CN111718371A - 一种膦配体及其制备方法和用途 - Google Patents
一种膦配体及其制备方法和用途 Download PDFInfo
- Publication number
- CN111718371A CN111718371A CN202010647161.5A CN202010647161A CN111718371A CN 111718371 A CN111718371 A CN 111718371A CN 202010647161 A CN202010647161 A CN 202010647161A CN 111718371 A CN111718371 A CN 111718371A
- Authority
- CN
- China
- Prior art keywords
- reaction
- olefin
- phosphine ligand
- catalyst
- rhodium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 title claims abstract description 96
- 239000003446 ligand Substances 0.000 title claims abstract description 53
- 229910000073 phosphorus hydride Inorganic materials 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 45
- 150000001336 alkenes Chemical class 0.000 claims abstract description 43
- 239000003054 catalyst Substances 0.000 claims abstract description 36
- 238000007037 hydroformylation reaction Methods 0.000 claims abstract description 32
- 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 abstract description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 65
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- QWXYZCJEXYQNEI-OSZHWHEXSA-N intermediate I Chemical compound COC(=O)[C@@]1(C=O)[C@H]2CC=[N+](C\C2=C\C)CCc2c1[nH]c1ccccc21 QWXYZCJEXYQNEI-OSZHWHEXSA-N 0.000 claims description 24
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical group [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 21
- XGRJZXREYAXTGV-UHFFFAOYSA-N chlorodiphenylphosphine Chemical compound C=1C=CC=CC=1P(Cl)C1=CC=CC=C1 XGRJZXREYAXTGV-UHFFFAOYSA-N 0.000 claims description 13
- 239000002994 raw material Substances 0.000 claims description 11
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 claims description 10
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 10
- 239000010941 cobalt Substances 0.000 claims description 9
- 229910017052 cobalt Inorganic materials 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 229910052703 rhodium Inorganic materials 0.000 claims description 9
- 239000010948 rhodium Substances 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 8
- WDOKISJWRVNYNS-UHFFFAOYSA-N dicyclohexylphosphanium;chloride Chemical compound Cl.C1CCCCC1PC1CCCCC1 WDOKISJWRVNYNS-UHFFFAOYSA-N 0.000 claims description 8
- 150000002009 diols Chemical class 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 8
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 7
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- FXNDIJDIPNCZQJ-UHFFFAOYSA-N 2,4,4-trimethylpent-1-ene Chemical group CC(=C)CC(C)(C)C FXNDIJDIPNCZQJ-UHFFFAOYSA-N 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- INSRQEMEVAMETL-UHFFFAOYSA-N decane-1,1-diol Chemical compound CCCCCCCCCC(O)O INSRQEMEVAMETL-UHFFFAOYSA-N 0.000 claims description 5
- GGQQNYXPYWCUHG-RMTFUQJTSA-N (3e,6e)-deca-3,6-diene Chemical compound CCC\C=C\C\C=C\CC GGQQNYXPYWCUHG-RMTFUQJTSA-N 0.000 claims description 4
- GQEZCXVZFLOKMC-UHFFFAOYSA-N 1-hexadecene Chemical compound CCCCCCCCCCCCCCC=C GQEZCXVZFLOKMC-UHFFFAOYSA-N 0.000 claims description 4
