CN115044022B - Fat and fat-aromatic copolyester capable of being rapidly recycled in closed loop under mild condition, and preparation method, application and recycling method thereof - Google Patents

Fat and fat-aromatic copolyester capable of being rapidly recycled in closed loop under mild condition, and preparation method, application and recycling method thereof Download PDF

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CN115044022B
CN115044022B CN202210689659.7A CN202210689659A CN115044022B CN 115044022 B CN115044022 B CN 115044022B CN 202210689659 A CN202210689659 A CN 202210689659A CN 115044022 B CN115044022 B CN 115044022B
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copolyester
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CN115044022A (en
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王玉忠
李兴亮
杜伟强
李耀
李郑明
付腾
汪秀丽
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Sichuan University
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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
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/199—Acids or hydroxy compounds containing cycloaliphatic rings
    • 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
    • C08G63/40—Polyesters derived from ester-forming derivatives of polycarboxylic acids or of polyhydroxy compounds, other than from esters thereof
    • C08G63/42—Cyclic ethers; Cyclic carbonates; Cyclic sulfites; Cyclic orthoesters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • 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
    • 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
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • 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
    • C08G63/685—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen
    • C08G63/6854—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen derived from polycarboxylic acids and polyhydroxy compounds
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    • C08J11/00—Recovery or working-up of waste materials
    • C08J11/04—Recovery or working-up of waste materials of polymers
    • C08J11/10—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation
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    • C08J11/04—Recovery or working-up of waste materials of polymers
    • C08J11/10—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation
    • C08J11/18—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material
    • C08J11/22—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material by treatment with organic oxygen-containing compounds
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    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers

Abstract

The invention discloses a fat, fat-aromatic copolyester capable of being quickly recycled in a closed loop under mild conditions, a preparation method and application thereof, wherein the copolyester is introduced with an ether bond structure monomer, an aromatic ring and a cyclic structure monomer with good heat stability and hydrophilicity, or a modified monomer of an amide structure monomer diol with easy formation of hydrogen bonds in a polymer, so that the prepared copolyester has high strength and excellent thermal property, hydrophilicity, mechanical property and barrier property, and can be singly applied to the fields of plastics, fibers, non-woven fabrics, films, medical packaging materials, container materials or 3D printing materials or used as a modified processing aid.

Description

Fat and fat-aromatic copolyester capable of being rapidly recycled in closed loop under mild condition, and preparation method, application and recycling method thereof
Technical Field
The invention belongs to the technical fields of copolyester, preparation, application and waste recovery, and in particular relates to fat, fat-aromatic copolyester capable of being rapidly recycled in a closed loop under mild conditions, a preparation method and application thereof, wherein the copolyester can simultaneously realize great improvement of heat performance, mechanical property and barrier property of the copolyester by only adding modified monomers with different structures, meanwhile, the copolyester can be further rapidly and chemically recycled after being used and abandoned, separation and collection of degradation products can be easily realized after degradation and recovery, degradation liquid can be recycled for multiple times, the separation process is simple, the energy consumption is low, and the polyester has good recovery performance.
Background
The high polymer material has the characteristics of light weight, adjustable performance, good processability and the like, and has become a typical material with the largest yield. Although their use brings great convenience, their full life cycle also brings problems of carbon emissions and exhaustion of fossil resources. How to polymerize and prepare a polyester material with excellent comprehensive properties such as mechanical property, thermal property and barrier property from the molecular structure design, and simultaneously, the polyester material which is abandoned after being used can be recycled with high efficiency, rapidness, conciseness and environmental protection is a problem to be solved urgently.
Aliphatic copolyesters and aliphatic-aromatic copolyesters have been attracting attention as a promising class of biobased materials, respectively, for their excellent processability and excellent gas barrier properties. In order to widen the application field of aliphatic copolyesters and aliphatic-aromatic copolyesters, polyester with excellent comprehensive properties such as mechanical properties, thermal properties and gas barrier properties is prepared, and different modifying monomers are introduced into the aliphatic copolyesters and the aliphatic-aromatic copolyesters to modify the aliphatic copolyesters and the aliphatic-aromatic copolyesters, such as Hu Han et al (H.Hu; R.zhang; J.Wang; W.B.ying; L.Shi; C.Yao; Z.Kong; K.Wang; J.Zhu.Green chemistry.2019 (21): 3013-3022), and glycolic acid is introduced into the furyl polyester to synthesize the poly (furandicarboxylic acid-glycolic acid-butanediol ester). Although the degradation performance of the polyester is partially improved by the introduction of the glycollic acid, the mechanical property and the barrier property of the polyester are both poor due to the lower molecular weight of the obtained polyester; poly (butylene succinate-isosorbide) was synthesized by incorporating isosorbide into an aliphatic polyester by Jiifei Qi et al (Q Jiifei, W Jing, C Jingang, W Huaping. Polymer Degradation and Stability,2019 (160): 229-241.). Although the addition of isosorbide increases the glass transition temperature of the polyester, the polyester has relatively low molecular weight, so that the comprehensive performance of the polyester is poor, and the mechanical property and the barrier property are not studied. Although the modification method can improve part of performances of the aliphatic copolyester and the aliphatic-aromatic copolyester, the aliphatic copolyester and the aliphatic-aromatic copolyester have poor natural degradation capability in the environment, and solid waste after the life cycle is finished can not only bring environmental problems, but also bring waste of resources.
In order to solve the problems of improving the comprehensive properties such as mechanical property, heat resistance, gas barrier property and the like of aliphatic copolyester and aliphatic-aromatic copolyester and disposing waste polyester after being used, the aliphatic copolyester and aliphatic-aromatic copolyester material with excellent comprehensive properties such as mechanical property, heat resistance, barrier property and the like is provided, and meanwhile, the chemical closed-loop recycling method which is beneficial to simplicity, high efficiency and greenness of waste after the use is provided, so that the method has very important practical significance for global sustainable development.
Disclosure of Invention
The invention aims at solving the problems existing in the prior art and provides a fat and fat-aromatic copolyester which can be rapidly recycled in a closed loop under mild conditions.
The second purpose of the invention is to provide a preparation method of the fat and fat-aromatic copolyester which can be rapidly recycled in a closed loop under the mild condition.
It is a further object of the present invention to provide the use of a fat, fat-aromatic copolyester which can be rapidly recovered in a closed loop under mild conditions as described above.
The fourth purpose of the invention is to provide a method for recovering the fat and the fat-aromatic copolyester which can be rapidly recycled in a closed loop under the mild condition, the recovered reaction liquid can be recycled for multiple times, the degradation products can be reused for polymerization, and the closed loop from the synthesis to the recovery of the materials can be realized.
The invention provides fat and fat-aromatic copolyester capable of being quickly recycled in a closed loop under mild conditions, which is composed of structural units represented by the following I, III, V or I, III, VI or I, III, IV, VII or I, III, VIII or I, III, IX or II, III, IV or II, III, V or II, III, VI or II, III, IV, VII or II, III, VIII or II, III and IX:
Figure BDA0003701097850000021
wherein R is 1 Is C 2 -C 10 Is used for the preparation of an alkylene group,
Figure BDA0003701097850000022
wherein R is 2 Is C 2 -C 10 Is used for the preparation of an alkylene group,
Figure BDA0003701097850000023
wherein R is 3 Is C 2 -C 10 The alkylene groups of (C) may be the same or different,
Figure BDA0003701097850000024
/>
Figure BDA0003701097850000031
wherein R is 4 Is C 1 -C 10 Is used for the preparation of an alkylene group,
Figure BDA0003701097850000032
wherein R is 5 Is C 1 -C 10 The alkylene groups of (C) may be the same or different,
Figure BDA0003701097850000033
wherein R is 6 Is C 1 -C 10 The alkylene groups of (C) may be the same or different,
Figure BDA0003701097850000041
wherein R is 7 、R 8 And R is 9 Each of the following groups:
Figure BDA0003701097850000042
[IV]the number of structural units of [ III ]]1 to 99% of the number of structural units [ II ]]The number of structural units: [ III+IV]The number of structural units of (1); [ V]The number of structural units of [ I ]]1 to 99% of the number of structural units [ III ]]The number of structural units: [ I+V]The number of structural units of (1); [ V]The number of structural units of [ III ]]1 to 99% of the number of structural units [ I ]]The number of structural units: [ III+V]The number of structural units of (1); [ V]The number of structural units of [ III ]]1 to 99% of the number of structural units [ II ] ]The number of structural units: [ III+V]The number of structural units of (1); [ VIII ]]The number of structural units of [ I ]]1 to 99% of the number of structural units [ III ]]The number of structural units: [ VIII+I ]]The number of structural units of (1); [ VIII ]]The number of structural units of [ II ]]1 to 99% of the number of structural units [ III ]]The number of structural units: [ VIII+II ]]The number of structural units of (1); [ VI ]]The number of structural units of [ III ]]1 to 99% of the number of structural units [ I ]]The number of structural units: [ III+VI ]]The number of structural units of (1); [ IV+VII ]]The number of structural units of [ III ]]1 to 99% of the number of structural units [ I ]]The number of structural units: [ III+IV+VII ]]The number of structural units of (1); [ IX ] A]The number of structural units of [ III ]]1 to 99% of the number of structural units [ I ]]The number of structural units: [ III+IX ]]The number of structural units of (1); [ V]The number of structural units of [ II ]]1 to 99% of the number of structural units [ III ]]The number of structural units: [ II+V]The number of structural units of (1); [ VI ]]The number of structural units of [ III ]]1 to 99% of the number of structural units [ II ]]The number of structural units: [ III+VI ]]The number of structural units of (1); [ IV+VII ]]The number of structural units of [ III ]]1 to 99% of the number of structural units [ II ]]The number of structural units: [ III+IV+VII ]]The number of structural units of (1); [ IX ] A ]The number of structural units of [ III ]]Structural unit of (2)1 to 99% of the number, [ II ]]The number of structural units: [ III+IX ]]The number of structural units of (1); the chain segment formed by each structural unit is formed by arbitrary connection and combination of carboxyl and hydroxyl functional groups, and the characteristic viscosity number [ eta ] of the copolyester]Is 0.5-2.8 dL/g; the tensile strength is 40.0-80.0 MPa; the elongation at break is 3.9-600.0%; CO 2 The permeability coefficient is 7.50E-16-2.25E-15 [ cm ] 3 ·cm/(cm 2 ·s·Pa)]；O 2 The permeability coefficient is 7.50E-16-3.00E-15 [ cm ] 3 ·cm/(cm 2 ·s·Pa)]The method comprises the steps of carrying out a first treatment on the surface of the The heat distortion temperature is 38-95 ℃; the initial decomposition temperature is 325-380 ℃.
Among the above copolyesters, [ IV ] is preferred]The number of structural units of [ III ]]8 to 80% of the number of structural units [ II ]]The number of structural units: [ III+IV]The number of structural units of (1); [ V]The number of structural units of [ I ]]8 to 80% of the number of structural units [ III ]]The number of structural units: [ I+V]The number of structural units of (1); [ V]The number of structural units of [ III ]]8 to 80% of the number of structural units [ I ]]The number of structural units: [ III+V]The number of structural units of (1); [ V]The number of structural units of [ III ]]8 to 80% of the number of structural units [ II ]]The number of structural units: [ III+V]The number of structural units of (1); [ VIII ]]The number of structural units of [ I ]]8 to 80% of the number of structural units [ III ] ]The number of structural units: [ VIII+I ]]The number of structural units of (1); [ VIII ]]The number of structural units of [ II ]]8 to 80% of the number of structural units [ III ]]The number of structural units: [ VIII+II ]]The number of structural units of (1); [ VI ]]The number of structural units of [ III ]]8 to 80% of the number of structural units [ I ]]The number of structural units: [ III+VI ]]The number of structural units of (1); [ IV+VII ]]The number of structural units of [ III ]]8 to 80% of the number of structural units [ I ]]The number of structural units: [ III+IV+VII ]]The number of structural units of (1); [ IX ] A]The number of structural units of [ III ]]8 to 80% of the number of structural units [ I ]]The number of structural units: [ III+IX ]]The number of structural units of (1); [ V]The number of structural units of [ II ]]8 to 80% of the number of structural units [ III ]]The number of structural units: [ II+V]The number of structural units of (1); [ VI ]]The number of structural units of [ III ]]8 to 80% of the number of structural units [ II ]]The number of structural units: [ III+VI ]]The number of structural units of (1); [ IV+VII ]]The number of structural units of [ III ]]8 to 80% of the number of structural units [ II ]]The number of structural units: [ III+IV+VII ]]Structural unit of (2)Number = 1; [ IX ] A]The number of structural units of [ III ]]8 to 80% of the number of structural units [ II ]]The number of structural units: [ III+IX ]]The number of structural units of (1); the chain segment formed by each structural unit is arbitrarily connected and combined according to carboxyl and hydroxyl functional groups, and the intrinsic viscosity [ eta ] of the intrinsic viscosity of the copolyester ]0.6-2.8 dL/g, and the tensile strength is 45.0-80.0 MPa; the breaking elongation is 50.0-600.0%; CO 2 The permeability coefficient is 7.50E-16-2.25E-15 [ cm ] 3 ·cm/(cm 2 ·s·Pa)]；O 2 The permeability coefficient is 7.50E-16-3.00E-15 [ cm ] 3 ·cm/(cm 2 ·s·Pa)]The method comprises the steps of carrying out a first treatment on the surface of the The heat distortion temperature is 42-90 ℃; the initial decomposition temperature is 330-375 ℃.
Of the above copolyesters, [ IV ] is more preferred]The number of structural units of [ III ]]10 to 50% of the number of structural units [ II ]]The number of structural units: [ III+IV]The number of structural units of (1); [ V]The number of structural units of [ I ]]10 to 50% of the number of structural units [ III ]]The number of structural units: [ I+V]The number of structural units of (1); [ V]The number of structural units of [ III ]]10 to 50% of the number of structural units [ I ]]The number of structural units: [ III+V]The number of structural units of (1); [ V]The number of structural units of [ III ]]10 to 50% of the number of structural units [ II ]]The number of structural units: [ III+V]The number of structural units of (1); [ VIII ]]The number of structural units of [ I ]]10 to 50% of the number of structural units [ III ]]The number of structural units: [ VIII+I ]]The number of structural units of (1); [ VIII ]]The number of structural units of [ II ]]10 to 50% of the number of structural units [ III ]]The number of structural units: [ VIII+II ]]The number of structural units of (1); [ VI ]]The number of structural units of [ III ]]10 to 50% of the number of structural units [ I ] ]The number of structural units: [ III+VI ]]The number of structural units of (1); [ IV+VII ]]The number of structural units of [ III ]]10 to 50% of the number of structural units [ I ]]The number of structural units: [ III+IV+VII ]]The number of structural units of (1); [ IX ] A]The number of structural units of [ III ]]10 to 50% of the number of structural units [ I ]]The number of structural units: [ III+IX ]]The number of structural units of (1); [ V]The number of structural units of [ II ]]10 to 50% of the number of structural units [ III ]]The number of structural units: [ II+V]The number of structural units of (1); [ VI ]]The number of structural units of [ III ]]10 to 50% of the number of structural units [ II ]]The number of structural units: [ III+VI ]]The number of structural units of (1); [ IV+VII ]]The number of structural units of [ III ]]10 to 50% of the number of structural units [ II ]]The number of structural units: [ III+IV+VII ]]The number of structural units of (1); [ IX ] A]The number of structural units of [ III ]]10 to 50 of the number of structural units [ II ]]The number of structural units: [ III+IX ]]The number of structural units of (1); the chain segment formed by each structural unit is arbitrarily connected and combined according to carboxyl and hydroxyl functional groups, and the intrinsic viscosity [ eta ] of the intrinsic viscosity of the copolyester]0.7-2.8 dL/g, and the tensile strength is 50.0-80.0 MPa; the elongation at break is 100.0-600.0%; CO 2 The permeability coefficient is 7.50E-16-1.50E-15 [ cm ] 3 ·cm/(cm 2 ·s·Pa)]；O 2 The permeability coefficient is 7.50E-16-2.25E-15 [ cm ] 3 ·cm/(cm 2 ·s·Pa)]The method comprises the steps of carrying out a first treatment on the surface of the The heat distortion temperature is 45-85 ℃; the initial decomposition temperature is 332-370 ℃.
The invention provides a preparation method of fat and fat-aromatic copolyester capable of being quickly recycled in a ring closure mode under the mild condition, which is characterized in that under the condition of a conventional catalyst, an equimolar amount of dibasic acid and dihydric alcohol are subjected to esterification reaction by adopting a direct esterification method or an equimolar amount of dibasic acid esterified substance and dihydric alcohol are subjected to transesterification reaction by adopting an ester exchange method and then are subjected to polycondensation reaction, and the preparation method is characterized in that before the esterification reaction, before the ester exchange reaction or before the ester exchange reaction, a modified monomer with the mole percentage of the dibasic acid or dibasic acid esterified substance being 1-99% is added into a reaction system.
The amount of the modified monomer added in the above preparation method is preferably 8 to 80%, more preferably 10 to 50% in terms of the mole percentage of the dibasic acid or dibasic acid ester in the polyester monomer.
The modified monomer in the preparation method is at least one of the following structural formulas:
Z 1 -O-Z 1
wherein Z is 1 Is C 2 ～C 10 May be the same or different,
Figure BDA0003701097850000061
Figure BDA0003701097850000071
/>
wherein Z is 2 Is C 1 ～C 10 Alkoxy radicals of (C), which may be identical or different, Z 3 Is C 2 ～C 10 May be the same or different,
Figure BDA0003701097850000072
wherein Z is 3 Is C 2 ～C 10 May be the same or different,
Figure BDA0003701097850000073
wherein Z is 3 Is C 2 ～C 10 May be the same or different,
Figure BDA0003701097850000074
wherein Z is 2 Is C 1 ～C 10 The alkoxy groups of (2) may be the same or different,
Figure BDA0003701097850000075
wherein Z is 3 Is C 2 ～C 10 May be the same or different, R 7 、R 8 And R is 9 Is the following group:
Figure BDA0003701097850000081
/>
the modified monomer described in the above preparation method is preferably at least one of the following structural formulas:
Z 1 -O-Z 1
wherein Z is 1 Is C 2 ～C 10 May be the same or different,
Figure BDA0003701097850000082
wherein Z is 2 Is C 1 ～C 10 Alkoxy radicals of (C), which may be identical or different, Z 3 Is C 2 ～C 10 May be the same or different,
Figure BDA0003701097850000083
wherein Z is 3 Is C 2 ～C 10 May be the same or different,
Figure BDA0003701097850000084
wherein Z is 3 Is C 2 ～C 10 May be the same or different,
Figure BDA0003701097850000091
wherein Z is 2 Is C 1 ～C 10 The alkoxy groups of (2) may be the same or different,
Figure BDA0003701097850000092
wherein Z is 3 Is C 2 ～C 10 May be the same or different, R 7 、R 8 And R is 9 Is the following group:
Figure BDA0003701097850000093
the synthesis of the modified monomers used above can be found in Polymer Chemistry,2018,9,4113-4119; ACS Sustainable Chemistry & Engineering,2021,9,1383-1397; green Chemistry,2021,23,9658-9668; journal of Organic Chemistry,2017,82,6082-6088; eurpean Journal of Organic Chemistry,2012,23,4283-4286; journal of Molecular Structure,2015,1081,146-158, etc.
The method adopts the following steps and specific conditions of the direct esterification method or the transesterification method:
direct esterification process: adding dibasic acid, dihydric alcohol, a catalyst and at least one modified monomer into a reaction container according to the proportion, pressurizing and heating to 160-180 ℃ for esterification reaction for 1.0-4.0 h; after the esterification reaction is finished, carrying out polycondensation reaction for 0.5-1.0 h under the condition of 180-200 ℃ and low vacuum, and then carrying out polycondensation reaction for 0.5-3.5 h under the condition of 210-230 ℃ and high vacuum; after the polycondensation reaction is completed, nitrogen is filled into the reaction vessel, and water cooling is performed, so that the target copolyester is obtained. Wherein, the modified monomer can be added into the reaction vessel before the esterification reaction or before the polycondensation reaction after the esterification reaction.
Transesterification process: adding an esterified product of dibasic acid, dihydric alcohol, a catalyst and at least one modified monomer into a reaction vessel according to the proportion, and carrying out transesterification reaction for 1.0-4.0 h at the normal pressure and the temperature of 160-180 ℃; after the transesterification reaction is finished, polycondensing for 0.5-1.0 h under the condition of 180-200 ℃ and low vacuum, and then polycondensing for 0.5-3.5 h under the condition of 210-230 ℃ and high vacuum; after the polycondensation reaction is completed, nitrogen is filled into the reaction vessel, and water cooling is performed, so that the target copolyester is obtained. Wherein, the modified monomer can be added into the reaction vessel before the transesterification or before the polycondensation after the transesterification.
The catalyst selected in the method is at least one of zinc acetate, manganese acetate, cobalt acetate, potassium acetate, antimonous oxide, ethylene glycol antimonic and titanate.
The application of the fat and fat-aromatic copolyester capable of being quickly recycled in a closed loop under the mild condition is characterized in that the copolyester is directly used as plastic, fiber, non-woven fabric, film, medical packaging material, container material or 3D printing material or used as a modified processing aid.
The invention provides a method for recovering fat and fat-aromatic copolyester which can be rapidly recovered in a closed loop under the mild condition, and the method comprises the following process steps and conditions:
(1) The used waste copolyester is divided into aliphatic structure copolyester or aliphatic-aromatic copolyester and is respectively crushed into 10-60 meshes, then the aliphatic structure copolyester or the aliphatic-aromatic copolyester is added into a mixed solution of an alkaline catalyst and a reaction solvent or the alkaline catalyst and a recovered reaction solution, and the mixture is reacted for 20-240 min at 50-80 ℃, wherein the mass volume ratio of the aliphatic structure copolyester or the aliphatic-aromatic copolyester to the reaction solvent or the recovered reaction solution is 0.004-0.2W/V, and the mass volume ratio of the alkaline catalyst to the reaction solvent or the alkaline catalyst to the recovered reaction solution is 0.04-0.2W/V;
(2) Cooling the reaction solution of the copolyester containing the fat structure obtained in the step (1) to 1-10 ℃, filtering, dissolving the obtained solid product in deionized water, and then adjusting the pH value of the solution to 1-6, or directly adjusting the pH value of the reaction solution of the copolyester containing the fat and the aromatic in the step (1) to 1-6, so that degradation products can be precipitated, degradation products and reaction solution are obtained, the degradation products can be collected and can be reused as raw materials for synthesizing new polyester, and the collected reaction solution can be used for replacing a reaction solvent for repeated use.
The reaction solvent used in the recovery method is at least one of methanol, ethanol, isopropanol, n-propanol, n-butanol, isobutanol, amyl alcohol, hexanol, 1, 4-butanediol, diethylene glycol and 1, 4-cyclohexanedimethanol, or a mixed solution of water and at least one of methanol, ethanol, isopropanol, n-propanol, n-butanol, isobutanol, amyl alcohol, hexanol, 1, 4-butanediol, diethylene glycol and 1, 4-cyclohexanedimethanol, and the volume ratio of the mixed solution is 20-80: 20-80 parts; the basic catalyst is at least one of alkoxide, basic metal salt, basic metal oxide and hydroxide.
The recycling of the collected reaction liquid described in the above recovery method includes: the separated reaction liquid is directly used as the reaction liquid for degrading and recycling the polyester next time, or the reaction liquid is further separated and recycled into the reaction solvent and the alcohol monomer by a separation method, the recycled reaction solvent is further used as the reaction solvent for recycling the waste polyester, and the recycled alcohol monomer can be used as the polymerization raw material of the polyester.
Compared with the prior art, the invention has the following positive effects:
1. the modified monomer selected by the invention has high polymerization activity, high polymerization reaction rate and mild polymerization conditions, so that even if the added amount is small, the copolyester can obtain enough high molecular weight, and the synthesized polyester material can still have the characteristic of high strength.
2. The copolyester provided by the invention has high strength, high heat resistance and high gas barrier property and adjustable performance, so that the copolyester can meet the requirements of the copolyester on materials such as fiber, non-woven fabrics, engineering plastics, films, medical packaging materials, container materials or 3D printing materials, and the like, and can further expand the application range of the copolyester, especially the fields with high requirements on the mechanical property, thermal property and barrier property of the materials. And can also be used as a modified processing aid.
3. Because the invention introduces the monomer containing ether bond structure ([ IV ]) with good thermal stability and hydrophilicity, the aromatic ring and the cyclic structure monomer ([ V ], [ VI ], [ VII ], VIII), or the monomer glycol containing amide structure ([ IX ]) which is easy to form hydrogen bond in the polymer to copolymerize, the invention endows the copolyester with more excellent thermal property, hydrophilicity, mechanical property and barrier property.
4. The preparation method of the polyester provided by the invention is easy to react, does not need to carry out activation treatment, can directly carry out copolymerization with the monomer, and is a conventional melt polycondensation method, so that the preparation method has the advantages of simplicity in operation, mature preparation process, easiness in control, suitability for large-scale industrial production and the like.
5. The invention can further carry out ring-closing chemical recovery after the polyester is abandoned after the use, and can easily separate and collect degradation products and reaction liquid after degradation recovery, thus having the advantages of high economic benefit, concise separation process, low energy consumption and the like.
6. The reaction solution used in the recovery process is the mixed solution of alcohol and water, and the alcohol and the water are solvents with low boiling points, so that the method has the advantages of environment friendliness, low price, easiness in obtaining and easiness in recovery.
7. The method can realize the rapid and effective degradation and separation of the waste aliphatic and furyl polyester materials under the conditions of low temperature and normal pressure, has the advantages of simple operation, mild reaction conditions, short degradation recovery time, high recovery rate and the like, is beneficial to reducing the recovery cost, and is suitable for industrial operation.
8. The invention not only synthesizes the polyester material with high strength, high heat resistance and high gas barrier property, but also realizes the closed-loop chemical recovery of the waste material after use, thereby solving the disposal problem of the waste material, improving the use benefit of the polyester material, reducing the carbon emission of the environment, being an efficient, low-carbon, green, economic and environment-friendly polyester material using and processing method, and having good social benefit and economic benefit.
Drawings
FIG. 1 is a nuclear magnetic resonance spectrum of a copolyester prepared in example 6 of the present invention. As can be seen from the spectra, the copolyester has been successfully prepared.
FIG. 2 is an infrared spectrum of the copolyester prepared in example 6 of the present invention. As can be seen from the spectra, the copolyester has been successfully prepared.
FIG. 3 is a nuclear magnetic resonance spectrum of the copolyester prepared in example 12 of the present invention. As can be seen from the spectra, the copolyester has been successfully prepared.
FIG. 4 is an infrared spectrum of the copolyester prepared in example 12 of the present invention. As can be seen from the spectra, the copolyester has been successfully prepared.
FIG. 5 is a nuclear magnetic resonance spectrum of the copolyester prepared in example 21 of the present invention. As can be seen from the spectra, the copolyester has been successfully prepared.
FIG. 6 is an infrared spectrum of the copolyester prepared in example 21 of the present invention. As can be seen from the spectra, the copolyester has been successfully prepared.
FIG. 7 is a nuclear magnetic resonance spectrum of a copolyester prepared in example 30 of the present invention. As can be seen from the spectra, the copolyester has been successfully prepared.
FIG. 8 is an infrared spectrum of the copolyester prepared in example 30 of the present invention. As can be seen from the spectra, the copolyester has been successfully prepared.
FIG. 9 is a thermogravimetric plot of the copolyester prepared in example 6 of the present invention. As can be seen from the thermogravimetric graph, the prepared copolyester has excellent thermal stability.
FIG. 10 is a stress-strain curve of the copolyester prepared in example 12 of the present invention. As can be seen from the stress-strain curve graph, the tensile strength of the prepared copolyester can reach 80MPa, and the copolyester has excellent mechanical properties.
FIG. 11 is a stress-strain curve of the copolyester prepared in example 21 of the present invention. As can be seen from the stress-strain curve graph, the prepared copolyester has excellent mechanical properties.
FIG. 12 is a stress-strain curve of the copolyester prepared in example 30 of the present invention. As can be seen from the stress-strain curve graph, the prepared copolyester has excellent mechanical properties.
FIG. 13 shows the oxygen barrier properties of commercial PBAT (permeability coefficient of 5.70E-13[ cm ] 3 ·cm/(cm 2 ·s·Pa)]) Variation of the ratio of oxygen barrier properties (BIF) to the copolyesters prepared in inventive examples 30, 31, 32 and 33. As can be seen from the graph, the BIF maximum value of the prepared copolyester can reach 760, and compared with commercial PBAT, the BIF maximum value of the copolyester greatly reduces the oxygen transmission amount and has excellent oxygen barrier property.
Detailed Description
The following examples are given to illustrate the present invention in further detail, but they should not be construed as limiting the scope of the invention, but as falling within the scope of the invention if some insubstantial modifications and adaptations of the invention are made by those skilled in the art in light of the disclosure herein, and in the field of technology, it is not to be construed as simply construed as possible, with only a limited number of experiments, given the partial overlap of materials, whereby the inventive concept is negated.
It is worth to describe the intrinsic viscosity [ eta ] of the high-strength, high-heat-resistance and high-gas barrier copolyesters obtained in examples 1 to 33]Phenol/1, 2-tetrachloroethane (1:1, v: v) was used as a solvent to prepare a solution having a concentration of 0.5g/dL, which was measured at 30℃using a black-bone viscometer; ATR-FTIR spectra of the copolyesters were measured on a Nicolet 6700 spectrophotometer with wavenumbers in the range 500-4000cm -1 . The mechanical properties of the copolyesters were measured at 25℃on an INSTRON 3366 universal tester at a tensile speed of 15mm/min, and five samples were repeated for each sample and averaged. The thermal stability of the copolyesters was measured on a thermogravimetric analyzer NETZSCH TG 209F1 instrument by heating the samples from 40 ℃ to 700 ℃ in a nitrogen atmosphere at a heating rate of 10 ℃. The heat distortion temperature of the copolyester is measured on a heat distortion instrument HDT-test. The gas barrier properties of the copolyesters were measured on a Labthink VAC-V2 by the national standard GB/T1038-2000 pressure measurement method.
Example 1
22.44g of succinic acid, 0.40g of (1R, 3S) - (+) -camphoric acid, 23.38g of tetrabutyl titanate catalyst accounting for 0.05wt% of the total mass of the reactants and tetraisopropyl titanate catalyst accounting for 0.05wt% of the total mass of the reactants are added into a polymerization device, direct esterification reaction is carried out for 1 hour under the nitrogen atmosphere at 180 ℃, pre-polycondensation is carried out for 1.0 hour under 200Pa at 200 ℃, then reaction is carried out for 3.5 hours under the condition of 220 ℃ and 50Pa, and finally material is taken under the nitrogen range.
The intrinsic viscosity [ eta ] of the copolyester obtained]2.4dL/g, and tensile strength of 40MPa; elongation at break of 278%; CO 2 Permeability coefficient of 2.25E-15[ cm ] 3 ·cm/(cm 2 ·s·Pa)]；O 2 Permeability coefficient of 3.00E-15[ cm ] 3 ·cm/(cm 2 ·s·Pa)]The method comprises the steps of carrying out a first treatment on the surface of the The heat distortion temperature is 95 ℃; the initial decomposition temperature was 325 ℃.
Example 2
Adding 21.26g of succinic acid, 4g of (1R, 3S) - (+) -camphoric acid, 21.63g of tetrabutyl titanate catalyst accounting for 0.05wt% of the total amount of the 1, 4-butanediol and reactants into a polymerization device, directly esterifying at 160 ℃ for 4 hours under nitrogen atmosphere, pre-polycondensing at 200 ℃ for 0.5 hour under 300Pa, then reacting at 230 ℃ for 3.5 hours under 40Pa, and finally taking materials under nitrogen range;
the intrinsic viscosity [ eta ] of the copolyester obtained]2.1dL/g, and a tensile strength of 51MPa; elongation at break of 344%; CO 2 Permeability coefficient of 1.50E-15[ cm ] 3 ·cm/(cm 2 ·s·Pa)]；O 2 Permeability coefficient of 2.25E-15[ cm ] 3 ·cm/(cm 2 ·s·Pa)]The method comprises the steps of carrying out a first treatment on the surface of the The heat distortion temperature is 85 ℃; the initial decomposition temperature was 335 ℃.
Example 3
20.08g of succinic acid, 6g of (1R, 3S) - (+) -camphoric acid, 21.63g of tetrabutyl titanate catalyst accounting for 0.05wt% of the total mass of the reactants and tetraisopropyl titanate catalyst accounting for 0.05wt% of the total mass of the reactants are added into a polymerization device, direct esterification reaction is carried out for 4 hours at 170 ℃ under nitrogen atmosphere, pre-polycondensation is carried out for 1.0 hour at 180 ℃ and 190Pa, then reaction is carried out for 3.0 hours at 210 ℃ and 45Pa, and finally material is taken under the nitrogen range.
The intrinsic viscosity [ eta ] of the copolyester obtained]2.0dL/g, and a tensile strength of 52MPa; elongation at break of 331%; CO 2 Permeability coefficient of 1.50E-15[ cm ] 3 ·cm/(cm 2 ·s·Pa)]；O 2 Permeability coefficient of 2.25E-15[ cm ] 3 ·cm/(cm 2 ·s·Pa)]The method comprises the steps of carrying out a first treatment on the surface of the The heat distortion temperature is 80 ℃; the initial decomposition temperature was 333 ℃.
Example 4
18.89g of succinic acid, 8.00g of (1R, 3S) - (+) -camphoric acid, 21.63g of tetrabutyl titanate catalyst accounting for 0.05 weight percent of the total mass of the reactants and tetraisopropyl titanate catalyst accounting for 0.05 weight percent of the total mass of the reactants are added into a polymerization device, the direct esterification reaction is carried out for 4 hours under the nitrogen atmosphere at 180 ℃, the pre-polycondensation is carried out for 0.5 hour under the temperature of 190 ℃ and 220Pa, the reaction is carried out for 3.0 hours under the temperature of 220 ℃ and the pressure of 65Pa, and finally the material is taken under the nitrogen range.
The intrinsic viscosity [ eta ] of the copolyester obtained]2.1dL/g, and the tensile strength is 56MPa; elongation at break 292%; CO 2 Permeability coefficient of 1.50E-15[ cm ] 3 ·cm/(cm 2 ·s·Pa)]；O 2 Permeability coefficient of 2.25E-15[ cm ] 3 ·cm/(cm 2 ·s·Pa)]The method comprises the steps of carrying out a first treatment on the surface of the The heat distortion temperature is 78 ℃; the initial decomposition temperature was 334 ℃.
Example 5
17.71g of succinic acid, 10.00g of (1R, 3S) - (+) -camphoric acid, 21.63g of tetrabutyl titanate catalyst accounting for 0.05wt% of the total mass of the reactants and tetraisopropyl titanate catalyst accounting for 0.05wt% of the total mass of the reactants are added into a polymerization device, direct esterification reaction is carried out for 4 hours at 180 ℃ under nitrogen atmosphere, pre-polycondensation is carried out for 0.5 hour at 190 ℃ under 220Pa, then reaction is carried out for 3.0 hours at 220 ℃ under 65Pa, and finally material is taken under the nitrogen range.
The intrinsic viscosity [ eta ] of the copolyester obtained]2.2dL/g, and the tensile strength is 60MPa; elongation at break 300%; CO 2 Permeability coefficient of 1.52E-15[ cm ] 3 ·cm/(cm 2 ·s·Pa)]；O 2 Permeability coefficient of 2.35E-15[ cm ] 3 ·cm/(cm 2 ·s·Pa)]The method comprises the steps of carrying out a first treatment on the surface of the The heat distortion temperature is 80 ℃; the initial decomposition temperature was 336 ℃.
Example 6
23.62g of succinic acid, 3.61g of (1R, 3S) - (+) -camphol, 18.93g of tetrabutyl titanate serving as a catalyst accounting for 0.05 weight percent of the total mass of the 1, 4-butanediol and tetraisopropyl titanate serving as a catalyst accounting for 0.05 weight percent of the total mass of reactants are added into a polymerization device, direct esterification reaction is carried out for 4 hours at 180 ℃ under nitrogen atmosphere, pre-polycondensation is carried out for 0.5 hour at 200 ℃ and 180Pa, then reaction is carried out for 2.5 hours at 220 ℃ and 55Pa is kept, and finally material is taken under the nitrogen range;
the intrinsic viscosity [ eta ] of the copolyester obtained]2.2dL/g, and a tensile strength of 50MPa; elongation at break of 347%; CO 2 Permeability coefficient of 1.50E-15[ cm ] 3 ·cm/(cm 2 ·s·Pa)]；O 2 Permeability coefficient of 2.25E-15[ cm ] 3 ·cm/(cm 2 ·s·Pa)]The method comprises the steps of carrying out a first treatment on the surface of the The heat distortion temperature is 81 ℃; the initial decomposition temperature was 332 ℃.
Example 7
Adding 22.4g of succinic acid, 2.0g of 3, 5-pyridine dimethyl diformate, 21.6g of 1, 4-butanediol and tetrabutyl titanate which is a catalyst accounting for 0.05 weight percent of the total mass of reactants into a polymerization device, performing direct esterification reaction for 4.0 hours at 170 ℃ under nitrogen atmosphere, performing pre-polycondensation for 0.5 hours at 200 ℃ and 200Pa, then performing reaction for 3.5 hours at 220 ℃ and 45Pa, and finally taking materials under the nitrogen range;
The intrinsic viscosity [ eta ] of the copolyester obtained]2.2dL/g, and the tensile strength is 41MPa; elongation at break 220%; CO 2 Permeability coefficient of 2.25E-15[ cm ] 3 ·cm/(cm 2 ·s·Pa)]；O 2 Permeability coefficient of 3.00E-15[ cm ] 3 ·cm/(cm 2 ·s·Pa)]The method comprises the steps of carrying out a first treatment on the surface of the The heat distortion temperature is 92 ℃; the initial decomposition temperature was 330 ℃.
Example 8
Adding 21.7g of succinic acid, 3.2g of 3, 5-pyridine dimethyl diformate, 21.6g of 1, 4-butanediol and tetrabutyl titanate which is a catalyst accounting for 0.05 weight percent of the total mass of reactants into a polymerization device, performing direct esterification reaction for 3 hours at 160 ℃ under nitrogen atmosphere, performing pre-polycondensation for 0.5 hours at 190 ℃ under 200Pa, then performing reaction for 3.0 hours at 220 ℃ under 40Pa, and finally taking materials under the nitrogen range;
the intrinsic viscosity [ eta ] of the copolyester obtained]2.2dL/g, and the tensile strength is 45MPa; elongation at break 200%; CO 2 Permeability coefficient of 2.25E-15[ cm ] 3 ·cm/(cm 2 ·s·Pa)]；O 2 Permeability coefficient of 3.00E-15[ cm ] 3 ·cm/(cm 2 ·s·Pa)]The method comprises the steps of carrying out a first treatment on the surface of the The heat distortion temperature is 90 ℃; the initial decomposition temperature was 330 ℃.
Example 9
Adding 20.1g of succinic acid, 6g of 3, 5-pyridine dimethyl diformate, 21.6g of 1, 4-butanediol and tetrabutyl titanate which is a catalyst accounting for 0.05 weight percent of the total mass of reactants into a polymerization device, performing direct esterification reaction for 4 hours at 170 ℃ under nitrogen atmosphere, performing pre-polycondensation for 1.0 hour at 190 ℃ under 200Pa, then performing reaction for 3.5 hours at 220 ℃ under 49Pa, and finally taking materials under the nitrogen range;
The intrinsic viscosity [ eta ] of the copolyester obtained]2.0dL/g, and a tensile strength of 64MPa; elongation at break 152%; CO 2 Permeability coefficient of 1.50E-15[ cm ] 3 ·cm/(cm 2 ·s·Pa)]；O 2 Permeability coefficient of 2.25E-15[cm 3 ·cm/(cm 2 ·s·Pa)]The method comprises the steps of carrying out a first treatment on the surface of the The heat distortion temperature is 81 ℃; the initial decomposition temperature was 336 ℃.
Example 10
Adding 18.9g of succinic acid, 8g of 3, 5-pyridine dimethyl diformate, 21.6g of 1, 4-butanediol and tetrabutyl titanate which is a catalyst accounting for 0.05 weight percent of the total mass of reactants into a polymerization device, performing direct esterification reaction for 4 hours at 175 ℃ under nitrogen atmosphere, performing pre-polycondensation for 0.5 hour at 200 ℃ and 200Pa, then performing reaction for 3.5 hours at 220 ℃ and 56Pa, and finally taking materials under the nitrogen range;
the intrinsic viscosity [ eta ] of the copolyester obtained]1.9dL/g, and a tensile strength of 68MPa; elongation at break 148%; CO 2 Permeability coefficient of 1.50E-15[ cm ] 3 ·cm/(cm 2 ·s·Pa)]；O 2 Permeability coefficient of 2.25E-15[ cm ] 3 ·cm/(cm 2 ·s·Pa)]The method comprises the steps of carrying out a first treatment on the surface of the The heat distortion temperature is 78 ℃; the initial decomposition temperature was 337 ℃.
Example 11
Adding 20.1g of succinic acid, 6g of 3, 5-pyridine dimethyl diformate, 21.6g of 1, 4-butanediol and tetrabutyl titanate which is a catalyst accounting for 0.1 weight percent of the total mass of reactants into a polymerization device, performing direct esterification reaction for 4 hours at 180 ℃ under nitrogen atmosphere, performing pre-polycondensation for 0.5 hour at 190 ℃ under 260Pa, then performing reaction for 3.5 hours at 210 ℃ under 60Pa, and finally taking materials under the nitrogen range;
The intrinsic viscosity [ eta ] of the copolyester obtained]2.2dL/g, and the tensile strength is 62MPa; elongation at break of 157%; CO 2 Permeability coefficient of 1.50E-15[ cm ] 3 ·cm/(cm 2 ·s·Pa)]；O 2 Permeability coefficient of 2.25E-15[ cm ] 3 ·cm/(cm 2 ·s·Pa)]The method comprises the steps of carrying out a first treatment on the surface of the The heat distortion temperature is 82 ℃; the initial decomposition temperature was 335 ℃.
Example 12
Adding 20.1g of succinic acid, 6g of 3, 5-pyridine dimethyl diformate, 21.6g of 1, 4-butanediol and tetrabutyl titanate which is a catalyst accounting for 0.1 weight percent of the total mass of reactants into a polymerization device, performing direct esterification reaction for 3.5 hours at 170 ℃ under nitrogen atmosphere, performing pre-polycondensation for 0.5 hour at 200 ℃ and 180Pa, then performing reaction for 3.5 hours at 230 ℃ and 58Pa, and finally taking materials under the nitrogen range;
the intrinsic viscosity [ eta ] of the copolyester obtained]2.1dL/g, and a tensile strength of 67MPa; elongation at break 150%; CO 2 Permeability coefficient of 1.42E-15[ cm ] 3 ·cm/(cm 2 ·s·Pa)]；O 2 The permeability coefficient is 1.95E-15[ cm ] 3 ·cm/(cm 2 ·s·Pa)]The method comprises the steps of carrying out a first treatment on the surface of the The heat distortion temperature is 81 ℃; the initial decomposition temperature was 336 ℃.
Example 13
Adding 21.2g of succinic acid, 4.2g of 4- (2-hydroxyethoxy) -3-methoxybenzoic acid, 20.5g of 1, 4-butanediol and tetrabutyl titanate serving as a catalyst accounting for 0.1wt% of the total mass of reactants into a polymerization device, performing direct esterification reaction for 4 hours at 180 ℃ under nitrogen atmosphere, performing pre-polycondensation for 0.5 hour at 200 ℃ and 200Pa, then performing reaction for 3.5 hours at 220 ℃ and 39Pa, and finally taking materials under the nitrogen range;
The intrinsic viscosity [ eta ] of the copolyester obtained]1.2dL/g, and a tensile strength of 50MPa; elongation at break 306%; CO 2 Permeability coefficient of 1.50E-15[ cm ] 3 ·cm/(cm 2 ·s·Pa)]；O 2 Permeability coefficient of 2.25E-15[ cm ] 3 ·cm/(cm 2 ·s·Pa)]The method comprises the steps of carrying out a first treatment on the surface of the The heat distortion temperature is 85 ℃; the initial decomposition temperature was 332 ℃.
Example 14
Adding 21.2g of succinic acid, 4.2g of 4- (2-hydroxyethoxy) -3-methoxybenzoic acid, 19.4g of 1, 4-butanediol and tetrabutyl titanate serving as a catalyst accounting for 0.1wt% of the total mass of reactants into a polymerization device, performing direct esterification reaction for 4 hours at 180 ℃ under nitrogen atmosphere, performing pre-polycondensation for 0.5 hour at 200 ℃ and 200Pa, then performing reaction for 2.5 hours at 220 ℃ and maintaining at 37Pa, and finally taking materials under the nitrogen range;
the intrinsic viscosity [ eta ] of the copolyester obtained]2.1dL/g, and a tensile strength of 61MPa; elongation at break of 256%; CO 2 Permeability coefficient of 1.50E-15[ cm ] 3 ·cm/(cm 2 ·s·Pa)]；O 2 Permeability coefficient of 2.25E-15[ cm ] 3 ·cm/(cm 2 ·s·Pa)]The method comprises the steps of carrying out a first treatment on the surface of the The heat distortion temperature is 82 ℃; initial separationThe decomposition temperature was 335 ℃.
Example 15
Adding 18.4g of succinic acid, 6.3g of 4- (2-hydroxyethoxy) -3-methoxybenzoic acid, 20.14g of 1, 4-butanediol and tetrabutyl titanate serving as a catalyst accounting for 0.1wt% of the total mass of reactants into a polymerization device, performing direct esterification reaction for 4 hours at 180 ℃ under nitrogen atmosphere, performing pre-polycondensation for 1.0 hour at 190 ℃ under 200Pa, then performing reaction for 3.0 hours at 220 ℃ under 38Pa, and finally taking materials under the nitrogen range;
The intrinsic viscosity [ eta ] of the copolyester obtained]2.3dL/g, and the tensile strength is 65MPa; elongation at break of 261%; CO 2 Permeability coefficient of 1.50E-15[ cm ] 3 ·cm/(cm 2 ·s·Pa)]；O 2 Permeability coefficient of 2.17E-15[ cm ] 3 ·cm/(cm 2 ·s·Pa)]The method comprises the steps of carrying out a first treatment on the surface of the The heat distortion temperature is 80 ℃; the initial decomposition temperature was 340 ℃.
Example 16
Adding 18.9g of succinic acid, 8.4g of 4- (2-hydroxyethoxy) -3-methoxybenzoic acid, 17.3g of 1, 4-butanediol and tetrabutyl titanate serving as a catalyst accounting for 0.1 weight percent of the total mass of reactants into a polymerization device, performing direct esterification reaction for 4 hours at 180 ℃ under nitrogen atmosphere, performing pre-polycondensation for 0.5 hours at 200 ℃ and 200Pa, then performing reaction for 3.0 hours at 220 ℃ and keeping at 42Pa, and finally taking materials under the nitrogen range;
the intrinsic viscosity [ eta ] of the copolyester obtained]1.8dL/g, and a tensile strength of 67MPa; elongation at break of 460%; CO 2 Permeability coefficient of 1.50E-15[ cm ] 3 ·cm/(cm 2 ·s·Pa)]；O 2 Permeability coefficient of 2.17E-15[ cm ] 3 ·cm/(cm 2 ·s·Pa)]The method comprises the steps of carrying out a first treatment on the surface of the The heat distortion temperature is 75 ℃; the initial decomposition temperature was 342 ℃.
Example 17
Adding 21.2g of succinic acid, 3.6g of 4- (2-hydroxyethoxy) benzoic acid, 19.4g of 1, 4-butanediol and tetrabutyl titanate serving as a catalyst accounting for 0.1wt% of the total mass of reactants into a polymerization device, performing direct esterification reaction for 4 hours at 175 ℃ under nitrogen atmosphere, performing pre-polycondensation for 0.5 hour at 180 ℃ under 210Pa, then performing reaction for 3.5 hours at 220 ℃ under 45Pa, and finally taking materials under the nitrogen range;
The intrinsic viscosity [ eta ] of the copolyester obtained]2.1dL/g, and the tensile strength is 62MPa; elongation at break 320%; CO 2 Permeability coefficient of 9.00E-16[ cm ] 3 ·cm/(cm 2 ·s·Pa)]；O 2 Permeability coefficient of 2.25E-15[ cm ] 3 ·cm/(cm 2 ·s·Pa)]The method comprises the steps of carrying out a first treatment on the surface of the The heat distortion temperature is 76 ℃; the initial decomposition temperature was 342 ℃.
