the steps are as follows:
(1) Preparation of the catalyst
In a Schlenk reaction tube which was dried and filled with argon, complex 1 (0.48 mg, 0.8. Mu. Mol) and redistilled methylcyclohexane (20 ml) were added and stirred for 5 minutes, and then modified methylaluminoxane MMAO-3A (0.48 mmol,1.12 mol/L) was added and reacted at room temperature for 5 minutes for further use.
(2) Oligomerization of ethylene
And (3) vacuumizing a 350mL stainless steel high-pressure gas reaction kettle on an oil bath at 120 ℃ for 3 hours to ensure the anhydrous and anaerobic environment of the reaction kettle, cooling to the reaction temperature, and ventilating the kettle with ethylene gas for three times. Then immediately sucking the prepared catalyst solution by a dry glass injector, injecting the catalyst solution into a high-pressure reaction kettle, sealing the reaction kettle, starting stirring, introducing ethylene gas, regulating the pressure to 550psig, and stirring and reacting at 50 ℃ for 30 minutes. After the reaction is finished, an ethylene gas supply valve is closed, the temperature is cooled to 0 ℃, the pressure is released, the reaction kettle is opened, and quantitative internal standard-nonane is added and stirred uniformly. The reaction was then quenched with 10wt% aqueous HCl for about 30mL and the organic phase was filtered and analyzed by GC. The remaining mixture in the reaction vessel was filtered and the solid was taken and added to 10wt% aqueous hcl and stirred for 2h, filtered, dried to constant weight and weighed, data shown in table 1.
Example 14
The difference from example 13 is that complex 1 used is replaced by complex 2 (0.52 mg, 0.8. Mu. Mol) and the data are given in Table 1.
Example 15
The difference from example 13 is that complex 1 used is replaced by complex 3 (0.58 mg, 0.8. Mu. Mol) and the data are given in Table 1.
Example 16
The difference from example 13 is that complex 1 used is replaced by complex 4 (0.53 mg, 0.8. Mu. Mol) and the data are given in Table 1.
Example 17
The difference from example 13 is that complex 1 used is replaced by complex 5 (0.50 mg, 0.8. Mu. Mol) and the data are given in Table 1.
Example 18
The difference from example 13 is that complex 1 used is replaced by complex 6 (0.62 mg, 0.8. Mu. Mol) and the data are given in Table 1.
Example 19
The difference from example 13 is that complex 1 used is replaced by complex 7 (0.50 mg, 0.8. Mu. Mol) and the data are given in Table 1.
Example 20
The difference from example 13 is that complex 1 used is replaced by complex 8 (0.52 mg, 0.8. Mu. Mol) and the data are given in Table 1.
Example 21
The difference from example 13 is that complex 1 used is replaced by complex 9 (0.49 mg, 0.8. Mu. Mol) and the data are given in Table 1.
Example 22
The difference from example 13 is that complex 1 used is replaced by complex 10 (0.52 mg, 0.8. Mu. Mol) and the data are given in Table 1.
Example 23
The difference from example 13 is that complex 1 used is replaced by complex 11 (0.52 mg, 0.8. Mu. Mol) and the data are given in Table 1.
Example 24
The difference from example 16 is that the ethylene oligomerization was carried out at 30℃and the data are shown in Table 1.
Example 25
The difference from example 16 is that the ethylene oligomerization was carried out at 70℃and the data are shown in Table 1.
Example 26
The difference from example 16 is that MMAO-3A was used in an amount of 0.32mmol, as shown in Table 1.
Example 27
The difference from example 16 is that MMAO-3A is used in an amount of 0.56mmol, as shown in Table 1.
Example 28
The difference from example 16 is that the reaction pressure for ethylene oligomerization was 600psig and the data are shown in Table 1.
Example 29
The difference from example 16 is that the reaction pressure for ethylene oligomerization is 650psig and the data are shown in Table 1.
Comparative example 1
The difference from example 16 is that complex 12 used is replaced by complex 4 (0.55 mg, 0.8. Mu. Mol) and the data are given in Table 1.
