CN114989403A - Betulinol-based bio-based copolyester and preparation method thereof - Google Patents
Betulinol-based bio-based copolyester and preparation method thereof Download PDFInfo
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- CN114989403A CN114989403A CN202210650173.2A CN202210650173A CN114989403A CN 114989403 A CN114989403 A CN 114989403A CN 202210650173 A CN202210650173 A CN 202210650173A CN 114989403 A CN114989403 A CN 114989403A
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- betulin
- copolyester
- dicarboxylic acid
- esterified product
- aliphatic dicarboxylic
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- FVWJYYTZTCVBKE-ROUWMTJPSA-N betulin Chemical compound C1C[C@H](O)C(C)(C)[C@@H]2CC[C@@]3(C)[C@]4(C)CC[C@@]5(CO)CC[C@@H](C(=C)C)[C@@H]5[C@H]4CC[C@@H]3[C@]21C FVWJYYTZTCVBKE-ROUWMTJPSA-N 0.000 title claims abstract description 84
- MVIRREHRVZLANQ-UHFFFAOYSA-N betulin Natural products CC(=O)OC1CCC2(C)C(CCC3(C)C2CC=C4C5C(CCC5(CO)CCC34C)C(=C)C)C1(C)C MVIRREHRVZLANQ-UHFFFAOYSA-N 0.000 title claims abstract description 79
- 229920001634 Copolyester Polymers 0.000 title claims abstract description 76
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- ZNUAKACHFYTNFX-UHFFFAOYSA-N Wallichenol Natural products CC12CCC(O)C(C)(C)C1CCC1(C)C2CCC2C3C(C(=C)CO)CCC3(C)CCC21C ZNUAKACHFYTNFX-UHFFFAOYSA-N 0.000 title 1
- JYDNKGUBLIKNAM-UHFFFAOYSA-N Oxyallobutulin Natural products C1CC(=O)C(C)(C)C2CCC3(C)C4(C)CCC5(CO)CCC(C(=C)C)C5C4CCC3C21C JYDNKGUBLIKNAM-UHFFFAOYSA-N 0.000 claims abstract description 78
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 40
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000003054 catalyst Substances 0.000 claims abstract description 20
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 16
- 239000003112 inhibitor Substances 0.000 claims abstract description 13
- 238000010526 radical polymerization reaction Methods 0.000 claims abstract description 13
- 239000003381 stabilizer Substances 0.000 claims abstract description 13
- 230000032050 esterification Effects 0.000 claims abstract description 12
- 238000005886 esterification reaction Methods 0.000 claims abstract description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 235000018185 Betula X alpestris Nutrition 0.000 claims abstract description 5
- 235000018212 Betula X uliginosa Nutrition 0.000 claims abstract description 5
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 5
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 5
- 125000004185 ester group Chemical group 0.000 claims abstract 2
- 150000002148 esters Chemical class 0.000 claims description 33
- 229920000728 polyester Polymers 0.000 claims description 24
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 20
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 14
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 claims description 10
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 10
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims description 10
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 10
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims description 10
- QUVMSYUGOKEMPX-UHFFFAOYSA-N 2-methylpropan-1-olate;titanium(4+) Chemical compound [Ti+4].CC(C)C[O-].CC(C)C[O-].CC(C)C[O-].CC(C)C[O-] QUVMSYUGOKEMPX-UHFFFAOYSA-N 0.000 claims description 8
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 239000004246 zinc acetate Substances 0.000 claims description 8
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims description 7
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 6
- WSXIMVDZMNWNRF-UHFFFAOYSA-N antimony;ethane-1,2-diol Chemical compound [Sb].OCCO WSXIMVDZMNWNRF-UHFFFAOYSA-N 0.000 claims description 6
- TVIDDXQYHWJXFK-UHFFFAOYSA-N dodecanedioic acid Chemical compound OC(=O)CCCCCCCCCCC(O)=O TVIDDXQYHWJXFK-UHFFFAOYSA-N 0.000 claims description 6
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 claims description 6
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 claims description 6
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 6
- 229940043375 1,5-pentanediol Drugs 0.000 claims description 4
- XESZUVZBAMCAEJ-UHFFFAOYSA-N 4-tert-butylcatechol Chemical compound CC(C)(C)C1=CC=C(O)C(O)=C1 XESZUVZBAMCAEJ-UHFFFAOYSA-N 0.000 claims description 4
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 claims description 4
- 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 4
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium oxide Inorganic materials O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 claims description 4
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 4
- PVADDRMAFCOOPC-UHFFFAOYSA-N oxogermanium Chemical compound [Ge]=O PVADDRMAFCOOPC-UHFFFAOYSA-N 0.000 claims description 4
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 claims description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical group [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 3
- 239000001361 adipic acid Substances 0.000 claims description 3
- 235000011037 adipic acid Nutrition 0.000 claims description 3