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims description 4
- HFDVRLIODXPAHB-UHFFFAOYSA-N 1-tetradecene Chemical compound CCCCCCCCCCCCC=C HFDVRLIODXPAHB-UHFFFAOYSA-N 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 claims description 4
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 claims description 4
- -1 ethylene, propylene, butene Chemical class 0.000 claims description 4
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 claims description 4
- VAMFXQBUQXONLZ-UHFFFAOYSA-N icos-1-ene Chemical compound CCCCCCCCCCCCCCCCCCC=C VAMFXQBUQXONLZ-UHFFFAOYSA-N 0.000 claims description 4
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N methylene hexane Natural products CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 claims description 4
- 239000004711 α-olefin Substances 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- FJDJVBXSSLDNJB-LNTINUHCSA-N cobalt;(z)-4-hydroxypent-3-en-2-one Chemical compound [Co].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FJDJVBXSSLDNJB-LNTINUHCSA-N 0.000 claims description 3
- OEIJHBUUFURJLI-UHFFFAOYSA-N octane-1,8-diol Chemical compound OCCCCCCCCO OEIJHBUUFURJLI-UHFFFAOYSA-N 0.000 claims description 3
- HDKCVDHYIIKWFM-UHFFFAOYSA-K octanoate;rhodium(3+) Chemical compound [Rh+3].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O.CCCCCCCC([O-])=O HDKCVDHYIIKWFM-UHFFFAOYSA-K 0.000 claims description 3
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical compound CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 claims description 3
- SVOOVMQUISJERI-UHFFFAOYSA-K rhodium(3+);triacetate Chemical compound [Rh+3].CC([O-])=O.CC([O-])=O.CC([O-])=O SVOOVMQUISJERI-UHFFFAOYSA-K 0.000 claims description 3
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1 -dodecene Natural products CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 claims description 2
- BZJTUOGZUKFLQT-UHFFFAOYSA-N 1,3,5,7-tetramethylcyclooctane Chemical group CC1CC(C)CC(C)CC(C)C1 BZJTUOGZUKFLQT-UHFFFAOYSA-N 0.000 claims description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 229940011182 cobalt acetate Drugs 0.000 claims description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- 229940044175 cobalt sulfate Drugs 0.000 claims description 2
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 2
- URYYVOIYTNXXBN-UPHRSURJSA-N cyclooctene Chemical compound C1CCC\C=C/CC1 URYYVOIYTNXXBN-UPHRSURJSA-N 0.000 claims description 2
- 239000004913 cyclooctene Substances 0.000 claims description 2
- 229940069096 dodecene Drugs 0.000 claims description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 2
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadecene Natural products CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 claims description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 claims description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 claims description 2
