CN115536697A - Phosphine ligand compound, catalyst composition for preparing aldehyde by catalytic hydroformylation and method - Google Patents
Phosphine ligand compound, catalyst composition for preparing aldehyde by catalytic hydroformylation and method Download PDFInfo
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- CN115536697A CN115536697A CN202110733820.1A CN202110733820A CN115536697A CN 115536697 A CN115536697 A CN 115536697A CN 202110733820 A CN202110733820 A CN 202110733820A CN 115536697 A CN115536697 A CN 115536697A
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- substituents
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- independently selected
- hydrogen
- alkyl
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- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 239000003054 catalyst Substances 0.000 title claims abstract description 42
- 239000003446 ligand Substances 0.000 title claims abstract description 37
- 238000007037 hydroformylation reaction Methods 0.000 title claims abstract description 28
- 239000000203 mixture Substances 0.000 title claims abstract description 28
- 229910000073 phosphorus hydride Inorganic materials 0.000 title claims abstract description 28
- 150000001875 compounds Chemical class 0.000 title claims abstract description 22
- 238000000034 method Methods 0.000 title claims abstract description 20
- 230000003197 catalytic effect Effects 0.000 title abstract description 9
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 title abstract 3
- 239000010948 rhodium Substances 0.000 claims abstract description 48
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 42
- -1 rhodium metal compound Chemical class 0.000 claims abstract description 29
- 125000001424 substituent group Chemical group 0.000 claims description 53
- 239000001257 hydrogen Substances 0.000 claims description 39
- 229910052739 hydrogen Inorganic materials 0.000 claims description 39
- 150000001299 aldehydes Chemical class 0.000 claims description 37
- 150000002431 hydrogen Chemical class 0.000 claims description 29
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 28
- 150000001336 alkenes Chemical class 0.000 claims description 22
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 20
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- 229910052736 halogen Inorganic materials 0.000 claims description 15
- 150000002367 halogens Chemical group 0.000 claims description 15
- 125000000217 alkyl group Chemical group 0.000 claims description 14
- 125000000027 (C1-C10) alkoxy group Chemical group 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 10
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 9
- 239000000460 chlorine Substances 0.000 claims description 8
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 7
- 125000003545 alkoxy group Chemical group 0.000 claims description 7
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 7
- 229910052801 chlorine Inorganic materials 0.000 claims description 7
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims description 6
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 6
- 229910052794 bromium Inorganic materials 0.000 claims description 6
- 150000002430 hydrocarbons Chemical group 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 5
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 5
- 125000005843 halogen group Chemical group 0.000 claims description 5
- 239000011630 iodine Substances 0.000 claims description 5
- 229910052740 iodine Inorganic materials 0.000 claims description 5
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 5
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 claims description 5
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 5
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 5
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 5
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 claims description 5
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 5
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 5
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 claims description 4
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 4
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 4
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 3
- 125000002252 acyl group Chemical group 0.000 claims description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 3
- 125000004185 ester group Chemical group 0.000 claims description 3
- 125000000623 heterocyclic group Chemical group 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000008096 xylene Substances 0.000 claims description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- 150000001491 aromatic compounds Chemical class 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 22
- 230000000694 effects Effects 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 238000009776 industrial production Methods 0.000 abstract description 3
- 230000002349 favourable effect Effects 0.000 abstract 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 21
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 18
- 239000000243 solution Substances 0.000 description 15
- 239000000047 product Substances 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 239000002202 Polyethylene glycol Substances 0.000 description 7
- 238000002474 experimental method Methods 0.000 description 7
- 229920001223 polyethylene glycol Polymers 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
- 230000009257 reactivity Effects 0.000 description 6
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 5
- 229910052731 fluorine Inorganic materials 0.000 description 5
- 239000011737 fluorine Substances 0.000 description 5
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 239000012074 organic phase Substances 0.000 description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 125000004191 (C1-C6) alkoxy group Chemical group 0.000 description 3
- NVHOWSXDIDUIDZ-UHFFFAOYSA-N 2,7-dibromo-9,9-dimethylxanthene Chemical compound C1=C(Br)C=C2C(C)(C)C3=CC(Br)=CC=C3OC2=C1 NVHOWSXDIDUIDZ-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000012295 chemical reaction liquid Substances 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- HTSGKJQDMSTCGS-UHFFFAOYSA-N 1,4-bis(4-chlorophenyl)-2-(4-methylphenyl)sulfonylbutane-1,4-dione Chemical compound C1=CC(C)=CC=C1S(=O)(=O)C(C(=O)C=1C=CC(Cl)=CC=1)CC(=O)C1=CC=C(Cl)C=C1 HTSGKJQDMSTCGS-UHFFFAOYSA-N 0.000 description 2
- CFMZSMGAMPBRBE-UHFFFAOYSA-N 2-hydroxyisoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(O)C(=O)C2=C1 CFMZSMGAMPBRBE-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- FKLJPTJMIBLJAV-UHFFFAOYSA-N Compound IV Chemical compound O1N=C(C)C=C1CCCCCCCOC1=CC=C(C=2OCCN=2)C=C1 FKLJPTJMIBLJAV-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- NLFBCYMMUAKCPC-KQQUZDAGSA-N ethyl (e)-3-[3-amino-2-cyano-1-[(e)-3-ethoxy-3-oxoprop-1-enyl]sulfanyl-3-oxoprop-1-enyl]sulfanylprop-2-enoate Chemical compound CCOC(=O)\C=C\SC(=C(C#N)C(N)=O)S\C=C\C(=O)OCC NLFBCYMMUAKCPC-KQQUZDAGSA-N 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000012362 glacial acetic acid Substances 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical compound CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 description 2
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 2
- 238000013517 stratification Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- SLNYBUIEAMRFSZ-UHFFFAOYSA-N 2-(2-{2-[2-(2-methoxy-ethoxy)-ethoxy]-ethoxy}-ethoxy)-ethanol Chemical compound COCCOCCOCCOCCOCCO SLNYBUIEAMRFSZ-UHFFFAOYSA-N 0.000 description 1
- BPRHSTFUDDBCAQ-UHFFFAOYSA-N 4,5-dibromo-9,9-dimethylxanthene Chemical compound C1=CC=C2C(C)(C)C3=CC=CC(Br)=C3OC2=C1Br BPRHSTFUDDBCAQ-UHFFFAOYSA-N 0.000 description 1
- MTVNAPYHLASOSX-UHFFFAOYSA-N 9,9-dimethylxanthene Chemical compound C1=CC=C2C(C)(C)C3=CC=CC=C3OC2=C1 MTVNAPYHLASOSX-UHFFFAOYSA-N 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical class [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- SLGBZMMZGDRARJ-UHFFFAOYSA-N Triphenylene Natural products C1=CC=C2C3=CC=CC=C3C3=CC=CC=C3C2=C1 SLGBZMMZGDRARJ-UHFFFAOYSA-N 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- CBHOOMGKXCMKIR-UHFFFAOYSA-N azane;methanol Chemical compound N.OC CBHOOMGKXCMKIR-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- VTJUKNSKBAOEHE-UHFFFAOYSA-N calixarene Chemical compound COC(=O)COC1=C(CC=2C(=C(CC=3C(=C(C4)C=C(C=3)C(C)(C)C)OCC(=O)OC)C=C(C=2)C(C)(C)C)OCC(=O)OC)C=C(C(C)(C)C)C=C1CC1=C(OCC(=O)OC)C4=CC(C(C)(C)C)=C1 VTJUKNSKBAOEHE-UHFFFAOYSA-N 0.000 description 1
- 239000012018 catalyst precursor Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- UHZZMRAGKVHANO-UHFFFAOYSA-M chlormequat chloride Chemical compound [Cl-].C[N+](C)(C)CCCl UHZZMRAGKVHANO-UHFFFAOYSA-M 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000013058 crude material Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 235000019256 formaldehyde Nutrition 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 125000001298 n-hexoxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- MXQOYLRVSVOCQT-UHFFFAOYSA-N palladium;tritert-butylphosphane Chemical compound [Pd].CC(C)(C)P(C(C)(C)C)C(C)(C)C.CC(C)(C)P(C(C)(C)C)C(C)(C)C MXQOYLRVSVOCQT-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 description 1
- 229910000342 sodium bisulfate Inorganic materials 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000012360 testing method Methods 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
- 238000012546 transfer Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000003039 volatile agent 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
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6558—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom containing at least two different or differently substituted hetero rings neither condensed among themselves nor condensed with a common carbocyclic ring or ring system
- C07F9/65586—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom containing at least two different or differently substituted hetero rings neither condensed among themselves nor condensed with a common carbocyclic ring or ring system at least one of the hetero rings does not contain nitrogen as ring hetero atom
-
- 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
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/2247—At least one oxygen and one phosphorous atom present as complexing atoms in an at least bidentate or bridging ligand
-
- 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
- Y02P20/584—Recycling of catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
技术领域technical field
本发明涉及膦配体化合物、用于催化氢甲酰化制备醛的催化剂组合物及催化氢甲酰化制备醛的方法。The invention relates to a phosphine ligand compound, a catalyst composition for preparing aldehyde by catalytic hydroformylation and a method for preparing aldehyde by catalytic hydroformylation.