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 239000011574 phosphorus Substances 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 239000001384 succinic acid Substances 0.000 claims description 3
- 238000005809 transesterification reaction Methods 0.000 claims description 3
- 229910052787 antimony Inorganic materials 0.000 claims 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 description 14
- 238000010438 heat treatment Methods 0.000 description 11
- 238000003756 stirring Methods 0.000 description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 8
- 230000009477 glass transition Effects 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 239000002861 polymer material Substances 0.000 description 7
- 238000001228 spectrum Methods 0.000 description 7
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 6
- 229920006125 amorphous polymer Polymers 0.000 description 6
- UDSFAEKRVUSQDD-UHFFFAOYSA-N Dimethyl adipate Chemical compound COC(=O)CCCCC(=O)OC UDSFAEKRVUSQDD-UHFFFAOYSA-N 0.000 description 5
- 238000005481 NMR spectroscopy Methods 0.000 description 4
- 230000000844 anti-bacterial effect Effects 0.000 description 4
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 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 description 4
- KKUKTXOBAWVSHC-UHFFFAOYSA-N Dimethylphosphate Chemical compound COP(O)(=O)OC KKUKTXOBAWVSHC-UHFFFAOYSA-N 0.000 description 3
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 3
- ASMQGLCHMVWBQR-UHFFFAOYSA-M diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(=O)([O-])OC1=CC=CC=C1 ASMQGLCHMVWBQR-UHFFFAOYSA-M 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- MUXOBHXGJLMRAB-UHFFFAOYSA-N Dimethyl succinate Chemical compound COC(=O)CCC(=O)OC MUXOBHXGJLMRAB-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 230000003385 bacteriostatic effect Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- KUMNEOGIHFCNQW-UHFFFAOYSA-N diphenyl phosphite Chemical compound C=1C=CC=CC=1OP([O-])OC1=CC=CC=C1 KUMNEOGIHFCNQW-UHFFFAOYSA-N 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000004611 spectroscopical analysis Methods 0.000 description 2
- 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 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- 229940035437 1,3-propanediol Drugs 0.000 description 1
- QFGCFKJIPBRJGM-UHFFFAOYSA-N 12-[(2-methylpropan-2-yl)oxy]-12-oxododecanoic acid Chemical compound CC(C)(C)OC(=O)CCCCCCCCCCC(O)=O QFGCFKJIPBRJGM-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920013724 bio-based polymer Polymers 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 150000003333 secondary alcohols Chemical class 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/52—Polycarboxylic acids or polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
- C08G63/54—Polycarboxylic acids or polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation the acids or hydroxy compounds containing carbocyclic rings
- C08G63/553—Acids or hydroxy compounds containing cycloaliphatic rings, e.g. Diels-Alder adducts
-
- 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)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention relates to a birch-fat-alcohol-based bio-based copolyester, which has a structural formula shown in a formula (1):
in the formula (1), x and y are integers of 1-20, n is an integer of 20-100, R 1 A fatty chain unit of an aliphatic dicarboxylic acid or an esterified product thereof, R 2 Represents an aliphatic chain unit of an aliphatic diol. The invention also relates to a preparation method of the birch fat alcohol-based bio-based copolyester, which comprises the following steps: mixing aliphatic dicarboxylic acid or its esterified product, betulin, aliphatic diol, esterification or ester exchange catalyst, adding polycondensation catalyst, free radical polymerization inhibitor, stabilizer and antioxidant, reacting at 160-180 deg.C for 1-3 hr under vacuum condition, and further reacting at 180-240 deg.CAnd reacting for 2h-22h to obtain the betulin-based bio-based copolyester, wherein the second temperature is higher than the first temperature. The copolyester of the invention has controllable heat resistance and mechanical property, and high transparency.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a birch fat alcohol-based bio-based copolyester and a preparation method thereof.
Background
Polyester, polyurethane and other polymer materials have wide and important application in agriculture, food packaging, household appliances, medical appliances and other fields. At present, most of polymer materials are petroleum-based polymer materials derived from non-renewable fossil resources, and although the petroleum-based polymer materials are widely applied and have excellent performance, the petroleum-based polymer materials cause pollution and a large amount of carbon emission in the production, use and waste processes. With the increasing severity of ecological and resource problems, the importance of bio-based polymer materials derived from renewable biomass resources is becoming more and more prominent.
