JP2012001476A - Method for producing carbodiimide compound - Google Patents
Method for producing carbodiimide compound Download PDFInfo
- Publication number
- JP2012001476A JP2012001476A JP2010137174A JP2010137174A JP2012001476A JP 2012001476 A JP2012001476 A JP 2012001476A JP 2010137174 A JP2010137174 A JP 2010137174A JP 2010137174 A JP2010137174 A JP 2010137174A JP 2012001476 A JP2012001476 A JP 2012001476A
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- JP
- Japan
- Prior art keywords
- formula
- compound
- group
- carbodiimide
- carbon atoms
- 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.)
- Granted
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- -1 carbodiimide compound Chemical class 0.000 title claims abstract description 50
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 23
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 claims abstract description 42
- UMGDCJDMYOKAJW-UHFFFAOYSA-N aminothiocarboxamide Natural products NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 40
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 29
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 claims abstract description 18
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 11
- 150000007514 bases Chemical class 0.000 claims abstract description 9
- 239000003054 catalyst Substances 0.000 claims abstract description 8
- 230000003009 desulfurizing effect Effects 0.000 claims abstract description 4
- 150000001718 carbodiimides Chemical class 0.000 claims description 40
- 238000000034 method Methods 0.000 claims description 26
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 125000004432 carbon atom Chemical group C* 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 16
- 150000001875 compounds Chemical class 0.000 claims description 14
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 8
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 7
- 239000003444 phase transfer catalyst Substances 0.000 claims description 7
- 238000000746 purification Methods 0.000 claims description 7
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 7
- 239000002516 radical scavenger Substances 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 229910052736 halogen Inorganic materials 0.000 claims description 5
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 150000001408 amides Chemical class 0.000 claims description 3
- 238000000605 extraction Methods 0.000 claims description 3
- 125000000623 heterocyclic group Chemical group 0.000 claims description 3
- 150000002466 imines Chemical class 0.000 claims description 3
- 238000001953 recrystallisation Methods 0.000 claims description 3
- 150000003512 tertiary amines Chemical class 0.000 claims description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 42
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 12
- 229910052717 sulfur Inorganic materials 0.000 description 12
- 239000011593 sulfur Substances 0.000 description 12
- 239000007864 aqueous solution Substances 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- 239000003960 organic solvent Substances 0.000 description 8
- 150000001412 amines Chemical class 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 238000011084 recovery Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 238000009776 industrial production Methods 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 description 2
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 2
- YYROPELSRYBVMQ-UHFFFAOYSA-N 4-toluenesulfonyl chloride Chemical compound CC1=CC=C(S(Cl)(=O)=O)C=C1 YYROPELSRYBVMQ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 2
- QSRFYFHZPSGRQX-UHFFFAOYSA-N benzyl(tributyl)azanium Chemical class CCCC[N+](CCCC)(CCCC)CC1=CC=CC=C1 QSRFYFHZPSGRQX-UHFFFAOYSA-N 0.000 description 2
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229960002887 deanol Drugs 0.000 description 2
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 239000012972 dimethylethanolamine Substances 0.000 description 2
- 230000007717 exclusion Effects 0.000 description 2
- 238000007429 general method Methods 0.000 description 2
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 description 2
- KYVBNYUBXIEUFW-UHFFFAOYSA-N 1,1,3,3-tetramethylguanidine Chemical compound CN(C)C(=N)N(C)C KYVBNYUBXIEUFW-UHFFFAOYSA-N 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- AVFZOVWCLRSYKC-UHFFFAOYSA-N 1-methylpyrrolidine Chemical compound CN1CCCC1 AVFZOVWCLRSYKC-UHFFFAOYSA-N 0.000 description 1
- GVNHOISKXMSMPX-UHFFFAOYSA-N 2-[butyl(2-hydroxyethyl)amino]ethanol Chemical compound CCCCN(CCO)CCO GVNHOISKXMSMPX-UHFFFAOYSA-N 0.000 description 1
- BFSVOASYOCHEOV-UHFFFAOYSA-N 2-diethylaminoethanol Chemical compound CCN(CC)CCO BFSVOASYOCHEOV-UHFFFAOYSA-N 0.000 description 1
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 208000033962 Fontaine progeroid syndrome Diseases 0.000 description 1
- 239000012359 Methanesulfonyl chloride Substances 0.000 description 1
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 1
- AKNUHUCEWALCOI-UHFFFAOYSA-N N-ethyldiethanolamine Chemical compound OCCN(CC)CCO AKNUHUCEWALCOI-UHFFFAOYSA-N 0.000 description 1
- AHVYPIQETPWLSZ-UHFFFAOYSA-N N-methyl-pyrrolidine Natural products CN1CC=CC1 AHVYPIQETPWLSZ-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- VBQDSLGFSUGBBE-UHFFFAOYSA-N benzyl(triethyl)azanium Chemical class CC[N+](CC)(CC)CC1=CC=CC=C1 VBQDSLGFSUGBBE-UHFFFAOYSA-N 0.000 description 1
- FWLORMQUOWCQPO-UHFFFAOYSA-N benzyl-dimethyl-octadecylazanium Chemical class CCCCCCCCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 FWLORMQUOWCQPO-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
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- 239000012141 concentrate Substances 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- 125000005982 diphenylmethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
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- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229910000464 lead oxide Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910000474 mercury oxide Inorganic materials 0.000 description 1
- UKWHYYKOEPRTIC-UHFFFAOYSA-N mercury(ii) oxide Chemical compound [Hg]=O UKWHYYKOEPRTIC-UHFFFAOYSA-N 0.000 description 1
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- 125000006178 methyl benzyl group Chemical group 0.000 description 1
- ZUZLIXGTXQBUDC-UHFFFAOYSA-N methyltrioctylammonium Chemical class CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC ZUZLIXGTXQBUDC-UHFFFAOYSA-N 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- 125000002958 pentadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
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- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
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- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical class CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 description 1
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical class CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 description 1
- 150000003556 thioamides Chemical class 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- 150000003585 thioureas Chemical class 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
本発明はカルボジイミド体の製造方法に関する、さらに詳しくは特定のカルボジイミド体の製造方法に関する。 The present invention relates to a method for producing a carbodiimide body, and more particularly to a method for producing a specific carbodiimide body.
ポリエステル等のエステル結合を有する化合物は、カルボキシル基等の極性基により加水分解が促進されるため、カルボキシル基の封止剤を適用して、カルボキシル基濃度を低減することが提案されている（特許文献１、特許文献２）。かかるカルボキシル基の封止剤として、カルボジイミド化合物が使用されている。
しかし、このカルボジイミド化合物は、いずれも線状の化合物であるため、使用時、揮発性のイソシアネート化合物が副生して、悪臭を発し、作業環境を悪化させるという欠点を有する。
そこで出願人は、封止剤として、カルボキシル基と反応してもイソシアネート化合物が副生しない環状カルボジイミド化合物を見出し国際出願した（特許文献３）。しかし、この有用な環状カルボジイミド化合物の工業的な製造方法は確立されていない。
Since a compound having an ester bond such as polyester is accelerated by a polar group such as a carboxyl group, it has been proposed to reduce the carboxyl group concentration by applying a carboxyl group sealant (patent) Literature 1, Patent Literature 2). A carbodiimide compound is used as such a carboxyl group sealing agent.
However, since all of these carbodiimide compounds are linear compounds, a volatile isocyanate compound is produced as a by-product during use, and has a drawback of producing a bad odor and deteriorating the working environment.
Therefore, the applicant has found a cyclic carbodiimide compound as an encapsulant in which an isocyanate compound is not by-produced even if it reacts with a carboxyl group, and has filed an international application (Patent Document 3). However, an industrial production method for this useful cyclic carbodiimide compound has not been established.
本発明の目的は、特定のアミン体からチオ尿素体を経由して、高純度のカルボジイミド体を、工業的に適用可能な方法を用いて効率よく得る手法を確立することにある。
下記式（Ｃ）で表わされるカルボジイミド体（Ｃ）の前駆体である下記式（Ｂ）で表わされるチオ尿素体（Ｂ）を得るために適用される一般的な方法は、下記式（Ａ）で表わされるアミン体（Ａ）と二硫化炭素を反応させ、脱硫化水素させる方法である。しかしながら、アリールアミンと二硫化炭素の反応は非常に遅く、収率が低いのが一般である。また大量の塩基を必要とし、反応も長時間を必要とするため、生産性に難がある。また、化学量論量副生する硫化水素を捕捉するための大規模な除外装置が必要となる。
An object of the present invention is to establish a method for efficiently obtaining a high-purity carbodiimide body from a specific amine body via a thiourea body using a method that can be industrially applied.
A general method applied to obtain a thiourea body (B) represented by the following formula (B) which is a precursor of the carbodiimide body (C) represented by the following formula (C) is represented by the following formula (A). In this method, the amine (A) represented by the formula (2) is reacted with carbon disulfide to dehydrosulfurize it. However, the reaction between arylamines and carbon disulfide is generally very slow and yields are generally low. Further, since a large amount of base is required and the reaction also requires a long time, productivity is difficult. In addition, a large-scale exclusion device is required to capture hydrogen sulfide produced as a by-product in the stoichiometric amount.
チオ尿素体（Ｂ）からカルボジイミド体（Ｃ）を得るために適用される一般的な方法は、チオ尿素体（Ｂ）からの酸化的脱硫反応である。なかでも簡便なのは酸化水銀や酸化鉛などを用いる方法であるが、環境に対する負荷が大きく工業的生産には適用できない。またピリジンなどの塩基性溶媒中、塩化トシルや塩化メタンスルホニル等の塩化スルホニル等を作用させる方法も一般であり、適用可能である。しかしながら、ピリジンなどは一般に高価であり、工業生産においては回収サイクルが必要であるが、水との相溶性や共沸現象など回収は困難である。また塩化スルホニルも一般に高価である。
チオ尿素類からカルボジイミド類を合成する方法として、工業的により望ましいのは次亜塩素酸塩を作用させる方法が挙げられるが、チオ尿素体（Ｂ）へ適用した例はない。
A general method applied to obtain the carbodiimide body (C) from the thiourea body (B) is an oxidative desulfurization reaction from the thiourea body (B). Among them, the method using mercury oxide, lead oxide or the like is simple, but it has a heavy environmental load and cannot be applied to industrial production. Further, a method in which a sulfonyl chloride such as tosyl chloride or methanesulfonyl chloride is allowed to act in a basic solvent such as pyridine is generally applicable. However, pyridine and the like are generally expensive, and a recovery cycle is required for industrial production, but recovery such as compatibility with water and azeotropic phenomenon is difficult. Also, sulfonyl chloride is generally expensive.
As a method for synthesizing carbodiimides from thioureas, industrially more desirable is a method in which hypochlorite is allowed to act. However, there is no example applied to thiourea (B).
本発明者らは、上記の課題について鋭意検討を重ねた結果、（１）工業的により有利に適用可能なアミン体からチオ尿素体を得る方法、（２）工業的により有利に適用可能なチオ尿素体からカルボジイミド体を得る方法、（３）カルボジイミド体の精製方法、を見出した。それらを組み合わせることによって、工業的に製造可能な方法として、高純度のカルボジイミド体を効率よく得ることができることを見出し、本発明を完成した。
即ち、本発明の目的は、（１）下記式（Ａ）で表わされるアミン体と二硫化炭素とを、触媒の存在下、反応温度５０〜１５０℃で反応させ、下記式（Ｂ）で表わされるチオ尿素体を得る工程（１）、
As a result of intensive studies on the above problems, the present inventors have (1) a method for obtaining a thiourea form from an amine form that can be applied more advantageously industrially, and (2) a thiol that can be applied more advantageously industrially. The present inventors have found a method for obtaining a carbodiimide body from a urea body and (3) a method for purifying a carbodiimide body. By combining them, it was found that a highly pure carbodiimide body can be efficiently obtained as a method that can be produced industrially, and the present invention has been completed.
That is, the object of the present invention is (1) reacting an amine compound represented by the following formula (A) with carbon disulfide at a reaction temperature of 50 to 150 ° C. in the presence of a catalyst, and represented by the following formula (B). Obtaining a thiourea compound (1),
（式（Ａ）中、Ｒは、水素原子または炭素数１〜６のアルキル基である。） (In the formula (A), R is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.)
（式（Ｂ）中、Ｒは、式（Ａ）と同じである。）
（２）得られたチオ尿素体を、塩基性化合物の存在下、次亜塩素酸塩で脱硫し、下記式（Ｃ）で表わされるカルボジイミド体を得る工程（２）、および
（３）得られたカルボジイミド体を精製する工程（３）、
を含むカルボジイミド体の製造方法によって達成される。
(In formula (B), R is the same as in formula (A).)
(2) Steps (2) and (3) obtained by desulfurizing the obtained thiourea compound with hypochlorite in the presence of a basic compound to obtain a carbodiimide compound represented by the following formula (C) The step (3) of purifying the obtained carbodiimide body,
It is achieved by a method for producing a carbodiimide body containing
（式（Ｃ）中、Ｒは、式（Ａ）と同じである。）
また本願発明は、以下の発明も包含する。
２．工程（１）を硫化水素捕捉剤の存在下で行う前項１記載の製造方法。
３．工程（１）を密閉条件下行なう前項１または２記載の製造方法。
４．工程（１）で用いる触媒が、共役酸のｐＫａが５以上の塩基性を有する化合物である前項１〜３のいずれか一項に記載の製造方法。
５．共役酸のｐＫａが５以上の塩基性を有する化合物が、置換３級アミン、置換イミン、置換アミドまたは置換ヘテロ環である前項４記載の製造方法。
６．工程（２）においてさらに、下記式（ｉ）で表される相間移動触媒を用いる前項１〜５のいずれか一項に記載の製造方法。
(In formula (C), R is the same as in formula (A).)
The present invention also includes the following inventions.
2. 2. The production method according to item 1, wherein step (1) is carried out in the presence of a hydrogen sulfide scavenger.
3. 3. The production method according to 1 or 2 above, wherein the step (1) is carried out under sealed conditions.
4). 4. The production method according to any one of items 1 to 3, wherein the catalyst used in the step (1) is a compound having a basicity with a pKa of the conjugate acid of 5 or more.
5). 5. The method according to item 4 above, wherein the compound having a basicity with a pKa of 5 or more is a substituted tertiary amine, a substituted imine, a substituted amide, or a substituted heterocycle.
6). 6. The production method according to any one of items 1 to 5, wherein a phase transfer catalyst represented by the following formula (i) is further used in the step (2).
（式（ｉ）中、Ｒ１〜Ｒ４は各々独立に、炭素原子数１〜２０のアルキル基、炭素数６〜２０のアリール基、炭素数７〜２０のアラルキル基から選ばれる基である。Ａ−はハロゲンアニオンである）
７．工程（２）で用いる次亜塩素酸塩が、次亜塩素酸ナトリウムである前項１〜６のいずれか一項に記載の製造方法。
８．工程（２）の塩基性化合物が、水酸化ナトリウム、水酸化カリウムまたはこれらの混合物である前項１〜７のいずれか一項に記載の製造方法。
９．工程（３）の精製が、再結晶あるいは抽出である前項１〜８のいずれか一項に記載の製造方法。
(In formula (i), R1 to R4 are each independently a group selected from an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms. - is a halogen anion)
7). The manufacturing method as described in any one of 1 to 6 above, wherein the hypochlorite used in the step (2) is sodium hypochlorite.
8). 8. The production method according to any one of items 1 to 7, wherein the basic compound in the step (2) is sodium hydroxide, potassium hydroxide or a mixture thereof.
9. 9. The production method according to any one of items 1 to 8, wherein the purification in step (3) is recrystallization or extraction.
本発明の製造方法によれば、ポリエステル等の末端封止剤として有用なカルボジイミド体を高純度、かつ効率よく製造することができる。 According to the production method of the present invention, a carbodiimide body useful as an end-capping agent such as polyester can be produced with high purity and efficiency.
〔工程（１）〕
工程（１）は、下記式（Ａ）で表わされるアミン体と二硫化炭素とを、触媒の存在下、反応温度５０〜１５０℃で反応させ、下記式（Ｂ）で表わされるチオ尿素体を得る工程である。
アミン体は、下記式（Ａ）で表わされる。
[Step (1)]
In the step (1), an amine body represented by the following formula (A) and carbon disulfide are reacted at a reaction temperature of 50 to 150 ° C. in the presence of a catalyst to obtain a thiourea body represented by the following formula (B). It is a process to obtain.
The amine body is represented by the following formula (A).
式（Ａ）中、Ｒは、水素原子または炭素数１〜６のアルキル基である。炭素原子数１〜６のアルキル基として、メチル基、エチル基、ｎ−プロピル基、ｓｅｃ−プロピル基、ｉｓｏ−プロピル基、ｎ−ブチル基、ｔｅｒｔ−ブチル基、ｓｅｃ−ブチル基、ｉｓｏ−ブチル基、ｎ−ペンチル基、ｓｅｃ−ペンチル基、ｉｓｏ−ペンチル基、ｎ−ヘキシル基、ｓｅｃ−ヘキシル基、ｉｓｏ−ヘキシル基等が挙げられる。 In formula (A), R is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. Examples of the alkyl group having 1 to 6 carbon atoms include methyl group, ethyl group, n-propyl group, sec-propyl group, iso-propyl group, n-butyl group, tert-butyl group, sec-butyl group and iso-butyl. Group, n-pentyl group, sec-pentyl group, iso-pentyl group, n-hexyl group, sec-hexyl group, iso-hexyl group and the like.
触媒は、共役酸のｐＫａが５以上の塩基性を有する化合物であることが好ましい。このような化合物として置換３級アミン、置換アルカノールアミン、置換イミン、置換アミド、置換ヘテロ環等が挙げられる。具体的には、トリエチルアミン、Ｎ−メチルピロリジン、Ｎ−メチルモルホリン、テトラメチルエチレンジアミン、ジメチルエタノールアミン、ジエチルエタノールアミン、エチルジエタノールアミン、ブチルジエタノールアミン、トリエタノールアミン、イミダゾール、Ｎ−メチル−２−メルカプトイミダゾール、ピリジン、４−ジメチルアミノピリジン、テトラメチルグアニジン、１，８−ジアザビシクロ［５．４．０］ウンデセ−７−エン、１，４−ジアザビシクロ［２．２．２］オクタン等が例示される。
触媒の量は、アミン体１モルに対して、好ましくは０．１〜５モル、より好ましくは０．３〜３モルである。二硫化炭素の量は、アミン体１モルに対し、好ましくは２〜８モル、より好ましくは３〜６モルである。
The catalyst is preferably a compound having a basicity with a pKa of the conjugate acid of 5 or more. Examples of such compounds include substituted tertiary amines, substituted alkanolamines, substituted imines, substituted amides, and substituted heterocycles. Specifically, triethylamine, N-methylpyrrolidine, N-methylmorpholine, tetramethylethylenediamine, dimethylethanolamine, diethylethanolamine, ethyldiethanolamine, butyldiethanolamine, triethanolamine, imidazole, N-methyl-2-mercaptoimidazole, Examples include pyridine, 4-dimethylaminopyridine, tetramethylguanidine, 1,8-diazabicyclo [5.4.0] undec-7-ene, 1,4-diazabicyclo [2.2.2] octane and the like.
The amount of the catalyst is preferably 0.1 to 5 mol, more preferably 0.3 to 3 mol, per 1 mol of the amine compound. The amount of carbon disulfide is preferably 2 to 8 mol, more preferably 3 to 6 mol, relative to 1 mol of the amine compound.
反応は、密閉条件下で行なうことが好ましい。反応温度は、５０〜１５０℃、好ましくは８０〜１３０℃である。密閉条件下で行うことにより、低沸点である二硫化炭素の影響を受けることなく反応系を加熱でき、反応を迅速に進めることが可能である。反応時間は、３〜２０時間、好ましくは５〜１５時間が適用される。
反応は、硫化水素捕捉剤の存在下で行うことが好ましい。硫化水素捕捉剤とは、硫化水素と反応できるもののことを指し、アルキルハライド、酸無水物、多重結合化合物などが挙げられる。副生する酸およびメルカプタン類の臭気、原料アミンとの反応性等を考慮すると、多重結合化合物が望ましい。さらに言えば、ニトリル化合物が好適に使用でき、アセトニトリル、ベンゾニトリルなどが用いられ、それらは溶媒として用いることも可能である。
反応終了後は過剰の二硫化炭素が含まれる。除外しなくても可能だが、ろ過前に濃縮除去した方が、安全上好ましい。その後、溶媒を添加してもよい。また回収された二硫化炭素は生産系へ戻すことも可能である。
The reaction is preferably performed under sealed conditions. The reaction temperature is 50 to 150 ° C, preferably 80 to 130 ° C. By carrying out under sealed conditions, the reaction system can be heated without being affected by carbon disulfide having a low boiling point, and the reaction can proceed rapidly. The reaction time is 3 to 20 hours, preferably 5 to 15 hours.
The reaction is preferably performed in the presence of a hydrogen sulfide scavenger. The hydrogen sulfide scavenger refers to those capable of reacting with hydrogen sulfide, and examples thereof include alkyl halides, acid anhydrides, and multiple bond compounds. Considering the odor of by-product acid and mercaptans, reactivity with raw material amines, etc., a multiple bond compound is desirable. Furthermore, nitrile compounds can be preferably used, and acetonitrile, benzonitrile and the like can be used, and these can also be used as a solvent.
Excess carbon disulfide is contained after completion of the reaction. Although it is possible to exclude it, it is preferable in terms of safety to concentrate and remove it before filtration. Thereafter, a solvent may be added. The recovered carbon disulfide can be returned to the production system.
工程（１）の方法によれば、塩基性化合物は触媒量でよく、かつ短時間で目的とするチオ尿素体を得ることができ、さらに脱離した硫化水素の大分部は捕捉剤で捕捉され系外へ出されることもないため、大規模な除外装置も必要としないなどの利点を有する。
また好適に使用されるニトリル類を捕捉剤として用いた場合、硫化水素との反応後は化学的に中性で安定なチオアミド類となるため、その後の処理も簡便である利点を有する。
工程（１）で得られるチオ尿素体は下記式（Ｂ）で表わされる。
According to the method of step (1), the basic compound may be a catalytic amount, and the desired thiourea compound can be obtained in a short time, and most of the released hydrogen sulfide is captured by the scavenger. Since it is not taken out of the system, there is an advantage that a large-scale exclusion device is not required.
Further, when suitably used nitriles are used as the scavenger, after the reaction with hydrogen sulfide, chemically neutral and stable thioamides are obtained, so that there is an advantage that the subsequent treatment is also simple.
The thiourea compound obtained in step (1) is represented by the following formula (B).
式（Ｂ）中、Ｒは、式（Ａ）と同じである。 In formula (B), R is the same as formula (A).
〔工程（２）〕
工程（２）は、得られたチオ尿素体を塩基性化合物の存在下、次亜塩素酸塩で脱硫し、下記式（Ｃ）で表わされるカルボジイミド体を得る工程である。
塩基性化合物は、水酸化ナトリウム、水酸化カリウム、またはこれらの混合物が使用され、連続に添加しても、分割に添加してもよい。使用量はチオ尿素体に対して、好ましくは０．３〜６当量、より好ましくは０．５〜４当量の範囲である。塩基性化合物は、水溶液として用いることが好ましい。水溶液の濃度は、好ましくは６０〜１０重量パーセント、より好ましくは工業的に入手容易な５０〜２０重量パーセントである。
次亜塩素酸塩として、次亜塩素酸ナトリウムが挙げられる。使用量はチオ尿素体に対して、好ましくは２〜１０当量、より好ましくは３〜５当量である。次亜塩素酸塩は水溶液として用いることが好ましい。水溶液の濃度は、工業的に入手容易な１５〜１０重量パーセントが好適に利用される。
[Step (2)]
Step (2) is a step of desulfurizing the obtained thiourea compound with hypochlorite in the presence of a basic compound to obtain a carbodiimide compound represented by the following formula (C).
As the basic compound, sodium hydroxide, potassium hydroxide, or a mixture thereof is used, and it may be added continuously or dividedly. The amount used is preferably 0.3 to 6 equivalents, more preferably 0.5 to 4 equivalents, relative to the thiourea form. The basic compound is preferably used as an aqueous solution. The concentration of the aqueous solution is preferably 60 to 10 weight percent, more preferably 50 to 20 weight percent, which is industrially available.
An example of hypochlorite is sodium hypochlorite. The amount used is preferably 2 to 10 equivalents, more preferably 3 to 5 equivalents, relative to the thiourea form. Hypochlorite is preferably used as an aqueous solution. The concentration of the aqueous solution is preferably 15 to 10 weight percent, which is industrially easily available.
反応は有機溶剤中で行なうことが好ましい。有機溶剤とは水と分離するものが好適に使用され、クロロホルム、トルエン、クロロベンゼン、キシレン等が例示される。使用量はチオ尿素体に対して、好ましくは２〜１５倍重量部、より好ましくは３〜８倍重量部である。また溶媒は単独で用いてもかまわないが、反応を円滑に進行させるためにメタノール、エタノール、イソプロパノール、プロパノール等の極性溶媒を添加してもよい。
工程（２）では円滑に反応を進めるためにさらに、相間移動触媒を使用することが好ましい。相間移動触媒は一般的な４級アンモニウム塩等が適用可能である。相間移動触媒として下記式（ｉ）で表される化合物が好ましい。
The reaction is preferably carried out in an organic solvent. What separates from water is used suitably with an organic solvent, and chloroform, toluene, chlorobenzene, xylene, etc. are illustrated. The amount used is preferably 2 to 15 times by weight, more preferably 3 to 8 times by weight, relative to the thiourea form. Moreover, although a solvent may be used independently, in order to advance reaction smoothly, you may add polar solvents, such as methanol, ethanol, isopropanol, propanol.
In the step (2), it is preferable to use a phase transfer catalyst in order to smoothly advance the reaction. A general quaternary ammonium salt or the like can be used as the phase transfer catalyst. As the phase transfer catalyst, a compound represented by the following formula (i) is preferable.
式（ｉ）中、Ｒ１〜Ｒ４各々独立に、炭素原子数１〜２０のアルキル基、炭素原子数６〜２０のアリール基、炭素原子数７〜２０のアラルキル基から選ばれる基である。Ａ−はハロゲンアニオンである。
炭素原子数１〜２０のアルキル基として、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基、ウンデシル基、ドデシル基、トリデシル基、テトラデシル基、ペンタデシル基、へキサデシル基、オクタデシル基、ノナデシル基等が挙げられる。炭素原子数６〜２０のアリール基として、フェニル基、ナフチル基等が挙げられる。これらは、炭素原子数１〜１０のアルキル基で置換されていても良い。置換基としての炭素原子数１〜１０のアルキル基として、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基等が挙げられる。炭素原子数７〜２０のアラルキル基として、ベンジル基、フェネチル基、メチルベンジル基、ジフェニルメチル基等が挙げられる。Ａ−のハロゲンアニオンとして、フッソイオン、塩素イオン、臭素イオン等が挙げられる。
In formula (i), R1 to R4 are each independently a group selected from an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms. A − is a halogen anion.
Examples of the alkyl group having 1 to 20 carbon atoms include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, Examples include a tetradecyl group, a pentadecyl group, a hexadecyl group, an octadecyl group, and a nonadecyl group. Examples of the aryl group having 6 to 20 carbon atoms include a phenyl group and a naphthyl group. These may be substituted with an alkyl group having 1 to 10 carbon atoms. Examples of the alkyl group having 1 to 10 carbon atoms as a substituent include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, and a decyl group. Examples of the aralkyl group having 7 to 20 carbon atoms include benzyl group, phenethyl group, methylbenzyl group and diphenylmethyl group. Examples of the halogen anion for A − include a fluorine ion, a chlorine ion, and a bromine ion.
相間移動触媒として、テトラエチルアンモニウム塩、テトラブチルアンモニウム塩、トリオクチルメチルアンモニウム塩、ベンジルジメチルオクタデシルアンモニウム塩、ベンジルトリエチルアンモニウム塩、ベンジルトリメチルアンモニウム塩、ベンジルトリブチルアンモニウム塩等を挙げることができ、これらは単独で用いても二種以上を併用してもよい。相間移動触媒として４級アンモニウム塩等が適用可能である。チオ尿素体に対して、０．０１〜０．２倍重量部、より好ましくは０．０３〜０．１倍重量部が使用可能である。
工程（２）で得られるカルボジイミド体は下記式（Ｃ）で表わされる。
Examples of the phase transfer catalyst include tetraethylammonium salt, tetrabutylammonium salt, trioctylmethylammonium salt, benzyldimethyloctadecylammonium salt, benzyltriethylammonium salt, benzyltributylammonium salt, benzyltributylammonium salt, and the like. Two or more types may be used in combination. A quaternary ammonium salt or the like is applicable as a phase transfer catalyst. 0.01 to 0.2 times by weight, more preferably 0.03 to 0.1 times by weight, with respect to the thiourea body can be used.
The carbodiimide body obtained in the step (2) is represented by the following formula (C).
式（Ｃ）中、Ｒは、式（Ａ）と同じである。 In formula (C), R is the same as formula (A).
反応終了後、化合物Ｃの収率・品位を向上させる目的で、有機溶媒を濃縮し新たな有機溶媒へ置換してもよい。つまり引き続く工程（３）を包含することも可能である。また工程（１）を経ずに合成されたチオ尿素体へも、本カルボジイミド合成方法つまり工程（２）が適用可能であることは無論である。 After completion of the reaction, the organic solvent may be concentrated and replaced with a new organic solvent for the purpose of improving the yield and quality of Compound C. That is, it is possible to include the subsequent step (3). Of course, the present carbodiimide synthesis method, that is, step (2) can be applied to a thiourea compound synthesized without going through step (1).
〔工程（３）〕
工程（３）は、得られたカルボジイミド体を精製する工程である。チオ尿素体から得られたカルボジイミド体には硫黄が含まれる場合が多い。精製によりカルボジイミド体の色調および純度が向上する。
精製は、再結晶あるいは抽出であることが好ましい。精製は、カルボジイミド体を有機溶媒中で加熱し、着色成分を含む不要物を抽出後、冷却し、ろ過後、洗浄する。
[Step (3)]
Step (3) is a step of purifying the obtained carbodiimide body. The carbodiimide body obtained from the thiourea body often contains sulfur. Purification improves the color tone and purity of the carbodiimide body.
The purification is preferably recrystallization or extraction. In the purification, the carbodiimide body is heated in an organic solvent, and unnecessary substances including coloring components are extracted, cooled, filtered, and washed.
有機溶媒は硫黄に対して微量でも溶解度をもつものであればよく、芳香族炭化水素、炭化水素、エーテル、ケトン、エステル、アルコール、含ハロゲン系溶媒等が挙げられる。具体的にはトルエン、キシレン、クロロベンゼン、ジクロロベンゼン、クロロトルエン、ヘキサン、ヘプタン、シクロヘキサン、テトラヒドロフラン、アセトン、メチルエチルケトン、酢酸エチル、メタノール、エタノール、ジクロロメタン、クロロホルム等が例示される。溶媒の使用量、脱色効果、硫黄の除去率、カルボジイミド体の回収率等から考慮すると、トルエン、キシレン、クロロベンゼン、テトラヒドロフラン、クロロホルム等が好適に使用される。
有機溶剤の使用量は、カルボジイミド体に対して、好ましくは２〜５０倍重量部、より好ましくは３〜１５倍重量部が適用される。また加熱処理後、カルボジイミド体の回収率を上げる目的で使用した有機溶媒を濃縮回収してもよい。
工程（２）、（３）を経由せずに合成されたカルボジイミド体であっても、本方法を用いれば、純度および色調の改善がなされるのは無論であるが、本発明の様にチオ尿素体を経由し合成されたカルボジイミド体の精製に特に有効である。
The organic solvent only needs to have solubility in a small amount with respect to sulfur, and examples thereof include aromatic hydrocarbons, hydrocarbons, ethers, ketones, esters, alcohols, and halogen-containing solvents. Specific examples include toluene, xylene, chlorobenzene, dichlorobenzene, chlorotoluene, hexane, heptane, cyclohexane, tetrahydrofuran, acetone, methyl ethyl ketone, ethyl acetate, methanol, ethanol, dichloromethane, chloroform, and the like. Considering the amount of solvent used, decoloring effect, sulfur removal rate, carbodiimide body recovery rate, etc., toluene, xylene, chlorobenzene, tetrahydrofuran, chloroform, etc. are preferably used.
The amount of the organic solvent used is preferably 2 to 50 times by weight, more preferably 3 to 15 times by weight with respect to the carbodiimide body. Moreover, you may concentrate-recover the organic solvent used in order to raise the recovery rate of a carbodiimide body after heat processing.
Even if it is a carbodiimide compound synthesized without going through steps (2) and (3), it is of course possible to improve the purity and color tone by using this method. This is particularly effective for purification of a carbodiimide compound synthesized via a urea compound.
以下、実施例により本発明をさらに具体的に説明する。
なお、各値は以下の方法に従って求めた。
Hereinafter, the present invention will be described more specifically with reference to examples.
Each value was determined according to the following method.
（１）化合物の同定：
各化合物の同定は、質量分析計：（株）島津製作所製ＧＣＭＳ―ＱＰ５０００により行った。
（２）収量、収率：
合成した中間体、最終生成物の収量および収率は、チオ尿素体の場合は原料アミン体を基準として、カルボジイミド体の場合は原料チオ尿素体を基準として、また精製カルボジイミド体の場合は精製前カルボジイミド体を基準として算出した。
（３）ＬＣ純度：
ＬＣ純度は、高速液体クロマトグラフィーを用いた分析により確認し、溶媒を除く各ピークの総面積値を１００としたときの、各化合物の面積パーセントを示す。
（４）硫黄含有量：
高速液体クロマトグラフィーを用いて、定量測定した。
（５）色調：
色調は、試料を粉砕し色差計で測定した。
色差計：ＮＩＰＰＯＮ ＤＥＮＳＨＯＫＵ Ｓｐｅｃｔｒｏ Ｃｏｌｏｒ Ｍｅｔｅｒ ＳＥ２０００
(1) Identification of compound:
Each compound was identified by mass spectrometer: GCMS-QP5000 manufactured by Shimadzu Corporation.
(2) Yield, yield:
Yields and yields of synthesized intermediates and final products are based on the raw material amine for thiourea, based on raw thiourea for carbodiimide, and before purification for purified carbodiimide. Calculation was based on the carbodiimide body.
(3) LC purity:
The LC purity is confirmed by analysis using high performance liquid chromatography, and indicates the area percentage of each compound when the total area value of each peak excluding the solvent is 100.
(4) Sulfur content:
Quantitative measurement was performed using high performance liquid chromatography.
(5) Color tone:
The color tone was measured with a color difference meter after pulverizing the sample.
Color difference meter: NIPPON DENSHOKU Spectro Color Meter SE2000
実施例１
（工程（１））
ＳＵＳ製オートクレーブに式（Ａ）においてＲが水素原子であるアミン体（Ａ１）（川口化学工業製：ＬＣ純度９６％品）：１００．０ｇ（０．２ｍｏｌ）、二硫化炭素：９１．２ｇ（１．２ｍｏｌ）、ジメチルエタノールアミン：８．９６ｇ（０．１ｍｏｌ）、アセトニトリル：４５０ｍｌを加え、密閉した。その後、撹拌下１００℃で１５時間反応させた。冷却後、圧開放し、過剰の二硫化炭素を回収した。その後、アセトニトリル：１００ｍｌを添加し濾過後、アセトニトリル：５００ｍｌで洗浄した。乾燥後、式（Ｂ）においてＲが水素原子であるチオ尿素体（Ｂ１）を得た。（収量：１０７．６ｇ／収率：９２．０％／ＬＣ純度：９７．８％）
（工程（２））
得られたチオ尿素体（Ｂ１）：５０．０ｇ（０．０８６ｍｏｌ）、クロロホルム：１２００ｇ、メタノール：４０ｇ、３０％水酸化ナトリウム水溶液：１３．２ｇ（０．１ｍｏｌ）、塩化ベンジルトリエチルアンモニウム：３．０ｇを仕込んだ。１３．９％次亜塩素酸ソーダ水溶液：１６５．６ｇ（０．３１ｍｏｌ）を反応機内温が４０℃を超えないように５０分間かけ滴下した。１時間の撹拌後、チオ尿素体（Ｂ１）：５０．０ｇ、３０％水酸化ナトリウム水溶液：１３．２ｇを再度投入した。１３．９％次亜塩素酸ソーダ水溶液：１６５．６ｇを反応機内温が２５〜４０℃で５０分間かけ滴下した。３０〜４０℃で３．５時間撹拌後、減圧下クロロホルムを留去し、トルエン：３００ｇを添加した。内容物を濾過し、水：２００ｇ、トルエン：１００ｇ、アセトン：１６０ｇで順次洗浄した。乾燥後、式（Ｃ）においてＲが水素原子であるカルボジイミド体（Ｃ１）を得た。（収量：７３．３ｇ／収率：８２．９％／ＬＣ純度：９９．０％／硫黄分：３９４ｐｐｍ）（色調：Ｌａｂ／ＹＩ：８６．６５，２．００，１０．３８／２３．３１）
（工程（３））
得られたカルボジイミド体（Ｃ１）：５．００ｇおよびトルエン：１５ｍｌを仕込み、３時間還流させた。冷却後ろ過し、アセトン：１０ｍｌで洗浄した。乾燥後、式（Ｃ）においてＲが水素原子である精製カルボジイミド体（Ｃ１）を得た。（収量：４．７５ｇ／収率：９５．０％）その際、硫黄の含有量は１２３ｐｐｍへ低減されており、ＬＣ純度は９９．３％であった。（色調：Ｌａｂ／ＹＩ：９０．５０，−０．１９，６．９６／１３．８３）
Example 1
(Process (1))
In an SUS autoclave, an amine compound (A1) in which R is a hydrogen atom in the formula (A) (manufactured by Kawaguchi Chemical Industry: LC purity 96% product): 100.0 g (0.2 mol), carbon disulfide: 91.2 g ( 1.2 mol), dimethylethanolamine: 8.96 g (0.1 mol), and acetonitrile: 450 ml were added and sealed. Then, it was made to react at 100 degreeC under stirring for 15 hours. After cooling, the pressure was released and excess carbon disulfide was recovered. Thereafter, acetonitrile: 100 ml was added, filtered, and washed with acetonitrile: 500 ml. After drying, a thiourea compound (B1) in which R in formula (B) is a hydrogen atom was obtained. (Yield: 107.6 g / Yield: 92.0% / LC purity: 97.8%)
(Process (2))
Obtained thiourea compound (B1): 50.0 g (0.086 mol), chloroform: 1200 g, methanol: 40 g, 30% aqueous sodium hydroxide solution: 13.2 g (0.1 mol), benzyltriethylammonium chloride: 3. 0 g was charged. A 13.9% sodium hypochlorite aqueous solution: 165.6 g (0.31 mol) was added dropwise over 50 minutes so that the reactor internal temperature did not exceed 40 ° C. After stirring for 1 hour, thiourea compound (B1): 50.0 g, 30% aqueous sodium hydroxide solution: 13.2 g were charged again. A 13.9% sodium hypochlorite aqueous solution: 165.6 g was added dropwise at a reactor internal temperature of 25 to 40 ° C. over 50 minutes. After stirring for 3.5 hours at 30 to 40 ° C., chloroform was distilled off under reduced pressure, and 300 g of toluene was added. The contents were filtered and washed sequentially with water: 200 g, toluene: 100 g, and acetone: 160 g. After drying, a carbodiimide body (C1) in which R is a hydrogen atom in the formula (C) was obtained. (Yield: 73.3 g / Yield: 82.9% / LC Purity: 99.0% / Sulfur content: 394 ppm) (Color: Lab / YI: 86.65, 2.00, 10.38 / 23.31) )
(Process (3))
The resulting carbodiimide body (C1): 5.00 g and toluene: 15 ml were charged and refluxed for 3 hours. After cooling, the mixture was filtered and washed with acetone: 10 ml. After drying, a purified carbodiimide body (C1) in which R in formula (C) is a hydrogen atom was obtained. (Yield: 4.75 g / Yield: 95.0%) At that time, the sulfur content was reduced to 123 ppm, and the LC purity was 99.3%. (Color tone: Lab / YI: 90.50, -0.19, 6.96 / 13.83)
実施例２
実施例１において工程（１）および（２）から得られた式（Ｃ）においてＲが水素原子であるカルボジイミド体（Ｃ１）を用いて工程（３）においてトルエンをテトラヒドロフランに変えた以外は同様にして、精製カルボジイミド体（Ｃ１）を得た。（収量：４．５０ｇ／収率：９０．０％）その際、硫黄の含有量は７３ｐｐｍへ低減されており、ＬＣ純度は９９．９％であった。（色調：Ｌａｂ／ＹＩ：９１．８３，０．０９，７．３０／１４．５１）
Example 2
In the same manner as in Example 1, except that carbodiimide body (C1) in which R is a hydrogen atom in formula (C) obtained from steps (1) and (2) was used, and toluene was changed to tetrahydrofuran in step (3). As a result, a purified carbodiimide body (C1) was obtained. (Yield: 4.50 g / Yield: 90.0%) At that time, the sulfur content was reduced to 73 ppm, and the LC purity was 99.9%. (Color tone: Lab / YI: 91.83, 0.09, 7.30 / 14.51)
実施例３
実施例１において工程（１）および（２）から得られた式（Ｃ）においてＲが水素原子であるカルボジイミド体（Ｃ１）を用いて工程（３）においてトルエンをクロロホルムに変えた以外は同様にして、精製カルボジイミド体（Ｃ１）を得た。（収量：４．６６ｇ／収率：９３．２％）その際、硫黄の含有量は２１６ｐｐｍへ低減されており、ＬＣ純度は９９．３％であった。（色調：Ｌａｂ／ＹＩ：９１．４５，０．１５，８．２０／１６．３８）
Example 3
In the same manner as in Example 1, except that carbodiimide body (C1) in which R is a hydrogen atom in formula (C) obtained from steps (1) and (2) was used, and toluene was changed to chloroform in step (3). As a result, a purified carbodiimide body (C1) was obtained. (Yield: 4.66 g / Yield: 93.2%) At that time, the sulfur content was reduced to 216 ppm, and the LC purity was 99.3%. (Color tone: Lab / YI: 91.45, 0.15, 8.20 / 16.38)
実施例４
実施例１において工程（１）および（２）から得られた式（Ｃ）においてＲが水素原子であるカルボジイミド体（Ｃ１）を用いて工程（３）においてトルエンをメチルエチルケトン：２０ｍｌに変えた以外は同様にして、精製カルボジイミド体（Ｃ１）を得た。（収量：４．７１ｇ／収率：９４．２％）その際、硫黄の含有量は２２３ｐｐｍへ低減されており、ＬＣ純度は９９．３％であった。（色調：Ｌａｂ／ＹＩ：９１．４７，０．４２，８．４２／１７．０３）
Example 4
In Example 1, except that the carbodiimide body (C1) in which R is a hydrogen atom in the formula (C) obtained from the steps (1) and (2) was used, and toluene was changed to 20 ml of methyl ethyl ketone in the step (3). Similarly, a purified carbodiimide body (C1) was obtained. (Yield: 4.71 g / Yield: 94.2%) At that time, the sulfur content was reduced to 223 ppm, and the LC purity was 99.3%. (Color tone: Lab / YI: 91.47, 0.42, 8.42 / 17.03)
実施例５
実施例１において工程（１）および（２）から得られた式（Ｃ）においてＲが水素原子であるカルボジイミド体（Ｃ１）：５．００ｇおよびトルエン：７５ｍｌを仕込み、１時間還流させる。その後、トルエン：４０ｍｌを濃縮した。冷却後ろ過し、アセトン：１０ｍｌで洗浄する。乾燥後式（Ｃ）においてＲが水素原子である精製カルボジイミド体（Ｃ１）を得た。（収量：４．７０ｇ／収率：９４．０％）その際、硫黄の含有量は９ｐｐｍへ低減されており、ＬＣ純度は９９．５％であった。
Example 5
In Formula (C) obtained from Steps (1) and (2) in Example 1, carbodiimide body (C1) in which R is a hydrogen atom (C1): 5.00 g and toluene: 75 ml are charged and refluxed for 1 hour. Thereafter, 40 ml of toluene was concentrated. After cooling, it is filtered and washed with acetone: 10 ml. After drying, a purified carbodiimide body (C1) in which R is a hydrogen atom in the formula (C) was obtained. (Yield: 4.70 g / Yield: 94.0%) At that time, the sulfur content was reduced to 9 ppm, and the LC purity was 99.5%.
実施例６
（工程（１））
ＳＵＳ製オートクレーブに式（Ａ）においてＲが水素原子であるアミン体（Ａ１）（川口化学工業製：ＬＣ純度９６％品）：４０．０ｇ（０．０８ｍｏｌ）、二硫化炭素：３６．６ｇ（０．４８ｍｏｌ）、イミダゾール：１０．９ｇ（０．１６ｍｏｌ）、アセトニトリル：１２０ｍｌを加え、密閉した。その後、撹拌下１００℃で１５時間反応させた。冷却後、圧開放し、過剰の二硫化炭素を蒸留回収した。その後、アセトニトリル：５０ｍｌを添加し濾過後、アセトニトリル：２００ｍｌで洗浄した。式（Ｂ）においてＲが水素原子であるチオ尿素体（Ｂ１）を得た。（乾燥前収量：４７．６ｇ／収率：１０１．８％／ＬＣ純度：９７．６％）
（工程（２））
得られた未乾燥チオ尿素体（Ｂ１）：９．０ｇ（純分０．０１３ｍｏｌ）、クロロホルム：９０ｇ、メタノール：３ｇ、３０％水酸化ナトリウム水溶液：２．０ｇ（０．０１５ｍｏｌ）、塩化ベンジルトリエチルアンモニウム：０．４５ｇを仕込んだ。１３．９％次亜塩素酸ソーダ水溶液：２５．１ｇ（０．０４７ｍｏｌ）を反応機内温が４０℃を超えないように２５分間かけ滴下した。１時間の撹拌後、得られた乾燥前チオ尿素体（Ｂ１）：９．０ｇ、３０％水酸化ナトリウム水溶液：２．０ｇを再度投入した。１３．９％次亜塩素酸ソーダ水溶液：２５．１ｇを反応機内温が２５〜４０℃で１５分間かけ滴下した。３０〜４０℃で４時間撹拌後、減圧下クロロホルムを留去し、トルエン：４５ｇを添加した。内容物を濾過し、水：３０ｇ、トルエン：１５ｇ、アセトン：２５ｇで順次洗浄する。乾燥後、式（Ｃ）においてＲが水素原子であるカルボジイミド体（Ｃ１）を得た。
（収量：１１．８ｇ／収率：８８．７％／ＬＣ純度：９８．８％／硫黄分：１０１８ｐｐｍ）
（工程（３））
得られたカルボジイミド体（Ｃ１）：５．００ｇおよびトルエン：５０ｍｌを仕込み、３時間還流させた。冷却後、ろ過し、アセトン：１０ｍｌで洗浄した。乾燥後、式（Ｃ）においてＲが水素原子である精製カルボジイミド体（Ｃ１）を得た。（収量：４．５３ｇ／収率：９０．６％）その際、硫黄の含有量は４７ｐｐｍへ低減されており、ＬＣ純度は９９．４％であった。
Example 6
(Process (1))
In an SUS autoclave, an amine compound (A1) in which R is a hydrogen atom in the formula (A) (manufactured by Kawaguchi Chemical Industry: LC purity 96% product): 40.0 g (0.08 mol), carbon disulfide: 36.6 g ( 0.48 mol), imidazole: 10.9 g (0.16 mol), and acetonitrile: 120 ml were added and sealed. Then, it was made to react at 100 degreeC under stirring for 15 hours. After cooling, the pressure was released and excess carbon disulfide was recovered by distillation. Thereafter, acetonitrile: 50 ml was added, filtered, and washed with acetonitrile: 200 ml. A thiourea compound (B1) in which R is a hydrogen atom in the formula (B) was obtained. (Yield before drying: 47.6 g / yield: 101.8% / LC purity: 97.6%)
(Process (2))
Non-dried thiourea compound (B1) obtained: 9.0 g (pure content 0.013 mol), chloroform: 90 g, methanol: 3 g, 30% aqueous sodium hydroxide solution: 2.0 g (0.015 mol), benzyltriethyl chloride Ammonium: 0.45 g was charged. 13.9% sodium hypochlorite aqueous solution: 25.1 g (0.047 mol) was added dropwise over 25 minutes so that the reactor internal temperature did not exceed 40 ° C. After stirring for 1 hour, the obtained pre-drying thiourea compound (B1): 9.0 g and 30% aqueous sodium hydroxide solution: 2.0 g were added again. 13.9% sodium hypochlorite aqueous solution: 25.1 g was added dropwise over 15 minutes at a reactor internal temperature of 25-40 ° C. After stirring at 30 to 40 ° C. for 4 hours, chloroform was distilled off under reduced pressure, and 45 g of toluene was added. The contents are filtered and washed sequentially with water: 30 g, toluene: 15 g, acetone: 25 g. After drying, a carbodiimide body (C1) in which R is a hydrogen atom in the formula (C) was obtained.
(Yield: 11.8 g / Yield: 88.7% / LC purity: 98.8% / sulfur content: 1018 ppm)
(Process (3))
The obtained carbodiimide body (C1): 5.00 g and toluene: 50 ml were charged and refluxed for 3 hours. After cooling, it was filtered and washed with 10 ml of acetone. After drying, a purified carbodiimide body (C1) in which R in formula (C) is a hydrogen atom was obtained. (Yield: 4.53 g / Yield: 90.6%) At that time, the sulfur content was reduced to 47 ppm, and the LC purity was 99.4%.
Claims (9)
（２）得られたチオ尿素体を、塩基性化合物の存在下、次亜塩素酸塩で脱硫し、下記式（Ｃ）で表わされるカルボジイミド体を得る工程（２）、および
（３）得られたカルボジイミド体を精製する工程（３）、
を含むカルボジイミド体の製造方法。
(2) Steps (2) and (3) obtained by desulfurizing the obtained thiourea compound with hypochlorite in the presence of a basic compound to obtain a carbodiimide compound represented by the following formula (C) The step (3) of purifying the obtained carbodiimide body,
The manufacturing method of the carbodiimide body containing this.
The production method according to any one of claims 1 to 8, wherein the purification in the step (3) is recrystallization or extraction.
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| JP2010137174A JP5615051B2 (en) | 2010-06-16 | 2010-06-16 | Method for producing carbodiimide body |
| US13/704,117 US9428521B2 (en) | 2010-06-16 | 2011-06-15 | Process for the production of a carbodiimide |
| CN201180029335.0A CN103025743B (en) | 2010-06-16 | 2011-06-15 | The manufacture method of carbon imide compound |
| EP11795860.3A EP2583971B1 (en) | 2010-06-16 | 2011-06-15 | Method for producing carbodiimide |
| PCT/JP2011/064193 WO2011158958A1 (en) | 2010-06-16 | 2011-06-15 | Method for producing carbodiimide |
| TW100120878A TWI486351B (en) | 2010-06-16 | 2011-06-15 | Production method of carbon imide body |
| KR1020127032612A KR20130129822A (en) | 2010-06-16 | 2011-06-15 | Method for producing carbodiimide |
| ES11795860.3T ES2538090T3 (en) | 2010-06-16 | 2011-06-15 | Process for the production of a carbodiimide |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS56118053A (en) * | 1980-02-22 | 1981-09-16 | Showa Denko Kk | Carbodiimide derivative, insecticidal and acaricidal agent |
| JPH08198836A (en) * | 1995-01-26 | 1996-08-06 | Sanshin Chem Ind Co Ltd | Production of 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide |
| WO2010071211A1 (en) * | 2008-12-15 | 2010-06-24 | 帝人株式会社 | Cyclic carbodiimide compounds |
| JP2011256139A (en) * | 2010-06-10 | 2011-12-22 | Teijin Ltd | Cyclic carbodiimide compound |
| JP2012001477A (en) * | 2010-06-16 | 2012-01-05 | Teijin Ltd | Method for producing thiourea compound |
| JP2012001475A (en) * | 2010-06-16 | 2012-01-05 | Kawaguchi Kagaku Kogyo Kk | Method for producing nitro compound |
-
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS56118053A (en) * | 1980-02-22 | 1981-09-16 | Showa Denko Kk | Carbodiimide derivative, insecticidal and acaricidal agent |
| JPH08198836A (en) * | 1995-01-26 | 1996-08-06 | Sanshin Chem Ind Co Ltd | Production of 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide |
| WO2010071211A1 (en) * | 2008-12-15 | 2010-06-24 | 帝人株式会社 | Cyclic carbodiimide compounds |
| JP2011256139A (en) * | 2010-06-10 | 2011-12-22 | Teijin Ltd | Cyclic carbodiimide compound |
| JP2012001477A (en) * | 2010-06-16 | 2012-01-05 | Teijin Ltd | Method for producing thiourea compound |
| JP2012001475A (en) * | 2010-06-16 | 2012-01-05 | Kawaguchi Kagaku Kogyo Kk | Method for producing nitro compound |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2016039486A1 (en) * | 2014-09-11 | 2016-03-17 | 帝人株式会社 | Thermosetting resin composition |
| KR20170057248A (en) * | 2014-09-11 | 2017-05-24 | 데이진 가부시키가이샤 | Thermosetting resin composition |
| JPWO2016039486A1 (en) * | 2014-09-11 | 2017-06-22 | 帝人株式会社 | Thermosetting resin composition |
| TWI667281B (en) * | 2014-09-11 | 2019-08-01 | 日商帝人股份有限公司 | Thermosetting resin composition |
| US10865272B2 (en) | 2014-09-11 | 2020-12-15 | Teijin Limited | Thermosetting resin composition |
| KR102393692B1 (en) * | 2014-09-11 | 2022-05-02 | 데이진 가부시키가이샤 | Thermosetting resin composition |
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