CN1032538C - 磺化2,2’-双(二苯膦甲基)-1,1’-联萘及其制备方法 - Google Patents
磺化2,2’-双(二苯膦甲基)-1,1’-联萘及其制备方法 Download PDFInfo
- Publication number
- CN1032538C CN1032538C CN93106100A CN93106100A CN1032538C CN 1032538 C CN1032538 C CN 1032538C CN 93106100 A CN93106100 A CN 93106100A CN 93106100 A CN93106100 A CN 93106100A CN 1032538 C CN1032538 C CN 1032538C
- Authority
- CN
- China
- Prior art keywords
- rhodium
- sulfonation
- reaction
- mole
- dinaphthalene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 150000001875 compounds Chemical class 0.000 claims abstract description 33
- 239000003054 catalyst Substances 0.000 claims abstract description 26
- 150000001336 alkenes Chemical class 0.000 claims abstract description 17
- 238000007037 hydroformylation reaction Methods 0.000 claims abstract description 15
- 229910052751 metal Inorganic materials 0.000 claims abstract description 14
- 239000002184 metal Substances 0.000 claims abstract description 14
- 239000001257 hydrogen Substances 0.000 claims abstract description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 12
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 4
- VURFVHCLMJOLKN-UHFFFAOYSA-N diphosphane Chemical compound PP VURFVHCLMJOLKN-UHFFFAOYSA-N 0.000 claims description 49
- 238000000034 method Methods 0.000 claims description 48
- 239000010948 rhodium Substances 0.000 claims description 48
- 238000006277 sulfonation reaction Methods 0.000 claims description 45
- 238000006243 chemical reaction Methods 0.000 claims description 42
- 229910052703 rhodium Inorganic materials 0.000 claims description 39
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 39
- -1 alkali metal hydrogen oxygen compound Chemical class 0.000 claims description 30
- 239000000243 solution Substances 0.000 claims description 29
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 17
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 claims description 11
- 150000001412 amines Chemical class 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 239000004215 Carbon black (E152) Substances 0.000 claims description 8
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 8
- 229930195733 hydrocarbon Natural products 0.000 claims description 8
- 230000007062 hydrolysis Effects 0.000 claims description 8
- 238000006460 hydrolysis reaction Methods 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- 150000001925 cycloalkenes Chemical class 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical class OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 229910052783 alkali metal Inorganic materials 0.000 claims description 6
- 239000000284 extract Substances 0.000 claims description 5
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 5
- LPULCTXGGDJCTO-UHFFFAOYSA-N 6-methylheptan-1-amine Chemical compound CC(C)CCCCCN LPULCTXGGDJCTO-UHFFFAOYSA-N 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 3
- 150000002431 hydrogen Chemical class 0.000 claims description 3
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims description 2
- 239000012267 brine Substances 0.000 claims 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims 1
- 239000000470 constituent Substances 0.000 abstract 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 abstract 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 239000003446 ligand Substances 0.000 description 11
- 239000000047 product Substances 0.000 description 10
- 239000007789 gas Substances 0.000 description 9
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 9
- 150000001299 aldehydes Chemical class 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 239000012074 organic phase Substances 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 239000011541 reaction mixture Substances 0.000 description 6
- 235000011121 sodium hydroxide Nutrition 0.000 description 6
- 230000035484 reaction time Effects 0.000 description 5
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 239000000126 substance Substances 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
- 229910052936 alkali metal sulfate Inorganic materials 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- 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 2
- MHNNAWXXUZQSNM-UHFFFAOYSA-N 2-methylbut-1-ene Chemical compound CCC(C)=C MHNNAWXXUZQSNM-UHFFFAOYSA-N 0.000 description 2
- 238000004679 31P NMR spectroscopy Methods 0.000 description 2
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 230000001133 acceleration Effects 0.000 description 2
- NENDHUHGFRLXEN-UHFFFAOYSA-N acetic acid;rhodium Chemical compound [Rh].CC(O)=O NENDHUHGFRLXEN-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 150000002366 halogen compounds Chemical class 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 150000002642 lithium compounds Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- 150000003284 rhodium compounds Chemical class 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000010517 secondary reaction Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 125000000542 sulfonic acid group Chemical group 0.000 description 2
- RRKODOZNUZCUBN-CCAGOZQPSA-N (1z,3z)-cycloocta-1,3-diene Chemical compound C1CC\C=C/C=C\C1 RRKODOZNUZCUBN-CCAGOZQPSA-N 0.000 description 1
- OTEKOJQFKOIXMU-UHFFFAOYSA-N 1,4-bis(trichloromethyl)benzene Chemical compound ClC(Cl)(Cl)C1=CC=C(C(Cl)(Cl)Cl)C=C1 OTEKOJQFKOIXMU-UHFFFAOYSA-N 0.000 description 1
- CMIMBQIBIZZZHQ-UHFFFAOYSA-N 1-bromo-2-methylnaphthalene Chemical compound C1=CC=CC2=C(Br)C(C)=CC=C21 CMIMBQIBIZZZHQ-UHFFFAOYSA-N 0.000 description 1
- SDRZFSPCVYEJTP-UHFFFAOYSA-N 1-ethenylcyclohexene Chemical compound C=CC1=CCCCC1 SDRZFSPCVYEJTP-UHFFFAOYSA-N 0.000 description 1
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- YJLPJNLZCOKVAM-UHFFFAOYSA-N 2-ethylhexanoic acid;rhodium Chemical compound [Rh].CCCCC(CC)C(O)=O YJLPJNLZCOKVAM-UHFFFAOYSA-N 0.000 description 1
- YKGBNAGNNUEZQC-UHFFFAOYSA-N 6-methyl-n,n-bis(6-methylheptyl)heptan-1-amine Chemical class CC(C)CCCCCN(CCCCCC(C)C)CCCCCC(C)C YKGBNAGNNUEZQC-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical group CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- HTQMQMXGCVXCHG-UHFFFAOYSA-N CC1=C(C=CC=C1)C1=CC=CC=C1.C1(=CC=CC=C1)PC1=CC=CC=C1 Chemical group CC1=C(C=CC=C1)C1=CC=CC=C1.C1(=CC=CC=C1)PC1=CC=CC=C1 HTQMQMXGCVXCHG-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- IEPRKVQEAMIZSS-UHFFFAOYSA-N Di-Et ester-Fumaric acid Natural products CCOC(=O)C=CC(=O)OCC IEPRKVQEAMIZSS-UHFFFAOYSA-N 0.000 description 1
- IEPRKVQEAMIZSS-WAYWQWQTSA-N Diethyl maleate Chemical compound CCOC(=O)\C=C/C(=O)OCC IEPRKVQEAMIZSS-WAYWQWQTSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- ZFDIRQKJPRINOQ-HWKANZROSA-N Ethyl crotonate Chemical compound CCOC(=O)\C=C\C ZFDIRQKJPRINOQ-HWKANZROSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- SUAKHGWARZSWIH-UHFFFAOYSA-N N,N‐diethylformamide Chemical compound CCN(CC)C=O SUAKHGWARZSWIH-UHFFFAOYSA-N 0.000 description 1
- OYTBLOLBENUVGR-UHFFFAOYSA-N OP(O)=O.C1=CC=CC=C1C1=CC=CC=C1 Chemical class OP(O)=O.C1=CC=CC=C1C1=CC=CC=C1 OYTBLOLBENUVGR-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 150000001298 alcohols Chemical group 0.000 description 1
- PZZYQPZGQPZBDN-UHFFFAOYSA-N aluminium silicate Chemical compound O=[Al]O[Si](=O)O[Al]=O PZZYQPZGQPZBDN-UHFFFAOYSA-N 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 150000001728 carbonyl compounds Chemical class 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- MLUCVPSAIODCQM-NSCUHMNNSA-N crotonaldehyde Chemical compound C\C=C\C=O MLUCVPSAIODCQM-NSCUHMNNSA-N 0.000 description 1
- MLUCVPSAIODCQM-UHFFFAOYSA-N crotonaldehyde Natural products CC=CC=O MLUCVPSAIODCQM-UHFFFAOYSA-N 0.000 description 1
- 238000006471 dimerization reaction Methods 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- LAWOZCWGWDVVSG-UHFFFAOYSA-N dioctylamine Chemical compound CCCCCCCCNCCCCCCCC LAWOZCWGWDVVSG-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 235000012204 lemonade/lime carbonate Nutrition 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000003791 organic solvent mixture Substances 0.000 description 1
- AUONHKJOIZSQGR-UHFFFAOYSA-N oxophosphane Chemical compound P=O AUONHKJOIZSQGR-UHFFFAOYSA-N 0.000 description 1
- SJLOMQIUPFZJAN-UHFFFAOYSA-N oxorhodium Chemical class [Rh]=O SJLOMQIUPFZJAN-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- BCQCECUZZYPFAX-UHFFFAOYSA-N propanedioic acid;rhodium Chemical compound [Rh].OC(=O)CC(O)=O BCQCECUZZYPFAX-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 150000003283 rhodium Chemical class 0.000 description 1
- 229910003450 rhodium oxide Inorganic materials 0.000 description 1
- VXNYVYJABGOSBX-UHFFFAOYSA-N rhodium(3+);trinitrate Chemical group [Rh+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VXNYVYJABGOSBX-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- IAQRGUVFOMOMEM-ONEGZZNKSA-N trans-but-2-ene Chemical compound C\C=C\C IAQRGUVFOMOMEM-ONEGZZNKSA-N 0.000 description 1
- ZFDIRQKJPRINOQ-UHFFFAOYSA-N transbutenic acid ethyl ester Natural products CCOC(=O)C=CC ZFDIRQKJPRINOQ-UHFFFAOYSA-N 0.000 description 1
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 description 1
- 239000005052 trichlorosilane Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
-
- 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
- C07F9/5027—Polyphosphines
-
- 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
- B01J31/2442—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems
- B01J31/2447—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems and phosphine-P atoms as substituents on a ring of the condensed system or on a further attached ring
- B01J31/2452—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems and phosphine-P atoms as substituents on a ring of the condensed system or on a further attached ring with more than one complexing phosphine-P atom
-
- 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
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
- C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
- C09J123/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
- C09J123/24—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having ten or more carbon atoms
-
- 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
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0261—Complexes comprising ligands with non-tetrahedral chirality
- B01J2531/0266—Axially chiral or atropisomeric ligands, e.g. bulky biaryls such as donor-substituted binaphthalenes, e.g. "BINAP" or "BINOL"
-
- 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
- B01J2531/90—Catalytic systems characterized by the solvent or solvent system used
- B01J2531/96—Water
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Enzymes And Modification Thereof (AREA)
Abstract
本发明涉及下式所示的新的磺化二膦化合物,式中Ar为m-C6H4SO3M,M是氢、铵、一价金属或当量的多价金属,ph是苯基,m是取相同或不同值,其值为1或2,n取相同或不同值,其值为0,1或2;本发明涉及其制备,使用此化合物作为水溶性催化剂体系的组分,对烯烃及不饱和烯烃类化合物的加氢甲酰化反应。
Description
本发明涉及新的磺化二膦及其制备。它们与元素周期表中第八族金属形成络合物,此络合物能用作催化剂。
含有以元素周期表中第八族金属作为中心原子、以P(III)化合物(如膦或亚膦酸盐)作为配位体化合物(其它有络合能力的基团也可供选用)的络合物近来迅速成为重要的催化剂。在工业实践中广泛应用的,由烯烃和一氧化碳及氢生成醛(加氢甲酰化)的这类反应是在有铑及三苯基膦组成的催化剂体系存在下进行的。还证实了以含有膦的络合物为基础的催化剂能成功地用于甲醇与合成气的反应生成更高级的醇尤其是乙醇和丙醇(同系列化)。要此情况下配位体一般是过量存在的,所以催化体系是由络合物及自由配位体组成的。根据此体系在有机介质中的溶解度,反应在均相进行。
此反应亦可不以均相而以非均相进行。这一变化了的方法特别方便,因为它提供了一种简单的并在温和条件下的分离方法,将溶于水中的催化剂与不溶于水的反应产物相分离。如在DE2627354C2中已叙述的加氢甲酰化就以此原理工作。用作催化剂的是铑/三苯膦三磺酸钠体系。
除了单膦化合物外也可以二膦化合物做此催化体系的组成部分,其它组分是周期表中第八族金属。比如在DE-A4040315中涉及由单烯烃,非共轭多烯烃,环烯烃或这类化合物的衍生物与一氧化碳及氢在铑/二膦催化剂存在下反应制备醛。在此方法中磺化了的2,2′-双(二苯膦甲基)联苯或2-(二苯膦甲基)-1-[2-(二苯膦甲基)苯基]萘作为二膦使用。与铑在一起化们给出了比已知的铑/单膦体系的催化活性显著地高的催化剂。
发展新配位体的任务的产生是根据这样的假设,即配位体的化学性质决定了铑络合催化剂的活性以及在催化作用下生成的产品组成。他们应开创改变反应途径的可能性,使特定的产品优先生成。(在某种场合下甚至做为唯一的产品进一步要求配位体及其所生成的络合物能溶于水,以便得到上述的在二相体系中进行加氢甲酰化的好处。
本发明提供了这种配位体.它涉及新的磺化了的2,2′-双(二苯膦甲基)-1,1′联萘,分子式如下:
式中Ar是间-C6H4-SO3M,M是氢、铵、一价金属或当量的多价金属,ph是苯基,m取相同或不同值,其值为1或2,n取相同或不同值,其值为0,1或2。
用于制备此新化合物的原始物质是2,2′-双(二苯膦甲基)-1,1′-联萘。此化合物是通过多步合成生成的,由1-溴-2-甲基萘和镁,通过还原性二聚,生成2,2′二甲基-1,1′-联萘。联萘和丁基锂反应生成二锂化合物。二锂化合物再和氯化二苯基膦反应。代替2,2′-二甲基-1,1′-联萘和丁基锂的金属化反应,也可以将它和N-溴代琥珀酰亚胺反应转化为2,2′-双(溴代甲基)-1,1′-联萘。二溴化合物和二苯基膦酸脂反应生成2.2′-双(二苯膦酰甲基)-1,1′-联萘。它再用三氯硅烷还原生成2,2′-双(二苯膦甲基)-1,1′-联萘。为在二萘基和苯基中引入磺酸基团,用含有过量三氧化硫的发烟硫酸作磺化剂处理二膦。
影响所得磺化程度的决定因素是发烟硫酸中SO3浓度,反应温度和反应时间。这些参数相互有影响。
已证实用含有10-65重量区分数或更多的三氧化硫的发烟硫酸是成功的。以二膦作为基准则磺化剂是过量使用的。每摩尔2,2′-双(二苯膦甲基)-1,1′联萘使用25到80摩尔,优选40到70摩尔SO3是适宜的。含有高浓度的游离SO3,即占重量的40-65%或更高的SO3的发烟硫酸能使产品中至少含有4个SO3H基,所以在水中有很好的溶解度。游离SO3浓度低于40重量百分数的发烟硫酸使产品具有较小的磺化程度也就是得到只能有限地溶于水的二膦。
反应温度是0到25℃优选到0到10℃。原料上可以用更高温度,但是这样二膦氧化成氧化膦反应的加速会比磺化反应的加速更为显著,导致磺化膦的总收率下降。所以也不推荐通过提高反应温度去补偿低浓度的游离SO3。另一方面有可能通过反应时间去影响二膦的磺化程度,与较短的反应时间相比,用较长时间得到的化合物具有较高的磺化程度。一般讲在所述的温度范围内反应需要10到60小时,优选为15到48小时。这一时间特别适合用于发烟硫酸含有40重量百分数或更多的游离SO3的场合。即使用长反应时间,低浓度的发烟硫酸也只会导致产生部分磺化的化合物,并且不能完全避免增加氧化产物的形成。所以适宜的是用更高浓度的发烟硫酸进行磺化反应,而通过反应时间去控制磺化程度。
已证实浓硫酸可成功地作为溶剂溶解需磺化的原始化合物即2,2′-双(二苯膦甲基)-1,1′-联萘。此溶液可分批加到发烟硫酸中去,或将发烟硫酸分批加到此溶液中去。推荐的是剧烈地搅拌反应混合物并充分冷却,使反应剂缓慢地小批量地相接触以便反应热能无困难地散走。因此方式而不是无控制地进行磺化反应的方式,能成功地将SO3H基团先后引入到联萘基和苯基中去。此外还有效地抑制了磷化合物的氧化。在加入所有的磺化试剂或者二膦后,在室温下也就是20到25℃进行后续反应,并且基本上需要外部冷却。在此阶段搅拌反应混合物同样是适宜的,这样所有产生的反应热能被均匀分散开并能立即被排数掉。
磺化以后,反应溶液被水解。在此方法阶段必须小心保证温度不超过30℃,保持温度在15到25℃是有利的。所以推荐将反应混合物小心地加到冰中去或者加入冰或冰水进行水解,并提供有力的外部冷却。此稀溶液主要含有不同磺化程度的2,2′-双(二苯膦甲基)-1,1′-联萘和硫酸。它们在另一方法阶段被进一步加工。
为此,含硫酸的溶液用碱性试剂如碱金属的氧氧化物或碱金属碳酸盐,优选氢氧化钠来中和。为了不使反应混合液体积不必要地增加,并沉淀掉大部分所生成的碱金属硫酸盐。所用的中和剂是高浓溶液或是未被溶解的固态即片状或粒状苛性钠。
由于在较低温度下溶解度的减少,大量的碱金属硫酸盐能通过冷却从溶液中除去。合适的温度取决于硫酸盐在溶液中的浓度和溶解度温度随变化曲线,最有利的条件必须根据各个情况由实验来决定。硫酸盐可以通过一级或几级分离出来,已证实,进行二级结晶是适宜的。
在分离出碱金属硫酸盐后,溶液最好能在真空油泵下浓缩到干,而不同磺化程度的二膦化物以碱金属盐形式从结晶化浆中苯取出来。适宜的苯取剂例如是低级醇混合物即分子中含有最多5个碳原子的醇类如含水的甲醇、乙醇或丙醇。用一级或多级的常规方法进行萃取,优选二到四级萃取。萃取液合并并浓缩到干。
已证实将含有硫酸的溶液与一种不溶于水的胺和有机溶剂混合物去反应并萃取胺盐形式的葡磺酸盐是成功的。适宜的是含有10到60,优选为13到36个碳原子的胺,如果基二辛基胺,三—正辛基胺,三异辛基胺,三-2-乙基已基胺和三—十二烷基胺,优选三异辛基胺。脂族和芳族碳氢化合物或碳氢化合物混合物如甲苯或煤油类混合物,尤其是甲苯可成功地用作有机溶剂。
每一个当量磺酸用0.5到1.5摩尔优选0.8到1.2摩尔胺。含有硫酸的溶液与胺溶液剧烈混合后,水相和有机相相互分离。含有胺盐的有机相与要制备的磺酸盐相对应的碱性水溶液相互反应。特别适合的碱的例子是氢氧化钠和氢氧化钾。此过程产生了水溶液,而所要的磺酸盐能从中离析出来。
除可以将碱性水溶液一下子加到在有机介质内的胺盐溶液中外,也可以分批加入。胺溶液的这种逐渐处理,如通过借助碱调节pH值在某一值或范围内能够使膦的氧化物从磺化混合物中基本上分离出来,后者又部分地分解成具有不同磺化程度的产品。
新的磺化了的二膦化物是无色固体。依据磺化条件不同,它们含有最多6个磺酸基团。碱金属盐可溶于水,溶解度随磺化程度而增加。
可以用酸型阳离子交换剂处理磺化二膦的碱金属盐水溶液制备游离酸。可以用此酸与氢氧化物,碳酸盐,氨或胺进行反应而得到新的磺化二膦的其它盐类。
已证实此新化合物能成功地作为含有周期表第八族金属的催化体系的组份。和铑一起,它们尤其能被用作加氢甲酰化催化剂。相应地,本发明进一步涉及通过反应制备醛的方法,反应是由单烯烃,非共轭烯烃,环烯烃或这些化合物的衍生物与一氧化碳和氢在20-150℃温度下在0.1到20兆帕压力下在由水溶性的铑和膦的络合物作为组分的催化剂存在下进行的。所述方法中所用的水溶性膦是上面提到的磺化2,2′-双(二苯膦甲基)-1,1′-联萘。
按本发明方法达到的此两指标值远远超过了现有技术能达到的水平。比起已知的方法,正醛的生成量更大而随反应产物排走的贵金属和膦化合物量更少。而且获得这些结果时所用的催化剂其配位体/铑的比值明显小于迄今所用催化剂的比值。这些和另一些对工业规模流程实施有重大价值的结果既不能从理论考虑中推导出来也不能通过实际经验来预言。
没有必要以纯化合物形式使用磺化二膦化合物。还可以用不同磺化程度的二膦化合物和/或具有不同阳离子的磺酸盐混合物。
已经成功地证实,按本发明的铑和二膦化合物可以不按化学当量比来使用,即不按照在加氢甲酰化反应过程中生成的铑络合物的化学组成,而是使用过量的二膦化物。因而铑对二膦化物的比率可在很宽范围内变化,对每一摩尔铑可以用大约1到130摩尔二膦化物。优选的铑/二膦化合物的摩尔比的范围是从1∶2到1∶25特别优选1∶2至1∶10。
铑既可以金属也可以以化合物形态使用。金属形态的铑是细分散的颗粒或沉积在载体上的薄层,诸如活性炭,碳酸钙,硅酸铝或粘土上。可能用的铑化合物是水溶性的或在反应条件下成为水溶性的物质。适合的化合物是各种铑氧化物,无机含氢酸或含氧酸的盐和脂族单羧酸或多羧酸盐。铑盐的例子是硝酸铑,硫酸铑,醋酸铑,2-乙基己酸铑和丙二酸铑。另一方面由于产生的络合物的活性低和卤素离子的腐蚀性,铑的卤素化合物很少被采用。还有可能用铑的羰基化合物诸如Rh3(CO)12或Rh6(CO)16或铑的络合盐如环状辛二烯基铑化合物。铑氧化物尤其是醋酸铑和2-乙基酸铑是优选的。可以认为在加氢甲酰化反应条件下在有合成气存在时生成了含有作为配位体的一氧化碳和二膦化物的水溶性铑络合物。它们与溶于水中的过量的二膦化物一起形成了催化体系。
由各组份制成催化剂溶液或者在加氢甲酰化反应器中完成或者事先在另一设备中完成后再引入加氢甲酰化反应器。
催化剂水溶液中铑的浓度为10-500重量ppm(以溶液为基准),优选10-100重量ppm,尤其优选15-50重量ppm。
烯烃和一氧化碳和氢的反应,在压力为约01到30兆帕下进行,优选1到12兆帕。尤其是1到5兆帕。合成气的组成也就是一氧化碳和氢的体积比可在很宽范围内扩展,并能在如1∶10-到10∶1范围内变化。通常所用气体混合物其一氧化碳和氢的体积比约为1∶1或只是稍稍偏离比值,略大或略小。
反应温度介于20到150℃之间,优选为80到140℃,尤其是100-125℃。
存在于气相和液相的反应剂在常规反应器内发生反应。催化剂水溶液必须用疏水的液态或气态烯烃以及合成气饱和,这对反应的过程有决定性的影响。所以必须创造尽可能大的两相接触面积。已证明为成功的方法是剧烈搅拌反应器内含物(催化剂溶液,有时有液态烃和反应产物),并通过分配装置往液相中引入气态反应物(合成气,有时有烯烃)。已被证明是很成功的方法是将反应混合物中有机相的比例保持得较小。令人惊奇的是有机相对于反应物在水相中的溶解度并无贡献,而且避免了反应产物进行不希望有的次级反应(当产物在反应器中停留时间增加时一般不能排除有次级反应)。水相和有机相体积比应相应地调整为1∶1到100∶1,优选10∶1到100∶1。通过从反应器中连续抽取部分反应混合物,使水相和有机相相互分离,并将水相再循环到反应器中去的方法可以保持体积比。反应可以间歇地进行或者最好是连续地进行。
本发明的方法可以成功地用于单烯烃,非共轭多烯烃,环烯烃及这些不饱和化合物的衍生物的反应。就分子大小来说所用的烯烃不受任何限制。已证实比过程可成功地用于含有2到20碳原子的化合物。不饱和烯烃化合物可以是直链或支化的。双键可以在链内或在端部。能采用新过程的烯烃例子有乙烯,丙烯,丁烯-1,丁烯-2,戊烯-1,2-甲基丁烯-1,己烯-1,己烯-2,庚烯-1,辛烯-1,辛-3,3-乙基己烯-1,癸烯-1,十一碳烯-3,4,4二甲基壬烯-1,二环戊二烯,乙烯基环己烯,环辛二烯和苯乙烯。能采用所得出的方法进行加氢甲酰化的所述烯烃类衍生物有如:醇、醛、羧酸、酯、腈和卤素化合物,烯丙醇、丙烯醛、异丁烯醛、巴豆醛、丙烯酸甲酯、巴豆酸乙酯、富马酸二乙酯、马来酸二乙酯和丙烯腈。对于含有2到20尤其是2到8个碳原子的烯烃及其衍生物用此过程进行加氢甲酰化特别成功。
下述实例叙述了新化合物的制备和性质(例1到10)以及它们的在饱和烯烃化合物的加氢甲酰化中作为催化剂组分的应用(例12到17)。
实施例1
10,11克(15。54毫摩尔)的2,2′-双(二苯膦甲基)-1,1′联萘在室温下溶于25毫升浓硫酸中。将此溶液冷却到0℃并滴加50毫升65%的发烟硫酸,温度保持最高为10℃。然后混合液在室温下搅拌48小时,再将其加入到冰中,用氢氧化钠溶液中和(NaOH含量50重量%)。水解和中和的条件是使温度不超过25℃。过滤掉沉淀的硫酸钠,滤液在甲醇中搅拌。分离掉产生的白色固体,滤液浓缩到干。残渣用恰到好处数量的水使之全部溶解,水溶液在二倍体积的甲醇中分散,过滤所得的悬浮液,将滤液浓缩至干。将此两次干滤液并在一起进行分析。特征:
溶解度:1300g/l水
元素分析:13.8%(重量)硫
4.42%(重量)磷
9.9%(重量)钠
由此得下列的摩尔比
P∶S=1∶3;P∶Na=1∶3;S∶Na=1∶1
这相当于在2,2′-双(二苯膦甲基)-1,1′联萘的分子中引入6个SO3H。
31P-NMR: δ=-9.0
该化合物在以下称为BINAS。实施例2
2,2′-双(二苯膦甲基)-1,1′联萘按实施例1进行磺化,反应的进展用硫酸溶液的核磁共振谱进行跟踪,得到下列测量结果。
31P-NMR:δ=-9.0 (6次磺化)
δ=-9.89 (5次磺化)
δ=-12.03 (4次磺化)实施例3-10
2,2′-双(二苯膦甲基)-1,1′联萘按实施例1进行磺化,只是反应参数中的温度,时间和SO3浓度作了改变,结果列于下表。实施例5,6和7是对照例,例中用了较高的反应温度。实施 灰烟硫酸中SO3 反应时 温度 氧化物例 含量(重量%) 间(时) (℃) 生成(%)a3 20 18 20 54 20 48 20 105 20 48 30 186 20 48 40 527 20 48 50 100 8 40 48 20 89 65 17 20 510 65 48 20 10
a用完全氧化的六磺化2,2′-双(二苯磷甲基)-1,1′-联萘作为上述标准
实施例11
60.7克(93.2毫摩尔)的2,2′-双(二苯膦甲基)-1,1′联萘在0-10℃下溶解于300克浓硫酸中。在保持温度为0-10℃下加入601.7克65%的发烟硫酸。混合液体在室温下搅拌48小时。水解时,磺化了的混合物在低于10℃下,在30分钟内滴到3879.2克水中去。
用237.4克三异辛胺在948.8克甲苯中的溶液在40℃萃取1小时,从水相中分离出磺化产物。在机相(1307.2克)再在40℃用3%(重)氢氧化钠溶液萃取。
pH达3.5的水相(357.6克)中含有16.8毫摩尔P(III)和2.6毫摩尔P(V)(在每种情况以1kg溶液为基准)并含3.8%硫酸盐。pH在3.5到4.8范围内水相(463.0克)中P(III)含量为163毫摩尔,P(V)含量为15.0毫摩尔(仍以每种情况下1kg溶液为基准),并且硫酸盐含量为0.05%。在pH范围为4.8到6.0时分离掉有用的产品部分(335.8克),以1kg溶液为基准,它含有212毫摩尔P(III)和1.0毫摩尔P(V)。
实施例12到17
丙烯以及等体积混合的CO/H2混合气引入装备有搅拌器的0.2升不锈钢高压釜,其量应能使10N/h〔标准升/小时〕的尾气从反应器抽出。同时在反应器循环有300毫升/小时的催化剂水溶液〔醋酸盐形式下的261毫克铑和BINAS形式下的13.9毫摩尔P(III)溶解于1000毫升先脱气后用氮气饱和的水中〕。磷和铑的分子比为5.5∶1,相应的配位体/铑比率为2.75∶1。反应物在5兆帕压力下反应,其余反应参数可见表。
在表中按本发明方法所得的结果(实施例12到16)与现有技术水平所得到的结果〔催化剂铑/三苯膦基三磺酸钠(TPPTS)〕(实施例17)相比较。实验清楚表明,具有极低Rh/p比的新方法获得了高的催化活性,n-/i-(正/异)比大大提高,甚至在显著提高烯烃负荷时(实施例15)仍得到高转化率。
表
实验条件 | 实施例12 | 实施例13 | 实施例14 | 实施例15 | 实施例16 | 实施例17(对照) |
催化剂铑/配位体(mol/mol)温度(℃)压力(MPa)丙烯负荷(g/h)实验结果转化率(%)活性mo1(正+异)醛mol铑,分钟产率g(正+异)醛ml催化剂溶液,小时正/异比值(重量分数) | Rh/BINAS1∶2.751105.040.044.743.920.48297/3 | Rh/BINAS1∶2.751165.040.040.442.810.47097/3 | Rh/BINAS1∶2.751225.040.050.855.480.60897/3 | Rh/BINAS1∶2.751225.0129.047.9163.31.7998/2 | Rh/BINAS1∶2.751285.040.057.861.410.67397/3 | Rh/BINAS1∶1001225.040.039.015.110.20693/7 |
Claims (31)
2.权利要求1所述化合物的制备方法,其特征在于;在0到25℃温度下,用发烟硫酸磺化2,2′-双(二苯膦甲基)-1,1′-联萘,水解磺化了的混合物,并从水解磺化混合液中分离出磺化了的2.2′-双(二苯膦甲基)-1,1′-联萘。
3.按权利要求2的方法,其特征在于:用于磺化的发烟硫酸含有10到65重量%的游离三氧化硫。
4.按权利要求3的方法,其特征在于:用于磺化的发烟硫酸含有40-65%的游离三氧化硫。
5.按权利要求1到4的方法,其特征在于:每摩尔2,2′-双(二苯膦甲基)-1,1′-联萘用25到80摩尔三氧化硫。
6.按权利要求5的方法,其特征在于:每摩尔2,2′-双(二苯膦甲基)-1,1′-联萘用40-70摩尔三氧化硫。
7.按权利要求1到4的一项或多项中的方法,其特征在于:磺化是在0-25℃下进行。
8.按权利要求7的方法,其特征在于:磺化是在0-10℃下进行。
9.按权利要求1到4的一项或多项的方法,其特征在于:磺化混合物水解是在最高为约30℃的温度下进行。
10.按权利要求9的方法,其特征在于:磺化混合物水解是在最高为约15-25℃下进行。
11.按权利要求1到4一项或多项的方法,其特征在于:水解后的磺化混合物用碱金属碳酸盐或碱金属氢氧化合物中和,碱金属硫酸盐水溶液被浓缩,然后用水和分子中含有最多达5个碳原子的醇的混合物从残渣中萃取出磺化2,2′-双(二苯膦甲基)-1,1′-联萘。
12.按权利要求1到4一项或多项的方法,其特征在于:不溶于水的胺和一种有机溶剂的混合物尤其是三异辛基胺和甲苯的混合物与水解了的磺化混合物反应,磺酸盐是以胺盐的形式被萃取出来,再往胺盐溶液中加入,也可以分批加入碱性水溶液,最好是氢氧化钠或氢氧化钾水溶液。
14.按权利要求13的方法,其特征在于:每摩尔铑要用1到130摩尔磺化二胺化合物。
15.按权利要求14的方法,其特征在于:每摩尔铑要用2到24摩尔磺化二膦化合物。
16.按权利要求15的方法,其特征在于:每摩尔铑要用2到10摩尔磺化二膦化合物。
17.按权利要求13的方法,其特征在于:催化剂水溶液中铑的浓度为10到500重量ppm(以溶液为基准)。
18.按权利要求17的方法,其特征在于:催化剂水溶液中铑的浓度为10到100重量ppm。
19.按权利要求18的方法,其特征在于:催化剂水溶液中铑的浓度为15到50重量ppm。
20.按权利要求13到19中一项或多项的方法,其特征在于:反应是在20到150℃下进行。
21.按权利要求20的方法,其特征在于:反应是在80到140℃下进行。
22.按权利要求21的方法,其特征在于:反应是在100到125℃下进行。
23.按权利要求13到19中的一项或多项的方法,其特征在于:反应是在0.1-30兆帕压力下进行。
24.按权利要求23的方法,其特征在于:反应是在1-12兆帕压力下进行。
25.按权利要求24的方法,其特征在于:反应是在1-5兆帕压力下进行。
26.按权利要求13到19中的一项或多项的方法,其特征在于:反应的烯烃或烯烃的衍生物含有2到40个碳原子。
27.按权利要求26的方法,其特征在于:反应的烯烃或烯烃的衍生物含2到20个碳原子。
28.按权利要求27的方法,其特征在于:反应的烯烃或烯烃的衍生物含2到8个碳原子。
29.权利要求1的磺化的2,2′-双(二苯膦甲基)—联萘的应用,用于制备单烯烃、非共轭多烯烃、环烯烃或它们的衍生物的加氢甲酰化的铑/二膦化物催化剂,催化剂中相应每摩尔铑含有1-130摩尔磺化的2,2′-双(二苯膦甲基)-1,1′-联萘。
30.按权利要求29的应用,用于制备单烯烃、非共轭多烯烃、环烯烃或它们的衍生物的加氢甲酰化的铑/二膦化物催化剂,催化剂中相应每摩尔铑含有1-25摩尔磺化的2,2′-双(二苯膦甲基)-1,1′-联萘。
31.按权利要求30的应用,用于制备单烯烃、非共轭多烯烃、环烯烃或它们的衍生物的加氢甲酰化的铑/二膦化物催化剂,催化剂中相应每摩尔铑含1-10摩尔磺化的2,2′-双(二苯膦甲基)-1,1′-联萘。
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DEP4217803.7 | 1992-05-29 | ||
DE4217803A DE4217803A1 (de) | 1992-05-29 | 1992-05-29 | Verfahren zur Herstellung von Aldehyden |
DE4244274A DE4244274A1 (de) | 1992-12-28 | 1992-12-28 | Sulfonierte 2,2'-Bis(diphenylphosphinomethyl)-1,1'-binaphthaline, Verfahren zu ihrer Herstellung und ihre Verwendung |
DEP4244274.5 | 1992-12-28 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN1080928A CN1080928A (zh) | 1994-01-19 |
CN1032538C true CN1032538C (zh) | 1996-08-14 |
Family
ID=25915257
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN93106100A Expired - Fee Related CN1032538C (zh) | 1992-05-29 | 1993-05-22 | 磺化2,2’-双(二苯膦甲基)-1,1’-联萘及其制备方法 |
Country Status (13)
Country | Link |
---|---|
US (3) | US5347045A (zh) |
EP (1) | EP0571819B1 (zh) |
JP (2) | JPH0794466B2 (zh) |
KR (1) | KR100265520B1 (zh) |
CN (1) | CN1032538C (zh) |
AT (1) | ATE173266T1 (zh) |
BR (1) | BR9302013A (zh) |
CA (1) | CA2096812C (zh) |
DE (1) | DE59309119D1 (zh) |
ES (1) | ES2126613T3 (zh) |
MX (1) | MX9303004A (zh) |
SG (1) | SG43948A1 (zh) |
TW (1) | TW225485B (zh) |
Families Citing this family (38)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE4338826A1 (de) * | 1993-11-13 | 1995-05-18 | Hoechst Ag | Verfahren zur Herstellung von 1,1`-Binaphthylen |
US5536858A (en) * | 1994-02-12 | 1996-07-16 | Hoffmann-La Roche Inc. | Tetrasulfonated diphosphine compounds and metal complexes thereof for asymmetric catalytic reactions |
US5935892A (en) | 1994-02-22 | 1999-08-10 | California Institute Of Technology | Supported phase catalyst |
US5736480A (en) * | 1994-02-22 | 1998-04-07 | California Institute Of Technology | Supported phase chiral sulfonated BINAP catalyst solubilized in alcohol and method of asymmetric hydrogenation |
DE4415682A1 (de) * | 1994-05-04 | 1995-11-09 | Hoechst Ag | Palladium Katalysatoren mit sulfonierten Bisphosphinen als Liganden, Verfahren zu ihrer Herstellung und ihre Verwendung für Carbonylierungsreaktionen |
DE4434844A1 (de) * | 1994-09-29 | 1996-04-04 | Hoechst Ag | Diphosphane und Verfahren zu ihrer Herstellung |
ZA96178B (en) * | 1995-01-18 | 1997-06-30 | Exxon Chemical Patents Inc | Organic compounds and processes for their manufacture |
DE19506279A1 (de) * | 1995-02-23 | 1996-08-29 | Hoechst Ag | Sulfonierte Diphosphane und ein Verfahren zu ihrer Herstellung |
DE19619527A1 (de) * | 1996-05-15 | 1997-11-20 | Hoechst Ag | Katalysatorsysteme auf der Basis von Rhodium-Komplexverbindungen mit Diphosphin-Liganden und ihre Verwendung bei der Herstellung von Aldehyden |
EP0842183B1 (de) * | 1995-07-25 | 2001-10-17 | Clariant GmbH | Katalysatoren zur durchführung von kreuzkupplungsreaktionen |
DE19609336C1 (de) * | 1996-03-11 | 1997-03-13 | Hoechst Ag | Substituierte Diphenyldiphosphane und ein Verfahren zu ihrer Herstellung |
DE19610869A1 (de) * | 1996-03-20 | 1997-09-25 | Hoechst Ag | Verfahren zur Herstellung von Aldehyden |
US6043398A (en) * | 1996-04-18 | 2000-03-28 | Celanese International Corporation | Chemical processes using aryl diphosphine containing catalysts |
US5777087A (en) * | 1996-04-18 | 1998-07-07 | Celanese International Corporation | Aryl diphosphines and catalysts containing the same |
DE19619528A1 (de) * | 1996-05-15 | 1997-11-20 | Hoechst Ag | Substituierte Diphosphine und ein Verfahren zu ihrer Herstellung |
US5753584A (en) * | 1996-06-04 | 1998-05-19 | Intevep, S.A. | Catalyst system for selective hydrogenation of heteroaromatic sulfur-containing and nitrogen-containing compounds |
DE59703813D1 (de) * | 1996-08-27 | 2001-07-19 | Celanese Chem Europe Gmbh | Verfahren zur telomerisierung von dienen |
IT1286879B1 (it) * | 1996-11-21 | 1998-07-17 | Consiglio Nazionale Ricerche | Leganti 1,3-difosfinopropanici e complessi da essi formati con metalli di transizione,loro preparazione e uso |
DE19742305A1 (de) | 1997-09-25 | 1999-04-01 | Hoechst Ag | Verfahren zur Herstellung von Aldehyden durch Hydroformylierung in Gegenwart von Kronenether |
US7223879B2 (en) * | 1998-07-10 | 2007-05-29 | Massachusetts Institute Of Technology | Ligands for metals and improved metal-catalyzed processes based thereon |
US6307087B1 (en) * | 1998-07-10 | 2001-10-23 | Massachusetts Institute Of Technology | Ligands for metals and improved metal-catalyzed processes based thereon |
DE19918284C1 (de) * | 1999-04-22 | 2000-12-14 | Celanese Chem Europe Gmbh | Verfahren zur Herstellung von sulfonierten Arylphosphinen |
GR20000100460A (el) * | 2000-12-27 | 2002-10-09 | Celanese Chemicals Europe Gmbh | Μεθοδος για την παρασκευη αλδευδων |
DE10114868C1 (de) * | 2001-03-26 | 2002-10-31 | Oxeno Olefinchemie Gmbh | Verfahren zur Herstellung von Diphosphinen und deren Verwendung |
DE10352261B4 (de) * | 2003-11-08 | 2006-08-24 | Celanese Chemicals Europe Gmbh | Verfahren zur Herstellung von TCD-Dialdehyd |
DE10352263A1 (de) | 2003-11-08 | 2005-06-23 | Celanese Chemicals Europe Gmbh | Verfahren zur Herstellung von TCD-Monenal |
US20050209469A1 (en) | 2004-03-22 | 2005-09-22 | Shutt John R | Converting propylene in an oxygenate-contaminated propylene stream to non-polymerization derivative products |
JP5442925B2 (ja) * | 2006-04-28 | 2014-03-19 | 一般財団法人電力中央研究所 | ポリ塩化ビフェニル類の分析方法 |
DE102008044783B4 (de) | 2008-08-28 | 2012-05-16 | Oxea Gmbh | Verfahren zur Gewinnung von aliphatischen C3- bis C10- Aldehyden aus Hochsiedern durch thermische Behandlung |
DE102009004655B4 (de) | 2009-01-15 | 2013-02-14 | Oxea Gmbh | Verfahren zur Herstellung von Aldehyden |
DE102009016651B4 (de) | 2009-04-07 | 2011-11-17 | Oxea Gmbh | Verfahren zur Herstellung von Aldehyden |
DE102014002103B4 (de) | 2014-02-15 | 2020-10-22 | Oxea Gmbh | Verfahren zur Regenerierung gebrauchter Hydroformylierungskatalysatoren |
WO2020242912A1 (en) | 2019-05-24 | 2020-12-03 | Eastman Chemical Company | Blend small amounts of pyoil into a liquid stream processed into a gas cracker |
US11365357B2 (en) | 2019-05-24 | 2022-06-21 | Eastman Chemical Company | Cracking C8+ fraction of pyoil |
KR20220041177A (ko) | 2019-07-29 | 2022-03-31 | 이스트만 케미칼 컴파니 | 열분해 및 가메탄올분해로부터의 재활용된 단량체를 갖는 폴리에스테르의 제조 방법 |
US11319262B2 (en) | 2019-10-31 | 2022-05-03 | Eastman Chemical Company | Processes and systems for making recycle content hydrocarbons |
US11945998B2 (en) | 2019-10-31 | 2024-04-02 | Eastman Chemical Company | Processes and systems for making recycle content hydrocarbons |
EP4054997A4 (en) | 2019-11-07 | 2024-02-21 | Eastman Chem Co | ALPHA-OLEFINS AND FAT ALCOHOLS WITH RECYCLING CONTENT |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4248802A (en) * | 1975-06-20 | 1981-02-03 | Rhone-Poulenc Industries | Catalytic hydroformylation of olefins |
EP0279018B1 (en) * | 1987-02-18 | 1992-01-29 | EASTMAN KODAK COMPANY (a New Jersey corporation) | Chelate ligands for low pressure hydroformylation catalyst and process employing same |
CA2002598A1 (en) * | 1988-11-30 | 1990-05-31 | Thomas Allen Puckette | Preparation of biaryl compounds |
DE4040315A1 (de) * | 1990-12-17 | 1992-06-25 | Hoechst Ag | Verfahren zur herstellung von aldehyden |
US5274183A (en) * | 1990-12-17 | 1993-12-28 | Hoechst Aktiengesellschaft | Water-soluble sulfonated diphosphines |
-
1993
- 1993-05-04 TW TW082103462A patent/TW225485B/zh active
- 1993-05-12 DE DE59309119T patent/DE59309119D1/de not_active Expired - Fee Related
- 1993-05-12 AT AT93107701T patent/ATE173266T1/de not_active IP Right Cessation
- 1993-05-12 ES ES93107701T patent/ES2126613T3/es not_active Expired - Lifetime
- 1993-05-12 SG SG1996006718A patent/SG43948A1/en unknown
- 1993-05-12 EP EP93107701A patent/EP0571819B1/de not_active Expired - Lifetime
- 1993-05-20 BR BR9302013A patent/BR9302013A/pt active IP Right Grant
- 1993-05-21 KR KR1019930008736A patent/KR100265520B1/ko not_active IP Right Cessation
- 1993-05-21 MX MX9303004A patent/MX9303004A/es not_active IP Right Cessation
- 1993-05-21 CA CA002096812A patent/CA2096812C/en not_active Expired - Fee Related
- 1993-05-22 CN CN93106100A patent/CN1032538C/zh not_active Expired - Fee Related
- 1993-05-24 JP JP5121646A patent/JPH0794466B2/ja not_active Expired - Fee Related
- 1993-05-25 US US08/066,553 patent/US5347045A/en not_active Expired - Fee Related
-
1994
- 1994-05-11 US US08/240,902 patent/US5481045A/en not_active Expired - Fee Related
-
1995
- 1995-03-20 JP JP7061233A patent/JP2680791B2/ja not_active Expired - Fee Related
- 1995-11-02 US US08/552,289 patent/US5565398A/en not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
---|---|
US5347045A (en) | 1994-09-13 |
JP2680791B2 (ja) | 1997-11-19 |
DE59309119D1 (de) | 1998-12-17 |
SG43948A1 (en) | 1997-11-14 |
CA2096812A1 (en) | 1993-11-30 |
KR100265520B1 (ko) | 2000-09-15 |
BR9302013A (pt) | 1993-12-07 |
JPH07252279A (ja) | 1995-10-03 |
EP0571819B1 (de) | 1998-11-11 |
ATE173266T1 (de) | 1998-11-15 |
US5565398A (en) | 1996-10-15 |
KR940005650A (ko) | 1994-03-22 |
ES2126613T3 (es) | 1999-04-01 |
CN1080928A (zh) | 1994-01-19 |
JPH06145181A (ja) | 1994-05-24 |
CA2096812C (en) | 1996-11-12 |
JPH0794466B2 (ja) | 1995-10-11 |
MX9303004A (es) | 1993-11-01 |
US5481045A (en) | 1996-01-02 |
TW225485B (zh) | 1994-06-21 |
EP0571819A1 (de) | 1993-12-01 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN1032538C (zh) | 磺化2,2’-双(二苯膦甲基)-1,1’-联萘及其制备方法 | |
CN109456154A (zh) | 一种通过氢甲酰化反应制备脂肪醛的方法 | |
JPH0687876A (ja) | 3,4−ジメチル−2,5,6−トリス(p−スルホナートフェニル)−1−ホスファノルボルナジエン、その製造方法およびオレフィン性不飽和化合物のヒドロホルミル化法 | |
JPH0544934B2 (zh) | ||
CN1202064C (zh) | 一种乙烯制丙醛的方法 | |
CN1171981A (zh) | 含有二膦配位体的铑配合物催化剂体系及其在制备醛方面的应用 | |
CN1227835A (zh) | 醛类的制备方法 | |
CN1051557C (zh) | 新型磺化膦,其制法及其作为催化剂体系组分的用途 | |
EP0491239B1 (de) | Verfahren zur Herstellung von Aldehyden | |
JPH0517213B2 (zh) | ||
CN107469862A (zh) | 一种铑/双亚膦酸酯催化剂的两步逆流萃取纯化方法 | |
US6613939B2 (en) | Purified sulfonated organophosphorus compounds and catalysis of organic reactions therewith | |
CN1132734A (zh) | 醛的制备方法 | |
ZA200107164B (en) | Method for producing sulfonated aryl phosphines. | |
CN1310129A (zh) | ZnS光催化剂、其制备方法和使用该催化剂制备氢的方法 | |
CN1050607C (zh) | 5h-苯基-3,13-二磺酸二苯并(磷杂-2,4-环戊二烯)及其制备方法 | |
CN107267200B (zh) | 一种由烷烃和烯烃进行烷基化的方法 | |
CA2080747A1 (en) | Process for recovering rhodium from the reaction products of the oxo synthesis | |
KR100521661B1 (ko) | 균질한하이드로포르밀화의반응혼합물로부터포스틴옥사이드와알킬아릴포스핀을분리하는방법 | |
US20040249195A1 (en) | Lithium rho-diarylphosphinobenzenesulfonates, process for preparation of the same and use thereof | |
CN1017144B (zh) | 制备醛的方法 | |
CN85105101A (zh) | 醛的制备方法 | |
MXPA97003390A (en) | Procedure to prepare aldehi | |
DE4217803A1 (de) | Verfahren zur Herstellung von Aldehyden | |
MXPA97003456A (en) | Catalyst systems based on complex rhodium compounds with lingandos de difosfina and its use in the production of aldhei |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C06 | Publication | ||
PB01 | Publication | ||
C14 | Grant of patent or utility model | ||
GR01 | Patent grant | ||
C19 | Lapse of patent right due to non-payment of the annual fee | ||
CF01 | Termination of patent right due to non-payment of annual fee |