TABLE 1
As can be seen from Table 1, the catalyst provided by the invention has higher catalytic performance, and when the activity reaches 5150kg/g Cr/h, the 1-octene selectivity reaches 65.3%, and the highest selectivity reaches 70.2%. As can be seen by comparing example 13 with comparative example 1, the substitution of the diphenylphosphine fragment with the cyclodiphosphine nitrogen fragment in the two-carbon bridged bisphosphine ligand effectively improves the overall selectivity of 1-hexene and 1-octene. The cyclic diphosphine-azane fragment introduced in the invention effectively limits the movement of substituent groups on phosphine atoms due to the action of a ring, so that the steric hindrance influence on a metal center is reduced, and the 1-octene selectivity is effectively improved.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the invention in any way, and any person skilled in the art may make modifications or alterations to the disclosed technical content to the equivalent embodiments. However, any simple modification, equivalent variation and variation of the above embodiments according to the technical substance of the present invention still fall within the protection scope of the technical solution of the present invention.
Claims (10)
1. A catalyst for ethylene selective tetramerization containing PCCP ligand, which is characterized by comprising ligand, transition metal compound and activator, wherein the chemical structural formula of the ligand is shown as the following formula (I):
In the method, in the process of the invention,
The groups R 1 and R 2 are each independently selected from hydrogen, alkyl, heteroatom-containing alkyl, alkenyl or aromatic groups; or R 1 and R 2 are linked to form a cyclic structure containing 5 to 10 atoms;
The groups R 3 to R 8 are each independently selected from hydrogen, alkyl, heteroatom-containing alkyl, alkenyl or aromatic groups; or R 7 and R 8 are linked to form a cyclic structure containing 5 to 10 atoms.
2. The catalyst for the selective tetramerization of ethylene containing PCCP ligand according to claim 1, wherein the alkyl group is a C 1-C50 alkyl group, specifically comprising methyl, ethyl, n-propyl, isopropyl, n-butyl, 1-methylpropyl, 2-methylpropyl, 1, 2-dimethylethyl, n-pentyl, 1-methylbutyl, 2-dimethylpropyl, cyclopentyl, n-hexyl, 2-methylpentyl, 3-methylpentyl, 1-dimethylpropyl, n-heptyl, cycloheptyl, n-octyl, n-decyl, 2-methylcyclopentyl or 2, 6-dimethylcyclohexyl;
The heteroatom-containing alkyl is C 1-C50 alkyl, and the heteroatom specifically comprises oxygen, sulfur, silicon, halogen (including fluorine and chlorine) and nitrogen atoms, and specifically comprises methoxy, ethoxy, propoxy, isopropoxy, butoxy, 1-methoxyethyl, ethoxymethyl, isopropoxymethyl, 1-isopropoxyethyl, methoxyethoxymethyl, methoxypropoxymethyl, methylthio, ethylthio, propylthio, isopropylthio, butylthio, trimethylsilyl, trifluoromethyl, 2-chlorocyclopentyl, methylamino, ethylamino, propylamino and isopropylamino;
The alkenyl is C 1-C50 alkenyl, which specifically comprises vinyl, allyl, 1-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-2-butenyl, 2-methyl-1-butenyl, 3-methyl-2-butenyl, cyclopentadienyl, 1-hexenyl, 5-hexenyl, 2-methylcyclohexenyl, 2, 6-dimethylcyclohexenyl, 3-cyclohexenyl or 2-methyl-2-cyclohexenyl;
The aromatic group is aryl of C 4-C50 and derivatives thereof, specifically included are phenyl, 4-fluorophenyl, 2-fluorophenyl, 3-fluorophenyl, 2-chlorophenyl, 4-chlorophenyl, 2- (trifluoromethyl) phenyl, 2, 4-di (trifluoromethyl) phenyl, 2, 6-difluorophenyl, 2, 5-difluorophenyl, 2, 4-difluorophenyl, 2, 3-difluorophenyl, 3, 4-difluorophenyl, 3, 5-difluorophenyl, 2, 6-dichlorophenyl, 2, 5-dichlorophenyl, 2, 4-dichlorophenyl, 2, 3-dichlorophenyl, 3, 4-dichlorophenyl, 3, 5-dichlorophenyl, 2-fluoro-4-chlorophenyl, 2,4, 6-trifluorophenyl, 4-methylphenyl, 2-ethylphenyl, 3-ethylphenyl 2, 4-dimethylphenyl, 2, 4-diisopropylphenyl, 2, 4-di-tert-butylphenyl, 2, 6-dimethylphenyl, 2, 6-diisopropylphenyl, 3, 5-dimethylphenyl, 3, 5-di-tert-butylphenyl, 2,4, 6-trimethylphenyl, naphthyl, anthracenyl, biphenyl, 2-thienyl, 3-thienyl, 5-fluoro-2-thienyl, 2-fluoro-3-thienyl, 2, 5-difluoro-3-thienyl, 2-fluoro-1-naphthyl, 7-fluoro-1-naphthyl, 8-fluoro-1-naphthyl, 7-chloro-1-naphthyl, 8-fluoro-1-anthracenyl, 9-fluoro-1-anthracenyl, 10-fluoro-1-anthryl, 8-chloro-1-anthryl or 2, 8-difluoro-1-naphthyl.
