CN106853378A - The ternary catalyst systems of the part of structural framework containing PNN and its application - Google Patents
The ternary catalyst systems of the part of structural framework containing PNN and its application Download PDFInfo
- Publication number
- CN106853378A CN106853378A CN201510894861.3A CN201510894861A CN106853378A CN 106853378 A CN106853378 A CN 106853378A CN 201510894861 A CN201510894861 A CN 201510894861A CN 106853378 A CN106853378 A CN 106853378A
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- Prior art keywords
- chromium
- catalyst
- catalyst system
- phenyl
- hexenes
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- 239000003054 catalyst Substances 0.000 title claims abstract description 49
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 68
- 239000011651 chromium Substances 0.000 claims abstract description 64
- 238000006243 chemical reaction Methods 0.000 claims abstract description 57
- 239000005977 Ethylene Substances 0.000 claims abstract description 53
- 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 claims abstract description 40
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical class CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 34
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 33
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 32
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 31
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 29
- 239000013638 trimer Substances 0.000 claims abstract description 27
- 239000003426 co-catalyst Substances 0.000 claims abstract description 18
- 239000012190 activator Substances 0.000 claims abstract description 11
- 150000001875 compounds Chemical class 0.000 claims abstract description 10
- 239000002243 precursor Substances 0.000 claims abstract description 7
- 229910052751 metal Inorganic materials 0.000 claims abstract description 5
- 239000002184 metal Substances 0.000 claims abstract description 5
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 39
- 239000002904 solvent Substances 0.000 claims description 21
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 239000003446 ligand Substances 0.000 claims description 15
- 239000002585 base Substances 0.000 claims description 13
- -1 cyclic aliphatic hydrocarbon Chemical class 0.000 claims description 13
- 239000012044 organic layer Substances 0.000 claims description 12
- 238000006073 displacement reaction Methods 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- 150000001845 chromium compounds Chemical class 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- BFGKITSFLPAWGI-UHFFFAOYSA-N chromium(3+) Chemical compound [Cr+3] BFGKITSFLPAWGI-UHFFFAOYSA-N 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 7
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 6
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 6
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 6
- 125000001637 1-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C(*)=C([H])C([H])=C([H])C2=C1[H] 0.000 claims description 4
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- OBETXYAYXDNJHR-SSDOTTSWSA-M (2r)-2-ethylhexanoate Chemical compound CCCC[C@@H](CC)C([O-])=O OBETXYAYXDNJHR-SSDOTTSWSA-M 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 claims description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 3
- MJSNUBOCVAKFIJ-LNTINUHCSA-N chromium;(z)-4-oxoniumylidenepent-2-en-2-olate Chemical compound [Cr].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O MJSNUBOCVAKFIJ-LNTINUHCSA-N 0.000 claims description 3
- UAIZDWNSWGTKFZ-UHFFFAOYSA-L ethylaluminum(2+);dichloride Chemical compound CC[Al](Cl)Cl UAIZDWNSWGTKFZ-UHFFFAOYSA-L 0.000 claims description 3
- 238000002347 injection Methods 0.000 claims description 3
- 239000007924 injection Substances 0.000 claims description 3
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 3
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 claims description 2
- 238000006467 substitution reaction Methods 0.000 claims 2
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims 1
- 125000003545 alkoxy group Chemical group 0.000 claims 1
- 239000004711 α-olefin Substances 0.000 abstract description 4
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 36
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 22
- 238000006384 oligomerization reaction Methods 0.000 description 18
- 239000000460 chlorine Substances 0.000 description 17
- 239000000243 solution Substances 0.000 description 17
- 0 CCC=CC(C(*)=NC(*)=*)=NC=* Chemical compound CCC=CC(C(*)=NC(*)=*)=NC=* 0.000 description 11
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 10
- 238000010791 quenching Methods 0.000 description 8
- 230000000171 quenching effect Effects 0.000 description 8
- 238000005829 trimerization reaction Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 6
- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
- 238000004679 31P NMR spectroscopy Methods 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 230000006837 decompression Effects 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 229910052593 corundum Inorganic materials 0.000 description 5
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 5
- 229910001845 yogo sapphire Inorganic materials 0.000 description 5
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 4
- 238000000967 suction filtration Methods 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 description 3
- 235000019341 magnesium sulphate Nutrition 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 3
- MZRVEZGGRBJDDB-UHFFFAOYSA-N n-Butyllithium Substances [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- WVSBQYMJNMJHIM-UHFFFAOYSA-N (benzene)chromium tricarbonyl Chemical compound [Cr].[O+]#[C-].[O+]#[C-].[O+]#[C-].C1=CC=CC=C1 WVSBQYMJNMJHIM-UHFFFAOYSA-N 0.000 description 2
