CN105728045B - Novel linear alhpa olefin catalyst and its preparation method and application - Google Patents
Novel linear alhpa olefin catalyst and its preparation method and application Download PDFInfo
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- CN105728045B CN105728045B CN201610164561.4A CN201610164561A CN105728045B CN 105728045 B CN105728045 B CN 105728045B CN 201610164561 A CN201610164561 A CN 201610164561A CN 105728045 B CN105728045 B CN 105728045B
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- catalyst
- phenyl
- phenyls
- aromatic ring
- compound
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- 239000003054 catalyst Substances 0.000 title claims abstract description 62
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 13
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title abstract description 7
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 239000004711 α-olefin Substances 0.000 claims abstract description 20
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 19
- 150000001875 compounds Chemical class 0.000 claims abstract description 18
- 239000005977 Ethylene Substances 0.000 claims abstract description 16
- 238000006384 oligomerization reaction Methods 0.000 claims abstract description 16
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 11
- 239000003426 co-catalyst Substances 0.000 claims abstract description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052742 iron Inorganic materials 0.000 claims abstract description 7
- 238000009826 distribution Methods 0.000 claims abstract description 6
- 229910005267 GaCl3 Inorganic materials 0.000 claims abstract description 5
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910000085 borane Inorganic materials 0.000 claims abstract description 4
- 239000003446 ligand Substances 0.000 claims abstract description 4
- UORVGPXVDQYIDP-UHFFFAOYSA-N trihydridoboron Substances B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 230000003197 catalytic effect Effects 0.000 claims abstract 2
- 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 40
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 31
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 29
- 239000002904 solvent Substances 0.000 claims description 26
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 22
- -1 2,4- dipropyl phenyl Chemical group 0.000 claims description 19
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N N-phenyl amine Natural products NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 239000003208 petroleum Substances 0.000 claims description 8
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical class ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 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 9
- 229910052736 halogen Inorganic materials 0.000 claims 3
- 150000002367 halogens Chemical class 0.000 claims 3
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims 2
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims 1
- JXUKFFRPLNTYIV-UHFFFAOYSA-N 1,3,5-trifluorobenzene Chemical class FC1=CC(F)=CC(F)=C1 JXUKFFRPLNTYIV-UHFFFAOYSA-N 0.000 claims 1
- DPKKOVGCHDUSAI-UHFFFAOYSA-N 1,3-dibromo-5-methylbenzene Chemical class CC1=CC(Br)=CC(Br)=C1 DPKKOVGCHDUSAI-UHFFFAOYSA-N 0.000 claims 1
- 125000004201 2,4-dichlorophenyl group Chemical group [H]C1=C([H])C(*)=C(Cl)C([H])=C1Cl 0.000 claims 1
- 125000004215 2,4-difluorophenyl group Chemical group [H]C1=C([H])C(*)=C(F)C([H])=C1F 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
- 125000002490 anilino group Chemical class [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims 1
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical class BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 claims 1
- ODLMAHJVESYWTB-UHFFFAOYSA-N propylbenzene Chemical class CCCC1=CC=CC=C1 ODLMAHJVESYWTB-UHFFFAOYSA-N 0.000 claims 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 12
- 239000002994 raw material Substances 0.000 abstract description 5
- 238000003912 environmental pollution Methods 0.000 abstract 1
- UPWPDUACHOATKO-UHFFFAOYSA-K gallium trichloride Chemical compound Cl[Ga](Cl)Cl UPWPDUACHOATKO-UHFFFAOYSA-K 0.000 abstract 1
- 125000003118 aryl group Chemical group 0.000 description 65
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 28
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 18
- RZXMPPFPUUCRFN-UHFFFAOYSA-N p-toluidine Chemical class 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
- 150000001448 anilines Chemical class 0.000 description 9
- 239000001257 hydrogen Substances 0.000 description 9
- 229910052739 hydrogen Inorganic materials 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 239000011261 inert gas Substances 0.000 description 8
- 239000000047 product Substances 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
- VOWZNBNDMFLQGM-UHFFFAOYSA-N 2,5-dimethylaniline Chemical class CC1=CC=C(C)C(N)=C1 VOWZNBNDMFLQGM-UHFFFAOYSA-N 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 239000012043 crude product Substances 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 239000012074 organic phase Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- KRIOVPPHQSLHCZ-UHFFFAOYSA-N propiophenone Chemical class CCC(=O)C1=CC=CC=C1 KRIOVPPHQSLHCZ-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
- MKARNSWMMBGSHX-UHFFFAOYSA-N 3,5-dimethylaniline Chemical compound CC1=CC(C)=CC(N)=C1 MKARNSWMMBGSHX-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
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- 229940126142 compound 16 Drugs 0.000 description 4
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- 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
- 238000012544 monitoring process Methods 0.000 description 4
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- 125000003944 tolyl group Chemical group 0.000 description 4
- NOXLGCOSAFGMDV-UHFFFAOYSA-N 2,3,4,5,6-pentafluoroaniline Chemical class 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 class 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 class FCC1=C(N)C=C(C(=C1)CF)CF OOMNPYBQJCAHFY-UHFFFAOYSA-N 0.000 description 3
- KWVPRPSXBZNOHS-UHFFFAOYSA-N 2,4,6-Trimethylaniline Chemical class CC1=CC(C)=C(N)C(C)=C1 KWVPRPSXBZNOHS-UHFFFAOYSA-N 0.000 description 3
- CZZZABOKJQXEBO-UHFFFAOYSA-N 2,4-dimethylaniline Chemical class CC1=CC=C(N)C(C)=C1 CZZZABOKJQXEBO-UHFFFAOYSA-N 0.000 description 3
- UFFBMTHBGFGIHF-UHFFFAOYSA-N 2,6-dimethylaniline Chemical class CC1=CC=CC(C)=C1N UFFBMTHBGFGIHF-UHFFFAOYSA-N 0.000 description 3
- DOLQYFPDPKPQSS-UHFFFAOYSA-N 3,4-dimethylaniline Chemical class CC1=CC=C(N)C=C1C DOLQYFPDPKPQSS-UHFFFAOYSA-N 0.000 description 3
- JJYPMNFTHPTTDI-UHFFFAOYSA-N 3-methylaniline Chemical class CC1=CC=CC(N)=C1 JJYPMNFTHPTTDI-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- AFBPFSWMIHJQDM-UHFFFAOYSA-N N-methylaniline Chemical class CNC1=CC=CC=C1 AFBPFSWMIHJQDM-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- 125000001246 bromo group Chemical group Br* 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 125000004836 hexamethylene group Chemical class [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 3
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- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
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- KLOQOWQKKZSVJD-UHFFFAOYSA-N n-fluoro-4-methylaniline Chemical class CC1=CC=C(NF)C=C1 KLOQOWQKKZSVJD-UHFFFAOYSA-N 0.000 description 3
- RNVCVTLRINQCPJ-UHFFFAOYSA-N o-toluidine Chemical compound CC1=CC=CC=C1N RNVCVTLRINQCPJ-UHFFFAOYSA-N 0.000 description 3
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical class CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 3
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- KYXNZQDZZRRNJP-UHFFFAOYSA-N 1,2,4-trifluoro-3,5-dimethylbenzene Chemical compound CC1=CC(F)=C(F)C(C)=C1F KYXNZQDZZRRNJP-UHFFFAOYSA-N 0.000 description 1
- VBAUJXBPWBROGJ-UHFFFAOYSA-N 1-(2,3-dimethylphenyl)-2,2,2-trifluoroethanone Chemical class CC1=CC=CC(C(=O)C(F)(F)F)=C1C VBAUJXBPWBROGJ-UHFFFAOYSA-N 0.000 description 1
- UNILWMWFPHPYOR-KXEYIPSPSA-M 1-[6-[2-[3-[3-[3-[2-[2-[3-[[2-[2-[[(2r)-1-[[2-[[(2r)-1-[3-[2-[2-[3-[[2-(2-amino-2-oxoethoxy)acetyl]amino]propoxy]ethoxy]ethoxy]propylamino]-3-hydroxy-1-oxopropan-2-yl]amino]-2-oxoethyl]amino]-3-[(2r)-2,3-di(hexadecanoyloxy)propyl]sulfanyl-1-oxopropan-2-yl Chemical compound O=C1C(SCCC(=O)NCCCOCCOCCOCCCNC(=O)COCC(=O)N[C@@H](CSC[C@@H](COC(=O)CCCCCCCCCCCCCCC)OC(=O)CCCCCCCCCCCCCCC)C(=O)NCC(=O)N[C@H](CO)C(=O)NCCCOCCOCCOCCCNC(=O)COCC(N)=O)CC(=O)N1CCNC(=O)CCCCCN\1C2=CC=C(S([O-])(=O)=O)C=C2CC/1=C/C=C/C=C/C1=[N+](CC)C2=CC=C(S([O-])(=O)=O)C=C2C1 UNILWMWFPHPYOR-KXEYIPSPSA-M 0.000 description 1
- 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 1
- MLDLPURSBQYOEP-UHFFFAOYSA-N 2,2-difluoro-1-(2-fluorophenyl)propan-1-one Chemical class CC(F)(F)C(=O)C1=CC=CC=C1F MLDLPURSBQYOEP-UHFFFAOYSA-N 0.000 description 1
- OISVCGZHLKNMSJ-UHFFFAOYSA-N 2,6-dimethylpyridine Chemical class CC1=CC=CC(C)=N1 OISVCGZHLKNMSJ-UHFFFAOYSA-N 0.000 description 1
- FTZQXOJYPFINKJ-UHFFFAOYSA-N 2-fluoroaniline Chemical class NC1=CC=CC=C1F FTZQXOJYPFINKJ-UHFFFAOYSA-N 0.000 description 1
- DGZJLMWKIQOQFA-UHFFFAOYSA-N 2-methyl-1-phenylbutan-1-one Chemical class CCC(C)C(=O)C1=CC=CC=C1 DGZJLMWKIQOQFA-UHFFFAOYSA-N 0.000 description 1
- BSMGLVDZZMBWQB-UHFFFAOYSA-N 2-methyl-1-phenylpropan-1-one Chemical class CC(C)C(=O)C1=CC=CC=C1 BSMGLVDZZMBWQB-UHFFFAOYSA-N 0.000 description 1
- XZUUYZVKCHWOGB-UHFFFAOYSA-N C(C)C(C(=O)C1=C(C=CC=C1)F)(F)F Chemical class C(C)C(C(=O)C1=C(C=CC=C1)F)(F)F XZUUYZVKCHWOGB-UHFFFAOYSA-N 0.000 description 1
- 0 CC(c1c(*/C=C/Cc2cccc(cc3)c22)c2c3c(C(C)=Nc(c(N)*2*=C)c(*)c(*)c2S)n1)=N[C@@]1C=CC(*)=C(C)C1I Chemical compound CC(c1c(*/C=C/Cc2cccc(cc3)c22)c2c3c(C(C)=Nc(c(N)*2*=C)c(*)c(*)c2S)n1)=N[C@@]1C=CC(*)=C(C)C1I 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
- MFESCIUQSIBMSM-UHFFFAOYSA-N I-BCP Chemical class ClCCCBr MFESCIUQSIBMSM-UHFFFAOYSA-N 0.000 description 1
- PHSPJQZRQAJPPF-UHFFFAOYSA-N N-alpha-Methylhistamine Chemical compound CNCCC1=CN=CN1 PHSPJQZRQAJPPF-UHFFFAOYSA-N 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
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 150000008062 acetophenones Chemical class 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
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000005234 alkyl aluminium group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- FFSAXUULYPJSKH-UHFFFAOYSA-N butyrophenone Chemical class CCCC(=O)C1=CC=CC=C1 FFSAXUULYPJSKH-UHFFFAOYSA-N 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 230000006315 carbonylation Effects 0.000 description 1
- 238000005810 carbonylation reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 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
- 229920001577 copolymer Polymers 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- ZQBFAOFFOQMSGJ-UHFFFAOYSA-N hexafluorobenzene Chemical class FC1=C(F)C(F)=C(F)C(F)=C1F ZQBFAOFFOQMSGJ-UHFFFAOYSA-N 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000000314 lubricant Substances 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
- 238000002156 mixing Methods 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
- 125000002524 organometallic group Chemical group 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- 230000032696 parturition Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- FZICYDAVRBDQFK-UHFFFAOYSA-N propan-2-one;1,3,5-trimethylbenzene Chemical compound CC(C)=O.CC1=CC(C)=CC(C)=C1 FZICYDAVRBDQFK-UHFFFAOYSA-N 0.000 description 1
- GYUBJCLBKFRYSN-UHFFFAOYSA-N propan-2-one;1,4-xylene Chemical compound CC(C)=O.CC1=CC=C(C)C=C1 GYUBJCLBKFRYSN-UHFFFAOYSA-N 0.000 description 1
- 238000004080 punching Methods 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
- 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
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical class ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/19—Catalysts containing parts with different compositions
-
- 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
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- 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
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- 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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- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
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Abstract
The present invention relates to novel linear alhpa olefin catalyst and its preparation method and application.The carbon monoxide-olefin polymeric is made up of major catalyst and co-catalyst, and wherein major catalyst is iron system imido ligands compound, and co-catalyst is MAO, triisobutyl aluminium, borine and GaCl3.The carbon monoxide-olefin polymeric is used to be catalyzed ethylene oligomerization preparation linear alpha olefin, and linear alpha olefin is selectively more than 96%, and carbon number distribution is in C4‑C28, wherein C6‑C20More than 75%.The catalyst of the present invention, Stability Analysis of Structures can be used in ethylene oligomerization, high catalytic efficiency, and preparation method of the invention is easy to operate, yield is high, raw material is easy to get, and cost is low, environmental pollution is small, it is easy to industrialized production.
Description
Technical field
The present invention relates to industrial catalyst field, more particularly to novel linear alhpa olefin catalyst and preparation method thereof and should
With.
Background technology
Linear alpha-alkene (LAO) refers to C4-C28Above high-carbon straight chain terminal olefine, is one kind weight developed rapidly over nearly 30 years
The Organic Chemicals wanted.Alpha-olefin main application has following five major class：1) comonomer, in LLDPE
(LLDPE) comonomer and in high density polyethylene (HDPE) (HDPE) production used mainly has 1- butylene, 1- hexenes and 1- octenes；2)
For producing detergent and detergent alcohol, the detergent alcohol synthesized by alpha-olefin has good biological degradability；3) synthesis profit
Lubricating oil, poly alpha olefin is the synthetic lubricant fluid of high-quality, and it is mainly the oligomer of 1- decene and 1- octenes；4) plasticizer alcohol, C8-
C10Linear alpha-olefin is low through plasticizer alcohol volatility made from carbonylation synthesis, and with good photostability and inoxidizability；
5) it is used to produce lube oil additive and drilling fluid, adhesive, sealant etc..There is more than 50% to be used as gathering in the consumption of alpha-olefin
The comonomer of ethene.
The production method of alpha-olefin mainly has wax destructive distillation method, dehydrating alkanes method, ethylene oligomerization method, extraction separating method.Mesh
Preceding ethylene oligomerization is the main method for producing alpha-olefin, and the alpha-olefin produced using this method accounts for whole alpha-olefin production
94.1%.Used catalyst mainly has alkyl aluminum system, titanium system, iron system, nickel system, chromium system etc..According to used catalyst and production work
The difference of skill, ethylene oligomerization method major technique has the Ziegler techniques of CPChem companies, the improved Ziegler of INEOS companies
Technique, the SHOP techniques of Shell companies.The Idemitsu techniques of Japanese light extraction petro-chemical corporation, the VERSIPOL of Dupond companies
Technique etc..The SHOP process routes of wherein Shell companies are complicated, and process route is long, in addition to oligomerization, is also disproportionated, isomery
Change etc., therefore production cost highest, but its good product quality, distribution is flexible, and can make alpha-olefin conversion production internal olefin.Ethene
The research of the catalyst of oligomerisation synthesis alpha-olefin obtains remarkable progress, occur in recent years using multi-phases process olefin(e) oligomerization prepare α-
The research report and patent of alkene.It is pungent to alpha-olefin, particularly 1- hexenes and 1- with developing rapidly for polyethylene (PE) industry
The demand of alkene is increasing.1- hervene copolymers PE is current fastest-rising kind.13 sets of 11 manufacturers are had in the world
Alpha-olefin process units production run, is concentrated mainly on North America, Europe, South Africa, Japan etc..World's alpha-olefin production energy in 2009
Power is 4334kt/a, and 2010 more than 4914kt/a.
With developing rapidly for polyolefin industry and Surfactant Industry, the C of comononer of polyolefin is used as6-C8And work
For the C of detergent primary raw material10-C18The demand of partial linear alpha-alkene increasingly increases, therefore makes great efforts to improve the partial line
Content of the property alpha-olefin in output aggregate has very important economic value and realistic meaning.
The content of the invention
The purpose of the present invention is exactly to be to provide a series of carbon number distributions that can improve for C6-C18Linear alpha-alkene production
It is prepared by carbon monoxide-olefin polymeric of relative amount in product and preparation method thereof and use carbon monoxide-olefin polymeric catalysis ethylene oligomerization
The method of linear alpha-alkene, to meet the active demand of current chemical industry.
The present invention relates to a series of iron catalyst composition series of ethylene oligomerizations and its application, it is characterized in that major catalyst is
Iron system (II) imido ligands compound, co-catalyst is MAO, triisobutyl chlorine and borine or GaCl3Mixing
Thing.These carbon monoxide-olefin polymerics are used to be catalyzed ethylene oligomerization, so as to get the carbon number distribution of linear alpha-alkene is in C4-C28Between, its
Middle C6-C20Component is more than 80%.
The major catalyst of the present invention is divided into three classes：
The first kind is pyridine not that ene derivative, and described catalyst is that non-alkene and substituted pyridines cyclization gained；
Equations of The Second Kind is pyridine derivate, and described catalyst is that 2- acetyl group -6- methylamino pyridines and substituted aniline react
Obtain, 2- formoxyl -6- methylamino pyridines are that raw material is obtained by the reaction of several steps from pyridine；
3rd class is the derivative for phenanthroline, described catalyst for 9,10- dihydrobenzos [b] [1,10] phenanthroline-
11 (8H) -one and substituted aniline reaction are obtained, and 9,10- dihydrobenzos [b] [1,10] (8H) -one of phenanthroline -11 is luxuriant and rich with fragrance by [1,10]
Quinoline is coughed up to be made by the reaction of several steps；
The co-catalyst is a kind of mixture, by MAO, triisobutyl aluminium and borine or GaCl3Three part groups
Into.Wherein MAO is mixed with the amount ratio of the material of triisobutyl aluminium for 100: 1 to 1: 1, and especially 90: 1 to 10: 1.
GaCl3Ratio with the amount of substance of MAO and triisobutyl aluminium is 1: 100: 10 to 1: 10000: 100.
Described iron catalyst composition series are used to be catalyzed the method that ethylene oligomerization prepares linear alpha-alkene, including：In nothing
Under water oxygen free condition, ethylene pressure be 0.1~20MPa, reaction temperature be 0-100 DEG C when, order add organic solvent (hexane or
Hexamethylene), co-catalyst and major catalyst solution, after reaction 5~60 minutes, be cooled to -10 DEG C~0 DEG C, add methanol and terminate
Reaction, most afterwards through the isolated linear alpha-alkene selectivity ＞ 97% of rectifying, carbon number distribution is in C4-C28Between, wherein C6-C20's
Component is more than 80%.
The application of described iron catalyst composition series, wherein described 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
Alkane, described co-catalyst and the amount ratio of the material of major catalyst are calculated as 5000: 1~500: 1 with Al/Fe, especially with 1000: 1
~500: 1 is optimal.
Embodiment
Not that alkene is substrate for embodiment 1,2,6- diformyls-pyridine
Compound 1 synthesis reference literature Chemische Berichte., Vol20, P662. compound 1 (10g,
Acetic acid 100mL 0.052mol) is dissolved in, AlCl is added3(35g, 0.26mol), reaction solution is heated to reflux 2 hours, and TLC displays are former
Material has been disappeared, and stops reaction, adds frozen water and is quenched, and dichloromethane extraction, organic phase is steamed with after anhydrous anhydrous sodium sulfate drying
Dry solvent, crude product obtained after column chromatography for separation (leacheate be petroleum ether and ethyl acetate) pure compound 2 (9g,
73%).1H NMR(CHCl3 d3)δppm：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 ammoniacal liquor (1.6g, 0.045mol), reaction
2 hours, then stop reaction, drain solvent and obtain compound 3 (8.93g, 100%).1H NMR(CHCl3d3)δppm：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
Hour, cooling, solvent evaporated rear pillar chromatographic purifying obtains compound 4 (11g, 90%).1H NMR(CHCl3 d3)δppm：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 R11By taking methyl as an example：Compound 4 (10g, 0.028mol) is dissolved in THF 50mL, -78 DEG C, dropwise addition are cooled to
It is warming up to after butyl lithium (0.06mol), completion of dropping after room temperature adds DMAC (21g, 0.29mol), completion of dropping and is warming up to 50
DEG C reaction 2 hours, stop reaction, add ammonium chloride solution be quenched, organic phase is extracted with dichloromethane.Organic phase anhydrous slufuric acid
After sodium is dried, filtering is evaporated.Ethanol punching crystallization can obtain pure compound 5 (3.5g, 48%).1H NMR(CHCl3 d3)δppm
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, CH3 CO-)
Compound 5 and substituted aniline are reacted under conditions of anhydrous and oxygen-free, and wherein compound 5 and substituted aniline is rubbed
You are than being 1: 1.2, and solvent is toluene, is to be carried out under catalyst backflow with p-methyl benzenesulfonic acid.Reaction time is 3-6 hour, TLC
Monitoring is reacted, after completion of the reaction, removed under reduced pressure solvent, then column chromatography (being leacheate with petroleum ether and ethyl acetate), you can
Obtain target product 6.Aniline in the inventive method can be 2-aminotoluene, 3- methylanilines, 4- methylanilines, 2,3- bis-
Methylaniline, 2,4- dimethylanilines, 2,5 dimethylanilines, 2,6- dimethylanilines, 3,4- dimethylanilines, 3,5- diformazans
Base aniline, 3,6- dimethylanilines, 2,4,6- trimethylanilines, bromo- 2, the 6- dimethylanilines of 4-, 2- MEAs, 2- ethyls-
6 methylanilines, 2- fluoroanilines, the fluoro- 4- methylanilines of 2-, 2,3,4- trifluoromethyl anilines, 2,4,5- trifluoromethyl anilines, 2,4,6- trifluoro-benzenes
Amine, most preferably 2,3,4,5,6- pentafluoroanilines, 4- methylanilines.
Here by taking 4- methylanilines as an example：Compound 5 (1g, 3.85mmol) is dissolved in 50 milliliters of toluene, and 1.2eq equivalents are added dropwise
4- methylanilines, add 0.1eq p-methyl benzenesulfonic acid after completion of dropping, backflow, TLC displays reaction is complete after 3 hours.Stop
Only react, 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)δppm：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, virtue
Ring H), 7.1 (m, 8H, aromatic ring H), 2.35 (s, 6H, CH3 ), 0.9 (s, 6H, CH3 N-)。
Here with 4- methylanilines, exemplified by 4- tolyl aldehydes, under the protection of inert gas, by compound 6 (1g,
2.3mmol) be dissolved in 50 milliliters of toluene, drive the oxygen in solvent away with inert gas, then add frerrous chloride (5.2g,
4.08mmol), it is stirred overnight under inert gas shielding, TLC detections are reacted completely, filtering, solvent evaporated, crude product second
Compound 7 (0.89g, 68%) can be obtained after ether washing.1H NMR(CHCl3 d3)δppm：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, CH3 ),
0.9 (s, 6H, CH3 N-)。
Embodiment 2, the methylamino of 2- acetyl group -6 are substrate
The method of compound 8 follows document Synthetic Communications, 2005,35,2317-2324 report
Obtained from 2,6- lutidines for raw material is oxidized in reduction.Compound 8 (10g, 0.07mol) is dissolved in dichloromethane, cooling
Ammoniacal liquor (1.2g, 0.079mol) is then added to 0 DEG C, stops reaction, solvent evaporated after stirring reaction half an hour.Column chromatography can be obtained
To mono-substituted compound 9 (5.8g, 60%).Feature：1H NMR(CHCl3 d3)δppm：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,CH2 -), 4.24 (m, 2H,CH2 -)。
Compound 9 (5g, 0.036mol) is dissolved in dichloromethane, adds PCC oxidants (8.6g, 0.04mol), room temperature reaction
2 hours, TLC showed that reaction terminates, and stops reaction, solvent evaporated.Column chromatography obtains the compound of 2- aldehyde radicals.2- aldehyde radicals
Compound be dissolved in dichloromethane, be cooled to -78 DEG C, dimethyl lithium solution (1.1eq) be added dropwise, reacted 2 hours after addition, added
Ammonium chloride solution is quenched, and organic phase is extracted with dichloromethane, dry, be evaporated after rear column chromatography can obtain compound 10 (4.5g,
92%).Feature：1H NMR(CHCl3 d3)δppm：8.24 (m, 1H, aromatic ring H), 8.22 (m, 1H, aromatic ring H), 8.08 (m, 1H, virtue
Ring H), 4.24 (m, 2H,CH2 -), 2.36 (s, 3H, CH 3 CO-)。
Compound 10 and substituted aniline are reacted under conditions of anhydrous and oxygen-free, wherein compound 10 and substituted aniline
Mol ratio is 1: 1.2, and solvent is toluene, is to be carried out under catalyst backflow with p-methyl benzenesulfonic acid.Reaction time is 3-6 hour,
TLC monitorings are reacted, after completion of the reaction, removed under reduced pressure solvent, then column chromatography (being leacheate with petroleum ether and ethyl acetate), i.e.,
It can obtain target product 11.Aniline in the inventive method can be 2-aminotoluene, 3- methylanilines, 4- methylanilines, 2,
3- dimethylanilines, 2,4- dimethylanilines, 2,5 dimethylanilines, 2,6- dimethylanilines, 3,4- dimethylanilines, 3,5-
Dimethylaniline, 3,6- dimethylanilines, 2,4,6- trimethylanilines, bromo- 2, the 6- dimethylanilines of 4-, 2- MEAs, 2-
The methylaniline of ethyl -6,2- fluoroanilines, the fluoro- 4- methylanilines of 2-, 2,3,4- trifluoromethyl anilines, 2,4,5- trifluoromethyl anilines, 2,4,6-
Trifluoromethyl aniline, most preferably 2,3,4,5,6- pentafluoroanilines, 4- methylanilines.
Here by taking 4- methylanilines as an example：Compound 10 (1g, 7mmol) is dissolved in 50 milliliters of toluene, and 1.2eq equivalents are added dropwise
0.1eq p-methyl benzenesulfonic acid is added after 4- methylanilines, completion of dropping, is flowed back, TLC displays reaction is complete after 3 hours.Stop
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)δppm：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,CH2 -), 2.35 (s, 3H, CH3 -), 0.9 (s, 3H, CH3 N-)。
Compound 11 and substitution benzophenone are reacted under conditions of anhydrous and oxygen-free, wherein compound 11 and substituted aniline
Mol ratio is 1: 1.2, and solvent is toluene, is to be carried out under catalyst backflow with p-methyl benzenesulfonic acid.Reaction time is 3-6 hour,
TLC monitorings are reacted, after completion of the reaction, removed under reduced pressure solvent, then column chromatography (being leacheate with petroleum ether and ethyl acetate), i.e.,
It can obtain target product 12.Substitution benzophenone in the inventive method, can be 2- methyl acetophenones, 3- methyl acetophenones, 4- first
Benzoylformaldoxime, 2,3- dimethyl acetophenones, 2,4- dimethyl acetophenones, 2,5 dimethyl acetophenones, 2,6- dimethyl acetophenones,
3,4- dimethyl acetophenones, 3,5- dimethyl acetophenones, 3,6- dimethyl acetophenones, 2,4,6- trimethylacetophenones, 4- bromo- 2,
6- dimethyl acetophenones, 2- ethyl acetophenones, the methyl acetophenone of 2- ethyls -6,2- fluoro acetophenones, the fluoro- 4- methyl acetophenones of 2-,
2,3,4- trifluoroacetophenones, 2,4,5- trifluoroacetophenones, 2,4,6- trifluoroacetophenones, 2,3,4,5,6- phenyl-pentafluoride ethyl ketones, 2- first
Base propiophenone, 3- methyl phenyl ketones, 4- methyl phenyl ketones, 2,3- dimethyl benzene acetone, 2,4- dimethyl benzene acetone, 2,5 diformazans
Base propiophenone, 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, bromo- 2, the 6- dimethyl benzenes acetone of 4-, 2- ethyl propiophenones, the methyl phenyl ketone of 2- ethyls -6,2- fluorine
Propiophenone, the fluoro- 4- methyl phenyl ketones of 2-, 2,3,4- trifluoro propiophenones, 2,4,5- trifluoro propiophenones, 2,4,6- trifluoro propiophenones,
2,3,4,5,6- phenyl-pentafluoride acetone, 2- methyl trifluoro acetophenones, 3- methyl trifluoro acetophenones, 4- methyl trifluoro acetophenones, 2,3-
Dimethyl trifluoroacetophenone, 2,4- dimethyl trifluoroacetophenones, 2,5 dimethyl trifluoroacetophenones, 2,6- dimethyl trifluoro-benzene second
Ketone, 3,4- dimethyl trifluoroacetophenones, 3,5- dimethyl trifluoroacetophenones, 3,6- dimethyl trifluoroacetophenones, 2,4,6- front threes
Base trifluoroacetophenone, bromo- 2, the 6- dimethyl trifluoroacetophenones of 4-, 2- ethyl trifluoroacetophenones, the methyl trifluoro benzene second of 2- ethyls -6
Ketone, 2- fluorine trifluoroacetophenones, the fluoro- 4- methyl trifluoros acetophenones of 2-, 2,3,4- trifluoro trifluoroacetophenones, 2,4,5- trifluoro trifluoro-benzenes
Ethyl ketone, 2,4,6- trifluoro trifluoroacetophenones, most preferably 2,3,4,5,6- five fluorine trifluoroacetophenones, 4- methyl acetophenones.
Here by taking 4- methyl acetophenones as an example：Compound 11 (1g, 4mmol) is dissolved in 50 milliliters of toluene, and 1.2eq equivalents are added dropwise
4- methyl acetophenones, add 0.1eq p-methyl benzenesulfonic acid after completion of dropping, backflow, TLC displays reaction is complete after 3 hours.
Stop reaction, removed under reduced pressure solvent.Column chromatography obtains R after purification8For the compound 12 (1.2g, 90%) of methyl.Feature：1H
NMR(CHCl3 d3)δppm：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,CH2 -), 2.35 (s, 6H, CH3 -), 0.9 (s, 3H, CH3 N-)。
Here with 4- methylanilines, exemplified by 4- methyl acetophenones, under the protection of inert gas, by compound 12 (1g,
3mmol) be dissolved in 50 milliliters of toluene, drive the oxygen in solvent away with inert gas, then add frerrous chloride (4.5g,
3.55mmol), it is stirred overnight under inert gas shielding, TLC detections are reacted completely, filtering, solvent evaporated, crude product second
Compound 13 (1.2g, 88%) can be obtained after ether washing.1H NMR(CHCl3 d3)δppm：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,CH2 -),
2.35 (s, 6H, CH3 -), 0.9 (s, 3H, CH3 N-)。
Embodiment 3, phenanthroline are substrate
The method of compound 15 follows document Organometallics, 25 (3), and 2006 report is from 1,10- phenanthroline
Raw material is obtained through two steps.
Compound 15 (2.2g, 1mmol) is dissolved in dichloromethane, is then added dropwise after 1.1eq thionyl chlorides, completion of dropping, stirs
Mix 2 hours, AlCl is directly added into without isolation3(2g, 1.5mmol) and 3- chlorobromopropanes (1.57g, 1.1mmol), room temperature reaction
Reaction is heated back after 1 hour to stay overnight, and is cooled down, will be poured into frozen water, extracted with dichloromethane after reaction, organic phase anhydrous slufuric acid
Sodium is dried, filtering, and the product of hastening parturition 3 are obtained after being evaporated.It is solid that crude product petroleum ether and re-crystallizing in ethyl acetate can obtain the white of compound 16
Body (1.4g, 56%).Feature：1H NMR(CHCl3 d3)δppm：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,
CH2 -), 2.40 (m, 2H, CH2 -), 1.95 (m, 2H, CH2 -)。
Compound 16 and substituted aniline are reacted under conditions of anhydrous and oxygen-free, wherein compound 16 and substituted aniline
Mol ratio is 1: 1.2, and solvent is toluene, is to be carried out under catalyst backflow with p-methyl benzenesulfonic acid.Reaction time is 3-6 hour,
TLC monitorings are reacted, after completion of the reaction, removed under reduced pressure solvent, then column chromatography (being leacheate with petroleum ether and ethyl acetate), i.e.,
It can obtain target product 17.Aniline in the inventive method can be 2-aminotoluene, 3- methylanilines, 4- methylanilines, 2,
3- dimethylanilines, 2,4- dimethylanilines, 2,5 dimethylanilines, 2,6- dimethylanilines, 3,4- dimethylanilines, 3,5-
Dimethylaniline, 3,6- dimethylanilines, 2,4,6- trimethylanilines, bromo- 2, the 6- dimethylanilines of 4-, 2- MEAs, 2-
The methylaniline of ethyl -6,2- fluoroanilines, the fluoro- 4- methylanilines of 2-, 2,3,4- trifluoromethyl anilines, 2,4,5- trifluoromethyl anilines, 2,4,6-
Trifluoromethyl aniline, most preferably 2,3,4,5,6- pentafluoroanilines, 4- methylanilines.
Here by taking 4- methylanilines as an example：Compound 16 (1g, 4mmol) is dissolved in 50 milliliters of toluene, and 1.2eq equivalents are added dropwise
0.1eq p-methyl benzenesulfonic acid is added after 4- methylanilines, completion of dropping, is flowed back, TLC displays reaction is complete after 3 hours.Stop
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)δppm：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, virtue
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, CH2 -), 2.35
(s, 3H,CH3 -), 1.70 (m, 2H, CH2 -), 1.30 (m, 2H, CH2 -)。
Here by taking 4- methylanilines as an example, under the protection of inert gas, compound 17 (1g, 3mmol) is dissolved in 50 millis
Rise in toluene, drive the oxygen in solvent away with inert gas, frerrous chloride (4.5g, 3.55mmol) is then added, in indifferent gas
It is stirred overnight under body protection, TLC detections are reacted completely, and filtering, solvent evaporated, crude product can obtain compound after being washed with ether
18 (1.1g, 80%).Feature：1H NMR(CHCl3 d3)δppm：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,
CH2 -), 2.35 (s, 3H,CH3 -), 1.70 (m, 2H, CH2 -), 1.30 (m, 2H, CH2 -)。
Ethylene oligomerization reaction experiment process and method：
The 250mL three-necked flasks that will be equipped with magnetic stir bar and drying are vacuumized while hot, nitrogen displacement is filled with second afterwards for several times
Alkene, sequentially adds quantitative toluene, co-catalyst MAO and catalyst, oligomerisation reaction, reaction system is carried out at a predetermined temperature
Pressure by magnetic valve automatically adjust holding it is constant, pressure changes with time in record buffer tank, and polymerization time is 30min,
Finally with the acidic ethanol terminating reaction that methanol or mass fraction are 10%.Ethylene oligomerization product is analyzed with GC-MS methods, is urged
The activity of agent is then obtained by the pressure drop of ethene surge tank.
Ethylene oligomerization experimental result example
Following table lists the experimental result of some embodiments.
Note：1. ethylene oligomerization catalysis reaction condition：1.5 μm of ol of catalyst concn, 50mL toluene makees solvent, and MAO urges to help
Agent；
2. alhpa olefin content is more than 99%, linear alpha olefin is selectively more than 96%.
3. the structure of each catalyst and it is described as follows：
A. catalyst 7-1 to 7-3 is：Major catalyst structure (compound 7 obtained in patent specification embodiment 1) is such as
Shown in figure below, wherein R11 is methyl, and R1, R2, R4 and R6, R7, R9 are hydrogen.Catalyst 7-1：R3 and R8 be methoxyl group, R5 and
R10 is methyl.Catalyst 7-2：R3 and R8 is methyl, and R5 and R10 are hydrogen.Catalyst 7-3：R5 and R10 is bromine, and R3 and R8 are
Hydrogen.
B. catalyst 13-1 to 13-3 is：Major catalyst structure (the compound obtained in patent specification embodiment 2
13) as shown below, wherein R11 and R12 are methyl, and R2, R4, R5 and R7, R9, R10 are hydrogen.Catalyst 13-1：R1 and R6 are
Methoxyl group, R3 and R8 are methyl.Catalyst 13-2：R3 and R8 is methyl, and R1 and R6 are 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 (the compound obtained in patent specification embodiment 3
18) as shown below, wherein R2 and R4 are hydrogen.Catalyst 18-1：R3 is methoxyl group, and R1 and R5 are methyl.Catalyst 18-2：R3
It is methyl with R5, 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, three in 120,7143-7144
Catalyst is planted, major catalyst structural formula is as shown below.Wherein catalyst 19 is structural formula 7, and R is methyl；Catalyst 20 is knot
Structure formula 8, R is ethyl；Catalyst 21 is structural formula 9, and R is isopropyl.
Particular embodiments described above, has been carried out further in detail to the purpose of the present invention, technical scheme and beneficial effect
Describe in detail bright.It should be appreciated that the foregoing is only the specific embodiment of the present invention, it is not intended to limit the invention.It is all this
Within the spirit and principle of invention, any modification, equivalent substitution and improvements done etc. should be included in the protection model of the present invention
Within enclosing.
Claims (8)
1. a kind of novel linear poly-alpha olefins catalyst, including major catalyst and co-catalyst, wherein the major catalyst is iron
It is imido ligands compound, its structural formula is (IA)：
Wherein, R1-R10It is each independently selected from H, C1-C6 alkyl, halogen, C1-C6 alkoxies；R11For C1-C6 alkyl, isopropyl
Or trifluoromethyl.
2. catalyst according to claim 1, wherein the structural formula of the major catalyst is (IA), the imido ligands
By 2,6- diacetyls-pyridine, not that alkene and substituted aniline reaction are obtained compound.
3. catalyst according to claim 1, wherein, the phenyl shown in structural formula (IA) is by C1-C4 alkyl one, two
Or trisubstd phenyl, it is：2- aminomethyl phenyls, 4- aminomethyl phenyls, 2,4- 3,5-dimethylphenyls, 2,6- 3,5-dimethylphenyls, 2,4,
6- trimethylphenyls, 2- ethylphenyls, 4- ethylphenyls, 2,4- diethyl phenyls, 2,4,6- triethyl group phenyl, 2- propylbenzenes
Base, 4- propyl group phenyl, 2,4- dipropyl phenyl, 2,6- dipropyl phenyl, 2,4,6- tripropyl phenyl, 2- isopropyl phenyls, 4-
Isopropyl phenyl, 2,4- diisopropyl phenyls, 2,6- diisopropyl phenyls, 2,4,6- triisopropyl phenyl, 2- butyl phenyls, 4-
Butyl phenyl, 2,4- dibutylphenyls, 2,6- dibutylphenyls, 2,4,6- tributyl phenyl, 2- tert-butyl-phenyls, the 4- tert-butyl groups
Phenyl, 2,4- di-tert-butyl-phenyls, 2,6- di-tert-butyl-phenyls, or 2,4,6- tri-tert phenyl.
4. catalyst according to claim 1, wherein, the phenyl shown in structural formula (IA) is by halogen one, two or three
Substituted phenyl, it is：2- chlorphenyls, 4- chlorphenyls, 2,4- dichlorophenyls, 2,4,6- trichlorophenyls, 2- bromophenyls, 4- bromobenzenes
Base, 2,4- dibromo phenyls, 2,4,6- tribromo phenyl, 2- fluorophenyls, 4- fluorophenyls, 2,4- difluorophenyls, or 2,4,6- trifluoro-benzenes
Base.
5. catalyst according to claim 1, wherein, the phenyl shown in structural formula (IA) is by halogen and C1-C4 alkane
Base one, two or trisubstd phenyl, it is：The bromo- 4- aminomethyl phenyls of 2-, the bromo- 6- aminomethyl phenyls of 2-, 2,6- bis- bromo- 4- methylbenzenes
Base, bromo- 2, the 6- 3,5-dimethylphenyls of 4-, the chloro- 4- aminomethyl phenyls of 2-, the chloro- 6- aminomethyl phenyls of 2-, 2,6- bis- chloro- 4- aminomethyl phenyls, or
Chloro- 2, the 6- 3,5-dimethylphenyls of 4-.
6. catalyst according to claim 1, wherein the co-catalyst be include MAO, triisobutyl aluminium,
And borine or GaCl3The mixture of three parts.
7. the catalyst described in claim 6 is used to be catalyzed the method that ethylene oligomerization prepares linear alpha olefin, it includes：Anhydrous
Under oxygen free condition, when ethylene pressure is that 0.1-20MPa, reaction temperature are 0-100 DEG C, order adds organic solvent, co-catalyst
With major catalyst solution, after reacting 5-60 minutes, -10 DEG C to 0 DEG C are cooled to, methanol terminating reaction is added, is most obtained afterwards through rectifying
To linear alpha olefin, wherein, the selective ＞ 97% of resulting linear alpha olefin, carbon number distribution is in C4-C28Between, wherein C6-
C20The percentage by weight of component is more than 80%.
8. the method described in claim 7, wherein, the organic solvent is petroleum ether, toluene or dimethylbenzene, the major catalyst
The solvent of solution is 1,2- dichloroethanes, dichloromethane, chloroform or o-dichlorohenzene, the co-catalyst and the main catalytic
The ratio of agent is using Al/Fe molar ratio computings as 5000: 1 to 500: 1.
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| US15/731,880 US10441946B2 (en) | 2016-03-22 | 2016-04-01 | Linear alpha-olefin catalysts and preparation and use thereof |
| BR112018017060-7A BR112018017060B1 (en) | 2016-03-22 | 2016-04-01 | LINEAR POLY-ALPHA-OLEFIN CATALYST AND PREPARATION METHOD THEREOF |
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Denomination of invention: New linear a Olefin catalyst and its preparation method and Application Effective date of registration: 20210913 Granted publication date: 20170922 Pledgee: Bank of Jiangsu Limited by Share Ltd. Hangzhou branch Pledgor: Abbott science and Technology (Hangzhou) Co.,Ltd. Registration number: Y2021980009219 |