Disclosure of Invention
In view of the above, there is a need to provide a betulin-based bio-based copolyester having controllable heat resistance and mechanical properties and high transparency, and a method for preparing the same.
A betulin-based bio-based copolyester, the structural formula of which is shown in formula (1):
in the formula (1), x and y are integers of 1-20, n is an integer of 20-100, R 1 A fatty chain unit of an aliphatic dicarboxylic acid or an esterified product thereof, R 2 Represents an aliphatic chain unit of an aliphatic diol.
In one embodiment, the aliphatic dicarboxylic acid or the ester thereof has 4 to 12 carbon atoms;
and/or the aliphatic diol has 2-6 carbon atoms.
In one embodiment, the aliphatic dicarboxylic acid or its ester is at least one selected from succinic acid or its ester, glutaric acid or its ester, adipic acid or its ester, suberic acid or its ester, sebacic acid or its ester, and dodecanedioic acid or its ester;
and/or the aliphatic diol is at least one selected from ethylene glycol, 1, 3-propylene glycol, 1, 4-butanediol, 1, 5-pentanediol and 1, 6-hexanediol.
The preparation method of the betulin-based bio-based copolyester comprises the following steps:
mixing and reacting aliphatic dicarboxylic acid or an esterified product thereof, betulin, aliphatic diol and an esterification or ester exchange catalyst to obtain a polyester prepolymer based on the betulin;
adding a polycondensation catalyst, a free radical polymerization inhibitor, a stabilizer and an antioxidant into the polyester prepolymer, reacting for 1h-3h at a first temperature under a vacuum condition, and then continuing to react for 2h-22h at a second temperature to obtain a birch fat alcohol-based bio-based copolyester; wherein the first temperature is 160-180 ℃, the second temperature is 180-240 ℃, and the second temperature is greater than the first temperature.
In one embodiment, the molar ratio of the sum of the used amount of the betulin and the aliphatic diol to the aliphatic dicarboxylic acid or the esterified product thereof is 3:1-5: 1.
In one embodiment, the molar ratio of the aliphatic dicarboxylic acid or the ester thereof to the betulin is 5:1-5: 3.
In one embodiment, the esterification or ester exchange catalyst is selected from at least one of zinc acetate, isobutyl titanate, tetrabutyl titanate, ethylene glycol antimony and dibutyl tin oxide, and is used in an amount of 0.1-0.2% of the mole of the aliphatic dicarboxylic acid or the esterified product thereof.
In one embodiment, in the step of mixing and reacting the aliphatic dicarboxylic acid or the esterified product thereof, the betulin, the aliphatic diol and the esterification or transesterification catalyst, the reaction temperature is 160-220 ℃ and the reaction time is 2-6 h.
In one embodiment, the free radical polymerization inhibitor is at least one selected from hydroquinone, p-methoxyphenol, p-tert-butylcatechol and p-benzoquinone, and the amount of the free radical polymerization inhibitor is 0.4-0.6% of the mole number of the aliphatic dicarboxylic acid or the ester thereof.
In one embodiment, the polycondensation catalyst is at least one selected from antimony trioxide, isobutyl titanate, tetrabutyl titanate, germanium oxide, ethylene glycol antimony, antimony acetate and dibutyltin oxide, and the amount of the polycondensation catalyst is 0.1 to 0.2 percent of the mole number of the aliphatic dicarboxylic acid or the esterified substance thereof;
and/or the stabilizer is selected from phosphorus stabilizers, and the using amount of the stabilizer is 0.12 to 0.15 percent of the mole number of the aliphatic dicarboxylic acid or the ester thereof.
The bio-based copolyester based on the betulin contains a betulin structural unit, and the structure of the betulin has large volume and extremely high rigidity, so that the rigidity of a polymer chain can be greatly improved, the copolyester has adjustable heat resistance and mechanical property, the structure of the betulin is introduced to greatly damage the regularity of the polymer chain, the copolyester can be in a completely amorphous state, and the transparency is high. Meanwhile, the structure of the betulin has antibacterial and bacteriostatic activities, so that the copolyester also has excellent antibacterial property.