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- CSDSSGBPEUDDEE-UHFFFAOYSA-N 2-formylpyridine Chemical class O=CC1=CC=CC=N1 CSDSSGBPEUDDEE-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- VGCXGMAHQTYDJK-UHFFFAOYSA-N Chloroacetyl chloride Chemical compound ClCC(Cl)=O VGCXGMAHQTYDJK-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- YPHGILDVYAYCCL-UHFFFAOYSA-N OC(C)[Fe](C1C=CC=C1)C1C=CC=C1 Chemical compound OC(C)[Fe](C1C=CC=C1)C1C=CC=C1 YPHGILDVYAYCCL-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 230000001476 alcoholic effect Effects 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 2
- XGRJZXREYAXTGV-UHFFFAOYSA-N chlorodiphenylphosphine Chemical compound C=1C=CC=CC=1P(Cl)C1=CC=CC=C1 XGRJZXREYAXTGV-UHFFFAOYSA-N 0.000 description 2
- SPKJCVZOZISLEI-UHFFFAOYSA-N cyclopenta-1,3-diene;1-cyclopenta-1,3-dien-1-ylethanone;iron(2+) Chemical compound [Fe+2].C=1C=C[CH-]C=1.CC(=O)C1=CC=C[CH-]1 SPKJCVZOZISLEI-UHFFFAOYSA-N 0.000 description 2
- GPAYUJZHTULNBE-UHFFFAOYSA-N diphenylphosphine Chemical compound C=1C=CC=CC=1PC1=CC=CC=C1 GPAYUJZHTULNBE-UHFFFAOYSA-N 0.000 description 2
- VURFVHCLMJOLKN-UHFFFAOYSA-N diphosphane Chemical compound PP VURFVHCLMJOLKN-UHFFFAOYSA-N 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- RQEUFEKYXDPUSK-UHFFFAOYSA-N 1-phenylethylamine Chemical compound CC(N)C1=CC=CC=C1 RQEUFEKYXDPUSK-UHFFFAOYSA-N 0.000 description 1
- PAPNRQCYSFBWDI-UHFFFAOYSA-N 2,5-Dimethyl-1H-pyrrole Chemical class CC1=CC=C(C)N1 PAPNRQCYSFBWDI-UHFFFAOYSA-N 0.000 description 1
- 125000004204 2-methoxyphenyl group Chemical group [H]C1=C([H])C(*)=C(OC([H])([H])[H])C([H])=C1[H] 0.000 description 1
- AHISYUZBWDSPQL-UHFFFAOYSA-N 6-methylpyridine-2-carbaldehyde Chemical class CC1=CC=CC(C=O)=N1 AHISYUZBWDSPQL-UHFFFAOYSA-N 0.000 description 1
- ZTMFEOXYCWBJDC-TXAHVKJLSA-N C/C(/CNCc1ccccn1)=C(\C=C/C=C)/P(c1ccccc1)c1ccccc1 Chemical compound C/C(/CNCc1ccccn1)=C(\C=C/C=C)/P(c1ccccc1)c1ccccc1 ZTMFEOXYCWBJDC-TXAHVKJLSA-N 0.000 description 1
- AKVDZOGYDJTSKY-KZHWDQGJSA-N CC(C(C)N(C)C(C)c(cccc1)c1P(c1ccccc1)c1ccccc1)/C=C\C=C/N Chemical compound CC(C(C)N(C)C(C)c(cccc1)c1P(c1ccccc1)c1ccccc1)/C=C\C=C/N AKVDZOGYDJTSKY-KZHWDQGJSA-N 0.000 description 1
- MAAPSOMZKCXOAR-VFCFBJKWSA-N CC(c(cccc1)c1P(c1ccccc1)c1ccccc1)/N=C/c1ncccc1 Chemical compound CC(c(cccc1)c1P(c1ccccc1)c1ccccc1)/N=C/c1ncccc1 MAAPSOMZKCXOAR-VFCFBJKWSA-N 0.000 description 1
- LCZVZLVJZBHEHW-UHFFFAOYSA-N CC(c(cccc1)c1P(c1ccccc1)c1ccccc1)N(C1C2CCCCC2)C1c1ncccc1 Chemical compound CC(c(cccc1)c1P(c1ccccc1)c1ccccc1)N(C1C2CCCCC2)C1c1ncccc1 LCZVZLVJZBHEHW-UHFFFAOYSA-N 0.000 description 1
- HMQJVZQCEFKMJL-UHFFFAOYSA-N CC(c(cccc1)c1P(c1ccccc1)c1ccccc1)NC(C)c1ccccn1 Chemical compound CC(c(cccc1)c1P(c1ccccc1)c1ccccc1)NC(C)c1ccccn1 HMQJVZQCEFKMJL-UHFFFAOYSA-N 0.000 description 1
- HQWTVAPYVHBESD-UHFFFAOYSA-N CC(c(cccc1)c1P(c1ccccc1)c1ccccc1)NC(c1ccccc1)c1ncccc1 Chemical compound CC(c(cccc1)c1P(c1ccccc1)c1ccccc1)NC(c1ccccc1)c1ncccc1 HQWTVAPYVHBESD-UHFFFAOYSA-N 0.000 description 1
- COOYEEIENGIDAD-UHFFFAOYSA-N CC(c1ccccc1P(c1ccccc1)c1ccccc1)NC(c1cccc(C)c1)c1ncccc1 Chemical compound CC(c1ccccc1P(c1ccccc1)c1ccccc1)NC(c1cccc(C)c1)c1ncccc1 COOYEEIENGIDAD-UHFFFAOYSA-N 0.000 description 1
- OLICYSBDINUXFD-UHFFFAOYSA-N CC(c1ccccc1P(c1ccccc1)c1ccccc1)NCc1ncccc1 Chemical compound CC(c1ccccc1P(c1ccccc1)c1ccccc1)NCc1ncccc1 OLICYSBDINUXFD-UHFFFAOYSA-N 0.000 description 1
- MBFFRCHRFPGHKS-UHFFFAOYSA-N CC(c1ncccc1)N(C)Cc(cccc1)c1P(c1ccccc1)c1ccccc1 Chemical compound CC(c1ncccc1)N(C)Cc(cccc1)c1P(c1ccccc1)c1ccccc1 MBFFRCHRFPGHKS-UHFFFAOYSA-N 0.000 description 1
- IQGCHLMPFACCSQ-UHFFFAOYSA-N CCC(c1ccccn1)NC(C)c(cccc1)c1P(c1ccccc1)c1ccccc1 Chemical compound CCC(c1ccccn1)NC(C)c(cccc1)c1P(c1ccccc1)c1ccccc1 IQGCHLMPFACCSQ-UHFFFAOYSA-N 0.000 description 1
- 229910021556 Chromium(III) chloride Inorganic materials 0.000 description 1
- 208000005156 Dehydration Diseases 0.000 description 1
- 238000005863 Friedel-Crafts acylation reaction Methods 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000002199 base oil Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 description 1
- 239000011636 chromium(III) chloride Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000006471 dimerization reaction Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- SHZIWNPUGXLXDT-UHFFFAOYSA-N ethyl hexanoate Chemical class CCCCCC(=O)OCC SHZIWNPUGXLXDT-UHFFFAOYSA-N 0.000 description 1
- QWUGXIXRFGEYBD-UHFFFAOYSA-M ethylmercuric chloride Chemical compound CC[Hg]Cl QWUGXIXRFGEYBD-UHFFFAOYSA-M 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 229920000092 linear low density polyethylene Polymers 0.000 description 1
- 239000004707 linear low-density polyethylene Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000011990 phillips catalyst Substances 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 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
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
- B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
-
- 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
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Abstract
A series of synthesis for preparing new PNN structural frameworks part in alpha-olefin catalyst system and catalyzing for ethylene selectivity oligomerisation belong to organic synthesis field.Prepare the synthesis containing PNN structural framework parts in alpha-olefin catalyst system and catalyzing the present invention relates to ethylene selectivity oligomerisation and provide the compound of a kind of metal precursor centered on chromium, PNN structural frameworks as part, activator or co-catalyst ternary catalyst systems and its catalysis high-selective ethylene trimer synthesis 1- hexenes, four aggregate into 1- octenes.Compared with traditional PNP chromium-based catalysts systems, improve the common Selectivity and activety of 1- hexenes and 1- octenes, reaction condition is gentle.
