JPS6314688B2 - - Google Patents
Info
- Publication number
- JPS6314688B2 JPS6314688B2 JP2501080A JP2501080A JPS6314688B2 JP S6314688 B2 JPS6314688 B2 JP S6314688B2 JP 2501080 A JP2501080 A JP 2501080A JP 2501080 A JP2501080 A JP 2501080A JP S6314688 B2 JPS6314688 B2 JP S6314688B2
- Authority
- JP
- Japan
- Prior art keywords
- acid
- reaction
- carbon monoxide
- formaldehyde
- examples
- 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
Links
- -1 glycolic acid ethers Chemical class 0.000 claims description 15
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 15
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Natural products OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 claims description 13
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 7
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 7
- 235000019253 formic acid Nutrition 0.000 claims description 7
- 239000003377 acid catalyst Substances 0.000 claims description 5
- 150000002148 esters Chemical class 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical class O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 14
- 239000002253 acid Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 150000007513 acids Chemical class 0.000 description 5
- 235000019256 formaldehyde Nutrition 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- BGJSXRVXTHVRSN-UHFFFAOYSA-N 1,3,5-trioxane Chemical compound C1OCOCO1 BGJSXRVXTHVRSN-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-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
- 229930040373 Paraformaldehyde Natural products 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229920002866 paraformaldehyde Polymers 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000010457 zeolite Substances 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- NMJJFJNHVMGPGM-UHFFFAOYSA-N butyl formate Chemical compound CCCCOC=O NMJJFJNHVMGPGM-UHFFFAOYSA-N 0.000 description 2
- 239000003729 cation exchange resin Substances 0.000 description 2
- 229940023913 cation exchange resins Drugs 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000002734 clay mineral Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 150000001875 compounds Chemical group 0.000 description 2
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 229910052809 inorganic oxide Inorganic materials 0.000 description 2
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- ILPBINAXDRFYPL-UHFFFAOYSA-N 2-octene Chemical compound CCCCCC=CC ILPBINAXDRFYPL-UHFFFAOYSA-N 0.000 description 1
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 1
- 229910021630 Antimony pentafluoride Inorganic materials 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000004113 Sepiolite Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 description 1
- VBVBHWZYQGJZLR-UHFFFAOYSA-I antimony pentafluoride Chemical compound F[Sb](F)(F)(F)F VBVBHWZYQGJZLR-UHFFFAOYSA-I 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 229960000892 attapulgite Drugs 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- YZYDPPZYDIRSJT-UHFFFAOYSA-K boron phosphate Chemical compound [B+3].[O-]P([O-])([O-])=O YZYDPPZYDIRSJT-UHFFFAOYSA-K 0.000 description 1
- 229910000149 boron phosphate Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229920001429 chelating resin Polymers 0.000 description 1
- 229910001919 chlorite Inorganic materials 0.000 description 1
- 229910052619 chlorite group Inorganic materials 0.000 description 1
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 1
- QBWCMBCROVPCKQ-UHFFFAOYSA-N chlorous acid Chemical compound OCl=O QBWCMBCROVPCKQ-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000008098 formaldehyde solution Substances 0.000 description 1
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229910052621 halloysite Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 229910052900 illite Inorganic materials 0.000 description 1
- 239000013462 industrial intermediate Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- LQFNMFDUAPEJRY-UHFFFAOYSA-K lanthanum(3+);phosphate Chemical compound [La+3].[O-]P([O-])([O-])=O LQFNMFDUAPEJRY-UHFFFAOYSA-K 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 229940017219 methyl propionate Drugs 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 229910052680 mordenite Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 150000002828 nitro derivatives Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 1
- VGIBGUSAECPPNB-UHFFFAOYSA-L nonaaluminum;magnesium;tripotassium;1,3-dioxido-2,4,5-trioxa-1,3-disilabicyclo[1.1.1]pentane;iron(2+);oxygen(2-);fluoride;hydroxide Chemical compound [OH-].[O-2].[O-2].[O-2].[O-2].[O-2].[F-].[Mg+2].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[K+].[K+].[K+].[Fe+2].O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2 VGIBGUSAECPPNB-UHFFFAOYSA-L 0.000 description 1
- WSGCRAOTEDLMFQ-UHFFFAOYSA-N nonan-5-one Chemical compound CCCCC(=O)CCCC WSGCRAOTEDLMFQ-UHFFFAOYSA-N 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 229910052625 palygorskite Inorganic materials 0.000 description 1
- OBCUTHMOOONNBS-UHFFFAOYSA-N phosphorus pentafluoride Chemical compound FP(F)(F)(F)F OBCUTHMOOONNBS-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052624 sepiolite Inorganic materials 0.000 description 1
- 235000019355 sepiolite Nutrition 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910021647 smectite Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- 229910052902 vermiculite Inorganic materials 0.000 description 1
- 239000010455 vermiculite Substances 0.000 description 1
- 235000019354 vermiculite Nutrition 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
Landscapes
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
本発明はグリコール酸のエーテルおよびエステ
ルの製造法に関するものである。
グリコール酸エステルは加水分解すればグリコ
ール酸が得られ水添分解すればエチレングリコー
ルが得られ、またグリコール酸のエーテルは水添
することによりセロソルブ類が得られるので、い
ずれも工業用中間体として重要な化合物である。
グリコール酸エステルの製造法としては、硫酸
または有機スルホン酸などの強酸触媒の存在下に
パラホルムアルデヒドまたはトリオキサンをギ酸
エステルと反応させる方法（特開昭53−98924）
が知られているが、反応速度が小さい点に不満が
ある。
本発明者らはホルムアルデヒドとギ酸エステル
と一酸化炭素を強酸触媒下に反応させることによ
り、良好な反応速度でグリコール酸エステルがグ
リコール酸のエーテルとともに得られることを見
い出し、本発明に到達した。
以下に本発明を詳細に説明する。
本発明方法において使用されるホルムアルデヒ
ドとしては、ガス状ホルムアルデヒド、トリオキ
サンおよびパラホルムアルデヒドが挙げられる。
所望によりホルムアルデヒド水溶液を使用するこ
ともできるが、本発明方法において水の存在下に
反応を行なうことは有利ではなく、ホルムアルデ
ヒド１モルに対して１モル以下、好ましくは0.5
モル以下に抑制すべきである。
ギ酸エステルとしては、炭素数１〜10のアルカ
ノールのギ酸エステルが使用され、特にギ酸メチ
ル、ギ酸エチル、ギ酸ブチル等の低級アルカノー
ルのギ酸エステルが好ましく使用される。これら
のギ酸エステルはホルムアルデヒド１モルに対し
て、通常0.05〜10モル、好ましくは0.1〜５モル
使用される。所望によりギ酸エステルを溶媒とし
て過剰に用いることもできる。
一酸化炭素は、純粋なものは勿論、窒素、ヘリ
ウム、アルゴン、水素等の反応に不活性なガスに
より希釈したものも使用し得る。反応系中の一酸
化炭素分圧は、通常10〜250Kg／cm2、好ましくは
20〜150Kg／cm2である。
本発明方法において使用される強酸触媒として
は、塩酸、臭化水素酸、沃化水素酸、弗化水素
酸、過塩素酸、硝酸、硫酸等の鉱酸、トリフルオ
ロ酢酸、メタンスルホン酸、ベンゼンスルホン
酸、ｐ−トルエンスルホン酸、クロロスルホン
酸、トリフルオロメタンスルホン酸等の有機酸、
三弗化硼素、五弗化燐、五弗化アンチモン等のル
イス酸あるいは強酸性陽イオン交換樹脂、粘土鉱
物、ゼオライト、固型化酸、無機酸化物、無機
塩、複合酸化物などのいわゆる固体酸が挙げられ
る。強酸性陽イオン交換樹脂としては官能基がス
ルホン酸であるもので、ダイヤイオンPK−
228、ダイヤイオンHPK25（以上、三菱化成工
業(株)製）、アンバーライト200（ロームアンドハ
ース社製）などのスチレン−ジビニルベンゼン共
重合体を骨格とするもの、ナフイオン501（デユ
ポン社製）などのテトラフルオロエチレン重合体
を骨格とするものが挙げられる。粘土鉱物および
ゼオライトとしては、モンモリロナイト、カオリ
ナイト、ベントナイト、ハロイサイト、スメクタ
イト、イライト、バーミキユライト、クロライ
ト、セピオライト、アタパルジヤイト、ポリゴル
スカイト、モルデナイトなどが挙げられるが、モ
ンモリロナイトKSF／Ｏ（ガードラー・ケミカル
社製）のような弗化水素などの酸により処理した
ものやＨ型ゼオライトのように交換可能な金属イ
オンを水素イオンと交換したものが好ましい。固
型化酸としては燐酸、硼酸などを担体に担持した
ものが挙げられる。無機酸化物、塩類としては、
青色酸化タングステン等の酸化物、珪タングステ
ン酸、燐タングステン酸、燐モリブデン酸等のヘ
テロポリ酸、燐酸硼素、燐酸ランタン、硫酸アル
ミニウム、硫酸亜鉛等の塩類が挙げられる。複合
酸化物としては、シリカ−アルミナ、シリカ−ジ
ルコニア、チタニア−ジルコニア、シリカ−チタ
ニア等が挙げられる。
なかでも酸強度がpKa値で２以下の強酸が好ま
しい。これらの強酸の使用量はホルムアルデヒド
１モルあたり0.1〜1000meqである。
本発明方法においては溶媒の使用は必須ではな
いが、反応をより円滑にするために溶媒を使用す
ることもできる。このような溶媒としては、ジエ
チルエーテル、ジフエニルエーテル、ジオキサ
ン、テトラヒドロフラン、エチレングリコールジ
メチルエーテル等のエーテル類、アセトン、エチ
ルメチルケトン、ジブチルケトン、アセトフエノ
ン等のケトン類、酢酸メチル、酢酸エチル、酢酸
ブチル、プロピオン酸メチル等のエステル類、ア
セトニトリル、プロピオニトリル、ベンゾニトリ
ル等のニトリル類、ベンゼン、トルエン、パラキ
シレン、エチルベンゼン等の芳香族炭化水素、ペ
ンタン、ヘキサン、オクタン等のパラフイン類、
ヘキセン−１、オクテン−２等のオレフイン類、
ジメチルホルムアミド、ジメチルアセトアミド、
Ｎ−メチルピロリドン等のＮ−置換アミド類、ジ
メチルスルホキシド、スルホラン等のスルホキシ
ド類、エチレンカーボネート、プロピレンカーボ
ネート等のカーボネート類、ニトロメタン、ニト
ロベンゼン等のニトロ化合物などが挙げられる。
本発明方法は室温以上の反応温度で実施し得る
が、通常は50〜250℃の反応温度条件下で行なわ
れる。
次に本発明を実施例により更に具体的に説明す
る。
実施例１〜11、比較例１
電磁融導撹拌式の300ml容チタン製オートクレ
ーブにトリオキサンまたはパラホルムアルデヒ
ド、ギ酸エステル、酸触媒および場合により水あ
るいは溶媒を仕込み、一酸化炭素または窒素ガス
を圧入したのち加熱し撹拌しながら所定時間反応
を行なつた。反応終了後、オートクレーブを氷水
中で冷却し、ガスおよび反応液をガスクロマトグ
ラフイーにより分析定量した。
反応原料、触媒の種類およびその使用量ならび
に反応条件などは表−１に示す。
The present invention relates to a process for producing ethers and esters of glycolic acid. Glycolic acid esters can be hydrolyzed to yield glycolic acid, hydrogenated to yield ethylene glycol, and glycolic acid ethers can be hydrogenated to yield cellosolves, so both are important as industrial intermediates. It is a chemical compound. A method for producing glycolic acid ester is a method in which paraformaldehyde or trioxane is reacted with formic acid ester in the presence of a strong acid catalyst such as sulfuric acid or an organic sulfonic acid (Japanese Patent Application Laid-open No. 53-98924).
is known, but is dissatisfied with its slow reaction rate. The present inventors have discovered that by reacting formaldehyde, formic acid ester, and carbon monoxide in the presence of a strong acid catalyst, glycolic acid ester can be obtained together with glycolic acid ether at a good reaction rate, and the present invention has been achieved. The present invention will be explained in detail below. Formaldehydes used in the method of the invention include gaseous formaldehyde, trioxane and paraformaldehyde.
Although it is possible to use an aqueous formaldehyde solution if desired, it is not advantageous to carry out the reaction in the presence of water in the method of the present invention, and it is less than 1 mol, preferably 0.5 mol per mol of formaldehyde.
It should be suppressed to less than mol. As the formic acid ester, a formic acid ester of an alkanol having 1 to 10 carbon atoms is used, and a formic acid ester of a lower alkanol such as methyl formate, ethyl formate, and butyl formate is particularly preferably used. These formic acid esters are generally used in an amount of 0.05 to 10 mol, preferably 0.1 to 5 mol, per 1 mol of formaldehyde. If desired, formate may be used in excess as a solvent. Carbon monoxide may not only be pure, but also carbon monoxide diluted with a gas inert to the reaction, such as nitrogen, helium, argon, hydrogen, or the like. The carbon monoxide partial pressure in the reaction system is usually 10 to 250 Kg/cm 2 , preferably
It is 20-150Kg/ cm2 . Strong acid catalysts used in the method of the present invention include mineral acids such as hydrochloric acid, hydrobromic acid, hydriodic acid, hydrofluoric acid, perchloric acid, nitric acid, and sulfuric acid, trifluoroacetic acid, methanesulfonic acid, and benzene. Organic acids such as sulfonic acid, p-toluenesulfonic acid, chlorosulfonic acid, trifluoromethanesulfonic acid,
So-called solids such as Lewis acids such as boron trifluoride, phosphorus pentafluoride, and antimony pentafluoride or strongly acidic cation exchange resins, clay minerals, zeolites, solidified acids, inorganic oxides, inorganic salts, and composite oxides. Examples include acids. Strongly acidic cation exchange resins have a sulfonic acid functional group, and Diaion PK-
228, those with a styrene-divinylbenzene copolymer skeleton such as Diaion HPK25 (manufactured by Mitsubishi Chemical Industries, Ltd.) and Amberlite 200 (manufactured by Rohm and Haas), Nafion 501 (manufactured by DuPont), etc. Examples include those having a tetrafluoroethylene polymer skeleton. Examples of clay minerals and zeolites include montmorillonite, kaolinite, bentonite, halloysite, smectite, illite, vermiculite, chlorite, sepiolite, attapulgite, polygorskite, mordenite, and montmorillonite KSF/O (manufactured by Girdler Chemical). ), which are treated with an acid such as hydrogen fluoride, and those in which exchangeable metal ions are exchanged with hydrogen ions, such as H-type zeolite, are preferable. Examples of the solidifying acid include those in which phosphoric acid, boric acid, etc. are supported on a carrier. As inorganic oxides and salts,
Examples include oxides such as blue tungsten oxide, heteropolyacids such as tungstic silicic acid, tungstic phosphoric acid, and molybdic phosphoric acid, and salts such as boron phosphate, lanthanum phosphate, aluminum sulfate, and zinc sulfate. Examples of the composite oxide include silica-alumina, silica-zirconia, titania-zirconia, and silica-titania. Among these, strong acids having an acid strength of 2 or less in pKa value are preferred. The amount of these strong acids used is 0.1 to 1000 meq per mole of formaldehyde. Although the use of a solvent is not essential in the method of the present invention, a solvent can also be used in order to make the reaction smoother. Examples of such solvents include ethers such as diethyl ether, diphenyl ether, dioxane, tetrahydrofuran, and ethylene glycol dimethyl ether, ketones such as acetone, ethyl methyl ketone, dibutyl ketone, and acetophenone, methyl acetate, ethyl acetate, butyl acetate, Esters such as methyl propionate, nitriles such as acetonitrile, propionitrile, and benzonitrile, aromatic hydrocarbons such as benzene, toluene, paraxylene, and ethylbenzene, paraffins such as pentane, hexane, and octane,
Olefins such as hexene-1 and octene-2,
dimethylformamide, dimethylacetamide,
Examples include N-substituted amides such as N-methylpyrrolidone, sulfoxides such as dimethyl sulfoxide and sulfolane, carbonates such as ethylene carbonate and propylene carbonate, and nitro compounds such as nitromethane and nitrobenzene. Although the method of the present invention can be carried out at a reaction temperature of room temperature or higher, it is usually carried out at a reaction temperature of 50 to 250°C. Next, the present invention will be explained in more detail with reference to Examples. Examples 1 to 11, Comparative Example 1 Trioxane or paraformaldehyde, formic acid ester, acid catalyst, and optionally water or solvent were charged into a 300 ml titanium autoclave with electromagnetic fusion stirring, and carbon monoxide or nitrogen gas was pressurized. The reaction was carried out for a predetermined period of time while heating and stirring. After the reaction was completed, the autoclave was cooled in ice water, and the gas and reaction solution were analyzed and quantified by gas chromatography. The reaction raw materials, the types and amounts of catalysts used, and reaction conditions are shown in Table 1.
【表】
反応生成物は下記表−２に掲げた六種の化合物
を含む。[Table] The reaction product contains six types of compounds listed in Table 2 below.
【表】
反応時に測定された一酸化炭素の吸収量、上記
各反応生成物の生成量、生成物のグリコール酸換
算収量（P1＋P2＋P3＋2P4＋2P5＋2P6）および収
率（ホルムアルデヒド基準）を表−３に示す。[Table] The amount of carbon monoxide absorbed during the reaction, the amount of each reaction product produced, the yield of the product in terms of glycolic acid (P 1 + P 2 + P 3 + 2P 4 + 2P 5 + 2P 6 ), and the yield (formaldehyde Standards) are shown in Table 3.
Claims (1)
酸エステルと一酸化炭素とを反応させることを特
徴とするグリコール酸のエーテルおよびエステル
の製造法。1. A method for producing glycolic acid ethers and esters, which comprises reacting formaldehyde, formic acid ester, and carbon monoxide in the presence of a strong acid catalyst.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2501080A JPS56122321A (en) | 1980-02-29 | 1980-02-29 | Preparation of glycolic ether and ester |
| DE19813107518 DE3107518A1 (en) | 1980-02-29 | 1981-02-27 | Process for the preparation of esters and ethers of glycolic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2501080A JPS56122321A (en) | 1980-02-29 | 1980-02-29 | Preparation of glycolic ether and ester |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS56122321A JPS56122321A (en) | 1981-09-25 |
| JPS6314688B2 true JPS6314688B2 (en) | 1988-04-01 |
Family
ID=12153947
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2501080A Granted JPS56122321A (en) | 1980-02-29 | 1980-02-29 | Preparation of glycolic ether and ester |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS56122321A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1064040C (en) * | 1997-09-29 | 2001-04-04 | 中国科学院成都有机化学研究所 | Method and catalyst of synthesis of methyl glycolate |
| US9114328B2 (en) | 2012-05-16 | 2015-08-25 | Eastman Chemical Company | Reactive distillation of a carboxylic acid and a glycol |
| US9040748B2 (en) | 2012-06-08 | 2015-05-26 | Eastman Chemical Company | Hydrocarboxylation of aqueous formaldehyde using a dehydrating recycle stream to decrease water concentration |
-
1980
- 1980-02-29 JP JP2501080A patent/JPS56122321A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS56122321A (en) | 1981-09-25 |
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