JP2008101229A - Glycolic acid copolymer - Google Patents
Glycolic acid copolymer Download PDFInfo
- Publication number
- JP2008101229A JP2008101229A JP2008008954A JP2008008954A JP2008101229A JP 2008101229 A JP2008101229 A JP 2008101229A JP 2008008954 A JP2008008954 A JP 2008008954A JP 2008008954 A JP2008008954 A JP 2008008954A JP 2008101229 A JP2008101229 A JP 2008101229A
- Authority
- JP
- Japan
- Prior art keywords
- acid
- glycolic acid
- molecular weight
- polymerization
- acid copolymer
- 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.)
- Pending
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- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Natural products OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 title claims abstract description 84
- 229920001577 copolymer Polymers 0.000 title claims abstract description 47
- 230000008859 change Effects 0.000 claims abstract description 13
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 15
- JVTAAEKCZFNVCJ-REOHCLBHSA-N L-lactic acid Chemical compound C[C@H](O)C(O)=O JVTAAEKCZFNVCJ-REOHCLBHSA-N 0.000 claims description 14
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical group OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 8
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 7
- ULQISTXYYBZJSJ-UHFFFAOYSA-N 12-hydroxyoctadecanoic acid Chemical compound CCCCCCC(O)CCCCCCCCCCC(O)=O ULQISTXYYBZJSJ-UHFFFAOYSA-N 0.000 claims description 6
- UGAGPNKCDRTDHP-UHFFFAOYSA-N 16-hydroxyhexadecanoic acid Chemical compound OCCCCCCCCCCCCCCCC(O)=O UGAGPNKCDRTDHP-UHFFFAOYSA-N 0.000 claims description 6
- WHBMMWSBFZVSSR-UHFFFAOYSA-N 3-hydroxybutyric acid Chemical compound CC(O)CC(O)=O WHBMMWSBFZVSSR-UHFFFAOYSA-N 0.000 claims description 6
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- SJZRECIVHVDYJC-UHFFFAOYSA-N 4-hydroxybutyric acid Chemical compound OCCCC(O)=O SJZRECIVHVDYJC-UHFFFAOYSA-N 0.000 claims description 4
- 229940006015 4-hydroxybutyric acid Drugs 0.000 claims description 4
- 229930182843 D-Lactic acid Natural products 0.000 claims description 4
- JVTAAEKCZFNVCJ-UWTATZPHSA-N D-lactic acid Chemical compound C[C@@H](O)C(O)=O JVTAAEKCZFNVCJ-UWTATZPHSA-N 0.000 claims description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 4
- 229940022769 d- lactic acid Drugs 0.000 claims description 4
- 150000002009 diols Chemical group 0.000 claims description 4
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 claims description 3
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims description 3
- 229940114072 12-hydroxystearic acid Drugs 0.000 claims description 3
- PHOJOSOUIAQEDH-UHFFFAOYSA-N 5-hydroxypentanoic acid Chemical compound OCCCCC(O)=O PHOJOSOUIAQEDH-UHFFFAOYSA-N 0.000 claims description 3
- IWHLYPDWHHPVAA-UHFFFAOYSA-N 6-hydroxyhexanoic acid Chemical compound OCCCCCC(O)=O IWHLYPDWHHPVAA-UHFFFAOYSA-N 0.000 claims description 3
- QEVGZEDELICMKH-UHFFFAOYSA-N Diglycolic acid Chemical compound OC(=O)COCC(O)=O QEVGZEDELICMKH-UHFFFAOYSA-N 0.000 claims description 3
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 claims description 3
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 claims description 3
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 3
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 3
- 238000007334 copolymerization reaction Methods 0.000 claims description 3
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 claims description 3
- 239000004220 glutamic acid Substances 0.000 claims description 3
- 235000013922 glutamic acid Nutrition 0.000 claims description 3
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 3
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- 229920000166 polytrimethylene carbonate Polymers 0.000 claims description 3
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000001361 adipic acid Substances 0.000 claims description 2
- 235000011037 adipic acid Nutrition 0.000 claims description 2
- 125000001142 dicarboxylic acid group Chemical group 0.000 claims description 2
- JRHWHSJDIILJAT-UHFFFAOYSA-N 2-hydroxypentanoic acid Chemical compound CCCC(O)C(O)=O JRHWHSJDIILJAT-UHFFFAOYSA-N 0.000 claims 1
- 239000003245 coal Substances 0.000 claims 1
- 238000006068 polycondensation reaction Methods 0.000 abstract description 31
- -1 phosphite compound Chemical class 0.000 abstract description 18
- 238000004519 manufacturing process Methods 0.000 abstract description 11
- 238000002844 melting Methods 0.000 abstract description 10
- 230000008018 melting Effects 0.000 abstract description 10
- 238000004040 coloring Methods 0.000 abstract description 9
- 238000010128 melt processing Methods 0.000 abstract description 4
- 239000000178 monomer Substances 0.000 abstract description 2
- 238000006116 polymerization reaction Methods 0.000 description 57
- 229920000642 polymer Polymers 0.000 description 47
- 238000000034 method Methods 0.000 description 27
- 229910052751 metal Inorganic materials 0.000 description 23
- 239000002184 metal Substances 0.000 description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 19
- 150000004703 alkoxides Chemical class 0.000 description 19
- 239000007790 solid phase Substances 0.000 description 15
- 239000003054 catalyst Substances 0.000 description 12
- 239000007789 gas Substances 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- 239000007864 aqueous solution Substances 0.000 description 10
- 239000011261 inert gas Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 239000000155 melt Substances 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 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 8
- 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 7
- 230000000052 comparative effect Effects 0.000 description 7
- 238000002425 crystallisation Methods 0.000 description 7
- LMDQRKJROSLEEI-UHFFFAOYSA-N germanium(4+) propan-2-olate Chemical compound [Ge+4].CC(C)[O-].CC(C)[O-].CC(C)[O-].CC(C)[O-] LMDQRKJROSLEEI-UHFFFAOYSA-N 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 229920000954 Polyglycolide Polymers 0.000 description 6
- 230000008025 crystallization Effects 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 230000018044 dehydration Effects 0.000 description 5
- 238000006297 dehydration reaction Methods 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 239000004633 polyglycolic acid Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- BYEAHWXPCBROCE-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropan-2-ol Chemical compound FC(F)(F)C(O)C(F)(F)F BYEAHWXPCBROCE-UHFFFAOYSA-N 0.000 description 4
- FMHKPLXYWVCLME-UHFFFAOYSA-N 4-hydroxy-valeric acid Chemical compound CC(O)CCC(O)=O FMHKPLXYWVCLME-UHFFFAOYSA-N 0.000 description 4
- 229910052787 antimony Inorganic materials 0.000 description 4
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 4
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 4
- 229910052746 lanthanum Inorganic materials 0.000 description 4
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 4
- 239000008188 pellet Substances 0.000 description 4
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 4
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 description 4
- 229920000747 poly(lactic acid) Polymers 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- 229910052772 Samarium Inorganic materials 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 229910052732 germanium Inorganic materials 0.000 description 3
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 229910052735 hafnium Inorganic materials 0.000 description 3
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 3
- 230000003301 hydrolyzing effect Effects 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 125000004430 oxygen atom Chemical group O* 0.000 description 3
- 239000004626 polylactic acid Substances 0.000 description 3
- HJCRVWSKQNDSPZ-UHFFFAOYSA-N propan-2-olate;samarium(3+) Chemical compound [Sm+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] HJCRVWSKQNDSPZ-UHFFFAOYSA-N 0.000 description 3
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 3
- UYCAUPASBSROMS-AWQJXPNKSA-M sodium;2,2,2-trifluoroacetate Chemical compound [Na+].[O-][13C](=O)[13C](F)(F)F UYCAUPASBSROMS-AWQJXPNKSA-M 0.000 description 3
- RKDVKSZUMVYZHH-UHFFFAOYSA-N 1,4-dioxane-2,5-dione Chemical compound O=C1COC(=O)CO1 RKDVKSZUMVYZHH-UHFFFAOYSA-N 0.000 description 2
- RVDLHGSZWAELAU-UHFFFAOYSA-N 5-tert-butylthiophene-2-carbonyl chloride Chemical compound CC(C)(C)C1=CC=C(C(Cl)=O)S1 RVDLHGSZWAELAU-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229920003232 aliphatic polyester Polymers 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 description 2
- 238000011088 calibration curve Methods 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000010828 elution Methods 0.000 description 2
- JTPUGUWXHGEEHW-UHFFFAOYSA-N ethanolate;iron(3+) Chemical compound [Fe+3].CC[O-].CC[O-].CC[O-] JTPUGUWXHGEEHW-UHFFFAOYSA-N 0.000 description 2
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 239000011491 glass wool Substances 0.000 description 2
- 150000004676 glycans Chemical class 0.000 description 2
- WZVIPWQGBBCHJP-UHFFFAOYSA-N hafnium(4+);2-methylpropan-2-olate Chemical compound [Hf+4].CC(C)(C)[O-].CC(C)(C)[O-].CC(C)(C)[O-].CC(C)(C)[O-] WZVIPWQGBBCHJP-UHFFFAOYSA-N 0.000 description 2
- 229920006158 high molecular weight polymer Polymers 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 239000004310 lactic acid Substances 0.000 description 2
- 235000014655 lactic acid Nutrition 0.000 description 2
- SORGMJIXNUWMMR-UHFFFAOYSA-N lanthanum(3+);propan-2-olate Chemical compound [La+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SORGMJIXNUWMMR-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 229920001282 polysaccharide Polymers 0.000 description 2
- 239000005017 polysaccharide Substances 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 2
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
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- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- AUPYNGCJRYOPQY-UHFFFAOYSA-N tris(2,5-ditert-butylphenyl) phosphite Chemical compound CC(C)(C)C1=CC=C(C(C)(C)C)C(OP(OC=2C(=CC=C(C=2)C(C)(C)C)C(C)(C)C)OC=2C(=CC=C(C=2)C(C)(C)C)C(C)(C)C)=C1 AUPYNGCJRYOPQY-UHFFFAOYSA-N 0.000 description 2
- SZPHBONKPMLMCA-UHFFFAOYSA-N tris(2-tert-butylphenyl) phosphite Chemical compound CC(C)(C)C1=CC=CC=C1OP(OC=1C(=CC=CC=1)C(C)(C)C)OC1=CC=CC=C1C(C)(C)C SZPHBONKPMLMCA-UHFFFAOYSA-N 0.000 description 2
- FEODVXCWZVOEIR-UHFFFAOYSA-N (2,4-ditert-butylphenyl) octyl hydrogen phosphite Chemical compound CCCCCCCCOP(O)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C FEODVXCWZVOEIR-UHFFFAOYSA-N 0.000 description 1
- LNAZSHAWQACDHT-XIYTZBAFSA-N (2r,3r,4s,5r,6s)-4,5-dimethoxy-2-(methoxymethyl)-3-[(2s,3r,4s,5r,6r)-3,4,5-trimethoxy-6-(methoxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6r)-4,5,6-trimethoxy-2-(methoxymethyl)oxan-3-yl]oxyoxane Chemical compound CO[C@@H]1[C@@H](OC)[C@H](OC)[C@@H](COC)O[C@H]1O[C@H]1[C@H](OC)[C@@H](OC)[C@H](O[C@H]2[C@@H]([C@@H](OC)[C@H](OC)O[C@@H]2COC)OC)O[C@@H]1COC LNAZSHAWQACDHT-XIYTZBAFSA-N 0.000 description 1
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- SDTMFDGELKWGFT-UHFFFAOYSA-N 2-methylpropan-2-olate Chemical compound CC(C)(C)[O-] SDTMFDGELKWGFT-UHFFFAOYSA-N 0.000 description 1
- 229920000945 Amylopectin Polymers 0.000 description 1
- 229920002101 Chitin Polymers 0.000 description 1
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
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- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
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- 229920002488 Hemicellulose Polymers 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 241001483078 Phyto Species 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- FJWGYAHXMCUOOM-QHOUIDNNSA-N [(2s,3r,4s,5r,6r)-2-[(2r,3r,4s,5r,6s)-4,5-dinitrooxy-2-(nitrooxymethyl)-6-[(2r,3r,4s,5r,6s)-4,5,6-trinitrooxy-2-(nitrooxymethyl)oxan-3-yl]oxyoxan-3-yl]oxy-3,5-dinitrooxy-6-(nitrooxymethyl)oxan-4-yl] nitrate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O)O[C@H]1[C@@H]([C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@@H](CO[N+]([O-])=O)O1)O[N+]([O-])=O)CO[N+](=O)[O-])[C@@H]1[C@@H](CO[N+]([O-])=O)O[C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O FJWGYAHXMCUOOM-QHOUIDNNSA-N 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
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- 239000003905 agrochemical Substances 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229920002988 biodegradable polymer Polymers 0.000 description 1
- 239000004621 biodegradable polymer Substances 0.000 description 1
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Landscapes
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Abstract
Description
本発明は、グリコール酸共重合体に関する。詳しくは、溶融加工時に着色することの少ないグリコール酸共重合体に関する。 The present invention relates to a glycolic acid copolymer. Specifically, the present invention relates to a glycolic acid copolymer that is hardly colored during melt processing.
ポリ乳酸、ポリグリコール酸又はこれらの共重合体に代表されるヒドロキシカルボン酸から製造される脂肪族ポリエステルは、生分解性の高分子として注目され、例えば、縫合糸等の医用材料、医薬、農薬、肥料等の徐放性材料等、多方面に利用されている。特に、ポリグリコール酸及びグリコール酸構造単位を主体とするグリコール酸共重合体は、ガスバリアー性に優れるという特徴を有し、フィルム等、包装材料用途に利用する提案が多数行われている。 Aliphatic polyesters produced from hydroxycarboxylic acids represented by polylactic acid, polyglycolic acid or copolymers thereof are attracting attention as biodegradable polymers, such as medical materials such as sutures, pharmaceuticals, and agricultural chemicals. It is used in various fields such as sustained-release materials such as fertilizers. In particular, glycolic acid copolymers mainly composed of polyglycolic acid and glycolic acid structural units have a feature of excellent gas barrier properties, and many proposals for use in packaging materials such as films have been made.
これらのポリマーを製造する方法としては、従来、乳酸、グリコール酸を一旦重縮合し、プレポリマーとした後、解重合によりラクチド及び／又はグリコリドを製造し、これらを用いて開環重合してポリラクチド及びポリグリコリドを製造していた。この方法によると、高分子量のポリマーが得られるものの、多数の工程を必要とし、また、ラクチド、グリコリドを得るために多大の労力がかかり、経済的とはいえなかった。 As a method for producing these polymers, conventionally, lactic acid and glycolic acid are once subjected to polycondensation to form a prepolymer, and then lactide and / or glycolide is produced by depolymerization, and ring-opening polymerization is performed using these to produce polylactide. And polyglycolide. According to this method, although a high molecular weight polymer can be obtained, many steps are required, and much labor is required to obtain lactide and glycolide, which is not economical.
本発明者らは、先に、特定の金属アルコキシドをグリコール酸存在下にて加水分解させることにより得られる加水分解生成物を触媒として用いて、グリコール酸等の原料を直接重縮合することにより、効率よく、高分子量で、重合時着色することの少ない高品質のグリコール酸共重合体が得られることを見出し、特許出願した（特願２００１−９３６７６号）。
しかしながら、グリコール酸構造単位を多く含むグリコール酸共重合体は、比較的高い融点を有するため、溶融加工時の温度が高くなり、成形加工等に供した場合、ポリマーの着色が著しかったり、大幅な分子量の低下がしばしば認められることがある。
The present inventors first polycondensed raw materials such as glycolic acid directly using a hydrolysis product obtained by hydrolyzing a specific metal alkoxide in the presence of glycolic acid as a catalyst, It was found that a high-quality glycolic acid copolymer having a high molecular weight and little coloration during polymerization was obtained, and a patent application was filed (Japanese Patent Application No. 2001-93676).
However, since the glycolic acid copolymer containing a large amount of glycolic acid structural units has a relatively high melting point, the temperature at the time of melt processing becomes high. A decrease in molecular weight is often observed.
このような問題を解決した、ポリ乳酸の製造方法として、特開平９−１５１２４３号公報には、ラクチドを錫等の金属触媒を用い、開環重合する際に、重合後半又は重合終了時にリン酸系エステルを添加することにより熱安定性、特に、分子量保持性に優れた高分子量のポリ乳酸を製造する方法が提案されている。しかしながら、この公報には、グリコール酸を出発原料としてポリグリコール酸及び／又はグリコール酸共重合体を製造する場合について、何ら記載されていない。本発明者らがグリコール酸共重合体を重縮合反応により製造する場合に、これを試みた結果では、融点以上、例えば、２３０℃での溶融保持時の分子量の保持性のわずかな改善が認められたものの、着色抑制効果に関しては満足できる効果が得られなかった。
このような事情に鑑み、重合時及び再溶融加工時にも着色することが少なく、高分子量を有するポリグリコール酸及び／又はグリコール酸共重合体を製造できる技術の登場が強く求められている。
As a method for producing polylactic acid that solves such a problem, Japanese Patent Application Laid-Open No. 9-151243 discloses phosphoric acid at the latter half of polymerization or at the end of polymerization when ring-opening polymerization of lactide using a metal catalyst such as tin. There has been proposed a method for producing a high molecular weight polylactic acid having excellent thermal stability, in particular, molecular weight retention, by adding a series ester. However, this publication does not describe anything about the production of polyglycolic acid and / or glycolic acid copolymer using glycolic acid as a starting material. When the inventors of the present invention produced a glycolic acid copolymer by a polycondensation reaction, a slight improvement in the molecular weight retention at the melting point or higher, for example, at 230 ° C., was observed. However, a satisfactory effect was not obtained with respect to the coloring suppression effect.
In view of such circumstances, there is a strong demand for the emergence of a technique that can produce polyglycolic acid and / or glycolic acid copolymer having a high molecular weight with little coloring during polymerization and remelting.
本発明の目的は、比較的高い温度における溶融加工においても着色が少なく、高い品質を維持できるグリコール酸共重合体及びそれを製造する方法を提供することを目的とする。 An object of the present invention is to provide a glycolic acid copolymer that is less colored even in melt processing at a relatively high temperature and can maintain high quality, and a method for producing the same.
本発明者らは、前記の課題を解決するため、鋭意検討を行った結果、特定の重縮合触媒の存在下に重合を行い、特定の分子量以上に達した段階において、特定のリン含有化合物を添加することにより、重合時の着色を抑制できるだけでなく、得られたポリマーを重合温度よりも更に高い温度で溶融加工した場合にも、ポリマーが着色することの少ないグリコール酸共重合体が得られることを見出した。
すなわち、本発明は、以下のとおりである。
（１） 重量平均分子量が５万以上であり、グリコール酸単位を７５ｍｏｌ％以上含有し、グリコール酸単位以外の共重合成分として、Ｌ−乳酸、Ｄ−乳酸、３−ヒドロキシ酪酸、４−ヒドロキシ酪酸、４−ヒドロキシ吉草酸、５−ヒドロキシ吉草酸及び６−ヒドロキシカプロン酸、１２−ヒドロキシステアリン酸、１６−ヒドロキシヘキサデカン酸を含むヒドロキシカルボン酸群、コハク酸、シュウ酸、マロン酸、グルタン酸、アジピン酸、ピメリン酸、ジグリコール酸を含むジカルボン酸群、エチレングリコール、ジエチレングリコール、トリエチレングリコール、プロピレングリコール、ジプロピレングリコール、１，３−プロパンジオール、１，４−ブタンジオール、ネオペンチルグリコール、１，６−ヘキサンジオール、及びジエチレングリコールを含むジオール群から選ばれる共重合成分を含有し、２３０℃で５分間、加熱溶融した後の着色度変化率が、加熱前着色度に対して１１０〜３００％であるグリコール酸共重合体。
As a result of intensive studies to solve the above problems, the present inventors conducted polymerization in the presence of a specific polycondensation catalyst, and at a stage where the molecular weight has reached or exceeded a specific phosphorus-containing compound. By adding, not only the coloration during polymerization can be suppressed, but also when the obtained polymer is melt-processed at a temperature higher than the polymerization temperature, a glycolic acid copolymer with little coloration of the polymer can be obtained. I found out.
That is, the present invention is as follows.
(1) The weight average molecular weight is 50,000 or more, contains 75 mol% or more of glycolic acid units, and L-lactic acid, D-lactic acid, 3-hydroxybutyric acid, 4-hydroxybutyric acid as copolymerization components other than glycolic acid units 4-hydroxyvaleric acid, 5-hydroxyvaleric acid and 6-hydroxycaproic acid, 12-hydroxystearic acid, hydroxycarboxylic acid group including 16-hydroxyhexadecanoic acid, succinic acid, oxalic acid, malonic acid, glutamic acid, adipine Acid, pimelic acid, dicarboxylic acid group including diglycolic acid, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, 1,3-propanediol, 1,4-butanediol, neopentyl glycol, 1, 6-hexanediol and diethyl Glycolic acid copolymer containing a copolymer component selected from a diol group containing lenglycol and having a coloration degree change rate of 110 to 300% with respect to the coloration degree before heating after heating and melting at 230 ° C. for 5 minutes. Coalescence.
本発明によれば、比較的高い溶融温度で再溶融し、成形加工に供する場合においても着色が少ない、高分子量で高品質のポリグリコール酸共重合体を製造することができる。 According to the present invention, it is possible to produce a high-quality polyglycolic acid copolymer having a high molecular weight that is less colored even when remelted at a relatively high melting temperature and subjected to a molding process.
以下、本発明について詳細に説明する。
本発明において、グリコール酸共重合体中に含まれるグリコール酸単位の含有率は７５ｍｏｌ％以上であり、好ましくは７５ｍｏｌ％以上、９９ｍｏｌ％以下の範囲、より好ましくは８０ｍｏｌ％以上、９５ｍｏｌ％以下の範囲、最も好ましくは８２ｍｏｌ％以上、９０ｍｏｌ％以下の範囲である。グリコール酸単位の含有率が７５ｍｏｌ％未満の場合には、得られる共重合体の強度、弾性率等の機械的物性、軟化温度等の熱的物性及びガスバリアー性が低下する。グリコール酸単位の含有量が９９ｍｏｌ％を超える場合には、共重合体の熱安定性が充分でなく、溶融成形加工時に熱分解して、着色及び分子量が低下しやすくなる傾向がある。
Hereinafter, the present invention will be described in detail.
In the present invention, the content of the glycolic acid unit contained in the glycolic acid copolymer is 75 mol% or more, preferably 75 mol% or more and 99 mol% or less, more preferably 80 mol% or more and 95 mol% or less. The most preferable range is 82 mol% or more and 90 mol% or less. When the content of glycolic acid units is less than 75 mol%, mechanical properties such as strength and elastic modulus of the resulting copolymer, thermal properties such as softening temperature, and gas barrier properties are lowered. When the content of glycolic acid units exceeds 99 mol%, the copolymer has insufficient thermal stability and tends to be thermally decomposed during melt molding, and the coloration and molecular weight tend to decrease.
グリコール酸単位以外の共重合成分の例としては、他のヒドロキシカルボン酸、ジカルボン酸、ジオール、３価以上の多価化合物及び多糖類等を挙げることができるが、グリコール酸と共重合可能なものであればこれらに限定されるものではない。
他のヒドロキシカルボン酸の例としては、Ｌ−乳酸、Ｄ−乳酸、３−ヒドロキシ酪酸、４−ヒドロキシ酪酸、４−ヒドロキシ吉草酸、５−ヒドロキシ吉草酸及び６−ヒドロキシカプロン酸、１２−ヒドロキシステアリン酸、１６−ヒドロキシヘキサデカン酸等が挙げられる。
Examples of copolymer components other than glycolic acid units include other hydroxycarboxylic acids, dicarboxylic acids, diols, trivalent or higher polyvalent compounds, polysaccharides, etc., but those copolymerizable with glycolic acid If it is, it will not be limited to these.
Examples of other hydroxycarboxylic acids include L-lactic acid, D-lactic acid, 3-hydroxybutyric acid, 4-hydroxybutyric acid, 4-hydroxyvaleric acid, 5-hydroxyvaleric acid and 6-hydroxycaproic acid, 12-hydroxystearic acid. Examples thereof include acid and 16-hydroxyhexadecanoic acid.
ジカルボン酸の例としては、例えば、コハク酸、シュウ酸、マロン酸、グルタン酸、アジピン酸、ピメリン酸、ジグリコール酸等の脂肪族ジカルボン酸等が挙げられる。
ジオールの例としては、例えば、エチレングリコール、ジエチレングリコール、トリエチレングリコール、プロピレングリコール、ジプロピレングリコール、１，３−プロパンジオール、１，４−ブタンジオール、ネオペンチルグリコール、１，６−ヘキサンジオール、及びジエチレングリコール等が挙げられる。
Examples of the dicarboxylic acid include aliphatic dicarboxylic acids such as succinic acid, oxalic acid, malonic acid, glutamic acid, adipic acid, pimelic acid, and diglycolic acid.
Examples of diols include, for example, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, 1,3-propanediol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, and Examples include diethylene glycol.
３価以上の多官能化合物の例としては、グリセリン、トリメチロールプロパン、ペンタエリスリトール、リンゴ酸、トリメリット酸、トリメシン酸、ピロメリット酸、トリカル
バリル酸、没食子酸等が挙げられる。
多糖類の例としては、例えば、セルロース、硝酸セルロース、酢酸セルロース、メチルセルロース、エチルセルロース、ＣＭＣ（カルボキ シメチルセルロース）、ヘミセルロース、デンプン、アミロペクチン、デキストリン、デキストラン、グリコーゲン、ペクチン、キチン、 キトサン等及びこれらの混合物及びこれらの誘導体等が挙げられる。
Examples of the trifunctional or higher polyfunctional compound include glycerin, trimethylolpropane, pentaerythritol, malic acid, trimellitic acid, trimesic acid, pyromellitic acid, tricarbaryl acid, gallic acid and the like.
Examples of polysaccharides include, for example, cellulose, cellulose nitrate, cellulose acetate, methylcellulose, ethylcellulose, CMC (carboxymethylcellulose), hemicellulose, starch, amylopectin, dextrin, dextran, glycogen, pectin, chitin, chitosan and mixtures thereof. And derivatives thereof.
共重合成分として好ましい例としては、Ｄ−乳酸及びＬ−乳酸が挙げられる。より好ましい例としては、Ｌ−乳酸が挙げられ、さらに好ましくは、光学純度が９５％以上、最も好ましくは９８％以上の、発酵法で製造されるＬ−乳酸である。所望により、上記の共重合成分の他に、グリコール酸単位を含むオリゴマーを一緒に用いることもできる。
これらのグリコール酸及び共重合成分は、固体状でも、水溶液の形でも、本発明のグリコール酸共重合体の製造に供することができる。
Preferable examples of the copolymer component include D-lactic acid and L-lactic acid. More preferred examples include L-lactic acid, and more preferred is L-lactic acid produced by a fermentation method with an optical purity of 95% or higher, most preferably 98% or higher. If desired, an oligomer containing a glycolic acid unit can be used together with the above copolymerization component.
These glycolic acid and copolymer component can be used for the production of the glycolic acid copolymer of the present invention in the form of a solid or an aqueous solution.
本発明のグリコール酸共重合体の重量平均分子量は５万以上であり、２３０℃で５分間、加熱溶融した後の着色度変化率が、加熱前着色度に対して１１０〜３００％である。
本発明で用いる重量平均分子量、及びグリコール酸共重合体の着色度及びその変化率については、後に述べる測定法により求められる。
グリコール酸共重合体の重量平均分子量が５万未満の場合には、成形加工に供するに充分な溶融粘度を有さず、得られる成形体も充分な強度をもたない。
The glycolic acid copolymer of the present invention has a weight average molecular weight of 50,000 or more, and a coloration degree change rate after heating and melting at 230 ° C. for 5 minutes is 110 to 300% with respect to the coloration degree before heating.
The weight average molecular weight used in the present invention, the degree of coloration of the glycolic acid copolymer and the rate of change thereof can be determined by the measurement method described later.
When the glycolic acid copolymer has a weight average molecular weight of less than 50,000, the glycolic acid copolymer does not have a sufficient melt viscosity for use in molding, and the resulting molded article does not have sufficient strength.
本発明において用いる着色度変化率とは、グリコール酸共重合体を２３０℃で５分間、加熱溶融した後の着色度を加熱前着色度で除した値を百分率で表した値である。本発明において、着色度変化率が１１０〜３００％、好ましく１１０〜２５０％、最も好ましくは１１０〜２００％の範囲であることが重要である。着色度変化率が３００％を越えると、加工製品として品位が大幅に低下する。
本発明のグリコール酸共重合体の製造において、触媒として、マグネシウム、鉄、ハフニウム、ゲルマニウム、アンチモン、ランタン、及びサマリウムからなる群より選ばれる少なくとも１種の金属のアルコキシドを、ヒドロキシカルボン酸存在下、加水分解させることにより得られる加水分解物を用いることが好ましい。
The coloration degree change rate used in the present invention is a value expressed as a percentage obtained by dividing the coloration degree after the glycolic acid copolymer is heated and melted at 230 ° C. for 5 minutes by the coloration degree before heating. In the present invention, it is important that the degree of color change is in the range of 110 to 300%, preferably 110 to 250%, and most preferably 110 to 200%. If the degree of color change exceeds 300%, the quality of the processed product will be significantly reduced.
In the production of the glycolic acid copolymer of the present invention, an alkoxide of at least one metal selected from the group consisting of magnesium, iron, hafnium, germanium, antimony, lanthanum, and samarium is used as a catalyst in the presence of a hydroxycarboxylic acid, It is preferable to use a hydrolyzate obtained by hydrolysis.
この金属アルコキシドは、アルキル基が結合した酸素原子と金属原子との結合が少なくとも１つ以上分子内に存在する化合物である。アルキル基と酸素原子の結合したものとしては、例えば、メトキシド、エトキシド、ｎ−プロポキシド、ｉｓｏ−プロポキシド、ｎ−ブトキシド、ｉｓｏ−ブトキシド、ｔｅｒｔ−ブトキシド、ｎ−ヘキシルアルコキシド、２−ヘキシルアルコキシド等の１価のアルコキシドや、エチレングリコキシド、１，２−プロパンジアルコキシド、１，３−プロパンアルコキシド、１，４−ブタンジアルコキシド等の２価のアルコキシド、ペンタエリスリトール等の４価のアルコキシド等が挙げられる。これらは、１種単独で、又は２種以上組み合わせて用いることができる。 This metal alkoxide is a compound in which at least one or more bonds between an oxygen atom to which an alkyl group is bonded and a metal atom are present in the molecule. Examples of the combination of an alkyl group and an oxygen atom include methoxide, ethoxide, n-propoxide, iso-propoxide, n-butoxide, iso-butoxide, tert-butoxide, n-hexyl alkoxide, 2-hexyl alkoxide and the like. Monovalent alkoxides of the above, divalent alkoxides such as ethylene glycoloxide, 1,2-propane dialkoxide, 1,3-propane dialkoxide, 1,4-butane dialkoxide, tetravalent alkoxides such as pentaerythritol, etc. Can be mentioned. These can be used individually by 1 type or in combination of 2 or more types.
アルキル基が結合した酸素原子と金属原子との結合の例としては、マグネシウムエトキシド、鉄トリエトキシド、ハフニウムテトラｔｅｒｔ−ブトキシド、ゲルマニウムテトラエトキシド、ゲルマニウムテトラｉｓｏ−プロポキシド、アンチモントリｉｓｏ−エトキシド、ランタントリｉｓｏ−プロポキシド、サマリウムｉｓｏ−プロポキシド等が挙げられる。
金属アルコキシドの加水分解物の詳細な化学構造は明確ではないが、金属アルコキシドがアルコールを脱離するとともに、水酸化物｛Ｍ−（ＯＨ）Ｘ｝、金属アルコキシドの縮重合反応物｛−Ｍ−Ｏ−Ｍ−｝、グリコール酸とのアルコール交換反応物｛Ｍ−（ＯＣＨ２ＣＯＯＨ）Ｘ｝、グリコール酸と反応した金属塩｛Ｍ−（ＯＣＯＣＨ２ＯＨ）Ｘ｝及び、グリコール酸の配位物等からなる、複数の化学構造を包含しているものと推測される。
Examples of the bond between the oxygen atom to which the alkyl group is bonded and the metal atom include magnesium ethoxide, iron triethoxide, hafnium tetratert-butoxide, germanium tetraethoxide, germanium tetraiso-propoxide, antimony triiso-ethoxide, lanthanum Examples include triiso-propoxide and samarium iso-propoxide.
Although the detailed chemical structure of the hydrolyzate of metal alkoxide is not clear, the metal alkoxide removes alcohol, and hydroxide {M- (OH) X}, condensation reaction product of metal alkoxide {-M- OM-}, an alcohol exchange reaction product with glycolic acid {M- (OCH2COOH) X}, a metal salt reacted with glycolic acid {M- (OCOCH2OH) X}, a coordination product of glycolic acid, and the like. Presumed to include multiple chemical structures.
金属アルコキシドの加水分解物を得る方法は、限定されるものではないが、例えば、（ａ）重縮合反応前に、予め、マグネシウム、鉄、ハフニウム、ゲルマニウム、アンチモン、ランタン及びサマリウムからなる群より選ばれる少なくとも１種の金属のアルコキシドを、グリコール酸と充分量の水を含む水溶液の存在下に加水分解させて加水分解物を調整する方法、（ｂ）マグネシウム、鉄、ハフニウム、ゲルマニウム、アンチモン、ランタン及びサマリウムからなる群より選ばれる少なくとも１種の金属のアルコキシドを、少なくとも３重量％を越える水及びグリコール酸を含む重合原料水溶液に添加し、脱水濃縮及び重縮合を行う工程中に、重合系中において加水分解物を形成させる方法等が挙げられる。工程が簡略化できる点からは、（ｂ）法の、重合系中において脱水濃縮及び重縮合反応とともに金属アルコキシドの加水分解物を形成させる方法が好ましい。 The method for obtaining the hydrolyzate of the metal alkoxide is not limited. For example, (a) before the polycondensation reaction, it is selected in advance from the group consisting of magnesium, iron, hafnium, germanium, antimony, lanthanum and samarium. A method of preparing a hydrolyzate by hydrolyzing at least one metal alkoxide in the presence of an aqueous solution containing glycolic acid and a sufficient amount of water, (b) magnesium, iron, hafnium, germanium, antimony, lanthanum And an alkoxide of at least one metal selected from the group consisting of samarium is added to a polymerization raw material aqueous solution containing at least 3% by weight of water and glycolic acid, followed by dehydration concentration and polycondensation, in the polymerization system And a method of forming a hydrolyzate. From the viewpoint that the process can be simplified, the method (b) of forming a hydrolyzate of metal alkoxide together with dehydration concentration and polycondensation reaction in the polymerization system is preferable.
グリコール酸共重合体の重縮合触媒として用いる金属アルコキシドの加水分解物の添加量としては、モノマー１ｇ当たり、金属原子として、通常、１×１０−７〜１×１０−２モル、好ましくは３×１０−７〜１×１０−３モルの範囲である。添加量が１×１０−７モル未満の場合には、重縮合速度を高めることが困難になり、添加量が１×１０−２モルを越えると、重合ポリマーが着色する等、副反応が増大し、分子量の増大が認められない場合がある。 The addition amount of the hydrolyzate of the metal alkoxide used as the polycondensation catalyst of the glycolic acid copolymer is usually 1 × 10 −7 to 1 × 10 −2 mol, preferably 3 ×, as metal atoms per 1 g of monomer. It is in the range of 10 −7 to 1 × 10 −3 mol. When the addition amount is less than 1 × 10 −7 mol, it is difficult to increase the polycondensation rate, and when the addition amount exceeds 1 × 10 −2 mol, the side reaction increases such as coloring of the polymer. In some cases, however, no increase in molecular weight is observed.
本発明において、重合段階で添加するトリアリールホスファイト化合物の例としては、亜リン酸トリフェニル、トリス（２−ｔｅｒｔ−ブチルフェニル）ホスファイト、トリス（２，４−ジｔｅｒｔ−ブチルフェニル）ホスファイト、トリス（２，５−ジｔｅｒｔ−ブチルフェニル）ホスファイト、トリス（２−ｔｅｒｔ−ブチル−４−メチルフェニル）ホスファイト、トリス（２−ｔｅｒｔ−ブチル−５−メチルフェニル）ホスファイト、トリス（２−ｔｅｒｔ−ブチル−４，６−ジメチルフェニル）ホスファイト、トリスノニルフェニルホスファ イト、トリス（モノ及びジノニルフェニル）ホスファ イト、等を挙げることができる。好ましくは、亜リン酸トリフェニル、トリス（２−ｔｅｒｔ−ブチルフェニル）ホスファイト、トリス（２，４−ジｔｅｒｔ−ブチルフェニル）ホスファイト、及びトリス（２，５−ジｔｅｒｔ−ブチルフェニル）ホスファイトが挙げられる。 In the present invention, examples of the triaryl phosphite compound added in the polymerization stage include triphenyl phosphite, tris (2-tert-butylphenyl) phosphite, tris (2,4-ditert-butylphenyl) phosphine. Phyto, Tris (2,5-ditert-butylphenyl) phosphite, Tris (2-tert-butyl-4-methylphenyl) phosphite, Tris (2-tert-butyl-5-methylphenyl) phosphite, Tris (2-tert-butyl-4,6-dimethylphenyl) phosphite, trisnonylphenyl phosphate, tris (mono and dinonylphenyl) phosphate, and the like. Preferably, triphenyl phosphite, tris (2-tert-butylphenyl) phosphite, tris (2,4-ditert-butylphenyl) phosphite, and tris (2,5-ditert-butylphenyl) phosphite Fight is mentioned.
トリアリールホスファイト化合物の添加量には制限はないが、重合に使用する触媒金属原子１モルに対して、通常、０．１〜１０モル、好ましくは０．３〜３モル、より好ましくは０．５〜２モルの範囲で用いる。添加量が０．１モル未満の場合には、溶融時の着色が充分に解消できないことがあり、１０モルを越えると、更に継続して重合を行う場合に分子量が増大せず、着色も逆に著しくなる場合がある。 Although there is no restriction | limiting in the addition amount of a triaryl phosphite compound, Usually, 0.1-10 mol with respect to 1 mol of catalyst metal atoms used for superposition | polymerization, Preferably it is 0.3-3 mol, More preferably, it is 0. Used in the range of 5 to 2 mol. If the amount added is less than 0.1 mol, the coloration at the time of melting may not be sufficiently eliminated. If the amount exceeds 10 mol, the molecular weight does not increase when the polymerization is further continued, and the coloration is also reversed. May become noticeable.
本発明において、グリコール酸共重合体を製造する際にトリアリールホスファイト化合物を添加する時期としては、重合反応によりその重量平均分子量が好ましくは３万以上、より好ましくは５万以上に達した段階である。重量平均分子量が３万未満の段階で添加した場合には、本発明の目的とする着色抑制効果が発揮されない。また、その後の重合速度が低下し、高い分子量を有するグリコール酸共重合体が得られない。 In the present invention, when the triaryl phosphite compound is added when producing the glycolic acid copolymer, the weight average molecular weight is preferably 30,000 or more, more preferably 50,000 or more by the polymerization reaction. It is. When added at a stage where the weight average molecular weight is less than 30,000, the coloring suppression effect intended by the present invention is not exhibited. Further, the subsequent polymerization rate decreases, and a glycolic acid copolymer having a high molecular weight cannot be obtained.
本発明におけるグリコール酸共重合体の製造方法は限定されない。例えば、（Ａ）水及びグリコール酸を含む原料水溶液の、脱水濃縮工程からそれに続く溶融重縮合工程の任意の時点に、予め、金属アルコキシドをヒドロキシカルボン酸の存在下で加水分解して調整した触媒を添加して、溶融重縮合を行い、その重量平均分子量が３万以上に達した段階でトリアリールホスファイト化合物を添加し、グリコール酸共重合体を製造する方法、（Ｂ）水及びヒドロキシカルボン酸を含む重合原料水溶液に金属アルコキシドを添加した後、脱水濃縮工程及び溶融重縮合工程を実施することにより、重合系中において触媒を形成させ、溶融重縮合を行い、その重量平均分子量が３万以上に達した段階でトリアリールホスファイト化合物を添加し、グリコール酸共重合体を製造する方法、（Ｃ）（Ａ）又は（Ｂ
）において、トリアリールホスファイトを添加することなく溶融重縮合を終了後、その重量平均分子量が３万以上に達した溶融ポリマーをペレット状に造粒する工程において、トリアリールホスファイト化合物を添加する方法、（Ｄ）（Ａ）又は（Ｂ）において、トリアリールホスファイトを添加することなく溶融重縮合を終了後、重量平均分子量３万以上の溶融ポリマーを冷却固化し、取り出し、汎用の押出機を用いて、冷却固化させたポリマーにトリアリールホスファイト化合物を添加し再溶融押出後、冷却固化し、所望の固形物、例えば、ペレット状、板状、フィルム状等の固形物にする方法、（Ｅ）（Ｃ）に加えて固相重合を実施する方法等いずれの方法等が挙げられる。
The manufacturing method of the glycolic acid copolymer in this invention is not limited. For example, (A) a catalyst prepared by hydrolyzing a metal alkoxide in the presence of a hydroxycarboxylic acid in advance at any time from a dehydration concentration step to a subsequent melt polycondensation step of a raw material aqueous solution containing water and glycolic acid A process for producing a glycolic acid copolymer by adding a triaryl phosphite compound when the weight average molecular weight reaches 30,000 or more, and (B) water and hydroxycarboxylic acid. After the metal alkoxide is added to the polymerization raw material aqueous solution containing an acid, a dehydration concentration step and a melt polycondensation step are performed to form a catalyst in the polymerization system and perform melt polycondensation, and the weight average molecular weight is 30,000. A method for producing a glycolic acid copolymer by adding a triaryl phosphite compound at the stage of reaching the above, (C) (A) or (B
), After completion of the melt polycondensation without adding a triaryl phosphite, a triaryl phosphite compound is added in the step of granulating the molten polymer having a weight average molecular weight of 30,000 or more into pellets In the method (D) (A) or (B), after completion of the melt polycondensation without adding a triaryl phosphite, a molten polymer having a weight average molecular weight of 30,000 or more is cooled and solidified and taken out. A method of adding a triaryl phosphite compound to a cooled and solidified polymer and remelting and extruding and then cooling and solidifying it into a desired solid, for example, a solid such as a pellet, plate, or film, (E) In addition to (C), any method such as a method for carrying out solid phase polymerization may be used.
以下にグリコール酸共重合体の製造方法の一例について説明する。
原料水溶液を脱水濃縮する工程では、脱水濃縮の条件は制限されるものではないが、例えば、窒素等の不活性ガス雰囲気下、不活性ガス流通下又は減圧下において、温度１００〜１５０℃、好ましくは１００〜１３０℃の範囲、減圧度１３．３〜１０１．３ｋＰａの範囲で、それぞれ多段階に変化させて実施する。このとき、（Ｂ）法のように、原料水溶液中に金属アルコキシドが添加されている場合、脱水濃縮及びこれに続く溶融重縮合工程において金属アルコキシドの加水分解反応を同時に行うことができる。
Below, an example of the manufacturing method of a glycolic acid copolymer is demonstrated.
In the step of dehydrating and concentrating the raw material aqueous solution, the conditions for dehydrating and concentrating are not limited, but for example, under an inert gas atmosphere such as nitrogen, under an inert gas flow or under reduced pressure, a temperature of 100 to 150 ° C., preferably Is carried out in a range of 100 to 130 ° C. and a degree of vacuum of 13.3 to 101.3 kPa, each of which is changed in multiple stages. At this time, when the metal alkoxide is added to the raw material aqueous solution as in the method (B), the hydrolysis reaction of the metal alkoxide can be performed simultaneously in the dehydration concentration and the subsequent melt polycondensation step.
溶融重縮合工程では、例えば、窒素等の不活性ガス雰囲気下、不活性ガス流通下又は減圧下において、反応温度１３０℃〜２２０℃の範囲で多段階に変化させて重縮合を行うことが好ましく、より好ましくは１５０℃〜２００℃の範囲である。重縮合温度が１３０℃未満の場合には、反応速度が遅く、非効率的であり、また高分子量のポリマーが得られないことがある。逆に ２２０℃を越える温度の場合には、ポリマーの着色及び分解、又は環状２量体等の副生物の留出が多くなる。 In the melt polycondensation step, for example, polycondensation is preferably carried out by changing the reaction temperature in a range of 130 ° C. to 220 ° C. in an inert gas atmosphere such as nitrogen, under an inert gas flow or under reduced pressure. More preferably, it is the range of 150 to 200 degreeC. When the polycondensation temperature is less than 130 ° C., the reaction rate is slow and inefficient, and a high molecular weight polymer may not be obtained. On the other hand, when the temperature exceeds 220 ° C., coloring and decomposition of the polymer, or distilling of by-products such as cyclic dimer increases.
本発明における溶融重縮合反応時の減圧度は、通常、１３．３Ｐａ〜６．７ｋＰａ、好ましくは６６．７Ｐａ〜６．０ｋＰａ、最も好ましくは０．４〜５．３ｋＰａの範囲で、多段階に変化させて重縮合を行う。６．７ｋＰａを越える圧力の場合には、重縮合時に発生する水を効率よく除去できない場合があり、１３．３Ｐａ未満の場合には、収率が低下する場合がある。
本発明における溶融重縮合反応の時間は２〜２０時間、好ましくは４〜１５時間の範囲である。２０時間を超えて実施する場合には、ポリマーの着色が生じやすくなる。
The degree of vacuum during the melt polycondensation reaction in the present invention is usually in the range of 13.3 Pa to 6.7 kPa, preferably 66.7 Pa to 6.0 kPa, and most preferably 0.4 to 5.3 kPa. Change the polycondensation. If the pressure exceeds 6.7 kPa, the water generated during polycondensation may not be removed efficiently, and if it is less than 13.3 Pa, the yield may decrease.
The time for the melt polycondensation reaction in the present invention is 2 to 20 hours, preferably 4 to 15 hours. When it is performed over 20 hours, the polymer is likely to be colored.
本発明においては、比較的高い蒸発比表面積が確保できる溶融重合反応装置を利用することにより、溶融重合単独でも高い分子量を有するグリコール酸共重合体を製造することができる。例えば、二軸横型高粘度反応機、塔内にワイヤーや金網等の溶融ポリマー支持体をその構造として保有する高比表面積重合装置を利用する方法等が挙げられる。
溶融重縮合によって製造したポリマーをプレポリマーとして、引き続き固相重合を実施し、着色も少なく、更に高分子量のグリコール酸共重合体を得ることもできる。プレポリマーとは、溶融重縮合により得られた生成物を意味するものであり、これを固相重合に供するまでに冷却固化せしめ、粒子状やペレット状に付形することができる。また、プレポリマーを結晶化させた後に固相重合に供することが好ましい。この結晶化条件を適切に選択することにより、プレポリマー粒子どうしの、固相重合時の融着・凝集を防止できるのみならず、固相重合時の重合反応速度を高めることもできる。
In the present invention, a glycolic acid copolymer having a high molecular weight can be produced even by melt polymerization alone by utilizing a melt polymerization reactor capable of ensuring a relatively high evaporation specific surface area. Examples thereof include a biaxial horizontal high-viscosity reactor and a method using a high specific surface area polymerization apparatus having a molten polymer support such as a wire or a wire mesh in its tower as its structure.
A polymer produced by melt polycondensation can be used as a prepolymer, followed by solid phase polymerization to obtain a high molecular weight glycolic acid copolymer with little coloration. The prepolymer means a product obtained by melt polycondensation, which can be cooled and solidified before being subjected to solid phase polymerization, and shaped into particles or pellets. Moreover, it is preferable to use for a solid phase polymerization after crystallizing a prepolymer. By appropriately selecting the crystallization conditions, it is possible not only to prevent fusion / aggregation of the prepolymer particles during solid phase polymerization but also to increase the polymerization reaction rate during solid phase polymerization.
得られた重合体の付形化の方法には制限はないが、例えば、溶融状態のプレポリマーを不活性ガスや水等の液体と接触させることにより塊状物にした後、粉砕し、粒子状にする方法、溶融状態のプレポリマーを押出機に移し、ペレット化する方法等が利用できる。プレポリマーを粒子状又はペレット状に付形した粒子径としては、結晶化工程や固相重合工程における取り扱い易さや、固相重合における重合速度を考慮して設定すればよいが、例えば、平均粒径が０．１〜１０ｍｍの範囲が好ましい。 There is no limitation on the method of shaping the obtained polymer. For example, the polymer is made into a lump by bringing it into contact with a liquid such as an inert gas or water, and then pulverized to form particles. And a method of transferring the molten prepolymer to an extruder and pelletizing it. The particle size obtained by shaping the prepolymer into particles or pellets may be set in consideration of the ease of handling in the crystallization process and the solid phase polymerization process, and the polymerization rate in the solid phase polymerization. The range whose diameter is 0.1-10 mm is preferable.
結晶化工程における結晶化の方法には制限は無く、公知の方法を利用できる。例えば、冷却固化したプレポリマーを気相中で加熱する方法、プレポリマーを溶解しない液体中で、結晶化温度にて加熱する方法等が挙げられる。
プレポリマーを結晶化させる条件にも制限はないが、例えば、窒素等の不活性ガス雰囲気下、不活性ガス流通下又は減圧下において、結晶化処理温度として、プレポリマーのガラス転移温度以上融点未満の範囲、結晶化時間１０分〜３６０分の範囲が用いられる。
There is no restriction | limiting in the crystallization method in a crystallization process, A well-known method can be utilized. For example, a method of heating the cooled and solidified prepolymer in a gas phase, a method of heating at a crystallization temperature in a liquid that does not dissolve the prepolymer, and the like can be mentioned.
There are no restrictions on the conditions for crystallizing the prepolymer, but, for example, in an inert gas atmosphere such as nitrogen, in an inert gas flow or under reduced pressure, the crystallization temperature is not less than the glass transition temperature of the prepolymer and less than the melting point. And a crystallization time of 10 minutes to 360 minutes is used.
結晶化したプレポリマーは、引き続き固相重合によって高分子量化を行う。 固相重合工程では、反応温度は、通常、結晶化プレポリマーのガラス転移温度以上、融解ピーク温度未満の範囲で実施することができる。
本発明の固相重合は、窒素等の不活性ガス雰囲気下、又は減圧下、更には加圧下で行うこともできる。反応系内の減圧度や反応系内の圧力は、充分に高い重量分子量を有するグリコール酸共重合体が得られる範囲であれば制限されない。
The crystallized prepolymer is subsequently polymerized by solid phase polymerization. In the solid phase polymerization step, the reaction temperature can usually be carried out in the range of not less than the glass transition temperature of the crystallized prepolymer and less than the melting peak temperature.
The solid phase polymerization of the present invention can also be carried out under an inert gas atmosphere such as nitrogen, or under reduced pressure, and further under pressure. The degree of vacuum in the reaction system and the pressure in the reaction system are not limited as long as a glycolic acid copolymer having a sufficiently high weight molecular weight is obtained.
本発明の固相重合で使用する不活性ガス、すなわち、反応系に流通させるガスの具体例としては、窒素ガス、ヘリウムガス、アルゴンガス、キセノンガス、クリプトン ガス等が挙げられる。流通させる不活性ガスに含まれる水分量は、できるだけ低く、実質的に無水状態のガスであることが好ましい。 含水量が多いと固相重合反応で生成した水が効率よく除去できないために重合速度が遅くなる。この場合、ガスをモレキュラーシーブ類やイオン交換樹脂類等を充填した層に通すことにより脱水して使用することができる。流通ガスの含水量を露点で示すと、ガスの露点は−２０℃以下、好ましくは−４０℃以下である。 Specific examples of the inert gas used in the solid phase polymerization of the present invention, that is, the gas to be circulated in the reaction system, include nitrogen gas, helium gas, argon gas, xenon gas, krypton gas and the like. The amount of water contained in the inert gas to be circulated is as low as possible, and is preferably a substantially anhydrous gas. If the water content is high, the water produced by the solid phase polymerization reaction cannot be removed efficiently, and the polymerization rate becomes slow. In this case, the gas can be used after being dehydrated by passing it through a layer filled with molecular sieves or ion exchange resins. When the water content of the circulating gas is indicated by a dew point, the dew point of the gas is −20 ° C. or lower, preferably −40 ° C. or lower.
固相重合反応の時間は５〜２００時間、好ましくは１０〜１２０時間の範囲である。
本発明のグリコール酸共重合体には、本発明の目的を損なわない範囲で、必要に応じて、フェノール系酸化防止剤、チオエーテル系酸化防止剤、紫外線防止剤、ヒンダードアミン系光安定剤、ステアリン酸カルシウム等の脂肪酸金属塩、核剤、可塑剤、他の脂肪族ポリエステル及びその前駆体等を添加することができる。
The time for the solid state polymerization reaction is in the range of 5 to 200 hours, preferably 10 to 120 hours.
In the glycolic acid copolymer of the present invention, a phenolic antioxidant, a thioether antioxidant, an ultraviolet ray inhibitor, a hindered amine light stabilizer, calcium stearate, as necessary, within a range not impairing the object of the present invention. Fatty acid metal salts such as nucleating agents, plasticizers, other aliphatic polyesters and precursors thereof can be added.
以下、本発明を実施例により具体的に説明するが、本発明はこれらの実施例に限定されるものではない。
本発明の各特性値は以下の方法により測定する。
（１）重量平均分子量
東ソ社製ゲルパーミエーションクロマトグラフィー（ＧＰＣ）分析装置８０２０ＧＰＣシステムを用い、以下の条件で求める。使用する溶媒として、予め、８０ｍＭのトリフルオロ酢酸ナトリウムを溶解したヘキサフルオロイソプロパノール（ＨＦＩＰ）を調製しておく。より具体的には、例えば、ＨＦＩＰ１０００ｇに対してトリフルオロ酢酸ナトリウムを６．４８ｇ溶解し調製する。
EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.
Each characteristic value of the present invention is measured by the following method.
(1) Weight average molecular weight Using a gel permeation chromatography (GPC) analyzer 8020GPC system manufactured by Tosoh Corporation, the weight average molecular weight is determined under the following conditions. As a solvent to be used, hexafluoroisopropanol (HFIP) in which 80 mM sodium trifluoroacetate is dissolved is prepared in advance. More specifically, for example, 6.48 g of sodium trifluoroacetate is dissolved in 1000 g of HFIP.
評価用ポリマー試料溶液には、試料２０ｍｇを精秤した後、上記トリフルオロ酢酸ナトリウム含有ＨＦＩＰ３ｇに溶解し、その後、０．２ミクロンのフィルターにて濾過したものを用いる。
測定条件は、カラム温度４０℃、留出速度１ｍｌ／分で実施し、使用するカラム構成としては、ガードカラムとして、ＴｓｋｇｕａｒｄｃｏｌｕｍｎＨＨＲ−Ｌ（登録商標）を使用し、Ｔｓｋｇｅｌ（登録商標）Ｇ５０００ＨＨＲ及びＴｓｋｇｅｌ（登録商標）Ｇ３０００ＨＨＲ（いずれも東ソ社製）からなるものを使用する。
測定値は、予め、ＰＭＭＡ標準物質を用い、ＲＩ検出器による、溶出時間と分子量との関係を示す検量線を作成しておき、評価用ポリマー試料溶液測定時の溶出曲線より重量平
均分子量を求めた値である。
検量線作成に際し、ＰＭＭＡ標準物質として、分子量が１，５７７、０００、６８５，０００、３３３，０００、１００，２５０、６２，６００、２４，３００、１２，７００、４，７００、１，６８０、及び１，１４０のもの（いずれもＰｏｌｙｍｅｒ Ｌａｂｏｒａｔｏｒｉｅｓ社製）を用いる。
As the polymer sample solution for evaluation, 20 mg of a sample is precisely weighed, dissolved in 3 g of HFIP containing sodium trifluoroacetate, and then filtered through a 0.2 micron filter.
The measurement conditions are a column temperature of 40 ° C. and a distillation rate of 1 ml / min. As a column configuration to be used, Tsquardcolumn HHR-L (registered trademark) is used as a guard column, and Tskel (registered trademark) G5000HHR and Tskel ( (Registered trademark) G3000HHR (both manufactured by Tosoh Corporation) is used.
For the measurement value, use a PMMA standard material in advance, create a calibration curve showing the relationship between the elution time and molecular weight using an RI detector, and obtain the weight average molecular weight from the elution curve when measuring the polymer sample solution for evaluation. Value.
When preparing a calibration curve, the molecular weights of 1,577,000, 685,000, 333,000, 100,250, 62,600, 24,300, 12,700, 4,700, 1,680, And 1,140 (both manufactured by Polymer Laboratories) are used.
（２）重合ポリマーの着色度
上記の方法にて重量平均分子量を求める際に、検出器として波長３５０ｎｍに設定したＵＶ検出器ＵＶ８０２０（東ソ社製）を接続し、その際、検出される全カウント数をもって評価する。カウント数が５０未満の場合、得られたポリマーは目視で白色〜淡黄色に相当し、カウント数が５０〜１００の範囲の場合は目視で黄色に相当し、カウント数が１００を越える場合には、得られるポリマーは目視で褐色〜黒褐色に相当する値である。
（３）グリコール酸共重合体中のグリコール酸単位の含有量
試料７０ｍｇを精秤し、ｄ化トリフルオロ酢酸１ｃｃに溶解し、基準物質としてＴＭＳを用い、１Ｈ−ＮＭＲにて測定する。
(2) Coloring degree of polymerized polymer When the weight average molecular weight is determined by the above method, a UV detector UV8020 (manufactured by Tosoh Corporation) set at a wavelength of 350 nm is connected as a detector, and all detected at that time Evaluate with the count. When the count number is less than 50, the obtained polymer visually corresponds to white to pale yellow. When the count number is in the range of 50 to 100, visually corresponds to yellow. When the count number exceeds 100, The obtained polymer has a value corresponding to brown to black brown visually.
(3) Content of glycolic acid unit in glycolic acid copolymer 70 mg of a sample is precisely weighed and dissolved in 1 cc of trifluoroacetic acid d and measured by 1H-NMR using TMS as a reference substance.
（４）再溶融時の熱安定性評価
重合により得られたポリマーを、予め、真空下８０℃で６時間乾燥しておく。予め、窒素置換されたフラスコに所定量のポリマーを窒素気流下にて投入し、攪拌しながら２３０℃に加熱し、溶融させ、溶融した５分後にサンプリングする。重合ポリマーの重量平均分子量及び着色度の評価と同様に上記記載の方法にしたがい、その重量平均分子量及び着色度を評価する。
着色度変化率は、この評価により得られた着色度を、加熱前着色度で除した値を百分率で表した値である。
(4) Thermal stability evaluation during remelting The polymer obtained by polymerization is previously dried at 80 ° C. under vacuum for 6 hours. A predetermined amount of polymer is put into a flask purged with nitrogen in advance under a nitrogen stream, heated to 230 ° C. with stirring, melted, and sampled 5 minutes after melting. The weight average molecular weight and coloring degree are evaluated according to the method described above in the same manner as the evaluation of the weight average molecular weight and coloring degree of the polymer.
The degree of color change is a value obtained by dividing the degree of color obtained by this evaluation by the degree of color before heating, expressed as a percentage.
［実施例１］
攪拌装置及び窒素導入管を備えた１００ｃｃ反応容器に、高純度グリコール酸（６５質量％水溶液；Ｄｕ Ｐｏｎｔ（株）社製グリピア７０（登録商標））及びＬ−乳酸（９０質量％水溶液；和光純薬（株）社製）をそれぞれ９３ｇ及び１１ｇとゲルマニウムテトライソプロポキシドをグリコール酸及び乳酸の合計量１ｇ当たり、０．００３ｍｍｏｌを仕込み、窒素置換を行った。次いで、窒素気流下、常圧、攪拌下にて１３０℃まで昇温し、原料水溶液の濃縮と同時にゲルマニウムテトラｉｓｏ−プロポキシドの加水分解反応を１時間行った。その際、留出物をトラップし、分析した結果、ゲルマニウムテトラｉｓｏ−プロポキシド１ｍｏｌに対して、３．９５ｍｏｌに相当するイソプロパノールを検出した。添加したゲルマニウムテトラｉｓｏ−プロポキシドはほぼ完全に加水分解されているといえる。
[Example 1]
In a 100 cc reaction vessel equipped with a stirrer and a nitrogen introduction tube, high-purity glycolic acid (65% by mass aqueous solution; Glipia 70 (registered trademark) manufactured by Du Pont Co., Ltd.) and L-lactic acid (90% by mass aqueous solution; Wako Jun) Yakuhin Co., Ltd.) (93 g and 11 g) and germanium tetraisopropoxide were charged in an amount of 0.003 mmol per 1 g of the total amount of glycolic acid and lactic acid, followed by nitrogen substitution. Subsequently, the temperature was raised to 130 ° C. under a nitrogen stream under normal pressure and stirring, and a hydrolysis reaction of germanium tetraiso-propoxide was performed for 1 hour simultaneously with the concentration of the raw material aqueous solution. At that time, the distillate was trapped and analyzed, and as a result, isopropanol corresponding to 3.95 mol was detected with respect to 1 mol of germanium tetraiso-propoxide. It can be said that the added germanium tetraiso-propoxide is almost completely hydrolyzed.
その後、常圧のまま、温度を１５０℃に上げ、６０分間保持し、濃縮を完結させた。更に、減圧を開始し、２７ｋＰａにて２０分、更に６．７ｋＰａにて２０分、更に０．４ｋＰａにて２０分保持し、反応を継続したのち、温度を２００℃に昇温させ、４時間重縮合反応を継続させた。
得られたグリコール酸共重合体は、重量平均分子量が２２０００であった。溶融状態のプレポリマーを冷却固化させた後取り出し、加熱された面ヒーターとその内部に内径６５ｍｍ、有効長さ１２０ｍｍのガラスチューブを有する横型回転式ガラスチューブオーブン型反応器（柴田化学（株）製ＧＴＯ−３５０ＲＧ）に得られた重合物を１５ｇ投入し、再溶融させ、回転数５ｒｐｍにて、重合時の圧力が０．４ｋＰａ、重合温度が２００℃の条件にて更に８時間重合を継続させた。その後、トリス（２，４−ジｔｅｒｔ−ブチルフェニル）ホスファイトを０．００３ｍｍｏｌ添加し、１５分反応を継続し、生成物を冷却固化させ、取り出した。得られたグリコール酸共重合体中のグリコール酸単位含有量は８８ｍｏｌ％であった。
Thereafter, while maintaining the normal pressure, the temperature was raised to 150 ° C. and held for 60 minutes to complete the concentration. Further, the pressure reduction was started, and the reaction was continued at 27 kPa for 20 minutes, further at 6.7 kPa for 20 minutes, and further at 0.4 kPa for 20 minutes. After the reaction was continued, the temperature was raised to 200 ° C. for 4 hours. The polycondensation reaction was continued.
The resulting glycolic acid copolymer had a weight average molecular weight of 22,000. The molten prepolymer is cooled and solidified, and then taken out. A horizontal rotary glass tube oven reactor having a heated surface heater and a glass tube having an inner diameter of 65 mm and an effective length of 120 mm (manufactured by Shibata Chemical Co., Ltd.) GTO-350RG) was charged with 15 g of the polymer obtained, remelted, and the polymerization was continued for another 8 hours at a rotation speed of 5 rpm, at a polymerization pressure of 0.4 kPa, and at a polymerization temperature of 200 ° C. It was. Thereafter, 0.003 mmol of tris (2,4-ditert-butylphenyl) phosphite was added, and the reaction was continued for 15 minutes to cool and solidify the product. The glycolic acid unit content in the resulting glycolic acid copolymer was 88 mol%.
得られたポリマーの重量平均分子量は１３９，０００、ポリマーの着色度は１７であった。得られたポリマーの再溶融時の熱安定性を評価した結果、重量平均分子量が１１２，０００、ポリマーの着色度変化率は１５９％、着色度は２７であった。
重合条件、製造された重合体の特性及び熱安定性評価結果を、以下の実施例及び比較例の結果と共に表１に示す。
The weight average molecular weight of the obtained polymer was 139,000, and the coloration degree of the polymer was 17. As a result of evaluating the thermal stability of the obtained polymer during remelting, the weight average molecular weight was 112,000, the rate of change in the degree of coloration of the polymer was 159%, and the degree of coloration was 27.
Table 1 shows the polymerization conditions, the properties of the produced polymer, and the thermal stability evaluation results together with the results of the following examples and comparative examples.
［比較例１］
トリス（２，４−ジｔｅｒｔ−ブチルフェニル）ホスファイトを添加しない以外は実施例１と同様に重合し、得られたポリマーを用いて溶融安定性を評価した。
得られたポリマーの重量平均分子量は１２９，０００、ポリマーの着色度は１７であった。得られたポリマーの再溶融時の熱安定性を評価した結果、重量平均分子量が７４，０００、ポリマーの着色度変化率は７４１％、着色度は１２６であった。
[Comparative Example 1]
Polymerization was conducted in the same manner as in Example 1 except that tris (2,4-ditert-butylphenyl) phosphite was not added, and melt stability was evaluated using the obtained polymer.
The weight average molecular weight of the obtained polymer was 129,000, and the degree of coloration of the polymer was 17. As a result of evaluating the thermal stability at the time of remelting of the obtained polymer, the weight average molecular weight was 74,000, the degree of color change of the polymer was 741%, and the degree of coloration was 126.
［比較例２］
トリス（２，４−ジｔｅｒｔ−ブチルフェニル）ホスファイトを添加する時期として、実施例１と同様に、１００ｃｃ反応容器にて２００℃にて４時間重縮合して重量平均分子量が２２０００に達した時点で添加した。添加後、更に１５分間重縮合を継続させる以外は実施例１と同様に重合を行い、得られたポリマーの溶融安定性を評価した。
得られたポリマーの重量平均分子量は４９，０００、ポリマーの着色度は３２であった。得られたポリマーの再溶融時の熱安定性を評価した結果、重量平均分子量が３４，０００、ポリマーの着色度変化率は１７５％、着色度は５６であった。
このように、重合初期にトリアリールホスファイトを添加した場合には、重合度の上昇が著しく遅くなり、より高分子量のグリコール酸共重合体を製造しようとする場合においては、好ましくなく実用的ではない。
[Comparative Example 2]
As the timing for adding tris (2,4-ditert-butylphenyl) phosphite, the polycondensation was carried out for 4 hours at 200 ° C. in a 100 cc reaction vessel in the same manner as in Example 1, and the weight average molecular weight reached 22,000. Added at the time. Polymerization was carried out in the same manner as in Example 1 except that polycondensation was continued for 15 minutes after the addition, and the melt stability of the obtained polymer was evaluated.
The weight average molecular weight of the obtained polymer was 49,000, and the degree of coloration of the polymer was 32. As a result of evaluating the thermal stability of the obtained polymer at the time of remelting, the weight average molecular weight was 34,000, the degree of color change of the polymer was 175%, and the degree of coloration was 56.
Thus, when triaryl phosphite is added at the initial stage of polymerization, the increase in the degree of polymerization is remarkably slow, and it is not preferable and practical in the case of producing a higher molecular weight glycolic acid copolymer. Absent.
［実施例２］
トリス（２，４−ジｔｅｒｔ−ブチルフェニル）ホスファイトに変えて亜リン酸トリフェニルを使用した以外は実施例１と同様に重合し、得られたポリマーを用いて溶融安定性を評価した。
[Example 2]
Polymerization was conducted in the same manner as in Example 1 except that triphenyl phosphite was used instead of tris (2,4-ditert-butylphenyl) phosphite, and melt stability was evaluated using the obtained polymer.
［比較例３］
実施例１において使用する重縮合触媒として三酸化アンチモンを使用した以外は実施例１と同様に重合した。得られたポリマーは、重量平均分子量が７５，０００、ポリマーの着色度は２３４と高かった。
このように、ポリエステルの重合において汎用に利用される三酸化アンチモンを使用した場合には、それなりの重縮合触媒性能が認められたが、得られるポリマーの着色が著しく、実用には耐えないものであった。
[Comparative Example 3]
Polymerization was conducted in the same manner as in Example 1 except that antimony trioxide was used as the polycondensation catalyst used in Example 1. The obtained polymer had a weight average molecular weight of 75,000 and the coloration degree of the polymer was as high as 234.
In this way, when using antimony trioxide, which is widely used in the polymerization of polyester, a certain degree of polycondensation catalyst performance was observed, but the resulting polymer was remarkably colored and could not stand practical use. there were.
［実施例３］
実施例１で得られたプレポリマー０．５ｇを、予め、１３０℃にて５時間結晶化させたのち、ガラスウールを充填したガラスＵ管内に仕込んだ。更に上部にもガラスウールを充填した後、固相重合温度１７０℃にて、窒素ガス流量として０．２ＮＬ／分にて１０時間固相重合を実施した。
[Example 3]
After 0.5 g of the prepolymer obtained in Example 1 was previously crystallized at 130 ° C. for 5 hours, it was charged into a glass U tube filled with glass wool. Further, glass wool was filled in the upper part, and then solid phase polymerization was carried out at a solid phase polymerization temperature of 170 ° C. and a nitrogen gas flow rate of 0.2 NL / min for 10 hours.
［実施例４〜８］
ゲルマニウムテトラｉｓｏ−プロポキシドに変えて、表１に示すようにそれぞれ、マグネシウムエトキシド、鉄トリエトキシド、アンチモントリｉｓｏ−プロポキシド、錫エトキシド、ハフニウムテトラｔｅｒｔ−ブトキシドに変更し、更に亜リン酸トリフェニルの添加量を表１に示すように変更した以外は実施例２と同様に重合を行い、溶融安定性の評
価を実施した。
[Examples 4 to 8]
In place of germanium tetraiso-propoxide, as shown in Table 1, magnesium ethoxide, iron triethoxide, antimony triiso-propoxide, tin ethoxide, hafnium tetratert-butoxide, and triphenyl phosphite were further changed. Polymerization was carried out in the same manner as in Example 2 except that the amount of addition was changed as shown in Table 1, and the melt stability was evaluated.
［実施例９及び１０］
ゲルマニウムテトラｉｓｏ−プロポキシドに替えて、それぞれ、ランタントリｉｓｏ−プロポキシド及びサマリウムトリｉｓｏ−プロポキシドを用い、更にトリアリールホスファイト化合物として、トリスノリルフェニルホスファイトに変更した以外は実施例１と同様に重合を行った。ランタントリｉｓｏ−プロポキシド及びサマリウムトリｉｓｏ−プロポキシドは特開平７−４８３０１号公報に記載された方法に準じて調製した。
[Examples 9 and 10]
Example 1 and Example 1 except that lanthanum triiso-propoxide and samarium triiso-propoxide were used instead of germanium tetraiso-propoxide, respectively, and the triaryl phosphite compound was changed to trisnorylphenyl phosphite. Polymerization was carried out in the same manner. Lanthanum triiso-propoxide and samarium triiso-propoxide were prepared according to the method described in JP-A-7-48301.
［比較例４］
実施例１において使用する重縮合触媒としてチタンテトラｉｓｏ−プロポキシドを使用した以外は実施例１と同様に重合を行った。
溶融重合により得られたポリマーは、重量平均分子量が７５，０００、ポリマーの着色度の指標であるＵＶ検出器による全カウント数は２５６であった。
本発明の請求の範囲記載以外の金属アルコキシドの代表例であるチタンテトラｉｓｏ−プロポキシドを使用した場合には、それなりの重縮合触媒性能が認められたが、得られるポリマーの着色が著しく、実用には耐えないものであった。
[Comparative Example 4]
Polymerization was carried out in the same manner as in Example 1 except that titanium tetraiso-propoxide was used as the polycondensation catalyst used in Example 1.
The polymer obtained by melt polymerization had a weight average molecular weight of 75,000 and a total count of 256 by a UV detector, which is an index of the degree of coloration of the polymer.
When titanium tetraiso-propoxide, which is a representative example of metal alkoxides other than those described in the claims of the present invention, was used, some polycondensation catalyst performance was observed, but the resulting polymer was remarkably colored and practically used. It was unbearable.
［比較例５］
トリス（２，４−ジｔｅｒｔ−ブチルフェニル）ホスファイトに替えてモノステアリルアシッドホスフェートを使用した以外は実施例１と同様に重合し、得られたポリマーを用いて溶融安定性を評価した。
[Comparative Example 5]
Polymerization was conducted in the same manner as in Example 1 except that monostearyl acid phosphate was used in place of tris (2,4-ditert-butylphenyl) phosphite, and melt stability was evaluated using the obtained polymer.
［比較例６］
トリス（２，４−ジｔｅｒｔ−ブチルフェニル）ホスファイトに替えて２，２−メチレンビス（４，６−ジｔｅｒｔ−ブチルフェニル）オクチルホスファイトを使用した以外は実施例１と同様に重合し、得られたポリマーを用いて溶融安定性を評価した。
[Comparative Example 6]
Polymerization was conducted in the same manner as in Example 1 except that 2,2-methylenebis (4,6-ditert-butylphenyl) octyl phosphite was used instead of tris (2,4-ditert-butylphenyl) phosphite. Melt stability was evaluated using the obtained polymer.
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| KR101775727B1 (en) * | 2010-12-15 | 2017-09-19 | 가톨릭대학교 산학협력단 | Polyalkylenglycol-linker-polyester copolymer, method preparing the same and usage thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1060137A (en) * | 1996-04-30 | 1998-03-03 | Kureha Chem Ind Co Ltd | Polyglycolic acid sheet and process for preparing the same |
| JPH11116666A (en) * | 1997-10-13 | 1999-04-27 | Kureha Chem Ind Co Ltd | Production of polyglycolic acid |
| JP4090299B2 (en) * | 2002-07-11 | 2008-05-28 | 旭化成ケミカルズ株式会社 | Method for producing glycolic acid copolymer |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1060137A (en) * | 1996-04-30 | 1998-03-03 | Kureha Chem Ind Co Ltd | Polyglycolic acid sheet and process for preparing the same |
| JPH11116666A (en) * | 1997-10-13 | 1999-04-27 | Kureha Chem Ind Co Ltd | Production of polyglycolic acid |
| JP4090299B2 (en) * | 2002-07-11 | 2008-05-28 | 旭化成ケミカルズ株式会社 | Method for producing glycolic acid copolymer |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101775727B1 (en) * | 2010-12-15 | 2017-09-19 | 가톨릭대학교 산학협력단 | Polyalkylenglycol-linker-polyester copolymer, method preparing the same and usage thereof |
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