Description
Technical field
The invention belongs to organic synthesis field, and in particular to ethylene selectivity oligomerisation prepares alpha-olefin catalyst system and catalyzing
In the synthesis containing PNN structural framework parts, and provide one kind centered on chromium metal precursor, PNN structures
Framework compound is part, activator or co-catalyst ternary catalyst systems and its catalysis high-selective ethylene
Trimerization synthesis 1- hexenes, four aggregate into 1- octenes.
Background technology
Alkene, particularly linear alpha-alkene (LAOs) are the important Organic Ingredients of a class and chemical products, master
To be used as the comonomer of LLDPE, synthetic lubricant base oil, alpha-alkene sulfonate, plasticising
The intermediates such as agent alcohol, aliphatic acid.The method of industrial production LAOs is mainly divided to two kinds at present：One kind is
Traditional super distributed mode of production, such as wax cracking method, n-octyl alcohol evaporation, Fischer-Tropsch synthesis, it is this
LAOs product purities that mode is produced are low, cost price is high etc..Another way is selective oligomerization, main
If directly respectively obtaining 1- butylene, 1- hexenes and 1- by the way that the dimerization of ethene high selectivity, trimerization and four are poly-
Octene.The latter has atom utilization and preferable economic benefit very high.
With the successful Application of ethylene trimer high selectivity 1- hexenes, the ethene Gao Xuan of metal centered on chromium
Selecting property oligomerization catalysis system mainly has following several：
(1) the Phillips pyrrole ligand catalyst for trimerization of Chevron Phillips
Chevron Phillips deliver patent EP0780353A1 (1997), and are realized in Qatar in 2003
Industrialization trimerization production 1- hexenes.It is chromium that Phillips catalyst for trimerization uses three (2- ethyl hexanoates) chromium (III)
Source, 2,5- dimethyl pyrroles are co-catalyst as catalyst ligand, a chlorine diethyl pin and triethyl group.
115 DEG C, the dilute trimerization reaction of second is catalyzed under the ethylene pressure of 10.0MPa, catalysis activity reaches 94.00kg/ (g Cr/h),
The selectivity of 1- hexenes is up to 93% in product liquid.Current China's sinopec (Yanshan Mountain), petrochina (grand celebration) are adopted
Industrialized production 1- hexenes are realized with the catalyst system and catalyzing.
(2) catalyst containing biphosphine ligand of British Petroleum (BP) company
This is biphosphine ligand Cr metallic catalyst of the class by N atom bridgings, by BP companies research group in
(Carter, A. are reported first within 2002；Cohen,S.A.；Cooley,N.A.；Murphy,A.；Scutt,J.；
Wass, D.F.Chem.Commun.2002,858.), the catalyst shows selectivity and high work higher
Property.In the activation of co-catalyst MAO (MAO, methyl aluminoxane), the ethene pressure of 20bar
Under power, part Ar2PN(Me)PAr2And [CrCl (Ar=2-methoxyphenyl)3(THF)3] composition catalytic body
It is ethylene trimer activity up to 1000kg/ (g Cr/h), the selectivity of 1- hexenes is 89.9%.
(3) tridentate ligand ([SNS], [PNP]) catalyst system and catalyzing of Sasol companies
This is that a class N (H) connects two containing P or two symmetrical part containing S groups, by Sasol companies
Research group reported first in 2003, deliver patent WO 03053890A1 (2003) and
WO 03053891A1 (2003), this kind of catalyst has showed catalysis activity and high choosing higher
Selecting property.Under the activation of MAO, under the dilute pressure of second of 20-30bar, the complex compound containing Phosphine ligands
CrCl3[(Ph2PCH2CH2)2NH] the dilute trimerization catalysis activity of second reach 37kg/ (g Cr/h), 1- oneself dilute selectivity be
93.2%；The complex compound CrCl of sulfur-containing ligand3[(nHexyl-SCH2CH2)2NH] ethylene trimer catalysis activity reach
160kg/ (g Cr/h), 1- oneself dilute selectivity is 98.1%.
As linear alpha-olefin demand is increasing, particularly trimerization product 1- hexenes, four poly- product 1-
Octene, exploitation high-selective ethylene catalyst for oligomerization, particularly chromium system ethylene trimer, four poly- catalyst are
Focus as current research.Chromium system ethylene trimer, the major catalyst of four poly- catalyst are gold centered on chromium source
Category precursor is obtained with bluk recombination, under conditions of chromium source is relatively fixed, the different skeleton structures of design synthesis
Part turns into the inevitable means for changing major catalyst structure and regulation catalytic performance, and generates therewith a series of
The part of new framework structure.At present the high selectivity catalyst for oligomerization reported can obtain nearly 90%1- oneself
Alkene/1- octenes are selective altogether, and the selectivity of particularly 1- octenes is unsatisfactory, are not met by industrialized wanting
Ask, therefore, still need to the part of further exploitation design new framework structure.