3. A catalyst for the selective tetramerisation of ethylene containing PCCP ligands according to claim 1 or 2, characterised in that the groups R 1 and R 2 are selected from hydrogen, alkyl or aromatic groups; the alkyl group comprises octyl, isopropyl or tertiary butyl, and the aromatic group comprises phenyl;
The groups R 3 and R 4 are selected from phenyl or substituted phenyl; the substituted phenyl comprises substituted phenyl 2-fluorophenyl or 2, 4-difluorophenyl;
The groups R 5 and R 6 are selected from alkyl; the alkyl comprises C 1-C4 alkyl, specifically comprises methyl, ethyl or propyl;
The radicals R 7 and R 8 are selected from alkyl groups, including alkyl groups of C 1-C4, including in particular methyl, or R 7 and R 8 are linked together to form a cyclodiphosphino nitrogen group.
4. A catalyst for the selective tetramerisation of ethylene containing PCCP ligands according to claim 3, characterised in that the alkyl groups in the radicals R 1 and R 2 comprise C 1-C4 alkyl groups, in particular t-butyl groups; the substituted phenyl groups in the groups R 3 and R 4 are 2, 4-difluorophenyl groups; the alkyl groups in the radicals R 5 and R 6 are propyl groups; the groups R 7 and R 8 are joined together to form a cyclodiphosphino nitrogen group.
5. A PCCP ligand-containing ethylene selective tetramerization catalyst according to claim 1, wherein the transition metal in the transition metal compound is selected from iron, cobalt, nickel, copper, titanium, vanadium, chromium, manganese, molybdenum, tungsten, nickel, palladium, zirconium or hafnium; the activator comprises an alkyl aluminum compound, an aluminoxane compound or an organoboron compound; the molar ratio of the ligand to the transition metal element in the transition metal compound is (0.1-100): 1; the mole ratio of the activator to the transition metal element in the transition metal compound is (1-10000): 1.
6. The PCCP ligand-containing ethylene selective tetramerization catalyst of claim 5, wherein the aluminoxane compound specifically comprises modified methylaluminoxane MMAO-3A; the molar ratio of the ligand to the transition metal element in the transition metal compound is 1:1; the mole ratio of the activator to the transition metal element in the transition metal compound is (400-700): 1.
7. A catalyst for the selective tetramerization of ethylene containing PCCP ligand according to claim 6, wherein the molar ratio of the activator to the transition metal element in the transition metal compound is (600-700): 1.
8. A process for the preparation of a catalyst for the selective tetramerisation of ethylene containing PCCP ligands according to any one of claims 1 to 7, characterized in that it comprises: the ligand, the transition metal compound and the activator are pre-mixed or directly added into a reaction system for in-situ synthesis, thus obtaining the catalyst containing PCCP ligand for ethylene selective tetramerization.
9. Use of the PCCP ligand-containing catalyst for the selective tetramerization of ethylene according to any one of claims 1 to 7, wherein the catalyst is used for the selective tetramerization of ethylene to 1-octene, the reaction is carried out in an inert solvent at a temperature of 0 to 250 ℃, a reaction pressure of 10 to 40000psig, and a concentration of transition metal in the transition metal compound in the inert solvent of 0.01 to 10000 μmol/L;
The inert solvent comprises one or more of alkane, substituted alkane, aromatic hydrocarbon, substituted aromatic hydrocarbon, alkene, substituted alkene or ionic liquid.
10. Use of a PCCP ligand-containing catalyst for the selective tetramerisation of ethylene according to claim 9, characterized in that the temperature of the reaction is 30-70 ℃, preferably 50-70 ℃, and the pressure is 550-650psig.
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