背景技术Background technique
近年来，随着世界范围内塑料加工、汽车工业、电缆工业以及建筑业的快速发展，全球对增塑剂的需求越来越大，进而增加了增塑剂醇的需求，尤其是对C6以上高碳醇的需求增长迅速。In recent years, with the rapid development of plastic processing, automobile industry, cable industry and construction industry worldwide, the global demand for plasticizers is increasing, which in turn increases the demand for plasticizer alcohols, especially for C6 and above The demand for higher carbon alcohols is growing rapidly.
目前，工业上氢甲酰化生产工艺所采用的催化剂主要有钴系催化剂和铑系催化剂，其中，使用钴系催化剂的工艺所需反应条件苛刻、选择性差、副反应多，且能耗高以及钴回收过程复杂等因素，其综合经济技术指标远不如使用铑系催化剂的工艺，因此，铑系催化剂逐渐成为工业氢甲酰化反应的主导催化剂。但是，铑催化剂价格昂贵，在一定程度上增加了产品的生产成本。如何进一步增加铑系催化剂的反应活性以及产品选择性，以达到降低铑催化剂使用量的目的，同时尽可能的回收再利用催化剂，是目前该领域急需解决的技术问题之一。At present, the catalysts used in the industrial hydroformylation production process mainly include cobalt-based catalysts and rhodium-based catalysts. Among them, the process using cobalt-based catalysts requires harsh reaction conditions, poor selectivity, many side reactions, and high energy consumption. Due to factors such as the complexity of the cobalt recovery process, its comprehensive economic and technical indicators are far inferior to those using rhodium-based catalysts. Therefore, rhodium-based catalysts have gradually become the leading catalysts for industrial hydroformylation reactions. However, the rhodium catalyst is expensive, which increases the production cost of the product to a certain extent. How to further increase the reactivity and product selectivity of rhodium-based catalysts to achieve the purpose of reducing the amount of rhodium catalyst used, while recycling the catalyst as much as possible is one of the technical problems urgently to be solved in this field.
Rh系催化剂在加氢甲酰化过程中体现的活性以及所生产的N/I选择性(正构醛与异构醛的比值)取决于催化剂前驱体和配体的组合以及操作条件。The activity of Rh-based catalysts in the hydroformylation process and the produced N/I selectivity (ratio of normal aldehydes to isomeric aldehydes) depend on the combination of catalyst precursors and ligands and operating conditions.
美国专利US8710276公开了配体CHDP表示的环己烷二苯基膦配体，该配体虽然增加了催化剂稳定性，但是N/I选择性明显降低；美国专利US8507731在实施例8至14中公开了Rh(CO)2(acac)和杯芳烃双齿膦配体组合催化剂，该组合催化剂显示了较高的N/I选择性，但是反应活性较低，此外，该配体较为复杂，合成步骤繁琐，使用成本较高。另外，中国专利CN101293818公开了一种氢甲酰化方法，通过对混合丁烯氢甲酰化进行两段反应，很好的解决了两种烯烃的反应差异问题，提高烯烃利用率，但该种方法只局限于低碳链烯烃的氢甲酰化。U.S. Patent No. 8,710,276 discloses a cyclohexanediphenylphosphine ligand represented by ligand CHDP. Although the ligand increases catalyst stability, N/I selectivity is significantly reduced; U.S. Patent No. 8,507,731 is disclosed in Examples 8 to 14 A combined catalyst of Rh(CO) 2 (acac) and calixarene bidentate phosphine ligand was developed, which showed high N/I selectivity, but low reactivity. In addition, the ligand was complex and the synthesis steps Complicated and expensive to use. In addition, the Chinese patent CN101293818 discloses a hydroformylation method, which solves the problem of reaction differences between two olefins and improves the utilization rate of olefins by performing a two-stage reaction on the hydroformylation of mixed butenes. The method is limited to the hydroformylation of light alkenes.
在催化剂回收方面，开发了两相催化工艺(尤其是油水两相催化)，但是，由于C6以上的高碳烯烃在水中的溶解性较差(有些甚至完全不溶)，导致传质速率慢，影响反应活性，限制了油水两相催化工艺在高碳烯烃氢甲酰化工业生产中的应用。In terms of catalyst recovery, a two-phase catalytic process (especially oil-water two-phase catalysis) has been developed. However, due to the poor solubility of high-carbon olefins above C6 in water (some are even completely insoluble), the mass transfer rate is slow and affects The reactivity limits the application of the oil-water two-phase catalytic process in the industrial production of high carbon olefin hydroformylation.
发明内容Contents of the invention
为了解决上述技术问题，本发明的发明人发现了一种膦配体化合物和包含该化合物的用于催化氢甲酰化制备醛的催化剂组合物及利用该组合物的均相氢甲酰化反应方法，本发明提供的组合物在氢甲酰化反应中具有较高的活性，并且能够高效分离回收。In order to solve the above technical problems, the inventors of the present invention have discovered a phosphine ligand compound and a catalyst composition comprising the compound for catalytic hydroformylation of aldehydes and a homogeneous hydroformylation reaction using the composition In the method, the composition provided by the invention has higher activity in hydroformylation reaction, and can be separated and recovered efficiently.
在第一方面，本发明提供了一种膦配体化合物，其结构如式(A)所示，In a first aspect, the present invention provides a phosphine ligand compound, the structure of which is shown in formula (A),
式(A)中，M1为式(I)所示的基团，M2为式(II)所示的基团，其中，R1、R2、R3和R4各自独立地选自含或不含取代基的含N的杂环、含或不含取代基的苯环和含苯环的烃基，p、q各自分别为0或1，任选地，R1、R2、P和/或R3、R4、P与额外的O连接成环；In formula (A), M 1 is a group represented by formula (I), M 2 is a group represented by formula (II), wherein R 1 , R 2 , R 3 and R 4 are each independently selected from N-containing heterocycles with or without substituents, benzene rings with or without substituents, and hydrocarbon groups containing benzene rings, p and q are each 0 or 1, optionally, R 1 , R 2 , P And/or R 3 , R 4 , P are connected with additional O to form a ring;
M3为式(III)所示的基团，M4为式(IV)所示的基团，其中，R1’、R2’、R3’和R4’各自独立地选自氢、含或不含取代基的烷基和含或不含取代基的烷氧基，m、n各自分别为1-200的自然数；M 3 is a group represented by formula (III), and M 4 is a group represented by formula (IV), wherein R 1 ', R 2 ', R 3 ' and R 4 ' are each independently selected from hydrogen, Alkyl groups with or without substituents and alkoxy groups with or without substituents, m and n are each a natural number from 1 to 200;
R11-R16各自独立地选自氢、含或不含取代基的烷基和含或不含取代基的烷氧基。根据本发明的一些实施方式，R1、R2、R3和R4各自独立地选自含N的五元环、六元环或苯并杂环。R 11 to R 16 are each independently selected from hydrogen, alkyl with or without substituents, and alkoxy with or without substituents. According to some embodiments of the present invention, R 1 , R 2 , R 3 and R 4 are each independently selected from N-containing five-membered rings, six-membered rings or benzoheterocyclic rings.
