CN116554452A - Polyester based on diglycolic acid or esterified product thereof, preparation method and product thereof - Google Patents
Polyester based on diglycolic acid or esterified product thereof, preparation method and product thereof Download PDFInfo
- Publication number
- CN116554452A CN116554452A CN202210103228.8A CN202210103228A CN116554452A CN 116554452 A CN116554452 A CN 116554452A CN 202210103228 A CN202210103228 A CN 202210103228A CN 116554452 A CN116554452 A CN 116554452A
- Authority
- CN
- China
- Prior art keywords
- diglycolic acid
- esterified product
- polyester
- cyclohexanedimethanol
- 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
Links
- QEVGZEDELICMKH-UHFFFAOYSA-N Diglycolic acid Chemical compound OC(=O)COCC(O)=O QEVGZEDELICMKH-UHFFFAOYSA-N 0.000 title claims abstract description 94
- 229920000728 polyester Polymers 0.000 title claims abstract description 69
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000003054 catalyst Substances 0.000 claims abstract description 77
- 239000000047 product Substances 0.000 claims abstract description 56
- 238000005886 esterification reaction Methods 0.000 claims abstract description 31
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000003381 stabilizer Substances 0.000 claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- 230000032050 esterification Effects 0.000 claims abstract description 23
- 238000005809 transesterification reaction Methods 0.000 claims abstract description 22
- 125000002723 alicyclic group Chemical group 0.000 claims abstract description 15
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 claims abstract description 14
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000013067 intermediate product Substances 0.000 claims abstract description 11
- 239000012298 atmosphere Substances 0.000 claims abstract description 10
- 230000001681 protective effect Effects 0.000 claims abstract description 8
- -1 alicyclic diol Chemical class 0.000 claims description 42
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 claims description 24
- 238000006068 polycondensation reaction Methods 0.000 claims description 18
- 150000002009 diols Chemical class 0.000 claims description 13
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 10
- 229910052719 titanium Inorganic materials 0.000 claims description 10
- 239000010936 titanium Substances 0.000 claims description 10
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 9
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 7
- 239000011701 zinc Substances 0.000 claims description 7
- 229910052725 zinc Inorganic materials 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 6
- 229910052787 antimony Inorganic materials 0.000 claims description 5
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 5
- PFURGBBHAOXLIO-UHFFFAOYSA-N cyclohexane-1,2-diol Chemical compound OC1CCCCC1O PFURGBBHAOXLIO-UHFFFAOYSA-N 0.000 claims description 5
- 150000002148 esters Chemical class 0.000 claims description 5
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical group [P] OAICVXFJPJFONN-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
- 229910052698 phosphorus Inorganic materials 0.000 claims description 4
- 239000011574 phosphorus Substances 0.000 claims description 4
- XDODWINGEHBYRT-UHFFFAOYSA-N [2-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCCCC1CO XDODWINGEHBYRT-UHFFFAOYSA-N 0.000 claims description 3
- LUSFFPXRDZKBMF-UHFFFAOYSA-N [3-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCCC(CO)C1 LUSFFPXRDZKBMF-UHFFFAOYSA-N 0.000 claims description 3
- RLMGYIOTPQVQJR-UHFFFAOYSA-N cyclohexane-1,3-diol Chemical compound OC1CCCC(O)C1 RLMGYIOTPQVQJR-UHFFFAOYSA-N 0.000 claims description 3
- OTLDLKLSNZMTTA-UHFFFAOYSA-N octahydro-1h-4,7-methanoindene-1,5-diyldimethanol Chemical compound C1C2C3C(CO)CCC3C1C(CO)C2 OTLDLKLSNZMTTA-UHFFFAOYSA-N 0.000 claims description 3
- PMMYEEVYMWASQN-IMJSIDKUSA-N cis-4-Hydroxy-L-proline Chemical compound O[C@@H]1CN[C@H](C(O)=O)C1 PMMYEEVYMWASQN-IMJSIDKUSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 6
- 239000000463 material Substances 0.000 abstract description 6
- 239000005003 food packaging material Substances 0.000 abstract description 4
- 229920001634 Copolyester Polymers 0.000 description 27
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 20
- 238000010438 heat treatment Methods 0.000 description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- 238000002411 thermogravimetry Methods 0.000 description 14
- 238000009264 composting Methods 0.000 description 11
- 238000005481 NMR spectroscopy Methods 0.000 description 9
- 230000015556 catabolic process Effects 0.000 description 8
- 238000006731 degradation reaction Methods 0.000 description 8
- 230000009477 glass transition Effects 0.000 description 8
- 238000002844 melting Methods 0.000 description 8
- 230000008018 melting Effects 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 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 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 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 7
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 description 6
- 239000004626 polylactic acid Substances 0.000 description 5
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 229920000954 Polyglycolide Polymers 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000008876 conformational transition Effects 0.000 description 3
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 description 3
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 3
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 229920000747 poly(lactic acid) Polymers 0.000 description 3
- 239000004633 polyglycolic acid Substances 0.000 description 3
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- 229940083957 1,2-butanediol Drugs 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- 239000004254 Ammonium phosphate Substances 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 2
- 235000019289 ammonium phosphates Nutrition 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- BMRWNKZVCUKKSR-UHFFFAOYSA-N butane-1,2-diol Chemical compound CCC(O)CO BMRWNKZVCUKKSR-UHFFFAOYSA-N 0.000 description 2
