CN105728045A - Novel linear alpha olefin catalyst and preparation method and application thereof - Google Patents
Novel linear alpha olefin catalyst and preparation method and application thereof Download PDFInfo
- Publication number
- CN105728045A CN105728045A CN201610164561.4A CN201610164561A CN105728045A CN 105728045 A CN105728045 A CN 105728045A CN 201610164561 A CN201610164561 A CN 201610164561A CN 105728045 A CN105728045 A CN 105728045A
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- CN
- China
- Prior art keywords
- phenyl
- catalyst
- butyl
- aromatic ring
- tert
- Prior art date
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- 239000003054 catalyst Substances 0.000 title claims abstract description 67
- 239000004711 α-olefin Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title abstract description 7
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000005977 Ethylene Substances 0.000 claims abstract description 19
- 150000001875 compounds Chemical class 0.000 claims abstract description 16
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims abstract description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000009826 distribution Methods 0.000 claims abstract description 6
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910000085 borane Inorganic materials 0.000 claims abstract description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 44
- 238000006243 chemical reaction Methods 0.000 claims description 41
- -1 2-aminomethyl phenyl Chemical group 0.000 claims description 39
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 31
- 238000000034 method Methods 0.000 claims description 31
- 239000002904 solvent Substances 0.000 claims description 26
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 21
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 21
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N N-phenyl amine Natural products NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 10
- 150000001336 alkenes Chemical class 0.000 claims description 8
- 239000003208 petroleum Substances 0.000 claims description 8
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 5
- 229910005267 GaCl3 Inorganic materials 0.000 claims description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052794 bromium Inorganic materials 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 239000003446 ligand Substances 0.000 claims description 3
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical class ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- 229920013639 polyalphaolefin Polymers 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims 5
- 229910052736 halogen Inorganic materials 0.000 claims 3
- 150000002367 halogens Chemical class 0.000 claims 3
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims 2
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims 2
- AVYPEYYPGYMFDO-UHFFFAOYSA-N 1,3,5-tributylbenzene Chemical class CCCCC1=CC(CCCC)=CC(CCCC)=C1 AVYPEYYPGYMFDO-UHFFFAOYSA-N 0.000 claims 1
- ZPQOPVIELGIULI-UHFFFAOYSA-N 1,3-dichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1 ZPQOPVIELGIULI-UHFFFAOYSA-N 0.000 claims 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical group ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 claims 1
- BEZVGIHGZPLGBL-UHFFFAOYSA-N 2,6-diacetylpyridine Chemical compound CC(=O)C1=CC=CC(C(C)=O)=N1 BEZVGIHGZPLGBL-UHFFFAOYSA-N 0.000 claims 1
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 claims 1
- 125000006276 2-bromophenyl group Chemical group [H]C1=C([H])C(Br)=C(*)C([H])=C1[H] 0.000 claims 1
- 125000004198 2-fluorophenyl group Chemical group [H]C1=C([H])C(F)=C(*)C([H])=C1[H] 0.000 claims 1
- 125000004860 4-ethylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])C([H])([H])[H] 0.000 claims 1
- 125000001255 4-fluorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1F 0.000 claims 1
- 125000004861 4-isopropyl phenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])(C([H])([H])[H])C([H])([H])[H] 0.000 claims 1
- 125000003545 alkoxy group Chemical group 0.000 claims 1
- 229910052782 aluminium Inorganic materials 0.000 claims 1
- 239000004411 aluminium Substances 0.000 claims 1
- 125000002490 anilino group Chemical class [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims 1
- 150000001555 benzenes Chemical class 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 229940117389 dichlorobenzene Drugs 0.000 claims 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims 1
- 238000006384 oligomerization reaction Methods 0.000 abstract description 13
- 239000002994 raw material Substances 0.000 abstract description 6
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract 1
- 125000001841 imino group Chemical group [H]N=* 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 abstract 1
- 125000003118 aryl group Chemical group 0.000 description 68
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 18
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Substances CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 17
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 15
- RZXMPPFPUUCRFN-UHFFFAOYSA-N p-toluidine Chemical compound CC1=CC=C(N)C=C1 RZXMPPFPUUCRFN-UHFFFAOYSA-N 0.000 description 15
- 238000005160 1H NMR spectroscopy Methods 0.000 description 14
- 238000004440 column chromatography Methods 0.000 description 12
- GNKZMNRKLCTJAY-UHFFFAOYSA-N 4'-Methylacetophenone Chemical compound CC(=O)C1=CC=C(C)C=C1 GNKZMNRKLCTJAY-UHFFFAOYSA-N 0.000 description 10
- 150000001448 anilines Chemical class 0.000 description 9
- 239000001257 hydrogen Substances 0.000 description 9
- 229910052739 hydrogen Inorganic materials 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 7
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 6
- KZJRKRQSDZGHEC-UHFFFAOYSA-N 2,2,2-trifluoro-1-phenylethanone Chemical compound FC(F)(F)C(=O)C1=CC=CC=C1 KZJRKRQSDZGHEC-UHFFFAOYSA-N 0.000 description 6
- CZZZABOKJQXEBO-UHFFFAOYSA-N 2,4-dimethylaniline Chemical compound CC1=CC=C(N)C(C)=C1 CZZZABOKJQXEBO-UHFFFAOYSA-N 0.000 description 6
- VOWZNBNDMFLQGM-UHFFFAOYSA-N 2,5-dimethylaniline Chemical class CC1=CC=C(C)C(N)=C1 VOWZNBNDMFLQGM-UHFFFAOYSA-N 0.000 description 6
- UFFBMTHBGFGIHF-UHFFFAOYSA-N 2,6-dimethylaniline Chemical compound CC1=CC=CC(C)=C1N UFFBMTHBGFGIHF-UHFFFAOYSA-N 0.000 description 6
- DOLQYFPDPKPQSS-UHFFFAOYSA-N 3,4-dimethylaniline Chemical compound CC1=CC=C(N)C=C1C DOLQYFPDPKPQSS-UHFFFAOYSA-N 0.000 description 6
- MKARNSWMMBGSHX-UHFFFAOYSA-N 3,5-dimethylaniline Chemical compound CC1=CC(C)=CC(N)=C1 MKARNSWMMBGSHX-UHFFFAOYSA-N 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 229910052756 noble gas Inorganic materials 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 208000035126 Facies Diseases 0.000 description 5
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 5
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 5
- QFLWZFQWSBQYPS-AWRAUJHKSA-N (3S)-3-[[(2S)-2-[[(2S)-2-[5-[(3aS,6aR)-2-oxo-1,3,3a,4,6,6a-hexahydrothieno[3,4-d]imidazol-4-yl]pentanoylamino]-3-methylbutanoyl]amino]-3-(4-hydroxyphenyl)propanoyl]amino]-4-[1-bis(4-chlorophenoxy)phosphorylbutylamino]-4-oxobutanoic acid Chemical compound CCCC(NC(=O)[C@H](CC(O)=O)NC(=O)[C@H](Cc1ccc(O)cc1)NC(=O)[C@@H](NC(=O)CCCCC1SC[C@@H]2NC(=O)N[C@H]12)C(C)C)P(=O)(Oc1ccc(Cl)cc1)Oc1ccc(Cl)cc1 QFLWZFQWSBQYPS-AWRAUJHKSA-N 0.000 description 4
- ONBQEOIKXPHGMB-VBSBHUPXSA-N 1-[2-[(2s,3r,4s,5r)-3,4-dihydroxy-5-(hydroxymethyl)oxolan-2-yl]oxy-4,6-dihydroxyphenyl]-3-(4-hydroxyphenyl)propan-1-one Chemical compound O[C@@H]1[C@H](O)[C@@H](CO)O[C@H]1OC1=CC(O)=CC(O)=C1C(=O)CCC1=CC=C(O)C=C1 ONBQEOIKXPHGMB-VBSBHUPXSA-N 0.000 description 4
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 4
- 229940125773 compound 10 Drugs 0.000 description 4
- 229940126142 compound 16 Drugs 0.000 description 4
- 229940125898 compound 5 Drugs 0.000 description 4
- 239000012043 crude product Substances 0.000 description 4
- 239000003599 detergent Substances 0.000 description 4
- ZLVXBBHTMQJRSX-VMGNSXQWSA-N jdtic Chemical compound C1([C@]2(C)CCN(C[C@@H]2C)C[C@H](C(C)C)NC(=O)[C@@H]2NCC3=CC(O)=CC=C3C2)=CC=CC(O)=C1 ZLVXBBHTMQJRSX-VMGNSXQWSA-N 0.000 description 4
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 4
- 229920000573 polyethylene Polymers 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- 230000004044 response Effects 0.000 description 4
- 125000003944 tolyl group Chemical group 0.000 description 4
- 0 *c1c(ccc2c3c(cc4)ccc2)c3c4c(*)n1 Chemical compound *c1c(ccc2c3c(cc4)ccc2)c3c4c(*)n1 0.000 description 3
- NOXLGCOSAFGMDV-UHFFFAOYSA-N 2,3,4,5,6-pentafluoroaniline Chemical compound NC1=C(F)C(F)=C(F)C(F)=C1F NOXLGCOSAFGMDV-UHFFFAOYSA-N 0.000 description 3
- IDPFUSFISAHBPQ-UHFFFAOYSA-N 2,3,4-tris(fluoromethyl)aniline Chemical compound NC1=CC=C(CF)C(CF)=C1CF IDPFUSFISAHBPQ-UHFFFAOYSA-N 0.000 description 3
- VVAKEQGKZNKUSU-UHFFFAOYSA-N 2,3-dimethylaniline Chemical compound CC1=CC=CC(N)=C1C VVAKEQGKZNKUSU-UHFFFAOYSA-N 0.000 description 3
- OOMNPYBQJCAHFY-UHFFFAOYSA-N 2,4,5-tris(fluoromethyl)aniline Chemical compound FCC1=C(N)C=C(C(=C1)CF)CF OOMNPYBQJCAHFY-UHFFFAOYSA-N 0.000 description 3
- KWVPRPSXBZNOHS-UHFFFAOYSA-N 2,4,6-Trimethylaniline Chemical compound CC1=CC(C)=C(N)C(C)=C1 KWVPRPSXBZNOHS-UHFFFAOYSA-N 0.000 description 3
- LGUKNGHOZGOFJL-UHFFFAOYSA-N 2,4,6-tris(fluoromethyl)aniline Chemical compound NC1=C(CF)C=C(CF)C=C1CF LGUKNGHOZGOFJL-UHFFFAOYSA-N 0.000 description 3
- JJVKJJNCIILLRP-UHFFFAOYSA-N 2-ethyl-6-methylaniline Chemical compound CCC1=CC=CC(C)=C1N JJVKJJNCIILLRP-UHFFFAOYSA-N 0.000 description 3
- ZQEXBVHABAJPHJ-UHFFFAOYSA-N 2-fluoro-4-methylaniline Chemical compound CC1=CC=C(N)C(F)=C1 ZQEXBVHABAJPHJ-UHFFFAOYSA-N 0.000 description 3
- FTZQXOJYPFINKJ-UHFFFAOYSA-N 2-fluoroaniline Chemical compound NC1=CC=CC=C1F FTZQXOJYPFINKJ-UHFFFAOYSA-N 0.000 description 3
- JJYPMNFTHPTTDI-UHFFFAOYSA-N 3-methylaniline Chemical compound CC1=CC=CC(N)=C1 JJYPMNFTHPTTDI-UHFFFAOYSA-N 0.000 description 3
- QGLAYJCJLHNIGJ-UHFFFAOYSA-N 4-bromo-2,6-dimethylaniline Chemical compound CC1=CC(Br)=CC(C)=C1N QGLAYJCJLHNIGJ-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Natural products CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 125000001246 bromo group Chemical group Br* 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 239000002027 dichloromethane extract Substances 0.000 description 3
- 229960002089 ferrous chloride Drugs 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 239000004700 high-density polyethylene Substances 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 3
- RNVCVTLRINQCPJ-UHFFFAOYSA-N o-toluidine Chemical compound CC1=CC=CC=C1N RNVCVTLRINQCPJ-UHFFFAOYSA-N 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
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- AOSZTAHDEDLTLQ-AZKQZHLXSA-N (1S,2S,4R,8S,9S,11S,12R,13S,19S)-6-[(3-chlorophenyl)methyl]-12,19-difluoro-11-hydroxy-8-(2-hydroxyacetyl)-9,13-dimethyl-6-azapentacyclo[10.8.0.02,9.04,8.013,18]icosa-14,17-dien-16-one Chemical compound C([C@@H]1C[C@H]2[C@H]3[C@]([C@]4(C=CC(=O)C=C4[C@@H](F)C3)C)(F)[C@@H](O)C[C@@]2([C@@]1(C1)C(=O)CO)C)N1CC1=CC=CC(Cl)=C1 AOSZTAHDEDLTLQ-AZKQZHLXSA-N 0.000 description 2
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- LNUFLCYMSVYYNW-ZPJMAFJPSA-N [(2r,3r,4s,5r,6r)-2-[(2r,3r,4s,5r,6r)-6-[(2r,3r,4s,5r,6r)-6-[(2r,3r,4s,5r,6r)-6-[[(3s,5s,8r,9s,10s,13r,14s,17r)-10,13-dimethyl-17-[(2r)-6-methylheptan-2-yl]-2,3,4,5,6,7,8,9,11,12,14,15,16,17-tetradecahydro-1h-cyclopenta[a]phenanthren-3-yl]oxy]-4,5-disulfo Chemical compound O([C@@H]1[C@@H](COS(O)(=O)=O)O[C@@H]([C@@H]([C@H]1OS(O)(=O)=O)OS(O)(=O)=O)O[C@@H]1[C@@H](COS(O)(=O)=O)O[C@@H]([C@@H]([C@H]1OS(O)(=O)=O)OS(O)(=O)=O)O[C@@H]1[C@@H](COS(O)(=O)=O)O[C@H]([C@@H]([C@H]1OS(O)(=O)=O)OS(O)(=O)=O)O[C@@H]1C[C@@H]2CC[C@H]3[C@@H]4CC[C@@H]([C@]4(CC[C@@H]3[C@@]2(C)CC1)C)[C@H](C)CCCC(C)C)[C@H]1O[C@H](COS(O)(=O)=O)[C@@H](OS(O)(=O)=O)[C@H](OS(O)(=O)=O)[C@H]1OS(O)(=O)=O LNUFLCYMSVYYNW-ZPJMAFJPSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 2
- 239000012965 benzophenone Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000001721 carbon Chemical class 0.000 description 2
- 229940125904 compound 1 Drugs 0.000 description 2
- 229940125758 compound 15 Drugs 0.000 description 2
- 229940125782 compound 2 Drugs 0.000 description 2
- 229940126214 compound 3 Drugs 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 2
- 229920001903 high density polyethylene Polymers 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- KRIOVPPHQSLHCZ-UHFFFAOYSA-N propiophenone Chemical compound CCC(=O)C1=CC=CC=C1 KRIOVPPHQSLHCZ-UHFFFAOYSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- GHYOCDFICYLMRF-UTIIJYGPSA-N (2S,3R)-N-[(2S)-3-(cyclopenten-1-yl)-1-[(2R)-2-methyloxiran-2-yl]-1-oxopropan-2-yl]-3-hydroxy-3-(4-methoxyphenyl)-2-[[(2S)-2-[(2-morpholin-4-ylacetyl)amino]propanoyl]amino]propanamide Chemical compound C1(=CCCC1)C[C@@H](C(=O)[C@@]1(OC1)C)NC([C@H]([C@@H](C1=CC=C(C=C1)OC)O)NC([C@H](C)NC(CN1CCOCC1)=O)=O)=O GHYOCDFICYLMRF-UTIIJYGPSA-N 0.000 description 1
- IVSZLXZYQVIEFR-UHFFFAOYSA-N 1,3-Dimethylbenzene Natural products CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 1
- VCXSJKJNPCPBOM-UHFFFAOYSA-N 1-(2,3,4-trifluorophenyl)ethanone Chemical compound CC(=O)C1=CC=C(F)C(F)=C1F VCXSJKJNPCPBOM-UHFFFAOYSA-N 0.000 description 1
- YXJIYJZHAPHBHG-UHFFFAOYSA-N 1-(2,3-dimethylphenyl)ethanone Chemical compound CC(=O)C1=CC=CC(C)=C1C YXJIYJZHAPHBHG-UHFFFAOYSA-N 0.000 description 1