根据本发明的一些实施方式，R1、R2、R3和R4各自独立地选自
根据本发明的一些实施方式，m、n各自分别为5-200的自然数。According to some embodiments of the present invention, m and n are each a natural number of 5-200.
根据本发明的一些具体的实施方式，m、n各自分别可以为1、3、5、10、15、20、50、100、150、200以及它们之间的任意值。According to some specific embodiments of the present invention, each of m and n can be 1, 3, 5, 10, 15, 20, 50, 100, 150, 200 and any value between them.
根据本发明的一些实施方式，R1、R2、R3和R4各自独立地选自
根据本发明的一些实施方式，所述卤素选自氟、氯、溴和碘。According to some embodiments of the present invention, the halogen is selected from fluorine, chlorine, bromine and iodine.
根据本发明的一些实施方式，R1’、R2’、R3’和R4’各自独立地选自氢、含或不含取代基的C1-C10烷基和含或不含取代基的C1-C10烷氧基。According to some embodiments of the present invention, R 1 ′, R 2 ′, R 3 ′, and R 4 ′ are each independently selected from hydrogen, C 1 -C 10 alkyl groups with or without substituents, and C 1 -C 10 alkyl groups with or without substituents. C 1 -C 10 alkoxy radicals.
根据本发明的一些实施方式，R1’、R2’、R3’和R4’各自独立地选自氢、含或不含取代基的C1-C6烷基和含或不含取代基的C1-C6烷氧基。According to some embodiments of the present invention, R 1 ′, R 2 ′, R 3 ′, and R 4 ′ are each independently selected from hydrogen, C 1 -C 6 alkyl with or without substituents, and C 1 -C 6 alkyl with or without substitution C 1 -C 6 alkoxy groups.
根据本发明的一些实施方式，R1’、R2’、R3’和R4’各自独立地选自氢、含或不含取代基的C1-C4烷基和含或不含取代基的C1-C4烷氧基。According to some embodiments of the present invention, each of R 1 ′, R 2 ′, R 3 ′, and R 4 ′ is independently selected from hydrogen, C 1 -C 4 alkyl with or without substituents, and C 1 -C 4 alkyl with or without substitution C 1 -C 4 alkoxy groups.
根据本发明的优选实施方式，式(III)中，R1’为C1-C6烷基，R2’为氢。According to a preferred embodiment of the present invention, in formula (III), R 1 ' is C 1 -C 6 alkyl, and R 2 ' is hydrogen.
根据本发明的一些具体的实施方式，式(III)中，R1’为甲基，R2’为氢。According to some specific embodiments of the present invention, in formula (III), R 1 ' is methyl, and R 2 ' is hydrogen.
根据本发明的优选实施方式，式(IV)中，R3’为C1-C6烷基，R4’为氢。According to a preferred embodiment of the present invention, in formula (IV), R 3 ' is C 1 -C 6 alkyl, and R 4 ' is hydrogen.
根据本发明的一些具体的实施方式，式(IV)中，R3’为甲基，R4’为氢。According to some specific embodiments of the present invention, in formula (IV), R 3 ' is methyl, and R 4 ' is hydrogen.
本发明中，式(I)、式(II)、式(III)、式(IV)中的*表示基团在式(A)中的连接处。In the present invention, * in formula (I), formula (II), formula (III) and formula (IV) represents the linking position of the group in formula (A).
根据本发明的一些实施方式，R11-R16各自独立地选自氢、含或不含取代基的C1-C10烷基和含或不含取代基的C1-C10烷氧基。According to some embodiments of the present invention, each of R 11 -R 16 is independently selected from hydrogen, C 1 -C 10 alkyl with or without substituents, and C 1 -C 10 alkoxy with or without substituents .
根据本发明的一些实施方式，R11-R16各自独立地选自氢、含或不含取代基的C1-C6烷基和含或不含取代基的C1-C6烷氧基。According to some embodiments of the present invention, R 11 -R 16 are each independently selected from hydrogen, C 1 -C 6 alkyl with or without substituents, and C 1 -C 6 alkoxy with or without substituents .
根据本发明的一些实施方式，R11-R16各自独立地选自氢、含或不含取代基的C1-C4烷基和含或不含取代基的C1-C4烷氧基。According to some embodiments of the present invention, R 11 -R 16 are each independently selected from hydrogen, C 1 -C 4 alkyl with or without substituents and C 1 -C 4 alkoxy with or without substituents .
根据本发明的一些实施方式，R11-R16各自独立选自氢、甲基、乙基、正丙基、异丙基、正丁基、叔丁基、异丁基、正戊基、异戊基、正己基、正庚基、甲氧基、乙氧基、正丙氧基、异丙氧基、正丁氧基、叔丁氧基、异丁氧基、正戊氧基、异戊氧基、正己氧基和正庚氧基。According to some embodiments of the present invention, R 11 -R 16 are each independently selected from hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, isobutyl, n-pentyl, iso Pentyl, n-hexyl, n-heptyl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, tert-butoxy, isobutoxy, n-pentyloxy, isopentyl Oxygen, n-hexyloxy and n-heptyloxy.
根据本发明的一些实施方式，所述取代基选自卤素、C1-C10烷基和C1-C10烷氧基。According to some embodiments of the present invention, the substituent is selected from halogen, C 1 -C 10 alkyl and C 1 -C 10 alkoxy.
根据本发明的一些实施方式，所述取代基选自卤素、C1-C6烷基和C1-C6烷氧基。According to some embodiments of the present invention, the substituent is selected from halogen, C 1 -C 6 alkyl and C 1 -C 6 alkoxy.
根据本发明的优选实施方式，所述取代基选自卤素、C1-C4烷基和C1-C4烷氧基。According to a preferred embodiment of the present invention, the substituent is selected from halogen, C 1 -C 4 alkyl and C 1 -C 4 alkoxy.
根据本发明的一些实施方式，所述取代基中，所述卤素选自氟、氯、溴和碘。According to some embodiments of the present invention, in the substituent, the halogen is selected from fluorine, chlorine, bromine and iodine.
根据本发明的一些实施方式，所述取代基中，所述C1-C10烷基选自甲基、乙基、正丙基、异丙基、正丁基、叔丁基、异丁基、正戊基、异戊基、正己基和正庚基。According to some embodiments of the present invention, in the substituent, the C 1 -C 10 alkyl group is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, isobutyl , n-pentyl, isopentyl, n-hexyl and n-heptyl.
根据本发明的一些实施方式，所述取代基中，所述C1-C10烷氧基选自甲氧基、乙氧基、正丙氧基、异丙氧基、正丁氧基、叔丁氧基、异丁氧基、正戊氧基、异戊氧基、正己氧基和正庚氧基。According to some embodiments of the present invention, in the substituent, the C 1 -C 10 alkoxy group is selected from methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, t- Butoxy, isobutoxy, n-pentyloxy, isopentyloxy, n-hexyloxy and n-heptyloxy.