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 claims description 2
- 229940095068 tetradecene Drugs 0.000 claims description 2
- FEQPHYCEZKWPNE-UHFFFAOYSA-K trichlororhodium;triphenylphosphane Chemical compound Cl[Rh](Cl)Cl.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 FEQPHYCEZKWPNE-UHFFFAOYSA-K 0.000 claims description 2
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 claims 1
- MHIBEGOZTWERHF-UHFFFAOYSA-N heptane-1,1-diol Chemical compound CCCCCCC(O)O MHIBEGOZTWERHF-UHFFFAOYSA-N 0.000 claims 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims 1
- FVXBCDWMKCEPCL-UHFFFAOYSA-N nonane-1,1-diol Chemical compound CCCCCCCCC(O)O FVXBCDWMKCEPCL-UHFFFAOYSA-N 0.000 claims 1
- HSJKGGMUJITCBW-UHFFFAOYSA-N 3-hydroxybutanal Chemical compound CC(O)CC=O HSJKGGMUJITCBW-UHFFFAOYSA-N 0.000 description 14
- 239000012071 phase Substances 0.000 description 14
- 238000003756 stirring Methods 0.000 description 12
- 239000007789 gas Substances 0.000 description 11
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 238000005303 weighing Methods 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 9
- 238000002474 experimental method Methods 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000000693 micelle Substances 0.000 description 7
- 239000007787 solid Substances 0.000 description 6
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 5
- 229960000583 acetic acid Drugs 0.000 description 5
- HEDRZPFGACZZDS-MICDWDOJSA-N deuterated chloroform Substances [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 5
- 238000000921 elemental analysis Methods 0.000 description 5
- 239000012362 glacial acetic acid Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 238000004949 mass spectrometry Methods 0.000 description 3
- 238000001819 mass spectrum Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 description 2
- YGHRJJRRZDOVPD-UHFFFAOYSA-N 3-methylbutanal Chemical compound CC(C)CC=O YGHRJJRRZDOVPD-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 238000006713 insertion reaction Methods 0.000 description 2
- MYAJTCUQMQREFZ-UHFFFAOYSA-K tppts Chemical compound [Na+].[Na+].[Na+].[O-]S(=O)(=O)C1=CC=CC(P(C=2C=C(C=CC=2)S([O-])(=O)=O)C=2C=C(C=CC=2)S([O-])(=O)=O)=C1 MYAJTCUQMQREFZ-UHFFFAOYSA-K 0.000 description 2
- BGEHHAVMRVXCGR-UHFFFAOYSA-N tridecanal Chemical compound CCCCCCCCCCCCC=O BGEHHAVMRVXCGR-UHFFFAOYSA-N 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- YSRSBDQINUMTIF-SNVBAGLBSA-N (2r)-decane-1,2-diol Chemical compound CCCCCCCC[C@@H](O)CO YSRSBDQINUMTIF-SNVBAGLBSA-N 0.000 description 1
- MBVAQOHBPXKYMF-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;rhodium Chemical compound [Rh].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O MBVAQOHBPXKYMF-LNTINUHCSA-N 0.000 description 1
- 229940043375 1,5-pentanediol Drugs 0.000 description 1
- ALVZNPYWJMLXKV-UHFFFAOYSA-N 1,9-Nonanediol Chemical compound OCCCCCCCCCO ALVZNPYWJMLXKV-UHFFFAOYSA-N 0.000 description 1
