WO2002100872A1 - Lithium p-diarylphosphinobenzenesulfonates, process for preparation of the same and use thereof - Google Patents
Lithium p-diarylphosphinobenzenesulfonates, process for preparation of the same and use thereof Download PDFInfo
- Publication number
- WO2002100872A1 WO2002100872A1 PCT/JP2002/005543 JP0205543W WO02100872A1 WO 2002100872 A1 WO2002100872 A1 WO 2002100872A1 JP 0205543 W JP0205543 W JP 0205543W WO 02100872 A1 WO02100872 A1 WO 02100872A1
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- Prior art keywords
- lithium
- group
- range
- water
- para
- Prior art date
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 77
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 238000000034 method Methods 0.000 title claims abstract description 41
- 238000007037 hydroformylation reaction Methods 0.000 claims abstract description 51
- 238000004519 manufacturing process Methods 0.000 claims abstract description 33
- 150000004696 coordination complex Chemical class 0.000 claims abstract description 25
- 150000002736 metal compounds Chemical class 0.000 claims abstract description 19
- 239000003054 catalyst Substances 0.000 claims description 69
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 65
- 238000006243 chemical reaction Methods 0.000 claims description 52
- -1 dimethyl compound Chemical class 0.000 claims description 43
- 239000011541 reaction mixture Substances 0.000 claims description 38
- 239000000203 mixture Substances 0.000 claims description 32
- 239000002253 acid Substances 0.000 claims description 31
- 150000003839 salts Chemical class 0.000 claims description 31
- 238000011084 recovery Methods 0.000 claims description 30
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims description 28
- 239000011591 potassium Substances 0.000 claims description 21
- 229910052700 potassium Inorganic materials 0.000 claims description 21
- 150000001875 compounds Chemical class 0.000 claims description 20
- 229910052751 metal Inorganic materials 0.000 claims description 20
- 239000002184 metal Substances 0.000 claims description 20
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 19
- 125000004429 atom Chemical group 0.000 claims description 17
- 239000007789 gas Substances 0.000 claims description 17
- 125000003118 aryl group Chemical group 0.000 claims description 11
- 239000001257 hydrogen Substances 0.000 claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 10
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 10
- 229910003002 lithium salt Inorganic materials 0.000 claims description 10
- 159000000002 lithium salts Chemical class 0.000 claims description 9
- 239000003960 organic solvent Substances 0.000 claims description 9
- 239000012298 atmosphere Substances 0.000 claims description 8
- 238000000605 extraction Methods 0.000 claims description 8
- 125000001424 substituent group 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 5
- 150000003284 rhodium compounds Chemical class 0.000 claims description 5
- 239000011261 inert gas Substances 0.000 claims description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims description 3
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 claims description 3
- 150000001869 cobalt compounds Chemical class 0.000 claims description 3
- 150000002506 iron compounds Chemical class 0.000 claims description 3
- 150000002641 lithium Chemical group 0.000 claims description 3
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 3
- 125000004437 phosphorous atom Chemical group 0.000 claims description 3
- 150000003304 ruthenium compounds Chemical class 0.000 claims description 3
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- VXNYVYJABGOSBX-UHFFFAOYSA-N rhodium(3+);trinitrate Chemical compound [Rh+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VXNYVYJABGOSBX-UHFFFAOYSA-N 0.000 claims description 2
- YWFDDXXMOPZFFM-UHFFFAOYSA-H rhodium(3+);trisulfate Chemical compound [Rh+3].[Rh+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O YWFDDXXMOPZFFM-UHFFFAOYSA-H 0.000 claims description 2
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims 2
- 125000005587 carbonate group Chemical group 0.000 claims 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims 1
- NENDHUHGFRLXEN-UHFFFAOYSA-N acetic acid;rhodium Chemical compound [Rh].CC(O)=O NENDHUHGFRLXEN-UHFFFAOYSA-N 0.000 claims 1
- SMBQBQBNOXIFSF-UHFFFAOYSA-N dilithium Chemical group [Li][Li] SMBQBQBNOXIFSF-UHFFFAOYSA-N 0.000 claims 1
- 239000001177 diphosphate Substances 0.000 claims 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 claims 1
- 235000011180 diphosphates Nutrition 0.000 claims 1
- KOZXCFTYVFLQGH-UHFFFAOYSA-M lithium 2-phosphanylbenzenesulfonate Chemical compound [Li+].PC1=C(C=CC=C1)S(=O)(=O)[O-] KOZXCFTYVFLQGH-UHFFFAOYSA-M 0.000 claims 1
- 150000002739 metals Chemical class 0.000 claims 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims 1
- 239000010452 phosphate Substances 0.000 claims 1
- KXAHUXSHRWNTOD-UHFFFAOYSA-K rhodium(3+);triiodide Chemical compound [Rh+3].[I-].[I-].[I-] KXAHUXSHRWNTOD-UHFFFAOYSA-K 0.000 claims 1
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 claims 1
- 150000001299 aldehydes Chemical class 0.000 abstract description 28
- 125000003107 substituted aryl group Chemical group 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 33
- 239000000243 solution Substances 0.000 description 26
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 20
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 19
- 239000007787 solid Substances 0.000 description 19
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 19
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 18
- 239000007788 liquid Substances 0.000 description 18
- 239000010948 rhodium Substances 0.000 description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 238000010992 reflux Methods 0.000 description 14
- 239000012044 organic layer Substances 0.000 description 13
- 229910052703 rhodium Inorganic materials 0.000 description 13
