WO2013039038A1 - グリコリドの製造方法 - Google Patents
グリコリドの製造方法 Download PDFInfo
- Publication number
- WO2013039038A1 WO2013039038A1 PCT/JP2012/073087 JP2012073087W WO2013039038A1 WO 2013039038 A1 WO2013039038 A1 WO 2013039038A1 JP 2012073087 W JP2012073087 W JP 2012073087W WO 2013039038 A1 WO2013039038 A1 WO 2013039038A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- glycolic acid
- glycolide
- group
- acid oligomer
- molecular weight
- Prior art date
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- RKDVKSZUMVYZHH-UHFFFAOYSA-N 1,4-dioxane-2,5-dione Chemical compound O=C1COC(=O)CO1 RKDVKSZUMVYZHH-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 32
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 claims abstract description 204
- 239000002530 phenolic antioxidant Substances 0.000 claims abstract description 31
- 239000002904 solvent Substances 0.000 claims description 78
- 238000009835 boiling Methods 0.000 claims description 36
- 239000003495 polar organic solvent Substances 0.000 claims description 18
- 150000003606 tin compounds Chemical class 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 16
- 230000008569 process Effects 0.000 claims description 5
- -1 1-methylcyclohexyl group Chemical group 0.000 description 62
- 125000004432 carbon atom Chemical group C* 0.000 description 44
- 229920001515 polyalkylene glycol Polymers 0.000 description 41
- 125000000217 alkyl group Chemical group 0.000 description 34
- 238000012691 depolymerization reaction Methods 0.000 description 32
- 229920001223 polyethylene glycol Polymers 0.000 description 27
- 239000002202 Polyethylene glycol Substances 0.000 description 26
- 125000002947 alkylene group Chemical group 0.000 description 16
- 150000001875 compounds Chemical class 0.000 description 15
- 239000003963 antioxidant agent Substances 0.000 description 13
- 239000000243 solution Substances 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 12
- 238000006116 polymerization reaction Methods 0.000 description 12
- 230000003078 antioxidant effect Effects 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 11
- 125000003118 aryl group Chemical group 0.000 description 10
- 230000007423 decrease Effects 0.000 description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 10
- 150000001346 alkyl aryl ethers Chemical class 0.000 description 9
- 238000004821 distillation Methods 0.000 description 9
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 9
- 230000009471 action Effects 0.000 description 8
- 150000002430 hydrocarbons Chemical group 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 229920000954 Polyglycolide Polymers 0.000 description 7
- 150000001298 alcohols Chemical class 0.000 description 7
- 238000000354 decomposition reaction Methods 0.000 description 7
- 238000002844 melting Methods 0.000 description 7
- 230000008018 melting Effects 0.000 description 7
- 239000004633 polyglycolic acid Substances 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 6
- 239000000155 melt Substances 0.000 description 6
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 6
- 150000002989 phenols Chemical class 0.000 description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 239000003513 alkali Substances 0.000 description 5
- 150000001983 dialkylethers Chemical class 0.000 description 5
- 238000004090 dissolution Methods 0.000 description 5
- 229920001748 polybutylene Polymers 0.000 description 5
- 238000006068 polycondensation reaction Methods 0.000 description 5
- 229920001451 polypropylene glycol Polymers 0.000 description 5
- 230000009257 reactivity Effects 0.000 description 5
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 description 4
- MQGIBEAIDUOVOH-UHFFFAOYSA-N 1-[2-[2-[2-(2-butoxyethoxy)ethoxy]ethoxy]ethoxy]butane Chemical compound CCCCOCCOCCOCCOCCOCCCC MQGIBEAIDUOVOH-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 239000007983 Tris buffer Substances 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 150000001987 diarylethers Chemical class 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- NKJOXAZJBOMXID-UHFFFAOYSA-N 1,1'-Oxybisoctane Chemical compound CCCCCCCCOCCCCCCCC NKJOXAZJBOMXID-UHFFFAOYSA-N 0.000 description 3
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 3
- DVXRZTUHTRMCTL-UHFFFAOYSA-N 1-[2-[2-(2-butoxyethoxy)ethoxy]ethoxy]octane Chemical compound CCCCCCCCOCCOCCOCCOCCCC DVXRZTUHTRMCTL-UHFFFAOYSA-N 0.000 description 3
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 3
- PFANXOISJYKQRP-UHFFFAOYSA-N 2-tert-butyl-4-[1-(5-tert-butyl-4-hydroxy-2-methylphenyl)butyl]-5-methylphenol Chemical compound C=1C(C(C)(C)C)=C(O)C=C(C)C=1C(CCC)C1=CC(C(C)(C)C)=C(O)C=C1C PFANXOISJYKQRP-UHFFFAOYSA-N 0.000 description 3
- GPNYZBKIGXGYNU-UHFFFAOYSA-N 2-tert-butyl-6-[(3-tert-butyl-5-ethyl-2-hydroxyphenyl)methyl]-4-ethylphenol Chemical compound CC(C)(C)C1=CC(CC)=CC(CC=2C(=C(C=C(CC)C=2)C(C)(C)C)O)=C1O GPNYZBKIGXGYNU-UHFFFAOYSA-N 0.000 description 3
- VSAWBBYYMBQKIK-UHFFFAOYSA-N 4-[[3,5-bis[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]-2,4,6-trimethylphenyl]methyl]-2,6-ditert-butylphenol Chemical compound CC1=C(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C1CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 VSAWBBYYMBQKIK-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 229930185605 Bisphenol Natural products 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical class OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 150000005690 diesters Chemical class 0.000 description 3
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 125000005843 halogen group Chemical group 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 125000001624 naphthyl group Chemical group 0.000 description 3
- 238000006384 oligomerization reaction Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 235000011150 stannous chloride Nutrition 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 description 3
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 description 3
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 description 3
- YPAQBHBHXFTALJ-UHFFFAOYSA-N 1-[2-[2-(2-butoxyethoxy)ethoxy]ethoxy]decane Chemical compound CCCCCCCCCCOCCOCCOCCOCCCC YPAQBHBHXFTALJ-UHFFFAOYSA-N 0.000 description 2
- VBHMJWLHXICEGS-UHFFFAOYSA-N 1-[2-[2-(2-hexoxyethoxy)ethoxy]ethoxy]hexane Chemical compound CCCCCCOCCOCCOCCOCCCCCC VBHMJWLHXICEGS-UHFFFAOYSA-N 0.000 description 2
- LTSWUFKUZPPYEG-UHFFFAOYSA-N 1-decoxydecane Chemical compound CCCCCCCCCCOCCCCCCCCCC LTSWUFKUZPPYEG-UHFFFAOYSA-N 0.000 description 2
- CMCBDXRRFKYBDG-UHFFFAOYSA-N 1-dodecoxydodecane Chemical compound CCCCCCCCCCCCOCCCCCCCCCCCC CMCBDXRRFKYBDG-UHFFFAOYSA-N 0.000 description 2
- ROHFBIREHKPELA-UHFFFAOYSA-N 2-[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]prop-2-enoic acid;methane Chemical compound C.CC(C)(C)C1=CC(CC(=C)C(O)=O)=CC(C(C)(C)C)=C1O.CC(C)(C)C1=CC(CC(=C)C(O)=O)=CC(C(C)(C)C)=C1O.CC(C)(C)C1=CC(CC(=C)C(O)=O)=CC(C(C)(C)C)=C1O.CC(C)(C)C1=CC(CC(=C)C(O)=O)=CC(C(C)(C)C)=C1O ROHFBIREHKPELA-UHFFFAOYSA-N 0.000 description 2
- UPGSWASWQBLSKZ-UHFFFAOYSA-N 2-hexoxyethanol Chemical compound CCCCCCOCCO UPGSWASWQBLSKZ-UHFFFAOYSA-N 0.000 description 2
- CRWNQZTZTZWPOF-UHFFFAOYSA-N 2-methyl-4-phenylpyridine Chemical compound C1=NC(C)=CC(C=2C=CC=CC=2)=C1 CRWNQZTZTZWPOF-UHFFFAOYSA-N 0.000 description 2
- HXIQYSLFEXIOAV-UHFFFAOYSA-N 2-tert-butyl-4-(5-tert-butyl-4-hydroxy-2-methylphenyl)sulfanyl-5-methylphenol Chemical compound CC1=CC(O)=C(C(C)(C)C)C=C1SC1=CC(C(C)(C)C)=C(O)C=C1C HXIQYSLFEXIOAV-UHFFFAOYSA-N 0.000 description 2
- PZRWFKGUFWPFID-UHFFFAOYSA-N 3,9-dioctadecoxy-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound C1OP(OCCCCCCCCCCCCCCCCCC)OCC21COP(OCCCCCCCCCCCCCCCCCC)OC2 PZRWFKGUFWPFID-UHFFFAOYSA-N 0.000 description 2
- MRBKEAMVRSLQPH-UHFFFAOYSA-N 3-tert-butyl-4-hydroxyanisole Chemical compound COC1=CC=C(O)C(C(C)(C)C)=C1 MRBKEAMVRSLQPH-UHFFFAOYSA-N 0.000 description 2
- PRWJPWSKLXYEPD-UHFFFAOYSA-N 4-[4,4-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butan-2-yl]-2-tert-butyl-5-methylphenol Chemical compound C=1C(C(C)(C)C)=C(O)C=C(C)C=1C(C)CC(C=1C(=CC(O)=C(C=1)C(C)(C)C)C)C1=CC(C(C)(C)C)=C(O)C=C1C PRWJPWSKLXYEPD-UHFFFAOYSA-N 0.000 description 2
- ADRNSOYXKABLGT-UHFFFAOYSA-N 8-methylnonyl diphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OCCCCCCCC(C)C)OC1=CC=CC=C1 ADRNSOYXKABLGT-UHFFFAOYSA-N 0.000 description 2
- IRIAEXORFWYRCZ-UHFFFAOYSA-N Butylbenzyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCC1=CC=CC=C1 IRIAEXORFWYRCZ-UHFFFAOYSA-N 0.000 description 2
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- GHKOFFNLGXMVNJ-UHFFFAOYSA-N Didodecyl thiobispropanoate Chemical compound CCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCC GHKOFFNLGXMVNJ-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
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- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- CGRTZESQZZGAAU-UHFFFAOYSA-N [2-[3-[1-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoyloxy]-2-methylpropan-2-yl]-2,4,8,10-tetraoxaspiro[5.5]undecan-9-yl]-2-methylpropyl] 3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C)=CC(CCC(=O)OCC(C)(C)C2OCC3(CO2)COC(OC3)C(C)(C)COC(=O)CCC=2C=C(C(O)=C(C)C=2)C(C)(C)C)=C1 CGRTZESQZZGAAU-UHFFFAOYSA-N 0.000 description 2
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- SESFRYSPDFLNCH-UHFFFAOYSA-N benzyl benzoate Chemical compound C=1C=CC=CC=1C(=O)OCC1=CC=CC=C1 SESFRYSPDFLNCH-UHFFFAOYSA-N 0.000 description 2
- XITRBUPOXXBIJN-UHFFFAOYSA-N bis(2,2,6,6-tetramethylpiperidin-4-yl) decanedioate Chemical compound C1C(C)(C)NC(C)(C)CC1OC(=O)CCCCCCCCC(=O)OC1CC(C)(C)NC(C)(C)C1 XITRBUPOXXBIJN-UHFFFAOYSA-N 0.000 description 2
- SXXILWLQSQDLDL-UHFFFAOYSA-N bis(8-methylnonyl) phenyl phosphite Chemical compound CC(C)CCCCCCCOP(OCCCCCCCC(C)C)OC1=CC=CC=C1 SXXILWLQSQDLDL-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- GVJHHUAWPYXKBD-UHFFFAOYSA-N d-alpha-tocopherol Natural products OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-UHFFFAOYSA-N 0.000 description 2
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 2
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- 239000000539 dimer Substances 0.000 description 2
- PWWSSIYVTQUJQQ-UHFFFAOYSA-N distearyl thiodipropionate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCCCCCCCC PWWSSIYVTQUJQQ-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
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- CRSOQBOWXPBRES-UHFFFAOYSA-N neopentane Chemical compound CC(C)(C)C CRSOQBOWXPBRES-UHFFFAOYSA-N 0.000 description 2
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- LVEOKSIILWWVEO-UHFFFAOYSA-N tetradecyl 3-(3-oxo-3-tetradecoxypropyl)sulfanylpropanoate Chemical compound CCCCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCCCC LVEOKSIILWWVEO-UHFFFAOYSA-N 0.000 description 2
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 2
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- LHFUJEOGSCPOBO-UHFFFAOYSA-N 1-[2-(2-hexoxyethoxy)ethoxy]octane Chemical compound CCCCCCCCOCCOCCOCCCCCC LHFUJEOGSCPOBO-UHFFFAOYSA-N 0.000 description 1
- MMVAEMFNVQIXIP-UHFFFAOYSA-N 1-[2-(2-octoxyethoxy)ethoxy]octane Chemical compound CCCCCCCCOCCOCCOCCCCCCCC MMVAEMFNVQIXIP-UHFFFAOYSA-N 0.000 description 1
- KTSVVTQTKRGWGU-UHFFFAOYSA-N 1-[2-[2-(2-butoxyethoxy)ethoxy]ethoxy]butane Chemical compound CCCCOCCOCCOCCOCCCC KTSVVTQTKRGWGU-UHFFFAOYSA-N 0.000 description 1
- RRSKCOXOBXOEDF-UHFFFAOYSA-N 1-[2-[2-(2-butoxyethoxy)ethoxy]ethoxy]hexane Chemical compound CCCCCCOCCOCCOCCOCCCC RRSKCOXOBXOEDF-UHFFFAOYSA-N 0.000 description 1
- NFQHLDNAGRNLBK-UHFFFAOYSA-N 1-[2-[2-(2-hexoxyethoxy)ethoxy]ethoxy]octane Chemical compound CCCCCCCCOCCOCCOCCOCCCCCC NFQHLDNAGRNLBK-UHFFFAOYSA-N 0.000 description 1
- DSPIZZQMSHIZLS-UHFFFAOYSA-N 1-[2-[2-(2-propoxyethoxy)ethoxy]ethoxy]propane Chemical compound CCCOCCOCCOCCOCCC DSPIZZQMSHIZLS-UHFFFAOYSA-N 0.000 description 1
- AEJZZLYTGBTRJI-UHFFFAOYSA-N 1-[2-[2-[2-(2-butoxyethoxy)ethoxy]ethoxy]ethoxy]hexane Chemical compound CCCCCCOCCOCCOCCOCCOCCCC AEJZZLYTGBTRJI-UHFFFAOYSA-N 0.000 description 1
- HKVKMZGRXWKGGV-UHFFFAOYSA-N 1-[2-[2-[2-(2-butoxyethoxy)ethoxy]ethoxy]ethoxy]octane Chemical compound CCCCCCCCOCCOCCOCCOCCOCCCC HKVKMZGRXWKGGV-UHFFFAOYSA-N 0.000 description 1
- UARCZASBKNVJMN-UHFFFAOYSA-N 1-[2-[2-[2-(2-hexoxyethoxy)ethoxy]ethoxy]ethoxy]hexane Chemical compound CCCCCCOCCOCCOCCOCCOCCCCCC UARCZASBKNVJMN-UHFFFAOYSA-N 0.000 description 1
- POPQOOKGONERGS-UHFFFAOYSA-N 1-[2-[2-[2-(2-propoxyethoxy)ethoxy]ethoxy]ethoxy]propane Chemical compound CCCOCCOCCOCCOCCOCCC POPQOOKGONERGS-UHFFFAOYSA-N 0.000 description 1
- KIAMPLQEZAMORJ-UHFFFAOYSA-N 1-ethoxy-2-[2-(2-ethoxyethoxy)ethoxy]ethane Chemical compound CCOCCOCCOCCOCC KIAMPLQEZAMORJ-UHFFFAOYSA-N 0.000 description 1
- BGCSUUSPRCDKBQ-UHFFFAOYSA-N 2,4,8,10-tetraoxaspiro[5.5]undecane Chemical compound C1OCOCC21COCOC2 BGCSUUSPRCDKBQ-UHFFFAOYSA-N 0.000 description 1
- TUMQOADTQWPLRW-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethoxybenzene Chemical compound CCCCOCCOCCOC1=CC=CC=C1 TUMQOADTQWPLRW-UHFFFAOYSA-N 0.000 description 1
- VSNOZZZVTWGUQB-UHFFFAOYSA-N 2-(2-hexoxyethoxy)ethoxybenzene Chemical compound CCCCCCOCCOCCOC1=CC=CC=C1 VSNOZZZVTWGUQB-UHFFFAOYSA-N 0.000 description 1
- IIRWJSUZOHLOHS-UHFFFAOYSA-N 2-(2-octoxyethoxy)ethoxybenzene Chemical compound CCCCCCCCOCCOCCOC1=CC=CC=C1 IIRWJSUZOHLOHS-UHFFFAOYSA-N 0.000 description 1
- PICKZMGDVSSGSC-UHFFFAOYSA-N 2-(2-phenoxyethoxy)ethoxybenzene Chemical compound C=1C=CC=CC=1OCCOCCOC1=CC=CC=C1 PICKZMGDVSSGSC-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- PASGEUBMIRZRJA-UHFFFAOYSA-N 2-[2-(2-butoxyethoxy)ethoxy]ethoxybenzene Chemical compound CCCCOCCOCCOCCOC1=CC=CC=C1 PASGEUBMIRZRJA-UHFFFAOYSA-N 0.000 description 1
- QJQIADUOTPUQGR-UHFFFAOYSA-N 2-[2-(2-hexoxyethoxy)ethoxy]ethoxybenzene Chemical compound CCCCCCOCCOCCOCCOC1=CC=CC=C1 QJQIADUOTPUQGR-UHFFFAOYSA-N 0.000 description 1
- KEZCATRDGGLWCY-UHFFFAOYSA-N 2-[2-(2-octoxyethoxy)ethoxy]ethoxybenzene Chemical compound CCCCCCCCOCCOCCOCCOC1=CC=CC=C1 KEZCATRDGGLWCY-UHFFFAOYSA-N 0.000 description 1
- UJVWKSNORBRUEC-UHFFFAOYSA-N 2-[2-(2-phenoxyethoxy)ethoxy]ethoxybenzene Chemical compound C=1C=CC=CC=1OCCOCCOCCOC1=CC=CC=C1 UJVWKSNORBRUEC-UHFFFAOYSA-N 0.000 description 1
- KYCPUFPGVOGLHE-UHFFFAOYSA-N 2-[2-(3-butyl-2-chlorophenoxy)ethoxy]ethanol Chemical compound CCCCC1=CC=CC(OCCOCCO)=C1Cl KYCPUFPGVOGLHE-UHFFFAOYSA-N 0.000 description 1
- UPWZCKDWBPQBGQ-UHFFFAOYSA-N 2-[2-[2-(2-butoxyethoxy)ethoxy]ethoxy]ethoxybenzene Chemical compound CCCCOCCOCCOCCOCCOC1=CC=CC=C1 UPWZCKDWBPQBGQ-UHFFFAOYSA-N 0.000 description 1
- VUEUVIPIBVJLCY-UHFFFAOYSA-N 2-[2-[2-(2-hexoxyethoxy)ethoxy]ethoxy]ethanol Chemical compound CCCCCCOCCOCCOCCOCCO VUEUVIPIBVJLCY-UHFFFAOYSA-N 0.000 description 1
- NHQYXSMSDVIADM-UHFFFAOYSA-N 2-[2-[2-(2-hexoxyethoxy)ethoxy]ethoxy]ethoxybenzene Chemical compound CCCCCCOCCOCCOCCOCCOC1=CC=CC=C1 NHQYXSMSDVIADM-UHFFFAOYSA-N 0.000 description 1
- MDRFXZFXGAHHIQ-UHFFFAOYSA-N 2-[2-[2-(2-octoxyethoxy)ethoxy]ethoxy]ethoxybenzene Chemical compound CCCCCCCCOCCOCCOCCOCCOC1=CC=CC=C1 MDRFXZFXGAHHIQ-UHFFFAOYSA-N 0.000 description 1
- PMOSUUISWPPIPO-UHFFFAOYSA-N 2-[2-[2-(2-phenoxyethoxy)ethoxy]ethoxy]ethoxybenzene Chemical compound C=1C=CC=CC=1OCCOCCOCCOCCOC1=CC=CC=C1 PMOSUUISWPPIPO-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- XOUQAVYLRNOXDO-UHFFFAOYSA-N 2-tert-butyl-5-methylphenol Chemical compound CC1=CC=C(C(C)(C)C)C(O)=C1 XOUQAVYLRNOXDO-UHFFFAOYSA-N 0.000 description 1
- HYDWALOBQJFOMS-UHFFFAOYSA-N 3,6,9,12,15-pentaoxaheptadecane Chemical compound CCOCCOCCOCCOCCOCC HYDWALOBQJFOMS-UHFFFAOYSA-N 0.000 description 1
- ZAAQJFLUOUQAOG-UHFFFAOYSA-N 4-benzyl-2,6-ditert-butylphenol Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CC=2C=CC=CC=2)=C1 ZAAQJFLUOUQAOG-UHFFFAOYSA-N 0.000 description 1
- FKIOYBLZUCCLTL-UHFFFAOYSA-N 4-butyl-2-tert-butyl-5-methylphenol Chemical compound CCCCC1=CC(C(C)(C)C)=C(O)C=C1C FKIOYBLZUCCLTL-UHFFFAOYSA-N 0.000 description 1
- 239000004255 Butylated hydroxyanisole Substances 0.000 description 1
- VOPWNXZWBYDODV-UHFFFAOYSA-N Chlorodifluoromethane Chemical compound FC(F)Cl VOPWNXZWBYDODV-UHFFFAOYSA-N 0.000 description 1
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 1
- PYGXAGIECVVIOZ-UHFFFAOYSA-N Dibutyl decanedioate Chemical compound CCCCOC(=O)CCCCCCCCC(=O)OCCCC PYGXAGIECVVIOZ-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001278 adipic acid derivatives Chemical class 0.000 description 1
- 150000008431 aliphatic amides Chemical class 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 125000005037 alkyl phenyl group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 150000001558 benzoic acid derivatives Chemical class 0.000 description 1
- 229960002903 benzyl benzoate Drugs 0.000 description 1
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 1
- ZFMQKOWCDKKBIF-UHFFFAOYSA-N bis(3,5-difluorophenyl)phosphane Chemical compound FC1=CC(F)=CC(PC=2C=C(F)C=C(F)C=2)=C1 ZFMQKOWCDKKBIF-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 235000019282 butylated hydroxyanisole Nutrition 0.000 description 1
- 229940043253 butylated hydroxyanisole Drugs 0.000 description 1
- 125000006297 carbonyl amino group Chemical group [H]N([*:2])C([*:1])=O 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- INSRQEMEVAMETL-UHFFFAOYSA-N decane-1,1-diol Chemical compound CCCCCCCCCC(O)O INSRQEMEVAMETL-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 125000004983 dialkoxyalkyl group Chemical group 0.000 description 1
- UCVPKAZCQPRWAY-UHFFFAOYSA-N dibenzyl benzene-1,2-dicarboxylate Chemical compound C=1C=CC=C(C(=O)OCC=2C=CC=CC=2)C=1C(=O)OCC1=CC=CC=C1 UCVPKAZCQPRWAY-UHFFFAOYSA-N 0.000 description 1
- 229960002380 dibutyl phthalate Drugs 0.000 description 1
- 150000004683 dihydrates Chemical class 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical group C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 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
- 230000000694 effects Effects 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 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 1
- 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 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N hydroquinone methyl ether Natural products COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229940057995 liquid paraffin Drugs 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- 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 1
- 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 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 150000003021 phthalic acid derivatives Chemical class 0.000 description 1
- 150000003053 piperidines Chemical class 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 150000003329 sebacic acid derivatives Chemical class 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000012321 sodium triacetoxyborohydride Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- FEOZZFHAVXYAMB-UHFFFAOYSA-N tetraethylene glycol monooctyl ether Chemical compound CCCCCCCCOCCOCCOCCOCCO FEOZZFHAVXYAMB-UHFFFAOYSA-N 0.000 description 1
- NQRYJNQNLNOLGT-UHFFFAOYSA-N tetrahydropyridine hydrochloride Natural products C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- WGKLOLBTFWFKOD-UHFFFAOYSA-N tris(2-nonylphenyl) phosphite Chemical compound CCCCCCCCCC1=CC=CC=C1OP(OC=1C(=CC=CC=1)CCCCCCCCC)OC1=CC=CC=C1CCCCCCCCC WGKLOLBTFWFKOD-UHFFFAOYSA-N 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D319/00—Heterocyclic compounds containing six-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D319/10—1,4-Dioxanes; Hydrogenated 1,4-dioxanes
- C07D319/12—1,4-Dioxanes; Hydrogenated 1,4-dioxanes not condensed with other rings
Definitions
- the present invention relates to a method for producing glycolide, and more particularly to a method for producing glycolide obtained by depolymerizing a glycolic acid oligomer.
- Polyglycolic acid is a resin material with excellent biodegradability, gas barrier properties, strength, etc., medical polymer materials such as sutures and artificial skin; packaging materials such as bottles and films; injection molded products, fibers, and vapor deposition It is used in a wide range of technical fields as resin materials for various industrial products such as films and fishing lines.
- Polyglycolic acid can be obtained by dehydrating polycondensation of glycolic acid.
- the polyglycolic acid obtained by this method has a low polymerization degree with a weight average molecular weight of 20,000 or less, and is excellent in biodegradability, but has characteristics such as gas barrier properties, strength, and durability in many fields. It was not satisfactory enough.
- polyglycolic acid is usually produced by ring-opening polymerization of glycolide.
- the degree of polymerization of polyglycolic acid can be easily controlled, and a polyglycolic acid having a high degree of polymerization having a weight average molecular weight exceeding 20,000 can be obtained.
- the glycolide used at this time is usually represented by the following formula (I):
- glycolic acid is subjected to dehydration polycondensation to synthesize a glycolic acid oligomer having a low polymerization degree, and this glycolic acid oligomer is then represented by the following formula (II):
- Patent Document 1 JP-A-9-328481 (Patent Document 1) and International Publication No. 02/014303 (Patent Document 2) disclose that a glycolic acid oligomer is depolymerized in a specific high-boiling polar organic solvent. It is disclosed that oligomerization can be suppressed. However, even in these methods, when the depolymerization reaction is repeated, the glycolic acid oligomer becomes heavy, and thus further improvement is necessary.
- This invention is made
- the inventors of the present invention can depolymerize glycolic acid oligomers in the presence of an antioxidant, thereby suppressing oligomers from becoming heavy.
- the inventors have found that glycolide can be produced over a long period of time, and have completed the present invention.
- the glycolide production method of the present invention is a method of depolymerizing a glycolic acid oligomer in the presence of a phenolic antioxidant.
- a phenolic antioxidant As the phenolic antioxidant, a phenolic antioxidant having a molecular weight of 300 or more is preferable.
- the glycolic acid oligomer is preferably depolymerized in a solvent, and the solvent is preferably a high boiling polar organic solvent having a boiling point of 230 to 450 ° C. Further, glycolide obtained by depolymerization in a solvent is preferably co-distilled with the solvent. Furthermore, in the glycolide production method of the present invention, it is also preferable to depolymerize the glycolic acid oligomer in the presence of a tin compound.
- the oligomer when glycolide is produced using a depolymerization reaction of a glycolic acid oligomer, the oligomer can be prevented from becoming heavy and glycolide can be produced over a long period of time.
- the method for producing glycolide of the present invention is a method for depolymerizing a glycolic acid oligomer in the presence of a phenolic antioxidant.
- the glycolic acid oligomer is preferably depolymerized in a solvent in the presence of a tin compound, in the presence of a solubilizer, or in a combination of two or more thereof.
- glycolic acid oligomer used in the present invention is polyglycolic acid having a weight average molecular weight of 20,000 or less. Such glycolic acid oligomers can be synthesized by a polycondensation reaction of glycolic acid.
- the weight average molecular weight of the glycolic acid oligomer is a standard polymethyl methacrylate conversion value measured by gel permeation chromatography (GPC) using hexafluoroisopropanol as an eluent.
- glycolic acid oligomer used in the present invention is not limited to that synthesized by this method.
- at least one of glycolic acid, its ester (for example, lower alkyl ester) and its salt (for example, sodium salt) is usually added in the presence of a polycondensation catalyst or a transesterification catalyst, if necessary in the range of 100 to 250.
- a glycolic acid oligomer is obtained by heating to a temperature of, preferably 140 to 230 ° C., and carrying out a polycondensation reaction or a transesterification reaction until low molecular weight substances such as water and alcohol are substantially not distilled off.
- the glycolic acid oligomer thus obtained may be used as it is as a raw material in the production method of the present invention, but it is washed with a poor solvent such as benzene or toluene to remove unreacted substances, low polymerization components and catalysts. It is preferably used after removal.
- a poor solvent such as benzene or toluene to remove unreacted substances, low polymerization components and catalysts. It is preferably used after removal.
- the degree of polymerization of the glycolic acid oligomer used in the present invention is not particularly limited, but the melting point (Tm) of the glycolic acid oligomer is 140 ° C. or higher (more preferably 160 ° C. or higher, particularly preferably 180 ° C. or higher). The degree of polymerization is preferred. When the melting point of the glycolic acid oligomer is less than the lower limit, the yield of glycolide obtained by the depolymerization reaction tends to decrease.
- the melting point of the glycolic acid oligomer is detected as an endothermic peak temperature observed when a calorimetric analysis is carried out using a differential scanning calorimeter (DSC) in an inert gas atmosphere at a heating rate of 10 ° C./min. Temperature.
- the upper limit of the melting point of the glycolic acid oligomer is about 220 ° C.
- the antioxidant used in the present invention is a phenolic antioxidant. By depolymerizing the glycolic acid oligomer in the presence of such a phenolic antioxidant, the oligomer can be prevented from becoming heavy, and glycolide can be produced over a long period of time.
- R 11 represents an alkyl group having 1 to 10 carbon atoms (preferably 1 to 5 carbon atoms)
- R 12 represents an alkylene group having 1 to 5 carbon atoms (preferably 1 to 3 carbon atoms)
- R 13 represents carbon atoms.
- An alkyl group having 1 to 30 (preferably 15 to 25)
- R 14 represents a hydrogen atom or an alkyl group having 1 to 5 (preferably 1 to 3) carbon atoms.
- Tocopherol represented by the following formula (CAS number: 1406-66-2, molecular weight: 417), the following formulas (2-1) to (2-2):
- R 21 represents a t-butyl group or 1-methylcyclohexyl group
- R 22 represents an alkyl group having 1 to 5 carbon atoms (preferably 1 to 3)
- R 23 represents 1 to 5 carbon atoms ( Preferably, it represents an alkylene group of 1 to 3)
- R 24 and R 25 each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms (preferably 1 to 3), preferably one of which is a hydrogen atom.
- the other is the alkyl group
- R 26 represents a sulfur atom, an alkylene group having 1 to 10 carbon atoms (preferably 1 to 5), or a divalent group having an oxaspiro ring.
- R 31 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms (preferably 1 to 5)
- R 32 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms (preferably 1 to 3).
- one of R 31 and R 32 is a hydrogen atom, the other is the alkyl group
- R 33 is a trivalent aliphatic hydrocarbon group, a trivalent aromatic group, or a trivalent heterocyclic group.
- R 41 represents an alkylene group having 1 to 5 (preferably 1 to 3) carbon atoms.
- R 41 represents an alkylene group having 1 to 5 (preferably 1 to 3) carbon atoms.
- the divalent group having an oxaspiro ring is represented by the following formula (2-2-1):
- R 34 represents an alkylene group having 1 to 5 (preferably 1 to 3) carbon atoms
- R 35 represents an alkyl group having 1 to 5 (preferably 1 to 3) carbon atoms.
- the alkylene group and the trivalent aliphatic hydrocarbon group may be linear or branched.
- Examples of the phenol compound represented by the formula (1-1) include 2,6-di-t-butyl-p-cresol [CAS number: 128-37-0, molecular weight: 220].
- Examples of the phenolic compound represented by the formula (1-2) include butylated hydroxyanisole [CAS number: 25013-16-5, molecular weight: 180], and the like, represented by the formula (1-3).
- Examples of the phenolic compound include methylhydroquinone [CAS number: 95-71-6, molecular weight: 124].
- phenolic compound represented by the formula (1-4) stearyl- ⁇ - (3 , 5-di-t-butyl-4-hydroxyphenyl) propionate [CAS number: 2082-79-3, molecular weight: 531] and the like, and represented by the above formula (1-5)
- phenolic compounds p- benzoquinone [CAS Number: 106-51-4, molecular weight: 108], methyl -p- base Nzokinon [CAS Number: 553-97-9, molecular weight: 122], and the like.
- Examples of the bisphenol compound represented by the formula (2-1) include 2,2′-methylenebis (4-methyl-6-t-butylphenol) [CAS number: 119-47-1, molecular weight: 341], 2 2,2'-methylenebis (4-ethyl-6-t-butylphenol) [CAS number: 88-24-4, molecular weight: 369], 2,2'-dihydroxy-3,3'-di ( ⁇ -methylcyclohexyl) -5,5'-dimethyldiphenylmethane [CAS number: 77-62-3, molecular weight: 421] and the like.
- Examples of the bisphenol compound represented by the formula (2-2) include 4,4'-thiobis.
- Examples of the triphenolic compound represented by the formula (3) include 1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane [CAS number: 1843-03-4, Molecular weight: 545], 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene [CAS number: 1709-70-2, molecular weight: 775] 1,3,5-tris (3,5-di-t-butyl-4-hydroxybenzyl) -sec-triazine-2,4,6- (1H, 3H, 5H) trione [CAS number: 27676-] 62-6, molecular weight: 784].
- Examples of the tetraphenol compound represented by the formula (4) include tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane [CAS number: 6683-19-8. , Molecular weight: 1178].
- Such phenolic antioxidants may be used alone or in combination of two or more. Further, among these phenolic antioxidants, a phenolic antioxidant having a molecular weight of 300 or more is more preferable, and a molecular weight of 500 or more is preferable from the viewpoint that it is difficult to distill at the time of a depolymerization reaction performed at a high temperature and under a high vacuum. Phenol-based antioxidants are more preferable, and phenol-based antioxidants having a molecular weight of 700 or more are particularly preferable.
- phenolic antioxidants having a molecular weight of 300 to 499 examples include 2,2′-methylenebis (4-methyl-6-tert-butylphenol) [molecular weight: 341], 2,2′-methylenebis (4-ethyl-6- t-butylphenol) [molecular weight: 369], 4,4'-thiobis (3-methyl-6-t-butylphenol) [molecular weight: 359], 4,4'-butylidenebis (3-methyl-6-t-butylphenol) [Molecular weight: 383], 2,2′-dihydroxy-3,3′-di ( ⁇ -methylcyclohexyl) -5,5′-dimethyldiphenylmethane [molecular weight: 421], tocopherol [molecular weight: 417] and the like.
- phenolic antioxidants having a molecular weight of 500 to 699 include stearyl- ⁇ - (3,5-di-t-butyl-4-hydroxyphenyl) propionate [molecular weight: 531], 1,1,3-tris. (2-methyl-4-hydroxy-5-t-butylphenyl) butane [molecular weight: 545]. Furthermore, as a phenolic antioxidant having a molecular weight of 700 or more, 3,9-bis [1,1-dimethyl-2- [ ⁇ - (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy is used.
- the amount of the phenolic antioxidant in the reaction system is preferably 0.5 to 5 parts by mass, more preferably 1 to 3 parts by mass with respect to 100 parts by mass of the glycolic acid oligomer. If the amount of the phenolic antioxidant is less than the lower limit, it tends to be impossible to sufficiently suppress the polymerization of the glycolic acid oligomer. On the other hand, if the amount exceeds the upper limit, the manufacturing cost increases, which is not preferable in terms of economy. There is a tendency.
- a phenol-based antioxidant is used from the viewpoint of hardly affecting the depolymerization reaction solution and glycolide such as coloring, modification, and deterioration.
- R 51 represents an alkylene group having 1 to 10 carbon atoms.
- the piperidine type compound represented by these is mentioned.
- the alkylene group may be linear or branched.
- Examples of the piperidine compound represented by the formula (5) include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate [CAS number: 52829-07-9, molecular weight: 481]. It is done.
- R 61 represents an alkyl group having 1 to 30 (preferably 10 to 20) carbon atoms.)
- the sulfide type compound represented by these is mentioned.
- the alkyl group may be linear or branched.
- Examples of the sulfide compound represented by the formula (6) include dilauryl 3,3′-thiodipropionate [CAS number: 123-28-4, molecular weight: 515], dimyristyl 3,3′-thiodipropionate. [CAS number: 16545-54-3, molecular weight: 571], distearyl 3,3′-thiodipropionate [CAS number: 693-36-7, molecular weight: 683] and the like.
- R 71 and R 72 each independently represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms (preferably 1 to 10), and R 73 has 1 to 20 carbon atoms (preferably 5 to 15 carbon atoms)).
- R 71 and R 72 each independently represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms (preferably 1 to 10), and R 73 has 1 to 20 carbon atoms (preferably 5 to 15 carbon atoms)).
- R 71 and R 72 each independently represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms (preferably 1 to 10), and R 73 has 1 to 20 carbon atoms (preferably 5 to 15 carbon atoms)).
- R 74 represents an alkyl group having 1 to 30 carbon atoms (preferably 15 to 25) or an aryl group having 6 to 30 carbon atoms (preferably 10 to 20 carbon atoms).
- R 75 represents an alkyl group having 1 to 30 carbon atoms (preferably 10 to 20 carbon atoms)
- R 76 represents an alkyl group having 1 to 5 carbon atoms (preferably 1 to 3 carbon atoms)
- R 77 represents carbon atoms.
- R 78 represents an alkyl group having 1 to 20 (preferably 5 to 15) carbon atoms.
- the alkyl group and alkylene group in the formulas (7-1) to (7-6) may be linear or branched.
- Examples of the phosphite compound represented by the formula (7-1) include triphenyl phosphite [CAS number: 101-02-0, molecular weight: 310], tris (nonylphenyl) phosphite [CAS number: 26523]. -78-4, molecular weight: 689], tris (2,4-di-t-butylphenyl) phosphite [CAS number: 31570-04-4, molecular weight: 647] and the like (7-2 As the phosphite compound represented by), diphenylisodecyl phosphite [CAS number: 26544-23-0, molecular weight: 374] and the like can be mentioned.
- Examples of the acid ester compound include phenyl diisodecyl phosphite [CAS number: 25550-98-5, molecular weight: 439].
- Examples of the phosphite compound represented by the formula (7-4) include cyclic neopentanetetraylbis (octadecyl phosphite) [CAS number: 3806-34-6, molecular weight: 733], cyclic neopentane. And tetraylbis (2,6-di-t-butyl-4-methylphenyl) phosphite [CAS number: 80693-00-1, molecular weight: 633].
- Examples of the phosphite compound represented by the formula (7-5) include 4,4′-butylidene-bis (3-methyl-6-tert-butylphenylditridecyl) phosphite [CAS number: 13003-12.
- Examples of the phosphite compound represented by the formula (7-6) include 2,2-methylenebis (4,6-di-t-butylphenyl) octyl phosphite [CAS number: 126050-54-2, molecular weight. : 583].
- Solvent in the present invention, it is preferable to use a solvent in order to improve the depolymerization reactivity of the glycolic acid oligomer.
- a solvent a polar organic solvent is preferable, and a high boiling polar organic solvent having a boiling point of 230 to 450 ° C. is more preferable.
- Such a high-boiling polar organic solvent acts as a solvent in the depolymerization reaction and also acts as a co-distilled component when taking out the produced glycolide from the reaction system, so that glycolide and the like adhere to the inner wall of the production line. Can be prevented.
- the boiling point of the polar organic solvent is more preferably 235 to 450 ° C, further preferably 255 to 430 ° C, and particularly preferably 280 to 420 ° C.
- the boiling point of the polar organic solvent is a value under normal pressure, and when the boiling point is measured under reduced pressure, it is converted to a value under normal pressure.
- the molecular weight of such a polar organic solvent is preferably 150 to 450, more preferably 180 to 420, and particularly preferably 200 to 400.
- the molecular weight of the polar organic solvent is out of the above range, co-distillation with glycolide tends to hardly occur.
- high-boiling polar organic solvents include aromatic dicarboxylic acid diesters, aromatic carboxylic acid esters, aliphatic dicarboxylic acid diesters, polyalkylene glycol diethers, aromatic dicarboxylic acid dialkoxyalkyl esters, and aliphatic dicarboxylic acids.
- aromatic dicarboxylic acid diesters aromatic carboxylic acid esters, aliphatic dicarboxylic acid diesters, polyalkylene glycol diethers, aromatic dicarboxylic acid dialkoxyalkyl esters, and aliphatic dicarboxylic acids.
- dialkoxyalkyl esters polyalkylene glycol diesters
- aromatic phosphate esters include dialkoxyalkyl esters, polyalkylene glycol diesters, and aromatic phosphate esters.
- aromatic dicarboxylic acid diesters aromatic carboxylic acid esters, aliphatic dicarboxylic acid diesters, and polyalkylene glycol diethers are preferred, and polyalkylene glycol diethers are less susceptible to thermal degradation. Is more preferable.
- the said high boiling polar organic solvent may be used individually by 1 type, or may use 2 or more types together.
- aromatic dicarboxylic acid diester examples include phthalic acid esters such as dibutyl phthalate, dioctyl phthalate, dibenzyl phthalate, and benzyl butyl phthalate.
- aromatic carboxylic acid ester examples include benzoic acid esters such as benzyl benzoate.
- aliphatic dicarboxylic acid diester examples include adipic acid esters such as dioctyl adipate and sebacic acid esters such as dibutyl sebacate.
- R 1 represents a methylene group or a linear or branched alkylene group having 2 to 8 carbon atoms
- X 1 represents a hydrocarbon group
- Y 1 represents an alkyl having 2 to 20 carbon atoms.
- p is an integer of 1 or more
- p is 2 or more, a plurality of R 1 may be the same or different. The compound represented by these is mentioned.
- R 1 in the formula (8) is not particularly limited as long as it is a methylene group or a linear or branched alkylene group having 2 to 8 carbon atoms.
- the polyalkylene glycol diester represented by the formula (8) is not limited. From the viewpoint of easy availability or synthesis of ether, an ethylene group is preferable.
- X 1 in the formula (8) is a hydrocarbon group such as an alkyl group or an aryl group, and among them, a hydrocarbon group having 1 to 20 carbon atoms is preferable.
- the alkyl group is a methyl group or an ethyl group.
- Examples include propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, lauryl group and the like. These alkyl groups may be branched or linear.
- Examples of the aryl group include a phenyl group, a naphthyl group, a substituted phenyl group, and a substituted naphthyl group.
- an alkyl group, an alkoxy group, and a halogen atom Cl, Br, I, etc.
- the number of such substituents is, for example, 1 to 5 in the case of a substituted phenyl group, preferably 1 to 3, and when there are a plurality of substituents, they may be the same or different. Also good.
- Such a substituent serves to adjust the boiling point and polarity of the polyalkylene glycol diether.
- Y 1 in the formula (8) is an alkyl group having 2 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms.
- the carbon number of Y 1 exceeds the upper limit, the polarity of the polyalkylene glycol diether represented by the formula (8) is lowered, the solubility of the glycolic acid oligomer is lowered, and co-distillation with glycolide is difficult. It becomes.
- Y 1 becomes a methyl group, in order for the polyalkylene glycol diether represented by the formula (8) to be a high boiling point solvent suitable for co-distillation with glycolide, the carbon number of R 1 is increased. There is a need to.
- a polyalkylene glycol diether in which Y 1 in the formula (8) is a methyl group is not preferable.
- the alkyl group and aryl group include those exemplified as the alkyl group and aryl group of X 1 .
- P in the formula (8) is an integer of 1 or more, but is preferably an integer of 2 or more.
- the upper limit of p is not particularly limited, but is preferably an integer of 8 or less, and more preferably an integer of 5 or less.
- p exceeds the above upper limit the degree of polymerization distribution becomes wider during the synthesis of polyalkylene glycol diether, and it tends to be difficult to isolate polyalkylene glycol diethers having the same p in the formula (8).
- the plurality of R 1 may be the same or different.
- X 1 and Y 1 in the formula (8) are both alkyl groups, and the total number of carbon atoms of X 1 and Y 1 is 3 to 21 (more preferably Polyalkylene glycol diethers 6 to 20) are preferred. In this case, X 1 and Y 1 may be the same alkyl group or different alkyl groups.
- polyalkylene glycol diethers include: Diethylene glycol dibutyl ether, diethylene glycol dihexyl ether, diethylene glycol dioctyl ether, diethylene glycol butyl-2-chlorophenyl ether, triethylene glycol diethyl ether, triethylene glycol dipropyl ether, triethylene glycol dibutyl ether, triethylene glycol dihexyl ether, triethylene glycol dihexyl ether , Triethylene glycol butyl octyl ether, triethylene glycol butyl decyl ether, tetraethylene glycol diethyl ether, tetraethylene glycol dipropyl ether, tetraethylene glycol dibutyl ether, tetraethylene glycol dihexyl ether, tetraethylene glycol Octyl ether, diethylene glycol butyl hexyl ether, diethylene glycol butyl octyl
- polyalkylene glycol dialkyl ethers are preferable from the viewpoint of easy synthesis and resistance to thermal degradation, and diethylene glycol dialkyl ethers, triethylene glycol dialkyl ethers, tetraethylene glycol dialkyl ethers are preferred. More preferred.
- the polyalkylene glycol diether used in the present invention preferably has a glycolide solubility at 25 ° C. of 0.1 to 10%.
- the solubility of glycolide is expressed as a percentage of the mass (g) of glycolide relative to the volume (ml) of polyalkylene glycol diether when glycolide is dissolved in 25 ° C. polyalkylene glycol diether until saturated. It is a thing.
- glycolide co-distilled with the polyalkylene glycol diether tends to precipitate in the middle of the production line and the production line tends to be blocked.
- tetraethylene glycol dibutyl ether and triethylene glycol butyl octyl ether are more preferable from the viewpoints of ease of synthesis, heat degradation, glycolic acid oligomer depolymerization reactivity, glycolide recovery, and the like.
- the amount of the solvent in the reaction system is preferably 30 to 5000 parts by mass, more preferably 50 to 2000 parts by mass, and particularly preferably 60 to 200 parts by mass with respect to 100 parts by mass of the glycolic acid oligomer.
- the amount of the solvent is less than the lower limit, the ratio of the solution phase of the glycolic acid oligomer in the reaction system decreases (the ratio of the melt phase of the glycolic acid oligomer increases) under the depolymerization temperature condition.
- the polymerization reactivity tends to decrease or the glycolic acid oligomer tends to become heavier in the melt phase.
- the upper limit is exceeded, the thermal efficiency during the depolymerization reaction decreases, and glycolide is produced by the depolymerization reaction. Tend to decrease.
- Tin Compound it is preferable to use a tin compound such as tin dichloride, tin tetrachloride, tin alkylcarboxylate.
- a tin compound such as tin dichloride, tin tetrachloride, tin alkylcarboxylate.
- Such tin compounds may be used alone or in combination of two or more.
- tin dichloride or tin octoate is preferable and tin octoate is more preferable from the viewpoint of improving the productivity of glycolide.
- the amount of tin compound in the reaction system is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 2 parts by mass, and more preferably 0.1 to 0. 5 parts by mass is particularly preferred.
- the amount of tin compound is less than the lower limit, the production of glycolic acid and its chain dimer in the depolymerization reaction is not sufficiently suppressed, and the yield of glycolide tends not to increase sufficiently. If it exceeds, the decomposition reaction of the solvent and the solubilizing agent is promoted, and the decomposition product co-distills with glycolide, so that the purity of glycolide tends to decrease.
- solubilizer may be added in order to improve the solubility characteristics (solubility and / or dissolution rate) of the glycolic acid oligomer in a solvent (particularly a high boiling polar organic solvent). preferable. Moreover, the depolymerization reactivity of a glycolic acid oligomer can also be improved by adding a solubilizer.
- a solubilizer is preferably a compound satisfying any one or more of the following requirements (1) to (5).
- the compound is compatible or soluble in the solvent. Any compound that is compatible or soluble in the solvent may be liquid or solid at room temperature.
- the solubilizer does not distill or the amount of distillate becomes extremely small during the co-distillation of glycolide and the solvent. Therefore, it is preferable. In many cases, good results can be obtained by using a compound having a boiling point of 450 ° C. or higher as a solubilizer.
- alcohols and the like can be suitably used as the solubilizer.
- a compound having a functional group such as OH group, COOH group, and CONH group.
- Affinity with glycolic acid oligomer is higher than that of the solvent.
- the affinity between the solubilizing agent and the glycolic acid oligomer is determined by heating the mixture of the glycolic acid oligomer and the solvent to a temperature of 230 ° C. or more to form a uniform solution phase, and further adding the glycolic acid oligomer thereto. Then, the concentration can be increased until the mixture does not form a homogeneous solution phase, and a solubilizer is added thereto, and it can be confirmed by visually observing whether a homogeneous solution phase is formed again. .
- a compound satisfying any one or more of these requirements is preferable to use as a solubilizer.
- alcohols, phenols, aliphatic carboxylic acids, aliphatic amides are used.
- alcohols are particularly effective.
- the alcohols include aliphatic alcohols such as decanol, tridecanol, decanediol, ethylene glycol, propylene glycol, and glycerin; aromatic alcohols such as cresol, chlorophenol, and naphthyl alcohol; polyalkylene glycol; polyalkylene glycol monoether, and the like. Can be mentioned. These alcohols may be used alone or in combination of two or more.
- R 2 represents a methylene group or a linear or branched alkylene group having 2 to 8 carbon atoms
- X 2 represents a hydrocarbon group
- q is an integer of 1 or more
- q is In the case of 2 or more, the plurality of R 2 may be the same or different from each other.
- the polyalkylene glycol monoether represented by these is preferable.
- R 2 in the formula (9) is not particularly limited as long as it is a methylene group or a linear or branched alkylene group having 2 to 8 carbon atoms, but the polyalkylene glycol diester represented by the formula (9) From the viewpoint of easy availability or synthesis of ether, an ethylene group is preferable.
- X 2 in the formula (9) is a hydrocarbon group such as an alkyl group or an aryl group. Among them, a hydrocarbon group having 1 to 18 carbon atoms is preferable, and a hydrocarbon group having 6 to 18 carbon atoms is preferable. More preferred.
- polyalkylene glycol monoethers polyethylene glycol monomethyl ether, polyethylene glycol monoethyl ether, polyethylene glycol monopropyl ether, polyethylene glycol monobutyl ether, polyethylene glycol monohexyl ether, polyethylene glycol monooctyl ether, polyethylene glycol monodecyl ether
- Polyethylene glycol monoalkyl ethers such as polyethylene glycol monolauryl ether; polyalkylene glycol monoalkyl ethers having propyleneoxy groups or butyleneoxy groups instead of ethyleneoxy groups of the polyethylene glycol monoalkyl ethers (for example, polypropylene glycol monoalkyl ethers)
- Polybutylene glycol monoalkyl ether polyethylene glycol monohexyl ether, polyethylene glycol monooctyl ether, polyethylene glycol monodecyl ether, polyethylene glycol monolauryl ether; propyleneoxy instead of the ethyleneoxy group of the polyethylene glyco
- R 3 represents a methylene group or a linear or branched alkylene group having 2 to 8 carbon atoms.
- R is an integer of 1 or more, and when r is 2 or more, a plurality of R 3 May be the same or different.
- the polyalkylene glycol represented by these is mentioned.
- R 3 in the formula (10) is not particularly limited as long as it is a methylene group or a linear or branched alkylene group having 2 to 8 carbon atoms, but the polyalkylene glycol represented by the formula (10) From the viewpoint of easy availability or synthesis, an ethylene group is preferable.
- polyalkylene glycols examples include polyethylene glycol, polypropylene glycol, polybutylene glycol and the like. These may be used alone or in combination of two or more.
- examples of polyalkylene glycol diether having a molecular weight exceeding 450 used as a solubilizer include polyethylene glycol dimethyl ether # 500 (average molecular weight 500), polyethylene glycol dimethyl ether # 2000 (average molecular weight 2000), and the like.
- the solubilizer also distills together with the glycolide during the depolymerization reaction, and the solubility of the glycolic acid oligomer in the mixture according to the present invention tends to decrease.
- the solubilizer in the depolymerization reaction of the glycolic acid oligomer is not sufficiently clear yet, but the present inventors infer as follows. That is, the solubilizer 1) reacts with the end of the glycolic acid oligomer to change the glycolic acid oligomer into a soluble state (state), 2) acts on the middle of the molecular chain of the glycolic acid oligomer to break the molecular chain 3) The action of changing the molecular weight to make the glycolic acid oligomer easy to dissolve 3) The action of changing the polarity of the entire solvent system to increase the hydrophilicity and the solubility of the glycolic acid oligomer 4) The emulsification of the glycolic acid oligomer 5) Action to disperse 5) Action to increase the depolymerization reaction point by binding to one end of glycolic acid oligomer, 6) Action to cut in the middle of glycolic acid oligomer and binding to the end of the broken molecular chain It is presumed that the solub
- the amount of the solubilizer in the reaction system is preferably 0.1 to 500 parts by mass, more preferably 1 to 300 parts by mass with respect to 100 parts by mass of the glycolic acid oligomer.
- the amount of the solubilizer is less than the lower limit, the solubility characteristics of the glycolic acid oligomer in a solvent (particularly, a high boiling polar organic solvent) may be deteriorated.
- the content of the solubilizer exceeds the above upper limit, it takes a cost to recover the solubilizer, which tends to be unfavorable in terms of economy.
- the glycolic acid oligomer is depolymerized in the presence of a phenolic antioxidant.
- This depolymerization is preferably performed in a solvent. Thereby, it becomes possible to improve the production
- a method for depolymerizing a glycolic acid oligomer in a solvent in the presence of a phenolic antioxidant will be described in detail.
- a glycolic acid oligomer, a phenolic antioxidant, and a solvent are mixed.
- the obtained mixture is heated to dissolve the glycolic acid oligomer and the phenolic antioxidant in the solvent.
- the solubility to the solvent of a glycolic acid oligomer improves, and it becomes possible to improve the production
- the heating temperature of the mixture is preferably 200 to 350 ° C, more preferably 210 to 310 ° C, particularly preferably 220 to 300 ° C, and most preferably 230 to 290 ° C.
- the heating temperature is less than the lower limit, the glycolic acid oligomer is difficult to dissolve in the solvent and a uniform solution is difficult to obtain, and therefore the depolymerization reactivity of the glycolic acid oligomer tends to decrease, and on the other hand, when the upper limit is exceeded. , Glycolic acid oligomers tend to be heavy.
- the mixture may be heated under normal pressure or under reduced pressure, but it may be 0.1 to 90 kPa (more preferably 1 to 30 kPa, particularly preferably 1.5 to 20 kPa, most preferably 2 to 10 kPa). ) Under reduced pressure. Furthermore, it is also preferable to heat in an inert gas atmosphere.
- the glycolic acid oligomer melt phase is 0.5 or less, the glycolic acid oligomer melt phase remains. Also good. “The residual ratio of the melt phase” means the temperature until the glycolic acid oligomer is depolymerized by adding a predetermined amount of the glycolic acid oligomer in a solvent that is substantially insoluble in the glycolic acid oligomer such as liquid paraffin.
- the volume of the glycolic acid oligomer melt phase formed when heated is a (ml)
- the same amount of glycolic acid oligomer is added to the solvent actually used and heated to a temperature at which the glycolic acid oligomer depolymerizes.
- the volume of the glycolic acid oligomer melt phase formed in is defined as b (ml)
- the residual ratio of such a melt phase is more preferably 0.3 or less, particularly preferably 0.1 or less, and most preferably substantially zero.
- the residual ratio of the melt phase exceeds the above upper limit, the produced glycolide hardly distills and the glycolic acid oligomer tends to become heavy in the melt phase.
- Preferred conditions such as temperature and pressure in this depolymerization reaction are the same as the preferred conditions in the dissolution step.
- the heating conditions in the dissolution step and the heating conditions in the depolymerization step may be the same or different.
- the pressure is preferably as low as possible from the viewpoint that the depolymerization reaction temperature decreases and the solvent recovery rate improves, and heating is usually performed under a pressure lower than the pressure in the dissolution step.
- the glycolide thus produced is distilled together with a solvent. Thereby, adhesion of glycolide to the inner wall of the production line is suppressed, and blockage of the line can be prevented. Further, since this depolymerization reaction is a reversible reaction, the glycolide oligomer depolymerization reaction proceeds efficiently by distilling glycolide from the reaction system. In particular, when the depolymerization reaction is performed under reduced pressure, glycolide is easily distilled off, and the depolymerization reaction proceeds more efficiently.
- glycolide When glycolide is continuously produced by the production method of the present invention, it is preferable to continuously or intermittently replenish the depolymerization reaction system with an amount of glycolic acid oligomer corresponding to the amount of glycolide distilled off. At this time, it is necessary to replenish so that the glycolic acid oligomer is uniformly dissolved in the solvent.
- phenolic antioxidants, solvents, solubilizers, and tin compounds are distilled, depolymerization reactions of phenolic antioxidants, solvents, solubilizers, and tin compounds corresponding to the amount of distillation It is preferred to replenish the system continuously or intermittently.
- about a phenolic antioxidant, a solvent, a solubilizer, and a tin compound you may supplement a new thing, but you may reuse what was collect
- glycolide distilled together with the solvent can be recovered by the method described in JP 2004-523596 A or International Publication No. WO 02/014303. For example, it can be recovered by cooling the co-distillate of glycolide and solvent and solidifying and precipitating by adding a poor solvent as necessary. Further, as described in International Publication No. WO02 / 014303, when a solvent having excellent thermal stability is used, it can be recovered by phase separation.
- the melting point of the glycolic acid oligomer was measured by the following method.
- Example 1 In a 100 ml pressure vessel, 4.57 g of the glycolic acid oligomer (GAO) obtained in Preparation Example 1, tetraethylene glycol dibutyl ether (TEG-DB, boiling point: 340 ° C., molecular weight: 306, solubility of glycolide: 4.
- GEO glycolic acid oligomer
- TAG-DB tetraethylene glycol dibutyl ether
- the solution was allowed to stand for 1 day while being heated to 260 ° C. to perform a depolymerization reaction to synthesize glycolide.
- 5 ml of a 0.1 g / ml sodium hydroxide aqueous solution was added and heated at 95 ° C. for 5 hours for alkali decomposition treatment.
- the solution was filtered, and the residue (alkali decomposition insoluble matter) was vacuum dried at 60 ° C. for 2 days. Then, the mass of the alkali decomposition insoluble matter was measured, and the concentration of the alkali decomposition insoluble matter in the solution after completion of the reaction was determined. However, it was 3.2 mass%.
- the present invention it is possible to suppress the oligomer from becoming heavy in the depolymerization reaction of the glycolic acid oligomer.
- the method for producing glycolide according to the present invention is less prone to problems such as blockage of the production line, and is stable for a long time (for example, 10 days or more, preferably 20 days or more, more preferably 50 days or more). And is useful as an industrially superior method for producing glycolide.
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Abstract
Description
本発明に用いられるグリコール酸オリゴマーは、重量平均分子量が2万以下のポリグリコール酸である。このようなグリコール酸オリゴマーはグリコール酸の重縮合反応によって合成することができる。なお、グリコール酸オリゴマーの重量平均分子量は、ヘキサフルオロイソプロパノールを溶離液としてゲルパーミエーションクロマトグラフィ(GPC)により測定した、標準ポリメチルメタクリレート換算値である。
本発明に用いられる酸化防止剤は、フェノール系酸化防止剤である。このようなフェノール系酸化防止剤の存在下で前記グリコール酸オリゴマーを解重合させることによって、オリゴマーの重質化を抑制することができ、長時間にわたってグリコリドを製造することが可能となる。
で表されるフェノール系化合物、下記式(1-6):
で表されるビスフェノール系化合物、下記式(3):
で表されるトリフェノール系化合物、下記式(4):
で表されるテトラフェノール系化合物などが挙げられる。
で表される基が挙げられる。
で表されるピペリジン系化合物が挙げられる。前記アルキレン基は直鎖状であっても分枝鎖状であってもよい。前記式(5)で表されるピペリジン系化合物としては、ビス(2,2,6,6-テトラメチル-4-ピペリジル)セバケート〔CAS番号:52829-07-9、分子量:481〕などが挙げられる。
で表されるスルフィド系化合物が挙げられる。前記アルキル基は直鎖状であっても分枝鎖状であってもよい。前記式(6)で表されるスルフィド系化合物としては、ジラウリル3,3’-チオジプロピオネート〔CAS番号:123-28-4、分子量:515〕、ジミリスチル3,3’-チオジプロピオネート〔CAS番号:16545-54-3、分子量:571〕、ジステアリル3,3’-チオジプロピオネート〔CAS番号:693-36-7、分子量:683〕などが挙げられる。
で表される亜リン酸エステル化合物、下記式(7-4):
で表される亜リン酸エステル化合物、下記式(7-5):
で表される亜リン酸エステル化合物、下記式(7-6):
で表される亜リン酸エステル化合物などが挙げられる。
本発明においては、グリコール酸オリゴマーの解重合反応性を向上させるために、溶媒を使用することが好ましい。このような溶媒としては極性有機溶媒が好ましく、沸点が230~450℃である高沸点極性有機溶媒がより好ましい。このような高沸点極性有機溶媒は、解重合反応において溶媒として作用するとともに、生成したグリコリドを反応系から取り出す際の共留出成分として作用し、製造ラインの内壁にグリコリドなどが付着することを防ぐことができる。したがって、極性有機溶媒の沸点が前記下限未満になると、解重合反応温度を高く設定することができず、グリコリドの生成速度が低下する傾向にある。他方、極性有機溶媒の沸点が前記上限を超えると、解重合反応時に極性有機溶媒が留出しにくく、生成したグリコリドとの共留出が困難となる傾向にある。このような観点から、高沸点極性有機溶媒の沸点としては235~450℃がより好ましく、255~430℃がさらに好ましく、280~420℃が特に好ましい。なお、本発明において極性有機溶媒の沸点は、常圧下での値であり、減圧下で沸点を測定した場合には常圧での値に換算する。
X1-O-(R1-O)p-Y1 (8)
(前記式(8)中、R1はメチレン基または炭素数2~8の直鎖状もしくは分岐状アルキレン基を表し、X1は炭化水素基を表し、Y1は炭素数2~20のアルキル基または炭素数6~20のアリール基を表す。pは1以上の整数であり、pが2以上の場合、複数のR1はそれぞれ同一であっても異なっていてもよい。)
で表される化合物が挙げられる。
ジエチレングリコールジブチルエーテル、ジエチレングリコールジヘキシルエーテル、ジエチレングリコールジオクチルエーテル、ジエチレングリコールブチル-2-クロロフェニルエーテル、トリエチレングリコールジエチルエーテル、トリエチレングリコールジプロピルエーテル、トリエチレングリコールジブチルエーテル、トリエチレングリコールジヘキシルエーテル、トリエチレングリコールジオクチルエーテル、トリエチレングリコールブチルオクチルエーテル、トリエチレングリコールブチルデシルエーテル、テトラエチレングリコールジエチルエーテル、テトラエチレングリコールジプロピルエーテル、テトラエチレングリコールジブチルエーテル、テトラエチレングリコールジヘキシルエーテル、テトラエチレングリコールジオクチルエーテル、ジエチレングリコールブチルヘキシルエーテル、ジエチレングリコールブチルオクチルエーテル、ジエチレングリコールヘキシルオクチルエーテル、トリエチレングリコールブチルヘキシルエーテル、トリエチレングリコールヘキシルオクチルエーテル、テトラエチレングリコールブチルヘキシルエーテル、テトラエチレングリコールブチルオクチルエーテル、テトラエチレングリコールヘキシルオクチルエーテルなどのポリエチレングリコールジアルキルエーテル;
このポリエチレングリコールジアルキルエーテルのエチレンオキシ基の代わりにプロピレンオキシ基またはブチレンオキシ基を有するポリアルキレングリコールジアルキルエーテル(例えば、ポリプロピレングリコールジアルキルエーテル、ポリブチレングリコールジアルキルエーテル);
ジエチレングリコールブチルフェニルエーテル、ジエチレングリコールヘキシルフェニルエーテル、ジエチレングリコールオクチルフェニルエーテル、トリエチレングリコールブチルフェニルエーテル、トリエチレングリコールヘキシルフェニルエーテル、トリエチレングリコールオクチルフェニルエーテル、テトラエチレングリコールブチルフェニルエーテル、テトラエチレングリコールヘキシルフェニルエーテル、テトラエチレングリコールオクチルフェニルエーテル、およびこれらのポリエチレングリコールアルキルフェニルエーテルのフェニル基の水素原子がアルキル基、アルコキシ基、ハロゲン原子などで置換された化合物といったポリエチレングリコールアルキルアリールエーテル;
このポリエチレングリコールアルキルアリールエーテルのエチレンオキシ基の代わりにプロピレンオキシ基またはブチレンオキシ基を有するポリアルキレングリコールアルキルアリールエーテル(例えば、ポリプロピレングリコールアルキルアリールエーテル、ポリブチレングリコールアルキルアリールエーテル);
ジエチレングリコールジフェニルエーテル、トリエチレングリコールジフェニルエーテル、テトラエチレングリコールジフェニルエーテル、およびこれらのポリエチレングリコールジフェニルエーテルのフェニル基の水素原子がアルキル基、アルコキシ基、ハロゲン原子などで置換された化合物といったポリエチレングリコールジアリールエーテル;
このポリエチレングリコールジアリールエーテルのエチレンオキシ基の代わりにプロピレンオキシ基またはブチレンオキシ基を有するポリアルキレングリコールジアリールエーテル(例えば、ポリプロピレングリコールジアリールエーテル、ポリブチレングリコールジアリールエーテル);
などが挙げられる。また、このようなポリアルキレングリコールジエーテルは、国際公開第02/014303号に記載の方法により合成することができる。
本発明においては、二塩化スズ、四塩化スズ、アルキルカルボン酸スズなどのスズ化合物を使用することが好ましい。このようなスズ化合物を使用することによって、解重合反応におけるグリコール酸やその鎖状二量体などの生成が抑制され、スズ化合物を使用しない場合に比べて、グリコリドの収量を大きく増大させることが可能となる。
本発明においては、溶媒(特に、高沸点極性有機溶媒)に対するグリコール酸オリゴマーの溶解特性(溶解度および/または溶解速度)を向上させるために、可溶化剤を添加することが好ましい。また、可溶化剤を添加することによってグリコール酸オリゴマーの解重合反応性を高めることもできる。このような可溶化剤としては、次の要件(1)~(5)のいずれか1つ以上を満たす化合物であることが好ましい。
HO-(R2-O)q-X2 (9)
(式(9)中、R2はメチレン基または炭素数2~8の直鎖状もしくは分岐状アルキレン基を表し、X2は炭化水素基を表す。qは1以上の整数であり、qが2以上の場合、複数のR2はそれぞれ同一であっても異なっていてもよい。)
で表されるポリアルキレングリコールモノエーテルが好ましい。
HO-(R3-O)r-H (10)
(式(10)中、R3はメチレン基または炭素数2~8の直鎖状もしくは分岐状アルキレン基を表す。rは1以上の整数であり、rが2以上の場合、複数のR3はそれぞれ同一であっても異なっていてもよい。)
で表されるポリアルキレングリコールが挙げられる。
本発明のグリコリドの製造方法においては、フェノール系酸化防止剤の存在下でグリコール酸オリゴマーを解重合させる。この解重合は、溶媒中で行うことが好ましい。これにより、グリコリドの生成および揮発速度を向上させることが可能となる。また、スズ化合物の存在下、可溶化剤の存在下、またはこれらを組み合わせた条件下で前記解重合を行うことも好ましい。以下、フェノール系酸化防止剤の存在下、溶媒中でグリコール酸オリゴマーを解重合させる方法について詳細に説明する。
先ず、グリコール酸オリゴマーとフェノール系酸化防止剤と溶媒とを混合する。得られた混合物を加熱して、溶媒にグリコール酸オリゴマーおよびフェノール系酸化防止剤を溶解させる。このとき、前記混合物には可溶化剤を混合することが好ましい。これにより、グリコール酸オリゴマーの溶媒への溶解性が向上し、グリコリドの生成および揮発速度を飛躍的に向上させることが可能となる。また、必要に応じてスズ化合物を混合してもよい。これにより、グリコリドの収量を増大させることができる。
次に、このようにして調製した溶液相(グリコール酸オリゴマーとフェノール系酸化防止剤と、必要に応じて可溶化剤およびスズ化合物とを溶媒中に実質的に均一に溶解したもの)の加熱をさらに継続し、前記溶液相中でグリコール酸オリゴマーを解重合させ、グリコリドを生成させる。本発明においては、フェノール系酸化防止剤の存在下でグリコール酸オリゴマーを解重合させるため、オリゴマーの重質化が抑制され、長時間にわたってグリコリドを製造することが可能となる。
次に、このようにして生成したグリコリドを溶媒とともに留出させる。これにより、製造ラインの内壁へのグリコリドの付着が抑制され、ラインの閉塞を防止することができる。また、この解重合反応は可逆反応であるため、グリコリドを反応系から留出させることによってグリコール酸オリゴマーの解重合反応が効率的に進行する。特に、減圧下で解重合反応を行うとグリコリドが留出しやすく、解重合反応がより効率的に進行する。
このように、溶媒とともに留出したグリコリドは、特開2004-523596号公報または国際公開第WO02/014303号に記載の方法により回収することができる。例えば、グリコリドと溶媒との共留出物を冷却し、必要に応じて貧溶媒を添加して固化・析出させることによって回収することができる。また、国際公開第WO02/014303号に記載されているように、熱安定性に優れた溶媒を用いた場合には、相分離によって回収することもできる。
示差走査熱量計(DSC)を用いて不活性ガス雰囲気下、昇温速度10℃/分の条件で測定した。
1リットルのセパラブルフラスコに、グリコール酸の70%水溶液(デュポン社製工業用グレード)1kgを仕込み、常圧で撹拌しながら加熱して室温から220℃まで4時間かけて昇温させた。この間、生成した水を留去しながら縮合反応を行なった。次に、フラスコ内を常圧から2kPaまで1時間かけて徐々に減圧した後、220℃で3時間加熱して縮合反応を継続した。その後、未反応原料などの低沸分を留去してグリコール酸オリゴマー(GAO)480gを得た。このグリコール酸オリゴマーの融点は211℃であった。
100mlの耐圧容器に、調製例1で得られたグリコール酸オリゴマー(GAO)4.57g、溶媒としてテトラエチレングリコールジブチルエーテル(TEG-DB、沸点:340℃、分子量:306、グリコリドの溶解度:4.6%)2.86g、可溶化剤としてオクチルトリエチレングリコール(OTEG)2.54g、触媒として二塩化スズ(SnCl2)二水和物0.071g、およびフェノール系酸化防止剤として1,3,5-トリメチル-2,4,6-トリス(3,5-ジ-t-ブチル-4-ヒドロキシベンジル)ベンゼン((株)ADEKA製「アデカスタブAO-330」、分子量:775)100mgを仕込み、260℃まで加熱して均一な溶液を調製した。
フェノール系酸化防止剤を使用しなかった以外は実施例1と同様にしてグリコリドを合成し、反応終了後の溶液中のアルカリ分解不溶物の濃度を求めたところ、11.6質量%であった。
Claims (6)
- フェノール系酸化防止剤の存在下でグリコール酸オリゴマーを解重合させるグリコリドの製造方法。
- 前記フェノール系酸化防止剤が、分子量300以上のフェノール系酸化防止剤である、請求項1に記載のグリコリドの製造方法。
- 前記グリコール酸オリゴマーを溶媒中で解重合させる請求項1または2に記載のグリコリドの製造方法。
- 前記溶媒が、沸点が230~450℃である高沸点極性有機溶媒である、請求項3に記載のグリコリドの製造方法。
- 前記解重合により得られたグリコリドと前記溶媒とを共留出させる請求項3または4に記載のグリコリドの製造方法。
- 前記グリコール酸オリゴマーをスズ化合物の存在下で解重合させる請求項1~5のうちのいずれか一項に記載のグリコリドの製造方法。
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WO2009077615A1 (fr) * | 2007-12-19 | 2009-06-25 | Futerro S.A. | Procédé d'obtention de lactide |
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WO2009077615A1 (fr) * | 2007-12-19 | 2009-06-25 | Futerro S.A. | Procédé d'obtention de lactide |
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US11046665B2 (en) | 2017-01-24 | 2021-06-29 | Kureha Corporation | Method for producing α-hydroxycarboxylic acid dimeric cyclic ester |
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