- OUFCBJZGDJFSIK-UHFFFAOYSA-N 11-methyldodecanal Chemical compound CC(C)CCCCCCCCCC=O OUFCBJZGDJFSIK-UHFFFAOYSA-N 0.000 description 1
- RWLALWYNXFYRGW-UHFFFAOYSA-N 2-Ethyl-1,3-hexanediol Chemical compound CCCC(O)C(CC)CO RWLALWYNXFYRGW-UHFFFAOYSA-N 0.000 description 1
- CXNIUSPIQKWYAI-UHFFFAOYSA-N 4,5-bis(diphenylphosphino)-9,9-dimethyl-xanthene Substances C=12OC3=C(P(C=4C=CC=CC=4)C=4C=CC=CC=4)C=CC=C3C(C)(C)C2=CC=CC=1P(C=1C=CC=CC=1)C1=CC=CC=C1 CXNIUSPIQKWYAI-UHFFFAOYSA-N 0.000 description 1
- JRPPVSMCCSLJPL-UHFFFAOYSA-N 7-methyloctanal Chemical compound CC(C)CCCCCC=O JRPPVSMCCSLJPL-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- SZKMTZNASRXXCE-UHFFFAOYSA-N [2-[2-(diphenylphosphanylmethyl)phenyl]phenyl]methyl-diphenylphosphane Chemical compound C=1C=CC=C(C=2C(=CC=CC=2)CP(C=2C=CC=CC=2)C=2C=CC=CC=2)C=1CP(C=1C=CC=CC=1)C1=CC=CC=C1 SZKMTZNASRXXCE-UHFFFAOYSA-N 0.000 description 1
- FGEASBKBMNLZQR-UHFFFAOYSA-N [C].[O].[O] Chemical group [C].[O].[O] FGEASBKBMNLZQR-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229940097037 decylene glycol Drugs 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 229960005082 etohexadiol Drugs 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- SXCBDZAEHILGLM-UHFFFAOYSA-N heptane-1,7-diol Chemical compound OCCCCCCCO SXCBDZAEHILGLM-UHFFFAOYSA-N 0.000 description 1
- 229940051250 hexylene glycol Drugs 0.000 description 1
- 238000007172 homogeneous catalysis Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 238000010606 normalization Methods 0.000 description 1
- 238000006464 oxidative addition reaction Methods 0.000 description 1
- WCVRQHFDJLLWFE-UHFFFAOYSA-N pentane-1,2-diol Chemical compound CCCC(O)CO WCVRQHFDJLLWFE-UHFFFAOYSA-N 0.000 description 1
- WJIBZZVTNMAURL-UHFFFAOYSA-N phosphane;rhodium Chemical class P.[Rh] WJIBZZVTNMAURL-UHFFFAOYSA-N 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 1
- 239000006200 vaporizer Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/46—Phosphinous acids [R2POH], [R2P(= O)H]: Thiophosphinous acids including[R2PSH]; [R2P(=S)H]; Aminophosphines [R2PNH2]; Derivatives thereof
-
- 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
- B01J31/1845—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 phosphorus
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/49—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide
- C07C45/50—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide by oxo-reactions
- C07C45/505—Asymmetric hydroformylation
-
- 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
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/32—Addition reactions to C=C or C-C triple bonds
- B01J2231/321—Hydroformylation, metalformylation, carbonylation or hydroaminomethylation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/822—Rhodium
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Materials Engineering (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明涉及一种新型膦配体及其制备方法,和其在氢甲酰化反应中的应用,其结构为:
Description
技术领域
本发明涉及一种膦配体及其制备方法,还涉及其在氢甲酰化反应中的应用。
技术背景