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 11
- 239000003446 ligand Substances 0.000 description 11
- JWAWWWWVVXIVGQ-UHFFFAOYSA-M lithium;4-diphenylphosphanylbenzenesulfonate Chemical compound [Li+].C1=CC(S(=O)(=O)[O-])=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 JWAWWWWVVXIVGQ-UHFFFAOYSA-M 0.000 description 11
- BALRIWPTGHDDFF-UHFFFAOYSA-N rhodium Chemical compound [Rh].[Rh] BALRIWPTGHDDFF-UHFFFAOYSA-N 0.000 description 11
- 229910052708 sodium Inorganic materials 0.000 description 11
- 239000011734 sodium Substances 0.000 description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- 238000003786 synthesis reaction Methods 0.000 description 10
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 10
- 239000004743 Polypropylene Substances 0.000 description 9
- 150000001768 cations Chemical class 0.000 description 9
- XLYOFNOQVPJJNP-ZSJDYOACSA-N Heavy water Chemical compound [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 8
- 238000000926 separation method Methods 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 235000019441 ethanol Nutrition 0.000 description 7
- 238000001914 filtration Methods 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- MDNWOSOZYLHTCG-UHFFFAOYSA-N Dichlorophen Chemical compound OC1=CC=C(Cl)C=C1CC1=CC(Cl)=CC=C1O MDNWOSOZYLHTCG-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- XGRJZXREYAXTGV-UHFFFAOYSA-N chlorodiphenylphosphine Chemical compound C=1C=CC=CC=1P(Cl)C1=CC=CC=C1 XGRJZXREYAXTGV-UHFFFAOYSA-N 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 6
- 239000000706 filtrate Substances 0.000 description 6
- LEMKWEBKVMWZDU-UHFFFAOYSA-N nonanedial Chemical compound O=CCCCCCCCC=O LEMKWEBKVMWZDU-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- ZKPFRIDJMMOODR-UHFFFAOYSA-N 2-Methyloctanal Chemical compound CCCCCCC(C)C=O ZKPFRIDJMMOODR-UHFFFAOYSA-N 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 238000005481 NMR spectroscopy Methods 0.000 description 5
- 239000002202 Polyethylene glycol Substances 0.000 description 5
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- SRSXLGNVWSONIS-UHFFFAOYSA-M benzenesulfonate Chemical compound [O-]S(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-M 0.000 description 5
- 229940077388 benzenesulfonate Drugs 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- RKGLUDFWIKNKMX-UHFFFAOYSA-L dilithium;sulfate;hydrate Chemical compound [Li+].[Li+].O.[O-]S([O-])(=O)=O RKGLUDFWIKNKMX-UHFFFAOYSA-L 0.000 description 5
- 238000004821 distillation Methods 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 229920001223 polyethylene glycol Polymers 0.000 description 5
- 230000035484 reaction time Effects 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 5
- VPFKYAOGDKHTPZ-UHFFFAOYSA-N 4-diphenylphosphanylbenzenesulfonic acid Chemical compound C1=CC(S(=O)(=O)O)=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 VPFKYAOGDKHTPZ-UHFFFAOYSA-N 0.000 description 4
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 239000004809 Teflon Substances 0.000 description 4
- 229920006362 Teflon® Polymers 0.000 description 4
- GPAYUJZHTULNBE-UHFFFAOYSA-N diphenylphosphine Chemical compound C=1C=CC=CC=1PC1=CC=CC=C1 GPAYUJZHTULNBE-UHFFFAOYSA-N 0.000 description 4
- VIDXETATLKBUBY-UHFFFAOYSA-M lithium;benzenesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C1=CC=CC=C1 VIDXETATLKBUBY-UHFFFAOYSA-M 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 4
- 229920001515 polyalkylene glycol Chemical class 0.000 description 4
- 159000000000 sodium salts Chemical class 0.000 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 description 4
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 238000004587 chromatography analysis Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- LIINGNMKNRSOGW-UHFFFAOYSA-N oct-7-enal Chemical compound C=CCCCCCC=O LIINGNMKNRSOGW-UHFFFAOYSA-N 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 3
- 229910001414 potassium ion Inorganic materials 0.000 description 3
- 238000011002 quantification Methods 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 229910001415 sodium ion Inorganic materials 0.000 description 3
- 125000000542 sulfonic acid group Chemical class 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical class C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 2
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- CTMHWPIWNRWQEG-UHFFFAOYSA-N 1-methylcyclohexene Chemical compound CC1=CCCCC1 CTMHWPIWNRWQEG-UHFFFAOYSA-N 0.000 description 2
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 2
- SWKVSFPUHCMFJY-UHFFFAOYSA-N 6-methyl-2-oxo-5-pyridin-4-yl-1h-pyridine-3-carboxamide Chemical compound N1C(=O)C(C(N)=O)=CC(C=2C=CN=CC=2)=C1C SWKVSFPUHCMFJY-UHFFFAOYSA-N 0.000 description 2
- FEEGRSNUPADTST-UHFFFAOYSA-N 8-oxononanal Chemical compound CC(=O)CCCCCCC=O FEEGRSNUPADTST-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 2
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-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
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- 235000011941 Tilia x europaea Nutrition 0.000 description 2
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- IAQRGUVFOMOMEM-UHFFFAOYSA-N but-2-ene Chemical compound CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 2
- 125000004744 butyloxycarbonyl group Chemical group 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- GGRQQHADVSXBQN-FGSKAQBVSA-N carbon monoxide;(z)-4-hydroxypent-3-en-2-one;rhodium Chemical compound [Rh].[O+]#[C-].[O+]#[C-].C\C(O)=C\C(C)=O GGRQQHADVSXBQN-FGSKAQBVSA-N 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 2
- URYYVOIYTNXXBN-UPHRSURJSA-N cyclooctene Chemical compound C1CCC\C=C/CC1 URYYVOIYTNXXBN-UPHRSURJSA-N 0.000 description 2
- 239000004913 cyclooctene Substances 0.000 description 2
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 description 2
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 2
