CN100404132C - 含磷催化剂组合物和使用该组合物的醛化方法 - Google Patents
含磷催化剂组合物和使用该组合物的醛化方法 Download PDFInfo
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- CN100404132C CN100404132C CNB2004800298617A CN200480029861A CN100404132C CN 100404132 C CN100404132 C CN 100404132C CN B2004800298617 A CNB2004800298617 A CN B2004800298617A CN 200480029861 A CN200480029861 A CN 200480029861A CN 100404132 C CN100404132 C CN 100404132C
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- carbon monoxide
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- carbonyl
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- 239000003054 catalyst Substances 0.000 title claims abstract description 48
- 238000007037 hydroformylation reaction Methods 0.000 title claims abstract description 18
- 238000000034 method Methods 0.000 title claims abstract description 13
- 230000008569 process Effects 0.000 title claims abstract description 7
- 229910052698 phosphorus Inorganic materials 0.000 title claims description 12
- 239000011574 phosphorus Substances 0.000 title claims description 12
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims description 7
- 239000000203 mixture Substances 0.000 title abstract description 13
- 239000003446 ligand Substances 0.000 claims abstract description 49
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 25
- 150000003624 transition metals Chemical class 0.000 claims abstract description 25
- -1 olefin compound Chemical class 0.000 claims abstract description 23
- 239000001257 hydrogen Substances 0.000 claims abstract description 17
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 17
- 150000001336 alkenes Chemical class 0.000 claims abstract description 15
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000007789 gas Substances 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims abstract description 6
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 5
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims abstract 2
- 239000010948 rhodium Chemical group 0.000 claims description 48
- GGRQQHADVSXBQN-FGSKAQBVSA-N carbon monoxide;(z)-4-hydroxypent-3-en-2-one;rhodium Chemical group [Rh].[O+]#[C-].[O+]#[C-].C\C(O)=C\C(C)=O GGRQQHADVSXBQN-FGSKAQBVSA-N 0.000 claims description 29
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 28
- 229910052799 carbon Inorganic materials 0.000 claims description 25
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 23