丙烯氢甲酰化制备丁醛的工业生产过程(RCH-RP工艺)采用水溶性三苯基膦的三磺酸钠盐(TPPTS)配位的铑配合物为催化剂,在水/有机两相体系中催化烯烃氢甲酰化反应,有效解决了均相催化体系中产物与催化剂难以分离的问题,引起了人们的高度关注。
但是水溶性铑膦配合物催化烯烃氢甲酰化反应需要解决反应速率慢的问题,因为与均相催化体系相比,由于烯烃在水溶液中的溶解度较小,水/有机两相体系中的反应速率较低,特别是长链烯烃氢甲酰化反应的速率更低。
以上问题促使人们探索合成了不同结构的新型水溶性膦配体,如BISBIS,BINAS,NORBOS,Sulfonated-Xantphos等,但是这些配体仍不能高效的催化氢甲酰化反应。
基于以上现状,需要开发一种水溶性膦配体,除了应具有合适的空间结构和电子效应,以及能够赋予配合物良好的催化性能外,还需要具有良好的水溶性,能高效催化烯烃在水相中发生氢甲酰化反应。
发明内容
本发明的目的在于提供一种膦配体及其制备方法和用途,通过开发一种全新的配体,提高两相氢甲酰化反应过程中烯烃的溶解度,使得不论高碳数还是低碳数的烯烃原料均可高效地反应,转化为目标的醛产物。
为了实现上述发明目的,本发明采用的技术方案如下:
一种膦配体,结构如下:
其中,R代表苯基或环己基,n为1-10的整数,m为1-20的整数。
膦配体的制备方法,包含以下步骤:二元醇与正丁基锂反应,加入二苯基氯化膦或二环己基氯化膦,生成中间体I,中间体I在碱催化剂下与环氧乙烷反应,生成膦配体。反应过程如下式所示;
本发明中,所用的二元醇为含有1-10个碳的二元醇,优选乙二醇,丙二醇,丁二醇,戊二醇,己二醇,庚二醇,辛二醇,壬二醇,癸二醇中的一种。
本发明中,正丁基锂与二元醇的投料摩尔比为1:1-1.1:1。反应温度-78-30℃,优选-30-0℃。反应时间0.5-3h,优选1-2h。反应结束后继续加入二苯基氯化膦或二环己基氯化膦,二苯基氯化膦或二环己基氯化膦与二元醇的投料摩尔比1:1-1.2:1,优选1.05:1-1.1:1。反应温度0-100℃,优选20-80℃,反应时间0.5-3h,优选1-2h。反应结束后低温冷却析出固体,过滤得到中间体I。中间体I与EO反应,催化剂为氢氧化钾和/或氢氧化钠,催化剂用量为中间体I质量的0.5wt%-1wt%,中间体I与EO投料摩尔比1:5-1:20,优选1:8-1:15。反应温度0-100℃,优选20-80℃,反应时间0.5-3h,优选1-2h。反应结束后进行中和,分离上层油相为膦配体产品。
本发明的膦配体用于烯烃氢甲酰化反应,具体地,以烯烃为原料,以含钴化合物或含铑化合物为催化剂,以水为溶剂,加入上述膦配体,催化烯烃氢甲酰化反应,反应结束后水油两相分层,分离上层油相为氢甲酰化产品,下层为催化剂水溶液,补加烯烃原料后,催化剂水溶液可继续循环套用,活性稳定。膦配体加入量为烯烃质量的0.2-20wt%,优选1-10wt%。
作为一种优选的方案,氢甲酰化反应中加入B(C6F5)3作为助催化剂。助催化剂B(C6F5)3加入量为烯烃质量的0.1-10wt%,优选1-5wt%。
助催化剂B(C6F5)3是一种强酸性大位阻路易斯酸,能够与金属活性中心钴或铑形成弱配位作用,强烈吸附金属中心的电子到硼原子上,使得金属中心的钴或铑显示一定的正电荷,金属中心缺电子,烯烃的配位能力增强,氢气的氧化加成和羰基的插入反应大大加快,氢甲酰化反应速率明显提高,催化活性显著增强。
本发明中,所用的烯烃选自碳数2-20的直链α-烯烃、直链内烯烃、支链α-烯烃、支链内烯烃中的一种或多种,包括但不限于乙烯,丙烯,丁烯,戊烯,己烯,庚烯,环己烯,环戊烯,异丁烯,1-辛烯、环辛烯、1-壬烯、1-癸烯、三聚丙烯、四聚丙烯、二聚正丁烯、三聚正丁烯、二异丁烯、三异丁烯,十二碳烯,十四碳烯,十六碳烯,十八碳烯,二十碳烯。
本发明中,所用的催化剂含铑化合物选自醋酸铑,辛酸铑,乙酰丙酮铑,乙酰丙酮羰基铑,三苯基膦铑,三苯基膦羰基铑,氯化铑,三苯基膦氯化铑中的一种或多种。含钴化合物选自醋酸钴,氯化钴,羰基钴,硫酸钴,乙酰丙酮钴中的一种或多种。催化剂用量为烯烃质量的0.1-10wt%,优选1-5wt%,反应温度100-200℃,优选120-170℃,反应时间0.5-10h,优选2-8h,反应压力8-20MPaG,优选10-18MpaG。
本发明氢甲酰化反应中,溶剂水的加入量为烯烃质量的10-500wt%,优选30-100wt%。合成气的投料摩尔数大于烯烃的投料摩尔数即可。
新型的膦配体结构上本质是一种非离子表面活性剂,膦配体在水溶液可以形成胶束结构,膦配体的疏水链向内形成一个疏水的胶束内核,使烯烃分子增溶在内核中。膦配体的极性乙氧基头朝向水相,形成胶束界面。加入到水相中的金属或者金属化合物与一个或者多个膦配体发生配位作用,金属活性中心在合成气环境下还原成为具有活性中心的羰基金属化合物,而烯烃能够在膦配体作用下增溶于胶束内核,大大提高了在水中的溶解度,在此反应微环境中的烯烃扩散势垒显著降低,它很容易扩散迁移到金属中心,发生配位插入反应形成最终的醛/醇产物。胶束好似一个微反应器,烯烃和催化剂都浓缩到此微反应器中,为它们之间的配位创造了有利条件,极大地加速了反应。
膦配体中配位膦原子与亲水性的乙氧基之间使用-O-(CH2)n-O-相连,碳链长度1-10,氧碳氧链兼具柔性和疏水性,可在溶液中规整排列,具有较高的溶解度和临界胶束浓度,大幅提高了催化剂在水中的溶解度,若膦原子与乙氧基之间采用刚性较强的苯环、萘环、环己基等相连,则分子的柔性和卷曲能力大大降低,分子溶解度和临界胶束浓度降低,催化剂溶解能力下降,并且环状结构的空间阻力增大,较大的空间位阻导致催化剂的配位困难,反应过程中烯烃与金属活性中心的配位阻力也明显增大,因此催化剂综合反应活性会下降很多,综合来看分子的微小结构的改变对催化剂的活性影响非常大,采用此种结构的新型膦配体具有显著的高催化活性。
本发明与现有技术相比,有以下优点:
(1)采用新型的膦配体,提高了烯烃在水中的溶解度,使得氢甲酰化反应效率大幅提升,生产成本显著降低。
(2)氢甲酰过程中加入助催化剂B(C6F5)3,使得氢甲酰化反应效率提升。
具体实施方式:
下面结合实施例对本发明作进一步的详细说明,本发明的范围包括但不局限于此类实施例。
实例用分析仪器及方法如下:
气相色谱仪:Agilent-7820;
气相色谱柱:0.25mm×30m的DB-5毛细管柱,检测器FID,气化室温度280℃,柱箱温度280℃,FID检测器温度300℃,氩气载流量2.1mL/min,氢气流量30mL/min,空气流量400mL/min,进样量1.0μL。使用面积归一化法计算烯烃的转化率及产物的选择性。升温程序:预热至柱温40℃,保持5min,15℃/min的速率从40℃升至280℃,保持2min。
质谱分析仪:Agilent7890B-5977A GC-MS
元素分析仪:Euro Vector EA3000
核磁分析仪:Bruker AVANCE III 400M
实施例1