根据本发明，在式(I)中，当不存在额外的O时，R1、R2、P不成环，即为，当存在额外的O时，R1、R2、P与O连接成环，即为。According to the present invention, in formula (I), when there is no additional O, R 1 , R 2 , P do not form a ring, that is, when there is additional O, R 1 , R 2 , P and O are connected to form Ring, that is.
根据本发明，在式(II)中，当不存在额外的O时，R1、R2、P不成环，当存在额外的O时，R3、R4、P与O连接成环。According to the present invention, in formula (II), when there is no additional O, R 1 , R 2 , P do not form a ring, and when there is additional O, R 3 , R 4 , P and O are connected to form a ring.
根据本发明的一些实施方式，M1、M2各自独立地选自
根据本发明的一些实施方式，所述膦配体化合物的结构如式(B)所示：According to some embodiments of the present invention, the structure of the phosphine ligand compound is shown in formula (B):
式(B)中，R1、R2、R3和R4各自独立地选自含或不含取代基的含N的杂环、含或不含取代基的苯环和含苯环的烃基；In formula (B), R 1 , R 2 , R 3 and R 4 are each independently selected from N-containing heterocycles with or without substituents, benzene rings with or without substituents, and hydrocarbon groups containing benzene rings ;
R5为
R11-R16各自独立地选自氢、含或不含取代基的烷基和含或不含取代基的烷氧基。R 11 to R 16 are each independently selected from hydrogen, alkyl with or without substituents, and alkoxy with or without substituents.
根据本发明的一些实施方式，式(B)中，R1、R2、R3和R4各自独立地选自
根据本发明的一些实施方式，式(B)中，m、n各自分别为5-200的自然数。According to some embodiments of the present invention, in formula (B), m and n are each a natural number of 5-200.
根据本发明的一些具体的实施方式，式(B)中，m、n各自分别可以为1、3、5、10、15、20、50、100、150、200以及它们之间的任意值。According to some specific embodiments of the present invention, in formula (B), m and n can be 1, 3, 5, 10, 15, 20, 50, 100, 150, 200 and any value between them.
根据本发明的一些实施方式，式(B)中，R1、R2、R3和R4各自独立地选自
根据本发明的一些实施方式，式(B)中，所述卤素选自氟、氯、溴和碘。According to some embodiments of the present invention, in formula (B), the halogen is selected from fluorine, chlorine, bromine and iodine.
根据本发明的一些实施方式，式(B)中，R1’、R2’、R3’和R4’各自独立地选自氢、含或不含取代基的C1-C10烷基和含或不含取代基的C1-C10烷氧基。According to some embodiments of the present invention, in formula (B), R 1 ′, R 2 ′, R 3 ′, and R 4 ′ are each independently selected from hydrogen, C 1 -C 10 alkyl groups with or without substituents and C 1 -C 10 alkoxy with or without substituents.
根据本发明的一些实施方式，式(B)中，R1’、R2’、R3’和R4’各自独立地选自氢、含或不含取代基的C1-C6烷基和含或不含取代基的C1-C6烷氧基。According to some embodiments of the present invention, in formula (B), R 1 ', R 2 ', R 3 ' and R 4 ' are each independently selected from hydrogen, C 1 -C 6 alkyl with or without substituents and C 1 -C 6 alkoxy with or without substituents.
根据本发明的一些实施方式，式(B)中，R1’、R2’、R3’和R4’各自独立地选自氢、含或不含取代基的C1-C4烷基和含或不含取代基的C1-C4烷氧基。According to some embodiments of the present invention, in formula (B), R 1 ', R 2 ', R 3 ' and R 4 ' are each independently selected from hydrogen, C 1 -C 4 alkyl with or without substituents and C 1 -C 4 alkoxy with or without substituents.
根据本发明的优选实施方式，式(B)中，R1’为C1-C6烷基，R2’为氢。According to a preferred embodiment of the present invention, in formula (B), R 1 ' is C 1 -C 6 alkyl, and R 2 ' is hydrogen.
根据本发明的一些具体的实施方式，式(B)中，R1’为甲基，R2’为氢。According to some specific embodiments of the present invention, in formula (B), R 1 ' is methyl, and R 2 ' is hydrogen.
根据本发明的优选实施方式，式(B)中，R3’为C1-C6烷基，R4’为氢。According to a preferred embodiment of the present invention, in formula (B), R 3 ' is C 1 -C 6 alkyl, and R 4 ' is hydrogen.
根据本发明的一些具体的实施方式，式(B)中，R3’为甲基，R4’为氢。According to some specific embodiments of the present invention, in formula (B), R 3 ' is methyl, and R 4 ' is hydrogen.
根据本发明的一些实施方式，式(B)中，R11-R16各自独立地选自氢、含或不含取代基的C1-C10烷基和含或不含取代基的C1-C10烷氧基。According to some embodiments of the present invention, in formula (B), R 11 -R 16 are each independently selected from hydrogen, C 1 -C 10 alkyl with or without substituents, and C 1 with or without substituents -C 10 alkoxy.
根据本发明的一些实施方式，式(B)中，R11-R16各自独立地选自氢、含或不含取代基的C1-C6烷基和含或不含取代基的C1-C6烷氧基。According to some embodiments of the present invention, in formula (B), R 11 -R 16 are each independently selected from hydrogen, C 1 -C 6 alkyl with or without substituents, and C 1 with or without substituents -C 6 alkoxy.
根据本发明的一些实施方式，式(B)中，R11-R16各自独立地选自氢、含或不含取代基的C1-C4烷基和含或不含取代基的C1-C4烷氧基。According to some embodiments of the present invention, in formula (B), R 11 -R 16 are each independently selected from hydrogen, C 1 -C 4 alkyl with or without substituents, and C 1 with or without substituents -C 4 alkoxy.
根据本发明的一些实施方式，式(B)中，R11-R16各自独立选自氢、甲基、乙基、正丙基、异丙基、正丁基、叔丁基、异丁基、正戊基、异戊基、正己基、正庚基、甲氧基、乙氧基、正丙氧基、异丙氧基、正丁氧基、叔丁氧基、异丁氧基、正戊氧基、异戊氧基、正己氧基和正庚氧基。According to some embodiments of the present invention, in formula (B), R 11 -R 16 are each independently selected from hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, isobutyl , n-pentyl, isopentyl, n-hexyl, n-heptyl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, tert-butoxy, isobutoxy, n- Pentyloxy, isopentyloxy, n-hexyloxy and n-heptyloxy.
根据本发明的一些实施方式，式(B)中，所述取代基选自卤素、C1-C10烷基和C1-C10烷氧基，优选选自卤素、C1-C6烷基和C1-C6烷氧基，更优选选自卤素、C1-C4烷基和C1-C4烷氧基。According to some embodiments of the present invention, in formula (B), the substituent is selected from halogen, C 1 -C 10 alkyl and C 1 -C 10 alkoxy, preferably selected from halogen, C 1 -C 6 alk and C 1 -C 6 alkoxy, more preferably selected from halogen, C 1 -C 4 alkyl and C 1 -C 4 alkoxy.