- FIQMHBFVRAXMOP-UHFFFAOYSA-N triphenylphosphane oxide Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)(=O)C1=CC=CC=C1 FIQMHBFVRAXMOP-UHFFFAOYSA-N 0.000 claims description 23
- 125000000217 alkyl group Chemical group 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 150000001875 compounds Chemical class 0.000 claims description 16
- 229910052703 rhodium Inorganic materials 0.000 claims description 15
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical group [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 15
- 125000003118 aryl group Chemical group 0.000 claims description 12
- 239000000460 chlorine Substances 0.000 claims description 11
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 10
- 150000002431 hydrogen Chemical class 0.000 claims description 9
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 9
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 8
- 125000003545 alkoxy group Chemical group 0.000 claims description 8
- 125000004453 alkoxycarbonyl group Chemical group 0.000 claims description 8
- 125000005161 aryl oxy carbonyl group Chemical group 0.000 claims description 8
- 229910052801 chlorine Inorganic materials 0.000 claims description 8
- 229910052741 iridium Chemical group 0.000 claims description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 8
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 claims description 7
- 230000014509 gene expression Effects 0.000 claims description 7
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical group [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 7
- 150000008300 phosphoramidites Chemical class 0.000 claims description 7
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 7
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052794 bromium Inorganic materials 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 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
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 6
- 229910017052 cobalt Inorganic materials 0.000 claims description 5
- 239000010941 cobalt Substances 0.000 claims description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical group [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 5
- 150000003233 pyrroles Chemical class 0.000 claims description 5
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims description 4