(1)配体合成:三口烧瓶中加入100g己二醇,氮气保护下滴加正丁基锂,正丁基锂与己二醇的投料摩尔比1:1,反应温度-78℃,反应时间0.5h,反应结束后继续加入二苯基氯化膦,二苯基氯化膦与己二醇的投料摩尔比1:1,反应温度0℃,反应时间0.5h,之后放置于0℃环境中析出固体,分离得到中间体I,称重计算收率92%。
三口烧瓶中加入100g中间体I,加入0.5g氢氧化钾,110℃,1Kpa下脱除水和其它轻组分,加入环氧乙烷,环氧乙烷与中间体I投料摩尔比5:1,反应温度0℃,反应0.5h,然后加入6g冰醋酸水溶液(10wt%),搅拌20分钟,分离上层油相得到膦配体,称重计算收率87%,配体分析表征结果如下:m=4
1HNMR(CDCl3溶剂):1.43-1.53(8H,m),3.44-3.80(24H,m),7.2-7.8(10H,m)
质谱:522.3(100.0%),523.3(31.0%),524.3(6.1%)
元素分析:C,64.35;H,8.29;O,21.43;P,5.93
(2)氢甲酰化:反应釜中加入60g三异丁烯和6g水,加入0.06g辛酸铑为催化剂,加入0.06g B(C6F5)3为助催化剂,加入0.12g上述膦配体,通入合成气30g,反应釜压力8MPaG,搅拌转速1500r/min,100℃反应0.5h,反应结束后静置分层,分离上层烯烃原料和醛醇产物,三异丁烯转化率85%,异构十三醛选择性91%。
(3)催化剂套用
分离下层水溶液,加入60g三异丁烯,按照步骤(2)中氢甲酰化条件重复实验,连续重复四次,转化率和选择性如下:
套用实验次数 | 转化率(%) | 选择性(%) |
1 | 85 | 91 |
2 | 82 | 90 |
3 | 86 | 88 |
4 | 84 | 89 |
实施例2
(1)三口烧瓶中加入100g辛二醇,氮气保护下滴加正丁基锂,正丁基锂与辛二醇的投料摩尔比1.1:1,反应温度30℃,反应时间3h,反应结束后继续加入二环己基氯化膦,二环己基氯化膦与二醇的投料摩尔比1.2:1,反应温度100℃,反应时间3h,放置于0℃环境中析出固体,分离得到中间体I,称重计算收率88%。
三口烧瓶中加入100g中间体I,加入1g氢氧化钾,110℃,1Kpa下脱除水和其它轻组分,加入环氧乙烷,环氧乙烷与中间体I投料摩尔比8:1,反应温度100℃,反应3h,然后加入12g冰醋酸水溶液(10wt%),搅拌20分钟,分离上层油相得到膦配体,称重计算收率85%,配体分析表征结果如下:m=7
1HNMR(CDCl3溶剂):1.43-1.53(34H,m),3.44-3.80(36H,m),7.2-7.8(10H,m)
质谱:694.5(100.0%),695.5(40.1%),696.5(9.9%),697.5(1.8%)
元素分析:C,62.22;H,10.30;O,23.02;P,4.46
(2)氢甲酰化:反应釜中加入60g二异丁烯和18g水,加入6g醋酸铑为催化剂,加入6g B(C6F5)3为助催化剂,加入12g上述膦配体,通入合成气25g,反应釜压力20MPaG,搅拌转速1500r/min,200℃反应10h,反应结束后静置分层,分离上层烯烃原料和醛醇产物,二异丁烯转化率95%,异壬醛选择性91%。
(3)催化剂套用
分离下层水溶液,加入60g二异丁烯,按照步骤(2)中氢甲酰化条件重复实验,连续重复四次,转化率和选择性如下:
套用实验次数 | 转化率(%) | 选择性(%) |
1 | 95 | 91 |
2 | 92 | 88 |
3 | 94 | 90 |
4 | 96 | 89 |
实施例3
(1)三口烧瓶中加入100g癸二醇,氮气保护下滴加正丁基锂,正丁基锂与癸二醇的投料摩尔比1.1:1,反应温度-30℃,反应时间1h,反应结束后继续加入二苯基氯化膦,二苯基氯化膦与二醇的投料摩尔比1.05:1,反应温度20℃,反应时间1h,放置于0℃环境中析出固体,分离得到中间体I,称重计算收率91%。
三口烧瓶中加入100g中间体I,加入0.8g氢氧化钾,110℃,1Kpa下脱除水和其它轻组分,加入环氧乙烷,环氧乙烷与中间体I投料摩尔比10:1,反应温度20℃,反应1h,然后加入10g冰醋酸水溶液(10wt%),搅拌20分钟,分离上层油相得到膦配体,称重计算收率95%,配体分析表征结果如下:m=9
1HNMR(CDCl3溶剂):1.43-1.53(16H,m),3.44-3.80(44H,m),7.2-7.8(10H,m)
质谱:798.5(100.0%),799.5(46.7%),800.5(13.1%),801.5(2.7%)
元素分析:C,63.14;H,8.96;O,24.03;P,3.88
(2)氢甲酰化:反应釜中加入60g正丁烯和60g水,加入0.6g乙酰丙酮羰基铑为催化剂,加入0.6g B(C6F5)3为助催化剂,加入0.6g上述膦配体,通入合成气75g,反应釜压力10MPaG,搅拌转速1500r/min,120℃反应2h,反应结束后静置分层,分离上层烯烃原料和醛醇产物,正丁烯转化率95%,异戊醛选择性91%。
(3)催化剂套用
分离下层水溶液,加入60g正丁烯,按照步骤(2)中氢甲酰化条件重复实验,连续重复四次,转化率和选择性如下:
实施例4
(1)三口烧瓶中加入100g戊二醇,氮气保护下滴加正丁基锂,正丁基锂与癸二醇的投料摩尔比1.05:1,反应温度0℃,反应时间2h,反应结束后继续加入二苯基氯化膦,二苯基氯化膦与二醇的投料摩尔比1.1:1,反应温度80℃,反应时间2h,放置于0℃环境中析出固体,分离得到中间体I,称重计算收率93%。
三口烧瓶中加入100g中间体I,加入0.7g氢氧化钾,110℃,1Kpa下脱除水和其它轻组分,加入环氧乙烷,环氧乙烷与中间体I投料摩尔比20:1,反应温度80℃,反应2h,然后加入10g冰醋酸水溶液(10wt%),搅拌20分钟,分离上层油相得到膦配体,称重计算收率94%。m=14
1HNMR(CDCl3溶剂):1.43-1.53(6H,m),3.44-3.80(64H,m),7.2-7.8(10H,m)
质谱:858.5(100.0%),859.5(46.7%),870.5(13.1%),871.5(2.7%)
元素分析:C,66.39;H,3.21;O,28.52;P,1.88
(2)氢甲酰化:反应釜中加入60g1-癸烯和300g水,加入3g羰基钴为催化剂,加入3gB(C6F5)3为助催化剂,加入6g上述膦配体,通入合成气150g,反应釜压力18MPaG,搅拌转速1500r/min,170℃反应8h,反应结束后静置分层,分离上层烯烃原料和醛醇产物,1-癸烯转化率95%,十一醛选择性90%。
(3)催化剂套用
分离下层水溶液,加入60g1-癸烯,按照步骤(2)中氢甲酰化条件重复实验,连续重复四次,转化率和选择性如下:
实施例5