In addition, the invention adopts a three-step method to prepare the birch-fat-alcohol-based bio-based copolyester, namely, firstly, esterification/ester exchange reaction is carried out to obtain the betulin-based polyester prepolymer, then, under the protection of a free radical polymerization inhibitor, the betulin-based polyester prepolymer is subjected to polycondensation at a relatively low temperature of 160-180 ℃ to form a low molecular prepolymer with the molecular weight of 2000g/mol-10000g/mol, the molecular chain of the low molecular prepolymer has high rigidity, so that the activation energy of oxidation reaction of a carbon-carbon double bond structure is greatly improved, therefore, when the temperature is increased to a relatively high temperature of 180-240 ℃ for reaction, the carbon-carbon double bond structure is not influenced, and the betulin-based bio-based copolyester with adjustable heat resistance and mechanical property and high transparency is finally obtained.
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 description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments described in the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a view showing the preparation of betulin-based biobased copolyester prepared in example 1 of the present invention 1 An H-NMR spectrum;
fig. 2 is a second temperature-rising DSC diagram of the bio-based copolyester based on betulin prepared in example 1 of the present invention.
Detailed Description
In order to facilitate an understanding of the present invention, the present invention will be described in more detail below. It should be understood, however, that the present invention may be embodied in many different forms and should not be construed as being limited to the embodiments or examples set forth herein. Rather, these embodiments or examples 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 in the description of the invention herein is for the purpose of describing particular embodiments or examples only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of two or more of the associated listed items, including any and all combinations of two or more of the associated listed items, or all of the associated listed items.
The structural formula of the betulin-based bio-based copolyester is shown as the formula (1):
in the formula (1), x and y are integers of 1-20, n is an integer of 20-100, R 1 A fatty chain unit of an aliphatic dicarboxylic acid or an esterified product thereof, R 2 Represents an aliphatic chain unit of an aliphatic diol.
In one embodiment, the aliphatic dicarboxylic acid or an ester thereof has 4 to 12 carbon atoms, i.e., R 1 Represented by an aliphatic chain unit having 4 to 12 carbon atoms; optionally, the aliphatic dicarboxylic acid or its ester is at least one selected from succinic acid or its ester, glutaric acid or its ester, adipic acid or its ester, suberic acid or its ester, sebacic acid or its ester, and dodecanedioic acid or its ester.
In one embodiment, the aliphatic diol has 2 to 6 carbon atoms, i.e., R 2 Represented by an aliphatic chain unit having 2 to 6 carbon atoms; optionally, the aliphatic diol is at least one selected from ethylene glycol, 1, 3-propylene glycol, 1, 4-butanediol, 1, 5-pentanediol and 1, 6-hexanediol.
The bio-based copolyester based on the betulin contains a betulin structural unit, and the structure of the betulin has large volume and extremely high rigidity, so that the rigidity of a polymer chain can be greatly improved, the heat resistance and the mechanical property of the copolyester can be adjusted according to the structure of the betulin, the introduced structure of the betulin has extremely great damage to the regularity of the polymer molecular chain, and the copolyester can be in a completely amorphous state and has high transparency.
Meanwhile, the structure of the betulin has antibacterial and bacteriostatic activities, so that the copolyester also has excellent antibacterial property.
Although the bio-based copolyester based on betulin has controllable heat resistance and mechanical properties and high transparency, the polycondensation reaction activity is low due to the presence of secondary hydroxyl groups in the betulin. Although the activity of the polycondensation reaction can be improved by increasing the reaction temperature, the carbon-carbon double bond structure of betulin is easily oxidized and crosslinked at high temperature. Thus, it is difficult to obtain a linear polyester of high molecular weight using the conventional two-step melt polycondensation.
Therefore, the invention also provides a preparation method of the betulin-based bio-based copolyester, which comprises the following steps:
s1, mixing and reacting aliphatic dicarboxylic acid or an esterified product thereof, betulin, aliphatic diol and an esterification or ester exchange catalyst to obtain a polyester prepolymer based on the betulin;
s2, adding a polycondensation catalyst, a free radical polymerization inhibitor, a stabilizer and an antioxidant into the polyester prepolymer, reacting for 1h-3h at a first temperature under a vacuum condition, and then continuing to react for 2h-22h at a second temperature to obtain a birch fat alcohol-based bio-based copolyester; wherein the first temperature is 160-180 ℃, the second temperature is 180-240 ℃, and the second temperature is greater than the first temperature.
The preparation of the betulin-based bio-based copolyester adopts a three-step method, namely, esterification/ester exchange reaction is firstly carried out to obtain a betulin-based polyester prepolymer.
Then, under the protection of a free radical polymerization inhibitor, polyester prepolymer based on betulin is subjected to polycondensation at a relatively low temperature of 160-180 ℃ to form low molecular prepolymer with the molecular weight of 2000g/mol-10000g/mol, the molecular chain of the low molecular prepolymer has high rigidity, so that the activation energy of oxidation reaction of a carbon-carbon double bond structure is greatly improved, and free radicals are difficult to react with the carbon-carbon double bond structure.
Therefore, when the temperature is raised to a relatively high temperature of 180-240 ℃ for reaction, the carbon-carbon double bond structure is not influenced, and finally the linear polyester with high molecular weight is obtained, so that the linear polyester has adjustable heat resistance and mechanical property and high transparency.
Specifically, in step S1, the molar ratio of the sum of the amounts of the betulin and the aliphatic diol to the aliphatic dicarboxylic acid or the ester thereof is 3:1-5:1, wherein the molar ratio of the aliphatic dicarboxylic acid or the ester thereof to the betulin is 5:1-5: 3.
In the step, the amount of the esterification or ester exchange catalyst is 0.1 to 0.2 percent of the mole number of the aliphatic dicarboxylic acid or the ester thereof, and the esterification or ester exchange catalyst is at least one of zinc acetate, isobutyl titanate, tetrabutyl titanate, ethylene glycol antimony and dibutyl tin oxide.
In the step, the reaction temperature is 160-220 ℃ and the reaction time is 2-6 h.
In step S2, the radical polymerization inhibitor is at least one selected from hydroquinone, p-methoxyphenol, p-tert-butylcatechol, and p-benzoquinone, and the amount of the radical polymerization inhibitor is 0.4 to 0.6 mole% of the aliphatic dicarboxylic acid or the ester thereof, and the radical polymerization inhibitor can react with the radical generated at high temperature to protect the carbon-carbon double bond structure.
In the step, the polycondensation catalyst is at least one selected from antimony trioxide, isobutyl titanate, tetrabutyl titanate, germanium oxide, ethylene glycol antimony, antimony acetate and dibutyl tin oxide, and the dosage of the polycondensation catalyst is 0.1-0.2% of the mole number of the aliphatic dicarboxylic acid or the ester thereof.
In the step, the stabilizer is selected from phosphorus stabilizers, specifically at least one selected from trimethyl phosphate, dimethyl phosphate, triphenyl phosphate, diphenyl phosphate, triphenyl phosphite and diphenyl phosphite, and the dosage of the stabilizer is 0.12 to 0.15 percent of the mole number of the aliphatic dicarboxylic acid or the esterified compound thereof.
In this step, the antioxidant is selected from at least one of antioxidant-1010, antioxidant-1076, or antioxidant-168.
In the preparation method of the invention, the bio-based copolyester based on betulin can be synthesized by three steps of reactions, and the number average molecular weight of the bio-based copolyester is up to 20000 g.mol -1 The above.
Hereinafter, the betulin-based bio-based copolyester and the method for preparing the same will be further described with reference to the following specific examples.
Example 1
Into a 3L three-necked flask equipped with a heating and stirring device, 1mol of dimethyl adipate, 0.4mol of betulin, 3.6mol of 1, 4-butanediol, 2mmol of dibutyltin oxide were charged and reacted at 180 ℃ for 4 hours to obtain a low molecular weight polyester prepolymer.
1mmol of dibutyltin oxide, 5mmol of p-methoxyphenol, 1.2mmol of trimethyl phosphate and 100mg of antioxidant-1010 are added into a 3L three-neck flask, and the mixture is reacted at 180 ℃ for 2h and then at 230 ℃ for 10h to obtain the product with 25200 g.mol -1 A betulin-based bio-based copolyester of number average molecular weight.
The nmr hydrogen spectrum of the copolyester obtained in this example is shown in fig. 1, wherein the betulin structure accounts for 46 mol% of the molecular mole fraction; the curve obtained by the second heating scanning through the differential scanning calorimeter is shown in figure 2, the copolyester is a completely amorphous polymer, and the glass transition temperature is 62 ℃; the tensile property test proves that the breaking strength of the copolyester is 70MPa, and the breaking elongation is 340%.
Example 2
Into a 3L three-necked flask equipped with a heating and stirring device, 1mol of dimethyl adipate, 0.5mol of betulin, 4.5mol of 1, 4-butanediol, 2mmol of tetrabutyl titanate were charged and reacted at 160 ℃ for 3 hours to obtain a low molecular weight polyester prepolymer.
1mmol of tetrabutyl titanate, 5mmol of p-benzoquinone, 1.5mmol of triphenyl phosphate and 120mg of antioxidant-1076 are added into a 3L three-neck flask, and the mixture is reacted for 2h at 180 ℃ and then for 15h at 220 ℃ to obtain the product with 22400 g.mol -1 A betulin-based bio-based copolyester of number average molecular weight.
By the representation of nuclear magnetic resonance hydrogen spectrum, the structure of the betulin in the copolyester obtained in the embodiment accounts for 65 mol% of the molecular mole fraction; the test of a differential scanning calorimeter proves that the copolyester is a completely amorphous macromolecule, and the glass transition temperature is 110 ℃; the tensile property test proves that the breaking strength of the copolyester is 87MPa, and the breaking elongation is 230%.
Example 3
Into a 3L three-necked flask equipped with a heating and stirring device, 1mol of dimethyl adipate, 0.2mol of betulin, 2.8mol of ethylene glycol, 1mmol of zinc acetate were charged and reacted at 190 ℃ for 6 hours to obtain a low molecular weight polyester prepolymer.
1.5mmol of antimony trioxide, 5mmol of hydroquinone, 1.3mmol of diphenyl phosphate and 150mg of antioxidant-168 were added into a 3L three-neck flask, and the mixture was reacted at 160 ℃ for 2 hours and then at 180 ℃ for 22 hours to obtain a solution having a molecular weight of 26700 g.mol -1 A betulin-based bio-based copolyester of number average molecular weight.
By the representation of nuclear magnetic resonance hydrogen spectrum, the structure of the betulin in the copolyester obtained in the embodiment accounts for 23 mol% of the molecular mole fraction; the test of a differential scanning calorimeter proves that the copolyester is a completely amorphous polymer, and the glass transition temperature is 85 ℃; the tensile property test proves that the breaking strength of the copolyester is 79MPa, and the breaking elongation is 270%.
Example 4
Into a 3L three-necked flask equipped with a heating and stirring device, 1mol of sebacic acid, 0.6mol of betulin, 4.4mol of 1, 3-propanediol, 2mmol of isobutyl titanate were charged and reacted at 220 ℃ for 2 hours to obtain a low molecular weight polyester prepolymer.
1mmol of isobutyl titanate, 5mmol of p-methoxyphenol, 1.2mmol of triphenyl phosphite and 100mg of antioxidant-1010 were added to a 3L three-necked flask, and the mixture was reacted at 170 ℃ for 2 hours and then at 240 ℃ for 6 hours to obtain a solution having a molecular weight of 27300 g.mol -1 A betulin-based bio-based copolyester of number average molecular weight.
The copolyester obtained in this example has a betulin structure accounting for 61 mol% of the molecular mole fraction, as characterized by nmr hydrogen spectrum; the test of a differential scanning calorimeter proves that the copolyester is a completely amorphous polymer, and the glass transition temperature is 91 ℃; the tensile property test proves that the breaking strength of the copolyester is 83MPa, and the breaking elongation is 170%.
Example 5
Into a 3L three-necked flask equipped with a heating and stirring device, 1mol of sebacic acid, 0.6mol of betulin, 2.4mol of 1, 6-hexanediol, 2mmol of zinc acetate were charged and reacted at 180 ℃ for 6 hours to obtain a low molecular weight polyester prepolymer.
1mmol of ethylene glycol antimony, 5mmol of p-tert-butylcatechol, 1.4mmol of dimethyl phosphate and 120mg of antioxidant 1076 are added into a 3L three-neck flask, and the mixture is reacted for 2 hours at 180 ℃ and then for 2 hours at 230 ℃ to obtain the product with 22600 g/mol -1 A betulin-based bio-based copolyester of number average molecular weight.
By the representation of nuclear magnetic resonance hydrogen spectrum, the structure of the betulin in the copolyester obtained in the embodiment accounts for 60 mol% of the molecular mole fraction; the test of a differential scanning calorimeter proves that the copolyester is a completely amorphous polymer, and the glass transition temperature is 78 ℃; the tensile property test proves that the breaking strength of the copolyester is 80MPa, and the breaking elongation is 240%.
Example 6
1mol of dimethyl succinate, 0.2mol of betulin, 2.8mol of 1, 5-pentanediol, 2mmol of zinc acetate were added to a 3L three-necked flask equipped with a heating and stirring device, and reacted at 190 ℃ for 3 hours to obtain a low molecular weight polyester prepolymer.
Adding 2mmol of germanium oxide, 5mmol of hydroquinone, 1.3mmol of dimethyl phosphate and 100mg of antioxidant-1010 into a 3L three-neck flask, reacting at 180 deg.C for 2h, and reacting at 240 deg.C for 4h to obtain a solution with 25200 g.mol -1 A betulin-based bio-based copolyester of number average molecular weight.
The copolyester obtained in this example has a betulin structure accounting for 26 mol% of the molecular mole fraction, as characterized by nmr hydrogen spectroscopy; the test of a differential scanning calorimeter proves that the copolyester is a completely amorphous polymer, and the glass transition temperature is 54 ℃; the tensile property test proves that the breaking strength of the copolyester is 70MPa, and the breaking elongation is 370%.
Example 7
To a 3L three-necked flask equipped with a heating and stirring device, 1mol of dimethyl succinate, 0.6mol of betulin, 4.4mol of 1, 4-butanediol, and 2mmol of tetrabutyl titanate were added and reacted at 180 ℃ for 4 hours to obtain a low molecular weight polyester prepolymer.
1mmol of tetrabutyl titanate, 5mmol of p-methoxyphenol, 1.5mmol of diphenyl phosphite and 100mg of antioxidant-1010 were added to a 3L three-necked flask, and the mixture was reacted at 180 ℃ for 2 hours and then at 220 ℃ for 12 hours to obtain a solution having 26800 g.mol -1 A number average molecular weight betulin-based biobased copolyester.
The copolyester obtained in this example has a betulin structure of 67 mol% in terms of molecular mole fraction, as characterized by nmr hydrogen spectroscopy; the test of a differential scanning calorimeter proves that the copolyester is a completely amorphous macromolecule, and the glass transition temperature is 124 ℃; the tensile property test proves that the breaking strength of the copolyester is 88MPa, and the breaking elongation is 100%.
Example 8
Into a 3L three-necked flask equipped with a heating and stirring device, 1mol of dodecanedioic acid, 0.5mol of betulin, 4.5mol of ethylene glycol, 2mmol of zinc acetate were charged and reacted at 180 ℃ for 5 hours to obtain a low-molecular-weight polyester prepolymer.
1.5mmol of antimony acetate, 5mmol of p-benzoquinone, 1.2mmol of trimethyl phosphate and 100mg of antioxidant 1076 are added into a 3L three-neck flask, and the mixture is reacted for 2h at 170 ℃ and then for 8h at 230 ℃ to obtain a solution with 25100g mol -1 A betulin-based bio-based copolyester of number average molecular weight.
By the representation of nuclear magnetic resonance hydrogen spectrum, the structure of the betulin in the copolyester obtained in the embodiment accounts for 55 mol% of the molecular mole fraction; the test of a differential scanning calorimeter proves that the copolyester is a completely amorphous polymer, and the glass transition temperature is 70 ℃; the tensile property test proves that the breaking strength of the copolyester is 75MPa, and the breaking elongation is 280%.
Comparative example 1
Into a 3L three-necked flask equipped with a heating and stirring device, 1mol of dimethyl adipate, 0.4mol of betulin, 3.6mol of 1, 4-butanediol, 2mmol of dibutyltin oxide were charged and reacted at 180 ℃ for 4 hours to obtain a low molecular weight polyester prepolymer.
1mmol of dibutyltin oxide, 1.2mmol of trimethyl phosphate and 100mg of antioxidant-1010 are added into a 3L three-neck flask, and the reaction is continued for 24h at 180 ℃ to obtain the birch-fat alcohol-based bio-based copolyester. However, the reaction temperature is low in the whole reaction process, the secondary alcohol in the betulin has low reaction activity at a lower temperature, and the number average molecular weight is lower than 10000g & mol -1 Low molecular weight oligomers of (2).
Comparative example 2
Into a 3L three-necked flask equipped with a heating and stirring device, 1mol of dimethyl adipate, 0.2mol of betulin, 2.8mol of ethylene glycol, 1mmol of zinc acetate were charged and reacted at 190 ℃ for 6 hours to obtain a low molecular weight polyester prepolymer.
And (3) continuously adding 1.5mmol of antimony trioxide, 1.3mmol of diphenyl phosphate and 150mg of antioxidant-168 into a 3L three-neck flask, continuously reacting at 220 ℃, and after the polycondensation reaction is carried out for 2 hours, crosslinking the product due to higher reaction temperature and no addition of a free radical polymerization inhibitor, so that the reaction fails.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is specific and detailed, but not to be understood as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. A betulin-based bio-based copolyester, characterized in that the structural formula of the copolyester is shown as formula (1):
in the formula (1), x and y are integers of 1-20, n is an integer of 20-100, R 1 A fatty chain unit of an aliphatic dicarboxylic acid or an esterified product thereof, R 2 Represents an aliphatic chain unit of an aliphatic diol.
2. The betulin-based biobased copolyester according to claim 1, wherein the aliphatic dicarboxylic acid or an esterified product thereof has 4 to 12 carbon atoms;
and/or the aliphatic diol has 2-6 carbon atoms.
3. The betulin-based biobased copolyester according to claim 2, wherein the aliphatic dicarboxylic acid or an esterified product thereof is at least one selected from succinic acid or an esterified product thereof, glutaric acid or an esterified product thereof, adipic acid or an esterified product thereof, suberic acid or an esterified product thereof, sebacic acid or an esterified product thereof, and dodecanedioic acid or an esterified product thereof;
and/or the aliphatic diol is at least one selected from ethylene glycol, 1, 3-propylene glycol, 1, 4-butanediol, 1, 5-pentanediol and 1, 6-hexanediol.
4. A process for the preparation of betulin-based biobased copolyesters according to any one of claims 1 to 3, characterized by the following steps:
mixing and reacting aliphatic dicarboxylic acid or an esterified product thereof, betulin, aliphatic diol and an esterification or ester exchange catalyst to obtain a polyester prepolymer based on the betulin;
adding a polycondensation catalyst, a free radical polymerization inhibitor, a stabilizer and an antioxidant into the polyester prepolymer, reacting for 1h-3h at a first temperature under a vacuum condition, and then continuing to react for 2h-22h at a second temperature to obtain a birch fat alcohol-based bio-based copolyester; wherein the first temperature is 160-180 ℃, the second temperature is 180-240 ℃, and the second temperature is greater than the first temperature.
5. The method for preparing bio-based copolyester based on betulin according to claim 4, wherein the molar ratio of the sum of the amounts of betulin and aliphatic diol to the aliphatic dicarboxylic acid or its esterified product is 3:1-5: 1.
6. The preparation method of betulin-based bio-based copolyester of claim 5, wherein the molar ratio of the aliphatic dicarboxylic acid or the esterified product thereof to the betulin is 5:1-5: 3.
7. The method for preparing bio-based copolyester based on betulin according to claim 4, wherein the esterification or transesterification catalyst is at least one selected from zinc acetate, isobutyl titanate, tetrabutyl titanate, ethylene glycol antimony and dibutyl tin oxide, and is used in an amount of 0.1-0.2% by mole of the aliphatic dicarboxylic acid or its esterified substance.
8. The method for preparing bio-based copolyester based on betulin according to claim 4, wherein the aliphatic dicarboxylic acid or its esterified product, betulin, aliphatic diol, and esterification or transesterification catalyst are mixed and reacted at 160-220 deg.C for 2-6 h.
9. The preparation method of betulin-based bio-based copolyester as claimed in claim 4, wherein the free radical polymerization inhibitor is at least one selected from hydroquinone, p-methoxyphenol, p-tert-butylcatechol, and p-benzoquinone, and is used in an amount of 0.4-0.6% by mole of the aliphatic dicarboxylic acid or its ester.
10. The method for preparing bio-based copolyester based on betulin according to claim 4, wherein the polycondensation catalyst is at least one selected from antimony trioxide, isobutyl titanate, tetrabutyl titanate, germanium oxide, antimony glycol, antimony acetate and dibutyltin oxide, and the amount of the polycondensation catalyst is 0.1-0.2% of the mole number of the aliphatic dicarboxylic acid or the esterified substance thereof;
and/or the stabilizer is selected from phosphorus stabilizers, and the using amount of the stabilizer is 0.12 to 0.15 percent of the mole number of the aliphatic dicarboxylic acid or the ester thereof.
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| CN111491979A (en) * | 2017-12-22 | 2020-08-04 | 汉高股份有限及两合公司 | Betulin-based amorphous polyesters |
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| CN111491979A (en) * | 2017-12-22 | 2020-08-04 | 汉高股份有限及两合公司 | Betulin-based amorphous polyesters |
| CN111484605A (en) * | 2020-05-18 | 2020-08-04 | 郑州大学 | Full-bio-based unsaturated polyester prepolymer for dynamically vulcanizing polylactic acid and preparation method thereof |
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