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims description 4
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 4
- 239000005864 Sulphur Chemical group 0.000 claims description 4
- 125000004448 alkyl carbonyl group Chemical group 0.000 claims description 4
- 125000003368 amide group Chemical group 0.000 claims description 4
- 125000005129 aryl carbonyl group Chemical group 0.000 claims description 4
- 125000004104 aryloxy group Chemical group 0.000 claims description 4
- 150000001924 cycloalkanes Chemical class 0.000 claims description 4
- 229910052731 fluorine Inorganic materials 0.000 claims description 4
- 239000011737 fluorine Substances 0.000 claims description 4
- 125000005843 halogen group Chemical group 0.000 claims description 4
- 125000001072 heteroaryl group Chemical group 0.000 claims description 4
- 150000002475 indoles Chemical class 0.000 claims description 4
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 claims description 4
- RRKODOZNUZCUBN-CCAGOZQPSA-N (1z,3z)-cycloocta-1,3-diene Chemical compound C1CC\C=C/C=C\C1 RRKODOZNUZCUBN-CCAGOZQPSA-N 0.000 claims description 2
- OJOWICOBYCXEKR-KRXBUXKQSA-N (5e)-5-ethylidenebicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(=C/C)/CC1C=C2 OJOWICOBYCXEKR-KRXBUXKQSA-N 0.000 claims description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical group CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 claims description 2
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 claims description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 2
- JVJQPDTXIALXOG-UHFFFAOYSA-N nitryl fluoride Chemical compound [O-][N+](F)=O JVJQPDTXIALXOG-UHFFFAOYSA-N 0.000 claims 2
- 230000003197 catalytic effect Effects 0.000 abstract description 29
- 150000001299 aldehydes Chemical class 0.000 description 24
- 230000000052 comparative effect Effects 0.000 description 18
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 14
- 229910052751 metal Inorganic materials 0.000 description 12
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 11
- 239000002184 metal Substances 0.000 description 11
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 8
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 5
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 150000001491 aromatic compounds Chemical class 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- AMIMRNSIRUDHCM-UHFFFAOYSA-N Isopropylaldehyde Chemical compound CC(C)C=O AMIMRNSIRUDHCM-UHFFFAOYSA-N 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000013537 high throughput screening Methods 0.000 description 2