根据本发明的一些实施方式，式(B)中，所述取代基中，所述卤素选自氟、氯、溴和碘；所述C1-C10烷基选自甲基、乙基、正丙基、异丙基、正丁基、叔丁基、异丁基、正戊基、异戊基、正己基和正庚基；所述C1-C10烷氧基选自甲氧基、乙氧基、正丙氧基、异丙氧基、正丁氧基、叔丁氧基、异丁氧基、正戊氧基、异戊氧基、正己氧基和正庚氧基。According to some embodiments of the present invention, in formula (B), in the substituent, the halogen is selected from fluorine, chlorine, bromine and iodine; the C 1 -C 10 alkyl group is selected from methyl, ethyl, N-propyl, isopropyl, n-butyl, t-butyl, isobutyl, n-pentyl, isopentyl, n-hexyl and n-heptyl; said C 1 -C 10 alkoxy group is selected from methoxy, Ethoxy, n-propoxy, isopropoxy, n-butoxy, tert-butoxy, isobutoxy, n-pentoxy, isopentyloxy, n-hexyloxy and n-heptoxy.
在第二方面，本发明提供了一种用于氢甲酰化制备醛的催化剂组合物，包括第一方面所述的膦配体化合物和铑金属化合物。In the second aspect, the present invention provides a catalyst composition for hydroformylation to prepare aldehydes, comprising the phosphine ligand compound and rhodium metal compound described in the first aspect.
根据本发明的一些实施方式，所述铑金属化合物的结构如式(B)所示：According to some embodiments of the present invention, the structure of the rhodium metal compound is shown in formula (B):
Rh(L1)x(L2)y(L3)z (B)Rh(L 1 ) x (L 2 ) y (L 3 ) z (B)
其中，L1、L2和L3各自独立地选自氢、CO、卤素、三苯基膦和乙酰丙酮；x、y和z各自独立地选自0到5的整数，x、y和z中至少一个不为0。Wherein, L 1 , L 2 and L 3 are each independently selected from hydrogen, CO, halogen, triphenylphosphine and acetylacetone; x, y and z are each independently selected from integers from 0 to 5, and x, y and z At least one of them is not 0.
根据本发明的一些实施方式，所述卤素选自氟、氯、溴和碘，优选为氯。According to some embodiments of the present invention, the halogen is selected from fluorine, chlorine, bromine and iodine, preferably chlorine.
根据本发明的一些实施方式，以金属铑计，所述膦配体与所述铑金属化合物的摩尔比为0.5:1-200:1，例如可以为0.5:1、1:1、5:1、10:1、20:1、50:1、100:1、120:1、150:1、180:1、200:1以及它们之间的任意值。According to some embodiments of the present invention, based on metal rhodium, the molar ratio of the phosphine ligand to the rhodium metal compound is 0.5:1-200:1, for example, it can be 0.5:1, 1:1, 5:1 , 10:1, 20:1, 50:1, 100:1, 120:1, 150:1, 180:1, 200:1 and any value in between.
根据本发明的一些实施方式，以金属铑计，所述膦配体与所述铑金属化合物的摩尔比为1:1-100:1。According to some embodiments of the present invention, based on rhodium metal, the molar ratio of the phosphine ligand to the rhodium metal compound is 1:1-100:1.
根据本发明的优选实施方式，以金属铑计，所述膦配体与所述铑金属化合物的摩尔比为2:1-50:1。According to a preferred embodiment of the present invention, based on rhodium metal, the molar ratio of the phosphine ligand to the rhodium metal compound is 2:1-50:1.
本发明所提供的组合物，引入具有聚乙二醇氨基单元的双膦配体，与铑金属化合物联合使用，可以提高氢甲酰化反应的反应活性，而且该组合物在氢甲酰化反应结束后还有很好的回收效果，分离的催化剂可以循环利用。The composition provided by the present invention introduces a bisphosphine ligand with a polyethylene glycol amino unit, and is used in conjunction with a rhodium metal compound to improve the reactivity of the hydroformylation reaction, and the composition can be used in the hydroformylation reaction There is also a good recovery effect after the end, and the separated catalyst can be recycled.
本发明提供的组合物用于均相催化氢甲酰化制备醛时能够显著提高反应活性，同时还能够高效分离回收。因此，在第三方面，本发明提供了一种氢甲酰化制备醛的方法，包括使烯烃原料和根据第二方面所述的催化剂组合物在有机溶剂存在的条件下与一氧化碳和氢气接触，以生成醛。When the composition provided by the invention is used for homogeneous catalytic hydroformylation to prepare aldehydes, the reaction activity can be significantly improved, and at the same time, it can be separated and recovered efficiently. Therefore, in a third aspect, the present invention provides a method for preparing aldehydes by hydroformylation, comprising contacting an olefin feedstock and the catalyst composition according to the second aspect with carbon monoxide and hydrogen in the presence of an organic solvent, to form aldehydes.
根据本发明的一些实施方式，所述烯烃为C2-C12烯烃。According to some embodiments of the present invention, the olefin is a C 2 -C 12 olefin.
根据本发明的优选实施方式，所述烯烃为C5-C12烯烃。According to a preferred embodiment of the present invention, the olefin is a C 5 -C 12 olefin.
根据本发明的进一步优选实施方式，所述烯烃为C6-C10烯烃。According to a further preferred embodiment of the present invention, the olefin is a C 6 -C 10 olefin.
根据本发明的一些实施方式，所述氢甲酰化反应在有机溶剂中进行，所述有机溶剂包括脂族烃类化合物和芳烃类化合物中的至少一种。According to some embodiments of the present invention, the hydroformylation reaction is performed in an organic solvent, and the organic solvent includes at least one of aliphatic hydrocarbon compounds and aromatic hydrocarbon compounds.
根据本发明的一些实施方式，所述脂族烃类化合物包括C4-C10的醛、C4-C10的酮和C4-C10的烷烃中的至少一种。According to some embodiments of the present invention, the aliphatic hydrocarbon compound includes at least one of C 4 -C 10 aldehydes, C 4 -C 10 ketones and C 4 -C 10 alkanes.
根据本发明的一些实施方式，所述芳烃类化合物包括乙酰苯、甲苯、二甲苯和氯苯中的至少一种。According to some embodiments of the present invention, the aromatic hydrocarbon compound includes at least one of acetophenone, toluene, xylene and chlorobenzene.
根据本发明的一些实施方式，以金属铑计，所述铑金属化合物的加入量为0.1-10mmol/L，例如可以为0.1mmol/L、0.25mmol/L、0.5mmol/L、1mmol/L、1.5mmol/L、2mmol/L、3mmol/L、4mmol/L、5mmol/L、6mmol/L、7mmol/L、8mmol/L、9mmol/L、10mmol/L以及它们之间的任意值。According to some embodiments of the present invention, in terms of rhodium metal, the added amount of the rhodium metal compound is 0.1-10mmol/L, such as 0.1mmol/L, 0.25mmol/L, 0.5mmol/L, 1mmol/L, 1.5mmol/L, 2mmol/L, 3mmol/L, 4mmol/L, 5mmol/L, 6mmol/L, 7mmol/L, 8mmol/L, 9mmol/L, 10mmol/L and any value between them.
根据本发明的一些实施方式，以金属铑计，所述铑金属化合物的加入量为0.2-5mmol/L。According to some embodiments of the present invention, based on rhodium metal, the added amount of the rhodium metal compound is 0.2-5 mmol/L.
根据本发明的一些实施方式，所述烯烃和所述催化剂组合物中铑的摩尔比例为(500-100000):1，例如可以是500:1、1000:1、2000:1、5000:1、8000:1、10000:1、20000:1、50000:1、80000:1、100000:1以及它们之间的任意值。According to some embodiments of the present invention, the molar ratio of rhodium in the olefin and the catalyst composition is (500-100000):1, for example, it can be 500:1, 1000:1, 2000:1, 5000:1, 8000:1, 10000:1, 20000:1, 50000:1, 80000:1, 100000:1 and any value in between.
根据本发明的优选实施方式，所述烯烃和所述催化剂组合物中铑的摩尔比例为为(1000-10000):1。According to a preferred embodiment of the present invention, the molar ratio of rhodium in the olefin to the catalyst composition is (1000-10000):1.
