JP6563948B2 - ポリエステル及びポリエステルを調製するための方法 - Google Patents
ポリエステル及びポリエステルを調製するための方法 Download PDFInfo
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- JP6563948B2 JP6563948B2 JP2016556833A JP2016556833A JP6563948B2 JP 6563948 B2 JP6563948 B2 JP 6563948B2 JP 2016556833 A JP2016556833 A JP 2016556833A JP 2016556833 A JP2016556833 A JP 2016556833A JP 6563948 B2 JP6563948 B2 JP 6563948B2
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- Prior art keywords
- polycondensation
- polyester
- ethylene glycol
- end groups
- reaction
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- 229920000728 polyester Polymers 0.000 title claims description 110
- 238000000034 method Methods 0.000 title claims description 53
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 183
- CHTHALBTIRVDBM-UHFFFAOYSA-N furan-2,5-dicarboxylic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)O1 CHTHALBTIRVDBM-UHFFFAOYSA-N 0.000 claims description 120
- 238000006068 polycondensation reaction Methods 0.000 claims description 83
- 238000005886 esterification reaction Methods 0.000 claims description 66
- 239000000203 mixture Substances 0.000 claims description 60
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 53
- 230000032050 esterification Effects 0.000 claims description 47
- 239000003054 catalyst Substances 0.000 claims description 42
- 150000001732 carboxylic acid derivatives Chemical group 0.000 claims description 38
- 150000002148 esters Chemical class 0.000 claims description 27
- 238000006243 chemical reaction Methods 0.000 claims description 24
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 15
- 230000008018 melting Effects 0.000 claims description 15
- 238000002844 melting Methods 0.000 claims description 15
- 238000002360 preparation method Methods 0.000 claims description 12
- DVVGBNZLQNDSPA-UHFFFAOYSA-N 3,6,11-trioxabicyclo[6.2.1]undeca-1(10),8-diene-2,7-dione Chemical group O=C1OCCOC(=O)C2=CC=C1O2 DVVGBNZLQNDSPA-UHFFFAOYSA-N 0.000 claims description 9
- 238000004821 distillation Methods 0.000 claims description 9
- 238000000113 differential scanning calorimetry Methods 0.000 claims description 8
- 229910052787 antimony Inorganic materials 0.000 claims description 7
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- 239000010936 titanium Substances 0.000 claims description 5
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- 239000011135 tin Substances 0.000 claims description 4
- 229910052718 tin Inorganic materials 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- 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 claims description 3
- 238000002835 absorbance Methods 0.000 claims description 3
- 238000006116 polymerization reaction Methods 0.000 description 31
- 239000002245 particle Substances 0.000 description 29
- -1 2,5-disubstituted furans Chemical class 0.000 description 23
- 239000000047 product Substances 0.000 description 20
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- 238000002474 experimental method Methods 0.000 description 17
- 229920000642 polymer Polymers 0.000 description 17
- 239000007790 solid phase Substances 0.000 description 16
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 13
- 239000000463 material Substances 0.000 description 13
- 239000007787 solid Substances 0.000 description 13
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- DNXDYHALMANNEJ-UHFFFAOYSA-N furan-2,3-dicarboxylic acid Chemical compound OC(=O)C=1C=COC=1C(O)=O DNXDYHALMANNEJ-UHFFFAOYSA-N 0.000 description 10
- 150000005690 diesters Chemical class 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 9
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- 238000005809 transesterification reaction Methods 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- 239000011572 manganese Substances 0.000 description 7
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- 229920000139 polyethylene terephthalate Polymers 0.000 description 7
- 239000005020 polyethylene terephthalate Substances 0.000 description 7
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 7
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 7
- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 6
- 238000005481 NMR spectroscopy Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- OJURWUUOVGOHJZ-UHFFFAOYSA-N methyl 2-[(2-acetyloxyphenyl)methyl-[2-[(2-acetyloxyphenyl)methyl-(2-methoxy-2-oxoethyl)amino]ethyl]amino]acetate Chemical compound C=1C=CC=C(OC(C)=O)C=1CN(CC(=O)OC)CCN(CC(=O)OC)CC1=CC=CC=C1OC(C)=O OJURWUUOVGOHJZ-UHFFFAOYSA-N 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 6
- 238000004448 titration Methods 0.000 description 6
- DGJKAGRTYAPHJB-UHFFFAOYSA-N O=C1OCCOC(=O)C2=C1C=CO2 Chemical compound O=C1OCCOC(=O)C2=C1C=CO2 DGJKAGRTYAPHJB-UHFFFAOYSA-N 0.000 description 5
- 229910019142 PO4 Inorganic materials 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
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- 229910052500 inorganic mineral Inorganic materials 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
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- 238000005453 pelletization Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- 238000010923 batch production Methods 0.000 description 4
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- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000002667 nucleating agent Substances 0.000 description 4
- 239000010452 phosphate Substances 0.000 description 4
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- 239000000243 solution Substances 0.000 description 4
- 239000007858 starting material Substances 0.000 description 4
- 239000012808 vapor phase Substances 0.000 description 4
- 229920001634 Copolyester Polymers 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 125000005907 alkyl ester group Chemical group 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 150000001991 dicarboxylic acids Chemical class 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
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- 229920000554 ionomer Polymers 0.000 description 3
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- 150000004702 methyl esters Chemical group 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
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- 239000000376 reactant Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- SMNDYUVBFMFKNZ-UHFFFAOYSA-N 2-furoic acid Chemical compound OC(=O)C1=CC=CO1 SMNDYUVBFMFKNZ-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 239000007848 Bronsted acid Substances 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 2
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
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- 125000001931 aliphatic group Chemical group 0.000 description 2
- 150000004703 alkoxides Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229910000410 antimony oxide Inorganic materials 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 150000007942 carboxylates Chemical class 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
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- 230000006837 decompression Effects 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 150000007517 lewis acids Chemical class 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 description 2
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 2
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
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- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 description 2
- ZHROMWXOTYBIMF-UHFFFAOYSA-M sodium;1,3,7,9-tetratert-butyl-11-oxido-5h-benzo[d][1,3,2]benzodioxaphosphocine 11-oxide Chemical compound [Na+].C1C2=CC(C(C)(C)C)=CC(C(C)(C)C)=C2OP([O-])(=O)OC2=C1C=C(C(C)(C)C)C=C2C(C)(C)C ZHROMWXOTYBIMF-UHFFFAOYSA-M 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
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- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
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- FTLYMKDSHNWQKD-UHFFFAOYSA-N (2,4,5-trichlorophenyl)boronic acid Chemical class OB(O)C1=CC(Cl)=C(Cl)C=C1Cl FTLYMKDSHNWQKD-UHFFFAOYSA-N 0.000 description 1
- YAPRWCFMWHUXRS-UHFFFAOYSA-N (2-hydroxyphenyl) propanoate Chemical compound CCC(=O)OC1=CC=CC=C1O YAPRWCFMWHUXRS-UHFFFAOYSA-N 0.000 description 1
- QPFMBZIOSGYJDE-ZDOIIHCHSA-N 1,1,2,2-tetrachloroethane Chemical class Cl[13CH](Cl)[13CH](Cl)Cl QPFMBZIOSGYJDE-ZDOIIHCHSA-N 0.000 description 1
- PIYNPBVOTLQBTC-UHFFFAOYSA-N 1-[8-propyl-2,6-bis(4-propylphenyl)-4,4a,8,8a-tetrahydro-[1,3]dioxino[5,4-d][1,3]dioxin-4-yl]ethane-1,2-diol Chemical compound O1C2C(CCC)OC(C=3C=CC(CCC)=CC=3)OC2C(C(O)CO)OC1C1=CC=C(CCC)C=C1 PIYNPBVOTLQBTC-UHFFFAOYSA-N 0.000 description 1
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 1
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- SDXXELNGBQBZDM-UHFFFAOYSA-N 3,4-bis(2-hydroxyethyl)furan-2,5-dicarboxylic acid Chemical compound OCCC=1C(CCO)=C(C(O)=O)OC=1C(O)=O SDXXELNGBQBZDM-UHFFFAOYSA-N 0.000 description 1
- HORNXRXVQWOLPJ-UHFFFAOYSA-N 3-chlorophenol Chemical compound OC1=CC=CC(Cl)=C1 HORNXRXVQWOLPJ-UHFFFAOYSA-N 0.000 description 1
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- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
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- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
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- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
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- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 description 1
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- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- OEYIOHPDSNJKLS-UHFFFAOYSA-N choline Chemical compound C[N+](C)(C)CCO OEYIOHPDSNJKLS-UHFFFAOYSA-N 0.000 description 1
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- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 238000001212 derivatisation Methods 0.000 description 1
- JVLRYPRBKSMEBF-UHFFFAOYSA-K diacetyloxystibanyl acetate Chemical compound [Sb+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JVLRYPRBKSMEBF-UHFFFAOYSA-K 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- FXJUUMGKLWHCNZ-UHFFFAOYSA-N dimethyl furan-2,3-dicarboxylate Chemical compound COC(=O)C=1C=COC=1C(=O)OC FXJUUMGKLWHCNZ-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
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- UAUDZVJPLUQNMU-KTKRTIGZSA-N erucamide Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-KTKRTIGZSA-N 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000005350 fused silica glass Substances 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 125000006289 hydroxybenzyl group Chemical group 0.000 description 1
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- CRGZYKWWYNQGEC-UHFFFAOYSA-N magnesium;methanolate Chemical compound [Mg+2].[O-]C.[O-]C CRGZYKWWYNQGEC-UHFFFAOYSA-N 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000002074 melt spinning Methods 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- FTQWRYSLUYAIRQ-UHFFFAOYSA-N n-[(octadecanoylamino)methyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCNC(=O)CCCCCCCCCCCCCCCCC FTQWRYSLUYAIRQ-UHFFFAOYSA-N 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 150000002895 organic esters Chemical class 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000012785 packaging film Substances 0.000 description 1
- 229920006280 packaging film Polymers 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920006149 polyester-amide block copolymer Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 230000000284 resting effect Effects 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 229940037312 stearamide Drugs 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000003856 thermoforming Methods 0.000 description 1
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- YNJBWRMUSHSURL-UHFFFAOYSA-N trichloroacetic acid Chemical compound OC(=O)C(Cl)(Cl)Cl YNJBWRMUSHSURL-UHFFFAOYSA-N 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 description 1
- 239000003039 volatile agent Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/80—Solid-state polycondensation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
- C08G63/86—Germanium, antimony, or compounds thereof
- C08G63/866—Antimony or compounds thereof
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Organic Chemistry (AREA)
- Polyesters Or Polycarbonates (AREA)
Description
ヒドロキシル末端基(HEG) = 5494 * 4.0ppmでの積分/2;
脱炭酸末端基(DecarbEG) = 5494 * 7.65ppmでの積分。
エステル末端基(EEG) = 5494 * 3.97ppmでの積分/3
として算出する。
固有粘度(IV) = {ηrel -1+3*ln(ηrel)}/(4*c)
を使用して、固有粘度を算出する。
エステル化ポテンシャル(EsPo) = (MR-1)2 * PH2O(T)、式中、MRは、エチレングリコールの2,5-フランジカルボン酸に対するモル比を表し、MRは1より大きく;
PH2O(T)は、温度Tにおける水の純粋成分蒸気圧(単位bar)を表し、この温度は、圧力が低減されて前重縮合段階に入る前のエステル化混合物における最終反応温度である。PH2Oは、純水の蒸気圧について確立された式に従って決定される。アントワン式
log10 P = A - B/(C + T)、式中、Tは、℃で表されるエステル化の終了時の温度であり、A = 5.2594、B = 1810.94及びC = 244.485は、純水の所要蒸気圧をbarで記す。重縮合物についての最良の結果は、エステル化ポテンシャルが、0.8以下、好ましくは0.05から0.5である場合に得られることが分かった。
本発明によるポリエステルの調製を示すために、複数の重合を行った。
実施例1の手順を、異なるMEG/FDCA比及び異なる温度を用いて繰り返した。各反応混合物は、80ppmのTEAOH (0.09mmol/molのFDCA)も含んでいた。実施例1よりも幾分高いIVが得られるまで、重縮合反応を続けた。相対CEGをCEG/(CEG + HEG)として決定した。条件及び結果を表2に示す。
0.61dL/gのIV、0.30の相対CEG比、及び25meq/kgの絶対CEG含有量を有する、上記の実施例2の実験7からの重縮合物を、その温度を125℃に増大させ、約1時間にわたって保持することによって結晶化し、その後、材料を冷却し、あらゆる凝集体を破壊した。次いで、材料を170℃に加熱し、約3時間にわたって保持し、続いて、195℃に温度傾斜(12.5℃/時の速度で)させ、約12時間にわたって保持した。このようにして得られた材料は、DSCによって決定される通り、204℃のピーク融点及び50J/gの結晶化度を呈した。材料を回転真空タンブル乾燥機に装填し、真空下で190〜195℃に加熱した。チップを周期的にサンプリングし、結果を以下の表3に示した。表中、固有粘度(IV)、ピーク融点(Tピーク)及び結晶化度(dHm)は、タンブル乾燥機への装填時並びにタンブル乾燥機内で13及び50時間後のものがそれぞれ示されている。
FDCAベースのポリマーは、FDCAのジメチルエステル及びエチレングリコールを1:2.0のモル比で含む出発混合物から出発し、エステル交換触媒としての120ppmの亜鉛(アセテートとして添加)及びエステル化のための300ppmのアンチモン(グリコレートとして添加)の存在下で、調製した。この実験は、WO 2013/120989の教示によるものである。エステル交換中に、形成されたメタノールを除去し、あらゆる蒸発したエチレングリコールを反応混合物に再生利用した。エステル交換を、210℃以下で2時間にわたって続けた。2時間後に得られた混合物を、減圧、並びに390から530mbar及び210℃の温度で2時間にわたる前重縮合に、その後、2mbar未満の圧力及び240℃の温度で4時間にわたる重縮合に供した。溶融重合後、材料は、0.33dL/gのIV、0.05未満の相対CEG比及び9meq/kgの絶対CEG含有量を有していた。メチルエステル含有量は、13meq/kgであった。HEG含有量は、200meq/kgより大きかった。比較的低い分子量のポリエステルを得るためのプロセスには、8時間超を要したように思われた。
エチレングリコール(MEG)及び2,5-フランジカルボン酸(FDCA)を、1.12のMEG:FDCAモル比で、アンチモン300ppmで存在する触媒としてのSb2O3とともに混合した。混合物は、80ppm (0.09mmol/mol FDCA)のTEAOHも含有していた。混合物を、エステル化触媒の添加なしに、時間(te)の期間にわたって昇温でエステル化に供した。形成された水を蒸発させ、蒸留カラムに入れた。凝縮水を除去し、同伴している又は蒸発したあらゆるMEGを、反応混合物に戻して再生利用した。フランジカルボン酸送給に対して理論水の40%が収集されるまで、反応を大気圧で続けた。そのときの温度は211℃であり、反応時間は130分であった。蒸留カラムに通過させることなく、あらゆる追加のエチレングリコールを除去できるように、この時点で真空テイクオフ点を切り替えた。圧力を低減させ、前重縮合を開始し、圧力はおよそ44分で20mbarに到達した。圧力を更に低減させて、5mbar未満とした。エステル組成物を触媒とともに、260℃の温度で追加の210分にわたって重縮合に供した。固有粘度(IV)は0.30dL/gであった。CEG含有量は260meq/kgであり、HEGは30meq/kg未満であると推定され、0.90超の相対CEG比が得られた。
第一連の実験において、FDCAのジエステルと比較して大きい過剰のエチレングリコールを持つFDCAのジメチルエステルから調製したポリエステルを使用して、精製されたビス(2-ヒドロキシエチル)-2,5-フランジカルボキシレートを調製した。これを、重縮合触媒としての300ppmのアンチモンの存在下で重縮合に供して、0.42dl/gのIVに対応する約15,000の数平均分子量(Mn)を持つポリ(エチレン-2,5-フランジカルボキシレート)を産出した。ポリエステルにおけるカルボン酸末端基(CEG)の量は10meq/kg未満であると評価され、ヒドロキシル末端基(HEG)の量は160meq/kg超であると評価された。CEG/(CEG+HEG)として表される相対含有率は、0.06未満であった。ポリエステルを、異なる粒径範囲の二つの画分に分割した。画分を、約200℃の温度で最大8時間の間、固相重合に供した。各画分について、重合中にMnを決定し、式IV (dL/g) = 1.62*10-4*Mn0.820を使用して同等物IVを決定した。結果を表5.1に示す。
Claims (18)
- エチレン2,5-フランジカルボキシレート単位を含むポリエステルであって、少なくとも0.45dL/gの固有粘度を有し、カルボン酸末端基のモル量をヒドロキシル末端基及びカルボン酸末端基のモル量の和で割った割合として表されるカルボン酸末端基の相対含有率が、0.10から0.70の範囲内である、ポリエステル。
- 1.0dl/g以下、好ましくは0.45から0.75dL/gの範囲内の固有粘度を有する、請求項1に記載のポリエステル。
- 前記カルボン酸末端基の相対含有率が、0.14から0.65の範囲内である、請求項1又は2に記載のポリエステル。
- 前記カルボン酸末端基の量が、15から122meq/kgの範囲内である、請求項1から3のいずれか一項に記載のポリエステル。
- 400nmでジクロロメタン:ヘキサフルオロイソプロパノール 8:2(vol/vol)混合物中の30mg/mL溶液として測定される吸光度が、0.08以下である、請求項1から4のいずれか一項に記載のポリエステル。
- 1.9から2.6の範囲内の多分散指数を有する、請求項1から5のいずれか一項に記載のポリエステル。
- 示差走査熱量測定(DSC)によって測定される結晶化度が、少なくとも25J/gである、請求項1から6のいずれか一項に記載のポリエステル。
- 少なくとも215℃の融点を有する、請求項7に記載のポリエステル。
- 水分含有量が、100ppmw以下である、請求項1から8のいずれか一項に記載のポリエステルを含む組成物。
- ポリエステルの調製のための方法であって、
2,5-フランジカルボン酸及びエチレングリコールを含む出発混合物をエステル化に供してエステル組成物を形成し、ここで、出発混合物中における2,5-フランジカルボン酸のエチレングリコールに対するモル比が1:1.01から1:1.15であり、
得られたエステル組成物を重縮合触媒の存在下、減圧下での重縮合に供して重縮合物を得、
2,5-フランジカルボン酸とエチレングリコールとの反応中に形成された水及びいくらかのエチレングリコールを蒸留システムにおいて除去し、
水とともに除去されたエチレングリコールを水から分離し、少なくとも部分的に再生利用する、
方法。 - 2,5-フランジカルボン酸とエチレングリコールとの間のエステル化反応が、160から240℃の温度及び0.9から5barの圧力で、0.5から4時間の間行われる、請求項10に記載の方法。
- 前記重縮合が、20から700mbarの圧力で行われる前重縮合反応及び0.05から20mbarの圧力で行われる重縮合反応を含む、請求項10又は11に記載の方法。
- 前記前重縮合及び重縮合反応の合わせた期間が、1.5から4時間の範囲内である、請求項12に記載の方法。
- 前記重縮合工程中に、形成されるエチレングリコールをエステル組成物から除去し、これを重縮合に供する、請求項10から13のいずれか一項に記載の方法。
- 前記重縮合工程が、重縮合触媒の存在下で行われる、請求項10から14のいずれか一項に記載の方法。
- 前記重縮合触媒が、スズ、亜鉛、チタン及びアンチモンから選択される1種又は複数の元素を含む触媒から選択される、請求項15に記載の方法。
- 前記重縮合が、245から270℃の温度及び0.05から5mbarの圧力で行われる、請求項10から16のいずれか一項に記載の方法。
- 前記重縮合物が、90から200℃の範囲内の温度で結晶化される、請求項10から17のいずれか一項に記載の方法。
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US20190202977A1 (en) | 2016-09-16 | 2019-07-04 | Micromidas, Inc. | Polymers and methods of producing thereof |
WO2018067007A1 (en) | 2016-10-05 | 2018-04-12 | Furanix Technologies B.V. | Process for the production of a solid-state polymerized poly (tetramethylene-2, 5-furan dicarboxylate) polymer and polymer thus produce |
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MY181276A (en) | 2020-12-21 |
TR201811203T4 (tr) | 2018-08-27 |
EP3116934B1 (en) | 2018-06-27 |
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CA2941238A1 (en) | 2015-09-17 |
WO2015137807A1 (en) | 2015-09-17 |
AU2015230099B2 (en) | 2016-12-15 |
AU2015230099A1 (en) | 2016-10-06 |
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