- 229940043265 methyl isobutyl ketone Drugs 0.000 description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 125000001462 1-pyrrolyl group Chemical group [*]N1C([H])=C([H])C([H])=C1[H] 0.000 description 1
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 1
- 206010011224 Cough Diseases 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000005575 aldol reaction Methods 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N dimethylmethane Natural products CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002527 isonitriles Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000036963 noncompetitive effect Effects 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- AUONHKJOIZSQGR-UHFFFAOYSA-N oxophosphane Chemical compound P=O AUONHKJOIZSQGR-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical compound [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 1
Classifications
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- 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
- B01J31/185—Phosphites ((RO)3P), their isomeric phosphonates (R(RO)2P=O) and RO-substitution derivatives thereof
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
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- 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
- B01J31/185—Phosphites ((RO)3P), their isomeric phosphonates (R(RO)2P=O) and RO-substitution derivatives thereof
- B01J31/186—Mono- or diamide derivatives thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
- B01J31/1865—Phosphonites (RP(OR)2), their isomeric phosphinates (R2(RO)P=O) and RO-substitution derivatives thereof
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- 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
- B01J31/1875—Phosphinites (R2P(OR), their isomeric phosphine oxides (R3P=O) and RO-substitution derivatives thereof)
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/20—Carbonyls
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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
- B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
- B01J31/2234—Beta-dicarbonyl ligands, e.g. acetylacetonates
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Abstract
本发明提供包括二齿配体、单齿配体和过渡金属催化剂的催化剂组合物,以及包括在上述催化剂组合物存在下、在高压和高温搅拌下烯烃化合物与氢气和一氧化碳的气体混合物反应生成醛的烯烃醛化方法。本发明的催化组合物表现出高催化活性、正醛对异醛的高选择性和高稳定性。
Description
技术领域
本发明涉及含磷催化剂组合物和使用该组合物的醛化方法,并且更具体而言,涉及其中单配位基磷化合物和二配位基磷化合物组合用作过渡金属催化剂的配体的含磷催化剂组合物,以及包括在上述催化剂组合物存在下、在高压和高温搅拌下,烯烃化合物与氢气和一氧化碳的气体混合物反应生成醛的烯烃化合物的醛化方法。
背景技术
醛化反应也称作羰基合成(Otto Roelen于1938年发现),该反应包括:在金属催化剂和配体存在下,烯烃与合成气(CO/H2)反应,生成比烯烃多一个碳原子的直链(正)醛和支链(异)醛。在2001年,全世界通过羰基合成生产了约8,400,000吨的各种醛(包括其醇衍生物)(SRIReport,November 2002,682.700A)。按照羰基合成制备的各种醛通过氧化和还原反应转化为酸和醇。醛可进行醛醇缩合反应,然后通过氧化和还原反应转化为长烷基链的酸和醇。所得到的酸和醇用作溶剂、添加剂、各种增塑剂的原料等。
在羰基合成中使用的催化剂主要基于钴(Co)或铑(Rh)金属。取决于配体的种类和操作条件,得到醛的不同N/I(直链(正)同分异构体与支链(异)同分异构体之比)选择性。
除钴(Co)或铑(Rh)之外,铱(Ir)、钌(Ru)、锇(Os)、铂(Pt)、钯(Pd)、铁(Fe)、和镍(Ni)可用作羰基合成的催化剂中的中心金属。这些金属络合物的催化活性可如下排序:Rh>>Co>Ir,Ru>Os>Pt>Pd>Fe>Ni。因此,大多数的研究和开发已集中于铑和钴。催化剂中配体的例子可包括膦(PR3,R=C6H5,n-C4H9)、氧化膦(O=P(C6H5)3)、亚磷酸盐、胺、酰胺、和异腈。鉴于催化活性、稳定性和成本,很少有配体比三苯膦(TPP)更具优势。因此,在大多数的羰基合成中,Rh金属用作催化剂和TPP用作配体。另外,为提高催化体系的稳定性,TPP配体以至少100当量的催化剂的量使用。
柯达公司(Eastman Kodak Company)和联合碳化公司(UnionCarbide Company)(并入Dow)开发了分别具有高催化活性和高N/I选择性的二齿膦配体(参见美国专利第4,694,109和4,668,651号)。
Moloy与同事开发了表现出高活性和选择性的N-吡咯基膦(JACS1995,117,7696)。
美国专利第5,710,344号描述了一种采用包含至少一个P-C或P-N键的二齿配体通过醛化制备直链醛的方法。
发明内容
技术目的
本发明提供一种醛化催化剂组合物,包括二齿配体、单齿配体和过渡金属催化剂,其具有较高的催化活性,同时保持与在单独使用二齿配体的情况下对正醛或异醛(N/I选择性)相同的选择性,并使催化体系稳定。
本发明还提供一种烯烃化合物的醛化方法,包括在上述催化剂组合物存在下、在高压和高温搅拌下烯烃化合物与氢气和一氧化碳的气体混合物反应生成醛。
技术方案
根据本发明的技术方案,提供包括通式1表示的二齿配体、通式2表示的单齿配体、和通式3表示的过渡金属催化剂的催化剂组合物:
其中,R1和R2各为取代或未取代的C1-20的烷基、取代或未取代的C1-20的烷氧基、取代或未取代的C5-20的环烷或环烯、取代或未取代的C6-36的芳基、取代或未取代的C1-20的杂烷基、取代或未取代的C4-36的杂芳基、或取代或未取代的C4-36的杂环基,
Ar1-Ar2是二芳基化合物,和
X是氧(O)或硫(S);
其中,R3、R4和R5各为取代或未取代的C1-20的烷基、取代或未取代的C1-20的烷氧基、取代或未取代的C5-20的环烷或环烯、取代或未取代的C6-36的芳基、取代或未取代的C1-20的杂烷基、取代或未取代的C4-36的杂芳基、或取代或未取代的C4-36的杂环基;各R3、R4和R5上非必要地被硝基(-NO2)、氟(F)、氯(Cl)、溴(Br)、或C1-4的烷基取代,和
Y是氧(O)或硫(S);
M(L1)l(L2)m(L3)n ...(3)
其中,M是过渡金属,
L1、L2和L3各为氢、CO、乙酰丙酮、环辛二烯、降冰片烯、氯、或三苯膦,和
l、m和n各为0~5的数字,条件是所有的l、m和n不同时为零。
根据本发明的另一技术方案,提供一种烯烃醛化的方法,包括在上述催化剂组合物存在下、在高压和高温搅拌下烯烃化合物与氢气和一氧化碳的气体混合物反应生成醛。
烯烃化合物可由通式4表示:
其中,R6和R7各为氢、C1-20的烷基、氟(-F)、氯(-Cl)、溴(-Br)、三氟甲基(-CF3)、或被0~5个选自包括硝基(-NO2)、氟(-F)、氯(-Cl)、溴(-Br)、甲基、乙基、丙基和丁基的组的取代基取代的C6-20的苯基。
有益效果
根据本发明的实施方案,采用包括单齿和二齿磷配体的催化剂组合物的烯烃醛化的方法,可提高催化活性和稳定性,同时保持与在单独使用二齿配体的情况下对正或异醛(N/I选择性)相似的选择性。
具体实施方式
根据本发明的实施方案的催化剂组合物包括二齿配体、单齿配体和过渡金属催化剂。
通式1表示的二齿配体可以其中R1和R2各为吡咯、苯基或吲哚,且当R1和R2各为吡咯或吲哚时,磷直接与氮原子相连。
在通式1中,二芳基化合物Ar1-Ar2可由通式5或通式6表示:
其中,R8、R9、R10和R11各为氢、C1-20的烷基、C6-20的芳基、三芳基甲硅烷基、三烷基甲硅烷基、烷氧羰基(carboalkoxy group)、芳氧羰基(carboaryloxy group)、芳氧基、烷氧基、烷基羰基、芳基羰基、酰胺基、卤素原子或腈基,上述烷氧羰基和芳氧羰基由-CO2R表示(其中R分别为C1-20的烷基和C6-20的芳基);并且优选,R8可为甲基、甲氧基或叔丁基,R9可为氢,R10可为甲基、甲氧基或叔丁基,和R11可为甲基或氢;
其中,R12、R13、R14、R15、R16、和R17各为氢、C1-20的烷基、C6-20的芳基、三芳基甲硅烷基、三烷基甲硅烷基、烷氧羰基、芳氧羰基、芳氧基、烷氧基、烷基羰基、芳基羰基、酰胺基、卤素原子或腈基,上述烷氧羰基和芳氧羰基由-CO2R表示(其中R分别为C1-20的烷基和C6-20的芳基)。
通式2表示的单齿配位体可以为其中Y为氧(O),R3、R4和R5各为苯基、苯氧基(phenyloxy)、环己基、或叔丁基的化合物。
在过渡金属催化剂中,过渡金属M可以为钴(Co)、铑(Rh)或铱(Ir)。过渡金属催化剂具体的例子可包括乙酰丙酮二羰基铑(Rh(AcAc)(CO)2、乙酰丙酮羰基三苯膦铑(Rh(AcAc)(CO)(TPP))、氢化羰基三(三苯膦)铑(HRh(CO)(TPP)3)、乙酰丙酮二羰基铱(Ir(AcAc)(CO)2)、或氢化羰基三(三苯膦)铱(HIr(CO)(TPP)3)。
在催化剂组合物中,基于催化剂组合物的量,过渡金属的浓度可为50~500ppm。如果过渡金属的浓度低于50ppm,则会降低醛化反应的速度,这在商业上是不合要求的。如果过渡金属的浓度高于500ppm,则由于过渡金属很昂贵,所以在成本上不具竞争性。另外,即使在高于500ppm的浓度下,没有有利地提高反应速度。
根据本发明的实施方案,如果将单齿配体加入到包括Rh金属和二齿配体的催化剂组合物中,则在醛化反应中可提高催化活性,并具有由于包含二齿配体而带来的高N/I选择性。此外,即使加入过量的单齿配位体,仍不降低催化活性和N/I选择性,并可使催化体系稳定。显然这些优点源于单齿配体与催化剂的金属中心具有弱配位和单齿配体不干扰过渡金属和二齿配体之间的相互作用。
为了实现上述优点,每mol过渡金属,二齿配体的浓度为0.5~20mol,单齿配体的浓度为0.1~200mol。优选每mol过渡金属,二齿配体与Rh金属的摩尔比为1~10,单齿配体与Rh金属的摩尔比为0.5~100。如果二齿配体与Rh金属的摩尔比低于0.5,则催化稳定性可能降低。如果二齿配体与Rh金属的摩尔比高于20,则催化活性可能显著降低。如果单齿配体与Rh金属的摩尔比低于0.1,则不能提高催化活性。如果单齿配体与Rh金属的摩尔比高于200,则不经济。
有利的是,过渡金属催化剂可为乙酰丙酮二羰基铑(Rh(AcAc)(CO)2),二齿配体可为1,1’-二苯基-2,2’-二基-二(二吡咯基亚磷酰胺)(1,1’-biphenyl-2,2’-diyl-bis(dipyrrolylphosphoramidite)(BPO-P(Pyl)2),以及单齿配体可为氧化三苯膦(TPPO)。
烯烃化合物可以为选自包括乙烯、丙烯、1-丁烯、1-戊烯、1-己烯、1-辛烯和苯乙烯的组的化合物。
在根据本发明实施方案的醛化反应中使用的溶剂可包括:醛,如丙醛(propane aldehyde)、丁醛和戊醛;酮,如丙酮、甲基乙基酮、甲基异丁基酮、苯乙酮和环已酮;芳族化合物,如苯、甲苯和二甲苯;包括邻-二氯苯的卤代芳族化合物;醚,如四氢呋喃、二甲氧基乙烷、和二噁烷;包括二氯甲烷的卤代链烷烃;如庚烷的链烷烃;优选各种醛和如甲苯的芳族化合物。
在根据本发明实施方案的醛化反应中使用的合成气CO/H2的组成可在一个宽的范围内变化。CO/H2的摩尔比可为约5∶95~70∶30,优选约40∶60~60∶40,且最好为约1∶1。
醛化反应的温度可一般为约20~180℃,优选约50~150℃。醛化反应的压力可一般为约1~700巴,优选1~300巴。
实施本发明的实施例
下文,参考下面的实施例将更详细地说明本发明,但不企图限制本发明的范围。
实施例1~12:采用乙酰丙酮二羰基铑(Rh(AcAc)(CO)
2
)催化剂、二配
位基磷化合物和单配位基磷化合物的丙烯的醛化
将10.0mg(37.8mmol)的Rh(AcAc)(CO)2催化剂、0.2mL作为GC分析内标物的十六烷、二齿配体BPO-P(Pyl)2和单齿配体TPPO加入甲苯中,以使溶液的总量为100mL,二齿配体和单齿配体各自与铑的比例列于表1中,并装入反应器(高通过量过滤装置(High ThroughputScreening Unit)(HTS),由Auto Clave制造)中。将摩尔比为1∶1∶1的丙烯∶CO∶H2的气体混合物注入到反应器中,以保持反应器中的压力为6巴。然后,在85℃搅拌下该混合物进行反应2.5小时。
所采用的催化剂和配体、各配体与催化剂的摩尔比、反应温度、N/I选择性和催化活性在表1中列出。
在表1中,N/I值表示所制备的正-丁醛和异-丁醛的相对比。基于作为内标物加入的十六烷的量,通过GC分析得到各丁醛的产率。
为计算各反应的催化活性,制备的正丁醛和异丁醛的总量除以丁醛的分子量、催化剂的浓度和反应时间。催化活性表示为mol(BAL)/mol(Rh)/h。
表1
催化剂 | 配体1(L1) | 配体2(L2) | L1/Rh(mol/mol) | L2/Rh(mol/mol) | N/I | 催化活性(mol<sub>(BAL)</sub>/mol<sub>(Rh)</sub>h) | |
实施例1 | Rh(AcAc)(CO)<sub>2</sub> | BPO-P(Pyl)<sub>2</sub> | TPPO | 1 | 1 | 8.9 | 262.3 |
实施例2 | Rh(AcAc)(CO)<sub>2</sub> | BPO-P(Pyl)<sub>2</sub> | TPPO | 1 | 3 | 8.3 | 256.2 |
实施例3 | Rh(AcAc)(CO)<sub>2</sub> | BPO-P(Pyl)<sub>2</sub> | TPPO | 1 | 5 | 8.3 | 270.0 |
实施例4 | Rh(AcAc)(CO)<sub>2</sub> | BPO-P(Pyl)<sub>2</sub> | TPPO | 1 | 10 | 8.5 | 264.6 |
实施例5 | Rh(AcAc)(CO)<sub>2</sub> | BPO-P(Pyl)<sub>2</sub> | TPPO | 3 | 1 | 13.8 | 227.1 |
实施例6 | Rh(AcAc)(CO)<sub>2</sub> | BPO-P(Pyl)<sub>2</sub> | TPPO | 3 | 3 | 13.8 | 181.8 |
实施例7 | Rh(AcAc)(CO)<sub>2</sub> | BPO-P(Pyl)<sub>2</sub> | TPPO | 3 | 5 | 14.2 | 176.0 |
实施例8 | Rh(AcAc)(CO)<sub>2</sub> | BPO-P(Pyl)<sub>2</sub> | TPPO | 3 | 10 | 14.2 | 182.9 |
实施例9 | Rh(AcAc)(CO)<sub>2</sub> | BPO-P(Pyl)<sub>2</sub> | TPPO | 5 | 1 | 16.8 | 140.8 |
实施例10 | Rh(AcAc)(CO)<sub>2</sub> | BPO-P(Pyl)<sub>2</sub> | TPPO | 5 | 3 | 16.5 | 148.6 |
实施例11 | Rh(AcAc)(CO)<sub>2</sub> | BPO-P(Pyl)<sub>2</sub> | TPPO | 5 | 5 | 16.4 | 143.4 |
实施例12 | Rh(AcAc)(CO)<sub>2</sub> | BPO-P(Pyl)<sub>2</sub> | TPPO | 5 | 10 | 16.5 | 140.0 |
对比实施例1:采用乙酰丙酮二羰基铑(Rh(AcAc)(CO)
2
)催化剂和三苯
膦(TPP)的丙烯的醛化
除了TPP单独用作配体和配体与铑的摩尔比为100以外,以与实施例1相同的方式进行催化活性实验。结果在表2中示出。
对比实施例2:采用乙酰丙酮二羰基铑(Rh(AcAc)(CO)
2
)催化剂和三吡
咯基膦(P(Pyl)
3
)的丙烯的醛化
除了P(Pyl)3代替TPP用作配体和配体与铑的摩尔比为50以外,以与对比实施例1相同的方式进行催化活性实验。结果在表2中示出。
对比实施例3~5:采用乙酰丙酮二羰基铑(Rh(AcAc)(CO)
2
)催化剂和
1,1’-二苯基-2,2’-二基-二(二吡咯基亚磷酰胺)(BPO-P(Pyl)
2
)的丙烯的
醛化
除了BPO-P(Pyl)2代替TPP用作配体和配体与铑的摩尔比分别为1、3和5以外,以与对比实施例1相同的方式进行催化活性实验。结果在表2中示出。
对比实施例6:采用乙酰丙酮羰基三苯膦铑(Rh(AcAc)(CO)(TPP))催化
剂和1,1’-二苯基-2,2’-二基-二(二吡咯基亚磷酰胺)(BPO-P(Pyl)
2
)的丙
烯的醛化
除了用Rh(AcAc)(CO)(TPP)代替Rh(AcAc)(CO)2以外,以与对比实施例4相同的方式进行催化活性实验。结果在表2中示出。
表2
催化剂 | 配体(L) | L/Rhmol/mol | 温度(℃) | N/I | 催化活性(mol<sub>(BAL)</sub>/mol<sub>(Rh)</sub>/h) | |
对比实施例1 | Rh(AcAc)(CO)<sub>2</sub> | TPP | 100 | 85 | 3.9 | 85.4 |
对比实施例2 | Rh(AcAc)(CO)<sub>2</sub> | P(Pyl)<sub>3</sub> | 50 | 85 | 10.1 | 80.3 |
对比实施例3 | Rh(AcAc)(CO)<sub>2</sub> | BPO-P(Pyl)<sub>2</sub> | 1 | 85 | 8.7 | 227.3 |
对比实施例4 | Rh(AcAc)(CO)<sub>2</sub> | BPO-P(Pyl)<sub>2</sub> | 3 | 85 | 14.9 | 179.8 |
对比实施例5 | Rh(AcAc)(CO)<sub>2</sub> | BPO-P(Pyl)<sub>2</sub> | 5 | 85 | 15.2 | 147.4 |
对比实施例6 | Rh(AcAc)(CO)(TPP) | BPO-P(Pyl)<sub>2</sub> | 3 | 85 | 15.0 | 131.4 |
在对比实施例1和2中,采用单齿配体进行丙烯的醛化。如表2中所示,当TPP用作配体(对比实施例1)时,催化活性为85.4mol(BAL)/mol(Rh)/h,且N/I选择性为3.9。当三吡咯基膦(P(Pyl)3)用作配体(对比实施例2)时,催化活性略微低些,但正丁醛对异丁醛的选择性(N/I选择性为10.1)比使用TPP时稍微高些。
从对比实施例3~6可看到,当作为二齿配体的1,1’-二苯基-2,2’-二基-二(二吡咯基亚磷酰胺)(BPO-P(Pyl)2)用作配体时,催化活性和对正丁醛的选择性均比TPP或P(Pyl)3用作配体时高。另外,乙酰丙酮二羰基铑(Rh(AcAc)(CO)2)用作催化剂比乙酰丙酮羰基三苯膦铑(Rh(AcAc)(CO)(TPP))用作催化剂,提供更高的催化活性。
如表1中所示,除了TPPO作为单齿配体被加入到催化剂组合物中之外,实施例1~12以与对比实施例3~5相同的方式进行。下面说明实施例1~12的结果。
从实施例1~4可看出,当作为二齿配体的1,1’-二苯基-2,2’-二基-二(二吡咯基亚磷酰胺)(BPO-P(Pyl)2)以基于催化剂摩尔比为1使用,同时作为单齿位体的TPPO以递增的摩尔比加入到催化剂中时,在保持N/I选择性的同时催化活性提高了15~20%。从实施例5~12可看出,当二齿配体以至少3摩尔比使用时,在单齿配体TPPO与催化剂的各摩尔比下催化活性和N/I选择性均被保持,且使用廉价配体TPPO提高了催化剂体系的稳定性。即,即使过量的TPPO被加入到包括Rh催化剂和BPO-P(Pyl)2的催化体系中时,催化活性仍保持恒定或甚至稍稍提高,且N/I选择性保持恒定。
由上述结果可以证实,当将作为单齿配体的TPPO加入到包括作为催化剂的乙酰丙酮二羰基铑(Rh(AcAc)(CO)2)和作为二齿配体的1,1’-二苯基-2,2’-二基-二(二吡咯基亚磷酰胺)(BPO-P(Pyl)2)的催化剂体系中时,可提高催化活性约最大20%,同时保持N/I选择性。因此,可采用过量的相对便宜的TPPO以稳定的方式进行醛化反应。
工业实用性
根据本发明的实施方案,包括过渡金属催化剂和单配位基磷化合物与二配位基磷化合物的组合作为配体的催化剂组合物,可用于烯烃醛化的方法以制备醛。
Claims (13)
1.一种催化剂组合物,包括通式1表示的二齿配体、通式2表示的单齿配体和通式3表示的过渡金属催化剂:
其中,R1和R2各为取代或未取代的C1-20的烷基、取代或未取代的C1-20的烷氧基、取代或未取代的C5-20的环烷或环烯、取代或未取代的C6-36的芳基、取代或未取代的C1-20的杂烷基、取代或未取代的C4-36的杂芳基或取代或未取代的C4-36的杂环基,
Ar1-Ar2是二芳基化合物,和
X是氧或硫;
其中,R3、R4和R5各为取代或未取代的C1-20的烷基、取代或未取代的C1-20的烷氧基、取代或未取代的C5-20的环烷或环烯、取代或未取代的C6-36的芳基、取代或未取代的C1-20的杂烷基、取代或未取代的C4-36的杂芳基或取代或未取代的C4-36的杂环基,和
Y是氧或硫;
M(L1)l(L2)m(L3)n ...(3)
其中,M是过渡金属,
L1、L2和L3各为氢、CO、乙酰丙酮、环辛二烯、降冰片烯、氯或三苯膦,和
l、m和n各为0~5的数字,条件是所有的l、m和n不同时为零。
2.根据权利要求1所述的催化剂组合物,其中,通式2中的R3、R4和R5各被硝基、氟、氯、溴或C1-4的烷基取代。
3.根据权利要求1所述的催化剂组合物,其中,在通式1中,R1和R2各为吡咯、苯基或吲哚,且当R1和R2各为吡咯或吲哚时,磷直接与氮原子相连。
4.根据权利要求1所述的催化剂组合物,其中,在通式1中,二芳基化合物Ar1-Ar2由通式5或通式6表示:
其中,R8、R9、R10和R11各为氢、C1-20的烷基、C6-20的芳基、三芳基甲硅烷基、三烷基甲硅烷基、烷氧羰基、芳氧羰基、芳氧基、烷氧基、烷基羰基、芳基羰基、酰胺基、卤素原子或腈基;上述烷氧羰基和芳氧羰基由-CO2R表示,其中R分别为C1-20的烷基和C6-20的芳基;
其中,R12、R13、R14、R15、R16和R17各为氢、C1-20的烷基、C6-20的芳基、三芳基甲硅烷基、三烷基甲硅烷基、烷氧羰基、芳氧羰基、芳氧基、烷氧基、烷基羰基、芳基羰基、酰胺基、卤素原子或腈基;上述烷氧羰基和芳氧羰基由-CO2R表示,其中R分别为C1-20的烷基和C6-20的芳基。
5.根据权利要求4所述的催化剂组合物,其中,在通式5中,R8为甲基、甲氧基或叔丁基;R9为氢;R10为甲基、甲氧基或叔丁基;和R11为甲基或氢。
6.根据权利要求1所述的催化剂组合物,其中,在通式2中,Y为氧;R3、R4和R5各为苯基、苯氧基、环己基或叔丁基。
7.根据权利要求1所述的催化剂组合物,其中,在通式3中,过渡金属M为钴、铑或铱。
8.根据权利要求1所述的催化剂组合物,其中,过渡金属催化剂为乙酰丙酮二羰基铑、乙酰丙酮羰基三苯膦铑、氢化羰基三(三苯膦)铑、乙酰丙酮二羰基铱或氢化羰基三(三苯膦)铱。
9.根据权利要求1所述的催化剂组合物,其中,基于催化剂组合物的量,过渡金属的浓度为50~500ppm;及每mol过渡金属,二齿配体的浓度为0.5~20mol,单齿配体的浓度为0.1~200mol。
10.根据权利要求1所述的催化剂组合物,其中,过渡金属催化剂为乙酰丙酮二羰基铑,二齿配体为1,1’-二苯基-2,2’-二基-二(二吡咯基亚磷酰胺),以及单齿配体为氧化三苯膦。
11.一种烯烃化合物醛化方法,包括在权利要求1~10任意一项的催化剂组合物存在下、在高压和高温搅拌下烯烃化合物与氢气和一氧化碳的气体混合物反应生成醛。
13.根据权利要求11所述的方法,其中,所述的烯烃化合物为选自包括乙烯、丙烯、1-丁烯、1-戊烯、1-己烯、1-辛烯和苯乙烯的组的化合物。
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US8710276B2 (en) | 2012-05-24 | 2014-04-29 | Lg Chem, Ltd. | Catalyst compositions for hydroformylation reaction and hydroformylation process using the same |
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