JPS6341380B2 - - Google Patents
Info
- Publication number
- JPS6341380B2 JPS6341380B2 JP55003412A JP341280A JPS6341380B2 JP S6341380 B2 JPS6341380 B2 JP S6341380B2 JP 55003412 A JP55003412 A JP 55003412A JP 341280 A JP341280 A JP 341280A JP S6341380 B2 JPS6341380 B2 JP S6341380B2
- Authority
- JP
- Japan
- Prior art keywords
- acid
- formaldehyde
- aliphatic carboxylic
- oxymethylene
- formula
- 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
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 36
- 239000003054 catalyst Substances 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 claims description 6
- 125000005704 oxymethylene group Chemical group [H]C([H])([*:2])O[*:1] 0.000 claims description 6
- -1 aliphatic carboxylic anhydride Chemical class 0.000 claims description 5
- 239000011973 solid acid Substances 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- BGJSXRVXTHVRSN-UHFFFAOYSA-N 1,3,5-trioxane Chemical compound C1OCOCO1 BGJSXRVXTHVRSN-UHFFFAOYSA-N 0.000 description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-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
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-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
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 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
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-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
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- JTKXHCGOXNVDPQ-UHFFFAOYSA-N acetylperoxymethyl acetate Chemical compound CC(=O)OCOOC(C)=O JTKXHCGOXNVDPQ-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- 239000003729 cation exchange resin Substances 0.000 description 2
- 239000007810 chemical reaction solvent Substances 0.000 description 2
- 239000002734 clay mineral Substances 0.000 description 2
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 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
- MNWFXJYAOYHMED-UHFFFAOYSA-N heptanoic acid Chemical compound CCCCCCC(O)=O MNWFXJYAOYHMED-UHFFFAOYSA-N 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- FBUKVWPVBMHYJY-UHFFFAOYSA-N nonanoic acid Chemical compound CCCCCCCCC(O)=O FBUKVWPVBMHYJY-UHFFFAOYSA-N 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 235000019260 propionic acid Nutrition 0.000 description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- FQERLIOIVXPZKH-UHFFFAOYSA-N 1,2,4-trioxane Chemical compound C1COOCO1 FQERLIOIVXPZKH-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- YZUPZGFPHUVJKC-UHFFFAOYSA-N 1-bromo-2-methoxyethane Chemical compound COCCBr YZUPZGFPHUVJKC-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
- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 description 1
- 239000005635 Caprylic acid (CAS 124-07-2) Substances 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- 239000005643 Pelargonic acid Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 239000004113 Sepiolite Substances 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
- 150000007513 acids Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 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
- 229910000147 aluminium phosphate Inorganic materials 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
- 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
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 229920001429 chelating resin Polymers 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910001919 chlorite Inorganic materials 0.000 description 1
- 229910052619 chlorite group Inorganic materials 0.000 description 1
- QBWCMBCROVPCKQ-UHFFFAOYSA-N chlorous acid Chemical compound OCl=O QBWCMBCROVPCKQ-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229920001577 copolymer Polymers 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
- 238000004821 distillation Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052621 halloysite Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 229910052900 illite Inorganic materials 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052809 inorganic oxide 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
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000004949 mass spectrometry Methods 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
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 229910052680 mordenite Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 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
- 229960002446 octanoic acid Drugs 0.000 description 1
- 229910052625 palygorskite Inorganic materials 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052624 sepiolite Inorganic materials 0.000 description 1
- 235000019355 sepiolite Nutrition 0.000 description 1
- CGFYHILWFSGVJS-UHFFFAOYSA-N silicic acid;trioxotungsten Chemical compound O[Si](O)(O)O.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 CGFYHILWFSGVJS-UHFFFAOYSA-N 0.000 description 1
- 229910021647 smectite Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 150000003467 sulfuric acid derivatives 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
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- 229940005605 valeric acid Drugs 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
- 239000010457 zeolite Substances 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
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
本発明はオキシメチレンビスカルボキシレート
類の製造法に関するものである。
オキシメチレンビスカルボキシレート類は穀物
貯蔵庫における湿度調節剤等に有用であるほか、
グリコール酸、エチレングリコールあるいはβ−
プロピオクラトン誘導体などの合成中間体として
有用な化合物である。
本発明者らはホルムアルデヒドと脂肪族カルボ
ン酸またはその無水物よりオキシメチレンビスカ
ルボキシレート類を製造する方法について種々検
討した結果、酸強度がpKa値で２以下である酸点
の酸性度が少くとも0.1meq／ｇである固体酸を
触媒として使用することにより容易にオキシメチ
レンビスカルボキシレート類が得られ、かつ、生
成物と触媒との分離が簡単であることを見い出し
本発明に到達したものである。
以下に本発明を詳細に説明する。
本発明方法において、ホルムアルデヒドとして
はガス状のホルムアルデヒド、ホルムアルデヒド
水溶液のほかにトリオキサン、パラホルムアルデ
ヒドなどの反応条件下でホルムアルデヒドとなる
ようなホルムアルデヒドのオリゴマーが使用され
る。ただし、反応系に多量の水が共存することは
好ましくなく、ホルムアルデヒドに対して等モル
以下に抑制することが望ましい。
脂肪族カルボン酸または脂肪族カルボン酸無水
物としては酢酸、プロピオン酸、酪酸、吉草酸、
カプロン酸、エナント酸、カプリル酸、ペラルゴ
ン酸、カプリン酸およびこれらの異性体などの炭
素原子数２〜10の脂肪族カルボン酸あるいはこれ
らの無水物が挙げられる。
これらの脂肪族カルボン酸または脂肪族カルボ
ン酸無水物はホルムアルデヒドに対して、通常、
等モル以上使用される。
本発明方法において触媒に使用される固体酸は
pKa値２以下の酸強度を有する酸点の酸性度が少
くとも0.1meq／ｇであるものであり、具体的に
は、スチレン−ジビニルベンゼン共重合体骨格ま
たはテトラフルオロエチレン骨格に官能基として
スルホン酸を有する強酸性陽イオン交換樹脂、た
とえば、ダイヤイオンPK−228、ダイヤイオン
HPK−55（いずれも三菱化成工業(株)製）、アン
バーライト200、アンバーリスト15（いずれも
ロームアンドハース社製）、ナフイオン501（デ
ユポン社製）など、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、ポリゴスカイ
ト、モルデナイトなどの粘土鉱質あるいはゼオラ
イトあるいはモンモリロナイトKSF／Ｏ（ガード
ラー社製）などのように上記の粘土鉱質を弗化水
素等の酸により処理したもの、燐酸、硼酸などを
担体に担持したもの、青色酸化タングステンなど
の無機酸化物、珪タングステン酸、燐モリブデン
酸などのヘテロポリ酸、燐酸硼素、燐酸ランタン
などの燐酸塩、硫酸アルミニウム、硫酸亜鉛など
の硫酸塩、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−チタニアな
どの複合酸化物が挙げられる。これらの固体酸触
媒はホルムアルデヒド１モルに対して通常0.1〜
1000meq／ｇの範囲で使用される。
反応溶媒の使用は必ずしも必要ではないが、反
応をより効果的に行なうために、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、メチルエチルケト
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ｎ−ブチル、
プロピオン酸メチル等のエステル類、ベンゼン、
トルエン、ｐ−キシレン、エチルベンゼン等の芳
香族炭化水素類、ｎ−ペンタン、ｎ−ヘキサン、
ｎ−オクタン等のアルカン類、ヘキセン−１、オ
クテン−２等のアルケン類、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
ネート類を反応溶媒として使用することができ
る。
本発明は気相法、液相法のいずれの方法でも、
また懸濁床方式、固定床方式のいずれの方式でも
実施可能であり、反応温度としては通常25〜200
℃、好ましくは50〜150℃の範囲内で適宜採用さ
れる。反応圧力は特に限定されるものではなく、
通常は常圧または若干の加圧下に、大気雰囲気下
もしくは窒素、ヘリウム、アルゴン等の不活性ガ
ス雰囲気下に行なわれる。
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
内容積100mlのガラス製反応器にトリオキサン
5.0ｇ（ホルムアルデヒド167mmoleに相当）、酢
酸70mlおよび強酸性陽イオン交換樹脂（ダイヤイ
オンHPK−55）2.0ｇ（13.6meqに相当）を仕
込み、撹拌下110℃で30分間反応させた。反応終
了後、反応生成液を冷却し、ガスクロマトグラフ
イーにより、オキシメチレンジアセテート、ジオ
キシメチレンジアセテートおよびトリオキシメチ
レンジアセテートの定量を行なつた。結果は表−
２に記す。
上記三種の生成物は触媒を別したのち蒸留に
より容易に単離され、赤外分光光度法、核磁気共
鳴スペクトル、GC−マススペクトルにより確認
された。
実施例 ２〜６
触媒、温度、反応時間等の条件を表−１に記載
したように変更したこと以外は実施例１と同様に
実験を行なつた。結果は表−２に記す。
The present invention relates to a method for producing oxymethylene biscarboxylates. Oxymethylene biscarboxylates are useful as humidity regulators in grain storage, etc.
Glycolic acid, ethylene glycol or β-
It is a useful compound as a synthetic intermediate for propiokratone derivatives. The present inventors have conducted various studies on methods for producing oxymethylene biscarboxylates from formaldehyde and aliphatic carboxylic acids or their anhydrides, and have found that the acidity of acid sites with pKa values of 2 or less is at least The present invention was achieved by discovering that oxymethylene biscarboxylates can be easily obtained by using a solid acid having a concentration of 0.1 meq/g as a catalyst, and that separation of the product and catalyst is easy. be. The present invention will be explained in detail below. In the method of the present invention, as formaldehyde, in addition to gaseous formaldehyde and aqueous formaldehyde solutions, oligomers of formaldehyde that become formaldehyde under reaction conditions such as trioxane and paraformaldehyde are used. However, it is not preferable for a large amount of water to coexist in the reaction system, and it is desirable to suppress the water to an equimolar amount or less relative to formaldehyde. Examples of aliphatic carboxylic acids or aliphatic carboxylic anhydrides include acetic acid, propionic acid, butyric acid, valeric acid,
Examples include aliphatic carboxylic acids having 2 to 10 carbon atoms, such as caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, and isomers thereof, or anhydrides thereof. These aliphatic carboxylic acids or aliphatic carboxylic acid anhydrides are usually resistant to formaldehyde.
Equimolar or more is used. The solid acid used as a catalyst in the method of the present invention is
The acidity of the acid site having an acid strength of pKa value 2 or less is at least 0.1meq/g, and specifically, sulfone is added as a functional group to the styrene-divinylbenzene copolymer skeleton or tetrafluoroethylene skeleton. Strongly acidic cation exchange resin with acid, such as Diaion PK-228, Diaion
HPK-55 (all manufactured by Mitsubishi Chemical Industries, Ltd.), Amberlite 200, Amberlyst 15 (all manufactured by Rohm and Haas), Nafion 501 (manufactured by DuPont), montmorillonite, kaolinite, bentonite, halloysite, Smectite, illite, vermiculite, chlorite,
Clay minerals such as sepiolite, attapulgite, polygoskite, mordenite, zeolite or montmorillonite KSF/O (manufactured by Girdler) are treated with the above clay minerals with acids such as hydrogen fluoride, phosphoric acid, boric acid, etc. Supported on carriers, inorganic oxides such as blue tungsten oxide, heteropolyacids such as silicotungstic acid and phosphomolybdic acid, phosphates such as boron phosphate and lanthanum phosphate, sulfates such as aluminum sulfate and zinc sulfate, silica-alumina , silica-zirconia, titania-zirconia, silica-titania, and other composite oxides. These solid acid catalysts are usually used in amounts of 0.1 to 1 mole of formaldehyde.
Used in the range of 1000meq/g. Although it is not necessary to use a reaction solvent, in order to make the reaction more effective, ethers such as diethyl ether, diphenyl ether, dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, acetone, methyl ethyl ketone, dibutyl ketone, acetophenone, etc. Ketones, methyl acetate, ethyl acetate, n-butyl acetate,
Esters such as methyl propionate, benzene,
Aromatic hydrocarbons such as toluene, p-xylene, ethylbenzene, n-pentane, n-hexane,
Alkanes such as n-octane, alkenes such as hexene-1 and octene-2, sulfoxides such as dimethyl sulfoxide and sulfolane, and carbonates such as ethylene carbonate and propylene carbonate can be used as the reaction solvent. The present invention can be applied to either a gas phase method or a liquid phase method.
In addition, it can be carried out using either a suspended bed method or a fixed bed method, and the reaction temperature is usually 25 to 200°C.
℃, preferably within the range of 50 to 150℃ as appropriate. The reaction pressure is not particularly limited,
It is usually carried out under normal pressure or slightly increased pressure, in an atmosphere of air, or an atmosphere of an inert gas such as nitrogen, helium, or argon. Next, the present invention will be explained in more detail with reference to Examples. Example 1 Trioxane was placed in a glass reactor with an internal volume of 100 ml.
5.0 g (equivalent to 167 mmole of formaldehyde), 70 ml of acetic acid, and 2.0 g (equivalent to 13.6 meq) of a strongly acidic cation exchange resin (Diaion HPK-55) were charged and reacted at 110° C. for 30 minutes with stirring. After the reaction was completed, the reaction product liquid was cooled, and oxymethylene diacetate, dioxymethylene diacetate, and trioxymethylene diacetate were quantitatively determined by gas chromatography. The results are in the table-
Described in 2. The above three products were easily isolated by distillation after separating the catalyst, and were confirmed by infrared spectroscopy, nuclear magnetic resonance spectroscopy, and GC-mass spectroscopy. Examples 2 to 6 Experiments were conducted in the same manner as in Example 1, except that conditions such as catalyst, temperature, and reaction time were changed as shown in Table 1. The results are shown in Table-2.
【表】【table】
【表】
実施例 ７
酢酸のかわりにプロピオン酸を使用したこと以
外は実施例１と同様に実験を行なつた。その結
果、ホルムアルデヒドの転化率は71.0％であり、
オキシメチレン、ジオキシメチレン、トリオキシ
メチレンがそれぞれ0.4ｇ、1.6ｇおよび0.4ｇ生成
していた。
実施例 ８
酢酸のかわりに無水酢酸を使用したこと以外は
実施例１と同様に実験を行なつた。その結果、ホ
ルムアルデヒドの転化率は100％であり、オキシ
メチレンジアセテート7.6ｇ、ジオキシメチレン
ジアセテート8.5ｇおよび微量のトリオキシメチ
レンジアセテートが生成していた。[Table] Example 7 An experiment was conducted in the same manner as in Example 1 except that propionic acid was used instead of acetic acid. As a result, the conversion rate of formaldehyde was 71.0%,
Oxymethylene, dioxymethylene, and trioxymethylene were produced in amounts of 0.4g, 1.6g, and 0.4g, respectively. Example 8 An experiment was conducted in the same manner as in Example 1 except that acetic anhydride was used instead of acetic acid. As a result, the conversion rate of formaldehyde was 100%, and 7.6 g of oxymethylene diacetate, 8.5 g of dioxymethylene diacetate, and a trace amount of trioxymethylene diacetate were produced.
Claims (1)
が少くとも0.1meq／ｇである固体酸触媒の存在
下にホルムアルデヒドを脂肪族カルボン酸または
脂肪族カルボン酸無水物と反応させることを特徴
とする一般式 （式中、ＲおよびR′は炭素原子数１〜９のア
ルキル基を表わし、ｎは１，２または３である。） で示されるオキシメチレンビスカルボキシレート
類の製造法。[Scope of Claims] 1. Formaldehyde is added to an aliphatic carboxylic acid or an aliphatic carboxylic anhydride in the presence of a solid acid catalyst whose acidity is at least 0.1 meq/g at an acid site whose pKa value is 2 or less. General formula characterized by reacting with a substance (In the formula, R and R' represent an alkyl group having 1 to 9 carbon atoms, and n is 1, 2 or 3.) A method for producing oxymethylene biscarboxylates represented by the formula:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP341280A JPS56100741A (en) | 1980-01-16 | 1980-01-16 | Preparation of oxymethylenebiscarboxylates |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP341280A JPS56100741A (en) | 1980-01-16 | 1980-01-16 | Preparation of oxymethylenebiscarboxylates |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS56100741A JPS56100741A (en) | 1981-08-12 |
| JPS6341380B2 true JPS6341380B2 (en) | 1988-08-17 |
Family
ID=11556660
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP341280A Granted JPS56100741A (en) | 1980-01-16 | 1980-01-16 | Preparation of oxymethylenebiscarboxylates |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS56100741A (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8466328B2 (en) | 2010-08-18 | 2013-06-18 | Eastman Chemical Company | Method for recovery and recycle of ruthenium homogeneous catalysts |
| US9227896B2 (en) | 2010-08-18 | 2016-01-05 | Eastman Chemical Company | Process for the separation and purification of a mixed diol stream |
| US8829248B2 (en) | 2010-08-18 | 2014-09-09 | Eastman Chemical Company | Method for recovery and recycle of ruthenium homogeneous catalysts |
| US8785686B2 (en) | 2010-09-23 | 2014-07-22 | Eastman Chemical Company | Process for recovering and recycling an acid catalyst |
| US8709376B2 (en) | 2010-09-23 | 2014-04-29 | Eastman Chemical Company | Process for recovering and recycling an acid catalyst |
| US8829234B2 (en) | 2012-03-27 | 2014-09-09 | Eastman Chemical Company | Hydrocarboxylation of formaldehyde in the presence of a higher order carboxylic acid and heterogeneous catalyst |
| US8927766B2 (en) | 2012-03-27 | 2015-01-06 | Eastman Chemical Company | Hydrocarboxylation of methylene dipropionate in the presence of a propionic acid and a homogeneous catalyst |
| US8703999B2 (en) | 2012-03-27 | 2014-04-22 | Eastman Chemical Company | Hydrocarboxylation of methylene dipropionate in the presence of propionic acid and a heterogeneous catalyst |
| US8765999B2 (en) | 2012-03-27 | 2014-07-01 | Eastman Chemical Company | Hydrocarboxylation of formaldehyde in the presence of a higher order carboxylic acid and a homogeneous catalyst |
| US9040748B2 (en) | 2012-06-08 | 2015-05-26 | Eastman Chemical Company | Hydrocarboxylation of aqueous formaldehyde using a dehydrating recycle stream to decrease water concentration |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5337332A (en) * | 1976-07-23 | 1978-04-06 | Steenken Magnetdruck | Identification card having data memory |
-
1980
- 1980-01-16 JP JP341280A patent/JPS56100741A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5337332A (en) * | 1976-07-23 | 1978-04-06 | Steenken Magnetdruck | Identification card having data memory |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS56100741A (en) | 1981-08-12 |
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