- GVTLJUZWNNFHMZ-UHFFFAOYSA-N 1-(2,4,5-trifluorophenyl)ethanone Chemical compound CC(=O)C1=CC(F)=C(F)C=C1F GVTLJUZWNNFHMZ-UHFFFAOYSA-N 0.000 description 1
- FFJSZHCBWFPSJI-UHFFFAOYSA-N 1-(2,4,6-trifluorophenyl)ethanone Chemical compound CC(=O)C1=C(F)C=C(F)C=C1F FFJSZHCBWFPSJI-UHFFFAOYSA-N 0.000 description 1
- XWCIICLTKWRWCI-UHFFFAOYSA-N 1-(2,4,6-trimethylphenyl)ethanone Chemical compound CC(=O)C1=C(C)C=C(C)C=C1C XWCIICLTKWRWCI-UHFFFAOYSA-N 0.000 description 1
- HSDSKVWQTONQBJ-UHFFFAOYSA-N 1-(2,4-dimethylphenyl)ethanone Chemical compound CC(=O)C1=CC=C(C)C=C1C HSDSKVWQTONQBJ-UHFFFAOYSA-N 0.000 description 1
- DDXBCZCBZGPSHD-UHFFFAOYSA-N 1-(2,6-dimethylphenyl)ethanone Chemical compound CC(=O)C1=C(C)C=CC=C1C DDXBCZCBZGPSHD-UHFFFAOYSA-N 0.000 description 1
- IBABHBXTLZNGAV-UHFFFAOYSA-N 1-(2-fluoro-4-methylphenyl)ethanone Chemical compound CC(=O)C1=CC=C(C)C=C1F IBABHBXTLZNGAV-UHFFFAOYSA-N 0.000 description 1
- WPRAXAOJIODQJR-UHFFFAOYSA-N 1-(3,4-dimethylphenyl)ethanone Chemical compound CC(=O)C1=CC=C(C)C(C)=C1 WPRAXAOJIODQJR-UHFFFAOYSA-N 0.000 description 1
- BKIHFZLJJUNKMZ-UHFFFAOYSA-N 1-(3,5-dimethylphenyl)ethanone Chemical compound CC(=O)C1=CC(C)=CC(C)=C1 BKIHFZLJJUNKMZ-UHFFFAOYSA-N 0.000 description 1
- YXWWHNCQZBVZPV-UHFFFAOYSA-N 2'-methylacetophenone Chemical compound CC(=O)C1=CC=CC=C1C YXWWHNCQZBVZPV-UHFFFAOYSA-N 0.000 description 1
- JHQDBQYFKARISA-UHFFFAOYSA-N 2,2,2-trifluoro-1-(2-methylphenyl)ethanone Chemical compound CC1=CC=CC=C1C(=O)C(F)(F)F JHQDBQYFKARISA-UHFFFAOYSA-N 0.000 description 1
- YOMBUJAFGMOIGS-UHFFFAOYSA-N 2-fluoro-1-phenylethanone Chemical compound FCC(=O)C1=CC=CC=C1 YOMBUJAFGMOIGS-UHFFFAOYSA-N 0.000 description 1
- YUPFQOHYIPYQII-UHFFFAOYSA-N CC(c1nc(C(C)=O)c(cc2)c3c1ccc1cccc2c31)=O Chemical compound CC(c1nc(C(C)=O)c(cc2)c3c1ccc1cccc2c31)=O YUPFQOHYIPYQII-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- MFESCIUQSIBMSM-UHFFFAOYSA-N I-BCP Chemical compound ClCCCBr MFESCIUQSIBMSM-UHFFFAOYSA-N 0.000 description 1
- 229920010126 Linear Low Density Polyethylene (LLDPE) Polymers 0.000 description 1
- PHSPJQZRQAJPPF-UHFFFAOYSA-N N-alpha-Methylhistamine Chemical compound CNCCC1=CN=CN1 PHSPJQZRQAJPPF-UHFFFAOYSA-N 0.000 description 1
- 241001597008 Nomeidae Species 0.000 description 1
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 description 1
- DCMYSLVKMAQCGG-UHFFFAOYSA-N O=C(C(C=C1)c2c3ccc4c2c1ccc4)NC3=O Chemical compound O=C(C(C=C1)c2c3ccc4c2c1ccc4)NC3=O DCMYSLVKMAQCGG-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000005234 alkyl aluminium group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- TXHIDIHEXDFONW-UHFFFAOYSA-N benzene;propan-2-one Chemical compound CC(C)=O.C1=CC=CC=C1 TXHIDIHEXDFONW-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000011097 chromatography purification Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229940125797 compound 12 Drugs 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 229920004889 linear high-density polyethylene Polymers 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- FSPSELPMWGWDRY-UHFFFAOYSA-N m-Methylacetophenone Chemical compound CC(=O)C1=CC=CC(C)=C1 FSPSELPMWGWDRY-UHFFFAOYSA-N 0.000 description 1
- 125000000040 m-tolyl group Chemical group [H]C1=C([H])C(*)=C([H])C(=C1[H])C([H])([H])[H] 0.000 description 1
- 125000000250 methylamino group Chemical group [H]N(*)C([H])([H])[H] 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000003261 o-tolyl group Chemical group [H]C1=C([H])C(*)=C(C([H])=C1[H])C([H])([H])[H] 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000032696 parturition Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- PMWXGSWIOOVHEQ-UHFFFAOYSA-N pyridine-2,6-dicarbaldehyde Chemical compound O=CC1=CC=CC(C=O)=N1 PMWXGSWIOOVHEQ-UHFFFAOYSA-N 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
Classifications
-
- B01J35/19—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1825—Ligands comprising condensed ring systems, e.g. acridine, carbazole
- B01J31/183—Ligands comprising condensed ring systems, e.g. acridine, carbazole with more than one complexing nitrogen atom, e.g. phenanthroline
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
- C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
- C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
- C07C2/08—Catalytic processes
- C07C2/26—Catalytic processes with hydrides or organic compounds
- C07C2/32—Catalytic processes with hydrides or organic compounds as complexes, e.g. acetyl-acetonates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/10—Polymerisation reactions involving at least dual use catalysts, e.g. for both oligomerisation and polymerisation
- B01J2231/12—Olefin polymerisation or copolymerisation
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/08—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of gallium, indium or thallium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0213—Complexes without C-metal linkages
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/842—Iron
-
- 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
- B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
- B01J31/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
- B01J31/143—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron of aluminium
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- 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
- B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
- B01J31/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
- B01J31/146—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron of boron
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- C07C2531/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- C07C2531/22—Organic complexes
-
- 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
Abstract
The invention relates to a novel linear alpha olefin catalyst and a preparation method and application thereof. A catalyst composition is composed of a main catalyst and an auxiliary catalyst, wherein the main catalyst refers to a ferric imino coordination compound, and the auxiliary catalyst comprises methylaluminoxane, triisobutyl aluminium, borane and CaCl3. The catalyst composition is used for catalyzing ethylene oligomerization for preparation of linear alpha olefin, selectivity of linear alpha olefin is larger than 96%, carbon number distribution of obtained linear alpha olefin is C4-C28, and C6-C20 content is larger than 75%. The catalyst is structurally simple and high in catalytic efficiency and can be used for ethylene oligomerization. The preparation method has the advantages of simplicity and convenience in operation, high yield, easiness in acquisition of raw materials, low cost, low environment pollution and easiness for industrial production.