- 235000019437 butane-1,3-diol Nutrition 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229920002961 polybutylene succinate Polymers 0.000 description 2
- 239000004631 polybutylene succinate Substances 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- LVZWSLJZHVFIQJ-UHFFFAOYSA-N Cyclopropane Chemical compound C1CC1 LVZWSLJZHVFIQJ-UHFFFAOYSA-N 0.000 description 1
- KKUKTXOBAWVSHC-UHFFFAOYSA-N Dimethylphosphate Chemical compound COP(O)(=O)OC KKUKTXOBAWVSHC-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- YAINYZJQSQEGND-UHFFFAOYSA-N [1-(hydroxymethyl)cyclopropyl]methanol Chemical compound OCC1(CO)CC1 YAINYZJQSQEGND-UHFFFAOYSA-N 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 1
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 1
- WSXIMVDZMNWNRF-UHFFFAOYSA-N antimony;ethane-1,2-diol Chemical compound [Sb].OCCO WSXIMVDZMNWNRF-UHFFFAOYSA-N 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000002361 compost Substances 0.000 description 1
- VKONPUDBRVKQLM-UHFFFAOYSA-N cyclohexane-1,4-diol Chemical compound OC1CCC(O)CC1 VKONPUDBRVKQLM-UHFFFAOYSA-N 0.000 description 1
- JVLRYPRBKSMEBF-UHFFFAOYSA-K diacetyloxystibanyl acetate Chemical compound [Sb+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JVLRYPRBKSMEBF-UHFFFAOYSA-K 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- LQRUPWUPINJLMU-UHFFFAOYSA-N dioctyl(oxo)tin Chemical compound CCCCCCCC[Sn](=O)CCCCCCCC LQRUPWUPINJLMU-UHFFFAOYSA-N 0.000 description 1
- ASMQGLCHMVWBQR-UHFFFAOYSA-M diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(=O)([O-])OC1=CC=CC=C1 ASMQGLCHMVWBQR-UHFFFAOYSA-M 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 229940119177 germanium dioxide Drugs 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229940071125 manganese acetate Drugs 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 235000019837 monoammonium phosphate Nutrition 0.000 description 1
- 239000006012 monoammonium phosphate Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- PVADDRMAFCOOPC-UHFFFAOYSA-N oxogermanium Chemical compound [Ge]=O PVADDRMAFCOOPC-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- 239000005014 poly(hydroxyalkanoate) Substances 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 229940005657 pyrophosphoric acid Drugs 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 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 description 1
- 238000002076 thermal analysis method Methods 0.000 description 1
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 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 1
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
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
- C08G63/66—Polyesters containing oxygen in the form of ether groups
- C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/672—Dicarboxylic acids and dihydroxy compounds
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention relates to a polyester based on diglycolic acid or an esterified product thereof, a preparation method and a product thereof, wherein the preparation method comprises the following steps: reacting a first mixed reaction system comprising diglycolic acid or an esterified product thereof, a glycol and an esterification or transesterification catalyst under a protective atmosphere to obtain an intermediate product, wherein the glycol comprises alicyclic glycol and/or butanediol, and the alicyclic glycol has at least two conformations capable of being mutually converted; and the second mixed reaction system containing the intermediate product and the stabilizer reacts under the vacuum condition, so that the obtained polyester has excellent heat resistance, toughness and degradability, can be used for preparing products such as food packaging materials, mulching films, tissue engineering materials and the like, and has wide application.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a polyester based on diglycolic acid or an esterified product thereof, a preparation method and a product thereof.
Background
Currently, widely used polyesters include polylactic acid (PLA), polyhydroxyalkanoate (PHA), polyglycolic acid (PGA), polybutylene succinate (PBS) and the like, wherein the polylactic acid (PLA) is most expected to replace petroleum-based high polymer materials due to the biomass source and the biodegradation characteristics thereof; however, polylactic acid is hard and brittle in nature, is unfavorable for processing into products, and is poor in heat resistance, thus greatly limiting the application range.
Disclosure of Invention
In view of the above, it is necessary to provide a polyester based on diglycolic acid or an esterified product thereof, which has excellent heat resistance, toughness and degradability, and can be used for preparing products such as food packaging materials, mulching films, tissue engineering materials and the like, and a preparation method and a product thereof.
The invention provides a preparation method of polyester based on diglycolic acid or esterified substances thereof, which comprises the following steps:
reacting a first mixed reaction system comprising diglycolic acid or an esterified product thereof, a glycol and an esterification or transesterification catalyst under a protective atmosphere to obtain an intermediate product, wherein the glycol comprises alicyclic glycol and/or butanediol, and the alicyclic glycol has at least two conformations capable of being mutually converted; and
and (3) reacting a second mixed reaction system containing the intermediate product and a stabilizer under vacuum condition to obtain the polyester based on diglycolic acid or the esterified product thereof.
In one embodiment, the molar ratio of the butanediol to the cycloaliphatic diol is 1:9 to 9:1.
In one embodiment, the alicyclic diol includes at least one of cis-1, 4-cyclohexanedimethanol, trans-1, 4-cyclohexanedimethanol, 1, 2-cyclohexanedimethanol, 1, 3-cyclohexanedimethanol, 4-dicyclohexyl diol, 1, 4-cyclohexanediol, 1, 3-cyclohexanediol, 1, 2-cyclohexanediol, tricyclodecanedimethanol, or pentacyclopentadecanediol.
In one embodiment, when the alicyclic diol includes cis-1, 4-cyclohexanedimethanol and trans-1, 4-cyclohexanedimethanol, the molar ratio of the cis-1, 4-cyclohexanedimethanol to the trans-1, 4-cyclohexanedimethanol is in the range of 0.25:1 to 4:1.
In one embodiment, the molar ratio of the glycol to the diglycolic acid or the ester thereof is from 120:100 to 300:100.
In one embodiment, the esterification or transesterification catalyst comprises at least one of zinc-based catalyst, manganese-based catalyst, titanium-based catalyst and tin-based catalyst, and the molar ratio of the esterification or transesterification catalyst to the diglycolic acid or the esterified product thereof is 0.3:1000-3.0:1000;
and/or the stabilizer is selected from phosphorus stabilizers, and the molar ratio of the stabilizer to the diglycolic acid or the esterified product thereof is 0.4:1000-3.0:1000.
In one embodiment, when the esterification or transesterification catalyst is selected from zinc-based catalysts, a polycondensation catalyst is further added in the step of reacting the second mixed reaction system comprising the intermediate product and a stabilizer under vacuum conditions, the polycondensation catalyst comprising at least one of a titanium-based catalyst, a tin-based catalyst, an antimony-based catalyst, and a germanium-based catalyst, and the molar ratio of the polycondensation catalyst to the diglycolic acid or the esterified product thereof is 0.3:1000 to 3.0:1000.
In one embodiment, the temperature of the first mixed reaction system for reaction under the protective atmosphere is 160-240 ℃ for 2-6 h, and the vacuum degree of the second mixed reaction system is within 200Pa, the temperature is 220-290 ℃ for 1.5-6 h in the step of reacting under the vacuum condition.
A diglycolic acid or its esterified product-based polyester is prepared by the preparation method of the diglycolic acid or its esterified product-based polyester.
An article made from a diglycolic acid or an ester thereof based polyester as described above.
In the preparation method of the polyester based on diglycolic acid or the esterified product thereof, the ether oxygen bond in the diglycolic acid or the esterified product thereof endows the polyester chain segment with excellent flexibility, which is beneficial to the regular arrangement of the polyester chain segment and promotes crystallization; meanwhile, when the dihydric alcohol comprises alicyclic dihydric alcohol, the alicyclic dihydric alcohol has the characteristics of larger rigidity and space non-planar structure than butanediol, the heat resistance of the polyester can be further improved, the conformations of the alicyclic dihydric alcohol can be mutually converted, and when the polyester is impacted, part of energy can be absorbed by the conversion between the conformations, so that the impact resistance of the polyester is improved, namely the toughness of the polyester is improved, and diglycolic acid or an esterified product thereof is cooperated with the dihydric alcohol, so that the heat resistance and the toughness of the prepared polyester are further improved; in addition, the structural formula of the polyester does not contain an aromatic structure, so the polyester has excellent degradability.
The diglycolic acid-based polyester provided by the invention has excellent temperature resistance, toughness and degradation performance, and further, the product prepared from the polyester can be well applied to the fields of food packaging materials, mulching films, fibers, tissue engineering materials and the like, so that the application field and the application range of the polyester are greatly widened.
Drawings
FIG. 1 is a polybutylene diglycolate prepared in example 1 1 H-NMR spectrum;
FIG. 2 is a DSC graph of polybutylene diglycolate prepared in example 1;
FIG. 3 is a TGA spectrum of polybutylene diglycolate prepared in example 1;
FIG. 4 is a DSC graph of polybutylene 1, 4-cyclohexanedimethanol copolyester prepared in example 2;
FIG. 5 is a TGA spectrum of polybutylene 1, 4-cyclohexanedimethanol copolyester prepared in example 2.
Detailed Description
In order that the invention may be readily understood, a more particular description of the invention will be rendered by reference to specific embodiments that are illustrated in the appended drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The term "and/or" as used herein includes any and all combinations of one or more of the associated listed items.
The present invention provides a polyester based on diglycolic acid or an esterified product thereof, a method for preparing the same, and a product thereof.
The preparation method of the polyester based on diglycolic acid or the esterified product thereof provided by the invention comprises the following steps:
s10, reacting a first mixed reaction system containing diglycolic acid or an esterified product thereof, dihydric alcohol and an esterification or transesterification catalyst in a protective atmosphere to obtain an intermediate product; and
s20, reacting a second mixed reaction system containing the intermediate product and a stabilizer under vacuum condition to obtain the polyester based on diglycolic acid or the esterified product thereof.
In the preparation method of the polyester based on diglycolic acid or the esterified product thereof, the ether oxygen bond in the diglycolic acid or the esterified product thereof endows the polyester chain segment with excellent flexibility, which is beneficial to the regular arrangement of the polyester chain segment and promotes crystallization.
Specifically, in the first mixed reaction system of step S10, the diol includes alicyclic diol and/or butanediol, and it is understood that in one embodiment, the diol is selected from butanediol; in one embodiment, the diols are all selected from cycloaliphatic diols; in one embodiment, the diols include both butanediol and cycloaliphatic diols; the molar ratio of the dihydric alcohol to the diglycolic acid or the esterified product thereof is 120:100-300:100.
In one embodiment, the butanediol comprises 1, 2-butanediol, 1, 3-butanediol, and 1, 4-butanediol, and the 1, 4-butanediol is capable of making the arrangement of the polyester segments more regular than the 1, 2-butanediol and 1, 3-butanediol, thereby facilitating crystallization of the polyester, and thus the butanediol is preferably selected from 1, 4-butanediol.
It should be noted that, when the diol includes alicyclic diol, the alicyclic diol has at least two conformations capable of being mutually converted, and the alicyclic diol has the characteristics of greater rigidity and space non-planar structure than butanediol, so that the heat resistance of the polyester can be further improved, and further, diglycolic acid or the esterified product thereof and the diol cooperate to further improve the heat resistance and toughness of the prepared polyester.
It should be noted that, compared with cyclopropane having only one conformation, i.e., a planar conformation, the alicyclic structures in the other alicyclic diol structures have two or more conformations, the conformational transition can be realized, the conformations of the alicyclic structures having different numbers of carbon atoms are named differently, the six-membered alicyclic structure has a boat-type and a chair-type conformation, the five-membered alicyclic structure has an envelope-type and a half-chair-type conformation, the conformational transition of the alicyclic diol can further improve the toughness of the polyester, for example, the six-membered alicyclic structure in 1, 4-cyclohexanedimethanol has two conformations of boat-type and chair-type, the two conformations can be mutually converted, and when the polyester material receives an impact, the six-membered alicyclic structure can absorb part of energy through the conformational transition, thereby improving the impact resistance, i.e., toughness.
In one embodiment, the cycloaliphatic diol comprises 1, 4-cyclohexanedimethanol1, 2-cyclohexanedimethanol +.>1, 3-cyclohexanedimethanol +.>4, 4-dicyclohexyl diol1, 4-cyclohexanediol->1, 3-cyclohexanediol1, 2-cyclohexanediol->Tricyclodecanedimethanol->Pentacyclopentadecanediol->At least one of them.
In one embodiment, the 1, 4-cyclohexanedimethanol is selected from at least one of cis-1, 4-cyclohexanedimethanol or trans-1, 4-cyclohexanedimethanol, and the molar ratio of cis-1, 4-cyclohexanedimethanol to trans-1, 4-cyclohexanedimethanol is from 0.25:1 to 4:1.
When the diol includes butanediol and alicyclic diol, in one embodiment, the molar ratio of butanediol to alicyclic diol is 1:9 to 9:1, and further preferably 7:3 to 5:5 for better balancing the properties such as crystallization ability and tensile toughness of the polyester.
In an embodiment, the esterification or transesterification catalyst in the first mixed reaction system of step S10 includes at least one of a zinc-based catalyst, a manganese-based catalyst, a titanium-based catalyst, and a tin-based catalyst; the molar ratio of the esterification or transesterification catalyst to diglycolic acid or the esterified product thereof is 0.3:1000-3.0:1000.
In one embodiment, the zinc-based catalyst includes, but is not limited to, zinc acetate; manganese-based catalysts include, but are not limited to, manganese acetate; the titanium-based catalyst includes, but is not limited to, at least one of tetrabutyl titanate, isopropyl titanate, titanium dioxide, or an inorganic supported titanium catalyst; the tin-based catalyst includes, but is not limited to, at least one of dibutyltin oxide, stannous iso-octoate, tin mono-butyl tri-iso-octoate, and dioctyltin oxide.
In one embodiment, the first mixed reaction system is reacted at 160-240 ℃ for 2-6 hours under a protective atmosphere, wherein the protective atmosphere can be nitrogen atmosphere or inert gas atmosphere.
In the second mixed reaction system of the step S20, the stabilizer is selected from phosphorus stabilizers, wherein the phosphorus stabilizers comprise at least one of phosphorous acid, hypophosphorous acid, pyrophosphoric acid, ammonium phosphate, trimethyl phosphate, dimethyl phosphate, triphenyl phosphate, diphenyl phosphate, ammonium phosphate and monoammonium phosphate, and the molar ratio of the stabilizer to diglycolic acid or the esterified product thereof is 0.4:1000-3.0:1000.
In one embodiment, especially when the esterification or transesterification catalyst is selected from zinc-based catalysts, a polycondensation catalyst is further added in the step of reacting the second mixed reaction system comprising the intermediate product and the stabilizer under vacuum conditions, the polycondensation catalyst comprises at least one of titanium-based catalyst, tin-based catalyst, antimony-based catalyst, or germanium-based catalyst, and it is understood that the titanium-based catalyst and tin-based catalyst may be selected by reference to the titanium-based catalyst and tin-based catalyst in the esterification or transesterification catalyst, and the molar ratio of the polycondensation catalyst to diglycolic acid or the esterification product thereof is 0.3:1000-3.0:1000.
In one embodiment, the antimony-based catalyst includes, but is not limited to, at least one of antimony trioxide, ethylene glycol antimony, antimony acetate, polyethylene glycol antimony; germanium based catalysts include, but are not limited to, germanium dioxide and/or germanium oxide.
In one embodiment, in the step of carrying out the reaction of the second mixed reaction system under vacuum condition, the vacuum degree is within 200Pa, the temperature is 220 ℃ to 290 ℃ and the time is 1.5h to 6h.
The preparation method of the polyester based on diglycolic acid or the esterified product thereof adopts an esterification-polycondensation process, is simple in preparation method, simple and convenient to operate, strong in controllability, easy to implement, suitable for large-scale industrial production, and realizes simple preparation of the polyester with excellent temperature resistance and toughness.
The invention also provides a polyester based on diglycolic acid or an esterified product thereof, which is prepared by the preparation method of the polyester based on diglycolic acid or the esterified product thereof.
The diglycolic acid-based polyester provided by the invention has excellent temperature resistance and toughness, and in an embodiment, the glass transition temperature of the diglycolic acid-based polyester or the esterified product thereof is-30-150 ℃, the melting point is 60-80 ℃, and the elongation at break is 100-1000%.
In addition, since the structural formula of the polyester does not contain an aromatic structure, the polyester has excellent degradability, and in one embodiment, a film made of the polyester has rapid degradability in seawater with a 30-day mass loss of 30-80%.
The present invention also provides an article made from a diglycolic acid or an ester thereof based polyester as described above.
In one embodiment, the step of preparing the diglycolic acid-based polyester into an article comprises: the diglycolic acid-based polyester is firstly prepared into polyester granules, and then further prepared into products.
In one embodiment, the step of preparing the diglycolic acid based polyester into polyester pellets comprises the steps of: and (3) carrying out melt extrusion and granulation on the diglycolic acid-based polyester.
In one embodiment, the step of preparing the polyester pellets into an article comprises melt extruding the polyester pellets and casting the melt stream onto a roll to obtain a cast slab; and then carrying out longitudinal stretching and transverse stretching on the casting thick sheet to obtain the polyester film or the plate.
The diglycolic acid-based polyester provided by the invention has excellent temperature resistance, toughness and degradability, and further, the product prepared from the polyester can be well applied to application scenes such as food packaging materials, mulching films, fibers and tissue engineering materials, and the application field and application range of the polyester are greatly widened.
Hereinafter, a polyester based on diglycolic acid or an esterified product thereof, and a method for preparing the same and a product thereof will be further described by the following specific examples.
In the following examples, nuclear magnetic resonance hydrogen spectra 1 H-NMR was performed on a Bruker 400 AVANCE III Spectrometer type instrument 400MHz, CF 3 COOD。
In the following examples, the intrinsic viscosity was measured using phenol/tetrachloroethane (1:1 m) as a solvent, and the intrinsic viscosity [ eta ] of the polyester and the copolyester was calculated by the formulas (1) and (2) using a Ubbelohde viscometer at 30.+ -. 0.05 ℃.
η sp ＝(t 1 -t 0 )/t 0 Formula (1)
[η]＝[(1+1.4η sp ) 1/2 -1]0.7c formula (2)
Wherein: t is t 0 For the flow-through time(s), t of the solvent 1 The flow-through time(s) of the solution was set at c, the concentration of the solution was 5g/L.
In the following examples, thermal analysis was performed using a differential scanning calorimeter (Mettler Toledo DSC) at a heating rate of 10 ℃/min at N 2 The atmosphere is carried out at a temperature in the range of 25 ℃ to 300 ℃.
In the following examples, thermogravimetric analysis (TGA) was performed on a Perkin-Elmer Diamond TG/DTA with a heating rate of 10℃per minute and a temperature in the range of 50-800 ℃.
In the following examples, elongation at break tests were carried out using an Instron model 5567 universal material tester with spline dimensions of 20.0mm long, 2.0mm wide and 1.0mm thick, and a 20mm/min draw speed.
Example 1
Adding diglycolic acid and 1, 4-butanediol into a reactor according to a molar ratio of 1:1.6, then adding an esterification or transesterification catalyst of 1%o of diglycolic acid to oxidize dibutyltin, gradually heating to 180 ℃ under the protection of high-purity nitrogen for esterification reaction, adding a polycondensation catalyst of 1.0%o of diglycolic acid to react for 4.0h, adding a stabilizer of triphenyl phosphate of 1.0%o of diglycolic acid, gradually heating to 200 ℃, gradually reducing the vacuum degree to 50Pa, and reacting for 4 hours to obtain the polyglycolic acid butanediol ester, wherein the structural formula of the diglycolic acid butanediol ester is shown as the formula (1), and n is 218.
The intrinsic viscosity, nuclear magnetic resonance, DSC, TGA, mechanical property and compost degradation test are respectively carried out on the polybutylene diglycolate, the intrinsic viscosity of the polybutylene diglycolate is 1.27dL/g, and the nuclear magnetism is high 1 As shown in FIG. 1 for H-NMR and FIG. 2 for DSC graph, it is clear from FIG. 2 that the glass transition temperature is-28 ℃, the melting point is 69 ℃, the melting enthalpy is 53.2J/g, and the thermal weight loss T 5％ The TGA spectrum is shown in figure 3 at 336 deg.C 5％ The mass loss of the film is tested under the composting condition, and the mass loss of the film after 30 days of degradation reaches 49.1 percent.
Example 2
Adding diglycolic acid, 1, 4-butanediol and trans-1, 4-cyclohexanedimethanol into a reactor according to a molar ratio of 1:1.2:0.4, then adding an esterification or transesterification catalyst of 1 permillage of diglycolic acid molar quantity to oxidize dibutyltin, gradually heating to 180 ℃ under the protection of high-purity nitrogen for esterification reaction, adding a polycondensation catalyst of tetrabutyl titanate of 1.0 permillage of diglycolic acid molar quantity and a stabilizer of 1.0 permillage of triphenyl phosphate, gradually heating to 220 ℃, gradually reducing the vacuum degree to 50Pa, and reacting for 4 hours to obtain the polybutylene 1, 4-cyclohexanedimethanol copolyester of the diglycolic acid, wherein the structural formula is shown in a formula (2), n is 129, and m is 81.
The intrinsic viscosity, nuclear magnetic resonance, DSC, TGA, mechanical properties and composting degradation tests are respectively carried out on the polybutylene 1, 4-cyclohexanedimethanol copolyester, a DSC graph is shown in figure 4, a TGA graph is shown in figure 5, the intrinsic viscosity of the polybutylene 1, 4-cyclohexanedimethanol copolyester is 0.98dL/g, the glass transition temperature is 27 ℃, the polybutylene 1, 4-cyclohexanedimethanol copolyester is made into a spline and a film, the breaking elongation of the spline is 413%, the film is degraded for 30 days under composting conditions, and the mass loss is 32.7%.
Example 3
Adding diglycolic acid, 1, 4-butanediol and pentacyclopentadecanediol into a reactor according to a molar ratio of 1:0.6:1, then adding an esterification or transesterification catalyst dibutyl tin oxide with a diglycolic acid molar amount of 1%o, gradually heating to 180 ℃ under the protection of high-purity nitrogen for esterification reaction, adding a polycondensation catalyst tetrabutyl titanate with a diglycolic acid molar amount of 1.0%o and a stabilizer triphenyl phosphate with a stabilizer molar amount of 1.0%o after reacting for 4.0h, gradually heating to 220 ℃, gradually reducing the vacuum degree to 50Pa, and reacting for 4 hours to obtain the polydiglycollic butanediol pentacyclopentadecanediol copolyester, wherein the structural formula is shown in a formula (3), and n is 84 and m is 59.
The intrinsic viscosity, nuclear magnetic resonance, DSC, TGA, mechanical property and composting degradation test are respectively carried out on the poly (butylene glycol pentadecanediol) copolyester, the intrinsic viscosity of the poly (butylene glycol pentadecanediol) copolyester is 0.92dL/g, the glass transition temperature is 73 ℃, the poly (butylene glycol pentadecanediol) copolyester is prepared into a spline and a film, the breaking elongation of the spline is 364%, and the film is degraded for 30 days under the composting condition, and the quality loss is 32.7%.
Example 4
Adding diglycolic acid, 1, 4-butanediol, trans-1, 4-cyclohexanedimethanol and cis-1, 4-cyclohexanedimethanol into a reactor according to a molar ratio of 1:1.2:0.08:0.32, then adding an esterification or transesterification catalyst dibutyl tin oxide with a diglycolic acid molar amount of 1%o, gradually heating to 180 ℃ under the protection of high-purity nitrogen for esterification reaction, after reacting for 4.0h, adding a polycondensation catalyst tetrabutyl titanate with a diglycolic acid molar amount of 1.0%o, and a stabilizer triphenyl phosphate with a diglycolic acid molar amount of 1.0%o, gradually heating to 220 ℃, gradually reducing the vacuum degree to 50Pa, and reacting for 4 hours to obtain the polybutylene diglycolic acid 1, 4-cyclohexanedimethanol copolyester with a structural formula shown in a formula (4), wherein x is 129, y is 15, and z is 64.
The intrinsic viscosity, nuclear magnetic resonance, DSC, TGA, mechanical property and composting degradation test are respectively carried out on the polybutylene 1, 4-cyclohexanedimethanol copolyester, the intrinsic viscosity of the polybutylene 1, 4-cyclohexanedimethanol copolyester is 0.81dL/g, the glass transition temperature is 19 ℃, the polybutylene 1, 4-cyclohexanedimethanol copolyester is prepared into a spline and a film, and the breaking elongation of the spline is 289%. The film was degraded for 30 days under composting conditions with a mass loss of 47.2%.
Example 5
Adding diglycolic acid, 1, 4-butanediol, trans-1, 4-cyclohexanedimethanol and cis-1, 4-cyclohexanedimethanol into a reactor according to a molar ratio of 1:1.2:0.32:0.08, then adding an esterification or transesterification catalyst dibutyl tin oxide with a diglycolic acid molar amount of 1%o, gradually heating to 180 ℃ under the protection of high-purity nitrogen for esterification reaction, after reacting for 4.0h, adding a polycondensation catalyst tetrabutyl titanate with a diglycolic acid molar amount of 1.0%o, and a stabilizer triphenyl phosphate with a diglycolic acid molar amount of 1.0%o, gradually heating to 220 ℃, gradually reducing the vacuum degree to 50Pa, and reacting for 4 hours to obtain the polybutylene diglycolic acid 1, 4-cyclohexanedimethanol copolyester with a structural formula shown in a formula (4), wherein x is 132, y is 68, and z is 17.
The intrinsic viscosity, nuclear magnetic resonance, DSC, TGA, mechanical property and composting degradation test are respectively carried out on the polybutylene 1, 4-cyclohexanedimethanol copolyester, the intrinsic viscosity of the polybutylene 1, 4-cyclohexanedimethanol copolyester is 0.87dL/g, the glass transition temperature is 23 ℃, the polybutylene 1, 4-cyclohexanedimethanol copolyester is prepared into a spline and a film, and the breaking elongation of the spline is 473%. The film was degraded for 30 days under composting conditions with a mass loss of 39.1%.
Example 6
Adding diglycolic acid, 1, 4-butanediol and tricyclodecane dimethanol into a reactor according to a molar ratio of 1:0.8:1, then adding an esterification or transesterification catalyst dibutyl tin oxide with a diglycolic acid molar amount of 1%o, gradually heating to 180 ℃ under the protection of high-purity nitrogen for esterification reaction, adding a polycondensation catalyst tetrabutyl titanate with a diglycolic acid molar amount of 1.0%o and a stabilizer triphenyl phosphate with a stabilizer molar amount of 1.0%o after reacting for 4.0h, gradually heating to 230 ℃, gradually reducing the vacuum degree to 50Pa, and reacting for 6 hours to obtain the polydiglycollic butanediol tricyclodecane dimethanol copolyester with a structural formula shown in a formula (5), wherein n is 127 and m is 35.
The intrinsic viscosity, nuclear magnetic resonance, DSC, TGA, mechanical properties and composting degradation test are respectively carried out on the poly-diglycolic acid butanediol tricyclodecane dimethanol copolyester, the intrinsic viscosity of the poly-diglycolic acid butanediol tricyclodecane dimethanol copolyester is 0.63dL/g, the glass transition temperature is 57 ℃, the poly-diglycolic acid butanediol pentacyclopentadecane diol copolyester is prepared into a spline and a film, the breaking elongation of the spline is 402%, and the film is degraded for 30 days under the composting condition, and the quality loss is 43.7%.
Comparative example 1
Lactide is taken as a raw material, stannous octoate with the molar weight of 0.8 per mill is added, the temperature is gradually increased to 150 ℃, the reaction is carried out for 5.0h, the lactide is subjected to ring-opening polymerization to obtain polylactic acid, the glass transition temperature is 55 ℃, the melting point is 170 ℃, the polylactic acid is prepared into a spline, and the breaking elongation of the spline is 5%.
Comparative example 2
Adding diglycolic acid and 1, 6-hexanediol into a reactor according to a molar ratio of 1:1.6, then adding an esterification or transesterification catalyst of 1 permillage of diglycolic acid to oxidize dibutyltin, gradually heating to 180 ℃ under the protection of high-purity nitrogen for esterification reaction, adding a polycondensation catalyst of 1.0 permillage of diglycolic acid to react for 4.0h, gradually heating to 220 ℃ and gradually reducing the vacuum degree to 50Pa, and reacting for 4 hours to obtain the 1, 6-hexanediol uniform polyester of the diglycolic acid, wherein n is 216.
The 1, 6-hexanediol polyester with the 1, 03dL/g intrinsic viscosity, 46 degree of melting point, 64.1J/g melting enthalpy is respectively subjected to intrinsic viscosity, nuclear magnetic resonance, DSC, TGA and mechanical property test, and is prepared into a sample bar, wherein the breaking elongation of the sample bar is 578 percent, and the tensile modulus is 19MPa.
Comparative example 3
Adding diglycolic acid, 1, 4-butanediol and 1, 1-cyclopropane dimethanol into a reactor according to a molar ratio of 1:1.3:0.3, then adding an esterification or transesterification catalyst dibutyl tin oxide with a diglycolic acid molar amount of 1 per mill, gradually heating to 180 ℃ under the protection of high-purity nitrogen for esterification reaction, adding a polycondensation catalyst tetrabutyl titanate with a diglycolic acid molar amount of 1.0 per mill after reacting for 4.0h, and adding a stabilizer triphenyl phosphate with a diglycolic acid molar amount of 1.0 per mill, gradually heating to 220 ℃, gradually reducing the vacuum degree to 50Pa, and reacting for 4 hours to obtain the poly (diglycolic acid butanediol-co-diglycolic acid cyclopropane dimethanol ester) copolyester with a structural formula shown in a formula (7), wherein n is 163 and m is 71.
The intrinsic viscosity, nuclear magnetic resonance, DSC, TGA and mechanical property tests are respectively carried out on the poly (butylene diglycolate-co-diglycolate cyclopropanedimethanol ester) copolyester, the intrinsic viscosity of the poly (butylene diglycolate-co-diglycolate cyclopropanedimethanol ester) copolyester is 0.84dL/g, the melting point is 46 ℃, the melting enthalpy is 64.1J/g, the poly (butylene diglycolate-co-diglycolate cyclopropanedimethanol ester) copolyester is made into a spline, and the breaking elongation of the spline is 73%.
The technical features of the above embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The foregoing examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.
Claims (10)
1. A process for the preparation of a polyester based on diglycolic acid or an ester thereof, comprising the steps of:
reacting a first mixed reaction system comprising diglycolic acid or an esterified product thereof, a glycol and an esterification or transesterification catalyst under a protective atmosphere to obtain an intermediate product, wherein the glycol comprises alicyclic glycol and/or butanediol, and the alicyclic glycol has at least two conformations capable of being mutually converted; and
and (3) reacting a second mixed reaction system containing the intermediate product and a stabilizer under vacuum condition to obtain the polyester based on diglycolic acid or the esterified product thereof.
2. The method for producing a diglycolic acid or an esterified product thereof according to claim 1, wherein the molar ratio of the butanediol to the alicyclic diol is 1:9 to 9:1.
3. The method for producing a diglycolic acid or an esterified polyester thereof according to claim 1, wherein the alicyclic diol comprises at least one of cis-1, 4-cyclohexanedimethanol, trans-1, 4-cyclohexanedimethanol, 1, 2-cyclohexanedimethanol, 1, 3-cyclohexanedimethanol, 4-dicyclohexyl diol, 1, 4-cyclohexanediol, 1, 3-cyclohexanediol, 1, 2-cyclohexanediol, tricyclodecanedimethanol or pentacyclopentadecanediol.
4. The method for producing a diglycolic acid or an esterified polyester thereof according to claim 3, wherein when the alicyclic diols include cis-1, 4-cyclohexanedimethanol and trans-1, 4-cyclohexanedimethanol, the molar ratio of the cis-1, 4-cyclohexanedimethanol to the trans-1, 4-cyclohexanedimethanol is from 0.25:1 to 4:1.
5. The method for producing a diglycolic acid or an esterified product thereof according to any one of claims 1 to 4, wherein the molar ratio of the glycol to the diglycolic acid or the esterified product thereof is from 120:100 to 300:100.
6. The method for producing a diglycolic acid or an esterified product thereof according to any one of claims 1 to 4, wherein the esterification or transesterification catalyst comprises at least one of a zinc-based catalyst, a manganese-based catalyst, a titanium-based catalyst and a tin-based catalyst, and the molar ratio of the esterification or transesterification catalyst to the diglycolic acid or the esterified product thereof is from 0.3:1000 to 3.0:1000;
and/or the stabilizer is selected from phosphorus stabilizers, and the molar ratio of the stabilizer to the diglycolic acid or the esterified product thereof is 0.4:1000-3.0:1000.
7. The method for producing a diglycolic acid or an esterified product thereof according to any one of claims 1 to 4, wherein when the esterification or transesterification catalyst is selected from zinc-based catalysts, a polycondensation catalyst is further added in the step of reacting a second mixed reaction system comprising the intermediate product and a stabilizer under vacuum conditions, the polycondensation catalyst comprising at least one of a titanium-based catalyst, a tin-based catalyst, an antimony-based catalyst, and a germanium-based catalyst, and the molar ratio of the polycondensation catalyst to the diglycolic acid or the esterified product thereof is from 0.3:1000 to 3.0:1000.
8. The process for producing a diglycolic acid or polyester based on an esterified product thereof according to any one of claims 1 to 4, wherein the first mixed reaction system is carried out at a temperature of 160℃to 240℃for a period of 2 hours to 6 hours under a protective atmosphere, and the second mixed reaction system is carried out at a vacuum condition in the step of carrying out the reaction under a vacuum of 200Pa or less at a temperature of 220℃to 290℃for a period of 1.5 hours to 6 hours.
9. A diglycolic acid or an esterified product thereof-based polyester prepared by the process for producing a diglycolic acid or an esterified product thereof according to any one of claims 1 to 8.
10. An article made from the diglycolic acid or the ester thereof according to claim 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210103228.8A CN116554452A (en) | 2022-01-27 | 2022-01-27 | Polyester based on diglycolic acid or esterified product thereof, preparation method and product thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210103228.8A CN116554452A (en) | 2022-01-27 | 2022-01-27 | Polyester based on diglycolic acid or esterified product thereof, preparation method and product thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116554452A true CN116554452A (en) | 2023-08-08 |
Family
ID=87495243
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210103228.8A Pending CN116554452A (en) | 2022-01-27 | 2022-01-27 | Polyester based on diglycolic acid or esterified product thereof, preparation method and product thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116554452A (en) |
-
2022
- 2022-01-27 CN CN202210103228.8A patent/CN116554452A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Barletta et al. | Poly (butylene succinate)(PBS): Materials, processing, and industrial applications | |
| JP5836121B2 (en) | Biodegradable polyester and method for preparing the same | |
| Zhu et al. | Synthesis and characterization of a novel multiblock copolyester containing poly (ethylene succinate) and poly (butylene succinate) | |
| JP4078855B2 (en) | Polylactic acid block copolymer, process for producing the same, molded article, and polylactic acid composition | |
| JP7404330B2 (en) | Semi-aromatic polyester, its production method and use | |
| JP6231549B2 (en) | Polymer, process for synthesizing it and composition comprising it | |
| CN113278137A (en) | Biodegradable PBST polymer, preparation method and application thereof, agricultural mulching film and preparation method | |
| CN116554452A (en) | Polyester based on diglycolic acid or esterified product thereof, preparation method and product thereof | |
| CN115322350B (en) | Degradable bio-based polyester and preparation method and application thereof | |
| CN114044888B (en) | Hydrolytically degradable polymer, preparation method and application thereof | |
| CN113773478B (en) | Poly (carbonate-ether) based biodegradable polyester and preparation method thereof | |
| CN112280015B (en) | Bio-based heat-resistant toughened polyester and preparation method thereof | |
| CN111116883B (en) | Biodegradable copolyester and preparation method thereof | |
| CN111101227B (en) | Full-biodegradable copolyester fiber and preparation method thereof | |
| Zhou et al. | A green and efficient synthetic strategy for the preparation of PBS ionomers with high molecular weight, high ionic group content and good combined properties | |
| EP1690881B1 (en) | Polyester, process for producing the same, fiber, and polymerization catalyst for polyester | |
| CN115260476A (en) | Degradable copolyester based on thiophenedicarboxylic acid and ethylene glycol and preparation method and product thereof | |
| JP3700040B2 (en) | Method for producing high molecular weight polylactic acid copolymer and copolymer | |
| JP2002053652A (en) | Biodegradable and recycled polyester resin and production method thereof | |
| Mao et al. | Highly Stretchable Biobased Poly (butylene succinate) Elastomer Copolymerized with Naphthalate-Monomer-Derived Shape Memory having Self-healing Properties | |
| CN116333277A (en) | Glycollic acid-based polyester elastomer and preparation method thereof | |
| Mao et al. | Highly Stretchable Biobased Poly (butylene succinate)-Based Copolyesters with Shape Memory and Self-Healing Properties | |
| CN117866179A (en) | Method for preparing PBAT copolyester by using PBT | |
| CN116589668A (en) | Degradable copolyester, preparation method and product thereof | |
| CN117209736A (en) | Antibacterial biodegradable multiblock polyester and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |