CN115044026A - Degradable high-barrier uvioresistant bio-based polyester and preparation method and application thereof - Google Patents
Degradable high-barrier uvioresistant bio-based polyester and preparation method and application thereof Download PDFInfo
- Publication number
- CN115044026A CN115044026A CN202210765188.3A CN202210765188A CN115044026A CN 115044026 A CN115044026 A CN 115044026A CN 202210765188 A CN202210765188 A CN 202210765188A CN 115044026 A CN115044026 A CN 115044026A
- Authority
- CN
- China
- Prior art keywords
- pyridone
- dicarboxylic acid
- acid
- dicarboxylate
- catalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- 229920000728 polyester Polymers 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- LVWZTYCIRDMTEY-UHFFFAOYSA-N metamizole Chemical compound O=C1C(N(CS(O)(=O)=O)C)=C(C)N(C)N1C1=CC=CC=C1 LVWZTYCIRDMTEY-UHFFFAOYSA-N 0.000 claims abstract description 76
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims abstract description 71
- 239000003054 catalyst Substances 0.000 claims abstract description 62
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 48
- -1 pyridone dicarboxylic acid ester Chemical class 0.000 claims abstract description 48
- 150000002148 esters Chemical class 0.000 claims abstract description 37
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims abstract description 35
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000000126 substance Substances 0.000 claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229930192474 thiophene Natural products 0.000 claims abstract description 17
- 239000003381 stabilizer Substances 0.000 claims abstract description 14
- 239000013067 intermediate product Substances 0.000 claims abstract description 12
- 230000032050 esterification Effects 0.000 claims abstract description 11
- 238000005886 esterification reaction Methods 0.000 claims abstract description 11
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 11
- 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 60
- 230000035699 permeability Effects 0.000 claims description 60
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 46
- 238000002834 transmittance Methods 0.000 claims description 32
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 30
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims description 26
- MUXOBHXGJLMRAB-UHFFFAOYSA-N Dimethyl succinate Chemical compound COC(=O)CCC(=O)OC MUXOBHXGJLMRAB-UHFFFAOYSA-N 0.000 claims description 24
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 23
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 22
- GZNZEMZRQVMDDH-UHFFFAOYSA-N dimethyl furan-2,4-dicarboxylate Chemical compound COC(=O)C1=COC(C(=O)OC)=C1 GZNZEMZRQVMDDH-UHFFFAOYSA-N 0.000 claims description 18
- HIHKYDVSWLFRAY-UHFFFAOYSA-N thiophene-2,3-dicarboxylic acid Chemical compound OC(=O)C=1C=CSC=1C(O)=O HIHKYDVSWLFRAY-UHFFFAOYSA-N 0.000 claims description 18
- 239000002202 Polyethylene glycol Substances 0.000 claims description 17
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 17
- DNXDYHALMANNEJ-UHFFFAOYSA-N furan-2,3-dicarboxylic acid Chemical compound OC(=O)C=1C=COC=1C(O)=O DNXDYHALMANNEJ-UHFFFAOYSA-N 0.000 claims description 17
- 229920001223 polyethylene glycol Polymers 0.000 claims description 17
- 239000001361 adipic acid Substances 0.000 claims description 16
- 229910052787 antimony Inorganic materials 0.000 claims description 16
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 16
- 235000011037 adipic acid Nutrition 0.000 claims description 14
- XTDYIOOONNVFMA-UHFFFAOYSA-N dimethyl pentanedioate Chemical compound COC(=O)CCCC(=O)OC XTDYIOOONNVFMA-UHFFFAOYSA-N 0.000 claims description 14
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 13
- FXJUUMGKLWHCNZ-UHFFFAOYSA-N dimethyl furan-2,3-dicarboxylate Chemical compound COC(=O)C=1C=COC=1C(=O)OC FXJUUMGKLWHCNZ-UHFFFAOYSA-N 0.000 claims description 13
- KJFYQQHJMMWTPL-UHFFFAOYSA-N 3,4-dimethyl-1h-pyridin-2-one Chemical compound CC1=CC=NC(O)=C1C KJFYQQHJMMWTPL-UHFFFAOYSA-N 0.000 claims description 12
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 claims description 12
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 claims description 12
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 claims description 11
- UDSFAEKRVUSQDD-UHFFFAOYSA-N Dimethyl adipate Chemical compound COC(=O)CCCCC(=O)OC UDSFAEKRVUSQDD-UHFFFAOYSA-N 0.000 claims description 11
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 claims description 11
- YCGAZNXXGKTASZ-UHFFFAOYSA-N thiophene-2,5-dicarboxylic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)S1 YCGAZNXXGKTASZ-UHFFFAOYSA-N 0.000 claims description 11
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 claims description 11
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 10
- 239000005022 packaging material Substances 0.000 claims description 10
- 229910052719 titanium Inorganic materials 0.000 claims description 10
- 239000010936 titanium Substances 0.000 claims description 10
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 10
- 229940071125 manganese acetate Drugs 0.000 claims description 9
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- KKUKTXOBAWVSHC-UHFFFAOYSA-N Dimethylphosphate Chemical compound COP(O)(=O)OC KKUKTXOBAWVSHC-UHFFFAOYSA-N 0.000 claims description 8
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 8
- CYUGNCLRGFKPAE-UHFFFAOYSA-N dimethyl thiophene-2,5-dicarboxylate Chemical compound COC(=O)C1=CC=C(C(=O)OC)S1 CYUGNCLRGFKPAE-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 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 8
- YSLIPUSJNFIFAB-UHFFFAOYSA-N 2-oxopyridine-1-carboxylic acid Chemical compound OC(=O)N1C=CC=CC1=O YSLIPUSJNFIFAB-UHFFFAOYSA-N 0.000 claims description 7
- BIGSLYNSINJVQY-UHFFFAOYSA-N CCCC1=C(CCC)C(O)=NC=C1 Chemical compound CCCC1=C(CCC)C(O)=NC=C1 BIGSLYNSINJVQY-UHFFFAOYSA-N 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims description 6
- BPNCYDPSYYXUNK-UHFFFAOYSA-N 3,4-diethyl-1h-pyridin-2-one Chemical compound CCC=1C=CNC(=O)C=1CC BPNCYDPSYYXUNK-UHFFFAOYSA-N 0.000 claims description 6
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 6
- PVADDRMAFCOOPC-UHFFFAOYSA-N oxogermanium Chemical compound [Ge]=O PVADDRMAFCOOPC-UHFFFAOYSA-N 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- WSXIMVDZMNWNRF-UHFFFAOYSA-N antimony;ethane-1,2-diol Chemical compound [Sb].OCCO WSXIMVDZMNWNRF-UHFFFAOYSA-N 0.000 claims description 5
- UWQOPFRNDNVUOA-UHFFFAOYSA-N dimethyl furan-2,5-dicarboxylate Chemical compound COC(=O)C1=CC=C(C(=O)OC)O1 UWQOPFRNDNVUOA-UHFFFAOYSA-N 0.000 claims description 5
- GUYGZVVCZMIUTA-UHFFFAOYSA-N dimethyl thiophene-2,4-dicarboxylate Chemical compound COC(=O)C1=CSC(C(=O)OC)=C1 GUYGZVVCZMIUTA-UHFFFAOYSA-N 0.000 claims description 5
- 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 5
- 239000003814 drug Substances 0.000 claims description 5
- 235000013305 food Nutrition 0.000 claims description 5
- JOTDFEIYNHTJHZ-UHFFFAOYSA-N furan-2,4-dicarboxylic acid Chemical compound OC(=O)C1=COC(C(O)=O)=C1 JOTDFEIYNHTJHZ-UHFFFAOYSA-N 0.000 claims description 5
- 229910052717 sulfur Inorganic materials 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
- QWGRWMMWNDWRQN-UHFFFAOYSA-N 2-methylpropane-1,3-diol Chemical compound OCC(C)CO QWGRWMMWNDWRQN-UHFFFAOYSA-N 0.000 claims description 4
- OEOIWYCWCDBOPA-UHFFFAOYSA-N 6-methyl-heptanoic acid Chemical compound CC(C)CCCCC(O)=O OEOIWYCWCDBOPA-UHFFFAOYSA-N 0.000 claims description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- LUSFFPXRDZKBMF-UHFFFAOYSA-N [3-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCCC(CO)C1 LUSFFPXRDZKBMF-UHFFFAOYSA-N 0.000 claims description 4
- 235000013361 beverage Nutrition 0.000 claims description 4
- 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 claims description 4
- 125000004122 cyclic group Chemical group 0.000 claims description 4
- LQRUPWUPINJLMU-UHFFFAOYSA-N dioctyl(oxo)tin Chemical compound CCCCCCCC[Sn](=O)CCCCCCCC LQRUPWUPINJLMU-UHFFFAOYSA-N 0.000 claims description 4
- KUMNEOGIHFCNQW-UHFFFAOYSA-N diphenyl phosphite Chemical compound C=1C=CC=CC=1OP([O-])OC1=CC=CC=C1 KUMNEOGIHFCNQW-UHFFFAOYSA-N 0.000 claims description 4
- 229910052732 germanium Inorganic materials 0.000 claims description 4
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 239000011572 manganese Substances 0.000 claims description 4
- REOJLIXKJWXUGB-UHFFFAOYSA-N mofebutazone Chemical group O=C1C(CCCC)C(=O)NN1C1=CC=CC=C1 REOJLIXKJWXUGB-UHFFFAOYSA-N 0.000 claims description 4
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 4
- OEIJHBUUFURJLI-UHFFFAOYSA-N octane-1,8-diol Chemical compound OCCCCCCCCO OEIJHBUUFURJLI-UHFFFAOYSA-N 0.000 claims description 4
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical compound CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 claims description 4
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 4
- 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 4
- 239000011701 zinc Substances 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 3
- XDODWINGEHBYRT-UHFFFAOYSA-N [2-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCCCC1CO XDODWINGEHBYRT-UHFFFAOYSA-N 0.000 claims description 3
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 3
- 229940079593 drug Drugs 0.000 claims description 3
- 229940119177 germanium dioxide Drugs 0.000 claims description 3
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 239000011574 phosphorus Substances 0.000 claims description 3
- 230000001681 protective effect Effects 0.000 claims description 3
- 239000013535 sea water Substances 0.000 claims description 3
- 239000004246 zinc acetate Substances 0.000 claims description 3
- 239000004254 Ammonium phosphate Substances 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
- INSRQEMEVAMETL-UHFFFAOYSA-N decane-1,1-diol Chemical compound CCCCCCCCCC(O)O INSRQEMEVAMETL-UHFFFAOYSA-N 0.000 claims description 2
- JVLRYPRBKSMEBF-UHFFFAOYSA-K diacetyloxystibanyl acetate Chemical compound [Sb+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JVLRYPRBKSMEBF-UHFFFAOYSA-K 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
- CGDDISBFSPJVPK-UHFFFAOYSA-N dimethyl thiophene-2,3-dicarboxylate Chemical compound COC(=O)C=1C=CSC=1C(=O)OC CGDDISBFSPJVPK-UHFFFAOYSA-N 0.000 claims description 2
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 claims description 2
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 2
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 claims description 2
- 229940005657 pyrophosphoric acid Drugs 0.000 claims description 2
- QYBBDSGVPGCWTO-UHFFFAOYSA-N thiophene-2,4-dicarboxylic acid Chemical compound OC(=O)C1=CSC(C(O)=O)=C1 QYBBDSGVPGCWTO-UHFFFAOYSA-N 0.000 claims description 2
- 239000004408 titanium dioxide Substances 0.000 claims description 2
- 239000012974 tin catalyst Substances 0.000 claims 4
- JDRJCBXXDRYVJC-UHFFFAOYSA-N OP(O)O.N.N.N Chemical compound OP(O)O.N.N.N JDRJCBXXDRYVJC-UHFFFAOYSA-N 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000004888 barrier function Effects 0.000 abstract description 7
- 230000015556 catabolic process Effects 0.000 abstract description 7
- 238000006731 degradation reaction Methods 0.000 abstract description 7
- 239000005003 food packaging material Substances 0.000 abstract description 2
- 239000007789 gas Substances 0.000 description 61
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 56
- 238000010438 heat treatment Methods 0.000 description 46
- 230000004224 protection Effects 0.000 description 31
- 229910052757 nitrogen Inorganic materials 0.000 description 28
- 229940057499 anhydrous zinc acetate Drugs 0.000 description 12
- DJWUNCQRNNEAKC-UHFFFAOYSA-L zinc acetate Chemical compound [Zn+2].CC([O-])=O.CC([O-])=O DJWUNCQRNNEAKC-UHFFFAOYSA-L 0.000 description 12
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 6
- 108010020346 Polyglutamic Acid Proteins 0.000 description 5
- 229920002643 polyglutamic acid Polymers 0.000 description 5
- 239000004698 Polyethylene Substances 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical group CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- 229920001748 polybutylene Polymers 0.000 description 4
- 229920000573 polyethylene Polymers 0.000 description 4
- 239000000047 product Substances 0.000 description 4
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- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
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- 230000006750 UV protection Effects 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
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- 230000007547 defect Effects 0.000 description 2
- 150000002009 diols Chemical class 0.000 description 2
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- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 description 2
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- AFGNPFWWBHDPEN-UHFFFAOYSA-N 1,6-dioxacyclododecane-2,5-dione Chemical compound O=C1CCC(=O)OCCCCCCO1 AFGNPFWWBHDPEN-UHFFFAOYSA-N 0.000 description 1
- ZMKVBUOZONDYBW-UHFFFAOYSA-N 1,6-dioxecane-2,5-dione Chemical compound O=C1CCC(=O)OCCCCO1 ZMKVBUOZONDYBW-UHFFFAOYSA-N 0.000 description 1
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- KYRZZPALUVQDRB-UHFFFAOYSA-N 2-methyl-1,4-dioxocane-5,8-dione Chemical compound CC1COC(=O)CCC(=O)O1 KYRZZPALUVQDRB-UHFFFAOYSA-N 0.000 description 1
- SJIWUNNSRFWATG-UHFFFAOYSA-N 4-[2-(2-hydroxyethoxy)ethoxy]-4-oxobutanoic acid Chemical compound OCCOCCOC(=O)CCC(O)=O SJIWUNNSRFWATG-UHFFFAOYSA-N 0.000 description 1
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 1
- 239000004201 L-cysteine Substances 0.000 description 1
- 235000013878 L-cysteine Nutrition 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 235000013405 beer Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 1
- PWFPXTOTJCXQEM-UHFFFAOYSA-N butanedioic acid;2-[2-(2-hydroxyethoxy)ethoxy]ethanol Chemical compound OC(=O)CCC(O)=O.OCCOCCOCCO PWFPXTOTJCXQEM-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000008157 edible vegetable oil Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000005014 poly(hydroxyalkanoate) Substances 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 239000004626 polylactic acid Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 230000005855 radiation 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
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/688—Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur
- C08G63/6884—Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/6886—Dicarboxylic acids and dihydroxy compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
- B65D65/38—Packaging materials of special type or form
- B65D65/46—Applications of disintegrable, dissolvable or edible materials
- B65D65/466—Bio- or photodegradable packaging materials
-
- 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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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biodiversity & Conservation Biology (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention discloses degradable high-barrier ultraviolet-resistant bio-based polyester and a preparation method and application thereof. The preparation method comprises the following steps: reacting a first mixed reaction system containing aliphatic diacid and/or aliphatic diacid ester, furan substances and/or thiophene substances, pyridone dicarboxylic acid and/or pyridone dicarboxylic acid ester, dihydric alcohol, an esterification catalyst and/or an ester exchange catalyst to obtain an intermediate product; and reacting the second mixed reaction system containing the polycondensation catalyst, the stabilizer and the intermediate product under the vacuum condition to prepare the degradable high-barrier uvioresistant biological-based polyester. The degradable high-barrier uvioresistant bio-based polyester prepared by the invention has quick degradation performance and excellent ultraviolet shielding property and gas barrier property, and can be widely applied to the fields of food packaging materials, mulching films and the like.
Description
Technical Field
The invention belongs to the technical field of functional materials, and particularly relates to degradable high-barrier ultraviolet-resistant bio-based polyester and a preparation method and application thereof.
Background
Although the degradation performance of common degradable polyesters such as polylactic acid (PLA), Polycaprolactone (PCL), polyglycolic acid (PGA), Polyhydroxyalkanoate (PHA), and the like is good, the problems of poor thermodynamic performance and barrier performance and lack of uv shielding capability also exist. For some food, beverage and medicine, the packaging material needs to have good gas barrier and ultraviolet resistance to protect the quality stability of the product. For example, VA and VC added to edible oil, beer and other fermented products are accelerated to deteriorate due to ultraviolet radiation. The lower oxygen barrier properties of the packaging material also accelerate oxidative deterioration of food and medicine. In addition, the packaging material is used as a disposable product, and the adverse effect of white pollution on the environment can be greatly reduced by endowing the packaging material with quick degradation performance. At present, a packaging material which has high barrier property, good ultraviolet shielding property and rapid degradation property is lacked.
Disclosure of Invention
The invention mainly aims to provide degradable high-barrier ultraviolet-resistant bio-based polyester and a preparation method and application thereof, so as to overcome the defects of the prior art.
In order to achieve the purpose, the technical scheme adopted by the invention comprises the following steps:
the embodiment of the invention provides a preparation method and application of degradable high-barrier ultraviolet-resistant bio-based polyester, which comprises the following steps:
reacting a first mixed reaction system containing aliphatic diacid and/or aliphatic diacid ester, furan substances and/or thiophene substances, pyridone dicarboxylic acid and/or pyridone dicarboxylic acid ester, dihydric alcohol, an esterification catalyst and/or an ester exchange catalyst to obtain an intermediate product;
and reacting the second mixed reaction system containing the polycondensation catalyst, the stabilizer and the intermediate product under the vacuum condition to prepare the degradable high-barrier uvioresistant biological-based polyester.
The embodiment of the invention also provides the degradable high-barrier ultraviolet-resistant bio-based polyester prepared by the preparation method, and the degradable high-barrier ultraviolet-resistant bio-based polyester has a structure shown as a formula (II):
wherein R is a carbon chain structure of cyclic dihydric alcohol or aliphatic dihydric alcohol, R' is a carbon chain structure of aliphatic dibasic acid, and p and q are independently selected from integers of 1-10; m and n are independently selected from integers of 0-10; x is-NH, -NCH 3 O or S, y is 1-2.
The embodiment of the invention also provides application of the degradable high-barrier ultraviolet-resistant bio-based polyester in packaging materials or mulching films of foods, beverages or medicines.
Compared with the prior art, the invention has the beneficial effects that:
(1) the invention achieves the effect of ultraviolet shielding by adding pyridone dicarboxylic acid, and the structure of the pyridone dicarboxylic acid is a condensed ring, so that the polyester chain segment has higher rigidity, thereby improving the heat resistance of the polyester;
(2) the invention endows the polyester product with anti-ultraviolet performance by adopting an in-situ polymerization mode, and the material property is uniform and stable;
(3) the pyridone diacid in the invention has green source and can be simply synthesized from bio-based monomers, namely citric acid and L-cysteine;
(4) in the invention, the gas barrier property of the system is improved without influencing the degradation performance by introducing the furan ring and thiophene ring structures with proper content;
(5) the degradable high-barrier uvioresistant bio-based polyester provided by the invention has quick degradation performance and excellent ultraviolet shielding property and gas barrier property, and can be widely applied to the fields of food packaging materials, mulching films and the like.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the embodiments or the description of 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 invention, and it is also possible for those skilled in the art to obtain other drawings based on the drawings without creative efforts.
FIG. 1 is a nuclear magnetic spectrum of a pyridonecarboxylic acid monomer used in example 1 of the present invention;
FIG. 2 is a nuclear magnetic hydrogen spectrum of poly (ethylene succinate-co-pyridone dicarboxylate) -co-2, 5-furandicarboxylate prepared in example 1 of the present invention;
FIG. 3 is a graph of the UV transmittance of the polyesters prepared in inventive example 1 and comparative example 1.
Detailed Description
In view of the defects of the prior art, the inventor of the present invention has made a long-term study and a great deal of practice to provide a technical solution of the present invention, which is to prepare a novel high-barrier ultraviolet-resistant degradable polyester by adding pyridone dicarboxylic acid, furandicarboxylic acid and thiophenedicarboxylic acid structures into the degradable polyester. The technical solutions of the present invention will be described clearly and completely below, and it should be apparent that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Specifically, as one aspect of the technical scheme of the invention, the preparation method of the degradable high-barrier ultraviolet-resistant bio-based polyester comprises the following steps:
reacting a first mixed reaction system containing aliphatic diacid and/or aliphatic diacid ester, furan substances and/or thiophene substances, pyridone dicarboxylic acid and/or pyridone dicarboxylic acid ester, dihydric alcohol, an esterification catalyst and/or an ester exchange catalyst to obtain an intermediate product;
and reacting the second mixed reaction system containing the polycondensation catalyst, the stabilizer and the intermediate product under the vacuum condition to prepare the degradable high-barrier uvioresistant biological-based polyester.
In some preferred embodiments, the molar ratio of the aliphatic diacid and/or aliphatic diacid ester, furan-based material and/or thiophene-based material to the pyridone dicarboxylic acid and/or pyridone dicarboxylate is (0.3-0.9): (0-0.69): (0.01-0.1)
In some preferred embodiments, the aliphatic diacid and/or aliphatic diacid ester includes any one or a combination of two or more of succinic acid, glutaric acid, adipic acid, dimethyl succinate, dimethyl glutarate, dimethyl adipate, and is not limited thereto.
In some preferred embodiments, the furanic species comprises furandicarboxylic acid and/or furandicarboxylic acid esters.
Further, the furan dicarboxylic acid and/or furan dicarboxylate includes any one or a combination of two or more of 2, 5-furan dicarboxylic acid, 2, 4-furan dicarboxylic acid, 2, 3-furan dicarboxylic acid, dimethyl 2, 5-furan dicarboxylate, dimethyl 2, 4-furan dicarboxylate, and dimethyl 2, 3-furan dicarboxylate, and is not limited thereto.
In some preferred embodiments, the thiophenic species comprises thiophenedicarboxylic acid and/or thiophenedicarboxylic acid esterified ester.
Further, the thiophenedicarboxylic acid and/or thiophenedicarboxylate includes any one or a combination of two or more of 2, 5-thiophenedicarboxylic acid, 2, 4-thiophenedicarboxylic acid, 2, 3-thiophenedicarboxylic acid, dimethyl 2, 5-thiophenedicarboxylate, dimethyl 2, 4-thiophenedicarboxylate, and dimethyl 2, 3-thiophenedicarboxylate, and is not limited thereto.
In some preferred embodiments, the pyridone dicarboxylic acid and/or pyridone dicarboxylate includes any one or a combination of two or more of dimethyl pyridone dicarboxylate, diethyl pyridone dicarboxylate, dipropyl pyridone dicarboxylate, dibutyl pyridone dicarboxylate, and the like, and is not limited thereto.
In some preferred embodiments, the diol includes a cyclic diol and/or an aliphatic diol, and the like, and is not limited thereto.
Further, the cyclic diol includes any one or a combination of two or more of cis-1, 4-cyclohexanedimethanol, trans-1, 4-cyclohexanedimethanol, 1, 2-cyclohexanedimethanol, 1, 3-cyclohexanedimethanol, 4-bicyclohexanediol, dicyclopentanediol, and the like, without being limited thereto.
Further, the aliphatic diol includes any one or a combination of two or more of ethylene glycol, propylene glycol, butylene glycol, pentanediol, hexanediol, octanediol, decanediol, diethylene glycol, triethylene glycol, neopentyl glycol, 2-methyl-1, 3-propanediol, and the like, and is not limited thereto.
In some preferred embodiments, the pyridonecarboxylic acid has the structure represented by formula (I):
wherein X is-NH, -NCH 3 O or S; y is 1 to 2.
Further, the pyridonecarboxylic acid has a structure represented by the following formula:
in some preferred embodiments, the preparation method specifically comprises: reacting a first mixed reaction system containing aliphatic diacid and/or aliphatic diacid ester, furan substances and/or thiophene substances, pyridone dicarboxylic acid and/or pyridone dicarboxylate, dihydric alcohol, an esterification catalyst and/or an ester exchange catalyst at 150-200 ℃ for 2.0-6.0 h under a protective atmosphere to obtain the intermediate product.
Further, the protective atmosphere includes nitrogen and the like.
In some preferred embodiments, the preparation method specifically comprises: and (3) reacting a second mixed reaction system containing the polycondensation catalyst, the stabilizer and the intermediate product for 1.5-6 h under the conditions that the temperature is 180-240 ℃ and the vacuum degree is below 200Pa, so as to obtain the degradable high-barrier ultraviolet-resistant bio-based polyester.
In some preferred embodiments, the molar ratio of the sum of the three components of the aliphatic diacid and/or aliphatic diacid ester, the furan substance and/or thiophene substance, and the pyridone dicarboxylic acid and/or pyridone dicarboxylate to the diol is 1: 1.2-3.0. That is, in another aspect, the component (1) is an aliphatic diacid and/or an aliphatic diacid ester; component (2) furan dicarboxylic acid and/or furan dicarboxylate, thiophene dicarboxylic acid and/or thiophene dicarboxylate; the content of the dihydric alcohol is 120 to 300mol percent calculated by the total molar weight of the pyridone dicarboxylic acid and/or the pyridone dicarboxylic ester of the component (3).
In some preferred embodiments, the molar ratio of the esterification catalyst and/or transesterification catalyst to the sum of the aliphatic diacid and/or aliphatic diacid ester, furan species and/or thiophene species, pyridone dicarboxylic acid and/or pyridone dicarboxylic acid ester is 0.03-0.3: 100.
In some preferred embodiments, the molar ratio of the polycondensation catalyst to the sum of the aliphatic diacid and/or aliphatic diacid ester, furan species and/or thiophene species, pyridone dicarboxylic acid and/or pyridone dicarboxylic acid ester is 0.03-0.3: 100.
In some preferred embodiments, the molar ratio of the stabilizer to the sum of the three components of the aliphatic diacid and/or aliphatic diacid ester, furan substance and/or thiophene substance, pyridone dicarboxylic acid and/or pyridone dicarboxylic acid ester is 0.05-0.3: 100.
That is, in another aspect, the component (1) is an aliphatic diacid and/or an aliphatic diacid ester; component (2) furan dicarboxylic acid and/or furan dicarboxylate, thiophene dicarboxylic acid and/or thiophene dicarboxylate; the total molar weight of the pyridone dicarboxylic acid and/or the pyridone dicarboxylate of the component (3) is calculated, the content of the esterification or ester exchange catalyst is 0.03mol percent to 0.3mol percent, the content of the polycondensation catalyst is 0.03mol percent to 0.3mol percent, and the content of the stabilizer is 0.05mol percent to 0.3mol percent.
In some preferred embodiments, the esterification catalyst and/or the transesterification catalyst includes any one or a combination of two or more of a zinc-based catalyst, a manganese-based catalyst, a titanium-based catalyst, and a tin-based catalyst, and is not limited thereto.
Further, the zinc-based catalyst includes zinc acetate and the like, and is not limited thereto.
Further, the manganese-based catalyst includes manganese acetate and the like, and is not limited thereto.
Further, the titanium-based catalyst includes tetrabutyl titanate, isopropyl titanate, and the like, and is not limited thereto.
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.
In some preferred embodiments, the polycondensation catalyst includes any one or a combination of two or more of a titanium-based catalyst, a tin-based catalyst, an antimony-based catalyst, and a germanium-based catalyst, and 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, and is not limited thereto.
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 antimony-based catalyst includes any one or a combination of two or more of antimony trioxide, ethylene glycol antimony, antimony acetate, polyethylene glycol antimony, and the like, but is not limited thereto.
Further, the germanium-based catalyst includes germanium dioxide, germanium oxide, and the like, but is not limited thereto.
In some preferred embodiments, the stabilizer includes a phosphorus-based stabilizer including any one or a combination of two or more 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 being limited thereto.
In another aspect of the embodiment of the present invention, there is also provided a degradable high-barrier ultraviolet-resistant bio-based polyester prepared by the foregoing preparation method, where the degradable high-barrier ultraviolet-resistant bio-based polyester has a structure shown in formula (II):
wherein R is a carbon chain structure of cyclic dihydric alcohol or aliphatic dihydric alcohol, R' is a carbon chain structure of aliphatic dibasic acid, and p and q are independently selected from integers of 1-10; m and n are independently selected from integers of 0-10; x is-NH, -NCH 3 O or S, y is 1-2.
Further, m and n are not 0 at the same time.
Further, R is the carbon chain structure of the cyclic diol or the aliphatic diol, and R' is the carbon chain structure of the aliphatic diacid.
Further, the degradable high-barrier uvioresistant biological-based polyester has the mass loss of 30-80% in seawater within 30 days, the ultraviolet transmittance below 400nm is lower than 6%, and CO is 2 Has a gas permeability coefficient of 0.01 to 0.05barrer, O 2 The gas permeability coefficient of (A) is 0.015 to 0.035 barrer.
For example, the degradable high-barrier ultraviolet-resistant bio-based polyester film has rapid degradation performance in seawater.
In another aspect of the embodiment of the invention, the application of the degradable high-barrier ultraviolet-resistant bio-based polyester in packaging materials or mulching films of foods, beverages or medicines is also provided.
Further, the packaging material is a degradable high-barrier ultraviolet-resistant material.
The technical solutions of the present invention are further described in detail below with reference to several preferred embodiments and the accompanying drawings, which are implemented on the premise of the technical solutions of the present invention, and a detailed implementation manner and a specific operation process are provided, but the scope of the present invention is not limited to the following embodiments.
The experimental materials used in the examples used below were all available from conventional biochemical reagents companies, unless otherwise specified. The pyridonecarboxylic acids used in the following examples have the structure shown by the following formula:
example 1
Adding succinic acid, 2, 5-furandicarboxylic acid, pyridone dicarboxylic acid and ethylene glycol into a reactor according to the molar ratio of 0.3: 0.6: 0.1: 3.0, then adding anhydrous zinc acetate with the total molar amount of 0.03 percent of the succinic acid, the 2, 5-furandicarboxylic acid and the pyridone dicarboxylic acid, gradually heating to 180 ℃ under the protection of nitrogen, reacting for 4.0h, then adding antimony trioxide with the total molar amount of 0.03 percent of the succinic acid, the 2, 5-furandicarboxylic acid and the pyridone dicarboxylic acid and trimethyl phosphate with the total molar amount of 0.05 percent, gradually heating to 220 ℃, reacting for 3.5h, and reducing the vacuum degree to 25Pa to obtain the poly (ethylene succinate-co-pyridone dicarboxylic acid glycol) -co-2, 5-furandicarboxylic acid glycol. The ultraviolet transmittance of the polyethylene succinate-co-pyridone dicarboxylate-co-2, 5-furan dicarboxylate in a 400-320 nm waveband is lower than 2.3%. Can be both biodegradable and hydrolytically degradable. CO2 2 Has a gas permeability coefficient of 0.01barrer, O 2 Has a gas permeability coefficient of 0.015 barrer.
The present inventors also analyzed pyridonecarboxylic acids used in this example. FIG. 1 is a nuclear magnetic hydrogen spectrum of polyethylene glycol succinate-co-pyridone dicarboxylate-co-2, 5-furandicarboxylate prepared in this example, wherein the structural correctness can be determined; in addition, fig. 3 is an ultraviolet transmission curve diagram of the polyethylene glycol succinate-co-pyridone dicarboxylate prepared in the embodiment and the pure ethylene glycol succinate in comparative example 1, and it can be seen that the original ethylene glycol succinate has no ultraviolet shielding capability at a wavelength of 400-320 nm, and the ultraviolet resistance of the polyethylene glycol succinate added with pyridone dicarboxylic acid is obviously improved, and the transmittance is lower than 2.3%.
Comparative example 1
Adding dimethyl succinate and ethylene glycol into a reactor according to the molar ratio of 1: 2.0, then adding dibutyltin oxide with the molar weight of 0.4% of dimethyl succinate, gradually heating to 175 ℃ under the protection of nitrogen, reacting for 4.5 hours, then adding polyethylene glycol antimony with the molar weight of 0.25% of dimethyl succinate and 0.05% of dimethyl phosphate, gradually heating to 240 ℃, reacting for 3.2 hours, and reducing the vacuum degree to 30Pa to obtain the poly (diethylene glycol succinate). The ultraviolet transmittance of the polyethylene glycol succinate in a 400-320 nm waveband is higher than 90.0%. Can be biologically or hydrolytically degraded. CO2 2 Has a gas permeability coefficient of 0.32barrer, O 2 Has a gas permeability coefficient of 0.066 barrer.
Comparative example 2
Adding 2, 5-furandicarboxylic acid, pyridone dicarboxylic acid and ethylene glycol into a reactor according to the molar ratio of 0.9: 0.1: 3.0, then adding anhydrous zinc acetate with the total molar amount of 0.05 percent of 2, 5-furandicarboxylic acid and pyridone dicarboxylic acid, gradually heating to 176 ℃ under the protection of nitrogen, reacting for 4.0h, then adding antimony trioxide with the total molar amount of 0.03 percent of 2, 5-furandicarboxylic acid and pyridone dicarboxylic acid and 0.05 percent diphenyl phosphite, gradually heating to 240 ℃, reacting for 4.0h, and reducing the vacuum degree to 35Pa to obtain the poly (pyridone dicarboxylic acid) ethylene glycol-co-2, 5-furandicarboxylic acid. The ultraviolet transmittance of the polyethylene pyridone dicarboxylate-co-2, 5-furandicarboxylate in a 400-320 nm waveband is lower than 2.5%. CO2 2 Has a gas permeability coefficient of 0.007barrer, O 2 Has a gas permeability coefficient of 0.01 barrer.
Comparative example 3
Adding succinic acid, pyridone dicarboxylic acid and ethylene glycol into a reactor according to the mol ratio of 0.9: 0.1: 3.0, then adding succinic acid, 2, 5-furandicarboxylic acid and pyridone dimethylAnhydrous zinc acetate with the total molar amount of acid of 0.03 percent, under the protection of nitrogen, gradually heating to 180 ℃, reacting for 4.0h, then adding antimony trioxide with the total molar amount of succinic acid and pyridone dicarboxylic acid of 0.03 percent and trimethyl phosphate with the total molar amount of 0.05 percent, gradually heating to 210 ℃, reacting for 3.5h, and reducing the vacuum degree to 25Pa to obtain the poly (ethylene succinate) -co-pyridone dicarboxylic acid glycol ester. The ultraviolet transmittance of the polyethylene glycol succinate-co-pyridone glycol diformate in a wave band of 400-320 nm is lower than 2.4%. Can be both biodegradable and hydrolytically degradable. CO2 2 Has a gas permeability coefficient of 0.32barrer, O 2 Has a gas permeability coefficient of 0.07 barrer.
Comparative example 4
Adding succinic acid, 2, 5-thiophenedicarboxylic acid and ethylene glycol into a reactor according to the molar ratio of 0.4: 0.6: 3.0, then adding anhydrous zinc acetate with the total molar amount of the succinic acid and the 2, 5-thiophenedicarboxylic acid being 0.03 percent, gradually heating to 180 ℃ under the protection of nitrogen, reacting for 4.0h, then adding antimony trioxide with the total molar amount of the succinic acid and the 2, 5-thiophenedicarboxylic acid being 0.03 percent and trimethyl phosphate with the total molar amount of the 0.05 percent, gradually heating to 230 ℃, reacting for 4h, and reducing the vacuum degree to 25Pa to obtain the poly (ethylene succinate) -co-2, 5-thiophenedicarboxylic acid ethylene glycol ester. The ultraviolet transmittance of the polyethylene succinate-co-2, 5-thiophene dicarboxylic acid glycol ester in a 400-320 nm waveband is higher than 89%. Can be both biodegradable and hydrolytically degradable. CO2 2 Has a gas permeability coefficient of 0.0.12barrer, O 2 Has a gas permeability coefficient of 0.016 barrer.
Example 2
Adding succinic acid, 2, 5-furandicarboxylic acid, pyridone dicarboxylic acid and propylene glycol into a reactor according to the molar ratio of 0.42: 0.5: 0.08: 3.0, then adding anhydrous zinc acetate with the total molar amount of 0.06% of the succinic acid, the 2, 5-furandicarboxylic acid and the pyridone dicarboxylic acid, gradually heating to 175 ℃ under the protection of nitrogen, reacting for 4.5h, then adding antimony trioxide with the total molar amount of 0.06% of the succinic acid, the 2, 5-furandicarboxylic acid and the pyridone dicarboxylic acid, 0.2% trimethyl phosphate and 0.05% diphenyl phosphite, gradually heating to 220 ℃ for reacting for 3.5h, and reducing the vacuum degree to 20Pa to obtain the polybutylece terephthalatePropylene glycol diacid-co-2, 5-furandicarboxylic acid propylene glycol-co-pyridonecarboxylic acid propylene glycol ester. The ultraviolet transmittance of the poly (propylene succinate) -co-2, 5-furandicarboxylic acid propylene glycol-co-pyridone diformic acid propylene glycol ester in a waveband of 400-320 nm is lower than 2.6%. Can be both biodegradable and hydrolytically degradable. CO2 2 Has a gas permeability coefficient of 0.018barrer, O 2 Has a gas permeability coefficient of 0.019 barrer.
Example 3
Glutaric acid, 2, 5-furandicarboxylic acid, pyridone dicarboxylic acid and butanediol are added into a reactor according to the molar ratio of 0.54: 0.4: 0.06: 2.6, then anhydrous zinc acetate with the total molar amount of 0.07 percent of glutaric acid, 2, 5-furandicarboxylic acid and pyridone dicarboxylic acid is added, under the protection of nitrogen, the temperature is gradually increased to 150 ℃ for reaction for 3.0h, then antimony trioxide with the total molar amount of 0.07 percent of glutaric acid, 2, 5-furandicarboxylic acid and pyridone dicarboxylic acid and trimethyl phosphate with the total molar amount of 0.3 percent are added, the temperature is gradually increased to 190 ℃, the reaction is carried out for 4.0h, the vacuum degree is reduced to 15Pa, and the polybutylene glutarate-co-2, 5-furandicarboxylic acid butanediol-co-pyridone dicarboxylic acid butanediol ester is obtained. The ultraviolet transmittance of the polybutylene glutarate-co-2, 5-furandicarboxylate-co-pyridone dicarboxylate in a 400-320 nm waveband is lower than 3.8%. Can be both biodegradable and hydrolytically degradable. CO2 2 Has a gas permeability coefficient of 0.027barrer, O 2 Has a gas permeability coefficient of 0.022 barrer.
Example 4
Adding adipic acid, 2, 4-furandicarboxylic acid, pyridone dicarboxylic acid and cis-1, 4-cyclohexanedimethanol into a reactor according to the molar ratio of 0.66: 0.3: 0.04: 2.0, then adding anhydrous manganese acetate with the total molar amount of 0.08 percent of the total molar amount of the adipic acid, the 2, 4-furandicarboxylic acid and the pyridone dicarboxylic acid, gradually heating to 175 ℃ under the protection of nitrogen, reacting for 2.0h, then adding ethylene glycol antimony with the total molar amount of 0.08 percent of the total molar amount of the adipic acid, the 2, 4-furandicarboxylic acid and the pyridone dicarboxylic acid, and 0.2 percent phosphorous acid, gradually heating to 230 ℃, reacting for 1.5h, and reducing the vacuum degree to 20Pa to obtain the poly (adipic acid) cis-1, 4-cyclohexanedimethanol-co-2, 4-furandicarboxylic acid cis-1, 4-cyclohexanedimethanol-co-2, 4-furandicarboxylic acidPyridone dicarboxylic acid cis-1, 4-cyclohexanedimethyl ester. The ultraviolet transmittance of the poly adipic acid cis-1, 4-cyclohexanedimethanol-co-2, 4-furandicarboxylic acid cis-1, 4-cyclohexanedimethanol-co-pyridone dicarboxylic acid cis-1, 4-cyclohexanedimethylene ester in a waveband of 400-320 nm is lower than 4.5%. Can be both biodegradable and hydrolytically degradable. CO2 2 Has a gas permeability coefficient of 0.031barrer, O 2 Has a gas permeability coefficient of 0.028 barrer.
Example 5
Adding dimethyl succinate, dimethyl 2, 4-furandicarboxylate, dimethyl pyridone dicarboxylate and pentanediol into a reactor according to the molar ratio of 0.78: 0.2: 0.02: 2.2, then adding anhydrous manganese acetate with the total molar amount of the dimethyl succinate, the dimethyl 2, 4-furandicarboxylate and the dimethyl pyridone dicarboxylate of 0.09%, under the protection of nitrogen, gradually heating to 160 ℃, reacting for 5.0h, then adding ethylene glycol antimony with the total molar amount of the dimethyl succinate, the dimethyl 2, 4-furandicarboxylate and the dimethyl pyridone dicarboxylate of 0.09%, and 0.15% phosphorous acid, gradually heating to 200 ℃, reacting for 4.0h, and reducing the vacuum degree to 10Pa to obtain the poly (pentanediol succinate-co-2, 4-pentanediol furandicarboxylate-co-pentanediol pyridone dicarboxylate). The ultraviolet transmittance of the poly (butylene succinate) -co-2, 4-furandicarboxylic acid pentanediol-co-pyridone dicarboxylic acid pentanediol ester at a waveband of 400-320 nm is lower than 5.6%. Can be both biodegradable and hydrolytically degradable. CO2 2 Has a gas permeability coefficient of 0.039barrer, O 2 Has a gas permeability coefficient of 0.031 barrer.
Example 6
Adding dimethyl succinate, dimethyl 2, 4-furandicarboxylate, diethyl pyridone dicarboxylate and hexanediol into a reactor according to the molar ratio of 0.89: 0.1: 0.01: 2.0, then adding anhydrous manganese acetate with the total molar amount of the dimethyl succinate, the dimethyl 2, 4-furandicarboxylate and the diethyl pyridonate of 0.1%, under the protection of nitrogen, gradually heating to 150 ℃, reacting for 6.0h, then adding ethylene glycol antimony morpholine with the total molar amount of the dimethyl succinate, the dimethyl 2, 4-furandicarboxylate and the diethyl pyridonate of 0.1%, and triphenyl phosphate with the total molar amount of 0.1%, gradually adding dimethyl succinate, dimethyl 2, 4-furandicarboxylate and diethyl pyridonateHeating to 180 ℃, reacting for 6.0h, and reducing the vacuum degree to 200Pa to obtain the poly (hexamethylene succinate-co-2, 4-furandicarboxylic acid hexanediol-co-pyridone dicarboxylic acid hexanediol ester). The ultraviolet transmittance of the poly (hexamethylene succinate) -co-2, 4-furandicarboxylic acid hexanediol-co-pyridone dioctyl phthalate) in a waveband of 400-320 nm is lower than 5.9%. Can be both biodegradable and hydrolytically degradable. CO2 2 Has a gas permeability coefficient of 0.050barrer, O 2 Has a gas permeability coefficient of 0.035 barrer.
Example 7
Dimethyl glutarate, dimethyl 2, 3-furandicarboxylate, dipropyl pyridone dicarboxylate and trans-1, 4-cyclohexanedimethanol are added into a reactor according to the molar ratio of 0.8: 0.1: 2.0, then dibutyltin oxide with the total molar amount of 0.2 percent of the total molar amount of the dimethyl glutarate, the dimethyl 2, 3-furandicarboxylate and the dipropyl pyridone dicarboxylate is added, under the protection of nitrogen, the temperature is gradually increased to 185 ℃ for reaction for 4.0h, then polyethylene glycol antimony with the total molar amount of 0.15 percent of the total molar amount of the dimethyl glutarate, the dimethyl 2, 3-furandicarboxylate and the dipropyl pyridone dicarboxylate and 0.1 percent of triphenyl phosphate are added, the temperature is gradually increased to 220 ℃, the reaction is carried out for 4.0h, the vacuum degree is reduced to 20Pa, and the trans-1, 4-cyclohexanedimethanol-co-2, 3-furandicarboxylic acid poly (1), 4-cyclohexanedimethanol-co-pyridone dicarboxylic acid trans-1, 4-cyclohexanedimethanol ester. The ultraviolet transmittance of the polyglutamic acid trans-1, 4-cyclohexanedimethanol-co-2, 3-furandicarboxylic acid trans-1, 4-cyclohexanedimethanol-co-pyridone dicarboxylic acid trans-1, 4-cyclohexanedimethanol ester at a waveband of 400-320 nm is lower than 2.1%. Can be both biodegradable and hydrolytically degradable. CO2 2 Has a gas permeability coefficient of 0.048barrer, O 2 Has a gas permeability coefficient of 0.033 barrer.
Example 8
Adding dimethyl adipate, dimethyl 2, 3-furandicarboxylate, dibutyl pyridone dicarboxylate and 4, 4-dicyclohexyl glycol into a reactor according to the molar ratio of 0.72: 0.2: 0.08: 1.2, then adding dibutyltin oxide accounting for 0.3 percent of the total molar amount of the dimethyl adipate, the dimethyl 2, 3-furandicarboxylate and the dibutyl pyridone dicarboxylate,gradually heating to 200 ℃ under the protection of nitrogen, reacting for 4.5h, then adding polyethylene glycol antimony with the total molar weight of dimethyl adipate and dibutyl pyridone of 0.2% and triphenyl phosphate with the total molar weight of 0.15%, gradually heating to 240 ℃, reacting for 1.5h, and reducing the vacuum degree to 40Pa to obtain 4, 4-dicyclohexyl glycol-co-2, 3-furandicarboxylic acid 4, 4-dicyclohexyl glycol-co-pyridone dicarboxylic acid 4, 4-dicyclohexyl glycol. The ultraviolet transmittance of the poly (4, 4-dicyclohexylene glycol-co-2, 3-furandicarboxylic acid 4, 4-dicyclohexylene glycol-co-pyridone dicarboxylic acid 4, 4-dicyclohexylene glycol ester at the waveband of 400-320 nm is lower than 2.8%. Can be both biodegradable and hydrolytically degradable. CO2 2 Has a gas permeability coefficient of 0.040barrer, O 2 Has a gas permeability coefficient of 0.030 barrer.
Example 9
Adding adipic acid, 2, 3-furandicarboxylic acid, pyridone dicarboxylic acid and diethylene glycol into a reactor according to the molar ratio of 0.64: 0.3: 0.06: 1.8, then adding dibutyltin oxide with the total molar amount of 0.04% of adipic acid, 2, 3-furandicarboxylic acid and pyridone dicarboxylic acid, gradually heating to 175 ℃ under the protection of nitrogen, reacting for 4.5 hours, then adding polyethylene glycol antimony with the total molar amount of 0.25% of adipic acid, 2, 3-furandicarboxylic acid and pyridone dicarboxylic acid and 0.05% of dimethyl phosphate, gradually heating to 200 ℃, reacting for 3.2 hours, and reducing the vacuum degree to 30Pa to obtain the polyethylene adipate diethylene glycol-co-2, 3-furandicarboxylic acid diethylene glycol-co-pyridone dicarboxylic acid diethylene glycol. The ultraviolet transmittance of the polydiethylene glycol adipate-co-2, 3-furandicarboxylic acid diethylene glycol-co-pyridone dicarboxylic acid diethylene glycol ester in a waveband of 400-320 nm is lower than 3.9%. Can be both biodegradable and hydrolytically degradable. CO2 2 Has a gas permeability coefficient of 0.031barrer, O 2 Has a gas permeability coefficient of 0.027 barrer.
Example 10
Adding succinic acid, 2, 5-furandicarboxylic acid, pyridone dicarboxylic acid and triethylene glycol into a reactor according to the mol ratio of 0.56: 0.4: 0.04: 1.8, and then adding anhydrous zinc acetate with the total molar weight of the succinic acid, the 2, 5-furandicarboxylic acid and the pyridone dicarboxylic acid being 0.03 percentGradually heating to 180 ℃ under the protection of nitrogen, reacting for 2.5h, then adding polyethylene glycol antimony with the total molar weight of succinic acid, 2, 5-furandicarboxylic acid and pyridone dicarboxylic acid being 0.3% and dimethyl phosphate with the total molar weight of 0.05%, gradually heating to 205 ℃, reacting for 2.0h, and reducing the vacuum degree to 20Pa to obtain the poly (triethylene glycol succinate) -co-2, 5-furandicarboxylic acid triethylene glycol-co-pyridone dicarboxylic acid triethylene glycol ester. The ultraviolet transmittance of the poly (triethylene glycol succinate-co-2, 5-furandicarboxylic acid-co-pyridone dicarboxylic acid triethylene glycol ester at the waveband of 400-320 nm is lower than 4.4%. Can be both biodegradable and hydrolytically degradable. CO2 2 Has a gas permeability coefficient of 0.026barrer, O 2 Has a gas permeability coefficient of 0.021 barrer.
Example 11
Glutaric acid, 2, 5-furandicarboxylic acid, pyridone dicarboxylic acid and neopentyl glycol are added into a reactor according to the molar ratio of 0.48: 0.5: 0.02: 2.0, then anhydrous zinc acetate with the total molar amount of 0.05 percent of glutaric acid, 2, 5-furandicarboxylic acid and pyridone dicarboxylic acid is added, under the protection of nitrogen, the temperature is gradually increased to 170 ℃, the reaction is carried out for 4.0h, then antimony trioxide with the total molar amount of 0.15 percent of glutaric acid, 2, 5-furandicarboxylic acid and pyridone dicarboxylic acid, 0.1 percent of germanium oxide and 0.2 percent of dimethyl phosphate are added, the temperature is gradually increased to 200 ℃, the reaction is carried out for 2.5h, the vacuum degree is reduced to 60Pa, and the neopentyl glycol-co-pyridone dicarboxylate is obtained. The ultraviolet transmittance of the neopentyl glycol polyglutamate-co-2, 5-furandicarboxylic acid neopentyl glycol-co-pyridone dicarboxylate in a 400-320 nm waveband is lower than 5.6%. Can be both biodegradable and hydrolytically degradable. CO2 2 Has a gas permeability coefficient of 0.017barrer, O 2 Has a gas permeability coefficient of 0.018 barrer.
Example 12
Adding adipic acid, 2, 5-furandicarboxylic acid, pyridone dicarboxylic acid and 2-methyl-1, 3-propanediol into a reactor according to the molar ratio of 0.39: 0.6: 0.01: 1.8, then adding anhydrous zinc acetate with the total molar weight of 0.07 percent of the adipic acid, the 2, 5-furandicarboxylic acid and the pyridone dicarboxylic acid, and gradually adding the mixture under the protection of nitrogenHeating to 190 ℃, reacting for 3.5h, then adding ethylene glycol antimony with the total molar weight of adipic acid, 2, 5-furandicarboxylic acid and pyridone dicarboxylic acid being 0.2 percent, germanium dioxide being 0.05 percent and dimethyl phosphate being 0.2 percent, gradually heating to 190 ℃, reacting for 5.5h, and reducing the vacuum degree to 100Pa to obtain the poly-2-methyl-1, 3-propanediol-co-2, 5-furandicarboxylic acid 2-methyl-1, 3-propanediol-co-pyridone dicarboxylic acid 2-methyl-1, 3-propanediol. The ultraviolet transmittance of the poly adipic acid 2-methyl-1, 3-propylene glycol-co-2, 5-furandicarboxylic acid 2-methyl-1, 3-propylene glycol-co-pyridone dicarboxylic acid 2-methyl-1, 3-propylene glycol ester in a waveband of 400-320 nm is lower than 5.8%. Can be both biodegradable and hydrolytically degradable. CO2 2 Has a gas permeability coefficient of 0.012barrer, O 2 Has a gas permeability coefficient of 0.016 barrer.
Example 13
Adding dimethyl glutarate, dimethyl 2, 4-furandicarboxylate, dibutyl pyridone dicarboxylate and trans-1, 4-cyclohexanedimethanol into a reactor according to the molar ratio of 0.3: 0.6: 0.1: 2.0, then adding anhydrous manganese acetate with the total molar amount of the dimethyl glutarate, the dimethyl 2, 4-furandicarboxylate and the dibutyl pyridone dicarboxylate of 0.08%, gradually heating to 180 ℃ under the protection of nitrogen, reacting for 4.0h, then adding germanium oxide with the total molar amount of the dimethyl glutarate, the dimethyl 2, 4-furandicarboxylate and the dibutyl pyridone dicarboxylate of 0.045%, gradually heating to 220 ℃ with 0.2% of phosphorous acid, reacting for 3.0h, and reducing the vacuum degree to 50Pa to obtain trans-1, 4-cyclohexanedimethanol-co-2, 4-furandicarboxylate 1 polyglutamic acid, 4-cyclohexanedimethanol-co-pyridone dicarboxylic acid trans-1, 4-cyclohexanedimethanol ester. The ultraviolet transmittance of the polyglutamic acid trans-1, 4-cyclohexanedimethanol-co-2, 4-furandicarboxylic acid trans-1, 4-cyclohexanedimethanol-co-pyridone dicarboxylic acid trans-1, 4-cyclohexanedimethanol ester at a waveband of 400-320 nm is lower than 2.2%. Can be both biodegradable and hydrolytically degradable. CO2 2 Has a gas permeability coefficient of 0.011barrer, O 2 Has a gas permeability coefficient of 0.016 barrer.
Example 14
Mixing dimethyl succinate and 2, 4-furandicarboxylic acidDimethyl ester, pyridone dimethyl phthalate and 1, 2-cyclohexanedimethanol are added into a reactor according to the mol ratio of 0.37: 0.55: 0.08: 2.0, then adding anhydrous manganese acetate with the total molar weight of dimethyl succinate, dimethyl 2, 4-furandicarboxylate and dimethyl pyridone dicarboxylate being 0.09%, gradually heating to 185 ℃ under the protection of nitrogen, reacting for 2.5h, then adding germanium oxide accounting for 0.05 percent of the total molar weight of dimethyl succinate, dimethyl 2, 4-furandicarboxylate and dimethyl pyridonate and 0.25 percent of phosphorous acid, gradually heating to 210 ℃, reacting for 4.0h, and reducing the vacuum degree to 30Pa to obtain the poly (1, 2-cyclohexanedimethanol-co-2, 4-furandicarboxylate 1, 2-cyclohexanedimethanol-co-pyridonate dicarboxylate). The ultraviolet transmittance of the poly (1, 2-cyclohexanedimethanol succinate) -co-2, 4-furandicarboxylic acid 1, 2-cyclohexanedimethanol-co pyridone dicarboxylic acid 1, 2-cyclohexanedimethanol ester at a waveband of 400-320 nm is lower than 2.8%. Can be both biodegradable and hydrolytically degradable. CO2 2 Has a gas permeability coefficient of 0.014barrer, O 2 Has a gas permeability coefficient of 0.017 barrer.
Example 15
Adding dimethyl glutarate, dimethyl 2, 4-furandicarboxylate, diethyl pyridone dicarboxylate and 1, 3-cyclohexanedimethanol into a reactor according to the molar ratio of 0.44: 0.5: 0.06: 2.0, then adding anhydrous manganese acetate with the total molar amount of the dimethyl glutarate, the dimethyl 2, 4-furandicarboxylate and the diethyl pyridone dicarboxylate of 0.1%, gradually heating to 180 ℃ under the protection of nitrogen, reacting for 5.0h, then adding polyethylene glycol antimony with the total molar amount of the dimethyl glutarate, the dimethyl 2, 4-furandicarboxylate and the diethyl pyridone dicarboxylate of 0.05%, and 0.25% phosphorous acid, gradually heating to 195 ℃, reacting for 4.0h, reducing the vacuum degree to 30Pa to obtain 1, 3-cyclohexanedimethanol-co-2, 4-furandicarboxylate, 3-cyclohexanedimethanol-co-pyridone dicarboxylate 1, 3-cyclohexanedimethanol ester. The ultraviolet transmittance of the 1, 3-cyclohexanedimethanol-co-2, 4-furandicarboxylic acid 1, 3-cyclohexanedimethanol-co-pyridone diformate 1, 3-cyclohexanedimethanol at a waveband of 400-320 nm is lower than 3.9%. Can be either biodegradable or biodegradableAnd (4) hydrolyzing and degrading. CO2 2 Has a gas permeability coefficient of 0.017barrer, O 2 Has a gas permeability coefficient of 0.19 barrer.
Example 16
Adding dimethyl adipate, dimethyl 2, 3-furandicarboxylate, dipropyl pyridone dicarboxylate and dicyclopentanediol into a reactor according to the mol ratio of 0.51: 0.45: 0.04: 1.8, then adding dibutyltin oxide with the total molar weight of 0.05 percent of dimethyl adipate, dimethyl 2, 3-furandicarboxylate and dipropyl pyridonecarboxylate, gradually heating to 185 ℃ under the protection of nitrogen, reacting for 2.5 hours, then polyethylene glycol antimony accounting for 0.1 percent of the total molar weight of dimethyl adipate, dimethyl 2, 3-furandicarboxylate and dipropyl pyridonecarboxylate and 0.25 percent diphenyl phosphate are added, the temperature is gradually increased to 210 ℃, the reaction lasts for 3.5 hours, the vacuum degree is reduced to 60Pa, and the dicyclopentadiene polyadipate-co-2, 3-furandicarboxylate-co-pyridonecarboxylate is obtained. The ultraviolet transmittance of the poly-adipic acid dicyclopentanediol-co-2, 3-furandicarboxylic acid dicyclopentanediol-co-pyridone dicarboxylic acid dicyclopentanediol ester in a waveband of 400-320 nm is lower than 4.3%. Can be both biodegradable and hydrolytically degradable. CO2 2 Has a gas permeability coefficient of 0.022barrer, O 2 Has a gas permeability coefficient of 0.021 barrer.
Example 17
Adding dimethyl succinate, dimethyl 2, 3-furandicarboxylate, dibutyl pyridone dicarboxylate and octanediol into a reactor according to the molar ratio of 0.58: 0.4: 0.02: 1.4, then adding dibutyltin oxide with the total molar amount of 0.2 percent of dimethyl succinate, dimethyl 2, 3-furandicarboxylate and dibutyl pyridone dicarboxylate, under the protection of nitrogen, gradually heating to 155 ℃, reacting for 4.5 hours, then adding polyethylene glycol antimony with the total molar amount of 0.12 percent of dimethyl succinate, dimethyl 2, 3-furandicarboxylate and dibutyl pyridone dicarboxylate and 0.1 percent of diphenyl phosphate, gradually heating to 180 ℃, reacting for 5.0 hours, and reducing the vacuum degree to 35Pa to obtain octanediol polysuccinate-co-2, 3-octanediol furandicarboxylate-co-dioctyl pyridone dicarboxylate. The polysuccinic acid octanediol-co-2, 3-furandicarboxylic acid octanediol-co-pyridone dimethyl esterThe ultraviolet transmittance of the dioctyl glycol ester in the 400-320 nm wave band is lower than 5.4%. Can be both biodegradable and hydrolytically degradable. CO2 2 Has a gas permeability coefficient of 0.029barrer, O 2 Has a gas permeability coefficient of 0.023 barrer.
Example 18
Adding dimethyl succinate, dimethyl 2, 5-furandicarboxylate, dimethyl pyridone dicarboxylate and triethylene glycol into a reactor according to the molar ratio of 0.6: 0.3: 0.1: 2.0, then adding anhydrous zinc acetate with the total molar amount of the dimethyl succinate, the dimethyl 2, 5-furandicarboxylate and the dimethyl pyridone dicarboxylate being 0.25%, under the protection of nitrogen, gradually heating to 185 ℃, reacting for 4.5h, then adding antimony trioxide with the total molar amount of the dimethyl succinate, the dimethyl 2, 5-furandicarboxylate and the dimethyl pyridone dicarboxylate being 0.25%, and 0.1% trimethyl phosphate, gradually heating to 200 ℃, and reacting for 4.0h to obtain the triethylene glycol succinate-co-2, 5-triethylene glycol furandicarboxylate-co-triethylene glycol pyridone dicarboxylate. The ultraviolet transmittance of the poly (triethylene glycol succinate-co-2, 5-furandicarboxylic acid-co-pyridone dicarboxylic acid triethylene glycol ester at the waveband of 400-320 nm is lower than 2.1%. Can be both biodegradable and hydrolytically degradable. CO2 2 Has a gas permeability coefficient of 0.032barrer, O 2 Has a gas permeability coefficient of 0.027 barrer.
Example 19
Glutaric acid, 2, 5-furandicarboxylic acid, 2, 5-thiophenedicarboxylic acid, pyridonecarboxylic acid and butanediol are added into a reactor according to the molar ratio of 0.54: 0.1: 0.3: 0.06: 2.6, then adding anhydrous zinc acetate with the total molar weight of 0.07 percent of glutaric acid, 2, 5-furandicarboxylic acid, 2, 5-thiophenedicarboxylic acid and pyridonecarboxylic acid, gradually heating to 150 ℃ under the protection of nitrogen, reacting for 3.0h, then adding antimony trioxide with the total molar weight of glutaric acid, 2, 5-furandicarboxylic acid, 2, 5-thiophenedicarboxylic acid and pyridonecarboxylic acid being 0.07 percent and trimethyl phosphate with the total molar weight of 0.3 percent, gradually heating to 190 ℃, reacting for 4.0h, and reducing the vacuum degree to 15Pa to obtain the polybutylene glutarate-co-2, 5-furandicarboxylic acid butanediol-co-2, 5-thiophenedicarboxylic acid butanediol-co-pyridonecarboxylic acid butanediol ester. The ultraviolet transmittance of the polybutylene glutarate-co-2, 5-furandicarboxylic acid butanediol-co-2, 5-thiophenedicarboxylic acid butanediol-co-pyridonecarboxylic acid butanediol ester at the waveband of 400-320 nm is lower than 3.8%. Can be both biodegradable and hydrolytically degradable. The gas permeability coefficient of CO2 was 0.027barrer, and the gas permeability coefficient of O2 was 0.022 barrer.
Example 20
Adding succinic acid, 2, 5-furandicarboxylic acid, 2, 5-thiophenedicarboxylic acid, pyridone dicarboxylic acid and ethylene glycol into a reactor according to the molar ratio of 0.3: 0.5: 0.1: 3.0, then adding anhydrous zinc acetate with the total molar amount of the succinic acid, the 2, 5-furandicarboxylic acid, the 2, 5-thiophenedicarboxylic acid and the pyridone dicarboxylic acid being 0.03 percent, gradually heating to 180 ℃ under the protection of nitrogen, reacting for 4.0h, then adding antimony trioxide with the total molar amount of the succinic acid, the 2, 5-furandicarboxylic acid, the 2, 5-thiophenedicarboxylic acid and the pyridone dicarboxylic acid being 0.03 percent, 0.05 percent trimethyl phosphate, gradually heating to 220 ℃, reacting for 3.5h, and reducing the vacuum degree to 25Pa to obtain polyethylene succinate-co-pyridone dicarboxylic acid-co-2, 5-furandicarboxylic acid co-2, 5-Thiophenedicarboxylic acid ethylene glycol ester. The ultraviolet transmittance of the polyethylene succinate-co-pyridone dicarboxylate-co-2, 5-furan dicarboxylate-co-2, 5-thiophene dicarboxylate in a 400-320 nm waveband is lower than 2.3%. Can be both biodegradable and hydrolytically degradable. The gas permeability coefficient of CO2 was 0.01barrer and the gas permeability coefficient of O2 was 0.015 barrer.
Example 21
Adding dimethyl succinate, dimethyl 2, 5-thiophenedicarboxylate, dimethyl pyridone dicarboxylate and triethylene glycol into a reactor according to the molar ratio of 0.6: 0.3: 0.1: 2.0, then adding anhydrous zinc acetate with the total molar amount of the dimethyl succinate, the dimethyl 2, 5-thiophenedicarboxylate and the dimethyl pyridone dicarboxylate of 0.25%, gradually heating to 185 ℃ under the protection of nitrogen, reacting for 4.5h, then adding antimony trioxide with the total molar amount of the dimethyl succinate, the dimethyl 2, 5-thiophenedicarboxylate and the dimethyl pyridone dicarboxylate of 0.25% and 0.1% trimethyl phosphate, gradually heating to 200 ℃, and reacting for 4.0h to obtain the triethylene glycol succinate-co-2, 5-thiophenedicarboxylate-co-triethylene glycol pyridone dicarboxylate. The ultraviolet transmittance of the poly (triethylene glycol succinate-co-2, 5-thiophene dicarboxylic acid triethylene glycol-co-pyridone dicarboxylic acid triethylene glycol ester at the waveband of 400-320 nm is lower than 2.1%. Can be both biodegradable and hydrolytically degradable. The gas permeability coefficient of CO2 was 0.032barrer, and the gas permeability coefficient of O2 was 0.027 barrer.
Example 22
Adding dimethyl adipate, dimethyl 2, 5-thiophenedicarboxylate, dipropyl pyridone dicarboxylate and dicyclopentanediol into a reactor according to the mol ratio of 0.51: 0.45: 0.04: 1.8, then adding dibutyl tin oxide with the total molar weight of dimethyl adipate, dimethyl 2, 5-thiophenedicarboxylate and dipropyl pyridonecarboxylate being 0.05 percent, gradually heating to 185 ℃ under the protection of nitrogen, reacting for 2.5h, then polyethylene glycol antimony accounting for 0.1 percent of the total molar weight of dimethyl adipate, dimethyl 2, 5-thiophenedicarboxylate and dipropyl pyridonecarboxylate and diphenyl phosphate accounting for 0.25 percent are added, the temperature is gradually increased to 210 ℃, the reaction lasts for 3.5 hours, the vacuum degree is reduced to 60Pa, and the dicyclopentadiene poly-co-2, 5-thiophenedicarboxylate-co-pyridonecarboxylic acid dicyclopentanol ester is obtained. The ultraviolet transmittance of the poly-adipic acid dicyclopentanediol-co-2, 5-thiophene dicarboxylic acid dicyclopentanediol-co-pyridone dicarboxylic acid dicyclopentanediol ester in a waveband of 400-320 nm is lower than 4.3%. Can be both biodegradable and hydrolytically degradable. The gas permeability coefficient of CO2 was 0.022barrer, and the gas permeability coefficient of O2 was 0.021 barrer.
Example 23
Adding adipic acid, 2, 3-thiophenedicarboxylic acid, pyridone dicarboxylic acid and diethylene glycol into a reactor according to a molar ratio of 0.64: 0.3: 0.06: 1.8, then adding dibutyltin oxide with the total molar amount of 0.04% of the adipic acid, the 2, 3-thiophenedicarboxylic acid and the pyridone dicarboxylic acid, gradually heating to 175 ℃ under the protection of nitrogen, reacting for 4.5 hours, then adding polyethylene glycol antimony with the total molar amount of 0.25% of the adipic acid, the 2, 3-thiophenedicarboxylic acid and the pyridone dicarboxylic acid, and 0.05% of dimethyl phosphate, gradually heating to 200 ℃, reacting for 3.2 hours, and reducing the vacuum degree to 30Pa to obtain the polyethylene adipate diethylene glycol-co-2, 3-thiophenedicarboxylic acid diethylene glycol-co-pyridone dicarboxylic acid diethylene glycol. The ultraviolet transmittance of the polydiethylene glycol adipate-co-2, 3-thiophene dicarboxylic acid diethylene glycol-co-pyridone dicarboxylic acid diethylene glycol ester in a wave band of 400-320 nm is lower than 3.9%. Can be both biodegradable and hydrolytically degradable. The gas permeability coefficient of CO2 was 0.031barrer and the gas permeability coefficient of O2 was 0.027 barrer.
Example 24
Adding dimethyl glutarate, dimethyl 2, 4-thiophenedicarboxylate, dibutyl pyridone dicarboxylate and trans-1, 4-cyclohexanedimethanol into a reactor according to the molar ratio of 0.3: 0.6: 0.1: 2.0, then adding anhydrous manganese acetate with the total molar amount of the dimethyl glutarate, the dimethyl 2, 4-thiophenedicarboxylate and the dibutyl pyridone dicarboxylate of 0.08%, gradually heating to 180 ℃ under the protection of nitrogen, reacting for 4.0h, then adding germanium oxide with the total molar amount of the dimethyl glutarate, the dimethyl 2, 4-thiophenedicarboxylate and the dibutyl pyridone dicarboxylate of 0.045%, gradually heating to 220 ℃ with 0.2% of phosphorous acid, reacting for 3.0h, and reducing the vacuum degree to 50Pa to obtain trans-1, 4-cyclohexanedimethanol-co-2, 4-thiophenedicarboxylic acid trans-1 of the polyglutamic acid, 4-cyclohexanedimethanol-co-pyridone dicarboxylic acid trans-1, 4-cyclohexanedimethanol ester. The ultraviolet transmittance of the polyglutamic acid trans-1, 4-cyclohexanedimethanol-co-2, 4-thiophenedicarboxylic acid trans-1, 4-cyclohexanedimethanol-co-pyridone dicarboxylic acid trans-1, 4-cyclohexanedimethanol ester at a waveband of 400-320 nm is lower than 2.2%. Can be both biodegradable and hydrolytically degradable. The gas permeability coefficient of CO2 was 0.011barrer and the gas permeability coefficient of O2 was 0.016 barrer.
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.
It should be understood that the technical solution of the present invention is not limited to the above-mentioned specific embodiments, and all technical modifications made according to the technical solution of the present invention fall within the protection scope of the present invention without departing from the spirit of the present invention and the protection scope of the claims.
Claims (10)
1. A preparation method of degradable high-barrier uvioresistant bio-based polyester is characterized by comprising the following steps:
reacting a first mixed reaction system containing aliphatic diacid and/or aliphatic diacid ester, furan substances and/or thiophene substances, pyridone dicarboxylic acid and/or pyridone dicarboxylic acid ester, dihydric alcohol, an esterification catalyst and/or an ester exchange catalyst to obtain an intermediate product;
and reacting the second mixed reaction system containing the polycondensation catalyst, the stabilizer and the intermediate product under the vacuum condition to prepare the degradable high-barrier uvioresistant biological-based polyester.
2. The method of claim 1, wherein: the molar ratio of the aliphatic diacid and/or aliphatic diacid esterified ester, furan substances and/or thiophene substances to the pyridone dicarboxylic acid and/or pyridone dicarboxylic acid esterified ester is (0.3-0.9) to (0-0.69) to (0.01-0.1).
3. The method of claim 1, wherein: the aliphatic diacid and/or the aliphatic diacid ester comprises any one or the combination of more than two of succinic acid, glutaric acid, adipic acid, dimethyl succinate, dimethyl glutarate and dimethyl adipate;
and/or the furan-like substance comprises furan dicarboxylic acid and/or furan dicarboxylic acid ester; preferably, the furan dicarboxylic acid and/or furan dicarboxylate comprises any one or a combination of more than two of 2, 5-furan dicarboxylic acid, 2, 4-furan dicarboxylic acid, 2, 3-furan dicarboxylic acid, dimethyl 2, 5-furan dicarboxylate, dimethyl 2, 4-furan dicarboxylate and dimethyl 2, 3-furan dicarboxylate;
and/or the thiophene substances comprise thiophene dicarboxylic acid and/or thiophene dicarboxylate; preferably, the thiophene dicarboxylic acid and/or thiophene dicarboxylate comprises any one or a combination of more than two of 2, 5-thiophene dicarboxylic acid, 2, 4-thiophene dicarboxylic acid, 2, 3-thiophene dicarboxylic acid, dimethyl 2, 5-thiophene dicarboxylate, dimethyl 2, 4-thiophene dicarboxylate and dimethyl 2, 3-thiophene dicarboxylate;
and/or the pyridone dicarboxylic acid and/or pyridone dicarboxylate comprises any one or the combination of more than two of dimethyl pyridone dicarboxylate, diethyl pyridone dicarboxylate, dipropyl pyridone dicarboxylate and dibutyl pyridone dicarboxylate;
and/or the dihydric alcohol comprises a cyclic dihydric alcohol and/or an aliphatic dihydric alcohol;
preferably, the cyclic diol comprises any one or a combination of more than two of cis-1, 4-cyclohexanedimethanol, trans-1, 4-cyclohexanedimethanol, 1, 2-cyclohexanedimethanol, 1, 3-cyclohexanedimethanol, 4-bicyclohexane diol and dicyclopentanediol; preferably, the aliphatic diol includes any one or a combination of two or more of ethylene glycol, propylene glycol, butylene glycol, pentanediol, hexanediol, octanediol, decanediol, diethylene glycol, triethylene glycol, neopentyl glycol, and 2-methyl-1, 3-propanediol.
4. The method of claim 1, wherein: the pyridonecarboxylic acid has a structure represented by formula (I):
wherein X is-NH, -NCH 3 O or S; y is 1 to 2.
5. The method according to claim 1, comprising: reacting a first mixed reaction system containing aliphatic diacid and/or aliphatic diacid ester, furan substances and/or thiophene substances, pyridone dicarboxylic acid and/or pyridone dicarboxylate, dihydric alcohol, an esterification catalyst and/or an ester exchange catalyst at 150-200 ℃ for 2.0-6.0 h under a protective atmosphere to obtain the intermediate product.
6. The method according to claim 1, comprising: and (3) reacting a second mixed reaction system containing the polycondensation catalyst, the stabilizer and the intermediate product for 1.5-6 h under the conditions that the temperature is 180-240 ℃ and the vacuum degree is below 200Pa, so as to obtain the degradable high-barrier ultraviolet-resistant bio-based polyester.
7. The production method according to claim 1, characterized in that: the molar ratio of the sum of the three components of the aliphatic diacid and/or the aliphatic diacid ester, the furan substance and/or the thiophene substance, and the pyridone dicarboxylic acid and/or the pyridone dicarboxylic acid ester to the dihydric alcohol is 1: 1.2-3.0;
and/or the molar ratio of the esterification catalyst and/or the ester exchange catalyst to the sum of the aliphatic diacid and/or the aliphatic diacid ester, the furan substance and/or the thiophene substance, and the pyridone dicarboxylic acid and/or the pyridone dicarboxylic acid ester is 0.03-0.3: 100;
and/or the molar ratio of the polycondensation catalyst to the sum of the aliphatic diacid and/or aliphatic diacid ester, furan substance and/or thiophene substance, and pyridone dicarboxylic acid and/or pyridone dicarboxylate is 0.03-0.3: 100;
and/or the molar ratio of the stabilizer to the total of the aliphatic diacid and/or aliphatic diacid ester, furan substance and/or thiophene substance, and pyridone dicarboxylic acid and/or pyridone dicarboxylate is 0.05-0.3: 100.
8. The method of claim 1, wherein: the esterification catalyst and/or the ester exchange catalyst comprises any one or the combination of more than two of a zinc catalyst, a manganese catalyst, a titanium catalyst and a tin catalyst; preferably, the zinc-based catalyst comprises zinc acetate; preferably, the manganese-based catalyst comprises manganese acetate; preferably, the titanium-based catalyst comprises tetrabutyl titanate and/or isopropyl titanate; preferably, the tin catalyst comprises any one or a combination of more than two of dibutyltin oxide, stannous isooctanoate, monobutyl triisooctanoate tin and dioctyltin oxide;
and/or the polycondensation catalyst comprises any one or the combination of more than two of a titanium catalyst, a tin catalyst, an antimony catalyst and a germanium catalyst; preferably, the titanium catalyst comprises one or a combination of more than two of tetrabutyl titanate, isopropyl titanate, titanium dioxide and inorganic framework-supported titanium catalyst; preferably, the tin catalyst comprises any one or a combination of more than two of dibutyltin oxide, stannous isooctanoate, monobutyl triisooctanoate tin and dioctyltin oxide; preferably, the antimony catalyst comprises any one or a combination of more than two of antimony trioxide, ethylene glycol antimony, antimony acetate and polyethylene glycol antimony; preferably, the germanium-based catalyst comprises germanium dioxide and/or germanium oxide;
and/or the stabilizer comprises a phosphorus stabilizer, and the phosphorus stabilizer comprises any one or a 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. The degradable high-barrier ultraviolet-resistant bio-based polyester prepared by the preparation method of any one of claims 1 to 8, having a structure as shown in formula (II):
wherein R is a carbon chain structure of cyclic dihydric alcohol or aliphatic dihydric alcohol, R' is a carbon chain structure of aliphatic dibasic acid, and p and q are independently selected from integers of 1-10; m and n are independently selected from integers of 0-10; x is-NH, -NCH 3 O or S, y is 1-2;
preferably, theThe degradable high-barrier uvioresistant biological-based polyester has the mass loss of 30-80 percent in 30 days in seawater, the ultraviolet transmittance below 400nm is lower than 6 percent, and CO is 2 Has a gas permeability coefficient of 0.01 to 0.05barrer, O 2 The gas permeability coefficient of (A) is 0.015 to 0.035 barrer.
10. The use of the degradable high-barrier ultraviolet-resistant bio-based polyester of claim 9 in packaging materials or mulching films for food, beverages or medicines; preferably, the packaging material is a degradable high-barrier ultraviolet-resistant material.
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