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- ILCLANVYOPHXJF-UHFFFAOYSA-N diphenylphosphane;sodium Chemical compound [Na].C=1C=CC=CC=1PC1=CC=CC=C1 ILCLANVYOPHXJF-UHFFFAOYSA-N 0.000 description 2
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- 150000003440 styrenes Chemical class 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- HIFJUMGIHIZEPX-UHFFFAOYSA-N sulfuric acid;sulfur trioxide Chemical compound O=S(=O)=O.OS(O)(=O)=O HIFJUMGIHIZEPX-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 description 1
- IGNTWNVBGLNYDV-UHFFFAOYSA-N triisopropylphosphine Chemical compound CC(C)P(C(C)C)C(C)C IGNTWNVBGLNYDV-UHFFFAOYSA-N 0.000 description 1
- FQLSDFNKTNBQLC-UHFFFAOYSA-N tris(2,3,4,5,6-pentafluorophenyl)phosphane Chemical compound FC1=C(F)C(F)=C(F)C(F)=C1P(C=1C(=C(F)C(F)=C(F)C=1F)F)C1=C(F)C(F)=C(F)C(F)=C1F FQLSDFNKTNBQLC-UHFFFAOYSA-N 0.000 description 1
- COIOYMYWGDAQPM-UHFFFAOYSA-N tris(2-methylphenyl)phosphane Chemical compound CC1=CC=CC=C1P(C=1C(=CC=CC=1)C)C1=CC=CC=C1C COIOYMYWGDAQPM-UHFFFAOYSA-N 0.000 description 1
- IQKSLJOIKWOGIZ-UHFFFAOYSA-N tris(4-chlorophenyl)phosphane Chemical compound C1=CC(Cl)=CC=C1P(C=1C=CC(Cl)=CC=1)C1=CC=C(Cl)C=C1 IQKSLJOIKWOGIZ-UHFFFAOYSA-N 0.000 description 1
- GEPJPYNDFSOARB-UHFFFAOYSA-N tris(4-fluorophenyl)phosphane Chemical compound C1=CC(F)=CC=C1P(C=1C=CC(F)=CC=1)C1=CC=C(F)C=C1 GEPJPYNDFSOARB-UHFFFAOYSA-N 0.000 description 1
- VDAQOERDAAOXQV-UHFFFAOYSA-N tris(4-methoxyphenyl) phosphite Chemical compound C1=CC(OC)=CC=C1OP(OC=1C=CC(OC)=CC=1)OC1=CC=C(OC)C=C1 VDAQOERDAAOXQV-UHFFFAOYSA-N 0.000 description 1
- UYUUAUOYLFIRJG-UHFFFAOYSA-N tris(4-methoxyphenyl)phosphane Chemical compound C1=CC(OC)=CC=C1P(C=1C=CC(OC)=CC=1)C1=CC=C(OC)C=C1 UYUUAUOYLFIRJG-UHFFFAOYSA-N 0.000 description 1
- FEVFLQDDNUQKRY-UHFFFAOYSA-N tris(4-methylphenyl) phosphite Chemical compound C1=CC(C)=CC=C1OP(OC=1C=CC(C)=CC=1)OC1=CC=C(C)C=C1 FEVFLQDDNUQKRY-UHFFFAOYSA-N 0.000 description 1
- WXAZIUYTQHYBFW-UHFFFAOYSA-N tris(4-methylphenyl)phosphane Chemical compound C1=CC(C)=CC=C1P(C=1C=CC(C)=CC=1)C1=CC=C(C)C=C1 WXAZIUYTQHYBFW-UHFFFAOYSA-N 0.000 description 1
- RWVACGVJXRKMIZ-UHFFFAOYSA-N tris[4-(trifluoromethyl)phenyl] phosphite Chemical compound C1=CC(C(F)(F)F)=CC=C1OP(OC=1C=CC(=CC=1)C(F)(F)F)OC1=CC=C(C(F)(F)F)C=C1 RWVACGVJXRKMIZ-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/50—Organo-phosphines
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
- B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/50—Organo-phosphines
- C07F9/5022—Aromatic phosphines (P-C aromatic linkage)
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/50—Organo-phosphines
- C07F9/505—Preparation; Separation; Purification; Stabilisation
- C07F9/5054—Preparation; Separation; Purification; Stabilisation by a process in which the phosphorus atom is not involved
-
- 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
-
- 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
- B01J2531/821—Ruthenium
-
- 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
-
- 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
- B01J2531/84—Metals of the iron group
- B01J2531/842—Iron
-
- 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
- B01J2531/84—Metals of the iron group
- B01J2531/845—Cobalt
Definitions
- the present invention relates to lithium p-diarylphosphinobenzenesulfonate, a method for producing the same, and uses thereof.
- the lithium para-diarylphosphinobenzenesulfonate provided by the present invention is useful as a ligand for a hydroformylation catalyst.
- the above-mentioned applications include a hydroformylation catalyst comprising the lithium para-darylphosphinobenzenesulfonate provided by the present invention as a component, and an aldehyde compound using the hydroformylation catalyst. Manufacturing methods are included.
- a rhodium complex having lithium paradiglylphosphinobenzensulfonate as a ligand is used as a catalyst to carry out the hydroformylation of 7-octen-111al, it is a linear aldehyde product.
- 1,9-Nonandial can be obtained with good selectivity. Further, lithium para-diarylphosphinobenzenesulfonate has a high solubility in water, and is easily recovered from the reaction mixture after the hydroformylation reaction by water extraction and reused.
- a Group VIII metal compound or a catalyst obtained by modifying the Group VIII metal compound with a ligand such as an organic phosphorus compound to convert it to an aldehyde Is called hydroformylation reaction or oxo reaction.
- the production of aldehydes has become extremely valuable industrially.
- Group VI II metal compounds are extremely expensive, and when they are used industrially as hydroformylation catalysts, they must be recovered in high yield and reused. Therefore, as a method for recovering the hydroformylation catalyst, an evaporative separation method of distilling a product and an unreacted raw material from a reaction mixture and recovering the hydroformylation catalyst as an evaporation residue is performed.
- hydroformylation catalysts are unstable to heat, and when the boiling point of the product is high, the decrease in activity due to heat cannot be ignored.
- the vapor separation method is said to be useful only when hydroformylating ethylenically unsaturated compounds having up to 5 carbon atoms.
- hydroformylation of 7-octen-11al in the presence of a rhodium compound, a phosphorus ligand having a sulfonic acid group, and a polyalkylene glycol derivative and adding water to the reaction mixture to form a catalyst component Extraction Separation and removal of water in the separated aqueous layer. Recycling of the polyalkylene glycol derivative containing the catalyst component obtained in the reactor to reuse it, and obtaining 1,9-nonandial from the organic layer.
- a group VIII noble metal-ligand complex catalyst complexed with a potassium salt of p-diphenylphosphinobenzenesulfonic acid See Japanese Patent No. 285705) and (2) a group VIII noble metal-ligand complex catalyst complexed with a potassium salt of p-diphenylphosphinobenzenesulfonic acid.