(1)三口烧瓶中加入100g戊二醇,氮气保护下滴加正丁基锂,正丁基锂与癸二醇的投料摩尔比1.05:1,反应温度15℃,反应时间1.5h,反应结束后继续加入二苯基氯化膦,二苯基氯化膦与二醇的投料摩尔比1.07:1,反应温度60℃,反应时间1.5h,放置于0℃环境中析出固体,分离得到中间体I,称重计算收率93%。
三口烧瓶中加入100g中间体I,加入0.6g氢氧化钾,110℃,1Kpa下脱除水和其它轻组分,加入环氧乙烷,环氧乙烷与中间体I投料摩尔比15:1,反应温度40℃,反应时间1.5h,然后加入10g冰醋酸水溶液(10wt%),搅拌20分钟,分离上层油相得到膦配体,称重计算收率95%。m=11
1HNMR(CDCl3溶剂):1.43-1.53(6H,m),3.44-3.80(52H,m),7.2-7.8(10H,m)
质谱:818.5(100.0%),819.5(46.7%),830.5(13.1%),831.5(2.7%)
元素分析:C,65.14;H,8.96;O,22.73;P,3.18
(2)氢甲酰化:反应釜中加入60g三聚正丁烯和60g水,加入1.8g乙酰丙酮钴为催化剂,加入1.8g B(C6F5)3为助催化剂,加入3g上述膦配体,通入合成气120g,反应釜压力15MPaG,搅拌转速1500r/min,150℃反应6h,反应结束后静置分层,分离上层烯烃原料和醛醇产物,三聚正丁烯转化率85%,十三醛选择性85%。
(3)催化剂套用
分离下层水溶液,加入60g三聚正烯,按照步骤(2)中氢甲酰化条件重复实验,连续重复四次,转化率和选择性如下:
套用实验次数 | 转化率(%) | 选择性(%) |
1 | 85 | 85 |
2 | 86 | 87 |
3 | 83 | 88 |
4 | 86 | 84 |
实施例6
反应釜中加入60g三异丁烯和6g水,加入0.06g辛酸铑为催化剂,加入0.12g实施例1中的膦配体,通入合成气30g,反应釜压力8MPaG,搅拌转速1500r/min,100℃反应0.5h,反应结束后静置分层,分离上层烯烃原料和醛醇产物,三异丁烯转化率55%,异构十三醛选择性93%。
对比例1
反应釜中加入60g三异丁烯和6g水,加入0.06g辛酸铑为催化剂,加入0.12g水溶性TPPTS膦配体,通入合成气30g,反应釜压力8MPaG,搅拌转速1500r/min,100℃反应0.5h,反应结束后静置分层,分离上层烯烃原料和醛醇产物,三异丁烯转化率3%,异构十三醛选择性94%。
Claims (10)
3.根据权利要求2所述的制备方法,其特征在于,正丁基锂与二元醇的投料摩尔比为1:1-1.1:1;和/或,反应温度为-78-30℃,优选-30-0℃;和/或;反应时间为0.5-3h,优选1-2h。
4.根据权利要求2或3所述的制备方法,其特征在于,二苯基氯化膦或二环己基氯化膦与二元醇的投料摩尔比为1:1-1.2:1,优选1.05:1-1.1:1;和/或,反应温度为0-100℃,优选20-80℃,反应时间为0.5-3h,优选1-2h。
5.根据权利要求2-4中任一项所述的制备方法,其特征在于,中间体I与环氧乙烷反应的催化剂为氢氧化钾和/或氢氧化钠,催化剂用量为中间体I质量的0.5wt%-1wt%,和/或,中间体I与EO投料摩尔比1:5-1:20,优选1:8-1:15,和/或,反应温度为0-100℃,优选20-80℃,和/或,反应时间为0.5-3h,优选1-2h。
6.根据权利要求1所述的膦配体或权利要求2-5中任一项制备方法制得的膦配体在烯烃氢甲酰化反应中的用途。
7.根据权利要求6所述的用途,其特征在于,以烯烃为原料,以含钴化合物或含铑化合物为催化剂,加入膦配体,以水为溶剂,催化烯烃氢甲酰化反应,反应结束后水油两相分层,分离上层油相为氢甲酰化产品,下层为催化剂水溶液;优选地,所用的烯烃选自碳数2-20的直链α-烯烃、直链内烯烃、支链α-烯烃、支链内烯烃中的一种或多种,更优选乙烯、丙烯、丁烯、戊烯、己烯、庚烯、环己烯、环戊烯、异丁烯、1-辛烯、环辛烯、1-壬烯、1-癸烯、三聚丙烯、四聚丙烯、二聚正丁烯、三聚正丁烯、二异丁烯、三异丁烯、十二碳烯、十四碳烯、十六碳烯、十八碳烯、二十碳烯中的一种或多种。
8.根据权利要求7所述的用途,其特征在于,氢甲酰化反应中还加入B(C6F5)3作为助催化剂,和/或,加入量为烯烃质量的0.1-10wt%,优选1-5wt%。
9.根据权利要求7或8所述的用途,其特征在于,膦配体加入量为烯烃质量的0.2-20wt%,优选1-10wt%;和/或;溶剂水的加入量为烯烃质量的10-500wt%,优选30-100wt%。
10.根据权利要求7-9中任一项所述的用途,其特征在于,含铑化合物选自醋酸铑,辛酸铑,乙酰丙酮铑,乙酰丙酮羰基铑,三苯基膦铑,三苯基膦羰基铑,氯化铑,三苯基膦氯化铑中的一种或多种;和/或,含钴化合物选自醋酸钴,氯化钴,羰基钴,硫酸钴,乙酰丙酮钴中的一种或多种;和/或,催化剂用量为烯烃质量的0.1-10wt%,优选1-5wt%,和/或,反应温度为100-200℃,优选120-170℃;和/或,反应时间为0.5-10h,优选2-8h;和/或,反应压力为8-20MPaG,优选10-18MpaG。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202010647161.5A CN111718371B (zh) | 2020-07-07 | 2020-07-07 | 一种膦配体及其制备方法和用途 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202010647161.5A CN111718371B (zh) | 2020-07-07 | 2020-07-07 | 一种膦配体及其制备方法和用途 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN111718371A true CN111718371A (zh) | 2020-09-29 |
CN111718371B CN111718371B (zh) | 2023-03-31 |
Family
ID=72573861
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202010647161.5A Active CN111718371B (zh) | 2020-07-07 | 2020-07-07 | 一种膦配体及其制备方法和用途 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN111718371B (zh) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN112679327A (zh) * | 2021-01-12 | 2021-04-20 | 四川大学 | 一种烯烃两相氢甲酰化制备醛类化合物的方法 |
CN114686733A (zh) * | 2022-04-12 | 2022-07-01 | 江苏中基复合材料有限公司 | 一种无菌包装用铸轧铝箔及其制备方法 |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1184710A (zh) * | 1997-10-24 | 1998-06-17 | 中国石油化工总公司 | 具有温控相转移功能的膦配体及其应用 |
-
2020
- 2020-07-07 CN CN202010647161.5A patent/CN111718371B/zh active Active
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1184710A (zh) * | 1997-10-24 | 1998-06-17 | 中国石油化工总公司 | 具有温控相转移功能的膦配体及其应用 |
Non-Patent Citations (3)
Title |
---|
JINAYANG JIANG等: "Thermoregulated phase transfer ligands and catalysis VII.Cloud point of nonionic surface-active phosphine ligands and their thermoregulated phase transfer property", 《JOURNAL OF MOLECULAR CATALYSIS A: CHEMICAL 》 * |
ZHIJIANG JI等: "A novel thermoregulated phosphine ligand used for the Rh-catalyzed hydroformylation of mixed C11–12 olefins in aqueous/organic biphasic system", 《CHINESE CHEMICAL LETTERS》 * |
吴丹: "温控相转移钴配合物催化水-有机两相高碳烯烃氢甲酰化反应研究", 《中国优秀博硕士学位论文全文数据库(博士) 工程科技I辑》 * |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN112679327A (zh) * | 2021-01-12 | 2021-04-20 | 四川大学 | 一种烯烃两相氢甲酰化制备醛类化合物的方法 |
CN114686733A (zh) * | 2022-04-12 | 2022-07-01 | 江苏中基复合材料有限公司 | 一种无菌包装用铸轧铝箔及其制备方法 |
CN114686733B (zh) * | 2022-04-12 | 2022-11-18 | 江苏中基复合材料有限公司 | 一种无菌包装用铸轧铝箔及其制备方法 |
Also Published As
Publication number | Publication date |
---|---|
CN111718371B (zh) | 2023-03-31 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
KR870000201B1 (ko) | 하이드로포르밀화에 의한 알데히드의 제조방법 | |
US8461394B2 (en) | Process for preparing C5 aldehyde mixtures with a high n-pentanal content | |
EP2114568B1 (en) | Phosphonite-containing catalysts for hydroformylation processes | |
CN111825542B (zh) | 一种碳原子数≥8的高碳烯烃氢甲酰化的方法 | |
CN111718371B (zh) | 一种膦配体及其制备方法和用途 | |
EP2240275B1 (en) | Fluorophosphite containing catalysts for hydroformylation processes | |
CN101160272A (zh) | 具有改进的iso-选择性的氢甲酰化方法 | |
WO1990006810A1 (en) | Low pressure rhodium catalyzed hydroformylation of olefins | |
SG188512A1 (en) | Use of supported ionic liquid phase (silp) catalyst systems in the hydroformylation of olefin-containing mixtures to give aldehyde mixtures with a high proportion of 2-unbranched aldehydes | |
CA1243687A (en) | Process for preparing aldehydes | |
CN106083551A (zh) | 一种丙烯氢甲酰化制备丁醛的方法 | |
CN110981709B (zh) | 一种内烯烃氢甲酰化制备醛的方法 | |
JPS6114131B2 (zh) | ||
CA2184048C (en) | Process for the hydroformylation of olefinically unsaturated compounds | |
CN1315572C (zh) | 包含氟亚磷酸酯的催化剂的稳定作用 | |
CN111606792A (zh) | 一种制备高碳醛的方法 | |
CN111333680A (zh) | 一种膦配体其制备方法及应用 | |
CA2256991A1 (en) | Process for preparing aldehydes | |
CN103269799B (zh) | 从加氢甲酰基化反应中除去降解酸的方法 | |
CN110605145B (zh) | 一种氢甲酯化反应催化剂及制备异壬酸的方法 | |
EP0107430B1 (en) | Method for the preparation of alcohols and aldehydes by reacting olefins with carbon monoxide and hydrogen | |
Ding et al. | New water soluble chelating phosphines for aqueous phase catalysis | |
CN101909753A (zh) | 用于醛化过程的含亚膦酸酯催化剂 | |
CN113583046B (zh) | 双齿膦配体及其制备方法、应用 | |
CN111729687B (zh) | 一种氢甲酰化催化剂的制备方法和应用 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |