TW389751B - Process for the hyoroformylation of olefinically unsaturated compounds - Google Patents
Process for the hyoroformylation of olefinically unsaturated compounds Download PDFInfo
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- TW389751B TW389751B TW085109975A TW85109975A TW389751B TW 389751 B TW389751 B TW 389751B TW 085109975 A TW085109975 A TW 085109975A TW 85109975 A TW85109975 A TW 85109975A TW 389751 B TW389751 B TW 389751B
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- 238000000034 method Methods 0.000 title claims abstract description 47
- 150000001875 compounds Chemical class 0.000 title claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims abstract description 47
- 239000003054 catalyst Substances 0.000 claims abstract description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 35
- -1 rhodium carbonyl compound Chemical class 0.000 claims abstract description 23
- 239000003495 polar organic solvent Substances 0.000 claims abstract description 14
- 150000003839 salts Chemical class 0.000 claims abstract description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 48
- 239000000243 solution Substances 0.000 claims description 31
- 150000001336 alkenes Chemical class 0.000 claims description 22
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 15
- 125000000217 alkyl group Chemical group 0.000 claims description 13
- 229910052702 rhenium Inorganic materials 0.000 claims description 11
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 9
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 9
- 150000002148 esters Chemical class 0.000 claims description 9
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 8
- 125000003118 aryl group Chemical group 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 229910052732 germanium Inorganic materials 0.000 claims description 6
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 6
- 125000001931 aliphatic group Chemical group 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- 235000021122 unsaturated fatty acids Nutrition 0.000 claims description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 3
- 239000007983 Tris buffer Substances 0.000 claims description 3
- YZCKVEUIGOORGS-NJFSPNSNSA-N Tritium Chemical compound [3H] YZCKVEUIGOORGS-NJFSPNSNSA-N 0.000 claims description 3
- 229910052744 lithium Inorganic materials 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- 235000015170 shellfish Nutrition 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 229910052722 tritium Inorganic materials 0.000 claims description 3
- 150000004670 unsaturated fatty acids Chemical class 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 125000002015 acyclic group Chemical group 0.000 claims description 2
- 150000005674 acyclic monoalkenes Chemical class 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 150000005673 monoalkenes Chemical class 0.000 claims description 2
- 150000003003 phosphines Chemical class 0.000 claims description 2
- 239000002798 polar solvent Substances 0.000 claims description 2
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims 2
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims 2
- 150000002191 fatty alcohols Chemical class 0.000 claims 2
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 claims 2
- 150000004714 phosphonium salts Chemical class 0.000 claims 2
- 238000002407 reforming Methods 0.000 claims 2
- 102000004190 Enzymes Human genes 0.000 claims 1
- 108090000790 Enzymes Proteins 0.000 claims 1
- JGOCKQCCDIRYEX-UHFFFAOYSA-N P(O)(O)=O.C1(=CC=CC=C1)P Chemical compound P(O)(O)=O.C1(=CC=CC=C1)P JGOCKQCCDIRYEX-UHFFFAOYSA-N 0.000 claims 1
- 150000001335 aliphatic alkanes Chemical class 0.000 claims 1
- 150000001621 bismuth Chemical class 0.000 claims 1
- 229910002092 carbon dioxide Inorganic materials 0.000 claims 1
- 239000001569 carbon dioxide Substances 0.000 claims 1
- 125000004122 cyclic group Chemical group 0.000 claims 1
- 201000010099 disease Diseases 0.000 claims 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 claims 1
- 238000000855 fermentation Methods 0.000 claims 1
- 230000004151 fermentation Effects 0.000 claims 1
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical class OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 claims 1
- 150000002291 germanium compounds Chemical class 0.000 claims 1
- 229910052762 osmium Inorganic materials 0.000 claims 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 claims 1
- 244000144977 poultry Species 0.000 claims 1
- 239000002689 soil Substances 0.000 claims 1
- 241000894007 species Species 0.000 claims 1
- 238000011282 treatment Methods 0.000 claims 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 abstract description 48
- 229910000073 phosphorus hydride Inorganic materials 0.000 abstract description 23
- 239000010948 rhodium Substances 0.000 abstract description 15
- 238000004821 distillation Methods 0.000 abstract description 6
- 239000011541 reaction mixture Substances 0.000 abstract description 6
- 229910052703 rhodium Inorganic materials 0.000 abstract description 5
- 239000012429 reaction media Substances 0.000 abstract description 4
- 238000007037 hydroformylation reaction Methods 0.000 abstract 2
- 238000010626 work up procedure Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 21
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 16
- 150000001299 aldehydes Chemical class 0.000 description 14
- 239000007795 chemical reaction product Substances 0.000 description 13
- 239000007789 gas Substances 0.000 description 13
- 239000007858 starting material Substances 0.000 description 9
- 229910052786 argon Inorganic materials 0.000 description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical class CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 7
- 239000001149 (9Z,12Z)-octadeca-9,12-dienoate Substances 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- XGQJZNCFDLXSIJ-UHFFFAOYSA-N pentadecanal Chemical compound CCCCCCCCCCCCCCC=O XGQJZNCFDLXSIJ-UHFFFAOYSA-N 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- BGHCVCJVXZWKCC-UHFFFAOYSA-N tetradecane Chemical compound CCCCCCCCCCCCCC BGHCVCJVXZWKCC-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 230000002079 cooperative effect Effects 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- 235000019198 oils Nutrition 0.000 description 5
- 229910052698 phosphorus Inorganic materials 0.000 description 5
- XPQPWPZFBULGKT-UHFFFAOYSA-N undecanoic acid methyl ester Natural products CCCCCCCCCCC(=O)OC XPQPWPZFBULGKT-UHFFFAOYSA-N 0.000 description 5
- DVWSXZIHSUZZKJ-UHFFFAOYSA-N 18:3n-3 Natural products CCC=CCC=CCC=CCCCCCCCC(=O)OC DVWSXZIHSUZZKJ-UHFFFAOYSA-N 0.000 description 4
- DTOSIQBPPRVQHS-PDBXOOCHSA-N alpha-linolenic acid Chemical compound CC\C=C/C\C=C/C\C=C/CCCCCCCC(O)=O DTOSIQBPPRVQHS-PDBXOOCHSA-N 0.000 description 4
- 235000020661 alpha-linolenic acid Nutrition 0.000 description 4
- 229960004488 linolenic acid Drugs 0.000 description 4
- KQQKGWQCNNTQJW-UHFFFAOYSA-N linolenic acid Natural products CC=CCCC=CCC=CCCCCCCCC(O)=O KQQKGWQCNNTQJW-UHFFFAOYSA-N 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- DVWSXZIHSUZZKJ-YSTUJMKBSA-N methyl linolenate Chemical compound CC\C=C/C\C=C/C\C=C/CCCCCCCC(=O)OC DVWSXZIHSUZZKJ-YSTUJMKBSA-N 0.000 description 4
- 125000001624 naphthyl group Chemical group 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 4
- HTDIUWINAKAPER-UHFFFAOYSA-N trimethylarsine Chemical compound C[As](C)C HTDIUWINAKAPER-UHFFFAOYSA-N 0.000 description 4
- MJHNFOWITPQFBW-UHFFFAOYSA-N 2-methyltetradecanal Chemical compound CCCCCCCCCCCCC(C)C=O MJHNFOWITPQFBW-UHFFFAOYSA-N 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 125000000753 cycloalkyl group Chemical group 0.000 description 3
- VURFVHCLMJOLKN-UHFFFAOYSA-N diphosphane Chemical compound PP VURFVHCLMJOLKN-UHFFFAOYSA-N 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- VMGAPWLDMVPYIA-HIDZBRGKSA-N n'-amino-n-iminomethanimidamide Chemical class N\N=C\N=N VMGAPWLDMVPYIA-HIDZBRGKSA-N 0.000 description 3
- 125000004437 phosphorous atom Chemical group 0.000 description 3
- WTTJVINHCBCLGX-UHFFFAOYSA-N (9trans,12cis)-methyl linoleate Natural products CCCCCC=CCC=CCCCCCCCC(=O)OC WTTJVINHCBCLGX-UHFFFAOYSA-N 0.000 description 2
- OBDUMNZXAIUUTH-HWKANZROSA-N (e)-tetradec-2-ene Chemical compound CCCCCCCCCCC\C=C\C OBDUMNZXAIUUTH-HWKANZROSA-N 0.000 description 2
- SPEUIVXLLWOEMJ-UHFFFAOYSA-N 1,1-dimethoxyethane Chemical compound COC(C)OC SPEUIVXLLWOEMJ-UHFFFAOYSA-N 0.000 description 2
- HPYNZHMRTTWQTB-UHFFFAOYSA-N 2,3-dimethylpyridine Chemical compound CC1=CC=CN=C1C HPYNZHMRTTWQTB-UHFFFAOYSA-N 0.000 description 2
- LNJCGNRKWOHFFV-UHFFFAOYSA-N 3-(2-hydroxyethylsulfanyl)propanenitrile Chemical compound OCCSCCC#N LNJCGNRKWOHFFV-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- OYHQOLUKZRVURQ-HZJYTTRNSA-N Linoleic acid Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC(O)=O OYHQOLUKZRVURQ-HZJYTTRNSA-N 0.000 description 2
- PKIXXJPMNDDDOS-UHFFFAOYSA-N Methyl linoleate Natural products CCCCC=CCCC=CCCCCCCCC(=O)OC PKIXXJPMNDDDOS-UHFFFAOYSA-N 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- 229910052778 Plutonium Inorganic materials 0.000 description 2
- NRWGWVPBBBHHSR-UHFFFAOYSA-N [Au].[Os] Chemical compound [Au].[Os] NRWGWVPBBBHHSR-UHFFFAOYSA-N 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 150000007942 carboxylates Chemical class 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- YCOZIPAWZNQLMR-UHFFFAOYSA-N heptane - octane Natural products CCCCCCCCCCCCCCC YCOZIPAWZNQLMR-UHFFFAOYSA-N 0.000 description 2
- 239000012456 homogeneous solution Substances 0.000 description 2
- 235000020778 linoleic acid Nutrition 0.000 description 2
- OYHQOLUKZRVURQ-IXWMQOLASA-N linoleic acid Natural products CCCCC\C=C/C\C=C\CCCCCCCC(O)=O OYHQOLUKZRVURQ-IXWMQOLASA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- RPNNPZHFJPXFQS-UHFFFAOYSA-N methane;rhodium Chemical compound C.[Rh] RPNNPZHFJPXFQS-UHFFFAOYSA-N 0.000 description 2
- 125000000962 organic group Chemical group 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- OYEHPCDNVJXUIW-UHFFFAOYSA-N plutonium atom Chemical compound [Pu] OYEHPCDNVJXUIW-UHFFFAOYSA-N 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 description 2
- SYUHGPGVQRZVTB-UHFFFAOYSA-N radon atom Chemical group [Rn] SYUHGPGVQRZVTB-UHFFFAOYSA-N 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- BOLDJAUMGUJJKM-LSDHHAIUSA-N renifolin D Natural products CC(=C)[C@@H]1Cc2c(O)c(O)ccc2[C@H]1CC(=O)c3ccc(O)cc3O BOLDJAUMGUJJKM-LSDHHAIUSA-N 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- 238000006277 sulfonation reaction Methods 0.000 description 2
- OYHQOLUKZRVURQ-NTGFUMLPSA-N (9Z,12Z)-9,10,12,13-tetratritiooctadeca-9,12-dienoic acid Chemical compound C(CCCCCCC\C(=C(/C\C(=C(/CCCCC)\[3H])\[3H])\[3H])\[3H])(=O)O OYHQOLUKZRVURQ-NTGFUMLPSA-N 0.000 description 1
- FQQQBTSSQGFFCW-YSTUJMKBSA-N (9z,12z,15z)-2-methyloctadeca-9,12,15-trienoic acid Chemical compound CC\C=C/C\C=C/C\C=C/CCCCCCC(C)C(O)=O FQQQBTSSQGFFCW-YSTUJMKBSA-N 0.000 description 1
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- QWUWMCYKGHVNAV-UHFFFAOYSA-N 1,2-dihydrostilbene Chemical group C=1C=CC=CC=1CCC1=CC=CC=C1 QWUWMCYKGHVNAV-UHFFFAOYSA-N 0.000 description 1
- PRBHEGAFLDMLAL-UHFFFAOYSA-N 1,5-Hexadiene Natural products CC=CCC=C PRBHEGAFLDMLAL-UHFFFAOYSA-N 0.000 description 1
- ZDZHCHYQNPQSGG-UHFFFAOYSA-N 1-naphthalen-1-ylnaphthalene Chemical compound C1=CC=C2C(C=3C4=CC=CC=C4C=CC=3)=CC=CC2=C1 ZDZHCHYQNPQSGG-UHFFFAOYSA-N 0.000 description 1
- HFDVRLIODXPAHB-UHFFFAOYSA-N 1-tetradecene Chemical compound CCCCCCCCCCCCC=C HFDVRLIODXPAHB-UHFFFAOYSA-N 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
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- 235000009804 Cucurbita pepo subsp pepo Nutrition 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 229910001111 Fine metal Inorganic materials 0.000 description 1
- 235000005206 Hibiscus Nutrition 0.000 description 1
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- HPEUJPJOZXNMSJ-UHFFFAOYSA-N Methyl stearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC HPEUJPJOZXNMSJ-UHFFFAOYSA-N 0.000 description 1
- 229910004786 P-Li Inorganic materials 0.000 description 1
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- 150000001298 alcohols Chemical class 0.000 description 1
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- BIEJIFBEEAKZOI-UHFFFAOYSA-N lithium rhenium Chemical compound [Li].[Re] BIEJIFBEEAKZOI-UHFFFAOYSA-N 0.000 description 1
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- 150000004702 methyl esters Chemical class 0.000 description 1
- KISVAASFGZJBCY-UHFFFAOYSA-N methyl undecenate Chemical compound COC(=O)CCCCCCCCC=C KISVAASFGZJBCY-UHFFFAOYSA-N 0.000 description 1
- 125000002950 monocyclic group Chemical group 0.000 description 1
- 235000021281 monounsaturated fatty acids Nutrition 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N o-biphenylenemethane Natural products C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 1
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- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
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- 150000003284 rhodium compounds Chemical class 0.000 description 1
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- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- NTUROZDXWLPVHB-UHFFFAOYSA-M sodium;3-diphenylphosphanylbenzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=CC(P(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 NTUROZDXWLPVHB-UHFFFAOYSA-M 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
- 239000002600 sunflower oil Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical compound C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 0.000 description 1
- 239000010496 thistle oil Substances 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- MYAJTCUQMQREFZ-UHFFFAOYSA-K tppts Chemical compound [Na+].[Na+].[Na+].[O-]S(=O)(=O)C1=CC=CC(P(C=2C=C(C=CC=2)S([O-])(=O)=O)C=2C=C(C=CC=2)S([O-])(=O)=O)=C1 MYAJTCUQMQREFZ-UHFFFAOYSA-K 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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Description
B7 五、發明説明(1 ) 本發明係關於烯烴系不飽和化合物之醛化方法,其醛 化生成物不溶於或僅微溶於水。在傲爲反應媒質的極性有 機溶劑內之均相,進行反應。包括姥碳醣化合物以及磺化 或羧化有機單膦或多膦塩之觸媒系統,可溶於槿性有機溶 劑和水。 近年來,二法均確立供烯烴系不飽和化合物醛化用。 其一是在均相內進行,即烯烴原料、觸媒系統(姥碳醯和 有機膦),以及反應生成物,在一起形成溶液。反應生成 物利用蒸餾從反應混合物分離。另一法的特點是呈現觸媒 水相,從反應生成物分離,包括铑碳醣和磺化或羧化有機 膦。此反應變化例可單離醛化生成物,而不用熱法步驟, 簡化觸媒的再循環,使用末端烯烴時,可得特別高比例的 非支鏈醛類。 經濟部中央橾準局員工消費合作杜印裝 較高級的烯烴系單不飽和或多不飽和化合物之醛化, 愈來愈引起注意。不但延伸至烴的反應,而且延伸到不僅 含有双鍵,又含有反應性官能基的化合物。具有工業上重 要性的此類化合物例,是不飽和脂肪酸酯。常爲天然物, 或由天然原料製成且能大量入手。醛化反應生成物、單甲 醯羧酸酯或多甲醯羧酸基,亦可含有尙未反應的双鍵,爲 被尋求的中間物,可進一步處理成廣用的生成物,諸如聚 胺類、聚氨基甲酸乙国類、醇酸樹脂、可塑劑和合成潤滑 劑。 較高級烯烴系單不飽和或多不飽和化合物,使用铑碳 醣/膦觸媒,利用均相法醛化,已一再被硏究。此法的經 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) 經濟部中夬標準局員工消費合作社印製 A7 B7五、發明説明(2 ) 濟性只有在均質溶化的觸媒系統,可從反應生成物分離而 不損失,並以活性型回流到醛化反應器,才能得到保證。 迄今爲止,只能從含有單不飽和脂肪酸酯醛化衍生的甲酸 脂肪酸酯之反應混合物,除去觸媒。然而,其程序需要複 雜的措施,此外,所得觸媒爲不活性型,而觸媒系統的膦 成份則完全損失(J. Amer. Oil Chem. Soc. 50 卷,455, (1973))。 若使用具有同時接近在一起的單離双鍵之多不飽和化 合物,可以進行醛化而避免双鍵異構化,但均勻溶於反應 生成物內的觸媒,則不可能例如利用蒸餾再循環。 亞油酸和亞麻酸的甲酯可在基於聚矽氧烷的異相化錯 碳醣/膦錯合物觸媒存在下醛化(化學雜誌,115 (1991) ,第39頁起)。若使用亞油酸甲酯,此法可得單甲醣硬脂 基醒,產率爲79%,就使用双重不飽和酯而言,在上述觸 媒系統存在下的醛化,亞麻酸可得最多50%的二甲醯化合 物,而三甲醯生成物頂多爲輔量(在10 %以下)。進行的 铑量平均爲原始所用貴金屬的約〇·5 %。不能排除觸媒金 靥在均質溶液內的平例與固定金靥平衡,故醛化不但在固 定床觸媒上,也在溶液內發生。 較高級烯烴系不飽和化合物在觸媒水溶液內醛化,並 不發生反應生成物和觸媒系統彼此分離上的困難°然而, 由於烯烴在水中的低溶解度,轉化率常不能令人滿意。按 照EP-B-157 316,其避免方法是,令分子內含C«以上烯烴 的醛化,是在包括姥錯合物爲觸媒而季銨塩爲增溶劑的存 ο (請先閲讀背面之注意事項再填寫本頁) -裝·
一、-IT i^r 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) 經濟部中央標準局員工消费合作社印裝 A7 _B7 __ 五、發明説明(3) 在下進行。此法另一發展是EP-B-163 234之標的。按照此 專利,C«-C2e烯烴在铑和磺化芳基膦塩(爲季銨塩)存在 下與氫和一氧化碳反應。膦的季銨塩在此不但有觸媒成份 的作用,同時還可做爲增溶劑。二者僅與不含官能基的單 不飽和化合物反應有關。 所以,本發明之目的,在於開發一種製法,可使較高 分子童的烯烴不飽和化合物醛,多不飽和出發物料不但部 份,而且完全反應成甲醯化合物。 此外,反應生成物和觸媒系統應容易彼此分離,而貴 金屬損失即可大爲避免。 上述目的是由烯烴系不飽和化合物的醛化方法達成, 其醛化生成物不溶於或僅稍溶於水中。包括令烯烴系不飽 和化合物在60至180 °C和1至35 MPa,與一氧化碳和氫, 在極性有機溶劑的均相內,以及在包括鍺碳醯化合物和磺 化或羧化有機單膦或多膦塩之觸媒系統存在下反應,該塩 可溶於極性有機溶劑和水內,從反應混合物餾除極性有機 溶劑,再用水從蒸餾殘餘物分離觸媒系統。 新法兼具在均相醛化的特徵和在多相(即觸媒水相) 存在下醛化的優點,提供新而前瞻性的操作方法,極爲適 宜較高分子量烯烴系單不飽和或多不飽和化合物的反應。 特別成功的是用於不飽和,尤指多不飽和脂肪酸酯的醒化。 出乎意外的是,本發明製法可使酸分子內存在的複數 双鍵(亦可在非末端位置)同時醛化,因此,例如双不飽 和化合物得二甲醯生成物,而三不飽和化合物得三甲醯生 3〜 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) (請先閲讀背面之注意事項I寫本頁 .裝. 旅 經濟部中央棣準局負工消費合作社印袈 A7 _B7___ 五、發明説明(4 ) 成物。此外,新法是以出發物料和觸媒的均相溶液,代替 包括烯烴不飽和化合物和EP-B-167 316和EP-B-163 234所 述反應特徵的觸媒水溶液之多相反應系統,結果可提高反 應率,並改善轉化率。 適用做本發明製法出發物料的較高分子量烯烴系不飽 和化合物,必須可溶於用做反應媒質之極性有機溶劑,且 必須有不溶於或僅稍溶於水中的醛化生成物。因此,分子 內具有Ce或以上的無環單烯烴,尤指Cle-C3e單烯烴,諸如 三和四丁烯類以及三和四異丁烯類,可按照新法反應。分 子內具有至少C«的多不飽和無環或環型烯烴,尤其是包含 單環和双環烯烴,亦可利用本發明製法成功醛化。此等化 合物類之例,有二環戊二烯、1,5 —環辛三烯、1,5,9 一 環十二碳三烯、1,5 —己二烯、1,7 —辛二烯、1,9 一癸 二烯。如上所述,新的製程特別宜於不飽和脂肪酸醒類之 醛化。此等酯類尤指衍生自分子內具有Ce-C«的双或三不 飽和脂肪酸,以Cie-C«爲佳,以及分子內具有Ci-Cu»的飽 和脂肪族單醇類,以甲醇爲佳。此等酯類可由天然油(如 有需要,先經提煉和蒸餾),利用圈基轉化作用而得。做 爲出發酯的酸成份基礎的天然油例,有棉耔油、薊子油、 花生油、南瓜核仁油、亞麻子油、玉米油、豆油和葵花子 油。 所請求製法中使用的觸媒系統,可溶於極性有機溶劑 和水中,並包括姥碳醯化合物爲一成份,而磺化或羧化有 機膦塩爲另一成份,該塩可溶於水和極性有機溶劑。
/^/ A 本紙張尺度適用中國國家標準(CNS ) Α4規格(210Χ297公釐) ----^--·-----—裝------.訂 -------- ^/ϊχ. (請先聞讀背面之注意事項再填寫本頁) 經濟部中央橾準局負工消費合作社印製 A7 B7 五、發明説明(5 ) 姥碳醯與膦反應形成錯合物,铑碳醢化合物內的部份 一氧化碳分子,被做爲配合基的膦分子所取代°姥/膦錯 合物的溶解度是以膦的溶解度所決定。對姥而言,膦常以 過暈存在,即觸媒系統不但含姥/膦錯合物,且含有游離 膦。 本發明中的有機膦係指單膦類或多膦類,其中烷基和 /或芳基係結合於三價磷原子,此等烷基和/或芳基至少 其一係單或多磺化或羧化者,脂肪族基之例有C2_C8飽和 烴,和c6-c8環型烴的直鏈或支鏈基。典型的芳香族基有 苯基、爭基和萘基。脂肪族和芳香族基二者均可再以烷基 、羥基或鹵素等取代。所述有機膦亦可含有三價磷化合物 ,其中磷原子爲雜環族環的組成份。 觸媒系統內存在的膦不必爲均勻化學化合物,而是可 具有不同的化學組成份。因此,有機基附設於磷原子的型 式和結合,磺化或羧化的程度,或陽離子類別,均可不同 。做爲觸媒組成份適用性的決定因素,在於水中和極性有 機溶劑中之溶解度。此項標準尤其由磺化或羧化膦之塩, 其陽離子爲鋰或式NiWWR4)+之銨離子者可以達成。R1 可相同或不同,爲氫、直鏈或支鏈烷基,尤其 是Cl-C*烷基。 磺化或羧化單膦之陰離子最後相當於式⑴: 〜5〜 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) — ·!11--II 1·1111 4 裝— -- ----訂—-----,J,-------- (請先閲讀背面之注意事項再填寫本頁) n I— I I —i h · A7 B7 五、發明説明(6 )
[(X8 )-]mi ⑴ (請先閲讀背面之注$項再填寫本頁) -裝. 其中Ar1,Ar2,Ars各爲苯基或萘基,X1,X*,Xa各爲 磺酸根(-S〇3_ )和/或羧酸根(-coo-),Y1,Y*,Y3各爲 Ch-C*直鏈或支鏈烷基、烷氧基、鹵素原子、〇H、CN、 NO*或(RsRe)N基,其中R*^R6各爲Ci-G直鏈或支鏈烷 基,m丨,m2,ma爲0至5的相同或不同整數,惟m丨,m2, im至少其一大於0,m,n2,n3爲0至5的相同或不同整 數。 特別通用的塩是衍自式⑴的陰離子,其中Ar1,Ar2 ,Ar3各爲苯基,X1,X2,X3各爲位在相對於膦間位的磺 酸根,即三(間磺酸根絡苯基)膦塩(簡稱TPPTS )。適 用做觸媒成份的其他塩,爲二苯基(間磺酸根絡苯基)膦 (簡稱TPPMS),尤其是鋰塩(Li-TPPMS)。 已知適合做觸媒成份的另一組單膦陰離子,爲下式⑵: 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐)
;1T ja 經濟部中央標準局貝工消费合作社印裂 A7 B7 五、發明説明(7 ⑵ A2P- (CH* )n -CH(R) -S〇3~ 其中A爲相同或不同之烷基和/或芳基,n爲〇,1或2 ,R爲氫或烷基。化合物係二烷基膦或二芳基膦以1,2-、 1,3-或1,4-碾經磺烷化而得:
R-CH (CH2) 0 so* (其中n=l,2或3,而R = H,烷基),例如按照 CH2 CH2 SO 2 A*P-Li + I I -> A2P(CH2)4-SO,Li CH2 O\ / ch2 請 先 聞 之 注
事 項 K 裝 頁 訂 經濟部中央標牟局貝工消費合作社印製 鹼金屬塩可利用常法轉化爲銨塩。 陰離子不但由單勝類,亦可由多膦類形成,尤其是二 膦類,含有至少一磺化或羧化有機基者。二膦陰離子最好 衍生自式⑶之二芳基化合物: (R7)*P P(R7 ) 2 (CH2 )m. (Η2〇ηΐ4
(R*)n ‘ (R8)i ⑶ 本紙張尺度適用中國國家標準(CNS ) A4規格(210X 297公釐) 經濟部中央標準局負工消费合作社印裂 A7 B7 五、發明説明(8 ) 可由至少一磺酸根(-so,-)或羧酸根(-COCT)取代。在式 中,R7爲相同或不同之烷基、環烷基、苯基、甲苯基或萘 基,R8相同或不同,爲氫、烷基或烷氧基,還有環 烷基、Ce-Cm芳基或芳氧基,或熔合苯環,相同或不同 ,爲0至5的整數,同樣相同或不同,爲〇至4的整數 。參見磺化化合物,可由習知方法製得。此類可用之化合 物代表例,有2,2^—双(二苯基膦甲基)一 Ι,Γ 一聯苯或 2,2〃 一双(二苯基膦甲基)一 I," 一聯萘,經磺化而得之 生成物。可資一提的雜環磷化合物陰離子之例爲,3,4 一 二甲基一 2,5,6—三(對磺酸根絡苯基)一1 一磷原水片 二烯。 烯烴系不飽和出發化合物與氫和一氧化碳之反應,是 在溫度60至180 °C,尤其是1〇〇至140 ,和壓力1至35 MPa進行。對烯烴的醛化而言,壓力2至35 MPa特別有用 ;不飽和脂肪酸之團類最好在壓力15至25 MPa反應。 反應是在包括不但溶化烯烴系不飽和出發化合物,還 能溶化反應生成物和觸媒系統的極性有撒溶劑之反應媒質 內進行。適當溶劑爲分子內具有Ci-G的低分子量脂肪族 醇。純溶劑亦可改用二種或多種此等醇類之混合物,諸如 甲醇/乙醇、甲醇/異丙醇混合物。發現特別有用的反應 媒質爲甲醇和乙醇,可含5 %重量水以下,但以無水型式 使用爲佳。 觸媒在添加於反應系統之前,可預形成。然而亦可在 反應混合物內,即烯烴系不飽和化合物和溶劑,在反應條 〜8 〜 本紙張尺度適用中國國家標準(CNS ) A4規格(210X297公釐) ----^--.----— 裝------,訂-------- (請先閲讀背面之注意事項&寫本頁) 經濟部中央標準局員工消費合作社印製 A7 B7 五、發明説明(9 ) 件下,由姥或铑化合物成份,以及磺化或羧化膦溶液,同 樣成功製成。除微細型金屬姥外,亦可使用無機姥塩,諸 如氣化姥、硫酸姥,有機酸的铑塩,諸如乙酸姥、2—乙 基己酸姥,或氧化姥,傲爲姥源。 反應溶液內的姥澳度,爲溶液的100至600 ppm重量 ,以300至400 ppm重量。膦用量使每莫耳姥,有至少20 莫耳POE)存在,以40至80莫耳爲佳。 反應溶液的pH不能在3以下。一般pH設定在4至 11。若使用甲醇爲溶劑,醛化形成的醛類會發生乙醯化。 如需保護碳醣基免於副反應,宜在pH 4.5至6.5作業, 以5.5至6.0爲佳。 合成氣內一氧化碳對氫之比,可在廣範圍內變化。一 般而言,所用合成氣中一氧化碳對氫之容量比爲1:1, 惟可稍有出入。 反應可以分批或連續方式進行。 爲處理反應生成物,先將極性有機溶劑餾除。蒸餾殘 渣再水洗,以在周遭溫度爲佳,從醛類除去觸媒系統,此 項處理可重複適當次數。爲完全回收姥,宜在洗淨水內添 加可與姥形成錯合物的膦,尤其是同時做爲觸媒成份的膦。 本發明製法可由下述實施例說明,惟不限於所示具體 例。 實施例1 以氩冲洗過的Schlenk管,充塡15毫升甲醇、60毫克( 0.05毫莫耳)8.5 %重量強度的铑溶液(爲Rh* (SO* )3水溶 本紙張尺度適用中國國家標準(CNS ) Α4規格(210X297公釐) -------------裝-------訂 J-----Λ (請先聞讀背面之注意事項寫本頁) 經濟部中央標準局員工消費合作社印東 A7 ___B7_________ 五、發明説明(10 ) 液),和700毫克(2毫莫耳)二笨基(4 一磺酸根絡丁 基鋰)膦。P/Rh莫耳比爲40。溶液的pH調至5,溶液再 利用注射筒引進利用氩冲洗並充滿的實驗室壓熱器內。取 15克90 %重量強度的亞麻酸甲酯(其餘爲亞油酸甲酯), 置放於壓熱器之耐壓滴液漏斗內。壓熱器以水煤氣冲洗, 隨即設定反應屋力爲20 MPa,反應溫度爲120 °C。預形成 1小時後,滴加亞麻酸甲酯,經由壓力察覺器和記錄器監 視壓力降。10小時後,氣體吸收完全。將壓熱器冷却,排 氣,利用不含空氣(氣)的蒸餾,使內容物排除甲醇◊殘 渣每次以15 — 20毫升無氧水洗二次,以萃取觸媒系統,再 分析。將亞麻酸和亞油酸酯的轉化率定量,產率爲: 5 %單甲釀生成物,對全部出發物料而言。 22%二甲醯生成物,對全部出發物料而言。 82%三甲醯生成物,對出發物料內所用亞麻酸甲围 的比例而言。 實施例2至6 實施例2至6是以實施例1的類似方式進行,惟g力 、觸媒溶液pH和P/Rh比改變。所得結果如下表所示。 10 ^ ^張尺度適用中國國家橾準(CNS ) A4規格(210X297公釐) (請先閱讀背面之注意事項再填寫本頁) •裝. .訂] A7 B7 經濟部中央標準局員工消費合作社印製 五、發明説明(π ) 表 1 寅施例 P/Rh pH 溫度 CC) 壓力 (MPa) 時間⑴MF⑵DF(3) (h) ( mol % > mm {%) 2 40 8.4 120 20 3 4 24 80 100 3 20 5.0 120 20 3 14 44 47 100 4 10 5.0 120 20 3 16 44 45 100 5 10 5.0 120 7 3 20 50 34 100 6 20 5.0 120 7 3 15 59 40 100 ⑴氣體被吸收90 — 95 %後的時間。 ⑵單甲醯生成物,對全部出發物料而言。 ⑶二甲醯生成物,對全部出發物料而言。 ⑷三甲醯生成物,對所用亞麻酸甲國而言。 實施例7 於用氩冲洗過,裝設有磁力攪拌器、耐壓計量容器、 溫度計支座和壓力察覺器(膨脹測量條)的100毫升V4A 不銹鏑壓熱器內,充塡24毫克姥(0.05毫莫耳),呈Rh2 (S〇4)3水溶液,和2.2克(3毫莫耳)三(四甲基銨間磺 酸根絡苯基)膦,溶於30毫升甲醇內(P/Rh莫耳比60 )。 將壓熱器關閉,以水煤氣冲洗,設定反應溫度120 °C,反 應壓力2 MPa。從計量容器添加】0克(50毫莫耳)10 —十 一烷酸甲酯。1小時後,轉化完成。形成71 % 11 _甲醢十 一烷酸甲酯和29%1〇 —甲醢十一烷酸甲酯的刃%混合物, 另3%爲加氫生成物十一烷酸甲酯。餾除甲醇後,觸媒系 〜11〜 本紙張尺度適用中國國家標準(CNS ) A4規格(210X:297公釐) ----^--.-----rr 裝-- (請先閱讀背面之注$項再填寫本頁) 訂 J/ 經濟部中央橾準局貝工消費合作社印褽 A7 B7__五、發明説明(Π ) 統可溶提於水中,利用分相從反應生成物分離。 實施例8 重複實施例7,反應屋力爲1 MPa,其他條件相同。 30分鐘後,轉化完成。除99%混合物(由70 %重量的11 一 甲醯十一烷酸甲酯和30 %重量的1〇 —甲醣十一烷酸_組成 )外,只有1%十一烷酸甲酯。餾除甲醇後,在水中溶提 觸媒系統,並從反應生成物分離。 寅施例9 在氩做爲保護氣體下,取15毫升甲醇,〇·〇5毫莫耳Rh ,爲60毫克8.5 %強度铑溶液的型式(Rh2(S〇d3水溶液) ,和348毫克(1毫莫耳)Li - TPPMS ( P/Rh莫耳比20 ) ,置放入Schlenk管內。溶液的pH調至6,將溶液在氣保 護下置入壓熱器內。壓熱器關閉並用水煤氣冲洗後,設定 反應壓力10 MPa,反應溫度120 °C。從計量容器添加12克 (60毫莫耳)正十四碳烯~1。1小時後,烯烴已完全反 應。形成98%醛化生成物(其組成份爲72 %重量正十五碳 醛和28%重量2 —甲基十四碳醛),以及2%加氫生成物 正十四烷。所得醛類主要爲二甲基縮醛的型式。大部份甲 醇溶劑餾除後,反應生成物與約10毫升水混合,將觸媒錯 合物分離。有機相再以約5毫升水萃取一次,水性萃取物 組合後,減壓餾除水,觸媒系統再溶於甲醇內。 實施例10至15 按實施例9所述回收的觸媒系統,重複使用於正十四 碳烯一 1的醛化。條件同實施例9,實驗結果如下表2。 12 I紙張尺度適用中國國家標準(CNS ) A4規格(210Χ297公釐) (請先閲讀背面之注意事項再填寫本頁) 裝· --、tr J%· B7 、發明説明( 13 ) 轉化率 寅施例 (%) 產率 (%) 正十五 碳醛 (%) 2 —甲基 十四碳醛 (%) 十四烷 (%) 10 100 98 72 28 2 11 100 96 70 30 4 12 100 98 71 29 2 13 100 99 70 30 1 14 100 98 71 29 2 15 100 97 70 30 3 寘施例 經濟部中央樣準局員工消費合作社印製 在氩保護氣體下,取25毫升甲醇,〇.05毫莫耳仙,爲 60毫克8.5 %強度姥溶液的型式(Rh“SO«)3水溶液),和 348毫克(1毫莫耳)Li - TPPMS ( P/Rh莫耳比20 ),置 入Schlenk管內。溶液的pH調至11,在氩保護下放入壓熱 器內。屋熱器關閉並以水煤氣冲洗後,設定反應壓力 MPa,反應溫度120 °C。從計量容器添加12克(60毫莫耳 )正十四碳烯一1。1小時後,烯烴完全反應。形成98% 醛化生成物(其組成份爲71 %重量正十五碳醛和29%重量 2 —甲基十四碳醛),以及2%加氫生成物正十四烷。形 成的醛類只有3%是二甲基縮醛(pH高達11的結罘)° 實施例17 在氩保護氣體下,將15毫升甲醇,〇.〇5毫莫耳Rh,爲 60毫克強度姥溶液的型式(Rh*(SCM,溶液),和 13 本紙張尺度適用中國國家標準(cns ) a4規格(210x297公釐) 389751 五、發明説明(Μ ) 348毫克(1毫 入Schlenk管內。 器內。屋熱器關 MPa,反應溫度 )工業級亞麻酸 酸甲酯和20 %油 生成物,22 %重 物,基於工業級 根據三醛化生成 A7 B7 莫耳)Li-TPPMS (P/Rh莫耳比20 ),置 溶液的pH調至6,在氬保護下放入壓熱 閉和用水煤氣冲洗後,設定反應壓力20 1 20 °C,從計量容器添加16克(50毫莫耳 甲幽(55%亞麻酸甲酯,其餘約15%亞油 酸甲酸)。反應混合物含23%重量單甲醯 量二甲醢生成物,和47 %重量三甲醢生成 生成物內亞麻酸甲酯55 %的比例,此代表 物的形成有85 %的選擇性。 (請先閱讀背面之注意事項寫本頁) 經濟部中央樣準局員工消費合作社印製 14 本紙張尺度適用中國國家揲準(CNS ) Α4規格(210X297公釐)
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- 一―' 一88 年 9 月 17 日修正^89751 ~ 、申请專利範圍---------------- ~ 1. 一種烯烴系不飽和化合物之醛化方法,其醛化生成 物不溶於或俥稍溶於水,此方法包括烯烴不飽和化合物在 至180ec和1至35 i^Pa,與一氧化碳和氳,在分子內真 有C「C4的低分子纛脂肪醇或此等酵類-種或以上之混合 物極性有機溶劑內,以及包括鍺碳鼸化合物和《化有機單 膦或多鱗鹽存在下,於均楮內反應,該鹽可溶於極性有檐 溶剤和水中,並具W下式:<: < < [(X1)- 1m, Yln, [(X2)- ]m2 Y?n2 [(X3)- ]m3 Υ3η, -------C— (請先閏讀背面之注$項再填寫本頁) 訂- -: 經濟部中央橾準局貞工消費合作社印裝 其中Ar1, Ar2, Ar3各爵苯基或荖基,X1, X2, X3各爲《酸根 (-S03-),Y1,Y2, Y3 各爲 C1-C4 直鍵或支 # 嬈基,m,,m2, m3相同或不同,爲〇至5之整數,_ «^,《»2,1113至少其一 大於〇,n,,n2,n3相同或不同,爲〇至5之整數,或臭有 下式: A2P- (CH2)m- Cil(R)- S03- 1 5 本紙張尺度逋用中國國家揉準(CNS ) A4规格(2丨0X297公釐) 一―' 一88 年 9 月 17 日修正^89751 ~ 、申请專利範圍---------------- ~ 1. 一種烯烴系不飽和化合物之醛化方法,其醛化生成 物不溶於或俥稍溶於水,此方法包括烯烴不飽和化合物在 至180ec和1至35 i^Pa,與一氧化碳和氳,在分子內真 有C「C4的低分子纛脂肪醇或此等酵類-種或以上之混合 物極性有機溶劑內,以及包括鍺碳鼸化合物和《化有機單 膦或多鱗鹽存在下,於均楮內反應,該鹽可溶於極性有檐 溶剤和水中,並具W下式:<: < < [(X1)- 1m, Yln, [(X2)- ]m2 Y?n2 [(X3)- ]m3 Υ3η, -------C— (請先閏讀背面之注$項再填寫本頁) 訂- -: 經濟部中央橾準局貞工消費合作社印裝 其中Ar1, Ar2, Ar3各爵苯基或荖基,X1, X2, X3各爲《酸根 (-S03-),Y1,Y2, Y3 各爲 C1-C4 直鍵或支 # 嬈基,m,,m2, m3相同或不同,爲〇至5之整數,_ «^,《»2,1113至少其一 大於〇,n,,n2,n3相同或不同,爲〇至5之整數,或臭有 下式: A2P- (CH2)m- Cil(R)- S03- 1 5 本紙張尺度逋用中國國家揉準(CNS ) A4规格(2丨0X297公釐) A8 B8 C8 D8 389751 夂、申請專利範固 其中A相同或不同芳朞,n爲〇、i或2, R爲氳贫烷碁; 從反應混合物蒸篇極铨有機瘠劑,並用水從蒸鏞殘渣分, 觴媒系鲜者。 2·如申請專利範園第1碉之方法,其中烯烴系不飽和 :(匕合物爲分子內具有C,。或以上的無環單烯烴類,分子內 有h或以上的多不飽和鉍環或環型烯烴,或不飽和脂肪酸 之酯類者。 3. 如申請專利範圍第1或2項之方法,其中烯鑼系不 飽和化合物爲無環Cm-Cs。單烯烴者。 4. 如申請專·利範藺第1或2項之方法,萁中烯烴系不 . ! 陴和化合物爲分子有(:6或以上之単環或雙環烯烴者。 5. 如申請專利範園第I或2項之方法,其中烯烴系不 飽和化侖物爲分子內有c*-c25的雙或三不飽和磨肪酸之酯 類者。 ¢.如申請專利範園第5項之方法,其中酯類係衍生自 分子內有雙或三不飽和諶肪酸者。 7.如申請專利範園飨2項之方法,其中_類係衍生自 分子內有G-C,。飽和脂肪族單醉者9 8·如申請專利範國第7項之方fe,其中脂肪族車醉爲 甲醇者。 9.如申猜專利箱園第1項之方法,其中棰性有機溶渐 爲申酵或乙》者。 10·如申請專利範園第1項之方法,其中磧化有機躡鹽 <可溶於極性有檐溶剤和水〉之陽醮子,禽鋰或式 1 (5 本紙張尺度適用中國國家梂準(CNS )八4規格(210X297公釐) (請先閱讀背面之注f項再4寫本頁) -订 經濟部中央標準局貝工消费合作社印31389751 申請專利範圍 〜^^)+的銨離子,其中Rl,R2, R3, R4相词玫不同, 爲Μ、直鍵或支鍵病基,尤指cvc·烷基者β ίΐ·如申猜專利範園第丨項之方法,其中磺化有機膦鹽 (可溶於極性有機溶剤和水)含三(問磧酸根絡苯基)膦 除離子者。 12. 如申請專利範困第」項之方法,其中烯烴系不飽和 化合物與氫和一氧化辑之反應,是在1〇〇率l4〇»C進行者。 13. 如申請專利範園第1項之方法,其中烯烴類與氳和 —氧化碳之反癉,是在壓力1至以MPa進行者6 K如申請專利範園第1項之方法,其中不飽和脂肪酸 酯舆一氧化碳和氫的反應,琴在15至25 MPa進行者。 15.如申請專利範國第1項之方法,其中觸媒溶液內的 鍺濃度爲溶液乏lb〇至600 ppm蓽灰者。 I6·如申請専利範圃第I5項土方法,其中反應溶液內 的鍺濃度爲溶液之300至400 ppm重置者。 ί7·如申請拿利範園第1項之方法,其中反嫵溶兪內每 莫耳鍺有至少20莫耳p(m>者。 1S.如申薄專利範面第17¾之方法,其中反應溶液內 毎莫耳鍺有40至80莫耳p(m)存奄者。 19. 如申請專利範園第1項之方法,其中反應溶液之 PH至少3者。 20. 如申請專利範豳第項之方法,其中反應溶液之 pH爲4至1ί者。 21. 如申請專利範園捧1項之方法,其中反應溶液之 本紙張尺度適用中國國家揉準(CNS ) A4规格(210X297公釐) (請先閱讀背面之注f項再填寫本頁) j—·-订· 經濟部中央梂率局貝工消費合作社印袈 A8 B8 C8 D8 389751 、申請專利範圍 pH爲4.5至6.5者。 22.如申轉專利範圔第21項之方法,其中反應溶液之 pH爲5.5至6.0者。 23 ·如申請專利範圃第1項之方毕,其中利用水多次處 理,而從蒸«殘渣分離觸媒系統者。 24.如申請專利辑園第1項之方法,其中對水添加可舆 鍺形成錯合物之膦_,以處理蒸餹殘渣者。 (請先《讀背面之注f項再填寫本頁) ·訂 r 經濟部中央梯隼局貞工消費合作社印袋 18- 本纸張尺度適用中國國家梂準(CNS ) A4規格(210X297公釐)
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DE19532393A DE19532393A1 (de) | 1995-09-02 | 1995-09-02 | Verfahren zur Hydroformylierung olefinisch ungesättigter Verbindungen |
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TW085109975A TW389751B (en) | 1995-09-02 | 1996-08-16 | Process for the hyoroformylation of olefinically unsaturated compounds |
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US (1) | US5756854A (zh) |
EP (1) | EP0761635B1 (zh) |
JP (1) | JP3042835B2 (zh) |
KR (1) | KR970015551A (zh) |
CN (1) | CN1149043A (zh) |
AT (1) | ATE182876T1 (zh) |
AU (1) | AU6439096A (zh) |
BR (1) | BR9603617A (zh) |
CA (1) | CA2184048C (zh) |
DE (2) | DE19532393A1 (zh) |
DK (1) | DK0761635T3 (zh) |
ES (1) | ES2137604T3 (zh) |
GR (1) | GR3031630T3 (zh) |
MX (1) | MX9603656A (zh) |
PL (1) | PL183632B1 (zh) |
TW (1) | TW389751B (zh) |
ZA (1) | ZA967228B (zh) |
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ID21537A (id) * | 1997-12-22 | 1999-06-24 | Celanese Gmbh | Proses pembuatan aldehid |
KR100308731B1 (ko) * | 1998-06-17 | 2001-11-14 | 박호군 | 로듐촉매/염조촉매시스템을사용한이산화탄소의수소화방법 |
US6307109B1 (en) | 2000-03-15 | 2001-10-23 | Union Carbide Chemicals & Plastics Technology Corporation | Separation processes |
US6303829B1 (en) | 2000-03-15 | 2001-10-16 | Union Carbide Chemicals & Plastics Technology Corporation | Separation processes |
US6307108B1 (en) | 2000-03-15 | 2001-10-23 | Union Carbide Chemicals & Plastics Technology Corporation | Metal-ligand complex catalyzed processes |
US6307110B1 (en) | 2000-03-15 | 2001-10-23 | Union Carbide Chemicals & Plastics Technology Corporation | Separation processes |
US6303830B1 (en) | 2000-03-15 | 2001-10-16 | Union Carbide Chemicals & Plastics Technology Corporation | Metal-ligand complex catalyzed processes |
US6310260B1 (en) | 2000-03-15 | 2001-10-30 | Union Carbide Chemicals & Plastics Technology Corporation | Separation processes |
US6294700B1 (en) | 2000-03-15 | 2001-09-25 | Union Carbide Chemicals & Plastics Technology Corporation | Separation processes |
KR100322616B1 (ko) * | 2000-08-29 | 2002-03-18 | 박호군 | 로듐 촉매/염 조촉매 시스템을 사용한 올레핀의하이드로포밀화 방법 |
KR100322617B1 (ko) * | 2000-08-29 | 2002-03-18 | 박호군 | 로듐 촉매/염 조촉매 시스템을 사용한 올레핀의카보알콕시화 및 카복실화 방법 |
US7615658B2 (en) * | 2003-04-25 | 2009-11-10 | Dow Global Technologies, Inc. | Aldehyde and alcohol compositions derived from seed oils |
CA2652016C (en) * | 2006-05-15 | 2015-02-03 | Dow Global Technologies Inc. | Hydroformylation process and product separation with improved recovery of rhodium |
CN100496736C (zh) * | 2007-05-31 | 2009-06-10 | 南京大学 | 一种用于双环戊二烯氢甲酰化制醛的水溶性配体铑配合物催化剂 |
CN101722048B (zh) * | 2008-10-31 | 2011-11-30 | 中国石油化工股份有限公司 | 一种两相催化氢甲酰化反应制备醛的催化剂及其应用 |
US9382180B2 (en) | 2012-12-06 | 2016-07-05 | Dow Technology Investments Llc | Hydroformylation process |
US9738853B2 (en) * | 2014-03-06 | 2017-08-22 | Elevance Renewable Sciences, Inc. | Renewably derived aldehydes and methods of making and using the same |
CN112570032A (zh) * | 2020-11-17 | 2021-03-30 | 广东仁康达材料科技有限公司 | 一种水溶性氢甲酰化催化剂及其应用 |
CN118204199B (zh) * | 2024-03-06 | 2024-09-20 | 淄博坤鑫选矿药剂有限公司 | 一种可用于锂辉石浮选磺化有机羧酸类捕收剂、制备方法、及其复配应用 |
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US4248802A (en) * | 1975-06-20 | 1981-02-03 | Rhone-Poulenc Industries | Catalytic hydroformylation of olefins |
JPS58216138A (ja) * | 1982-06-09 | 1983-12-15 | Kuraray Co Ltd | 1,8−オクタンジア−ルまたは1,10−デカンジア−ルの製造法 |
FR2571725B1 (fr) * | 1984-10-16 | 1987-09-18 | Rhone Poulenc Chim Base | Complexes rhodies, dinucleaires et hydrosolubles et leur utilisation comme catalyseur d'hydroformylation |
US4808756A (en) * | 1986-04-07 | 1989-02-28 | Kuraray Co., Ltd. | Method for production of α,ω-dialdehydes |
US4731486A (en) * | 1986-11-18 | 1988-03-15 | Union Carbide Corporation | Hydroformylation using low volatile phosphine ligands |
JP2775907B2 (ja) * | 1989-07-12 | 1998-07-16 | 三菱化学株式会社 | ヒドロホルミル化法 |
DE3942954A1 (de) * | 1989-12-23 | 1991-06-27 | Hoechst Ag | Verfahren zur herstellung von aldehyden |
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1995
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1996
- 1996-08-16 TW TW085109975A patent/TW389751B/zh active
- 1996-08-23 CA CA002184048A patent/CA2184048C/en not_active Expired - Fee Related
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CA2184048A1 (en) | 1997-03-03 |
BR9603617A (pt) | 1998-05-19 |
DK0761635T3 (da) | 1999-12-06 |
DE19532393A1 (de) | 1997-03-06 |
EP0761635A1 (de) | 1997-03-12 |
ES2137604T3 (es) | 1999-12-16 |
PL315833A1 (en) | 1997-03-03 |
US5756854A (en) | 1998-05-26 |
PL183632B1 (pl) | 2002-06-28 |
MX9603656A (es) | 1997-03-29 |
GR3031630T3 (en) | 2000-01-31 |
EP0761635B1 (de) | 1999-08-04 |
KR970015551A (ko) | 1997-04-28 |
DE59602596D1 (de) | 1999-09-09 |
JPH09124534A (ja) | 1997-05-13 |
JP3042835B2 (ja) | 2000-05-22 |
AU6439096A (en) | 1997-03-06 |
ZA967228B (en) | 1997-03-03 |
CA2184048C (en) | 1999-05-25 |
CN1149043A (zh) | 1997-05-07 |
ATE182876T1 (de) | 1999-08-15 |
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