- the hydroformylation method (W ⁇ 94Z1.7081, see Japanese Patent Application Laid-Open No. 8-506110) is known.
- the above method (1) performs a hydroformylation reaction at a low rhodium concentration of 25 ppm or less using meta-diphenylphosphinobenzenesulfonic acid sodium salt as a water-soluble ligand.
- the catalyst can be recovered and reused.
- the reaction mixture contains only about 10% of the polyalkylenedarilic derivative in addition to the unreacted raw material and the reaction product, and is an excellent method in terms of volumetric efficiency.
- this method there is a problem that even when the ratio of the linear aldehyde to the branched aldehyde is high, it remains at 3.5.
- the above method (2) is carried out by using para-diphenylphosphinobenzenesulfonic acid potassium salt as a water-soluble ligand, using an aqueous solution of sodium bicarbonate in which lauric acid is dissolved, and an auxiliary solvent.
- a hydroformylation reaction is carried out in a heterogeneous system.
- This method has the advantage that the ratio of linear aldehyde to branched aldehyde is as high as about 13, but the rhodium concentration in the aqueous layer is as high as 500 ppm and the raw material olefin is 1 part by weight.
- An object of the present invention is to provide a novel ligand for a hydroformylation catalyst which is excellent in economical efficiency in the hydroformylation reaction of an ethylenically unsaturated compound and gives a linear aldehyde with high selectivity, and the coordination thereof. It is an object of the present invention to provide a method for industrially and advantageously producing particles with high purity and high yield.
- Another object of the present invention is to provide an economically efficient reaction for hydroformylation of an ethylenically unsaturated compound and to provide a linear aldehyde with high selectivity.
- a further object of the present invention is to provide a simple and industrially advantageous method for producing an aldehyde compound by a hydroformylation reaction using the group VIII metal complex.
- Still another object of the present invention is to provide a method capable of easily recovering a catalyst component from a hydroformylation reaction mixture in a high yield.
- the present invention provides a compound represented by the general formula (I):
- R 1 and R 2 each represent an aryl group which may have a substituent.
- lithium parasulfonylphosphinobenzenesulfonate (I)
- potassium sulfonic acid salt (II) in the following.
- the present invention relates to a Group VIII metal complex in which lithium sulfonate (I) is coordinated to a Group VIII metal compound [hereinafter sometimes abbreviated as Group VIII metal complex (I)]. is there.
- the present invention provides a method for hydroformylating an ethylenically unsaturated compound with carbon monoxide and hydrogen in the presence of a catalyst to produce the corresponding aldehyde, using a Group VIII metal complex (I) as a catalyst.
- This is a method for producing an aldehyde characterized by the following.
- the reaction mixture in recovering a catalyst component from a reaction mixture obtained by the above-mentioned method for producing an aldehyde, the reaction mixture is brought into contact with water to extract the catalyst component into an aqueous layer, and to remove water from the aqueous layer.
- the present invention also includes the above-mentioned method for recovering a catalyst component, which is characterized by being removed.
- the aryl groups represented by R 1 and R 2 include, for example, a phenyl group, a naphthyl group, an anthryl group and the like. Of these aryl groups, a phenyl group is particularly preferred.
- aryl groups may have a substituent, and such substituents include, for example, Halogen atoms such as fluorine, chlorine, bromine and iodine; methyl, ethyl, propyl, isopropyl, butyl, isobutyl, S-butyl, t-butyl, cyclohexyl
- Halogen atoms such as fluorine, chlorine, bromine and iodine
- Alkyl groups such as difluoromethyl group, trifluoromethyl group, 1,1-difluoroethyl group, 2,2-difluoroethyl group, and fluoroalkyl group such as 1-fluoropropyl group; methoxy group, ethoxy group, propoxy group, and isopropoxy group
- Siloxy group Alkoxy force of methoxycarbon group, ethoxycarbonyl group, methoxycarbonyl group, isopropoxycarbonyl group, butoxycarbonyl group, isobutoxycarbonyl group, s_butoxycarbonyl group, t-butoxycarbonyl group, etc.
- Amino group such as amino group, methylamino group, dimethylamino group, acetylamino group; sulfonic acid group or its metal salt; sulfonic acid group or its metal salt; phosphite group or its metal salt.
- lithium sulfonate (I) examples include lithium p-diphenylphosphinobenzenesulfonate, lithium para-bis (ortho-tolyl) phosphinobenzenesulfonate, and parabis (meta-tolyl) phosphinobenzenesulfonic acid.
- Lithium salt parabis (para-tolyl) phosphinobenzenesulfonic acid lithium salt, para-bis (para-methoxyphenyl) phosphinobenzenesulfonic acid lithium salt, para-bis (para-fluorophenyl) phosphinobenzene sulfone Lithium acid salt, para-bis (para-trifluoromethylphenyl) phosphino benzenesulfonic acid lithium salt, bis (para-sulfophenyl) phenyl Diphosphorus dilithium salt, bis (parasulfophenyl) (paratrifluoromethylphenyl) phosphine dilithium salt and the like.
- lithium p-diphenylphosphinobenzenesulfonate is particularly preferred.
- a method for producing the lithium sulfonate (I) will be described. It is necessary to use a lithium acid salt having a solubility in water of 20 ° C. and a range of 5 to 30% by weight based on 100 g of water. In the case of an acid lithium salt capable of forming a hydrate, the solubility of the anhydride in water should be in the range of 20: 5 to 30% by weight based on 100 g of water.
- the raw material lithium salt and the by-product acid potassium salt are separated from the reaction mixture obtained by reacting the sulfonic acid potassium salt (II) with the lithium acid salt by filtration. This makes it possible to easily isolate the target lithium sulfonate (I).
- lithium acid salts include carbonates, phosphates, phosphites, nilinates, sulfates, sulfites, and hydrochlorides. Of these, carbonates, sulfates, and sulfites Salts are preferred.
- the amount of the lithium acid salt to be used is preferably such that the lithium atom in the lithium acid salt is in the range of 4 to 40 atoms per 1 atom of potassium in the potassium sulfonate salt (II),
- An amount in the range of 6 to 10 atoms is more preferable from the viewpoint of improving operability and yield.
- This reaction is carried out in the presence of water or a mixture of water and a water-miscible organic solvent.
- water-miscible organic solvent include alcohols such as methyl alcohol, ethyl alcohol, propyl alcohol, ethylene glycol, and ethylene glycol; acetone, ethyl methyl ketone, and methyl alcohol.
- Ketones such as tyl ketone; esters such as methyl formate, ethyl formate, methyl acetate, ethyl acetate, methyl propionate, and ethyl propionate; dimethyl ether, ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol monoethyl ether, ethylene glycol gel Ethers such as tyl ether, ethylene glycol ethyl methyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, and diethylene dalicol getyl ether are used. These organic solvents are preferably poor solvents for lithium acid salts.
- the above organic solvents are used alone or as a mixture of two or more.
- the amount of water used is preferably in the range of 1 to 50 times by weight, more preferably in the range of 2 to 20 times by weight, relative to the potassium sulfonate (II).
- the amount of the organic solvent used is preferably 1 to 50 times the weight of potassium sulfonate (II), more preferably 2 to 20 times the weight. More preferred.
- the usage ratio of the organic solvent to water is preferably not more than 3 times by volume, and more preferably not more than 1.5 times by volume.
- the reaction temperature can be appropriately selected up to the reflux temperature, but it is preferable to carry out the reaction at the reflux temperature from the viewpoint of improving the reaction efficiency.
- the reaction time is preferably in the range of 0.5 to 10 hours, more preferably in the range of 1 to 4 hours.
- the reaction can be carried out in the atmosphere, but is preferably carried out in an atmosphere of an inert gas such as nitrogen or argon from the viewpoint of suppressing the oxidation of lithium sulfonate (I).
- an inert gas such as nitrogen or argon from the viewpoint of suppressing the oxidation of lithium sulfonate (I).
- the reaction is carried out, for example, by mixing potassium sulfonate (II) and lithium acid salt in an inert gas atmosphere such as nitrogen or argon, in the presence of water or water and a water-miscible organic solvent, and then reacting at a predetermined temperature. It is better to stir with Good.
- an inert gas atmosphere such as nitrogen or argon
- the lithium sulfonate (I) thus obtained can be isolated and purified by a method usually used for isolating and purifying an organic compound. For example, after concentrating the reaction mixture, adding a poor solvent for an acid metal salt such as methyl alcohol, ethyl alcohol, propyl alcohol, and acetone, filtering off solids, and concentrating the obtained filtrate to obtain a product. Can be isolated.
- a poor solvent for an acid metal salt such as methyl alcohol, ethyl alcohol, propyl alcohol, and acetone
- the lithium sulfonate (I) obtained by the above method has high purity and low chlorine content, and thus can be used as it is as a ligand for a noble metal catalyst.
- the sulfonic acid potassium salt (II) used as a raw material is as follows: (1) Chlorodiarylphosphine is reacted with metal sodium to obtain diarylphosphine sodium salt, and the diarylphosphine sodium salt is added to the parachloride.
- the group VIII metal complex (I) obtained by coordinating a lithium sulfonic acid salt (I) with a group VIII metal compound has a catalytic ability to promote a hydroformylation reaction of an ethylenically unsaturated compound.
- the Group VIII metal complex (I) is water-soluble, and can be used, for example, in a known hydroformylation reaction using a catalyst comprising a Group VIII metal compound modified with a water-soluble ligand. it can.
- the Group VIII metal compound is a compound which has a catalytic ability to promote the hydroformylation reaction of an ethylenically unsaturated compound from the beginning or acquires such a catalytic ability under the conditions of the hydroformylation reaction.
- Rhodium compounds, cobalt compounds, ruthenium compounds, iron compounds and the like used as catalysts in the hydroformylation reaction are listed.
- the rhodium compounds for example, Rh_ ⁇ , Rh 2 ⁇ , Rh 2 0 3, rhodium oxide, such as R h 0 2; rhodium nitrate, rhodium sulfate, LOGIS ⁇ beam chloride, iodide, rhodium salts such as rhodium acetate; R h 4 (CO) 12 , R h 6 (CO) 16 , R h C 1 (CO) (PP h 3 ) 2 , R h C 1 (PP h 3 ) 3 , Rh B r (CO) (PP h 3) 2, R h C 1 (CO) (a s PP h 3) 2, etc.
- rhodium oxide such as R h 0 2
- rhodium nitrate, rhodium sulfate LOGIS ⁇ beam chloride, iodide, rhodium salts such as rhodium acetate
- the cobalt compound for example, HC o (CO) 4, C o 2 (CO) 8, HC o (CO) 3, HC o 3 (CO) 9 , and the like cobalt complex compounds, such as.
- the ruthenium compound for example, Ru 3 (CO) 12, R u (CO) 3 (PP h 3) 2, R u C 1 3 (PP h 3) 3, R u C 1 2 (PP h 3) 3 , etc. And the like.
- As the iron compounds for example, F e (CO) 5, F e (CO) 4 PP h 3, F e (CO) 4 (PP h 3) and iron complex compounds such as 2.
- it is preferable to use a rhodium compound from the viewpoint that the reaction conditions for the hydroformylation reaction are mild, it is preferable to use a rhodium compound, and it is particularly preferable to use Rh (acac)
- lithium sulfonate (I) may be used alone or in combination of two or more.
- the amount of the lithium sulfonate (I) to be used is preferably in the range of 1 to 100 mol, in terms of phosphorus atoms, per 1 mol of group VIII metal compound in terms of group VIII metal atom, More preferably, it is in the range of 100 moles. If the amount of lithium sulfonate (I) used is below this range, the stability of the catalyst will be impaired, and if it exceeds this range, the reaction rate will tend to decrease.
- the method for preparing the Group VIII metal complex (I) is not particularly limited. Prepared separately using a solvent that does not affect the droformylation reaction,
- It can be prepared by separately introducing a Group VI metal compound solution and a lithium sulfonate (I) solution into a hydroformylation reaction system, and reacting the two in the system to form a complex.
- it can be prepared by adding lithium sulfonate (I) to the above-mentioned VIII group metal compound solution, and then adding a solvent that does not affect the hydroformylation reaction to form a uniform solution.
- a method for producing an aldehyde will be described.
- the ethylenically unsaturated compound may be a linear, branched or cyclic terminal or internal olefin.
- ethylenically unsaturated compounds include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 2-butene, isobutene, 2-octene , 1,7-octane, vinylcyclohexene, cyclooctene, dicyclopentene, butadiene polymer, isoprene polymer and other unsaturated aliphatic hydrocarbons; styrene, ⁇ -methylstyrene, / 3- Styrenes such as methylstyrene, alkyl-substituted styrene, and divinylbenzene; alicyclic olefinic hydrocarbons such as cyclopentene, cyclohexene, 1-methylcycl
- the H 2 C molar ratio is preferably in the range of 0.1 to 10 as the incoming gas composition, and more preferably in the range of 0.5 to 2 from the viewpoint of easy maintenance of the mixed gas composition.
- the reaction pressure is preferably in the range of 0.1 to 10 MPa, and more preferably in the range of 0.5 to 5 MPa from the viewpoint of the reaction rate.
- the reaction temperature is preferably in the range of 40 to 150, and more preferably in the range of 60 to 130 ° C from the viewpoint of suppressing the deactivation of the catalyst.
- the reaction can be carried out using a stirred type reaction vessel, a liquid circulation type reaction vessel, a gas circulation type reaction vessel, a bubble column type reaction vessel, or the like. Further, the reaction can be performed in a continuous mode or a batch mode.
- the amount of the Group VIII metal complex (I) used should be selected so as to be in the range of 0.001 to 100 milligram atoms in terms of Group VIII metal atoms per liter of the reaction solution. More preferably, the amount is selected to be in the range of 0.005 to 10 milligram atoms. If the amount of the Group VIII metal complex (I) is below this range, the reaction rate is too slow, and even if it is used beyond this range, the reaction rate cannot be further increased effectively. However, the catalyst cost increases, which is not preferable.
- a solvent in the reaction system.
- the solvent include aprotic polar solvents such as dimethyl sulfoxide, N-methylpyrrolidone, sulfolane, dimethylformamide, acetonitrile, acetone, dioxane, and tetrahydrofuran; methyl alcohol, ethyl alcohol, propyl alcohol, and Alcohols such as isopropyl alcohol, butyl alcohol, s-butyl alcohol, t-butyl alcohol; ethylene glycol, propylene glycol, diethylene glycol, ethylene glycol monomethyl alcohol Dalicols such as ethylene glycol, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol, triethylene glycol dimethyl ether, tetraethylene glycol, tetraethylene glycol dimethyl
- aprotic polar solvents such as dimethyl sulfoxide, N-methylpyrrolidone, sulfolane, dimethylformamide, ace
- solvents may be used alone or in combination of two or more.
- the use of polyalkylene glycols is preferable from the viewpoint of preventing the precipitation of the catalyst component during the catalyst extraction and improving the recovery efficiency of the catalyst component, and polyethylene glycol, polyethylene glycol dimethyl ether, and the like are preferable. used.
- the amount of these solvents to be used is preferably selected to be in the range of 2 to 50% by volume in the hydroformylation reaction mixture, and to be in the range of 5 to 20% by volume. It is more preferable to select.
- the aldehyde obtained by the above method can be isolated and purified by a method generally used for isolating and purifying organic compounds. For example, it is isolated and purified from the organic layer obtained through the later-described catalyst component recovery step by distillation, recrystallization, power chromatography, and the like. Next, a method for recovering the catalyst component will be described.
- the catalyst component is a group VIII metal complex (I), and It means the lithium sulfonate (I) usually used in excess with respect to the group VIII metal compound.
- water is added to the reaction mixture after the hydroformylation reaction.
- the amount of water used in the reaction mixture is not particularly limited. However, considering the operability and the solubility of the catalyst components in water, an amount that is in the range of 1 to 200% by volume based on the reaction mixture is selected. Preferably, the amount is selected to be in the range of 5 to 50% by volume.
- the reaction mixture is brought into contact with water by stirring or the like, and the catalyst component is extracted with water.
- the temperature is preferably in the range of 20 to 90, and it is preferably performed in an atmosphere of an inert gas such as nitrogen, helium, or argon, or a mixed gas of hydrogen and carbon monoxide. .
- an organic layer containing a hydroformylation reaction product and an aqueous layer containing a catalyst component are separated.
- a centrifugal separation operation or the like can be used in combination to promote the layer separation.
- layer separation can be promoted by adding a hydrocarbon having a specific gravity lower than that of water, such as hexane and cyclohexane.
- the organic layer contains unreacted ethylenically unsaturated compounds and a small amount of catalyst components in addition to the reaction products.
- the organic layer is washed with water and the washing is performed.
- the water is combined with the aqueous layer.
- the catalyst component By removing water from the obtained aqueous layer, the catalyst component can be recovered. Removal of water is performed by a conventional method such as distillation under reduced pressure. When performing distillation under reduced pressure, it is preferable to carry out the distillation at a low temperature in order to prevent the thermal deterioration of the Group VIII metal complex (I), etc., at a temperature of 30 to 100 mm and a temperature of 10 to 300 mm. It is preferably carried out under Hg pressure conditions. The degree of water distillation depends on the catalyst composition. It is preferable that the concentration of the water-containing concentrate is such that no separated water is present in the reaction system when the concentrate is reused in the hydroformylation reaction. The resulting catalyst component can be reused for the hydroformylation reaction.
- the lithium sulfonate (I) used in the present invention for example, lithium para-diphenylphosphinobenzenesulfonate
- a diphenylphosphine lithium salt is synthesized by reacting diphenylphosphine with an alkyl lithium such as butyllithium, and the obtained diphenylphosphine lithium salt is reacted with a lithium parabenzene benzenesulfonate, followed by column purification. And the like.
- Quantification of chlorine, lithium, sodium and potassium was performed using ion chromatography (DX-120, manufactured by Nippon Dionex Co., Ltd.).
- the quantification of the benzene sulfonate at the paraclo mouth was performed using a 1 H-NMR spectrometer (Lambda 500, manufactured by JEOL Ltd.), and the para-diarylphosphinobenzenesulfonate and its oxide were determined.
- the quantification was carried out using a 31 P-NMR spectrometer (Lambda 500, manufactured by JEOL Ltd.).
- the temperature of the solution was adjusted to 35 ° C., and 74 g (0.373 mol 1) of lithium benzenesulfonic acid parachloride was added to the solution, followed by stirring at a bath temperature of 50 for 45 minutes.
- tetrahydrofuran 350 ml was distilled off from the obtained reaction mixture, and diisopropyl ether (300 ml) and water (700 ml) were added to the obtained solution, followed by extraction.
- a mixed layer consisting of a water layer and a tetrahydrofuran layer was obtained. This mixed layer was washed with 300 ml of diisopropyl ether to obtain an aqueous layer.
- the cations are all potassium ions, the chloride ion content is 0.06 m 0 1%, the oxide content of para-diphenylphosphinobenzenesulfonic acid potassium salt is 0.47 mo 1%, The content of potassium benzenesulfonate was 0.03 mo 1% or less.
- ⁇ -NMR 500 MHz, heavy water, TSP, p pm
- ⁇ 7.3 p pm (m, 14 H), 7.7 ppm (d, 2 H)
- the temperature of the resulting solution was 35 t: and 25 Oml of tetrahydrofuran was added to the solution.
- a 2-liter 3-neck flask equipped with a reflux tube, a dropping funnel, a thermometer and a mechanical stirrer 89 g (l. 10 g (0.55 mol) and 750 ml of tetrahydrofuran were added, and the mixture was stirred under reflux conditions for 30 minutes. Then, the sodium salt of diphenylphosphine prepared above was added dropwise from the dropping funnel over 2 hours at such a rate as to maintain the liquid temperature at 60 to 70, and the mixture was further stirred at the same liquid temperature for 1 hour. A mixture was obtained.
- the cations are 99% potassium ion and 1% sodium ion, the content of chloride ion is 0.004mo 1%, and the content of oxide of potassium para-diphenylphosphinobenzenesulfonic acid salt is 0.12mol%. The content of potassium para-benzenebenzenesulfonate was 0.03 mo 1% or less.
- Reference example 3
- the temperature of the resulting solution was brought to 35 and 250 ml of tetrahydrofuran were added to the solution. Meanwhile, 110 g (0.55 mo1) of tetracyclofuran lithium benzenesulfonate and tetrahydrofuran were placed in a 2 L 3-volume flask equipped with a reflux tube, a dropping funnel, a thermometer and a mechanical stirrer. 75 ml was added, and the mixture was stirred for 30 minutes under reflux conditions. Then, the sodium salt of diphenylphosphine prepared above was added dropwise from the dropping funnel over 2 hours at a rate to maintain the liquid temperature of 60 to 70 :, and the mixture was further stirred at the same liquid temperature for 1 hour. The reaction A mixture was obtained.
- the obtained filtrate was concentrated to dryness using a low-pressure evaporator, and as a white solid, 42 g of lithium para-diphenylphosphinobenzenesulfonate having the following physical properties (92% yield) was obtained.
- the cations are all lithium ions, and the chloride ion content is 0.01 33mo 1%, the content of oxides of lithium p-diphenylphosphinobenzenesulfonate is 0.32mo 1%, and the content of lithium parabenzene benzenesulfonate is 0.03mo 1% or less.
- iH—NMR (500 MHz, heavy water, TSP, p pm) 6 7.3 p pm (m, 14 H), 7.7 ppm (d, 2 H)
- the cations are all lithium ions, the chlorine ion content is 0.013 3mo 1%, the oxide content of lithium para-diphenylphosphinobenzenesulfonate is 0.30mo 1%, — The content of lithium salt of benzene sulfonate was 0.03mo 1% or less.
- Example 3 Synthesis of lithium p-diphenylphosphinobenzenesulfonate In a 500-ml 3-volume flask equipped with a reflux tube, a thermometer, and a magnetic rotator, water 20 Om 1 was added, and the same as in Reference Example 1.
- the cations are all lithium ions, the chloride ion content is 0.133 mol 1%, the oxide content of lithium para-diphenylphosphinobenzenesulfonate is 0.330 mol%, The content of lithium benzenesulfonate at the mouth was 0.03mo 1% or less.
- the cations are all lithium ions, the chloride ion content is 0.08 mo 1%, the oxide content of lithium para-diphenylphosphinobenzenesulfonate is 0.27mo 1%, the para-channel The content of lithium benzenesulfonate was 0.03mo 1% or less.
- the mixture was stirred for 14 hours under the following conditions.
- the obtained solution was diluted with 5 L of ice-cooled water over 2 hours so as to maintain a liquid temperature of 1 Ot: or less.
- 4 L of methyl isobutyl ketone was added to the obtained diluted sulfuric acid solution, and an extraction operation was performed to obtain an organic layer.
- the organic layer was neutralized by adding about 300 ml of a 5% by weight aqueous sodium hydroxide solution. After the neutralization was completed, the solution was separated into two layers, and the aqueous layer was obtained. The aqueous layer was washed with 250 ml of methyl isobutyl ketone.
- the aqueous layer was concentrated to about 200 ml, cooled to 10 ° C with ice, and the precipitated colorless solid was collected by filtration. The colorless solid was further recrystallized twice with water to obtain 35 g (yield: 1%) of sodium metadiphenylphosphinobenzenesulfonate.
- the cation is sodium ion at 100%, the chloride ion content is 0.02mo1%, and the oxide content of sodium meta-diphenylphosphinobenzenesulfonate is 0.5mol%. there were.
- Teflon (registered trademark) 3-neck flask having an inner volume of 1 0 Om 1 equipped with a magnetic rotor, Rh (acac) (CO) 2 3. 9 mg (0. 0 1 5m mo 1) and Example 2 After adding 1 mg (1.2 mmo 1) of lithium p-diphenylphosphinobenzensulfonate synthesized in the above, and adding 6 ml of polyethylene daricol dimethyl ether, the mixture was stirred at 50 for 30 minutes to obtain a homogeneous catalyst. A solution was prepared.
- the conversion of 7-octene-111R was 96%, and the production ratio of the linear aldehyde compound to the branched aldehyde compound was 4.65 to 1.
- the rhodium concentration in this embodiment is about 20 ppm.
- reaction mixture was pressure-fed so as not to come into contact with air to a 3 O flask with an internal volume of 5 Om1, which had been sufficiently replaced with a mixed gas of hydrogen Z and carbon oxide in advance, and 9 ml of water was added.
- the mixture was stirred for 20 minutes in an atmosphere of a mixed gas having the above composition while maintaining the temperature at 30 ° C. After stopping the stirring, the lower aqueous layer was removed.
- the recovery of lithium p-diphenylphosphinobenzenebenzenesulfonate was 82%.
- ICP emission analysis the recovery of rhodium was 97%.
- Example 7 421 mg (1.2 mmo1) of lithium p-diphenylphosphinobenzenesulfonate was changed to 105 mg (0.3 mmo1), the pressure was set to IMpa, and the reaction time was set to The same operation was performed except that the time was set to 4 hours, and 2,9-nonandial 21.1 g (0.135 mo 1, yield 81%) and 2-methyloctanal 4.1 g (0. 0 26 mo 1, yield 16%). The conversion of 7-octene-11-al is 97%, and the ratio of linear aldehyde compounds to branched aldehyde compounds was 5.06 to 1.
- Example 7 the same operation as in Example 7 was performed to separate an organic layer and an aqueous layer.
- the recovery of lithium p-diphenylphosphinobenzenesulfonate was 83%.
- the recovery of rhodium was 97%. Comparative Example 1
- Example 7 the same operation as in Example 7 was performed to separate an organic layer and an aqueous layer.
- the recovery of potassium para-diphenylphosphinobenzenesulfonate was 33%.
- the recovery of rhodium was 40%. Comparative Example 3
- Example 7 the same operation as in Example 7 was performed to separate an organic layer and an aqueous layer.
- the recovery of sodium metadiphenylphosphinobenzenesulfonate was 70%.
- the recovery of rhodium was 94%.
- Comparative Examples 1 and 2 when para-diphenylphosphinobenzenesulfonic acid potassium salt was used, the ratio of linear aldehyde to branched aldehyde was as low as 3.13. Moreover, the recovery of the catalyst component is low.
- the ratio of the linear aldehyde to the branched aldehyde is 4.65 or more, and the catalyst component Recovery rate is high.
- Comparative Example 3 when sodium meta-diphenylphosphinobenzenesulfonate was used, the recovery of the catalyst component was high, but the conversion of linear aldehyde to branched aldehyde was higher. The ratio is as low as 2.70.
- the method of the present invention is excellent in both selectivity of linear aldehyde and economic efficiency. Industrial applicability
- lithium para-diarylphosphinobenzenesulfonate can be industrially advantageously produced with high purity and high yield.
- a Group VIII metal complex which is excellent in economy in the hydroformylation reaction of an ethylenically unsaturated compound and which gives a linear aldehyde with high selectivity is obtained.
- Aldehyde compounds can be produced simply and industrially advantageously by a hydroformylation reaction using Further, according to the present invention, the catalyst component can be easily recovered from the hydroformylation reaction mixture in high yield.
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Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
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EP02733309A EP1405854A4 (en) | 2001-06-07 | 2002-06-05 | LITHIUM P-DIARYLPHOSPHINOBENZENESULFONATES, PROCESS FOR THE PREPARATION AND USE OF SUCH COMPOUNDS |
KR10-2003-7015871A KR20040007650A (ko) | 2001-06-07 | 2002-06-05 | 파라-디아릴포스피노벤젠설폰산 리튬염, 이의 제조방법 및이의 용도 |
CA002447730A CA2447730A1 (en) | 2001-06-07 | 2002-06-05 | Lithium p-diarylphosphinobenzenesulfonates, process for preparation of the same and use thereof |
US10/479,859 US20040249195A1 (en) | 2001-06-07 | 2002-06-05 | Lithium rho-diarylphosphinobenzenesulfonates, process for preparation of the same and use thereof |
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JP2001-172229 | 2001-06-07 | ||
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JP2001-257197 | 2001-08-28 |
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US (1) | US20040249195A1 (ja) |
EP (1) | EP1405854A4 (ja) |
KR (1) | KR20040007650A (ja) |
CN (1) | CN1538971A (ja) |
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US7592483B2 (en) * | 2004-07-01 | 2009-09-22 | Basf Aktiengesellschaft | Preparation of acrolein or acrylic acid or a mixture thereof by heterogeneously catalyzed partial gas phase oxidation of propylene |
KR101035146B1 (ko) | 2006-11-06 | 2011-05-17 | 주식회사 엘지화학 | 옥소 공정에서 재결정화 과정에 의한 촉매 리간드 산화물의 분리 방법 |
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US4731486A (en) * | 1986-11-18 | 1988-03-15 | Union Carbide Corporation | Hydroformylation using low volatile phosphine ligands |
US5180854A (en) * | 1988-07-14 | 1993-01-19 | Union Carbide Chemicals & Plastics Technology Corporation | Process for catalyst aldehyde product separation |
US5300617A (en) * | 1993-01-21 | 1994-04-05 | Exxon Chemical Patents Inc. | Potassium para-diphenyl phosphino benzene sulfonate ligand |
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- 2002-06-05 CN CNA028153456A patent/CN1538971A/zh active Pending
- 2002-06-05 US US10/479,859 patent/US20040249195A1/en not_active Abandoned
- 2002-06-05 CA CA002447730A patent/CA2447730A1/en not_active Abandoned
- 2002-06-05 KR KR10-2003-7015871A patent/KR20040007650A/ko not_active Application Discontinuation
- 2002-06-05 EP EP02733309A patent/EP1405854A4/en not_active Withdrawn
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EP1405854A4 (en) | 2004-11-03 |
US20040249195A1 (en) | 2004-12-09 |
CN1538971A (zh) | 2004-10-20 |
EP1405854A1 (en) | 2004-04-07 |
CA2447730A1 (en) | 2002-12-19 |
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