Description
Technical field
The present invention relates to industrial catalyst field, particularly relate to novel linear alhpa olefin catalyst and its preparation method and application.
Background technology
Linear alpha-alkene (LAO) refers to C4-C28Above high-carbon straight chain terminal olefine, is a kind of important Organic Chemicals developed rapidly over nearly 30 years.Alpha-olefin main uses has following five big classes: 1) comonomer, and the comonomer used in linear low density polyethylene (LLDPE) and high density polyethylene (HDPE) (HDPE) produce mainly has 1-butylene, 1-hexene and 1-octene；2) be used for producing detergent and detergent alcohol, alpha-olefin the detergent alcohol synthesized has good biological degradability；3) synthetic lubricant fluid, poly alpha olefin is the synthetic lubricant fluid of high-quality, and it is mainly 1-decene and the oligomer of 1-octene；4) plasticizer alcohol, C8-C10The plasticizer alcohol volatility that linear alpha-olefin prepares through oxo process is low, and has good light stability and non-oxidizability；5) it is used for producing lube oil additive and drilling fluid, binding agent, sealant etc..The consumption of alpha-olefin has more than 50% comonomer being used as polyethylene.
The production method of alpha-olefin mainly has wax destructive distillation method, dehydrating alkanes method, ethylene oligomerization method, extraction separating method.Ethylene oligomerization is the main method producing alpha-olefin at present, and the alpha-olefin utilizing the method to produce accounts for the 94.1% of whole alpha-olefin production.Used catalyst mainly has alkyl aluminum system, titanium system, ferrum system, nickel system, chromium system etc..According to used catalyst and the difference of production technology, ethylene oligomerization method major technique has the Ziegler technique of CPChem company, the Ziegler technique of the improvement of INEOS company, the SHOP technique of Shell company.The Idemitsu technique of Chu Guang petro-chemical corporation of Japan, the VERSIPOL technique etc. of Dupond company.Wherein the SHOP process route of Shell company is complicated, and process route is long, in addition to oligomerization, and also disproportionation, isomerization etc., therefore production cost is the highest, but its good product quality, distribution flexibly, and can make alpha-olefin convert production internal olefin.The research of the catalyst of ethylene oligomerization synthesis alpha-olefin obtains remarkable progress, occurs research report and the patent using multi-phases process olefin(e) oligomerization to prepare alpha-olefin in recent years.Along with developing rapidly of polyethylene (PE) industry, to alpha-olefin, the demand of particularly 1-hexene and 1-octene is increasing.1-hervene copolymer PE is current fastest-rising kind.Have the 13 set alpha-olefin process units production runs of 11 manufacturers in the world, be concentrated mainly on North America, Europe, South Africa, Japan etc..Within 2009, world's alpha-olefin production capacity is 4334kt/a, and 2010 more than 4914kt/a.
Along with developing rapidly, as the C of comononer of polyolefin of polyolefin industry and Surfactant Industry6-C8With the C as detergent primary raw material10-C18The demand of the linear alpha-alkene of part increases day by day, therefore makes great efforts to improve this partial linear alpha-olefin content in output aggregate and has very important economic worth and realistic meaning.
Summary of the invention
The purpose of the present invention is that providing a series of carbon number distribution that can improve is C exactly6-C18The linear alpha-alkene carbon monoxide-olefin polymeric of relative amount in the product and preparation method thereof and use the method that this carbon monoxide-olefin polymeric catalyzed ethylene oligomerisation prepares linear alpha-alkene, to meet the urgent needs of current chemical industry.
The present invention relates to iron catalyst composition series and the application thereof of a series of ethylene oligomerization, it is characterized in that major catalyst is ferrum system (II) imido ligands compound, promoter is MAO, triisobutyl chlorine and borine or GaCl3Mixture.These carbon monoxide-olefin polymerics are used for catalyzed ethylene oligomerisation so as to get the carbon number distribution of linear alpha-alkene is at C4-C28Between, wherein C6-C20Component is more than 80%.
The major catalyst of the present invention is divided three classes:
The first kind is pyridine not that ene derivative, and described catalyst is that alkene non-and substituted pyridines cyclization gained；
Equations of The Second Kind is pyridine derivate, and described catalyst is 2-acetyl group-6-methylamino pyridine and substituted aniline reaction acquisition, and 2-formoxyl-6-methylamino pyridine is that raw material obtains through the reaction of several steps from pyridine；
3rd class is the derivant for phenanthroline, described catalyst is 9,10-dihydrobenzo [b] [1,10] phenanthroline-11 (8H)-one and substituted aniline reaction obtain, 9,10-dihydrobenzo [b] [1,10] phenanthroline-11 (8H)-one is prepared through the reaction of several steps by [1,10] phenanthroline；
Described promoter is a kind of mixture, by MAO, triisobutyl aluminium and borine or GaCl3Three part compositions.Wherein MAO and the amount ratio of the material of triisobutyl aluminium are to mix at 100: 1 to 1: 1, especially 90: 1 to 10: 1.GaCl3It is 1: 100: 10 to 1: 10000: 100 with the ratio of the material amount of MAO and triisobutyl aluminium.
The method that described iron catalyst composition series prepares linear alpha-alkene for catalyzed ethylene oligomerisation, including: under the conditions of anhydrous and oxygen-free, ethylene pressure is 0.1～20MPa, when reaction temperature is 0-100 DEG C, order adds organic solvent (hexane or hexamethylene), promoter and major catalyst solution, after reacting 5～60 minutes, it is cooled to-10 DEG C～0 DEG C, add methanol and terminate reaction, after through rectification isolated linear alpha-alkene selectivity ＞ 97%, carbon number distribution is at C4-C28Between, wherein C6-C20Component more than 80%.
The application of described iron catalyst composition series, wherein said organic solvent is petroleum ether, toluene, dimethylbenzene, the solvent of described major catalyst solution is 1,2-dichloroethanes, dichloromethane, chloroform, o-dichlorohenzene, hexane or hexamethylene, described promoter is calculated as 5000: 1～500: 1 with the amount of the material of major catalyst than with Al/Fe, especially optimal with 1000: 1～500: 1.
Detailed description of the invention
Embodiment 1,2,6-diformyl-pyridine not that alkene is substrate
The synthesis reference literature Chemische Berichte. of compound 1, Vol20, P662. compound 1 (10g, 0.052mol) is dissolved in acetic acid 100mL, adds AlCl3(35g, 0.26mol), reaction solution is heated to reflux 2 hours, TLC display raw material has disappeared, and stopped reaction adds frozen water cancellation, dichloromethane extracts, the organic facies dried solvent evaporated of anhydrous anhydrous sodium sulfate, thick product obtains pure compound 2 (9g, 73%) after column chromatography for separation (leacheate is petroleum ether and ethyl acetate).1H NMR(CHCl3 d3) δ ppm:8.06 (d, 1H, aromatic ring H), 7.72 (d, 1H, aromatic ring H), 7.52 (d, 1H, aromatic ring H), 7.35 (d, 1H, aromatic ring H), 7.24 (d, 1H, aromatic ring H), 6.31 (d, 1H, aromatic ring H), 6.23 (d, 1H, aromatic ring H), 4.29 (d, 1H).
Compound 2 (9g, 0.038mol) is dissolved in 50mL methanol, is cooled to 0 DEG C, adds ammonia (1.6g, 0.045mol), reacts 2 hours, then stopped reaction, drain solvent and obtain compound 3 (8.93g, 100%).1H NMR(CHCl3d3) δ ppm:10.0 (s, 1H, NH-), 7.88 (d, 1H, aromatic ring H), 7.69 (d, 1H, aromatic ring H), 7.52 (d, 1H, aromatic ring H), 7.35 (d, 1H, aromatic ring H), 7.24 (d, 1H, aromatic ring H), 6.31 (d, 1H, aromatic ring H), 6.23 (d, 1H, aromatic ring H), 4.40 (d, 1H).
Compound 3 (8g, 0.034mol) is dissolved in 50mL toluene, adds phosphorus tribromide (46g, 0.17mol), back flow reaction 2 hours, and cooling, solvent evaporated rear pillar chromatography purification obtains compound 4 (11g, 90%).1H NMR(CHCl3 d3) δ ppm:8.08 (d, 2H, aromatic ring H), 7.62 (d, 2H, aromatic ring H), 7.39 (d, 2H, aromatic ring H), 7.32 (d, 2H, aromatic ring H).
Here R11As a example by methyl: by compound 4 (10g, 0.028mol) it is dissolved in THF 50mL, it is cooled to-78 DEG C, dropping butyl lithium (0.06mol), is warming up to room temperature and adds DMAC (21g, 0.29mol) after dropping, it is warming up to 50 DEG C after dropping react 2 hours, stopped reaction, adds ammonium chloride solution cancellation, and organic facies dichloromethane extracts.Organic facies is dried with anhydrous sodium sulfate, filters, is evaporated.The available pure compound 5 (3.5g, 48%) of ethanol punching crystallization.1H NMR(CHCl3 d3) δ ppm 8.45 (d, 2H, aromatic ring H), 7.73 (d, 2H, aromatic ring H), 7.49 (d, 2H, aromatic ring H), 7.32 (d, 2H, aromatic ring H), 2.55 (s, 6H, CH 3 CO-)
Compound 5 and substituted aniline react under conditions of anhydrous and oxygen-free, and wherein the mol ratio of compound 5 and substituted aniline is 1: 1.2, and solvent is toluene, are to carry out under catalyst backflow with p-methyl benzenesulfonic acid.Response time is 3-6 hour, and TLC monitors reaction, after completion of the reaction, removed under reduced pressure solvent, and then column chromatography (being leacheate by petroleum ether and ethyl acetate), i.e. can get target product 6.Aniline in the inventive method can be 2-aminotoluene, 3-monomethylaniline., 4-monomethylaniline., 2, 3-dimethylaniline, 2, 4-dimethylaniline, 2, 5 dimethylanilines, 2, 6-dimethylaniline, 3, 4-dimethylaniline, 3, 5-dimethylaniline, 3, 6-dimethylaniline, 2, 4, 6-trimethylaniline, 4-bromo-2, 6-dimethylaniline, 2-MEA, 2-ethyl-6 monomethylaniline., 2-fluoroaniline, 2-fluoro-4-monomethylaniline., 2, 3, 4-trifluoromethyl aniline, 2, 4, 5-trifluoromethyl aniline, 2, 4, 6-trifluoromethyl aniline, 2, 3, 4, 5, 6-pentafluoroaniline, most preferably 4-monomethylaniline..
Here, as a example by 4-monomethylaniline.: compound 5 (1g, 3.85mmol) is dissolved in 50 milliliters of toluene, the 4-monomethylaniline. of dropping 1.2eq equivalent, adds the p-methyl benzenesulfonic acid of 0.1eq after dropping, backflow, after 3 hours, TLC display reaction is completely.Stopped reaction, removed under reduced pressure solvent.Column chromatography obtains the compound 6 (1.35g, 80%) that R3 is methyl after purification.Feature:1H NMR(CHCl3 d3) δ ppm:7.87 (d, 2H, aromatic ring H), 7.50 (d, 2H, aromatic ring H), 7.49 (d, 2H, aromatic ring H), 7.32 (d, 1H, aromatic ring H), 7.1 (m, 8H, aromatic ring H), 2.35 (s, 6H, CH 3 ), 0.9 (s, 6H, CH 3 N-)。
Here with 4-monomethylaniline., as a example by 4-tolyl aldehyde, under the protection of noble gas; compound 6 (1g, 2.3mmol) is dissolved in 50 milliliters of toluene, drives the oxygen in solvent with noble gas away; it is subsequently adding ferrous chloride (5.2g; 4.08mmol), being stirred overnight under inert gas shielding, TLC detection is the most reacted completely; filter; solvent evaporated, can obtain compound 7 (0.89g, 68%) after the washing of crude product ether.1H NMR(CHCl3 d3) δ ppm:7.90 (d, 2H, aromatic ring H), 7.50 (d, 2H, aromatic ring H), 7.49 (d, 2H, aromatic ring H), 7.32 (d, 1H, aromatic ring H), 7.1 (m, 8H, aromatic ring H), 2.35 (s, 6H, CH 3 ), 0.9 (s, 6H, CH 3 N-)。
Embodiment 2,2-acetyl group-6 methylamino are substrate
The method of compound 8 follows document Synthetic Communications, and the report of 2005,35,2317-2324 is from 2, and 6-lutidines is that raw material is oxidized to be obtained in reduction.Compound 8 (10g, 0.07mol) is dissolved in dichloromethane, is cooled to 0 DEG C and is subsequently adding ammonia (1.2g, 0.079mol), and stopped reaction after half an hour, solvent evaporated are reacted in stirring.Column chromatography can get mono-substituted compound 9 (5.8g, 60%).Feature:1H NMR(CHCl3 d3) δ ppm:8.12 (m, 1H, aromatic ring H), 7.66 (m, 1H, aromatic ring H), 7.60 (m, 1H, aromatic ring H), 5.12 (m, 2H,CH 2 -), 4.24 (m, 2H,CH 2 -)。
Compound 9 (5g, 0.036mol) is dissolved in dichloromethane, adds PCC oxidant (8.6g, 0.04mol), room temperature reaction 2 hours, and TLC display reaction terminates, stopped reaction, solvent evaporated.Column chromatography obtains the compound of 2-position aldehyde radical.The compound of 2-position aldehyde radical is dissolved in dichloromethane, is cooled to-78 DEG C, dropping dimethyl lithium solution (1.1eq), reacting 2 hours after addition, add ammonium chloride solution cancellation, organic facies dichloromethane extracts, it is dried, compound 10 (4.5g, 92%) after being evaporated rear column chromatography, can be obtained.Feature:1H NMR(CHCl3 d3) δ ppm:8.24 (m, 1H, aromatic ring H), 8.22 (m, 1H, aromatic ring H), 8.08 (m, 1H, aromatic ring H), 4.24 (m, 2H,CH 2 -), 2.36 (s, 3H, CH 3 CO-)。
Compound 10 and substituted aniline react under conditions of anhydrous and oxygen-free, and wherein the mol ratio of compound 10 and substituted aniline is 1: 1.2, and solvent is toluene, are to carry out under catalyst backflow with p-methyl benzenesulfonic acid.Response time is 3-6 hour, and TLC monitors reaction, after completion of the reaction, removed under reduced pressure solvent, and then column chromatography (being leacheate by petroleum ether and ethyl acetate), i.e. can get target product 11.Aniline in the inventive method can be 2-aminotoluene, 3-monomethylaniline., 4-monomethylaniline., 2, 3-dimethylaniline, 2, 4-dimethylaniline, 2, 5 dimethylanilines, 2, 6-dimethylaniline, 3, 4-dimethylaniline, 3, 5-dimethylaniline, 3, 6-dimethylaniline, 2, 4, 6-trimethylaniline, 4-bromo-2, 6-dimethylaniline, 2-MEA, 2-ethyl-6 monomethylaniline., 2-fluoroaniline, 2-fluoro-4-monomethylaniline., 2, 3, 4-trifluoromethyl aniline, 2, 4, 5-trifluoromethyl aniline, 2, 4, 6-trifluoromethyl aniline, 2, 3, 4, 5, 6-pentafluoroaniline, most preferably 4-monomethylaniline..
Here, as a example by 4-monomethylaniline.: compound 10 (1g, 7mmol) is dissolved in 50 milliliters of toluene, the 4-monomethylaniline. of dropping 1.2eq equivalent, adds the p-methyl benzenesulfonic acid of 0.1eq after dropping, backflow, after 3 hours, TLC display reaction is completely.Stopped reaction, removed under reduced pressure solvent.Column chromatography obtains the compound 11 (1.3g, 85%) that R3 is methyl after purification.Feature:1H NMR(CHCl3 d3) δ ppm:8.06 (m, 1H, aromatic ring H), 7.93 (m, 1H, aromatic ring H), 7.82 (m, 1H, aromatic ring H), 4.24 (m, 2H,CH 2 -), 2.35 (s, 3H, CH 3 -), 0.9 (s, 3H, CH 3 N-)。
Compound 11 and replacement benzophenone react under conditions of anhydrous and oxygen-free, and wherein the mol ratio of compound 11 and substituted aniline is 1: 1.2, and solvent is toluene, are to carry out under catalyst backflow with p-methyl benzenesulfonic acid.Response time is 3-6 hour, and TLC monitors reaction, after completion of the reaction, removed under reduced pressure solvent, and then column chromatography (being leacheate by petroleum ether and ethyl acetate), i.e. can get target product 12.nullReplacement benzophenone in the inventive method，It can be 2-methyl acetophenone，3-methyl acetophenone，4-methyl acetophenone，2，3-dimethyl acetophenone，2，4-dimethyl acetophenone，2，5 dimethyl acetophenones，2，6-dimethyl acetophenone，3，4-dimethyl acetophenone，3，5-dimethyl acetophenone，3，6-dimethyl acetophenone，2，4，6-trimethylacetophenone，4-bromo-2，6-dimethyl acetophenone，2-ethylo benzene ethyl ketone，2-ethyl-6 methyl acetophenone，2-fluoro acetophenone，2-fluoro-4-methyl acetophenone，2，3，4-trifluoroacetophenone，2，4，5-trifluoroacetophenone，2，4，6-trifluoroacetophenone，2，3，4，5，6-phenyl-pentafluoride ethyl ketone，2-methyl phenyl ketone，3-methyl phenyl ketone，4-methyl phenyl ketone，2，3-dimethyl benzene acetone，2，4-dimethyl benzene acetone，2，5 dimethyl benzene acetone，2，6-dimethyl benzene acetone，3，4-dimethyl benzene acetone，3，5-dimethyl benzene acetone，3，6-dimethyl benzene acetone，2，4，6-trimethylbenzene acetone，4-bromo-2，6-dimethyl benzene acetone，2-ethylo benzene acetone，2-ethyl-6 methyl phenyl ketone，2-fluorobenzene acetone，2-fluoro-4-methyl phenyl ketone，2，3，4-trifluoro-benzene acetone，2，4，5-trifluoro-benzene acetone，2，4，6-trifluoro-benzene acetone，2，3，4，5，6-phenyl-pentafluoride acetone，2-methyl trifluoro 1-Phenylethanone.，3-methyl trifluoro 1-Phenylethanone.，4-methyl trifluoro 1-Phenylethanone.，2，3-dimethyl trifluoroacetophenone，2，4-dimethyl trifluoroacetophenone，2，5 dimethyl trifluoroacetophenones，2，6-dimethyl trifluoroacetophenone，3，4-dimethyl trifluoroacetophenone，3，5-dimethyl trifluoroacetophenone，3，6-dimethyl trifluoroacetophenone，2，4，6-trimethyl trifluoroacetophenone，4-bromo-2，6-dimethyl trifluoroacetophenone，2-ethyl trifluoroacetophenone，2-ethyl-6 methyl trifluoro 1-Phenylethanone.，2-fluorine trifluoroacetophenone，2-fluoro-4-methyl trifluoro 1-Phenylethanone.，2，3，4-trifluoro trifluoroacetophenone，2，4，5-trifluoro trifluoroacetophenone，2，4，6-trifluoro trifluoroacetophenone，2，3，4，5，6-five fluorine trifluoroacetophenone，Most preferably 4-methyl acetophenone.
Here, as a example by 4-methyl acetophenone: compound 11 (1g, 4mmol) is dissolved in 50 milliliters of toluene, the 4-methyl acetophenone of dropping 1.2eq equivalent, adds the p-methyl benzenesulfonic acid of 0.1eq after dropping, backflow, after 3 hours, TLC display reaction is completely.Stopped reaction, removed under reduced pressure solvent.Column chromatography obtains R after purification8Compound 12 (1.2g, 90%) for methyl.Feature:1H NMR(CHCl3 d3) δ ppm:8.11 (s, 1H, CHN-), 7.98 (m, 1H, aromatic ring H), 7.86 (m, 1H, aromatic ring H), 7.51 (m, 3H, aromatic ring H), 7.09 (m, 2H, aromatic ring H), 5.14 (m, 2H,CH 2 -), 2.35 (s, 6H, CH 3 -), 0.9 (s, 3H, CH 3 N-)。
Here with 4-monomethylaniline., as a example by 4-methyl acetophenone, under the protection of noble gas; compound 12 (1g, 3mmol) is dissolved in 50 milliliters of toluene, drives the oxygen in solvent with noble gas away; it is subsequently adding ferrous chloride (4.5g; 3.55mmol), being stirred overnight under inert gas shielding, TLC detection is the most reacted completely; filter; solvent evaporated, can obtain compound 13 (1.2g, 88%) after the washing of crude product ether.1H NMR(CHCl3 d3) δ ppm:7.98 (m, 1H, aromatic ring H), 7.86 (m, 1H, aromatic ring H), 7.51 (m, 3H, aromatic ring H), 7.50 (s, 1H, CHN-), 7.10 (m, 2H, aromatic ring H), 5.10 (m, 2H,CH 2 -), 2.35 (s, 6H, CH 3 -), 0.9 (s, 3H, CH 3 N-)。
Embodiment 3, phenanthroline are substrate
The method of compound 15 follows document Organometallics, and 25 (3), the report of 2006 is from 1, and 10-phenanthroline is that raw material obtains through two steps.
Compound 15 (2.2g, 1mmol) is dissolved in dichloromethane, and then dropping 1.1eq thionyl chloride, after dropping, stirs 2 hours, be directly added into AlCl without isolation3(2g, 1.5mmol) and 3-chlorobromopropane (1.57g, 1.1mmol), 1 hour post-heating of room temperature reaction returns reaction overnight, cooling, by pouring into after reaction in frozen water, extracts with dichloromethane, organic facies anhydrous sodium sulfate is dried, and filters, obtains the product of hastening parturition 3 after being evaporated.Crude product petroleum ether and re-crystallizing in ethyl acetate can obtain compound 16 white solid (1.4g, 56%).Feature:1H NMR(CHCl3 d3) δ ppm:8.81 (m, 1H, aromatic ring H), 8.00 (m, 1H, aromatic ring H), 7.87 (s, 1H, aromatic ring H), 7.68 (m, 1H, aromatic ring H), 7.43 (m, 1H, aromatic ring H), 7.26 (m, 1H, aromatic ring H), 2.55 (m, 2H, CH 2 -), 2.40 (m, 2H, CH 2 -), 1.95 (m, 2H, CH 2 -)。
Compound 16 and substituted aniline react under conditions of anhydrous and oxygen-free, and wherein the mol ratio of compound 16 and substituted aniline is 1: 1.2, and solvent is toluene, are to carry out under catalyst backflow with p-methyl benzenesulfonic acid.Response time is 3-6 hour, and TLC monitors reaction, after completion of the reaction, removed under reduced pressure solvent, and then column chromatography (being leacheate by petroleum ether and ethyl acetate), i.e. can get target product 17.Aniline in the inventive method can be 2-aminotoluene, 3-monomethylaniline., 4-monomethylaniline., 2, 3-dimethylaniline, 2, 4-dimethylaniline, 2, 5 dimethylanilines, 2, 6-dimethylaniline, 3, 4-dimethylaniline, 3, 5-dimethylaniline, 3, 6-dimethylaniline, 2, 4, 6-trimethylaniline, 4-bromo-2, 6-dimethylaniline, 2-MEA, 2-ethyl-6 monomethylaniline., 2-fluoroaniline, 2-fluoro-4-monomethylaniline., 2, 3, 4-trifluoromethyl aniline, 2, 4, 5-trifluoromethyl aniline, 2, 4, 6-trifluoromethyl aniline, 2, 3, 4, 5, 6-pentafluoroaniline, most preferably 4-monomethylaniline..
Here, as a example by 4-monomethylaniline.: compound 16 (1g, 4mmol) is dissolved in 50 milliliters of toluene, the 4-monomethylaniline. of dropping 1.2eq equivalent, adds the p-methyl benzenesulfonic acid of 0.1eq after dropping, backflow, after 3 hours, TLC display reaction is completely.Stopped reaction, removed under reduced pressure solvent.Column chromatography obtains the compound 17 (1.1g, 80%) that R3 is methyl after purification.Feature:1H NMR(CHCl3 d3) δ ppm:8.81 (m, 1H, aromatic ring H), 8.03 (m, 1H, aromatic ring H), 8.00 (m, 1H, aromatic ring H), 7.68 (m, 1H, aromatic ring H), 7.43 (m, 1H, aromatic ring H), 7.26 (m, 1H, aromatic ring H), 7.1 (m, 4H, aromatic ring H), 2.55 (m, 2H, CH 2 -), 2.35 (s, 3H,CH 3 -), 1.70 (m, 2H, CH 2 -), 1.30 (m, 2H, CH 2 -)。
Here as a example by 4-monomethylaniline., under the protection of noble gas, by compound 17 (1g; 3mmol) it is dissolved in 50 milliliters of toluene; drive the oxygen in solvent with noble gas away, be subsequently adding ferrous chloride (4.5g, 3.55mmol); it is stirred overnight under inert gas shielding; TLC detection is the most reacted completely, filters, solvent evaporated; compound 18 (1.1g, 80%) can be obtained after the washing of crude product ether.Feature:1H NMR(CHCl3 d3) δ ppm:8.81 (m, 1H, aromatic ring H), 8.00 (m, 2H, aromatic ring H), 7.70 (m, 1H, aromatic ring H), 7.40 (m, 1H, aromatic ring H), 7.30 (m, 1H, aromatic ring H), 7.1 (m, 4H, aromatic ring H), 2.55 (m, 2H, CH 2 -), 2.35 (s, 3H,CH 3 -), 1.70 (m, 2H, CH 2 -), 1.30 (m, 2H, CH 2 -)。
Ethylene oligomerization reaction experiment process and method:
Will be equipped with magnetic stir bar and dry 250mL there-necked flask evacuation while hot, nitrogen displacement is filled with ethylene the most afterwards, it is sequentially added into quantitative toluene, promoter MAO and catalyst, carry out oligomerisation reaction at a predetermined temperature, it is constant that the pressure of reaction system is automatically adjusted holding by electromagnetic valve, in record buffer tank, pressure is over time, polymerization time is 30min, finally terminates reaction with methanol or acidic ethanol that mass fraction is 10%.Ethylene oligomerization product GC-MS method is analyzed, and the activity of catalyst is then obtained by the pressure drop of ethylene surge tank.
Ethylene oligomerization experimental result example
Following table lists the experimental result of some embodiments.
Note: 1. ethylene oligomerization catalysis reaction condition: catalyst concn 1.5 μm ol, 50mL toluene makees solvent, and MAO is promoter；
2. alhpa olefin content is more than 99%, and linear alpha olefin selectivity is more than 96%.
The structure of the most each catalyst and being described as follows:
A. catalyst 7-1 to 7-3 is: major catalyst structure (compound 7 obtained in patent specification embodiment 1) is as follows, and wherein R11 is methyl, and R1, R2, R4 and R6, R7, R9 are hydrogen.Catalyst 7-1:R3 and R8 is methoxyl group, R5 and R10 is methyl.Catalyst 7-2:R3 and R8 is methyl, R5 and R10 is hydrogen.Catalyst 7-3:R5 and R10 is bromine, R3 and R8 is hydrogen.
B. catalyst 13-1 to 13-3 is: major catalyst structure (compound 13 obtained in patent specification embodiment 2) is as follows, and wherein R11 and R12 is methyl, and R2, R4, R5 and R7, R9, R10 are hydrogen.Catalyst 13-1:R1 and R6 is methoxyl group, R3 and R8 is methyl.Catalyst 13-2:R3 and R8 is methyl, R1 and R6 is hydrogen.Catalyst 13-3:R1 and R6 is bromine, R3 and R8 is hydrogen.
C. catalyst 18-1 to 18-3 is: major catalyst structure (compound 18 obtained in patent specification embodiment 3) is as follows, and wherein R2 and R4 is hydrogen.Catalyst 18-1:R3 is methoxyl group, R1 and R5 is methyl.Catalyst 18-2:R3 and R5 is methyl, and R1 is hydrogen.Catalyst 18-3:R1 is bromine, and R5 is methyl, and R3 is hydrogen.
D. catalyst 19 to 21 is comparative example: document J.Am.Chem.Soc.1998, and three kinds of catalyst in 120,7143-7144, major catalyst structural formula is as follows.Wherein catalyst 19 is structural formula 7, and R is methyl；Catalyst 20 is structural formula 8, and R is ethyl；Catalyst 21 is structural formula 9, and R is isopropyl.
Particular embodiments described above, is further described the purpose of the present invention, technical scheme and beneficial effect.Should be appreciated that the specific embodiment that the foregoing is only the present invention, be not limited to the present invention.All within the spirit and principles in the present invention, any modification, equivalent substitution and improvement etc. done, should be included within the scope of the present invention.
Claims (8)
1. a novel linear poly-alpha olefins catalyst, including major catalyst and promoter, wherein said sponsors
Agent is ferrum system imido ligands compound, and its structural formula is (IA):
Wherein, R1-R11It is each independently selected from H, C1-C6 alkyl, halogen, C1-C6 alkoxyl；R11For
C1-C6 alkyl, isopropyl or trifluoromethyl.
Catalyst the most according to claim 1, the structural formula of wherein said major catalyst is (IA), institute
Stating imido ligands compound by 2,6-diacetyl-pyridine not that alkene and substituted aniline reaction obtain.
Catalyst the most according to claim 1, wherein, by C1-C4 alkyl one, two or trisubstituted benzene
Base is: 2-aminomethyl phenyl, 4-aminomethyl phenyl, 2,4-3,5-dimethylphenyls, 2,6-3,5-dimethylphenyls, 2,4,
6-trimethylphenyl, 2-ethylphenyl, 4-ethylphenyl, 2,4-diethyl phenyl, 2,4,6-tri-second
Base phenyl, 2-propyl group phenyl, 4-propyl group phenyl, 2,4-dipropyl phenyl, 2,6-dipropyl phenyl, 2,
4,6-tripropyl phenyl, 2-isopropyl phenyl, 4-isopropyl phenyl, 2,4-diisopropyl phenyls, 2,
6-diisopropyl phenyl, 2,4,6-triisopropyl phenyl, 2-butyl phenyl, 4-butyl phenyl, 2,4-
Dibutylphenyl, 2,6-dibutylphenyl, 2,4,6-tributyl phenyl, 2-tert-butyl-phenyl, uncle 4-
Butyl phenyl, 2,4-di-tert-butyl-phenyls, 2,6-di-tert-butyl-phenyls, 2,4,6-tri-butyl benzenes
Base, 2-tert-butyl-phenyl, 4-tert-butyl-phenyl, 2,4-di-tert-butyl-phenyls, 2,6-di-tert-butyl-phenyls,
Or 2,4,6-tri-tert phenyl.
Catalyst the most according to claim 1, wherein, by halogen one, two or trisubstd phenyl be:
2-chlorphenyl, 4-chlorphenyl, 2,4-Dichlorobenzene base, 2,4,6-trichlorophenyl, 2-bromophenyl, 4-bromine
Phenyl, 2,4-dibromo phenyls, 2,4,6-tribromo phenyl, 2-fluorophenyl, 4-fluorophenyl, 2,4-difluoros
Phenyl, or 2,4,6-trifluorophenyls.
Catalyst the most according to claim 1, wherein, is taken by halogen and C1-C4 alkyl one, two or three
The phenyl in generation is: 2-bromo-4-aminomethyl phenyl, 2-bromo-6-aminomethyl phenyl, 2,6-bis-bromo-4-aminomethyl phenyls, 4-
Bromo-2,6-3,5-dimethylphenyl, 2-chloro-4-aminomethyl phenyl, 2-chloro-6-aminomethyl phenyl, 2,6-bis-chloro-4-methyl
Phenyl, or 4-chloro-2,6-3,5-dimethylphenyl.
Catalyst the most according to claim 1, wherein said promoter for include MAO, three
Aluminium isobutyl and borine or GaCl3The mixture of three parts.
7. the method that the catalyst described in claim 1 prepares linear alpha olefin for catalyzed ethylene oligomerisation, its bag
Include: under the conditions of anhydrous and oxygen-free, when ethylene pressure is 0.1-20MPa, reaction temperature is 0-100 DEG C, suitable
Sequence adds organic solvent, promoter and major catalyst solution, after reacting 5-60 minute, be cooled to-
10 DEG C to 0 DEG C, add methanol and terminate reaction, be finally rectifying to obtain linear alpha olefin, wherein, obtained
The selectivity ＞ 97% of linear alpha olefin, carbon number distribution is at C4-C28Between, wherein C6-C20Component is more than
80%.
8. the method described in claim 7, wherein, described organic solvent is petroleum ether, toluene or dimethylbenzene,
The solvent of described major catalyst solution is 1,2-dichloroethanes, dichloromethane, chloroform or adjacent dichloro
Benzene, described promoter is calculated as 5000: 1 to 500 with the ratio of described major catalyst with Al/Fe: 1.
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|---|---|---|---|---|
| CN109111393A (en) * | 2018-08-29 | 2019-01-01 | 中国科学院青岛生物能源与过程研究所 | A kind of NNN ligand compound, cobalt-NNN complex compound, and preparation method and application |
| KR20190039706A (en) * | 2016-08-30 | 2019-04-15 | 제이엑스티지 에네루기 가부시키가이샤 | Processes and catalysts for preparing oligomers |
| CN112387311A (en) * | 2020-10-22 | 2021-02-23 | 杭州小菱科技有限公司 | Ethylene oligomerization catalyst system, preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6465396B1 (en) * | 1999-03-04 | 2002-10-15 | Nara Institute Of Science And Technology | Method to promote growth of a plant |
| CN101412771A (en) * | 2008-11-25 | 2009-04-22 | 中山大学 | Pyridine diimine iron olefin polymerizing catalyst, as well as preparation method and application thereof |
| CN101906009A (en) * | 2010-07-29 | 2010-12-08 | 浙江大学 | Method for preparing linear alpha-olefin |
| CN105315309A (en) * | 2014-07-31 | 2016-02-10 | 中国科学院化学研究所 | 2,6-diimine pyridinocycloheptane iron and cobalt complex catalyst and preparation method therefor and application thereof |
-
2016
- 2016-03-22 CN CN201610164561.4A patent/CN105728045B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6465396B1 (en) * | 1999-03-04 | 2002-10-15 | Nara Institute Of Science And Technology | Method to promote growth of a plant |
| CN101412771A (en) * | 2008-11-25 | 2009-04-22 | 中山大学 | Pyridine diimine iron olefin polymerizing catalyst, as well as preparation method and application thereof |
| CN101906009A (en) * | 2010-07-29 | 2010-12-08 | 浙江大学 | Method for preparing linear alpha-olefin |
| CN105315309A (en) * | 2014-07-31 | 2016-02-10 | 中国科学院化学研究所 | 2,6-diimine pyridinocycloheptane iron and cobalt complex catalyst and preparation method therefor and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| 姜平元: "聚合催化剂吡啶二亚胺铁配合物专利研究进展", 《化工管理》 * |
| 马志等: "一种新型双亚胺吡啶铁系催化剂的乙烯低聚研究", 《高分子学报》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20190039706A (en) * | 2016-08-30 | 2019-04-15 | 제이엑스티지 에네루기 가부시키가이샤 | Processes and catalysts for preparing oligomers |
| KR102448156B1 (en) | 2016-08-30 | 2022-09-29 | 에네오스 가부시키가이샤 | Methods and catalysts for preparing oligomers |
| CN109111393A (en) * | 2018-08-29 | 2019-01-01 | 中国科学院青岛生物能源与过程研究所 | A kind of NNN ligand compound, cobalt-NNN complex compound, and preparation method and application |
| CN109111393B (en) * | 2018-08-29 | 2021-08-27 | 中国科学院青岛生物能源与过程研究所 | NNN ligand compound, cobalt-NNN complex, preparation method and application thereof |
| CN112387311A (en) * | 2020-10-22 | 2021-02-23 | 杭州小菱科技有限公司 | Ethylene oligomerization catalyst system, preparation method and application thereof |
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| CN105728045B (en) | 2017-09-22 |
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