CN116970154A - Degradable polyester, preparation method thereof and degradable plastic product - Google Patents
Degradable polyester, preparation method thereof and degradable plastic product Download PDFInfo
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- CN116970154A CN116970154A CN202310801889.2A CN202310801889A CN116970154A CN 116970154 A CN116970154 A CN 116970154A CN 202310801889 A CN202310801889 A CN 202310801889A CN 116970154 A CN116970154 A CN 116970154A
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- degradable polyester
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- degradable
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- 229920000728 polyester Polymers 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 229920006238 degradable plastic Polymers 0.000 title claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 58
- 239000003054 catalyst Substances 0.000 claims abstract description 45
- QYQADNCHXSEGJT-UHFFFAOYSA-N cyclohexane-1,1-dicarboxylate;hydron Chemical compound OC(=O)C1(C(O)=O)CCCCC1 QYQADNCHXSEGJT-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000000047 product Substances 0.000 claims abstract description 24
- 239000013067 intermediate product Substances 0.000 claims abstract description 22
- 239000003381 stabilizer Substances 0.000 claims abstract description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 230000032050 esterification Effects 0.000 claims abstract description 11
- 238000005886 esterification reaction Methods 0.000 claims abstract description 11
- 238000005809 transesterification reaction Methods 0.000 claims abstract description 11
- 230000001681 protective effect Effects 0.000 claims abstract description 8
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 5
- 238000006068 polycondensation reaction Methods 0.000 claims description 14
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 10
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims description 8
- 229910052787 antimony Inorganic materials 0.000 claims description 7
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- 239000010936 titanium Substances 0.000 claims description 5
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 claims description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical group [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 239000011572 manganese Substances 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 239000011574 phosphorus Substances 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 229910052732 germanium Inorganic materials 0.000 claims description 2
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 2
- 229940051250 hexylene glycol Drugs 0.000 claims description 2
- 239000012974 tin catalyst Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 6
- 230000009477 glass transition Effects 0.000 abstract description 14
- 239000002904 solvent Substances 0.000 abstract description 11
- 239000005022 packaging material Substances 0.000 abstract description 4
- 239000004033 plastic Substances 0.000 abstract description 4
- 229920003023 plastic Polymers 0.000 abstract description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 17
- 238000010438 heat treatment Methods 0.000 description 13
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 150000002148 esters Chemical class 0.000 description 8
- 230000001276 controlling effect Effects 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 238000005979 thermal decomposition reaction Methods 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 6
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 6
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- WSXIMVDZMNWNRF-UHFFFAOYSA-N antimony;ethane-1,2-diol Chemical compound [Sb].OCCO WSXIMVDZMNWNRF-UHFFFAOYSA-N 0.000 description 4
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 4
- 238000007334 copolymerization reaction Methods 0.000 description 4
- -1 polybutylene succinate Polymers 0.000 description 4
- 229920001707 polybutylene terephthalate Polymers 0.000 description 4
- 238000002411 thermogravimetry Methods 0.000 description 4
- 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 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 3
- 239000001361 adipic acid Substances 0.000 description 3
- 235000011037 adipic acid Nutrition 0.000 description 3
- 229940057499 anhydrous zinc acetate Drugs 0.000 description 3
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-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
- 239000010408 film Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- DJWUNCQRNNEAKC-UHFFFAOYSA-L zinc acetate Chemical compound [Zn+2].CC([O-])=O.CC([O-])=O DJWUNCQRNNEAKC-UHFFFAOYSA-L 0.000 description 3
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- 229940035437 1,3-propanediol Drugs 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- 239000004254 Ammonium phosphate Substances 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 229920000954 Polyglycolide Polymers 0.000 description 2
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 2
- 235000019289 ammonium phosphates Nutrition 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- JVLRYPRBKSMEBF-UHFFFAOYSA-K diacetyloxystibanyl acetate Chemical compound [Sb+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JVLRYPRBKSMEBF-UHFFFAOYSA-K 0.000 description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 2
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 description 2
- 229940119177 germanium dioxide Drugs 0.000 description 2
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 229940071125 manganese acetate Drugs 0.000 description 2
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 2
- CAAULPUQFIIOTL-UHFFFAOYSA-N methyl dihydrogen phosphate Chemical compound COP(O)(O)=O CAAULPUQFIIOTL-UHFFFAOYSA-N 0.000 description 2
- 229920002961 polybutylene succinate Polymers 0.000 description 2
- 239000004631 polybutylene succinate Substances 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 239000004633 polyglycolic acid Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 2
- KAJBSGLXSREIHP-UHFFFAOYSA-N 2,2-bis[(2-sulfanylacetyl)oxymethyl]butyl 2-sulfanylacetate Chemical compound SCC(=O)OCC(CC)(COC(=O)CS)COC(=O)CS KAJBSGLXSREIHP-UHFFFAOYSA-N 0.000 description 1
- 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
- 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
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 239000002253 acid Substances 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
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- GGCUUOGRTPMFQK-UHFFFAOYSA-N dimethyl cyclohexane-1,1-dicarboxylate Chemical compound COC(=O)C1(C(=O)OC)CCCCC1 GGCUUOGRTPMFQK-UHFFFAOYSA-N 0.000 description 1
- LQRUPWUPINJLMU-UHFFFAOYSA-N dioctyl(oxo)tin Chemical compound CCCCCCCC[Sn](=O)CCCCCCCC LQRUPWUPINJLMU-UHFFFAOYSA-N 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 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
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- OEIJHBUUFURJLI-UHFFFAOYSA-N octane-1,8-diol Chemical compound OCCCCCCCCO OEIJHBUUFURJLI-UHFFFAOYSA-N 0.000 description 1
- PVADDRMAFCOOPC-UHFFFAOYSA-N oxogermanium Chemical compound [Ge]=O PVADDRMAFCOOPC-UHFFFAOYSA-N 0.000 description 1
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical compound CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- 239000004626 polylactic acid Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 229940005657 pyrophosphoric acid Drugs 0.000 description 1
- 230000001105 regulatory effect Effects 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
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 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
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/682—Polyesters containing atoms other than carbon, hydrogen and oxygen containing halogens
- C08G63/6824—Polyesters containing atoms other than carbon, hydrogen and oxygen containing halogens derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/6826—Dicarboxylic acids and dihydroxy compounds
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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 application relates to a preparation method of degradable polyester, which comprises the following steps: reacting a first mixed reaction system containing cyclohexane dicarboxylic acid or an esterified product thereof, 2,3,5, 6-tetrafluoro-1, 4-terephthalyl alcohol, aliphatic dihydric alcohol and an esterification or transesterification catalyst in a protective atmosphere to obtain an intermediate product; and (3) reacting a second mixed reaction system containing the intermediate product and a stabilizer under vacuum condition to obtain the degradable polyester. The application also relates to the degradable polyester prepared by the preparation method and a degradable plastic product prepared by the degradable polyester. The degradable polyester has high glass transition temperature, transparency, solvent resistance, degradability and the like, so that the degradable polyester can be better applied to products with high requirements on heat resistance, solvent resistance, transparency and degradability, such as packaging materials, films, plastic containers and the like, and the degradable plastic products prepared from the degradable polyester have excellent comprehensive properties.
Description
Technical Field
The application relates to the technical field of high polymer materials, in particular to degradable polyester, a preparation method thereof and a degradable plastic product.
Background
Polymers such as polylactic acid (PLA), polyhydroxyfatty acid (PHA), polyglycolic acid (PGA), polybutylene succinate (PBS), polybutylene terephthalate (PBAT) and the like, which are widely used in the market, have excellent biodegradability, but products made of these polymers have the following disadvantages: (1) Poor heat resistance, and is extremely easy to deform under the condition of being higher than normal temperature to influence the use; (2) Poor solvent resistance and is extremely easy to damage in an environment containing organic matters; (3) The transparency is poor, and the use effect of products such as films, containers and the like is affected.
Disclosure of Invention
Based on this, it is necessary to provide a degradable polyester having high glass transition temperature, transparency, solvent resistance, degradability and the like, and a process for producing the same, and a degradable plastic article having excellent overall properties.
In order to achieve the above purpose, the technical scheme adopted by the application is as follows: a process for the preparation of a degradable polyester comprising the steps of:
reacting a first mixed reaction system containing cyclohexane dicarboxylic acid or an esterified product thereof, 2,3,5, 6-tetrafluoro-1, 4-terephthalyl alcohol, aliphatic dihydric alcohol and an esterification or transesterification catalyst in a protective atmosphere to obtain an intermediate product;
and (3) reacting a second mixed reaction system containing the intermediate product and a stabilizer under vacuum condition to obtain the degradable polyester.
In one embodiment, the molar ratio of the 2,3,5, 6-tetrafluoro-1, 4-terephthalyl alcohol to the cyclohexanedicarboxylic acid or its esters is from 5:100 to 60:100.
In one embodiment, the molar ratio of the sum of the molar amounts of the 2,3,5, 6-tetrafluoro-1, 4-terephthalyl alcohol and the aliphatic diol to the cyclohexanedicarboxylic acid or its esters is from 120:100 to 300:100.
In one embodiment, the aliphatic diol is at least one selected from propylene glycol, butylene glycol, hexylene glycol.
In one embodiment, in the step of reacting the first mixed reaction system under a protective atmosphere, the temperature is 180-240 ℃ and the time is 1.5-6 h;
and/or in the step of carrying out the reaction of the second mixed reaction system under the vacuum condition, the vacuum degree is within 200Pa, the temperature is 220-280 ℃ and the time is 1-8 h.
In one embodiment, the esterification or transesterification catalyst is selected from at least one of zinc-based catalyst, manganese-based catalyst, titanium-based catalyst, and antimony-based catalyst, and the molar ratio of the esterification or transesterification catalyst to the cyclohexanedicarboxylic acid or its esterified product is 0.2:1000-2.0:1000.
In one embodiment, the stabilizer is selected from phosphorus based stabilizers, the molar ratio of the stabilizer to the cyclohexanedicarboxylic acid or its esters being from 0.2:1000 to 3.0:1000.
In one embodiment, the second mixed reaction system further includes a polycondensation catalyst, where the polycondensation catalyst is at least one selected from a titanium catalyst, a tin catalyst, an antimony catalyst, and a germanium catalyst, and a molar ratio of the polycondensation catalyst to the cyclohexanedicarboxylic acid or the esterified product thereof is 0.2:1000-2.0:1000.
A degradable polyester is prepared by a preparation method of the degradable polyester.
A degradable plastic article made from the degradable polyester.
In the application, 2,3,5, 6-tetrafluoro-1, 4-terephthalyl alcohol and cyclohexane dicarboxylic acid or esters thereof are used as copolymerization units, so that the glass transition temperature and solvent resistance of the polyester can be improved simultaneously, and the 2,3,5, 6-tetrafluoro-1, 4-terephthalyl alcohol can break the ordered structure of the polyester in the copolymerization process, so that the transparency of the polyester can be effectively improved, and further, the degradable polyester disclosed by the application has high glass transition temperature, transparency, solvent resistance, degradability and the like, and is excellent in comprehensive performance. Therefore, the degradable polyester can be better applied to products with high requirements on heat resistance, solvent resistance, transparency and degradability, such as packaging materials, films, plastic containers and the like, and the degradable plastic products prepared from the degradable polyester can have excellent comprehensive properties.
In addition, the preparation method adopts an esterification-polycondensation process for preparation, is simple in preparation method, simple and convenient to operate, high in controllability and easy to implement, and is suitable for large-scale industrial production.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings that are required to be used in the embodiments or the description of the prior art will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments described in the present application, and other drawings may be obtained according to the drawings without inventive effort to those skilled in the art.
FIG. 1 is a degradable polyester prepared in example 1 1 H-NMR spectrum;
FIG. 2 is a DCS spectrum of the degradable polyester prepared in example 1;
FIG. 3 is a TGA spectrum of the degradable polyester prepared in example 1.
Detailed Description
The present application will be described in more detail below in order to facilitate understanding of the present application. It should be understood, however, that the application may be embodied in many different forms and is not limited to the implementations or embodiments described 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 application belongs. The terminology used in the description of the application herein is for the purpose of describing particular embodiments or examples only and is not intended to be limiting of the application. As used herein, the optional scope of the term "and/or" includes any one of the two or more related listed items, as well as any and all combinations of related listed items, including any two or more of the related listed items, or all combinations of related listed items.
Furthermore, the terms "first," "second," and the like, are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include at least one such feature. In the description of the present application, the meaning of "plurality" means at least two, for example, two, three, etc., unless specifically defined otherwise.
The preparation method of the degradable polyester provided by the application comprises the following steps:
s1, reacting a first mixed reaction system containing cyclohexane dicarboxylic acid or an esterified substance thereof, 2,3,5, 6-tetrafluoro-1, 4-terephthalyl alcohol, aliphatic dihydric alcohol and an esterification or transesterification catalyst in a protective atmosphere to obtain an intermediate product;
s2, reacting a second mixed reaction system containing the intermediate product and the stabilizer under a vacuum condition to obtain the degradable polyester.
In order to provide the degradable polyester with higher glass transition temperature, transparency, solvent resistance, degradability, etc., the molar ratio of the 2,3,5, 6-tetrafluoro-1, 4-terephthalyl alcohol to the cyclohexanedicarboxylic acid or its esters in step S1 is preferably 5:100 to 60:100, including but not limited to 5:100, 8:100, 10:100, 12:100, 15:100, 18:100, 20:100, 23:100, 25:100, 18:100, 30:100, 33:100, 35:100, 38:100, 40:100, 42:100, 45:100, 48:100, 50:100, 52:100, 55:100, 58:100, 60:100, further preferably 10:100 to 50:100; and the molar ratio of the sum of the molar amounts of the 2,3,5, 6-tetrafluoro-1, 4-terephthalyl alcohol and the aliphatic diol to the cyclohexanedicarboxylic acid or its esters is preferably 120:100 to 300:100, including but not limited to 120:100, 125:100, 130:100, 135:100, 140:100, 145:100, 150:100, 155:100, 160:100, 165:100, 170:100, 175:100, 180:100, 185:100, 190:100, 195:100, 200:100, 205:100, 210:100, 220:100, 225:100, 230:100, 240:100, 245:100, 250:100, 255:100, 260:100, 265:100, 270:100, 275:100, 280:100, 285:100, 290:100, 295:100, 300:100, further preferably 120:100 to 200:100.
Alternatively, the esterified product of cyclohexanedicarboxylic acid is selected from the group consisting of dimethyl cyclohexanedicarboxylate and the like, and in the present application, it is preferable to react cyclohexanedicarboxylic acid with 2,3,5, 6-tetrafluoro-1, 4-terephthalyl alcohol and an aliphatic diol.
Optionally, the aliphatic diol is selected from propylene glycol, butanediol, pentanediol, hexanediol, octanediol, and the like, and is preferably at least one of propylene glycol, butanediol, and hexanediol, so that the degradation performance of the degradable polyester can be better regulated and controlled.
Optionally, the esterification or transesterification catalyst is selected from at least one of zinc-based catalyst, manganese-based catalyst, titanium-based catalyst, and antimony-based catalyst, specifically includes at least one of anhydrous zinc acetate, anhydrous manganese acetate, tetrabutyl titanate, isopropyl titanate, antimony trioxide, ethylene glycol antimony, antimony acetate, or polyethylene glycol antimony, and the molar ratio of the esterification or transesterification catalyst to the cyclohexanedicarboxylic acid or its esterified product is preferably 0.2:1000-2.0:1000, including but not limited to 0.2:1000, 0.3:1000, 0.4:1000, 0.5:1000, 0.6:1000, 0.7:1000, 0.8:1000, 0.9:1000, 1.0:1000, 1.1:1000, 1.2:1000, 1.3:1000, 1.4:1000, 1.5:1000, 1.6:1000, 1.7:1000, 1.8:1000, 1.9:1000, and 2.0:1000.
Optionally, in the step of performing the reaction of the first mixed reaction system under a protective atmosphere, the temperature is preferably 180 ℃ to 240 ℃, including but not limited to 180 ℃, 185 ℃, 190 ℃, 200 ℃, 205 ℃, 210 ℃, 215 ℃, 220 ℃, 225 ℃, 230 ℃, 235 ℃, 240 ℃ for 1.5h to 6h, and the protective atmosphere is selected from nitrogen, argon and the like, preferably nitrogen.
In the step S2, the second mixed reaction system is reacted under vacuum condition, the vacuum degree is preferably within 200Pa, the temperature is preferably 220-280 ℃, including but not limited to 220 ℃, 225 ℃, 230 ℃, 235 ℃, 240 ℃, 245 ℃, 250 ℃, 255 ℃, 260 ℃, 265 ℃, 270 ℃, 275 ℃, 280 ℃ and the time is preferably 1-8 h.
Specifically, the second mixed reaction system is heated to 220 ℃ to 280 ℃ and slowly vacuumized for pre-polycondensation, and then the vacuum degree is controlled to be below 200Pa for reaction, so that the degradable polyester is obtained.
Optionally, the stabilizer is selected from phosphorus stabilizers, specifically including 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 the cyclohexane dicarboxylic acid or the ester thereof is 0.2:1000-3.0:1000, including but not limited to 0.2:1000, 0.3:1000, 0.4:1000, 0.5:1000, 0.6:1000, 0.7:1000, 0.8:1000, 0.9:1000, 1.0:1000, 1.1:1000, 1.2:1000, 1.3:1000, 1.4:1000, 1.5:1000, 1.6:1000, 1.7:1000, 1.8:1000, 1.9:1000, 2.0:1000, 2.1:1000, 2.2:1000, 2.6:1000, 2.7:1000, 2.8:1000, and 2.3:1000:1000.2.5:1000.
Optionally, the second mixed reaction system further comprises a polycondensation catalyst, wherein the polycondensation catalyst is at least one selected from titanium-series catalyst, tin-series catalyst, antimony-series catalyst and germanium-series catalyst, and especially, when the esterification or transesterification catalyst is selected from zinc-series catalyst, the polycondensation catalyst is further added into the second mixed reaction system.
Specifically, the polycondensation catalyst includes at least one of tetrabutyl titanate, isopropyl titanate, antimony trioxide, ethylene glycol antimony, antimony acetate, polyethylene glycol antimony, dibutyl tin oxide, stannous octoate, tin monobutyl triisooctoate, dioctyl tin oxide, germanium dioxide, and germanium oxide, and the molar ratio of the polycondensation catalyst to the cyclohexane dicarboxylic acid or the esterified product thereof is 0.2:1000-2.0:1000, including but not limited to 0.2:1000, 0.3:1000, 0.4:1000, 0.5:1000, 0.6:1000, 0.7:1000, 0.8:1000, 0.9:1000, 1.0:1000, 1.1:1000, 1.2:1000, 1.3:1000, 1.4:1000, 1.5:1000, 1.6:1000, 1.7:1000, 1.8:1000, 1.9:1000, and 2.0:1000.
In the preparation method, 2,3,5, 6-tetrafluoro-1, 4-terephthalyl alcohol and cyclohexane dicarboxylic acid or esters thereof are used as copolymerization units, so that the glass transition temperature and solvent resistance of the polyester can be improved simultaneously, and the 2,3,5, 6-tetrafluoro-1, 4-terephthalyl alcohol can break the ordered structure of the polyester in the copolymerization process, so that the transparency of the polyester can be improved effectively. In addition, the preparation method adopts an esterification-polycondensation process for preparation, is simple in preparation method, simple and convenient to operate, high in controllability and easy to implement, and is suitable for large-scale industrial production.
Therefore, the application also provides the degradable polyester prepared by the preparation method of the degradable polyester, and the degradable polyester has high glass transition temperature, transparency, solvent resistance, degradability and the like and excellent comprehensive performance.
Furthermore, the degradable polyester can be better applied to products with high requirements on heat resistance, solvent resistance, transparency and degradability such as packaging materials, films, plastic containers and the like, and the degradable plastic products prepared from the degradable polyester can have excellent comprehensive performance.
The present application therefore also provides a degradable plastic article, such as a packaging material, film, plastic container, etc., made of the degradable polyester.
Hereinafter, the degradable polyester, the method for preparing the same and the degradable plastic article 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 Bruker400AVANCE III Spectrometer type instrument 400MHz, CDCl 3 。
In the examples below, the thermal analysis uses a differential scanning calorimeter (mettler toledoDSC) at a heating rate of 10℃per minute at N 2 The atmosphere is carried out at a temperature in the range of-70 ℃ to 250 ℃.
In the following examples, thermogravimetric analysis (TGA) was performed on a Perkin-Elmer Diamond TMTG/DTA with a heating rate of 20℃per minute and a temperature in the range of 50℃to 800 ℃.
Example 1
Adding 0.1mol of cyclohexane dicarboxylic acid, 0.02mol of 2,3,5, 6-tetrafluoro-1, 4-terephthalyl alcohol, 0.2mol of 1, 4-butanediol and 0.12% of anhydrous zinc acetate based on cyclohexane dicarboxylic acid into a reaction kettle to obtain a first mixed reaction system, vacuumizing, filling nitrogen for replacement twice, starting stirring, gradually heating to 180 ℃, and reacting for 4 hours to obtain an intermediate product.
Adding 0.1% of antimony trioxide and 0.15% of triphenyl phosphate based on the molar weight of cyclohexane dicarboxylic acid into the intermediate product to obtain a second mixed reaction system, heating the second mixed reaction system to 220 ℃, slowly vacuumizing and pre-polycondensing for 1h, and then controlling the vacuum degree to be below 200Pa for 4h to obtain the degradable polyester.
The degradable polyester obtained in this example 1 The H-NMR is shown in FIG. 1, the DSC spectrum is shown in FIG. 2, the glass transition temperature is 12.4 ℃, the TGA spectrum is shown in FIG. 3, and the T is shown in FIG. 3 d,5％ The thermal decomposition temperature is 399 ℃, the visible light transmittance of the cut-off 700nm wavelength is 88 percent, and the cut-off material is indissolvable in methanol, ethanol, acetone and cyclohexane.
Example 2
Adding 0.1mol of cyclohexane dicarboxylic acid, 0.005mol of 2,3,5, 6-tetrafluoro-1, 4-terephthalyl alcohol, 0.115mol of 1, 4-butanediol and 0.08 percent of anhydrous manganese acetate based on cyclohexane dicarboxylic acid into a reaction kettle to obtain a first mixed reaction system, vacuumizing, filling nitrogen for replacement twice, starting stirring, gradually heating to 220 ℃, and reacting for 1.5 hours to obtain an intermediate product.
Adding 0.02% of antimonous oxide and 0.05% of methyl phosphate based on the molar weight of cyclohexane dicarboxylic acid into the intermediate product to obtain a second mixed reaction system, heating the second mixed reaction system to 230 ℃, slowly vacuumizing and pre-condensing for 0.6h, and then controlling the vacuum degree to be lower than 150Pa for reaction for 3h to obtain the degradable polyester.
The degradable polyester obtained in this example has a glass transition temperature of 9.3℃T d,5％ The thermal decomposition temperature is 395 ℃, the visible light transmittance of the cut-off 700nm wavelength is 90 percent, and the cut-off material is indissolvable in methanol, ethanol, acetone and cyclohexane.
Example 3
Adding 0.1mol of cyclohexane dicarboxylic acid, 0.03mol of 2,3,5, 6-tetrafluoro-1, 4-terephthalyl alcohol, 0.22mol of 1, 3-propanediol and 0.02 percent of tetrabutyl titanate based on cyclohexane dicarboxylic acid into a reaction kettle to obtain a first mixed reaction system, vacuumizing, filling nitrogen for replacement twice, starting stirring, gradually heating to 180 ℃, and reacting for 3.5 hours to obtain an intermediate product.
Adding triphenyl phosphate with the molar weight of 0.1% based on cyclohexane dicarboxylic acid into the intermediate product to obtain a second mixed reaction system, heating the second mixed reaction system to 220 ℃, slowly vacuumizing and pre-polycondensing for 1h, and then controlling the vacuum degree to be less than 50Pa for 2h to obtain the degradable polyester.
The degradable polyester obtained in this example has a glass transition temperature of 44.8℃T d,5％ The thermal decomposition temperature is 383 ℃, the visible light transmittance of the cut-off 700nm wavelength is 90 percent, and the cut-off material is indissolvable in methanol, ethanol, acetone and cyclohexane.
Example 4
0.1mol of cyclohexane dicarboxylic acid, 0.04mol of 2,3,5, 6-tetrafluoro-1, 4-terephthalyl alcohol, 0.26mol of 1, 3-propanediol and 0.2 percent of ethylene glycol antimony based on cyclohexane dicarboxylic acid are added into a reaction kettle to obtain a first mixed reaction system, then the reaction system is vacuumized, replaced by nitrogen for two times, stirring is started, the temperature is gradually raised to 190 ℃, and the reaction is carried out for 3.5 hours, thus obtaining an intermediate product.
Adding 0.2% of dibutyl tin oxide and 0.02% of diphenyl phosphate based on the molar weight of cyclohexane dicarboxylic acid into the intermediate product to obtain a second mixed reaction system, heating the second mixed reaction system to 220 ℃, slowly vacuumizing and pre-condensing for 0.8h, and then controlling the vacuum degree to be below 70Pa for 2h to obtain the degradable polyester.
The degradable polyesters obtained in this example have, as tested, a glass transition temperature of52.6℃，T d,5％ The thermal decomposition temperature was 388 ℃.
Example 5
0.1mol of cyclohexane dicarboxylic acid, 0.05mol of 2,3,5, 6-tetrafluoro-1, 4-terephthalyl alcohol, 0.11mol of 1, 6-hexanediol and 0.15 percent of ethylene glycol antimony based on cyclohexane dicarboxylic acid are added into a reaction kettle to obtain a first mixed reaction system, then the first mixed reaction system is vacuumized, replaced by nitrogen for two times, stirring is started, the temperature is gradually increased to 230 ℃, and the reaction is carried out for 3.5 hours, thus obtaining an intermediate product.
Adding 0.15% isopropyl titanate and 0.08% methyl phosphate based on the molar weight of cyclohexane dicarboxylic acid into the intermediate product to obtain a second mixed reaction system, heating the second mixed reaction system to 260 ℃, slowly vacuumizing and pre-condensing for 0.5h, and then controlling the vacuum degree to be below 70Pa for reaction for 8h to obtain the degradable polyester.
The degradable polyester obtained in this example has a glass transition temperature of 3.2℃T d,5％ The thermal decomposition temperature was 401 ℃.
Example 6
Adding 0.1mol of cyclohexane dicarboxylic acid, 0.06mol of 2,3,5, 6-tetrafluoro-1, 4-terephthalyl alcohol, 0.24mol of 1, 6-hexanediol and 0.1% tetrabutyl titanate based on cyclohexane dicarboxylic acid into a reaction kettle to obtain a first mixed reaction system, vacuumizing, filling nitrogen for replacement twice, starting stirring, gradually heating to 240 ℃, and reacting for 6 hours to obtain an intermediate product.
Adding germanium dioxide 0.18% and diphenyl phosphate 0.15% based on the molar weight of cyclohexane dicarboxylic acid into the intermediate product to obtain a second mixed reaction system, heating the second mixed reaction system to 280 ℃, slowly vacuumizing and pre-polycondensing for 1h, and then controlling the vacuum degree to be below 20Pa for reacting for 1h to obtain the degradable polyester.
The degradable polyester obtained in this example has a glass transition temperature of 13.8℃T d,5％ The thermal decomposition temperature was 406 ℃.
Comparative example 1
0.045mol of terephthalic acid, 0.055mol of adipic acid and 0.16mol of butanediol, and 0.12% of anhydrous zinc acetate based on the sum of the molar amounts of the terephthalic acid and the adipic acid are added into a reaction kettle to obtain a first mixed reaction system, then vacuumizing and nitrogen filling are carried out for two times, stirring is started, the temperature is gradually increased to 180 ℃, and the reaction is carried out for 4 hours, so as to obtain an intermediate product.
Adding 0.1% of antimony trioxide and 0.15% of triphenyl phosphate based on the sum of the molar amounts of terephthalic acid and adipic acid into the intermediate product to obtain a second mixed reaction system, heating the second mixed reaction system to 220 ℃, slowly vacuumizing and pre-polycondensing for 1h, and then controlling the vacuum degree to be below 200Pa for 4h to obtain polybutylene terephthalate adipate (PBAT).
The polybutylene terephthalate obtained in this comparative example has a glass transition temperature of-29.3℃T d,5％ The thermal decomposition temperature was 375 ℃.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described 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 above examples illustrate only a few embodiments of the application, which are described in detail and are not to be construed as limiting the scope of the application. 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 application, which are all within the scope of the application. Accordingly, the scope of protection of the present application is to be determined by the appended claims.
Claims (10)
1. A process for the preparation of a degradable polyester comprising the steps of:
reacting a first mixed reaction system containing cyclohexane dicarboxylic acid or an esterified product thereof, 2,3,5, 6-tetrafluoro-1, 4-terephthalyl alcohol, aliphatic dihydric alcohol and an esterification or transesterification catalyst in a protective atmosphere to obtain an intermediate product;
and (3) reacting a second mixed reaction system containing the intermediate product and a stabilizer under vacuum condition to obtain the degradable polyester.
2. The method for producing a degradable polyester according to claim 1, wherein the molar ratio of 2,3,5, 6-tetrafluoro-1, 4-terephthalyl alcohol to the cyclohexanedicarboxylic acid or its esterified product is 5:100 to 60:100.
3. The method for producing a degradable polyester according to claim 1, wherein the molar ratio of the sum of the molar amounts of 2,3,5, 6-tetrafluoro-1, 4-terephthalyl alcohol and the aliphatic dihydric alcohol to the cyclohexanedicarboxylic acid or its esterified product is 120:100 to 300:100.
4. The method for producing a degradable polyester according to claim 1, wherein the aliphatic diol is at least one selected from the group consisting of propylene glycol, butylene glycol, and hexylene glycol.
5. The method for producing a degradable polyester according to claim 1, wherein in the step of reacting the first mixed reaction system under a protective atmosphere, the temperature is 180 ℃ to 240 ℃ for 1.5h to 6h;
and/or in the step of carrying out the reaction of the second mixed reaction system under the vacuum condition, the vacuum degree is within 200Pa, the temperature is 220-280 ℃ and the time is 1-8 h.
6. The method for producing a degradable polyester according to any one of claims 1 to 5, wherein the esterification or transesterification catalyst is at least one selected from zinc-based catalyst, manganese-based catalyst, titanium-based catalyst, and antimony-based catalyst, and the molar ratio of the esterification or transesterification catalyst to the cyclohexanedicarboxylic acid or the esterified product thereof is 0.2:1000 to 2.0:1000.
7. The method for producing a degradable polyester according to any one of claims 1 to 5, wherein the stabilizer is selected from phosphorus stabilizers, and the molar ratio of the stabilizer to the cyclohexanedicarboxylic acid or the esterified product thereof is 0.2:1000 to 3.0:1000.
8. The method according to any one of claims 1 to 5, wherein the second mixed reaction system further comprises a polycondensation catalyst, wherein the polycondensation catalyst is at least one selected from a titanium catalyst, a tin catalyst, an antimony catalyst, and a germanium catalyst, and the molar ratio of the polycondensation catalyst to the cyclohexanedicarboxylic acid or the esterified product thereof is 0.2:1000 to 2.0:1000.
9. A degradable polyester prepared by the process of any one of claims 1 to 8.
10. A degradable plastic article, characterized in that it is made of the degradable polyester according to claim 9.
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