The content of the invention
It is an object of the invention to synthesize a series of PNN structural frameworks parts, and provide a kind of centered on chromium
Metal precursor, PNN structural frameworks compound be part, activator or co-catalyst ternary catalyst systems and
Its catalysis high-selective ethylene trimer synthesis 1- hexenes, four aggregate into 1- octenes.Urged with traditional PNP chromium system
Agent system is compared, and improves the common Selectivity and activety of 1- hexenes and 1- octenes, and reaction condition is gentle.
The technical scheme is that：
One kind centered on chromium metal precursor, PNN structural framework compounds as part, activator or co-catalysis
Agent ternary catalyst systems, it is characterised in that：Including three below part：
1) a kind of chromium compound；
2) PNN structural frameworks compound is part, and its general structure is as follows：
Wherein R1It is phenyl, the alkyl or cycloalkyl of synthesis, R2、R3、R4、R5It is hydrogen, phenyl, alkane
Base or cycloalkyl；
3) a kind of activator or co-catalyst.
According to the catalyst system that the present invention is provided, it is preferred that the chromium compound is selected from the nothing of trivalent chromium
The co-ordination complex of machine salt, co-ordination complex, organic salt, metal-organic complex or bivalent chromium.According to
The catalyst system that the present invention is provided, it is preferred that the chromium compound is selected from Cr (THF)3Cl3、
Cr(acac)3, 2 ethyl hexanoic acid chromium (III), sad chromium (III), chromium carbonyl, benzene tricarbonyl chromium, Cr (THF)2Cl2
In one kind.
According to the catalyst system that the present invention is provided, it is preferred that the R in the ligand structure formula1Group
Selected from one or more in phenyl, 1- naphthyls, the phenyl of substituted base, cyclohexyl, R2、R3、R4、
R5Group preferably is selected from one or more in hydrogen, methyl, ethyl, isopropyl, cyclohexyl, phenyl.
The present invention essentially consists in the synthesis of PNN structural framework parts, and the part formula is as follows：
Wherein, 1- hexenes and 1- Octenes selectivities part higher such as following formula are generated for ethylene oligomerization.
The part of new PNN skeleton structures of the present invention, wherein, R1It is phenyl, the benzene of substituted base
One kind in base, R2、R3、R4、R5During a kind of in for hydrogen, methyl, ethyl, isopropyl, benzene, such as
Part listed by following formula：
According to the catalyst system and catalyzing that the present invention is provided, it is preferred that the activator or co-catalyst are selected from front three
Base aluminium, triethyl aluminum, triisopropylaluminiuand, diethyl aluminum chloride, ethylaluminum dichloride, MAO or
One or more in modified methylaluminoxane.
According to the catalyst system and catalyzing that the present invention is provided, it is preferred that the solvent is selected from aromatic hydrocarbon, direct-connected or ring
One kind in shape aliphatic hydrocarbon.
According to the catalyst system and catalyzing that the present invention is provided, it is preferred that the solvent is aromatic hydrocarbon, cyclic aliphatic hydrocarbon.
According to the present invention provide catalyst system and catalyzing, it is further preferred that, the solvent be selected from toluene, ethylbenzene,
One kind in chlorobenzene, hexamethylene, hexahydrotoluene.
According to the catalyst system and catalyzing that the present invention is provided, it is preferred that the chromium concn is 0.01-100mmol/L.
According to the catalyst system and catalyzing that the present invention is provided, it is further preferred that, the chromium concn is 0.1-10mmol/
L。
According to the catalyst system and catalyzing that the present invention is provided, it is preferred that the part is 0.1-10 with the mol ratio of chromium
mol/mol。
According to the catalyst system and catalyzing that the present invention is provided, it is further preferred that, the part is with the mol ratio of chromium
0.3-3mol/mol。
According to the catalyst system and catalyzing that the present invention is provided, it is preferred that the co-catalyst is with the mol ratio of chromium
1-1000mol/mol。
According to the catalyst system and catalyzing that the present invention is provided, it is further preferred that, the part is with the mol ratio of chromium
10-500mol/mol。
The present invention also provide by the PNN structural frameworks compound for synthesizing be part, metal precursor centered on Cr,
The ternary system catalysis high-selective ethylene trimer synthesis 1- hexenes of co-catalyst, four aggregate into 1- octenes, its
It is characterised by, comprises the following steps：
1) in 200ml autoclaves, autoclave is dried, nitrogen displacement, then carry out ethylene gas displacement；
Then to injecting solvent in autoclave.
2) by above-mentioned part and chromium compound injection autoclave, established temperature stirring 1h is heated to, past
Above-mentioned co-catalyst is wherein injected, then to being passed through ethylene gas in reactor and adjust pressure in kettle, oligomerisation
Reaction starts.
3) after oligomerisation reaction 30min to 2h, ethylene gas are closed, and reaction system is quickly cooled to 0
Below degree, kettle is driven in deflation, is quenched with 10%HCl (aq) and reacted, layering.1- hexenes and 1- in organic layer
Octene n -nonane makees internal standard detection.
1- octenes are aggregated into according to the catalysis high-selective ethylene trimer synthesis 1- hexenes for providing of the invention, four,
Preferably, the ligand structure formula is as follows：
Wherein R1Group is selected from one or more in phenyl, 1- naphthyls, the phenyl of substituted base, cyclohexyl, R2、
R3、R4、R5Group preferably is selected from the one kind or several in hydrogen, methyl, ethyl, isopropyl, cyclohexyl, phenyl
Kind.
1- octenes are aggregated into according to the catalysis high-selective ethylene trimer synthesis 1- hexenes for providing of the invention, four,
Preferably, the chromium compound is selected from Cr (THF)3Cl3、Cr(acac)3, 2 ethyl hexanoic acid chromium (III),
Sad chromium (III), chromium carbonyl, benzene tricarbonyl chromium, Cr (THF)2Cl2In one kind.
1- octenes are aggregated into according to the catalysis high-selective ethylene trimer synthesis 1- hexenes for providing of the invention, four,
Preferably, the activator or co-catalyst are selected from trimethyl aluminium, triethyl aluminum, triisopropylaluminiuand, two
One or more in ethylmercury chloride aluminium, ethylaluminum dichloride, MAO or modified methylaluminoxane.
1- octenes are aggregated into according to the catalysis high-selective ethylene trimer synthesis 1- hexenes for providing of the invention, four,
Preferably, the solvent is selected from the one kind in toluene, ethylbenzene, chlorobenzene, hexamethylene, hexahydrotoluene.
1- octenes are aggregated into according to the catalysis high-selective ethylene trimer synthesis 1- hexenes for providing of the invention, four,
Preferably, the chromium concn is 0.01-100mmol/L.
1- octenes are aggregated into according to the catalysis high-selective ethylene trimer synthesis 1- hexenes for providing of the invention, four,
It may further be preferable that the chromium concn is 0.1-10mmol/L.
1- octenes are aggregated into according to the catalysis high-selective ethylene trimer synthesis 1- hexenes for providing of the invention, four,
Preferably, the part and the mol ratio of chromium are 0.1-10mol/mol.
1- octenes are aggregated into according to the catalysis high-selective ethylene trimer synthesis 1- hexenes for providing of the invention, four,
It may further be preferable that the part is 0.3-3mol/mol with the mol ratio of chromium.
1- octenes are aggregated into according to the catalysis high-selective ethylene trimer synthesis 1- hexenes for providing of the invention, four,
Preferably, the co-catalyst and the mol ratio of chromium are 1-1000mol/mol.
1- octenes are aggregated into according to the catalysis high-selective ethylene trimer synthesis 1- hexenes for providing of the invention, four,
It may further be preferable that the part is 10-500mol/mol with the mol ratio of chromium.
1- octenes are aggregated into according to the catalysis high-selective ethylene trimer synthesis 1- hexenes for providing of the invention, four,
Preferably, the pressure of the oligomerisation reaction is 0.1-100bar.
1- octenes are aggregated into according to the catalysis high-selective ethylene trimer synthesis 1- hexenes for providing of the invention, four,
It may further be preferable that the pressure of the oligomerisation reaction is 1-30bar.
1- octenes are aggregated into according to the catalysis high-selective ethylene trimer synthesis 1- hexenes for providing of the invention, four,
Preferably, the temperature of the oligomerisation reaction is 10-150 DEG C.
1- octenes are aggregated into according to the catalysis high-selective ethylene trimer synthesis 1- hexenes for providing of the invention, four,
It may further be preferable that the temperature of the oligomerisation reaction is 40-100 DEG C.
1- octenes are aggregated into according to the catalysis high-selective ethylene trimer synthesis 1- hexenes for providing of the invention, four,
Preferably, the oligomerisation reaction time is 10min-5h.
1- octenes are aggregated into according to the catalysis high-selective ethylene trimer synthesis 1- hexenes for providing of the invention, four,
It may further be preferable that oligomerisation reaction time 30min-2h.
According to the preparation method of part of the present invention：
Under minus 20 degrees, n-BuLi is added dropwise toward solution A, 1h is stirred after dripping ClPR is added dropwise again1 2,
3h is stirred after dripping.It is warmed to room temperature and is quenched reaction with 10%HCl (aq).Compound B is finally recrystallized to obtain,
Then toward dropwise addition pyridine compounds in B solution in MgSO4/Al2O3It is heated overnight under catalysis, is finally weighed
Crystallize to obtain compound C.
With ferrocene as initiation material, by experiments such as friedel-crafts acylation, reduction, esterification, amine generation, dehydrations
Step most sums up into target PNN framework counterparts.
The beneficial effects of the invention are as follows：
The present invention has synthesized a series of part of PNN classes skeleton structures, additionally provides centered on chromium before metal
Body, PNN classes backbone structure ligand, activator or co-catalyst ternary catalyst systems its catalysis high selectivity
Ethylene trimer synthesis 1- hexenes, four aggregate into 1- octenes.Compared with traditional PNP chromium-based catalysts systems,
The common Selectivity and activety of 1- hexenes and 1- octenes is improve, reaction condition is gentle.
Specific embodiment
The following examples will be further described to the present invention, but not thereby limiting the invention.
Nuclear magnetic resonance is by Bruker nmr determinations.
Embodiment 1
1 prepares part 5
Under minus 20 degrees, toward the diethyl ether solution of α-phenylethylamine be added dropwise n-BuLi (1.2equiv), it is complete after
Stirring 15min, then trim,ethylchlorosilane (1.1equiv) is added dropwise thereto, 1h is stirred after dripping off, thereto
N-BuLi (3equiv) is added dropwise, drop finishes, stirring 2h is warmed to room temperature after stirring 3h, be cooled to subzero 20
Degree, instills diphenyl phosphorus chloride (1.1equiv) thereto, 2h is stirred after adding and is warmed to room temperature stirring 4h,
Then reaction is quenched with 10%HCl (aq), layering, organic layer is spin-dried for, and recrystallizes white solid with n-hexane
Body (is abbreviated as DPPNH2), yield 38%.
By DPPNH2 and 2- pyridine carboxaldehydes (1equiv) in toluene solution, urged with MgSO4/Al2O3
It is heated to reflux under change.After having reacted, suction filtration is spin-dried for, and part 5 is recrystallized to obtain with n-hexane.Yield：88%.
The nuclear magnetic resoance spectrum of part 5：
1H NMR(400MHz,CDCl3):δ8.61(s,1H),8.18(s,1H),7.90-7.64(m,3H),
7.41-7.12 (m, 13H), 6.89-6.86 (m, 1H), 5.48-5.50 (m, 1H), 1.47 (d, J=6.4Hz, 3H)；31P
NMR(CDCl3):δ-16.5；13C NMR(100MHz,CDCl3):δ160.8,154.7,147.4,149.2,
149.0,136.8,136.7,136.2,134.5,134.3,134.1,133.9,133.7,133.5,132.3,132.2,
131.8,131.7,129.3,128.7,128.6,128.5,128.6,127.4,127.3,127.0,124.4,121.7,
121.5,66.3,66.1,24.8。
2 ethylene oligomerizations react
Ethylene oligomerization reaction is carried out in 200mL autoclaves.Before oligomerisation starts, nitrogen is carried out to reactor and is put
Change three times and ethene displacement is secondary.Then toward toluene solvant is injected in reactor, Cr (THF) is added3Cl3And
Part 5, stirs 1h, then injection MAO (MAO) thereto, then after being heated to design temperature
Ethene is passed through toward reactor and pressure in kettle is adjusted and reaches setting value, reaction starts.It is fast after reaction 30min
Speed is cooled to 0 degree.Deflate, drive kettle.10%HCl (aq) quenching reactions are added toward reaction solution, are layered,
Organic layer adds n -nonane to do internal standard.Wherein, MAO, part and Cr (THF)3Cl3Molar ratio 400:2:
1, reaction temperature is 60 degree, and pressure is 10bar, and each reacting dose is 3 μm of ol Cr, and solvent is 100mL.
End reaction the results are shown in Table 1.
Embodiment 2
1 prepares ligand 11
In Pd/C catalytic hydrogenations, last n-hexane recrystallizes to obtain ligand 11 to part 5.Yield 95%.
The nuclear magnetic resoance spectrum of ligand 11：
1H NMR(400MHz,CDCl3):δ8.49-8.50(d,1H),7.70-7.73(m,1H),7.47-7.52
(m,1H),7.34-7.38(m,1H),7.23-7.31(m,10H),7.03-7.14(m,3H),6.87-6.91(m,
1H),4.72-4.78(m,1H),3.56-3.65(dd,2H),2.24(s,NH),1.26-1.27(d,1H)。31P
NMR(CDCl3):δ-17.45,49.70；13C NMR(100MHz,CDCl3):δ11.67,23.99,46.30,
52.95,54.65,54.90,121.72,122.27,128.50,128.57,128.68,128.72,129.57,133.85,
134.03,134.04,134.22,136.22,149.19,149.95,150.17,159.87。
2 ethylene oligomerizations react
Ethylene oligomerization reaction is carried out in 200mL autoclaves.Before oligomerisation starts, nitrogen is carried out to reactor and is put
Change three times and ethene displacement is secondary.Then toward toluene solvant is injected in reactor, Cr (THF) is added3Cl3And
Ligand 11,1h is stirred after being heated to design temperature, then injects MAO thereto, is then led to toward in reactor
Enter ethene and adjust pressure in kettle and reach setting value, reaction starts.0 degree is cooled to after reaction 30min rapidly.
Deflate, drive kettle.10%HCl (aq) quenching reactions are added toward reaction solution, layering, organic layer adds positive nonyl
Alkane does internal standard.Wherein, MAO, part and Cr (THF)3Cl3Molar ratio 400:2:1, reaction temperature is
60 degree, pressure is 10bar, and each reacting dose is 3 μm of ol Cr, and solvent is 100mL.End reaction result
It is shown in Table 1.
Embodiment 3
1 prepares part 22
Under stirring, chloroacetic chloride (1.1equiv) is added toward the dichloromethane solution of ferrocene, be then cooled to
0 degree, it is dividedly in some parts AlCl3(1equiv), it is complete after, temperature rising reflux 2h, then be cooled to 0 degree is slowly added dropwise
Water quenching reaction.Solvent is sloughed in layering, organic layer decompression, and product n-hexane recrystallizes to obtain acetylferrocene
(F-1).Yield：77%.
NaBH is dividedly in some parts toward the ethanol water of F-14(1.5equiv), it is complete after, temperature rising reflux 2h,
Most of ethanol is sloughed in decompression, then toward water is added in system, has substantial amounts of solid to separate out, and is dried, with just oneself
Alkane recrystallizes to obtain Alpha-hydroxy ethyl dicyclopentadienyl iron (F-2).Yield：88%.
F-2 is dissolved in pyridine and dichloromethane mixed solution, 0 degree is cooled to, chloroacetic chloride (1.1 is added dropwise thereto
Equiv), 2h is stirred at room temperature after complete.It is quenched with water again and is reacted, solvent is sloughed in layering, organic layer decompression,
The alcoholic solution of dimethylamine is charged with, closed room temperature reaction overnight, after solvent is sloughed in decompression, uses diatomite
Drainage removes floccule, and filtrate sloughs solvent, and product n-hexane recrystallizes to obtain N, N- dimethyl-α-ferrocene
Ethamine (F-3).Yield：80%.
Under 0 degree, toward the diethyl ether solution of F-3 instill n-BuLi (1.1equiv), it is complete after 1h is stirred at room temperature,
Instill diphenyl phosphorus chloride (1.1equiv), complete rear backflow 3h thereto again.0 degree is cooled to, 10% is added
HCl (aq) quenching reactions, solvent is sloughed in layering, organic layer decompression, then recrystallizes to obtain 1- (N, N- with n-hexane
Dimethyl amine base) -2- (diphenylphosphine) ferrocene (PPFNMe2).Yield：53%.
By PPFNMe2Airtight heating spends night to 100 in autoclave with the alcoholic solution of ammonia, lowers the temperature, and puts
Gas drives kettle, and solvent is sloughed in decompression, then recrystallizes to obtain 1- ethylamino-s -2- (diphenylphosphine) ferrocene with n-hexane
(PPFNH2).Yield：70%.
By PPFNH2With 2- pyridine carboxaldehydes (1equiv) in toluene solution, it is catalyzed with MgSO4/Al2O3
Under be heated to reflux.After having reacted, suction filtration is spin-dried for, and part 22 is recrystallized to obtain with n-hexane.Yield：68%.
The nuclear magnetic resoance spectrum of part 22：
1H NMR(400MHz,CDCl3):δ8.41(s,1H),8.12(s,1H),7.51-7.28(m,7H),
7.12(t,1H),6.99-7.01(m,2H),6.84-6.86(m,2H),6.74-6.76(m,1H),4.93-4.95(m,
1H), 4.66 (s, 1H), 4.33 (s, 1H), 4.08 (s, 5H), 3.76 (s, 1H), 1.67 (d, J=8.0Hz, 3H)；31P
NMR(CDCl3):δ-24.5；13C NMR(100MHz,CDCl3):δ160.8,154.2,148.6,138.8,
138.7,137.4,137.3,135.6,135.2,135.0,132.7,132.5,128.9,128.0,127.6,127.5,
127.1,123.9,121.3,95.8,75.9,71.7,69.3,69.1,63.9,63.8,21.4。
2 ethylene oligomerizations react
Ethylene oligomerization reaction is carried out in 200mL autoclaves.Before oligomerisation starts, nitrogen is carried out to reactor and is put
Change three times and ethene displacement is secondary.Then toward toluene solvant is injected in reactor, Cr (THF) is added3Cl3And
Part 22,1h is stirred after being heated to design temperature, then injects MAO thereto, is then led to toward in reactor
Enter ethene and adjust pressure in kettle and reach setting value, reaction starts.0 degree is cooled to after reaction 30min rapidly.
Deflate, drive kettle.10%HCl (aq) quenching reactions are added toward reaction solution, layering, organic layer adds positive nonyl
Alkane does internal standard.Wherein, MAO, part and Cr (THF)3Cl3Molar ratio 400:2:1, reaction temperature is
60 degree, pressure is 10bar, and each reacting dose is 3 μm of ol Cr, and solvent is 100mL.End reaction result
It is shown in Table 1.
Embodiment 4
1 prepares part 29
In Pd/C catalytic hydrogenations, last n-hexane recrystallizes to obtain part 29 to part 27.Yield 92%.
The nuclear magnetic resoance spectrum of part 25：
1H NMR(400MHz,CDCl3):δ8.41(s,1H),7.47-7.52(m,3H),7.36(m,3H),
7.21-7.27(m,5H),6.98-7.12(m,7H),5.02(s,1H),4.50(s,1H),4.28(s,1H),3.94(s,
6H),3.78(s,1H),1.69(s,NH),1.45(s,3H)；31P NMR(CDCl3):δ-24.5；13C NMR
(100MHz,CDCl3):δ162.6,148.7,136.4,135.4,135.2,132.6,132.4,129.0,128.3,
128.2,128.1,128.0,127.8,127.2,126.8,121.7,74.7,71.3,69.6,69.2,66.4,48.9,
19.9。
2 ethylene oligomerizations react
Ethylene oligomerization reaction is carried out in 200mL autoclaves.Before oligomerisation starts, nitrogen is carried out to reactor and is put
Change three times and ethene displacement is secondary.Then toward toluene solvant is injected in reactor, Cr (THF) is added3Cl3And
Part 29,1h is stirred after being heated to design temperature, then injects MAO thereto, is then led to toward in reactor
Enter ethene and adjust pressure in kettle and reach setting value, reaction starts.0 degree is cooled to after reaction 30min rapidly.
Deflate, drive kettle.10%HCl (aq) quenching reactions are added toward reaction solution, layering, organic layer adds positive nonyl
Alkane does internal standard.Wherein, MAO, part and Cr (THF)3Cl3Molar ratio 400:2:1, reaction temperature is
60 degree, pressure is 10bar, and each reacting dose is 3 μm of ol Cr, and solvent is 100mL.End reaction result
It is shown in Table 1.
Embodiment 5
1 prepares part 30
By PPFNH2With 6- methyl 2- pyridine carboxaldehydes (1equiv) in toluene solution, with MgSO4/Al2O3
It is heated to reflux under catalysis.After having reacted, suction filtration is spin-dried for, and part 30 is recrystallized to obtain with n-hexane.Yield：72%.
The nuclear magnetic resoance spectrum of part 30：
1H NMR(400MHz,CDCl3):δ8.10(s,1H),7.49-7.50(m,2H),7.28-7.35(m,
4H),7.11-7.13(m,1H),6.96-7.01(m,3H),6.85-6.87(m,2H),6.76-6.78(m,1H),
4.95-4.97(m,1H),4.64(s,1H),4.32(s,1H),4.07(s,5H),3.76(s,1H),2.47(s,3H),
1.65 (d, J=8.0Hz, 3H)；31P NMR(CDCl3):δ-24.5；13C NMR(100MHz,CDCl3):δ
161.2,157.1,153.8,139.0,138.9,137.6,137.5,135.9,135.3,135.1,132.8,132.6,
128.9,128.0,127.6,127.5,127.1,123.6,118.2,96.3,76.0,71.8,71.7,69.7,69.3,
69.1,63.7,63.6,24.2,21.4。
2 ethylene oligomerizations react
Ethylene oligomerization reaction is carried out in 200mL autoclaves.Before oligomerisation starts, nitrogen is carried out to reactor and is put
Change three times and ethene displacement is secondary.Then toward toluene solvant is injected in reactor, Cr (THF) is added3Cl3And
Part 30,1h is stirred after being heated to design temperature, then injects MAO thereto, is then led to toward in reactor
Enter ethene and adjust pressure in kettle and reach setting value, reaction starts.0 degree is cooled to after reaction 30min rapidly.
Deflate, drive kettle.10%HCl (aq) quenching reactions are added toward reaction solution, layering, organic layer adds positive nonyl
Alkane does internal standard.Wherein, MAO, part and Cr (THF)3Cl3Molar ratio 400:2:1, reaction temperature is
60 degree, pressure is 10bar, and each reacting dose is 3 μm of ol Cr, and solvent is 100mL.End reaction result
It is shown in Table 1.
Embodiment 6
1 prepares part 33
By DPPNH2 and 6- methoxyl group 2- pyridine carboxaldehydes (1equiv) in toluene solution, with MgSO4
It is heated to reflux under/Al2O3 catalysis.After having reacted, suction filtration is spin-dried for, and part 33 is recrystallized to obtain with n-hexane.Receive
Rate：69%.
The nuclear magnetic resoance spectrum of part 33：
1H NMR(400MHz,CDCl3):δ8.02(s,1H),7.49-7.51(m,2H),7.26-7.48(m,
4H), 6.96-7.00 (m, 3H), 6.86-6.88 (m, 2H), 6.80-6.84 (m, 1H), 6.56 (d, J=8.0Hz,
1H),4.95-4.97(m,1H),4.65(s,1H),4.33(s,1H),4.07(s,5H),3.86(s,3H),1.66(d,
J=8.0Hz, 3H)；31P NMR(CDCl3):δ-24.2；13C NMR(100MHz,CDCl3):δ163.1,
161.1,151.8,138.7,138.6,138.0,137.4,135.3,135.1,132.7,132.5,129.0,128.0,
127.6,127.5,127.2,113.7,111.2,96.3,96.0,75.7,71.8,69.7,69.3,64.1,64.0,52.2,
21.4。
2 ethylene oligomerizations react
Ethylene oligomerization reaction is carried out in 200mL autoclaves.Before oligomerisation starts, nitrogen is carried out to reactor and is put
Change three times and ethene displacement is secondary.Then toward toluene solvant is injected in reactor, Cr (THF) is added3Cl3And
Part 33,1h is stirred after being heated to design temperature, then injects MAO thereto, is then led to toward in reactor
Enter ethene and adjust pressure in kettle and reach setting value, reaction starts.0 degree is cooled to after reaction 30min rapidly.
Deflate, drive kettle.10%HCl (aq) quenching reactions are added toward reaction solution, layering, organic layer adds positive nonyl
Alkane does internal standard.Wherein, MAO, part and Cr (THF)3Cl3Molar ratio 400:2:1, reaction temperature is
60 degree, pressure is 10bar, and each reacting dose is 3 μm of ol Cr, and solvent is 100mL.End reaction result
It is shown in Table 1.
Influence of the difference PNN parts of table 1 to ethylene oligomerization reaction selectivity and activity
Compared with traditional PNP chromium-based catalysts systems, the present invention improves the common choosing of 1- hexenes and 1- octenes
Selecting property and activity, reaction condition are gentle.
Claims (10)
1. ternary catalyst systems of the part of structural framework containing PNN, it is characterised in that：The metal centered on chromium
Precursor, PNN structural frameworks compound are part, activator or co-catalyst, including three below composition portion
Point：
A kind of (i) chromium compound；
(ii) PNN classes part, one or two or more kinds during its general structure is following：
Wherein R1For phenyl, 1- naphthyls, the substitution phenyl of base, C1-C10 alkyl or C3-C10
Cycloalkyl, replace the substitution base on the phenyl of base to be the alkyl of C1-C10, the alkoxy of C1-C10,
Halogeno-group, CF3In one or two or more kinds, the number of base is replaced on phenyl for 1-5；R2、
R3、R4、R5It is the cycloalkyl of hydrogen, phenyl, the alkyl of C1-C10 or C3-C-10；
(iii) a kind of activator or co-catalyst, the activator or co-catalyst be selected from trimethyl aluminium,
Triethyl aluminum, triisopropylaluminiuand, diethyl aluminum chloride, ethylaluminum dichloride, MAO or modified first
One or two or more kinds in base aikyiaiurnirsoxan beta.
2. catalyst system according to claim 1, it is characterised in that：The chromium compound is selected from
Cr(THF)3Cl3、Cr(acac)3, 2 ethyl hexanoic acid chromium (III), sad chromium (III), chromium carbonyl, benzene three
Chromium carbonyl, Cr (THF)2Cl2In one kind.
3. catalyst system according to claim 1, it is characterised in that：In the ligand structure formula
R1Group be selected from phenyl, 1- naphthyls, band replace base phenyl, cyclohexyl in one or two or more kinds,
R2、R3、R4、R5Group preferably is selected from the one kind in hydrogen, methyl, ethyl, isopropyl, cyclohexyl, phenyl
Or more than two kinds.
4. catalyst system according to claim 1, it is characterised in that：In the catalyst system also
Including a kind of solvent；The solvent is selected from the one kind in aromatic hydrocarbon, direct-connected or cyclic aliphatic hydrocarbon.
5. catalyst system according to claim 4, it is characterised in that：The solvent be selected from toluene,
One kind in ethylbenzene, chlorobenzene, hexamethylene, hexahydrotoluene.
6. the catalyst system according to claim 4 or 5, it is characterised in that：The chromium concn is
0.01-100mmol/L。
7. catalyst system according to claim 1, it is characterised in that：The part and chromium mole
Than being 0.1-10mol/mol.
8. catalyst system according to claim 1, it is characterised in that：The co-catalyst and chromium
Mol ratio is 1-1000mol/mol.
9. the catalyst system catalysis high-selective ethylene trimer described in a kind of any one of claim 1-8 is closed
The application of 1- octenes is aggregated into 1- hexenes, four, it is characterised in that：Comprise the following steps：
1) in autoclave, autoclave is dried, nitrogen displacement, then carry out ethylene gas displacement；Then to
Solvent is injected in autoclave；
2) by above-mentioned part and chromium compound injection autoclave, established temperature stirring more than 1h is heated to,
Above-mentioned co-catalyst is injected thereto, then to being passed through ethylene gas in reactor and adjusting pressure in kettle, together
Poly- reaction starts；
3) after oligomerisation reaction 30min to 2h, ethylene gas are closed, and reaction system is quickly cooled to 0
Below degree, kettle is driven in deflation, is quenched with mass concentration (10%) HCl (aq) and reacted, layering；In organic layer i.e.
It is 1- hexenes and 1- octenes.
10. catalysis high-selective ethylene trimer synthesis 1- hexenes according to claim 9, four aggregate into
The application of 1- octenes, it is characterised in that：The pressure of the oligomerisation reaction is 0.1-100bar；The oligomerisation reaction
Temperature be 10-150 DEG C；The oligomerisation reaction time is 10min-5h.
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