CN113956452A - Hydrolytically degradable high-gas barrier copolyester, and preparation method and application thereof - Google Patents
Hydrolytically degradable high-gas barrier copolyester, and preparation method and application thereof Download PDFInfo
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- CN113956452A CN113956452A CN202111488417.3A CN202111488417A CN113956452A CN 113956452 A CN113956452 A CN 113956452A CN 202111488417 A CN202111488417 A CN 202111488417A CN 113956452 A CN113956452 A CN 113956452A
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- acid
- dihydric alcohol
- gas barrier
- hydrolytically degradable
- esterified product
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- 229920001634 Copolyester Polymers 0.000 title claims abstract description 80
- 230000004888 barrier function Effects 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 46
- 125000003118 aryl group Chemical group 0.000 claims abstract description 39
- 239000002253 acid Substances 0.000 claims abstract description 36
- 125000004122 cyclic group Chemical group 0.000 claims abstract description 24
- -1 cyclic diol Chemical class 0.000 claims abstract description 15
- OTLDLKLSNZMTTA-UHFFFAOYSA-N octahydro-1h-4,7-methanoindene-1,5-diyldimethanol Chemical compound C1C2C3C(CO)CCC3C1C(CO)C2 OTLDLKLSNZMTTA-UHFFFAOYSA-N 0.000 claims abstract description 15
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 9
- HIHKYDVSWLFRAY-UHFFFAOYSA-N thiophene-2,3-dicarboxylic acid Chemical compound OC(=O)C=1C=CSC=1C(O)=O HIHKYDVSWLFRAY-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims description 85
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 67
- 239000000047 product Substances 0.000 claims description 61
- 239000003054 catalyst Substances 0.000 claims description 60
- 239000007789 gas Substances 0.000 claims description 58
- 150000002148 esters Chemical group 0.000 claims description 56
- 238000006068 polycondensation reaction Methods 0.000 claims description 50
- 230000032050 esterification Effects 0.000 claims description 46
- 238000005886 esterification reaction Methods 0.000 claims description 46
- QEVGZEDELICMKH-UHFFFAOYSA-N Diglycolic acid Chemical compound OC(=O)COCC(O)=O QEVGZEDELICMKH-UHFFFAOYSA-N 0.000 claims description 40
- 239000001361 adipic acid Substances 0.000 claims description 33
- 235000011037 adipic acid Nutrition 0.000 claims description 33
- 238000010438 heat treatment Methods 0.000 claims description 32
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 27
- 239000013067 intermediate product Substances 0.000 claims description 23
- 239000003381 stabilizer Substances 0.000 claims description 22
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 21
- 239000012298 atmosphere Substances 0.000 claims description 19
- 238000001816 cooling Methods 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 17
- 230000001681 protective effect Effects 0.000 claims description 14
- 150000002009 diols Chemical class 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 9
- QWGRWMMWNDWRQN-UHFFFAOYSA-N 2-methylpropane-1,3-diol Chemical compound OCC(C)CO QWGRWMMWNDWRQN-UHFFFAOYSA-N 0.000 claims description 8
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 8
- OEIJHBUUFURJLI-UHFFFAOYSA-N octane-1,8-diol Chemical compound OCCCCCCCCO OEIJHBUUFURJLI-UHFFFAOYSA-N 0.000 claims description 8
- INSRQEMEVAMETL-UHFFFAOYSA-N decane-1,1-diol Chemical compound CCCCCCCCCC(O)O INSRQEMEVAMETL-UHFFFAOYSA-N 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 6
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 claims description 6
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 claims description 6
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical compound CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 6
- 239000010936 titanium Substances 0.000 claims description 6
- 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 claims description 6
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims description 5
- 229910052732 germanium Inorganic materials 0.000 claims description 5
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 5
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 claims description 5
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 239000007943 implant Substances 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000005022 packaging material Substances 0.000 claims description 4
- ASMQGLCHMVWBQR-UHFFFAOYSA-M diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(=O)([O-])OC1=CC=CC=C1 ASMQGLCHMVWBQR-UHFFFAOYSA-M 0.000 claims description 3
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 claims description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 claims description 3
- 229940005657 pyrophosphoric acid Drugs 0.000 claims description 3
- 239000004254 Ammonium phosphate Substances 0.000 claims description 2
- KKUKTXOBAWVSHC-UHFFFAOYSA-N Dimethylphosphate Chemical compound COP(O)(=O)OC KKUKTXOBAWVSHC-UHFFFAOYSA-N 0.000 claims description 2
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 2
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 2
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 2
- KUMNEOGIHFCNQW-UHFFFAOYSA-N diphenyl phosphite Chemical compound C=1C=CC=CC=1OP([O-])OC1=CC=CC=C1 KUMNEOGIHFCNQW-UHFFFAOYSA-N 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims description 2
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 claims description 2
- 239000012974 tin catalyst Substances 0.000 claims 2
- JDRJCBXXDRYVJC-UHFFFAOYSA-N OP(O)O.N.N.N Chemical compound OP(O)O.N.N.N JDRJCBXXDRYVJC-UHFFFAOYSA-N 0.000 claims 1
- 230000015556 catabolic process Effects 0.000 abstract description 18
- 238000006731 degradation reaction Methods 0.000 abstract description 18
- 230000003301 hydrolyzing effect Effects 0.000 abstract description 7
- 238000006065 biodegradation reaction Methods 0.000 abstract description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 36
- 229920000728 polyester Polymers 0.000 description 19
- 229910052757 nitrogen Inorganic materials 0.000 description 18
- 230000009477 glass transition Effects 0.000 description 12
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 10
- 229920001577 copolymer Polymers 0.000 description 10
- 229920000642 polymer Polymers 0.000 description 10
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 239000012299 nitrogen atmosphere Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 229910002092 carbon dioxide Inorganic materials 0.000 description 6
- CYUGNCLRGFKPAE-UHFFFAOYSA-N dimethyl thiophene-2,5-dicarboxylate Chemical compound COC(=O)C1=CC=C(C(=O)OC)S1 CYUGNCLRGFKPAE-UHFFFAOYSA-N 0.000 description 5
- YCGAZNXXGKTASZ-UHFFFAOYSA-N thiophene-2,5-dicarboxylic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)S1 YCGAZNXXGKTASZ-UHFFFAOYSA-N 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 230000035699 permeability Effects 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- OEOIWYCWCDBOPA-UHFFFAOYSA-N 6-methyl-heptanoic acid Chemical compound CC(C)CCCCC(O)=O OEOIWYCWCDBOPA-UHFFFAOYSA-N 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 description 3
- 229920000123 polythiophene Polymers 0.000 description 3
- 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 3
- 238000005809 transesterification reaction Methods 0.000 description 3
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 2
- IHLDFUILQQSDCQ-UHFFFAOYSA-L C(C)(=O)[O-].[Ge+2].C(C)(=O)[O-] Chemical compound C(C)(=O)[O-].[Ge+2].C(C)(=O)[O-] IHLDFUILQQSDCQ-UHFFFAOYSA-L 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- UDSFAEKRVUSQDD-UHFFFAOYSA-N Dimethyl adipate Chemical compound COC(=O)CCCCC(=O)OC UDSFAEKRVUSQDD-UHFFFAOYSA-N 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 2
- 108090000790 Enzymes Proteins 0.000 description 2
- 229920000954 Polyglycolide Polymers 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 2
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 2
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229920006280 packaging film Polymers 0.000 description 2
- 239000012785 packaging film Substances 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 239000008055 phosphate buffer solution Substances 0.000 description 2
- 229920001610 polycaprolactone Polymers 0.000 description 2
- 239000004632 polycaprolactone Substances 0.000 description 2
- 239000004633 polyglycolic acid Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- ZWWLLYJRPKYTDF-UHFFFAOYSA-N thiophene-3,4-dicarboxylic acid Chemical compound OC(=O)C1=CSC=C1C(O)=O ZWWLLYJRPKYTDF-UHFFFAOYSA-N 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- 229940035437 1,3-propanediol Drugs 0.000 description 1
- 229940043375 1,5-pentanediol Drugs 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- JWOWBYUGDZGIAQ-UHFFFAOYSA-N C(CCC)(O)O.C(CCCCC(=O)O)(=O)O.C(C=1C(C(=O)OCCCCCCCC)=CC=CC1)(=O)OCCCCCCCC Chemical compound C(CCC)(O)O.C(CCCCC(=O)O)(=O)O.C(C=1C(C(=O)OCCCCCCCC)=CC=CC1)(=O)OCCCCCCCC JWOWBYUGDZGIAQ-UHFFFAOYSA-N 0.000 description 1
- 239000004367 Lipase Substances 0.000 description 1
- 102000004882 Lipase Human genes 0.000 description 1
- 108090001060 Lipase Proteins 0.000 description 1
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical group C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 229920003232 aliphatic polyester Polymers 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- PTIXVVCRANICNC-UHFFFAOYSA-N butane-1,1-diol;hexanedioic acid Chemical compound CCCC(O)O.OC(=O)CCCCC(O)=O PTIXVVCRANICNC-UHFFFAOYSA-N 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- FOTKYAAJKYLFFN-UHFFFAOYSA-N decane-1,10-diol Chemical compound OCCCCCCCCCCO FOTKYAAJKYLFFN-UHFFFAOYSA-N 0.000 description 1
- PJZOOQHKDLZCMD-UHFFFAOYSA-N diethyl thiophene-3,4-dicarboxylate Chemical compound CCOC(=O)C1=CSC=C1C(=O)OCC PJZOOQHKDLZCMD-UHFFFAOYSA-N 0.000 description 1
- MEPFISOQOOJNJL-UHFFFAOYSA-N dimethyl thiophene-3,4-dicarboxylate Chemical compound COC(=O)C1=CSC=C1C(=O)OC MEPFISOQOOJNJL-UHFFFAOYSA-N 0.000 description 1
- LQRUPWUPINJLMU-UHFFFAOYSA-N dioctyl(oxo)tin Chemical compound CCCCCCCC[Sn](=O)CCCCCCCC LQRUPWUPINJLMU-UHFFFAOYSA-N 0.000 description 1
- CTCOPPBXAFHGRB-UHFFFAOYSA-N ethanolate;germanium(4+) Chemical compound [Ge+4].CC[O-].CC[O-].CC[O-].CC[O-] CTCOPPBXAFHGRB-UHFFFAOYSA-N 0.000 description 1
- 229940119177 germanium dioxide Drugs 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 229940051250 hexylene glycol Drugs 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 235000019421 lipase Nutrition 0.000 description 1
- KUCRTUQUAYLJDC-UHFFFAOYSA-N methyl 2-(2-methoxy-2-oxoethoxy)acetate Chemical compound COC(=O)COCC(=O)OC KUCRTUQUAYLJDC-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- REOJLIXKJWXUGB-UHFFFAOYSA-N mofebutazone Chemical group O=C1C(CCCC)C(=O)NN1C1=CC=CC=C1 REOJLIXKJWXUGB-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- WCVRQHFDJLLWFE-UHFFFAOYSA-N pentane-1,2-diol Chemical compound CCCC(O)CO WCVRQHFDJLLWFE-UHFFFAOYSA-N 0.000 description 1
- 239000005014 poly(hydroxyalkanoate) Substances 0.000 description 1
- 239000004626 polylactic acid Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000010512 thermal transition Effects 0.000 description 1
Images
Classifications
-
- 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
- C08G63/64—Polyesters containing both carboxylic ester groups and carbonate groups
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
- C08L69/005—Polyester-carbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/06—Biodegradable
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/14—Gas barrier composition
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Biological Depolymerization Polymers (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention discloses a hydrolytically degradable high-gas barrier copolyester, a preparation method and application thereof. The structural formula of the hydrolytically degradable high gas barrier copolyester is as follows:
wherein R is1Is a structural unit of bio-based aromatic dibasic acid, R2、R3、R4The structural unit is cyclic dihydric alcohol or a combination of aliphatic dihydric alcohol and cyclic dihydric alcohol, x, y and z are integers of 1-10, and m is an integer of 15-150; the bio-based aromatic dibasic acid comprises thiophenedicarboxylic acid; the cyclic diol comprises any one or more of tricyclodecanedimethanol, tricyclodecanediol and tetracyclodiolCombinations of (a) and (b). The copolyester prepared by the invention has excellent comprehensive performance, can be subjected to biodegradation and hydrolytic degradation, has excellent gas barrier property, mechanical property, heat resistance and the like, and has wide application prospect.
Description
Technical Field
The invention relates to polyester, in particular to hydrolytically degradable high-gas barrier copolyester and a preparation method and application thereof, and belongs to the technical field of high polymer materials.
Background
Common degradable polyesters such as polyglycolic acid (PGA), polylactic acid (PLA), Polycaprolactone (PCL), Polyhydroxyalkanoate (PHA), and the like all belong to aliphatic polyesters, and although the degradation performance of these polyesters is good, the mechanical properties, gas barrier properties, heat resistance, and the like are poor. It is reported in the literature that polyesters based on aromatic diacids have very excellent gas barrier properties, and the presence of aromatic structures can impart better mechanical and heat resistance properties to the polyesters. Meanwhile, the literature also proves that polyesters based on aromatic dibasic acids are often well biodegraded under severe conditions of enzymes, bacteria and the like, and are difficult to hydrolytically degrade under mild aqueous conditions. At present, no report on hydrolytically degradable high gas barrier polyesters is available.
Disclosure of Invention
The invention mainly aims to provide a hydrolytically degradable high-gas-barrier copolyester, a preparation method and application thereof, so as to overcome the defects of poor mechanical property, gas-barrier property, heat resistance and the like of the existing degradable polyester. In addition, the introduction of the aromatic structure can also endow the copolymer with excellent mechanical property, gas barrier property and heat resistance.
In order to achieve the purpose, the invention adopts the following technical scheme:
some embodiments of the present invention provide a hydrolytically degradable high gas barrier copolyester having the following structural formula (I):
wherein R is1Is a structural unit of bio-based aromatic dibasic acid, R2、R3、R4The structural unit is cyclic dihydric alcohol or a combination of aliphatic dihydric alcohol and cyclic dihydric alcohol, x, y and z are integers of 1-10, and m is an integer of 15-150;
the bio-based aromatic dibasic acid comprises thiophenedicarboxylic acid;
the cyclic dihydric alcohol comprises any one or the combination of more than two of tricyclodecanedimethanol, tricyclodecanediol and tetracyclodiol, and the aliphatic dihydric alcohol comprises any one or the combination of more than two of ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, 2-methyl-1, 3-propanediol, neopentyl glycol, octanediol and decanediol.
Some embodiments of the present invention provide a method of preparing a hydrolytically degradable high gas barrier copolyester comprising:
(1) uniformly mixing bio-based aromatic dibasic acid and/or an esterified product thereof, adipic acid and/or an esterified product thereof, diglycolic acid and/or an esterified product thereof, dihydric alcohol and an esterification or ester exchange catalyst to obtain a first mixed reaction system, wherein the molar ratio of the adipic acid and/or the esterified product thereof to the diglycolic acid and/or the esterified product thereof is 20-80: 80-20;
(2) under a protective atmosphere, carrying out esterification or ester exchange reaction on the first mixed reaction system at 140-230 ℃, and obtaining a first intermediate product after the esterification or ester exchange reaction is finished;
(3) carrying out polycondensation reaction on a second mixed reaction system containing the first intermediate product, a polycondensation catalyst and a stabilizer under a vacuum condition at 200-295 ℃ to obtain the hydrolytically degradable high-gas barrier copolyester;
alternatively, the preparation method comprises:
(i) uniformly mixing bio-based aromatic dibasic acid and/or an esterified product thereof, adipic acid and/or an esterified product thereof, diglycolic acid and/or an esterified product thereof, dihydric alcohol, an esterification or ester exchange catalyst, a polycondensation catalyst and a stabilizer to obtain a third mixed reaction system, wherein the molar ratio of the adipic acid and/or the esterified product thereof to the diglycolic acid and/or the esterified product thereof is 20-80: 80-20;
(ii) carrying out esterification or ester exchange reaction on the third mixed reaction system at 140-230 ℃ under a protective atmosphere to obtain a second intermediate product;
(iii) carrying out polycondensation reaction on the second intermediate product at 200-295 ℃ under a vacuum condition to obtain the hydrolytically degradable high-gas-barrier copolyester;
wherein the bio-based aromatic dibasic acid and/or the esterified product thereof comprises thiophene dicarboxylic acid and/or an esterified product thereof;
the dihydric alcohol comprises a cyclic dihydric alcohol, or a combination of a fatty dihydric alcohol and a cyclic dihydric alcohol;
the cyclic diol comprises any one or the combination of more than two of tricyclodecane dimethanol, tricyclodecane diol and tetracyclic diol; the aliphatic diol comprises any one or the combination of more than two of ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, 2-methyl-1, 3-propanediol, neopentyl glycol, octanediol and decanediol.
Embodiments of the present invention also provide a composition for synthesizing a hydrolytically degradable high gas barrier copolyester, comprising:
a component (a) comprising a bio-based aromatic dibasic acid and/or an esterified product thereof;
component (b) comprising adipic acid and/or an esterified product thereof;
component (c) comprising diglycolic acid and/or an esterified product thereof; and
component (d), comprising a glycol,
wherein the bio-based aromatic dibasic acid and/or the esterified product thereof comprises thiophene dicarboxylic acid and/or an esterified product thereof;
the dihydric alcohol comprises a cyclic dihydric alcohol, or a combination of a fatty dihydric alcohol and a cyclic dihydric alcohol;
the cyclic dihydric alcohol comprises any one or the combination of more than two of tricyclodecanedimethanol, tricyclodecanediol and tetracyclodiol, and the aliphatic dihydric alcohol comprises any one or the combination of more than two of ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, 2-methyl-1, 3-propanediol, neopentyl glycol, octanediol and decanediol.
Some embodiments of the present invention also provide uses of the hydrolytically degradable high gas barrier copolyesters, such as in the fields of making packaging materials (e.g., packaging bags, packaging films, etc.), containers (e.g., shopping bags), mulching films, structural members, body implants, and the like.
Compared with the prior art, the invention has the beneficial effects that:
1) the selected bio-based aromatic dibasic acid or the ester thereof contains the sulfur heteroatom, has the structural specificity of the cross axis asymmetry, can ensure that the prepared polyester has excellent gas barrier property, has good hydrophilic property due to ether bond contained in the molecular structure of the diglycolic acid, and can obviously improve the hydrophilicity of the polyester by introducing the diglycolic acid into the molecular chain segment of the polyester. Therefore, the polyester can be biodegraded and can be hydrolyzed and degraded;
2) the cyclic dihydric alcohol is introduced into the copolyester, different cyclic dihydric alcohols can play different roles, and different cyclic dihydric alcohols can be introduced according to requirements to adjust the mechanical property, the heat resistance and the like of the copolyester so as to obtain a copolyester product with excellent comprehensive properties;
3) the diglycolic acid and the adipic acid are used in a combined mode, so that the hydrolytic degradation capability of the polymer can be maintained, and the degradation rate can be controlled to prevent the mechanical property and other losses from being too fast due to too fast degradation.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings needed to be used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments described in the present application, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is a stress-strain plot of a hydrolytically degradable high gas barrier copolyester prepared in example 1 of the present invention;
FIG. 2 is a DSC plot of a hydrolytically degradable high gas barrier copolyester prepared according to example 1 of the present invention.
Detailed Description
As described above, in view of the defects of the prior art, the inventors of the present invention have made extensive studies and extensive practices to propose a technical solution of the present invention. The present invention will be more fully understood from the following detailed description, which should be read in conjunction with the accompanying drawings. Detailed embodiments of the present invention are disclosed herein; however, it is to be understood that the disclosed embodiments are merely exemplary of the invention, which can be embodied in various forms. Therefore, specific functional details disclosed herein are not to be interpreted as limiting, but merely as a basis for the claims and as a representative basis for teaching one skilled in the art to variously employ the present invention in virtually any appropriately detailed embodiment.
The technical solution, its implementation and principles, etc. will be further explained as follows.
One aspect of the embodiments of the present invention provides a hydrolytically degradable high gas barrier copolyester having the following structural formula (I):
wherein R is1Is a structural unit of bio-based aromatic dibasic acid, R2、R3、R4The structural unit is cyclic diol or a combination of aliphatic diol and cyclic diol, x, y and z are integers of 1-10, and m is an integer of 15-150.
Wherein R is as defined above2、R3、R4The selection of the kind of (A) is not limited herein, and may be the same or different.
In some embodiments, the bio-based aromatic diacid may include, but is not limited to, thiophenedicarboxylic acid.
One aspect of the embodiments of the present invention provides a method for preparing a hydrolytically degradable high gas barrier copolyester, comprising:
(1) uniformly mixing bio-based aromatic dibasic acid and/or an esterified product thereof, adipic acid and/or an esterified product thereof, diglycolic acid and/or an esterified product thereof, dihydric alcohol and an esterification or ester exchange catalyst to obtain a first mixed reaction system, wherein the molar ratio of the adipic acid and/or the esterified product thereof to the diglycolic acid and/or the esterified product thereof is 20-80: 80-20;
(2) under a protective atmosphere, carrying out esterification or ester exchange reaction on the first mixed reaction system at 140-230 ℃, and obtaining a first intermediate product after the esterification or ester exchange reaction is finished;
(3) and carrying out polycondensation reaction on a second mixed reaction system containing the first intermediate product, a polycondensation catalyst and a stabilizer under a vacuum condition at 200-295 ℃ to obtain the hydrolytically degradable high-gas-barrier copolyester.
Another aspect of the embodiments of the present invention provides a method for preparing the hydrolytically degradable high gas barrier copolyester, comprising:
(i) uniformly mixing bio-based aromatic dibasic acid and/or an esterified product thereof, adipic acid and/or an esterified product thereof, diglycolic acid and/or an esterified product thereof, dihydric alcohol, an esterification or ester exchange catalyst, a polycondensation catalyst and a stabilizer to obtain a third mixed reaction system, wherein the molar ratio of the adipic acid and/or the esterified product thereof to the diglycolic acid and/or the esterified product thereof is 20-80: 80-20;
(ii) carrying out esterification or ester exchange reaction on the third mixed reaction system at 140-230 ℃ under a protective atmosphere to obtain a second intermediate product;
(iii) and carrying out polycondensation reaction on the second intermediate product at 200-295 ℃ under a vacuum condition to obtain the hydrolytically degradable high-gas-barrier copolyester.
The diglycolic acid selected by the invention is derived from biomass raw materials and can be prepared in a green way, and the hydrophilicity of the polyester can be obviously improved by introducing the diglycolic acid into a molecular chain segment of the copolyester because ether bonds contained in the molecular structure of the diglycolic acid have good hydrophilic performance. Therefore, the diglycolic acid-based polyester can be subjected to biodegradation and hydrolytic degradation without adding other substances such as enzyme, bacteria and the like.
The preparation principle of the invention is as follows: the introduction of diglycolic acid obviously improves the degradation performance of the polymer, not only can hydrolysis degradation occur in a short time, but also the biodegradation rate is greatly improved, the mechanical properties and the like of the polymer can be weakened gradually along with the degradation, and if the mechanical properties are weakened to a certain degree, the practicability of the polymer is lost. Therefore, a balance between the degradation performance and practical performance such as mechanical properties is required. It is well known that the structure of adipic acid can impart a certain biodegradability to polymers, but does not have a hydrolytic degradability. The experimental data show that the degradation rate of the polyester containing the adipic acid structure is much slower than that of the polymer containing the diglycolic acid structure. Therefore, the combination of adipic acid and/or its ester, diglycolic acid and/or its ester can be used simultaneously, not only the hydrolytic degradation capability of the polymer can be maintained, but also the degradation rate can be controlled, so as to prevent the mechanical property and the like from being lost too fast due to too fast degradation.
In some embodiments, the bio-based aromatic dibasic acid and/or its ester includes, but is not limited to, thiophenedicarboxylic acid and/or its ester.
In some more specific embodiments, the bio-based aromatic dibasic acid and/or the ester thereof comprises a structure represented by any one or a combination of two of the following formulas:
wherein R is a hydrogen atom or a carbon chain with the carbon number not more than 4.
For example, the bio-based aromatic dibasic acid and/or the esterified compound thereof may preferably be 2, 5-thiophenedicarboxylic acid, dimethyl 2, 5-thiophenedicarboxylate, 3, 4-thiophenedicarboxylic acid, dimethyl 3, 4-thiophenedicarboxylate, or the like, but is not limited thereto.
The selected bio-based aromatic dibasic acid can be prepared from biomass raw materials, and the use of the bio-based aromatic dibasic acid can gradually reduce the dependence of polyester materials on petrochemical resources and reduce the burden of the petrochemical resources. In addition, the bio-based aromatic dibasic acid contains sulfur heteroatom and has asymmetric structure specificity in the transverse axis, so that the polyester based on the aromatic dibasic acid has more excellent gas barrier property than the traditional polyester based on terephthalic acid.
In some embodiments, the diol comprises a cyclic diol, or a combination of both a cyclic diol and a fatty diol.
Further, the aliphatic diol includes any one or a combination of two or more of ethylene glycol, propylene glycol, butylene glycol, pentylene glycol, hexylene glycol, 2-methyl-1, 3-propanediol, neopentyl glycol, octanediol, decanediol, and the like, but is not limited thereto.
In some embodiments, the cyclic diol includes any one or a combination of two of tricyclodecane dimethanol, tricyclodecane diol, tetracyclic diol, and the like, but is not limited thereto, and the specific structure may be as shown in the following formula:
the invention introduces the cyclic dihydric alcohol into the copolyester, or the combination of aliphatic dihydric alcohol and cyclic dihydric alcohol, different cyclic dihydric alcohols can play different roles, for example, tricyclodecanedimethanol and tricyclodecanediol contain three five-membered ring structures, have greater rigidity, play a better role in improving tensile modulus, tensile strength and heat resistance, and can destroy the crystallization of the polymer and improve the transparency of the polymer; the tetracyclic diol contains four aliphatic rings, and has more alicyclic rings than tricyclodecanediol and tricyclodecanedimethanol, so that the adjustment of the comprehensive properties of the polymer, such as heat resistance, crystallization property, mechanical property and the like, can be better realized. Specifically, different cyclic diols can be introduced according to the needs to adjust the mechanical property, heat resistance and the like of the copolymer, so as to obtain a copolyester product with excellent comprehensive properties.
In some embodiments, in step (1) or step (i), the molar ratio of the combination of the bio-based aromatic dibasic acid and/or its ester, adipic acid and/or its ester and diglycolic acid and/or its ester to the diol is 1: 1.2-3.0.
In some embodiments, the first transesterification catalyst is added in an amount of 0.01 to 0.5% of the theoretical mass of the first intermediate product.
Further, the addition amount of the esterification or ester exchange catalyst is 0.01-0.5% of the theoretical mass of the hydrolytically degradable high-gas barrier copolyester.
In some embodiments, in step (3) or step (i), the mass of the polycondensation catalyst is 0.01 to 0.5% of the theoretical mass of the hydrolytically degradable high gas barrier copolyester, and the mass of the stabilizer is 0.01 to 0.5% of the theoretical mass of the hydrolytically degradable high gas barrier copolyester.
In some embodiments, the method of making comprises: in the step (2), under a protective atmosphere, the first mixed reaction system is subjected to esterification or ester exchange reaction for 1.5-6.0 h at 140-230 ℃, and a first intermediate product is formed after the esterification or ester exchange reaction is finished.
Further, the preparation method comprises the following steps: in the step (3), the second mixed reaction system is vacuumized to be below 30Pa, and then gradually heated to 200-295 ℃ for polycondensation reaction for 2.0-10.0 h, so as to obtain the hydrolytically degradable high-gas barrier copolyester.
In some embodiments, the method of making comprises: in the step (ii), under a protective atmosphere, the third mixed reaction system is subjected to esterification or ester exchange reaction at 140-230 ℃ for 1.5-6.0 h, and a second intermediate product is formed after the esterification or ester exchange reaction is finished.
Further, in the step (iii), the reaction system containing the second intermediate product is vacuumized to be below 30Pa, and then gradually heated to 200-295 ℃ for polycondensation reaction for 2.0-10.0 hours, so as to obtain the hydrolytically degradable high-gas barrier copolyester.
Further, in the step (3) or the step (iii), the vacuum is pumped to below 30Pa at room temperature, the temperature is gradually increased to 200-295 ℃ for polycondensation reaction, and the vacuum is continuously pumped to keep the vacuum not to exceed 30Pa in the whole polycondensation process.
As a more preferable embodiment, both of the step (2) and the step (ii) further comprise: and after the reaction is finished, reducing the temperature to room temperature, and then keeping the temperature in a protective atmosphere for 1.0-5.0 h. According to the preparation method, after the esterification or ester exchange reaction is finished, the temperature is reduced to room temperature under the action of protective atmosphere and is kept for a period of time, and the room temperature is vacuumized to be below 30Pa and then is heated to the polycondensation temperature, compared with the traditional process without a cooling step and high-temperature vacuumization, the cooling rate is 1-50 ℃/min to be reduced to the room temperature, the lower the cooling rate is, the more perfect the crystallization of the product can be, in addition, the side reactions of high-temperature oxidation and the like of the product can be avoided, and the colorless or white high-quality product can be obtained.
In some more specific embodiments, the preparation method of the hydrolytically degradable high gas barrier copolyester specifically comprises the following steps:
(1) uniformly mixing bio-based aromatic dibasic acid and/or an esterified product thereof, adipic acid and/or an esterified product thereof, diglycolic acid and/or an esterified product thereof, dihydric alcohol and an esterification or ester exchange catalyst to form a first mixed reaction system;
(2) carrying out ester exchange reaction on the first mixed reaction system at 140-230 ℃ for 1.5-6.0 h under the protection of nitrogen or inert atmosphere, reducing the temperature to room temperature at a cooling rate of 1-50 ℃/min after the ester exchange reaction is finished, and keeping the temperature for 1.0-5.0 h under the protection of nitrogen or inert atmosphere to obtain a first intermediate product;
(3) and uniformly mixing the first intermediate product, a polycondensation catalyst and a stabilizer to form a second mixed reaction system, vacuumizing to below 30Pa, gradually heating to 200-295 ℃ to perform polycondensation for 2.0-10.0 hours to obtain the hydrolytically degradable high-gas barrier copolyester, and continuously vacuumizing to keep the vacuum in the whole polycondensation process not to exceed 30 Pa.
In some more specific embodiments, the preparation method of the hydrolytically degradable high gas barrier copolyester specifically comprises the following steps:
(i) uniformly mixing bio-based aromatic dibasic acid and/or an esterified product thereof, adipic acid and/or an esterified product thereof, diglycolic acid and/or an esterified product thereof, dihydric alcohol, an esterification or ester exchange catalyst, a polycondensation catalyst and a stabilizer to form a third mixed reaction system;
(ii) under the protection of nitrogen or inert atmosphere, carrying out esterification or ester exchange reaction on the third mixed reaction system at 140-230 ℃ for 1.5-6.0 hours, reducing the temperature to room temperature at a cooling rate of 1-50 ℃/min after the reaction is finished, and keeping the temperature for 1.0-5.0 hours under the protection of nitrogen or inert atmosphere to obtain a second intermediate product;
(iii) and (3) vacuumizing the reaction system containing the second intermediate product to below 30Pa at room temperature, gradually heating to 200-295 ℃ for polycondensation reaction for 2.0-10.0 hours to obtain the hydrolytically degradable high-gas barrier copolyester, and continuously vacuumizing to keep the vacuum in the whole polycondensation process not to exceed 30 Pa.
In some embodiments, the transesterification catalyst is selected from a combination of one or more of a titanium-based catalyst, a tin-based catalyst, a germanium-based catalyst, and the like, but is not limited thereto.
In some embodiments, the polycondensation catalyst is selected from the group consisting of one or more combinations of titanium-based catalysts, tin-based catalysts, germanium-based catalysts, and the like, but is not limited thereto.
Further, the titanium-based catalyst includes any one or a combination of two or more of tetrabutyl titanate, isopropyl titanate, titanium dioxide, an inorganic supported titanium catalyst, and the like, but is not limited thereto.
Further, the tin-based catalyst includes any one or a combination of two or more of dibutyltin oxide, stannous isooctanoate, monobutyl triisooctanoate, dioctyltin oxide, and the like, but is not limited thereto.
Further, the germanium-based catalyst includes any one or a combination of two or more of germanium dioxide, germanium acetate, germanium tetraethoxide, and the like, but is not limited thereto.
In some embodiments, the stabilizer is selected from the group consisting of phosphorous acid, hypophosphorous acid, pyrophosphoric acid, ammonium phosphate, trimethyl phosphate, dimethyl phosphate, triphenyl phosphate, diphenyl phosphate, triphenyl phosphite, diphenyl phosphite, ammonium dihydrogen phosphate, and the like, without limitation.
Yet another aspect of an embodiment of the present invention provides a composition for preparing a hydrolytically degradable high gas barrier copolyester of the preceding embodiments, comprising:
a component (a) comprising a bio-based aromatic dibasic acid and/or an esterified product thereof;
component (b) comprising adipic acid and/or an esterified product thereof;
component (c) comprising diglycolic acid and/or an esterified product thereof; and
component (d), comprises a glycol.
The bio-based aromatic dibasic acid and/or its ester, diol, etc. are defined as described above.
Another aspect of the embodiments of the present invention also provides the use of the hydrolytically degradable high gas barrier copolyester, for example, in the field of preparing packaging materials (such as packaging bags, packaging films, etc.), containers (such as shopping bags), mulching films, structural members, human body implants, etc.
The technical solutions of the present invention will be described in further detail below with reference to several preferred embodiments and accompanying drawings, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention. The experimental procedures, in which specific conditions are not noted in the following examples, are generally carried out under conventional conditions or conditions recommended by the manufacturers.
In the following examples, thermal transition properties were carried out using a differential scanning calorimeter (Mettler Toledo DSC)Test, N2The temperature range of the atmosphere is-100-300 ℃, and the heating rate is 10 ℃/min.
In the following examples, mechanical properties were measured in a Zwick i 1kN type universal material tester, and the specimens were 20.0mm in length, 2.0mm in width, 1.0mm in thickness and 20mm/min in tensile speed.
In the following examples, Labthink VAC-V2 was used to determine the barrier properties for oxygen and carbon dioxide, respectively as CO2And O2Is used as air source, and is tested under the conditions of 23 deg.C and 50% RH, sample size phi is 97mm, and permeation area is 38.5cm2。
In the following examples, hydrolytic degradation and biodegradation tests were carried out using a phosphate buffer solution and a phosphate buffer solution containing 0.2mg/ml of lipase as degradation solvents, respectively, at a constant temperature of 37 ℃ and samples having a length of 20mm, a width of 20mm and a thickness of 0.5mm were measured.
Example 1
Putting 2, 5-thiophenedicarboxylic acid, adipic acid, diglycolic acid and tricyclodecanedimethanol into a reactor according to the molar ratio of 40: 30: 150, simultaneously adding tetrabutyl titanate with the theoretical mass of 0.1% of copolyester as an esterification catalyst and a polycondensation catalyst, gradually heating to 180 ℃ under the protection of nitrogen, carrying out esterification or ester exchange reaction for 5.0h, reducing the temperature to room temperature at the cooling rate of 10 ℃/min after finishing, keeping the temperature in a nitrogen atmosphere, adding trimethyl phosphate with the theoretical mass of 0.1% of copolyester as a stabilizer into the reactor, vacuumizing to 10Pa, gradually heating to 245 ℃, continuously vacuumizing to keep the vacuum degree of a reaction system lower than 10Pa, carrying out polycondensation reaction for 4.0h, and obtaining the hydrolyzable and degradable high-gas barrier copolyester with the structure shown as formula (II).
Wherein x, y and z are integers of 1-10, and m is an integer of 15-150.
The hydrolytically degradable high gas barrier material obtained in this example was testedThe polyester was white, had a tensile modulus of 438.3MPa, a tensile strength of 31.4MPa, an elongation at break of 171%, a glass transition temperature of 40.7 ℃ and CO2Permeability coefficient of 3.65X 10-11cm3·cm/cm2·s·cmHg，O2Permeability coefficient of 9.6X 10-12cm3·cm/cm2s.cmHg is either biodegradable or hydrolytically degradable.
Method for preparing hydrolytically degradable high gas barrier copolyesters1On an H-NMR spectrum, a peak H (2H) on a thiophene ring is at 7.66ppm, a peak H (4H) on a methylene group close to a carbonyl group in adipic acid is at 2.24ppm, a peak H (4H) on two methylene groups in the middle of the adipic acid is at 1.48ppm, a peak H (4H) on diglycolic acid is at 4.14ppm, a peak H (4H) connected with a hydroxyl group on tricyclodecanedimethanol is at 3.09-3.25 ppm, and a peak H (4H) on a tricyclodecanedimethanol aliphatic ring is at 0.77-2.35 ppm.
The stress-strain curve of the hydrolytically degradable high gas barrier copolyester obtained in this example is shown in fig. 1.
The DSC curve of the hydrolytically degradable high gas barrier copolyester obtained in this example is shown in FIG. 2.
Example 2
Putting the combination of 2, 5-thiophenedicarboxylic acid, adipic acid, diglycolic acid, 1, 4-butanediol and tricyclodecanedimethanol into a reactor according to the molar ratio of 40: 36: 24: 290: 10, simultaneously adding tetrabutyl titanate with 0.05 percent of the theoretical mass of the copolyester as an esterification catalyst and a polycondensation catalyst, gradually heating to 190 ℃ under the protection of nitrogen, carrying out esterification or ester exchange reaction for 5.0h, reducing the temperature to room temperature at the cooling rate of 15 ℃/min after the reaction is finished, then keeping the temperature in a nitrogen atmosphere, adding trimethyl phosphate with 0.12 percent of the theoretical mass of the copolyester as a stabilizer into the reactor, then vacuumizing to 5Pa, gradually heating to 200 ℃, continuously vacuumizing to keep the vacuum degree of the reaction system lower than 5Pa, carrying out polycondensation reaction for 3.5h, and obtaining the hydrolytically degradable high-gas barrier copolyester after the reaction is finished, the structure is shown in formula (III).
Wherein x, y, z, u, v and w are integers of 1-10, and m is an integer of 15-150.
The hydrolytically degradable high gas barrier copolymer obtained in this example was found to be white in color, to have a tensile modulus of 207.3MPa, a tensile strength of 21.8MPa, an elongation at break of 517%, a glass transition temperature of 18.0 ℃ and a CO content of 18.0 ℃2Permeability coefficient of 4.73X 10-11cm3·cm/cm2·s·cmHg，O2Permeability coefficient of 1.09X 10-11cm3·cm/cm2s.cmHg is either biodegradable or hydrolytically degradable.
Example 3
Putting 2, 5-thiophenedicarboxylic acid, adipic acid, diglycolic acid and tricyclodecanediol into a reactor according to the molar ratio of 40: 12: 48: 180, simultaneously adding tetrabutyl titanate with the theoretical mass of 0.12% of copolyester as an esterification catalyst and a polycondensation catalyst, gradually heating to 200 ℃ under the protection of nitrogen, carrying out esterification or ester exchange reaction for 3.5h, reducing the temperature to room temperature at the cooling rate of 20 ℃/min after finishing, keeping the temperature in a nitrogen atmosphere, adding trimethyl phosphate with the theoretical mass of 0.01% of copolyester as a stabilizer into the reactor, vacuumizing to 15Pa, gradually heating to 240 ℃, continuously vacuumizing to keep the vacuum degree of the reaction system lower than 15Pa, carrying out polycondensation reaction for 3.5h, and obtaining the hydrolyzable and degradable high-gas barrier copolyester with the structure as shown in formula (IV).
Wherein x, y and z are integers of 1-10, and m is an integer of 15-150.
The hydrolytically degradable high gas barrier copolymer obtained in this example was found to be white in color, to have a tensile modulus of 411.6MPa, a tensile strength of 33.6MPa, an elongation at break of 153%, a glass transition temperature of 46.2 ℃ and a CO temperature of 46.2 DEG2Permeability coefficient of 2.36X 10-11cm3·cm/cm2·s·cmHg，O2Permeability coefficient of 8.72X 10-12cm3·cm/cm2s.cmHg is either biodegradable or hydrolytically degradable.
Example 4
Putting the combination of 2, 5-thiophenedicarboxylic acid dimethyl ester, adipic acid, diglycolic acid, 1, 4-butanediol and tetracyclodiol into a reactor according to the molar ratio of 40: 48: 12: 200: 5, simultaneously adding tetrabutyl titanate with the theoretical mass of 0.15 percent of copolyester as an esterification/ester exchange catalyst and a polycondensation catalyst, and triphenyl phosphate with the theoretical mass of 0.06 percent as a stabilizer, gradually heating to 200 deg.C under nitrogen protection, performing esterification or ester exchange reaction for 6.0h, cooling to room temperature at a cooling rate of 5 deg.C/min, maintaining in nitrogen atmosphere, then vacuumizing to 15Pa, gradually heating to 240 ℃, continuously vacuumizing to maintain the vacuum degree of the reaction system to be lower than 15Pa, carrying out polycondensation reaction for 5.5h, and obtaining the hydrolytically degradable high-gas-barrier copolyester with the structure shown in formula (V).
Wherein x, y, z, u, v and w are integers of 1-10, and m is an integer of 15-150.
The hydrolytically degradable high gas barrier copolymer obtained in this example was found to be white in color, to have a tensile modulus of 182.6MPa, a tensile strength of 21.2MPa, an elongation at break of 543%, a glass transition temperature of 16.3 ℃ and a CO content of 16.3 ℃2Permeability coefficient of 4.92X 10-11cm3·cm/cm2·s·cmHg，O2Permeability coefficient of 1.32X 10-11cm3·cm/cm2s.cmHg is either biodegradable or hydrolytically degradable.
Example 5
3, 4-thiophenedicarboxylic acid, adipic acid, diglycolic acid and tetracyclodiol are put into a reactor according to the molar ratio of 40: 42: 18: 160, simultaneously adding tetrabutyl titanate with the theoretical mass of 0.15 percent of copolyester as an esterification/ester exchange catalyst and a polycondensation catalyst, and triphenyl phosphate with the theoretical mass of 0.1 percent as a stabilizer, gradually heating to 230 ℃ under the protection of nitrogen, carrying out esterification or ester exchange reaction for 4.0h, closing heating after the reaction is finished, reducing the temperature to room temperature at the cooling rate of 5 ℃/min, cooling to room temperature under the protection of nitrogen, maintaining for 3.0h, vacuumizing to 30Pa at room temperature, gradually heating to 240 ℃, and continuously vacuumizing to maintain the vacuum degree of the reaction system to be lower than 30Pa, carrying out polycondensation reaction for 10.0h, and obtaining the hydrolytically degradable high-gas-barrier copolyester with the structure shown in formula (VI).
Wherein x, y and z are integers of 1-10, and m is an integer of 15-150.
The hydrolytically degradable high gas barrier copolymer obtained in this example was found to be white in color, had a tensile modulus of 387.7MPa, a tensile strength of 32.5MPa, an elongation at break of 198%, a glass transition temperature of 37.3 ℃ and a CO temperature of 37.3 ℃2Permeability coefficient of 4.55X 10-11cm3·cm/cm2·s·cmHg，O2Permeability coefficient of 1.04X 10-11cm3·cm/cm2s.cmHg is either biodegradable or hydrolytically degradable.
Example 6
Putting dimethyl 2, 5-thiophenedicarboxylate, adipic acid, diglycolic acid, neopentyl glycol and tricyclodecanedimethanol into a reactor according to the mol ratio of 60: 10: 30: 100: 20, simultaneously adding isopropyl titanate with 0.05 percent of the theoretical mass of copolyester as an esterification catalyst, gradually heating to 220 ℃ under the protection of nitrogen, carrying out esterification or ester exchange reaction for 1.5h, reducing the temperature to room temperature at the cooling rate of 50 ℃/min, keeping the temperature in a nitrogen atmosphere, adding dibutyltin oxide with 0.10 percent of the theoretical mass of copolyester as a polycondensation catalyst and 0.5 percent of pyrophosphoric acid as a stabilizer into the reactor, vacuumizing to 15Pa, gradually heating to 295 ℃, continuously vacuumizing to maintain the vacuum degree of the reaction system to be lower than 15Pa, carrying out polycondensation reaction for 2.0h, and obtaining the hydrolytically degradable high-gas barrier copolyester after the completion, the structure is shown in formula (VII).
Wherein x, y, z, u, v and w are integers of 1-10, and m is an integer of 15-150.
The hydrolytically degradable high gas barrier copolymer obtained in this example was found to be white in color, to have a tensile modulus of 264.4MPa, a tensile strength of 23.1MPa, an elongation at break of 470%, a glass transition temperature of 20.2 ℃ and a CO content of 20.2 ℃2Permeability coefficient of 2.12X 10-11cm3·cm/cm2·s·cmHg，O2Permeability coefficient of 7.60X 10-12cm3·cm/cm2s.cmHg is either biodegradable or hydrolytically degradable.
Example 7
Putting 2, 5-thiophenedicarboxylic acid, adipic acid, diglycolic acid, 1, 8-octanediol, 1, 3-propanediol and tetracyclic diol into a reactor according to the mol ratio of 80: 10: 100: 20: 30, simultaneously adding isopropyl titanate with the theoretical mass of 0.5% of copolyester as an esterification catalyst, gradually heating to 140 ℃ under the protection of nitrogen, carrying out esterification or ester exchange reaction for 3.5h, reducing the temperature to room temperature at the cooling rate of 5 ℃/min after the reaction is finished, then keeping the reaction in a nitrogen atmosphere, adding dibutyltin oxide with the theoretical mass of 0.10% of copolyester as a polycondensation catalyst and 0.3% of hypophosphorous acid as a stabilizer into the reactor, vacuumizing to 15Pa, gradually heating to 285 ℃, continuously vacuumizing to maintain the vacuum degree of the reaction system to be lower than 15Pa, carrying out polycondensation reaction for 3.0h, and obtaining the hydrolytically degradable high-gas barrier copolyester after the reaction is finished, the structure is shown as formula (VIII).
Wherein x, y, z, u, v, w, a, b and c are integers of 1-10, and m is an integer of 15-150.
The hydrolytically degradable high gas barrier copolymer obtained in this example was found to be white in color, had a tensile modulus of 285.2MPa, a tensile strength of 27.3MPa, an elongation at break of 426%, a glass transition temperature of 23.6 ℃ and a CO temperature of 23.6 ℃2Permeability coefficient of 1.25X 10-11cm3·cm/cm2·s·cmHg，O2Permeability coefficient of 6.45X 10-12cm3·cm/cm2s.cmHg is either biodegradable or hydrolytically degradable.
Example 8
Putting 3, 4-thiophene di-n-butyl dicarboxylate, adipic acid, diglycolic acid, 2-methyl-1, 3-propanediol, 1, 10-decanediol and tricyclodecanediol into a reactor according to the mol ratio of 70: 6: 24: 120: 50: 60, simultaneously adding stannous isooctanoate with 0.3 percent of the theoretical mass of copolyester as an esterification catalyst, gradually heating to 180 ℃ under the protection of nitrogen, carrying out esterification or ester exchange reaction for 3.5h, reducing the temperature to room temperature at the cooling rate of 15 ℃/min after the reaction is finished, then keeping the reaction in a nitrogen atmosphere, adding germanium acetate with 0.10 percent of the theoretical mass of the copolyester as a polycondensation catalyst and 0.3 percent diphenyl phosphate as a stabilizer into the reactor, then vacuumizing to 15Pa, gradually heating to 280 ℃, continuously vacuumizing to maintain the vacuum degree of the reaction system to be lower than 15Pa, carrying out polycondensation reaction for 3.5h, after that, the hydrolysable and degradable copolyester with high gas barrier property is obtained, and the structure is shown as formula (IX).
Wherein x, y, z, u, v, w, a, b and c are integers of 1-10, and m is an integer of 15-150.
The hydrolytically degradable high gas barrier copolymer obtained in this example was found to be white in color, to have a tensile modulus of 316.4MPa, a tensile strength of 25.6MPa, an elongation at break of 369%, a glass transition temperature of 29.3 ℃ and a CO content of2Permeability coefficient of 1.82X 10-11cm3·cm/cm2·s·cmHg，O2The permeability coefficient is 8.73 multiplied by 10-12cm3·cm/cm2s.cmHg is either biodegradable or hydrolytically degradable.
Example 9
Putting 3, 4-thiophene dicarboxylic acid diethyl ester, adipic acid, diglycolic acid, 1, 6-hexanediol, tricyclodecane dimethanol and tetracyclodiol into a reactor according to the mol ratio of 30: 21: 49: 100: 40: 50, simultaneously adding titanium dioxide with the theoretical mass of 0.2% of copolyester as an esterification catalyst, gradually heating to 185 ℃ under the protection of nitrogen, carrying out esterification or ester exchange reaction for 3.5h, reducing the temperature to room temperature at the cooling rate of 25 ℃/min, keeping in nitrogen atmosphere, adding stannous isooctanoate with the theoretical mass of 0.20% of copolyester as a polycondensation catalyst and 0.3% triphenyl phosphite as a stabilizer into the reactor, vacuumizing to 15Pa, gradually heating to 250 ℃, continuously vacuumizing to maintain the vacuum degree of the reaction system to be lower than 15Pa, carrying out polycondensation reaction for 4h, and obtaining the hydrolytically degradable high-barrier gas copolyester, the structure is shown as formula (X).
Wherein x, y, z, u, v, w, a, b and c are integers of 1-10, and m is an integer of 15-150.
The hydrolytically degradable high gas barrier copolymer obtained in this example was found to be white in color, to have a tensile modulus of 370.2MPa, a tensile strength of 28.4MPa, an elongation at break of 231%, a glass transition temperature of 33.9 ℃ and a CO content of 33.9 ℃2Permeability coefficient of 5.27X 10-11cm3·cm/cm2·s·cmHg，O2Permeability coefficient of 1.16X 10-11cm3·cm/cm2s.cmHg is either biodegradable or hydrolytically degradable.
Comparative example 1
Putting 2, 5-thiophenedicarboxylic acid dimethyl ester, adipic acid dimethyl ester and 1, 4-butanediol into a reactor according to the molar ratio of 45: 160, adding tetrabutyl titanate with the theoretical mass of 0.1% of copolyester as a catalyst, gradually heating to 180 ℃ under the protection of nitrogen, reacting for 4.0 hours, then vacuumizing to 30Pa, gradually heating to 230 ℃, continuously vacuumizing to maintain the vacuum degree of the reaction system to be lower than 30Pa, and finishing the reaction after 4.0 hours to obtain the polythienyldicarboxylic acid butanediol adipate.
The detection proves that the polythiophene dioctyl phthalate butanediol adipate obtained in the comparative example has the tensile modulus of 106.2MPa, the tensile strength of 17.1MPa, the elongation at break of 855 percent, the glass transition temperature of-20.7 ℃, and CO2Permeability coefficient of 0.48barrer, O2The permeability coefficient is 0.63barrer, and the biodegradable material can be biodegraded but cannot be hydrolytically degraded.
Comparative example 2
Putting 2, 5-thiophenedicarboxylic acid dimethyl ester, diglycolic acid and 1, 4-butanediol into a reactor according to the molar ratio of 45: 55: 160, adding tetrabutyl titanate with the theoretical mass of copolyester of 0.1 percent as a catalyst, gradually heating to 170 ℃ under the protection of nitrogen, reacting for 5.0h, adding 0.2g of triphenyl phosphate into the reactor after the reaction is finished, vacuumizing to 15Pa, gradually heating to 230 ℃, continuously vacuumizing to maintain the vacuum degree of the reaction system to be lower than 15Pa, and reacting for 5.0h to obtain the polythiophene dicarboxylic acid diglycolic acid butanediol ester.
Through detection, the polythiophene diglycolic acid butanediol ester obtained in the embodiment has the tensile modulus of 145.8MPa, the tensile strength of 20.9MPa, the elongation at break of 438 percent, the glass transition temperature of-15.5 ℃ and CO2Permeability coefficient of 0.88barrer, O2The permeability coefficient was 0.72barrer and was either biodegradable or hydrolytically degradable, but both the biodegradation rate and the hydrolytic degradation rate were faster than the degradation rate of the products of all examples.
Comparative example 3
Putting dimethyl terephthalate, dimethyl adipate, dimethyl diglycolate and 1, 4-butanediol into a reactor according to the molar ratio of 45: 50: 5: 160, simultaneously adding tetrabutyl titanate with the theoretical mass of 0.1% of copolyester as a catalyst, gradually heating to 180 ℃ under the protection of nitrogen, reacting for 5.0 hours, then vacuumizing to 30Pa, gradually heating to 230 ℃, continuously vacuumizing to maintain the vacuum degree of a reaction system to be lower than 30Pa, and finishing the reaction after 4.0 hours to obtain the polybutylene terephthalate adipate-butanediol diglycolate.
The detection proves that the polybutylene terephthalate adipate-adipate obtained by the comparative example has the tensile modulus of 124.7MPa, the tensile strength of 18.2MPa, the elongation at break of 746 percent, the glass transition temperature of-16.8 ℃ and CO2Permeability coefficient of 5.61barrer, O2The permeability coefficient is 7.54barrer, and the biodegradable material can be biodegraded but cannot be hydrolytically degraded.
Comparative example 4
This comparative example differs from example 1 in that: after the transesterification reaction, the temperature was not lowered to room temperature, and the reaction was not maintained under nitrogen. Adding a stabilizer at the temperature of 180 ℃ in the ester exchange reaction, directly vacuumizing, and gradually heating to 245 ℃ to carry out polycondensation reaction.
The comparative example adopts the traditional process without temperature reduction step and high-temperature vacuum pumping, the obtained product can generate side reactions such as high-temperature oxidation and the like, and the obtained product is light yellow in color.
Example 10
Some embodiments of the present invention also provide uses of the hydrolytically degradable high gas barrier copolyesters, such as in the manufacture of packaging materials, containers, geomembranes, structural members, body implants, and the like.
In addition, the inventors of the present invention have also made experiments with other materials, process operations, and process conditions described in the present specification with reference to the above examples, and have obtained preferable results.
While the invention has been described with reference to illustrative embodiments, it will be understood by those skilled in the art that various other changes, omissions and/or additions may be made and substantial equivalents may be substituted for elements thereof without departing from the spirit and scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from its scope. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed for carrying out this invention, but that the invention will include all embodiments falling within the scope of the appended claims. Moreover, unless specifically stated any use of the terms first, second, etc. do not denote any order or importance, but rather the terms first, second, etc. are used to distinguish one element from another.
Claims (10)
1. A hydrolytically degradable high gas barrier copolyester having the structural formula (I):
wherein R is1Is a structural unit of bio-based aromatic dibasic acid, R2、R3、R4The structural unit is cyclic dihydric alcohol or a combination of aliphatic dihydric alcohol and cyclic dihydric alcohol, x, y and z are integers of 1-10, and m is an integer of 15-150;
the bio-based aromatic dibasic acid comprises thiophenedicarboxylic acid;
the cyclic dihydric alcohol comprises any one or the combination of more than two of tricyclodecanedimethanol, tricyclodecanediol and tetracyclodiol, and the aliphatic dihydric alcohol comprises any one or the combination of more than two of ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, 2-methyl-1, 3-propanediol, neopentyl glycol, octanediol and decanediol.
2. A process for preparing a hydrolytically degradable high gas barrier copolyester as claimed in claim 1, which comprises:
(1) uniformly mixing bio-based aromatic dibasic acid and/or an esterified product thereof, adipic acid and/or an esterified product thereof, diglycolic acid and/or an esterified product thereof, dihydric alcohol and an esterification or ester exchange catalyst to obtain a first mixed reaction system, wherein the molar ratio of the adipic acid and/or the esterified product thereof to the diglycolic acid and/or the esterified product thereof is 20-80: 80-20;
(2) under a protective atmosphere, carrying out esterification or ester exchange reaction on the first mixed reaction system at 140-230 ℃, and obtaining a first intermediate product after the esterification or ester exchange reaction is finished;
(3) carrying out polycondensation reaction on a second mixed reaction system containing the first intermediate product, a polycondensation catalyst and a stabilizer under a vacuum condition at 200-295 ℃ to obtain the hydrolytically degradable high-gas barrier copolyester;
alternatively, the preparation method comprises:
(i) uniformly mixing bio-based aromatic dibasic acid and/or an esterified product thereof, adipic acid and/or an esterified product thereof, diglycolic acid and/or an esterified product thereof, dihydric alcohol, an esterification or ester exchange catalyst, a polycondensation catalyst and a stabilizer to obtain a third mixed reaction system, wherein the molar ratio of the adipic acid and/or the esterified product thereof to the diglycolic acid and/or the esterified product thereof is 20-80: 80-20;
(ii) carrying out esterification or ester exchange reaction on the third mixed reaction system at 140-230 ℃ under a protective atmosphere to obtain a second intermediate product;
(iii) carrying out polycondensation reaction on the second intermediate product at 200-295 ℃ under a vacuum condition to obtain the hydrolytically degradable high-gas-barrier copolyester;
wherein the bio-based aromatic dibasic acid and/or the esterified product thereof comprises thiophene dicarboxylic acid and/or an esterified product thereof;
the dihydric alcohol comprises a cyclic dihydric alcohol, or a combination of a fatty dihydric alcohol and a cyclic dihydric alcohol;
the cyclic diol comprises any one or the combination of more than two of tricyclodecane dimethanol, tricyclodecane diol and tetracyclic diol; the aliphatic diol comprises any one or the combination of more than two of ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, 2-methyl-1, 3-propanediol, neopentyl glycol, octanediol and decanediol.
3. The method according to claim 2, wherein the bio-based aromatic dibasic acid and/or the ester thereof has one or more structures represented by the following formulae:
wherein R is a hydrogen atom or a carbon chain with the carbon number not more than 4.
4. The method of claim 2, wherein: in the step (1) or the step (i), the molar ratio of the combination of the bio-based aromatic dibasic acid and/or the ester thereof, the adipic acid and/or the ester thereof, the diglycolic acid and/or the ester thereof and the dihydric alcohol is 1: 1.2-3.0;
and/or the addition amount of the esterification or ester exchange catalyst is 0.01-0.5% of the theoretical mass of the hydrolytically degradable high-gas barrier copolyester.
5. The method of claim 2, wherein: in the step (3) or the step (i), the mass of the polycondensation catalyst is 0.01-0.5% of the theoretical mass of the hydrolytically degradable high-gas barrier copolyester, and the mass of the stabilizer is 0.01-0.5% of the theoretical mass of the hydrolytically degradable high-gas barrier copolyester.
6. The method of claim 2, wherein: in the step (2), carrying out esterification or ester exchange reaction on the first mixed reaction system at 140-230 ℃ for 1.5-6.0 h in a protective atmosphere, reducing the temperature to room temperature at a cooling rate of 1-50 ℃/min after the reaction is finished, and then keeping for 1.0-5.0 h in the protective atmosphere to form a first intermediate product;
and/or in the step (3), vacuumizing the second mixed reaction system to below 30Pa, gradually heating to 200-295 ℃ for polycondensation reaction for 2.0-10.0 hours, and obtaining the hydrolytically degradable high-gas-barrier copolyester.
7. The method of claim 2, wherein: in the step (ii), carrying out esterification or ester exchange reaction for 1.5-6.0 h at 140-230 ℃ in a protective atmosphere, reducing the temperature to room temperature at a cooling rate of 1-50 ℃/min after the reaction is finished, and then keeping for 1.0-5.0 h in the protective atmosphere to form a second intermediate product;
and/or in the step (iii), vacuumizing a reaction system containing a second intermediate product to below 30Pa, gradually heating to 200-295 ℃ for polycondensation reaction for 2.0-10.0 h, and obtaining the hydrolytically degradable high-gas barrier copolyester;
and/or in the step (3) or the step (iii), vacuumizing to below 30Pa at room temperature, gradually heating to 200-295 ℃ to perform polycondensation reaction, and continuously vacuumizing to keep the vacuum in the whole polycondensation process not to exceed 30 Pa.
8. The method of claim 2, wherein: the esterification or ester exchange catalyst comprises any one or the combination of more than two of titanium catalyst, tin catalyst and germanium catalyst;
and/or the polycondensation catalyst comprises any one or the combination of more than two of a titanium catalyst, a tin catalyst and a germanium catalyst;
and/or the stabilizer comprises any one or the combination of more than two of phosphorous acid, hypophosphorous acid, pyrophosphoric acid, ammonium phosphate, trimethyl phosphate, dimethyl phosphate, triphenyl phosphate, diphenyl phosphate, triphenyl phosphite, diphenyl phosphite, ammonium phosphite and ammonium dihydrogen phosphate.
9. A composition for synthesizing a hydrolytically degradable high gas barrier copolyester characterized by comprising:
a component (a) comprising a bio-based aromatic dibasic acid and/or an esterified product thereof;
component (b) comprising adipic acid and/or an esterified product thereof;
component (c) comprising diglycolic acid and/or an esterified product thereof; and
component (d), comprising a glycol,
wherein the bio-based aromatic dibasic acid and/or the esterified product thereof comprises thiophene dicarboxylic acid and/or an esterified product thereof;
the dihydric alcohol comprises a cyclic dihydric alcohol, or a combination of a fatty dihydric alcohol and a cyclic dihydric alcohol;
the cyclic dihydric alcohol comprises any one or the combination of more than two of tricyclodecanedimethanol, tricyclodecanediol and tetracyclodiol, and the aliphatic dihydric alcohol comprises any one or the combination of more than two of ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, 2-methyl-1, 3-propanediol, neopentyl glycol, octanediol and decanediol.
10. Use of the hydrolytically degradable high gas barrier copolyester of claim 1 in the field of making packaging materials, containers, geomembranes, structural members or body implants.
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