根据本发明的进一步优选实施方式，所述烯烃和所述催化剂组合物中铑的摩尔比例为(2000-8000):1。According to a further preferred embodiment of the present invention, the molar ratio of rhodium in the olefin to the catalyst composition is (2000-8000):1.
根据本发明的一些实施方式，所述接触的温度为50℃-120℃，例如可以是50℃、55℃、60℃、65℃、70℃、75℃、80℃、85℃、90℃、100℃、110℃、120℃以及它们之间的任意值。According to some embodiments of the present invention, the contacting temperature is 50°C-120°C, such as 50°C, 55°C, 60°C, 65°C, 70°C, 75°C, 80°C, 85°C, 90°C, 100°C, 110°C, 120°C and any value between them.
根据本发明的优选实施方式，所述接触的温度为80℃-100℃。According to a preferred embodiment of the present invention, the contacting temperature is 80°C-100°C.
根据本发明的一些实施方式，所述接触的压力为0.1MPa-10MPa，例如可以是例如0.1MPa、0.5MPa、1.0MPa、1.5MPa、2.0MPa、2.5MPa、3.0MPa、3.5MPa、4.0MPa、4.5MPa、5.0MPa、6.0MPa、7.0MPa、8.0MPa、9.0MPa、10MPa以及它们之间的任意值。According to some embodiments of the present invention, the contact pressure is 0.1MPa-10MPa, such as 0.1MPa, 0.5MPa, 1.0MPa, 1.5MPa, 2.0MPa, 2.5MPa, 3.0MPa, 3.5MPa, 4.0MPa, 4.5MPa, 5.0MPa, 6.0MPa, 7.0MPa, 8.0MPa, 9.0MPa, 10MPa and any value between them.
根据本发明的优选实施方式，所述接触的压力为0.1MPa-4MPa。According to a preferred embodiment of the present invention, the contact pressure is 0.1MPa-4MPa.
根据本发明的一些实施方式，所述接触的时间为1小时-8小时。According to some embodiments of the present invention, the contact time is 1 hour to 8 hours.
根据本发明的优选实施方式，所述接触的时间为2小时-5小时。According to a preferred embodiment of the present invention, the contact time is 2 hours to 5 hours.
根据本发明的一些实施方式，所述方法还包括：在所述接触之前，所述烯烃与所述催化剂组合物进行预混合。According to some embodiments of the present invention, the method further comprises: prior to the contacting, the olefin is premixed with the catalyst composition.
根据本发明的一些实施方式，所述预混合时间为小于10min。According to some embodiments of the present invention, the premixing time is less than 10 minutes.
根据本发明的优选实施方式，所述预混合时间为小于5min。According to a preferred embodiment of the present invention, the pre-mixing time is less than 5 minutes.
根据本发明的进一步优选实施方式，所述预混合时间为1-3min。According to a further preferred embodiment of the present invention, the pre-mixing time is 1-3 minutes.
本发明通过引入含有聚乙二醇氨基的膦配体，与铑金属化合物联合使用，提高了氢甲酰化反应的反应活性，而且该组合物在氢甲酰化反应结束后还有很好的回收效果，分离的催化剂可以循环利用，降低生产成本，有利于工业化生产应用。The present invention improves the reactivity of the hydroformylation reaction by introducing a phosphine ligand containing a polyethylene glycol amino group and using it in conjunction with a rhodium metal compound, and the composition has a good performance after the hydroformylation reaction is completed. The recovery effect, the separated catalyst can be recycled, the production cost is reduced, and it is beneficial to the application of industrial production.
具体实施方式detailed description
下列实施例仅用于对本发明进行详细说明，但应理解的是本发明的范围并不限于这些实施例。The following examples are only used to illustrate the present invention in detail, but it should be understood that the scope of the present invention is not limited to these examples.
制备例1Preparation Example 1
实施例1中所用含有聚乙二醇氨基的膦配体的合成路线如下：The synthetic route of the phosphine ligand that contains polyethylene glycol amino used in embodiment 1 is as follows:
(1)化合物I制备：(1) Preparation of compound I:
参照中国专利CN111440087A。With reference to Chinese patent CN111440087A.
称取一定量五乙二醇单甲醚于圆底烧瓶中，加入干燥的二氯甲烷，将装有混合液的圆底烧瓶置于冰水浴中，在搅拌的条件下分别逐滴加入三苯基膦、N-羟基邻苯二甲酰亚胺(NHPI)、偶氮二甲酸二异丙酯(DIAD)，在室温条件下搅拌12小时。反应结束后减压浓缩除去挥发物，剩余物质放入真空干燥箱至质量不发生变化。取出干燥后的物质，将其溶解在氨-甲醇溶液中，搅拌溶解，待溶解完全后升温至40℃，反应12小时。反应结束后除去溶剂，将剩余物溶于二氯甲烷中，抽滤，滤饼用二氯甲烷洗涤，合并滤液，调节滤液的pH值至4.0左右，静置分层，分离水相，水相以二氯甲烷洗涤。然后再往水相中缓慢滴加饱和碳酸钠溶液调节溶液pH至9.0左右，再用二氯甲烷萃取三次，合并有机相，并用无水硫酸镁干燥，抽滤，减压浓缩得化合物Ⅰ。Weigh a certain amount of pentaethylene glycol monomethyl ether into a round-bottomed flask, add dry dichloromethane, place the round-bottomed flask containing the mixed solution in an ice-water bath, and add triphenylene glycol dropwise under stirring conditions. phosphine, N-hydroxyphthalimide (NHPI), diisopropyl azodicarboxylate (DIAD), and stirred at room temperature for 12 hours. After the reaction was completed, the volatiles were removed by concentration under reduced pressure, and the remaining substances were put into a vacuum drying oven until the quality did not change. Take out the dried substance, dissolve it in ammonia-methanol solution, stir to dissolve, after the dissolution is complete, raise the temperature to 40°C, and react for 12 hours. After the reaction, remove the solvent, dissolve the residue in dichloromethane, filter with suction, wash the filter cake with dichloromethane, combine the filtrate, adjust the pH value of the filtrate to about 4.0, let stand and separate the water phase, and the water phase Wash with dichloromethane. Then slowly add saturated sodium carbonate solution dropwise to the water phase to adjust the pH of the solution to about 9.0, then extract three times with dichloromethane, combine the organic phases, dry over anhydrous magnesium sulfate, suction filter, and concentrate under reduced pressure to obtain compound I.
(2)2,7-双溴-9,9-二甲基氧杂蒽制备：(2) Preparation of 2,7-bisbromo-9,9-dimethylxanthene:
参考文献Tetrahedron 60(2004)4079–4085。References Tetrahedron 60 (2004) 4079–4085.
将Br2加入冰醋酸中，然后在0℃条件下缓慢加入到9,9-二甲基氧杂蒽的乙酸酐溶液中。滴加完成后将溶液加热至室温，搅拌2小时，然后将溶液倒入过量的冰水中，过滤收集沉淀物。用硫酸氢钠(10％水溶液)和水洗涤白色固体，真空干燥，得到2,7-双溴-9,9-二甲基氧杂蒽。Add Br2 into glacial acetic acid , and then slowly add it to 9,9-dimethylxanthene in acetic anhydride solution at 0°C. After the dropwise addition, the solution was heated to room temperature and stirred for 2 hours, then the solution was poured into excess ice water, and the precipitate was collected by filtration. The white solid was washed with sodium bisulfate (10% in water) and water, and dried in vacuo to give 2,7-dibromo-9,9-dimethylxanthene.
(3)化合物II制备：(3) Preparation of Compound II:
氮气保护下，将2,7-双溴-9,9-二甲基氧杂蒽、化合物I和叔丁醇钠在搅拌下依次加入二甲苯中，混合均匀后加入双(三叔丁基膦)钯(BTP)，加热回流8h。反应结束后降温，抽滤用氯仿洗涤滤饼，收集滤液，使用饱和盐水洗涤有机相后用在有机相中加入无水硫酸镁浸泡除水，浸泡一晚上后过滤，将滤液在真空条件下旋蒸浓缩，用硅胶层析柱分离回收产物。Under the protection of nitrogen, add 2,7-bisbromo-9,9-dimethylxanthene, compound I and sodium tert-butoxide into xylene in turn under stirring, and add bis(tri-tert-butylphosphine ) Palladium (BTP), heated to reflux for 8h. Cool down after the reaction is over, wash the filter cake with chloroform for suction filtration, collect the filtrate, wash the organic phase with saturated brine, soak the organic phase with anhydrous magnesium sulfate to remove water, soak for one night and then filter, and spin the filtrate under vacuum conditions After evaporation and concentration, the product was separated and recovered by silica gel chromatography.
(4)化合物III制备：(4) Preparation of compound III:
先将化合物II溶解于冰醋酸中，然后在一定时间内内逐滴加入Br2。将混合物在50℃条件下搅拌20小时，冷却至室温，在反应瓶中加入水。连续低速加入K2CO3溶液。混合物经CH2Cl2萃取，有机相使用无水硫酸镁干燥，过滤成粗料后用四氢呋喃和乙醇重结晶得到化合III。Compound II was first dissolved in glacial acetic acid, and then Br 2 was added dropwise within a certain period of time. The mixture was stirred at 50° C. for 20 hours, cooled to room temperature, and water was added to the reaction flask. The K2CO3 solution was added continuously at low speed. The mixture was extracted with CH 2 Cl 2 , the organic phase was dried over anhydrous magnesium sulfate, filtered into a crude material and recrystallized from THF and ethanol to obtain compound III.
(5)化合物V制备：(5) Preparation of compound V:
在-50℃和氮气保护下将一定量的中间产物III与干燥的THF放入反应釜中，逐滴加入2.5M正丁基锂的己烷溶液，滴加完成后与-50℃下继续搅拌2h，生成沉淀。降低温度至-70℃，加入化合物IV的甲苯溶液，搅拌1h，将温度升至室温，然后减压蒸发，将蒸发残余物溶于二氯甲烷，再次蒸发，在搅拌的条件下加己烷。生成的固体从热甲醇中重结晶，得到目标产物。1H NMR(CDCl3):δ＝7.28(m,8H),6.66(s,2H),6.55(s,2H),6.27(m,8H),3.46(m,4H),3.54–3.73(m,36H),3.30(s,6H),.1.72(s,6H).Put a certain amount of intermediate product III and dry THF into the reactor at -50°C under the protection of nitrogen, add 2.5M n-butyllithium hexane solution dropwise, and continue stirring at -50°C after the addition is complete 2h, a precipitate was formed. Lower the temperature to -70°C, add a toluene solution of compound IV, stir for 1 h, raise the temperature to room temperature, then evaporate under reduced pressure, dissolve the evaporation residue in dichloromethane, evaporate again, and add hexane while stirring. The resulting solid was recrystallized from hot methanol to give the desired product. 1 H NMR (CDCl3): δ=7.28(m,8H),6.66(s,2H),6.55(s,2H),6.27(m,8H),3.46(m,4H),3.54–3.73(m, 36H), 3.30(s,6H), .1.72(s,6H).
制备例2Preparation example 2
对比例1中所用膦配体的合成路线如下：The synthetic route of phosphine ligand used in comparative example 1 is as follows:
在-50℃和氮气保护下将一定量的4,5-二溴-9,9-二甲基氧杂蒽与干燥的THF放入反应釜中，逐滴加入2.5M正丁基锂的己烷溶液，滴加完成后于-50℃下继续搅拌2h，生成沉淀。降低温度至-70℃，加入化合物IV的甲苯溶液，搅拌1h，将温度升至室温，然后减压蒸发，将蒸发残余物溶于二氯甲烷，再次蒸发，在搅拌的条件下加己烷。生成的固体从热甲醇中重结晶，得到目标产物。1H NMR(CDCl3):δ＝7.30(m,8H),7.28(dd,J＝7.8,1.0Hz,2H),7.16(dd,J＝7.4,1.4Hz,2H),7.09(t,J＝7.7Hz,2H),6.28(m,8H),1.71(s,6H),.Put a certain amount of 4,5-dibromo-9,9-dimethylxanthene and dry THF into the reaction kettle at -50°C under the protection of nitrogen, and add 2.5M n-butyl lithium in hexyl After the dropwise addition was completed, the mixture was continuously stirred at -50°C for 2 h to form a precipitate. Lower the temperature to -70°C, add a toluene solution of compound IV, stir for 1 h, raise the temperature to room temperature, then evaporate under reduced pressure, dissolve the evaporation residue in dichloromethane, evaporate again, and add hexane while stirring. The resulting solid was recrystallized from hot methanol to give the desired product. 1 H NMR (CDCl 3 ): δ=7.30(m,8H),7.28(dd,J=7.8,1.0Hz,2H),7.16(dd,J=7.4,1.4Hz,2H),7.09(t,J ＝7.7Hz, 2H), 6.28(m, 8H), 1.71(s, 6H),.
实施例1Example 1
采用乙酰丙酮二羰基铑为主催化剂，制备例1制备的含有聚乙二醇氨基的膦配体(其中m＝n＝5)为配体，主催化剂(以铑计)与配体的摩尔比为1:5，以总的摩尔数计，1-辛烯：Rh的摩尔比为10000:1，Rh的浓度为1.6mmol/L。氢甲酰化反应装置采用50mL高压釜反应装置。将密闭的反应系统用N2吹扫后，用合成气(CO:H2＝1:1)置换数次并打开系统的温控系统以维持整个系统的温度为80℃，将放空阀打开，然后迅速将催化剂的甲苯溶液加入到反应釜内，然后将1-辛烯加入到反应釜内。将放空阀关闭，预混合搅拌2min，设定压力为2MPa，向其中通入合成气体(CO:H2＝1:1)进行反应，反应2h，降温至20℃以下后泄压，通过高压釜底阀将反应液放入分离器分液，下层为催化剂层，上层为有机产品层。有机产品层通过气相色谱分析，1-辛烯转化率为95.4％，醛选择性为95.0％，正异比(直链醛/支链醛)为204。ICP分析金属铑在有机产品层的含量为2.04ppm。Adopt rhodium acetylacetonate dicarbonyl as the main catalyst, the phosphine ligand (wherein m=n=5) containing polyethylene glycol amino prepared by Preparation Example 1 is the ligand, the mol ratio of the main catalyst (in rhodium) and the ligand 1:5, in terms of total moles, the molar ratio of 1-octene:Rh is 10000:1, and the concentration of Rh is 1.6mmol/L. The hydroformylation reaction device adopts a 50mL autoclave reaction device. After purging the closed reaction system with N 2 , replace it with synthesis gas (CO:H 2 =1:1) several times and open the temperature control system of the system to maintain the temperature of the whole system at 80°C, open the vent valve, Then quickly add the toluene solution of the catalyst into the reactor, and then add 1-octene into the reactor. Close the vent valve, pre-mix and stir for 2 minutes, set the pressure at 2MPa, feed synthesis gas (CO:H 2 =1:1) into it for reaction, react for 2 hours, release the pressure after cooling down to below 20°C, and pass through the autoclave The bottom valve puts the reaction liquid into the separator for liquid separation, the lower layer is the catalyst layer, and the upper layer is the organic product layer. The organic product layer was analyzed by gas chromatography. The 1-octene conversion rate was 95.4%, the aldehyde selectivity was 95.0%, and the anisotropic ratio (linear aldehyde/branched aldehyde) was 204. ICP analysis metal rhodium content in the organic product layer is 2.04ppm.
实施例2Example 2
实验方法同实施例1，其中含有聚乙二醇氨基的膦配体结构改变(式(A)结构的化合物，其中m＝3，其余结构不变)，其余实验条件不变，1-辛烯转化率为93.0％，醛选择性为93.8％，正异比(直链醛/支链醛)为147，ICP分析金属铑在有机产品层的含量为37.6ppm。The experimental method is the same as in Example 1, wherein the structure of the phosphine ligand containing polyethylene glycol amino groups is changed (the compound of the formula (A) structure, wherein m=3, and the rest of the structure is unchanged), and the rest of the experimental conditions are unchanged. 1-octene The conversion rate is 93.0%, the aldehyde selectivity is 93.8%, the isotropic ratio (linear aldehyde/branched aldehyde) is 147, and the content of metal rhodium in the organic product layer by ICP analysis is 37.6ppm.
实施例3Example 3
实验方法同实施例1，其中含有聚乙二醇氨基的膦配体结构改变(式(A)结构的化合物，其中m＝1，其余结构不变)，其余实验条件不变，1-辛烯转化率为91.3％，醛选择性为91.9％，正异比(直链醛/支链醛)为106，反应液在分离器中没有明显分层。The experimental method is the same as in Example 1, wherein the structure of the phosphine ligand containing polyethylene glycol amino groups is changed (the compound of the formula (A) structure, wherein m=1, and the rest of the structure is unchanged), and the rest of the experimental conditions are unchanged. 1-octene The conversion rate was 91.3%, the aldehyde selectivity was 91.9%, the anisotropic ratio (linear aldehyde/branched aldehyde) was 106, and the reaction liquid had no obvious stratification in the separator.
实施例4Example 4
实施例4的实验方法同实施例1，其中将溶液中主催化剂(以铑计)与配体的摩尔比分别变为1:2，其余实验条件不变，1-辛烯转化率为83.2％，醛选择性为72.5％，正异比(直链醛/支链醛)为88，ICP分析金属铑在有机产品层的含量为2.96ppm。The experimental method of embodiment 4 is the same as that of embodiment 1, wherein the mol ratio of the main catalyst (in rhodium) and the ligand in the solution is changed to 1:2 respectively, and all the other experimental conditions are constant, and the conversion rate of 1-octene is 83.2%. , The aldehyde selectivity is 72.5%, and the normal ratio (linear aldehyde/branched aldehyde) is 88, and the content of ICP analysis metal rhodium in the organic product layer is 2.96ppm.
实施例5Example 5
实施例5的实验方法同实施例1，其中将溶液中主催化剂(以铑计)与配体的摩尔比变为1:30，其余实验条件不变，1-辛烯转化率为95.71％，醛选择性为96.2％，正异比为(直链醛/支链醛)224，ICP分析金属铑在有机产品层的含量为1.99ppm。The experimental method of embodiment 5 is the same as embodiment 1, wherein the mol ratio of procatalyst (in rhodium) and ligand in the solution is changed to 1:30, all the other experimental conditions are constant, 1-octene conversion rate is 95.71%, Aldehyde selectivity is 96.2%, positive isotropic ratio is (straight-chain aldehyde/branched-chain aldehyde) 224, and ICP analysis metal rhodium content in organic product layer is 1.99ppm.
实施例6Example 6
实施例6的实验方法同实施例1，其中将溶液中铑的浓度变为0.25mmol/L，其余实验条件不变，1-辛烯转化率为70.6％，醛选择性为87.3％，正异比(直链醛/支链醛)为166，ICP分析金属铑在有机产品层的含量为2.01pm。The experimental method of embodiment 6 is the same as that of embodiment 1, wherein the concentration of rhodium in the solution is changed to 0.25mmol/L, all the other experimental conditions are constant, the conversion rate of 1-octene is 70.6%, the aldehyde selectivity is 87.3%, and the iso-iso The ratio (straight-chain aldehyde/branched-chain aldehyde) is 166, and the content of metal rhodium in the organic product layer by ICP analysis is 2.01pm.
实施例7Example 7
实施例7的实验方法同实施例1，其中将溶液中铑的浓度变为2.5mmol/L，其余实验条件不变，1-辛烯转化率为96.0％，醛选择性为96.5％，正异比(直链醛/支链醛)为207，ICP分析金属铑在有机产品层的含量为2.13ppm。The experimental method of embodiment 7 is the same as that of embodiment 1, wherein the concentration of rhodium in the solution is changed to 2.5mmol/L, all the other experimental conditions are constant, the conversion rate of 1-octene is 96.0%, the aldehyde selectivity is 96.5%, and the iso-iso Ratio (straight-chain aldehyde/branched-chain aldehyde) is 207, and the content of ICP analysis metal rhodium in organic product layer is 2.13ppm.
对比例1Comparative example 1
实验方法同实施例1，不同之处仅在于所加膦配体为制备例2制备的不含聚乙二醇氨基侧链基团的化合物，其余实验条件不变，测试结果如下：1-辛烯转化率为63.8％，醛选择性为96.2％，正异比(直链醛/支链醛)为34.4，反应液在分离器中没有明显分层。The experimental method is the same as in Example 1, except that the added phosphine ligand is a compound that does not contain polyethylene glycol amino side chain groups prepared in Preparation Example 2, and all the other experimental conditions are unchanged. The test results are as follows: 1-octyl The olefin conversion rate is 63.8%, the aldehyde selectivity is 96.2%, the isotropic ratio (linear aldehyde/branched aldehyde) is 34.4, and the reaction liquid has no obvious stratification in the separator.
从对比例中可以看出，不含侧链的膦配体，催化剂反应活性略有降低，更重要的是反应结束后降温无法使催化剂分离。It can be seen from the comparative examples that without side-chain phosphine ligands, the reactivity of the catalyst is slightly reduced, and more importantly, the catalyst cannot be separated by cooling after the reaction.
应当注意的是，以上所述的实施例应用于解释本发明，并不构成对本发明的任何限制。通过参照上述典型实施例对本发明进行了描述，但应当理解为其中所所有的词语为描述性和解释性词汇，而不是限定性词汇。可以按照规定在本发明权利要求的范围内对本发明做出修改，以及在不背离本发明的范围和精神内对本发明进行修订。尽管其中描述的本发明涉及特定的方法、材料和实施例，但是并不意味着本发明限于其中公开的特定例，相反，本发明可扩展至其他所有具有相同功能的方法和应用。It should be noted that the above-mentioned embodiments are used to explain the present invention, and do not constitute any limitation to the present invention. The invention has been described with reference to the foregoing exemplary embodiments, but it should be understood that all words used therein are words of description and explanation rather than words of limitation. The present invention can be modified as prescribed within the scope of the claims of the present invention, and the present invention can be revised without departing from the scope and spirit of the present invention. Although the invention described therein refers to specific methods, materials and examples, it is not intended that the invention be limited to the specific examples disclosed therein, but rather, the invention extends to all other methods and applications having the same function.
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| US20120059195A1 (en) * | 2010-09-02 | 2012-03-08 | Lg Chem, Ltd. | Catalyst composition for hydroformylation reaction and hydroformylation process using the same |
| CN104822456A (en) * | 2012-12-04 | 2015-08-05 | 陶氏技术投资有限责任公司 | Bidentate ligands for hydroformylation of ethylene |
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| US20120059195A1 (en) * | 2010-09-02 | 2012-03-08 | Lg Chem, Ltd. | Catalyst composition for hydroformylation reaction and hydroformylation process using the same |
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