Example 18
21.2g of succinic acid, 4.9g of 4- (2-hydroxyethoxy) -3, 5-dimethoxy benzoic acid, 19.4g of 1, 4-butanediol and tetrabutyl titanate which is a catalyst accounting for 0.1 weight percent of the total mass of reactants are added into a polymerization device, direct esterification reaction is carried out for 4 hours at 180 ℃ under nitrogen atmosphere, pre-polycondensation is carried out for 0.5 hour at 200 ℃ and 200Pa, then reaction is carried out for 3.0 hours at 220 ℃ and 48Pa, and finally material is taken under the nitrogen range;
the intrinsic viscosity [ eta ] of the copolyester obtained]2.2dL/g, and a tensile strength of 59MPa; elongation at break 180%; CO 2 Permeability coefficient of 1.35E-15[ cm ] 3 ·cm/(cm 2 ·s·Pa)]；O 2 Permeability coefficient of 2.02E-15[ cm ] 3 ·cm/(cm 2 ·s·Pa)]The method comprises the steps of carrying out a first treatment on the surface of the The heat distortion temperature is 78 ℃; the initial decomposition temperature was 337 ℃.
Example 19
21.2g of succinic acid, 4.8g of (+/-) -3- (4- (2-hydroxyethoxy) -3-methoxyphenyl) acrylic acid, 19.4g of tetrabutyl titanate which is a catalyst and accounting for 0.1 weight percent of the total mass of the reactants are added into a polymerization device, direct esterification reaction is carried out for 3.5 hours at 170 ℃ under nitrogen atmosphere, pre-polycondensation is carried out for 0.5 hour at 200 ℃ and 200Pa, then reaction is carried out for 3.5 hours at 230 ℃ and 62Pa, and finally material is taken under nitrogen range;
The intrinsic viscosity [ eta ] of the copolyester obtained]2.1dL/g, and a tensile strength of 67MPa; elongation at break 320%; CO 2 Permeability coefficient of 1.20E-15[ cm ] 3 ·cm/(cm 2 ·s·Pa)]；O 2 The permeability coefficient is 1.95E-15[ cm ] 3 ·cm/(cm 2 ·s·Pa)]The method comprises the steps of carrying out a first treatment on the surface of the The heat distortion temperature is 75 ℃; the initial decomposition temperature was 348 ℃.
Example 20
21.2g of succinic acid, 4.1g of (+/-) -3- (4- (2-hydroxyethoxy) phenyl) acrylic acid, 19.4g of 1, 4-butanediol and tetrabutyl titanate which is a catalyst accounting for 0.1 weight percent of the total mass of reactants are added into a polymerization device, direct esterification reaction is carried out for 4 hours at 180 ℃ under nitrogen atmosphere, pre-polycondensation is carried out for 0.6 hour at 175 ℃ under 200Pa, then reaction is carried out for 3.5 hours at 220 ℃ under 58Pa, and finally material is taken under the nitrogen range;
the intrinsic viscosity [ eta ] of the copolyester obtained]2.2dL/g, and the tensile strength is 65MPa; elongation at break 320%; CO 2 Permeability coefficient of 1.27E-15 cm 3 ·cm/(cm 2 ·s·Pa)]；O 2 The permeability coefficient is 1.87E-15[ cm ] 3 ·cm/(cm 2 ·s·Pa)]The method comprises the steps of carrying out a first treatment on the surface of the The heat distortion temperature is 78 ℃; the initial decomposition temperature was 348 ℃.
Example 21
21.2g of succinic acid, 5.5g of (+/-) -3- (4- (2-hydroxyethoxy) -3, 5-dimethoxyphenyl) acrylic acid, 19.4g of tetrabutyl titanate which is a catalyst and is 0.1 weight percent of the total mass of the 1, 4-butanediol and reactants are added into a polymerization device, direct esterification reaction is carried out for 4 hours at 180 ℃ under nitrogen atmosphere, pre-polycondensation is carried out for 0.5 hour at 200 ℃ and 200Pa, then reaction is carried out for 3.5 hours at 220 ℃ and 56Pa, and finally material is taken under the nitrogen range;
The intrinsic viscosity [ eta ] of the copolyester obtained]2.3dL/g, and the tensile strength is 58MPa; elongation at break 140%; CO 2 Permeability coefficient of 1.12E-15[ cm ] 3 ·cm/(cm 2 ·s·Pa)]；O 2 The permeability coefficient is 1.95E-15[ cm ] 3 ·cm/(cm 2 ·s·Pa)]The method comprises the steps of carrying out a first treatment on the surface of the The heat distortion temperature is 74 ℃; the initial decomposition temperature was 350 ℃.
Example 22
94.40g of succinic acid, 65.05g of 1, 4-butanediol, 2.49g of diethylene glycol, 5.83g of ethylene glycol and catalyst ethylene glycol antimony accounting for 0.1wt% of the total mass of reactants are added into a polymerization device, direct esterification reaction is carried out for 4 hours at 180 ℃ under nitrogen atmosphere, pre-polycondensation is carried out for 1.0 hour at 200 ℃ under 200Pa, then reaction is carried out for 3.5 hours at 230 ℃ under 58Pa, and finally material is taken under nitrogen.
The intrinsic viscosity [ eta ] of the copolyester obtained]2.8dL/g, and the tensile strength is 60MPa; elongation at break 376%; CO 2 Permeability coefficient of 1.42E-15[ cm ] 3 ·cm/(cm 2 ·s·Pa)]；O 2 Permeability coefficient of 2.25E-15[ cm ] 3 ·cm/(cm 2 ·s·Pa)]The method comprises the steps of carrying out a first treatment on the surface of the The heat distortion temperature is 85 ℃; the initial decomposition temperature was 335 ℃.
Example 23
94.40g of succinic acid, 65.05g of 1, 4-butanediol, 4.99g of diethylene glycol, 4.38g of ethylene glycol and catalyst ethylene glycol antimony accounting for 0.1wt% of the total mass of reactants are added into a polymerization device, direct esterification reaction is carried out for 4 hours at 180 ℃ under nitrogen atmosphere, pre-polycondensation is carried out for 0.5 hour at 200 ℃ under 200Pa, then reaction is carried out for 3.0 hours at 220 ℃ under 58Pa, and finally material is taken under nitrogen.
The intrinsic viscosity [ eta ] of the copolyester obtained]1.92dL/g, and the tensile strength is 55MPa; elongation at break 600%; CO 2 Permeability coefficient of 1.27E-15 cm 3 ·cm/(cm 2 ·s·Pa)]；O 2 The permeability coefficient is 1.87E-15[ cm ] 3 ·cm/(cm 2 ·s·Pa)]The method comprises the steps of carrying out a first treatment on the surface of the The heat distortion temperature is 82 ℃; the initial decomposition temperature was 339 ℃.
Example 24
23.60g of succinic acid, 16.26g of 1, 4-butanediol, 3.47g of isosorbide, 0.62g of diethylene glycol and catalyst ethylene glycol antimony accounting for 0.1wt% of the total mass of reactants are added into a polymerization device, direct esterification reaction is carried out for 3 hours at 175 ℃ under nitrogen atmosphere, pre-polycondensation is carried out for 1.0 hour at 190 ℃ under 200Pa, then reaction is carried out for 3.5 hours at 230 ℃ under 54Pa, and finally material is taken under nitrogen.
The intrinsic viscosity [ eta ] of the copolyester obtained]2.26dL/g, and the tensile strength is 63MPa; elongation at break 224%; CO 2 Permeability coefficient of 1.05E-15[ cm ] 3 ·cm/(cm 2 ·s·Pa)]；O 2 Permeability coefficient of 2.10E-15[ cm ] 3 ·cm/(cm 2 ·s·Pa)]The method comprises the steps of carrying out a first treatment on the surface of the The heat distortion temperature is 80 ℃; the initial decomposition temperature was 335 ℃.
Example 25
23.60g of succinic acid, 16.26g of 1, 4-butanediol, 2.12g of 1, 4-dimethylcyclohexane, 1.56g of diethylene glycol and catalyst ethylene glycol antimony accounting for 0.1wt% of the total mass of reactants are added into a polymerization device, direct esterification reaction is carried out for 4 hours at 180 ℃ under nitrogen atmosphere, pre-polycondensation is carried out for 0.5 hour at 200 ℃ and 200Pa, then reaction is carried out for 3.5 hours at 220 ℃ and 49Pa, and finally material is taken under nitrogen.
The intrinsic viscosity [ eta ] of the copolyester obtained]2.12dL/g, and a tensile strength of 61MPa; elongation at break 376%; CO 2 Permeability coefficient of 1.12E-15[ cm ] 3 ·cm/(cm 2 ·s·Pa)]；O 2 Permeability coefficient of 1.80E-15[ cm ] 3 ·cm/(cm 2 ·s·Pa)]The method comprises the steps of carrying out a first treatment on the surface of the The heat distortion temperature is 80 ℃; the initial decomposition temperature was 336 ℃.
Example 26
31.2g of dimethyl 2, 5-furandicarboxylate, 1.47g of 4-hydroxy-N- (2-hydroxyethyl) butyl amide, 38.7g of tetrabutyl titanate serving as a catalyst accounting for 0.1wt% of the total mass of the 1, 4-butanediol and reactants are added into a polymerization device, transesterification reaction is carried out for 3.5 hours at 175 ℃ under nitrogen atmosphere, pre-polycondensation is carried out for 0.5 hour at 180 ℃ under 240Pa, then reaction is carried out for 2.5 hours at 230 ℃ under 55Pa, and finally material is taken under nitrogen.
The intrinsic viscosity [ eta ] of the copolyester obtained]1.21dL/g, and a tensile strength of 60MPa; elongation at break 300%; CO 2 The permeability coefficient is 1.87E-15[ cm ] 3 ·cm/(cm 2 ·s·Pa)]；O 2 Permeability coefficient of 1.42E-15[ cm ] 3 ·cm/(cm 2 ·s·Pa)]The method comprises the steps of carrying out a first treatment on the surface of the The heat distortion temperature is 42.1 ℃; the initial decomposition temperature was 340 ℃.
Example 27
31.2g of dimethyl 2, 5-furandicarboxylate, 2.94g of 4-hydroxy-N- (2-hydroxyethyl) butyl amide, 37.8g of tetrabutyl titanate serving as a catalyst accounting for 0.1wt% of the total mass of the reactants are added into a polymerization device, transesterification is carried out for 4 hours at 165 ℃ under nitrogen atmosphere, pre-polycondensation is carried out for 1.0 hour at 200 ℃ and 200Pa, then reaction is carried out for 3 hours at 220 ℃ and 58Pa, and finally material is taken under nitrogen.
The obtained co-polymerIntrinsic viscosity [ eta ] of polyester]1.15dL/g, and the tensile strength is 66MPa; elongation at break of 335%; CO 2 Permeability coefficient of 2.17E-15[ cm ] 3 ·cm/(cm 2 ·s·Pa)]；O 2 Permeability coefficient of 1.72E-15[ cm ] 3 ·cm/(cm 2 ·s·Pa)]The method comprises the steps of carrying out a first treatment on the surface of the The heat distortion temperature is 45.3 ℃; the initial decomposition temperature was 335 ℃.
Example 28
31.2g of dimethyl 2, 5-furandicarboxylate, 5.88g of 4-hydroxy-N- (2-hydroxyethyl) butyl amide, 36.0g of tetrabutyl titanate serving as a catalyst accounting for 0.1wt% of the total mass of the 1, 4-butanediol and reactants are added into a polymerization device, transesterification reaction is carried out for 4 hours at 180 ℃ under nitrogen atmosphere, pre-polycondensation is carried out for 0.5 hour at 200 ℃ under 200Pa, then reaction is carried out for 3 hours at 210 ℃ under 49Pa, and finally material is taken under nitrogen.
The intrinsic viscosity [ eta ] of the copolyester obtained]1.08dL/g, and a tensile strength of 75MPa; elongation at break 199%; CO 2 Permeability coefficient of 2.25E-15[ cm ] 3 ·cm/(cm 2 ·s·Pa)]；O 2 Permeability coefficient of 3.00E-15[ cm ] 3 ·cm/(cm 2 ·s·Pa)]The method comprises the steps of carrying out a first treatment on the surface of the The heat distortion temperature is 48.5 ℃; the initial decomposition temperature was 333 ℃.
Example 29
31.2g of dimethyl 2, 5-furandicarboxylate, 19.38g of 4-hydroxy-N- (2-hydroxyethyl) butyl amide, 27.72g of tetrabutyl titanate serving as a catalyst accounting for 0.1wt% of the total mass of the 1, 4-butanediol and reactants are added into a polymerization device, transesterification reaction is carried out for 4 hours at 180 ℃ under nitrogen atmosphere, pre-polycondensation is carried out for 0.5 hour at 200 ℃ under 200Pa, then reaction is carried out for 3 hours at 210 ℃ under 49Pa, and finally material is taken under nitrogen.
The intrinsic viscosity [ eta ] of the copolyester obtained]1.02dL/g, and a tensile strength of 78MPa; elongation at break 150%; CO 2 Permeability coefficient of 2.12E-15[ cm ] 3 ·cm/(cm 2 ·s·Pa)]；O 2 Permeability coefficient of 2.82E-15 cm 3 ·cm/(cm 2 ·s·Pa)]The method comprises the steps of carrying out a first treatment on the surface of the The heat distortion temperature is 49.0 ℃; the initial decomposition temperature was 335 ℃.
Implementation 30
31.2g of dimethyl 2, 5-furandicarboxylate, 23.26g of 4-hydroxy-N- (2-hydroxyethyl) butyl amide, 25.34g of tetrabutyl titanate serving as a catalyst accounting for 0.1wt% of the total mass of the reactants are added into a polymerization device, transesterification reaction is carried out for 4 hours at 180 ℃ under nitrogen atmosphere, pre-polycondensation is carried out for 0.5 hour at 200 ℃ under 200Pa, then reaction is carried out for 3 hours at 210 ℃ under 49Pa, and finally material is taken under nitrogen.
The intrinsic viscosity [ eta ] of the copolyester obtained]0.98dL/g, and a tensile strength of 76MPa; elongation at break 112%; CO 2 Permeability coefficient of 2.05E-15[ cm ] 3 ·cm/(cm 2 ·s·Pa)]；O 2 Permeability coefficient of 2.63E-15[ cm ] 3 ·cm/(cm 2 ·s·Pa)]The method comprises the steps of carrying out a first treatment on the surface of the The heat distortion temperature is 49.3 ℃; the initial decomposition temperature was 336 ℃.
Example 31
31.2g of dimethyl 2, 5-furandicarboxylate, 25.87g of 2-hydroxy-N- (2-hydroxyethyl) ethylamide, 19.8g of tetrabutyl titanate serving as a catalyst accounting for 0.1wt% of the total mass of the reactants are added into a polymerization device, transesterification reaction is carried out for 4 hours at 180 ℃ under nitrogen atmosphere, pre-polycondensation is carried out for 0.5 hour at 200 ℃ under 200Pa, then reaction is carried out for 3 hours at 210 ℃ under 56Pa, and finally material is taken under nitrogen.
The intrinsic viscosity [ eta ] of the copolyester obtained]0.7dL/g, and a tensile strength of 70MPa; elongation at break 100%; CO 2 Permeability coefficient of 7.50E-16[ cm ] 3 ·cm/(cm 2 ·s·Pa)]；O 2 Permeability coefficient of 7.50E-16[ cm ] 3 ·cm/(cm 2 ·s·Pa)]The method comprises the steps of carrying out a first treatment on the surface of the The heat distortion temperature is 45 ℃; the initial decomposition temperature was 370 ℃.
Example 32
31.2g of dimethyl 2, 5-furandicarboxylate, 2.38g of 2-hydroxy-N- (2-hydroxyethyl) ethylamide, 37.8g of tetrabutyl titanate serving as a catalyst accounting for 0.1wt% of the total mass of the reactants are added into a polymerization device, transesterification is carried out for 2 hours at 170 ℃ under nitrogen atmosphere, pre-polycondensation is carried out for 0.5 hour at 200 ℃ under 200Pa, then reaction is carried out for 3 hours at 210 ℃ under 48Pa, and finally material is taken under nitrogen.
The intrinsic viscosity [ eta ] of the copolyester obtained]1.1dL/g, and a tensile strength of 72MPa; elongation at break 120%; CO 2 Permeability coefficient of 1.12E-15[ cm ] 3 ·cm/(cm 2 ·s·Pa)]；O 2 Permeability coefficient of 9.00E-16[ cm ] 3 ·cm/(cm 2 ·s·Pa)]The method comprises the steps of carrying out a first treatment on the surface of the The heat distortion temperature is 44 ℃; the initial decomposition temperature was 330 ℃.
Example 33
31.2g of dimethyl 2, 5-furandicarboxylate, 4.76g of 2-hydroxy-N- (2-hydroxyethyl) ethylamide, 36.0g of tetrabutyl titanate serving as a catalyst accounting for 0.1wt% of the total mass of the 1, 4-butanediol and reactants are added into a polymerization device, transesterification reaction is carried out for 4 hours at 180 ℃ under nitrogen atmosphere, pre-polycondensation is carried out for 0.5 hour at 200 ℃ under 200Pa, then reaction is carried out for 2.5 hours at 210 ℃ under 39Pa, and finally material is taken under nitrogen.
The intrinsic viscosity [ eta ] of the copolyester obtained]1.0dL/g, and a tensile strength of 72MPa; elongation at break 153%; CO 2 Permeability coefficient of 1.20E-15[ cm ] 3 ·cm/(cm 2 ·s·Pa)]；O 2 Permeability coefficient of 1.35E-15[ cm ] 3 ·cm/(cm 2 ·s·Pa)]The method comprises the steps of carrying out a first treatment on the surface of the The heat distortion temperature is 49 ℃; the initial decomposition temperature was 332 ℃.
Example 34
31.2g of dimethyl 2, 5-furandicarboxylate, 1.33g of 2-hydroxy-N- (2-hydroxyisopropyl) ethylamide, 38.7g of tetrabutyl titanate serving as a catalyst accounting for 0.1wt% of the total mass of the reactants are added into a polymerization device, transesterification reaction is carried out for 4 hours at 180 ℃ under nitrogen atmosphere, pre-polycondensation is carried out for 0.8 hour at 190 ℃ under 250Pa, then reaction is carried out for 2.5 hours at 230 ℃ under 59Pa, and finally material is taken under nitrogen.
The intrinsic viscosity [ eta ] of the copolyester obtained]1.2dL/g, and a tensile strength of 59MPa; elongation at break 312%; CO 2 Permeability coefficient of 1.12E-15[ cm ] 3 ·cm/(cm 2 ·s·Pa)]；O 2 Permeability coefficient of 1.35E-15[ cm ] 3 ·cm/(cm 2 ·s·Pa)]The method comprises the steps of carrying out a first treatment on the surface of the The heat distortion temperature is 42 ℃; the initial decomposition temperature was 339 ℃.
Example 35
31.2g of dimethyl 2, 5-furandicarboxylate, 2.66g of 2-hydroxy-N- (2-hydroxyisopropyl) ethylamide, 37.8g of tetrabutyl titanate serving as a catalyst accounting for 0.1wt% of the total mass of the reactants are added into a polymerization device, transesterification reaction is carried out for 4 hours at 180 ℃ under nitrogen atmosphere, pre-polycondensation is carried out for 0.5 hour at 200 ℃ under 200Pa, then reaction is carried out for 3 hours at 210 ℃ under 68Pa, and finally material is taken under nitrogen.
The intrinsic viscosity [ eta ] of the copolyester obtained]1.1dL/g, and a tensile strength of 62MPa; elongation at break 320%; CO 2 Permeability coefficient of 9.75E-16[ cm ] 3 ·cm/(cm 2 ·s·Pa)]；O 2 Permeability coefficient of 1.12E-15[ cm ] 3 ·cm/(cm 2 ·s·Pa)]The method comprises the steps of carrying out a first treatment on the surface of the The heat distortion temperature is 45 ℃; the initial decomposition temperature was 330 ℃.
Example 36
31.2g of dimethyl 2, 5-furandicarboxylate, 5.32g of 2-hydroxy-N- (2-hydroxyisopropyl) ethylamide, 36.0g of tetrabutyl titanate serving as a catalyst accounting for 0.1wt% of the total mass of the 1, 4-butanediol and reactants are added into a polymerization device, transesterification reaction is carried out for 4 hours at 180 ℃ under nitrogen atmosphere, pre-polycondensation is carried out for 0.5 hour at 200 ℃ under 200Pa, then reaction is carried out for 3 hours at 210 ℃ under 50Pa, and finally material is taken under nitrogen.
The intrinsic viscosity [ eta ] of the copolyester obtained]1.1dL/g, and the tensile strength is 77MPa; elongation at break 150%; CO 2 Permeability coefficient of 1.20E-15[ cm ] 3 ·cm/(cm 2 ·s·Pa)]；O 2 Permeability coefficient of 1.42E-15[ cm ] 3 ·cm/(cm 2 ·s·Pa)]The method comprises the steps of carrying out a first treatment on the surface of the The heat distortion temperature is 49 ℃; the initial decomposition temperature was 336 ℃.
Example 37
31.2g of dimethyl 2, 5-furandicarboxylate, 2.43g of g N- (4-hydroxy-methylpropyl) -4- (hydroxymethyl) cyclohexane-1-amide, 38.7g of tetrabutyl titanate which is a catalyst accounting for 0.1wt% of the total mass of the 1, 4-butanediol and the reactants are added into a polymerization device, transesterification is carried out for 3 hours at 175 ℃ under nitrogen atmosphere, pre-polycondensation is carried out for 0.5 hour at 200 ℃ under 200Pa, then reaction is carried out for 1 hour at 210 ℃ under 49Pa, and finally material is taken under nitrogen.
The intrinsic viscosity [ eta ] of the copolyester obtained]0.9dL/g, and a tensile strength of 54MPa; elongation at break of 324%; CO 2 Permeability coefficient of 1.57E-15[ cm ] 3 ·cm/(cm 2 ·s·Pa)]；O 2 Permeability coefficient of 1.72E-15[ cm ] 3 ·cm/(cm 2 ·s·Pa)]The method comprises the steps of carrying out a first treatment on the surface of the The heat distortion temperature is 39 ℃; the initial decomposition temperature was 339 ℃.
Example 38
31.2g of dimethyl 2, 5-furandicarboxylate, 4.84g of g N- (4-hydroxy-methylpropyl) -4- (hydroxymethyl) cyclohexane-1-amide, 37.8g of tetrabutyl titanate which is a catalyst accounting for 0.1wt% of the total mass of the 1, 4-butanediol and reactants are added into a polymerization device, transesterification reaction is carried out for 4 hours at 180 ℃ under nitrogen atmosphere, pre-polycondensation is carried out for 1.0 hour at 190 ℃ under 240Pa, then reaction is carried out for 1.5 hours at 210 ℃ under 48Pa, and finally material is taken under nitrogen.
The intrinsic viscosity [ eta ] of the copolyester obtained]0.8dL/g, and a tensile strength of 56MPa; elongation at break of 305%; CO 2 The permeability coefficient is 1.87E-15[ cm ] 3 ·cm/(cm 2 ·s·Pa)]；O 2 Permeability coefficient of 2.10E-15[ cm ] 3 ·cm/(cm 2 ·s·Pa)]The method comprises the steps of carrying out a first treatment on the surface of the The heat distortion temperature is 40 ℃; the initial decomposition temperature was 335 ℃.
Example 39
31.2g of dimethyl 2, 5-furandicarboxylate, 9.72g of 2-hydroxy-N- (4-hydroxy-2-methyl butyl) -2- (naphthyl) acetamide, 36.0g of 1, 4-butanediol and tetrabutyl titanate which is a catalyst accounting for 0.1 weight percent of the total mass of reactants are added into a polymerization device, transesterification reaction is carried out for 4 hours at 180 ℃ under nitrogen atmosphere, pre-polycondensation is carried out for 0.5 hour at 200 ℃ and 200Pa, then reaction is carried out for 0.5 hour at 230 ℃ and 49Pa, and finally material is taken under nitrogen;
The intrinsic viscosity [ eta ] of the copolyester obtained]0.7dL/g, and a tensile strength of 56MPa; elongation at break of 268%; CO 2 Permeability coefficient of 2.25E-15[ cm ] 3 ·cm/(cm 2 ·s·Pa)]；O 2 Permeability coefficient of 2.17E-15[ cm ] 3 ·cm/(cm 2 ·s·Pa)]The method comprises the steps of carrying out a first treatment on the surface of the The heat distortion temperature is 43 ℃; the initial decomposition temperature was 330 ℃.
Example 40
31.2g of dimethyl 2, 5-furandicarboxylate, 2.87g of 2-hydroxy-N- (4-hydroxy-2-methyl butyl) -2- (naphthyl) acetamide, 38.7g of 1, 4-butanediol and tetrabutyl titanate as a catalyst accounting for 0.1wt% of the total mass of the reactants are added into a polymerization device, transesterification reaction is carried out for 4 hours at 180 ℃ under nitrogen atmosphere, pre-polycondensation is carried out for 0.5 hour at 200 ℃ under 200Pa, then reaction is carried out for 3 hours at 210 ℃ under 58Pa, and finally material is taken under nitrogen.
The intrinsic viscosity [ eta ] of the copolyester obtained]0.8dL/g, and a tensile strength of 61MPa; elongation at break of 129%; CO 2 Permeability coefficient of 1.72E-15[ cm ] 3 ·cm/(cm 2 ·s·Pa)]；O 2 The permeability coefficient is 1.95E-15[ cm ] 3 ·cm/(cm 2 ·s·Pa)]The method comprises the steps of carrying out a first treatment on the surface of the The heat distortion temperature is 43 ℃; the initial decomposition temperature was 328 ℃.
Example 41
31.2g of dimethyl 2, 5-furandicarboxylate, 5.76g of 2-hydroxy-N- (4-hydroxy-2-methylbutyl) -2- (naphthyl) acetamide, 37.8g of 1, 4-butanediol and tetrabutyl titanate catalyst accounting for 0.1wt% of the total mass of the reactants are added into a polymerization device, transesterification reaction is carried out for 4 hours at 180 ℃ under nitrogen atmosphere, pre-polycondensation is carried out for 0.5 hour at 200 ℃ under 200Pa, reaction is carried out for 3 hours at 230 ℃ under 47Pa, and finally material is taken under nitrogen.
The intrinsic viscosity [ eta ] of the copolyester obtained]0.7dL/g, and the tensile strength is 69MPa; elongation at break of 73%; CO 2 Permeability coefficient of 1.42E-15[ cm ] 3 ·cm/(cm 2 ·s·Pa)]；O 2 Permeability coefficient of 1.57E-15[ cm ] 3 ·cm/(cm 2 ·s·Pa)]The method comprises the steps of carrying out a first treatment on the surface of the The heat distortion temperature is 46 ℃; the initial decomposition temperature was 325 ℃.
Example 42
31.2g of dimethyl 2, 5-furandicarboxylate, 11.52g of 2-hydroxy-N- (4-hydroxy-2-methylbutyl) -2- (naphthyl) acetamide, 36.0g of 1, 4-butanediol and tetrabutyl titanate catalyst accounting for 0.1wt% of the total mass of the reactants are added into a polymerization device, transesterification reaction is carried out for 3 hours at 170 ℃ under nitrogen atmosphere, pre-polycondensation is carried out for 1.0 hour at 180 ℃ under 210Pa, reaction is carried out for 3 hours at 210 ℃ under 48Pa, and finally material is taken under nitrogen.
The intrinsic viscosity [ eta ] of the copolyester obtained]0.7dL/g, and a tensile strength of 71MPa; elongation at break of 63%; CO 2 Permeability coefficient of 1.35E-15[ cm ] 3 ·cm/(cm 2 ·s·Pa)]；O 2 Permeability coefficient of 1.43E-15[ cm ] 3 ·cm/(cm 2 ·s·Pa)]The method comprises the steps of carrying out a first treatment on the surface of the The heat distortion temperature is 52 ℃; the initial decomposition temperature was 332 ℃.
Example 43
31.2g of dimethyl 2, 5-furandicarboxylate, 1.61g of 2-hydroxy-N- (4-hydroxybutyl) valeramide, 38.7g of 1, 4-butanediol and tetrabutyl titanate which is a catalyst accounting for 0.1 weight percent of the mass of the reactants are added into a polymerization device, transesterification reaction is carried out for 4 hours at 180 ℃ under nitrogen atmosphere, pre-polycondensation is carried out for 0.5 hour at 200 ℃ under 200Pa, then reaction is carried out for 2 hours at 210 ℃ under 50Pa, and finally material is taken under nitrogen.
The intrinsic viscosity [ eta ] of the copolyester obtained]1.1dL/g, and a tensile strength of 56MPa; elongation at break 289; CO 2 Permeability coefficient of 1.42E-15[ cm ] 3 ·cm/(cm 2 ·s·Pa)]；O 2 Permeability coefficient of 1.57E-15[ cm ] 3 ·cm/(cm 2 ·s·Pa)]The method comprises the steps of carrying out a first treatment on the surface of the The heat distortion temperature is 41 ℃; the initial decomposition temperature was 336 ℃.
Example 44
31.2g of dimethyl 2, 5-furandicarboxylate, 3.22g of 2-hydroxy-N- (4-hydroxybutyl) valeramide, 37.8g of tetrabutyl titanate serving as a catalyst accounting for 0.1wt% of the total mass of the reactants are added into a polymerization device, transesterification reaction is carried out for 4 hours at 180 ℃ under nitrogen atmosphere, pre-polycondensation is carried out for 0.5 hour at 200 ℃ under 200Pa, then reaction is carried out for 3 hours at 210 ℃ under 62Pa, and finally material is taken under nitrogen.
The intrinsic viscosity [ eta ] of the copolyester obtained]1.0dL/g, and a tensile strength of 60MPa; elongation at break of 256%; CO 2 Permeability coefficient of 1.65E-15[ cm ] 3 ·cm/(cm 2 ·s·Pa)]；O 2 The permeability coefficient is 1.87E-15[ cm ] 3 ·cm/(cm 2 ·s·Pa)]The method comprises the steps of carrying out a first treatment on the surface of the The heat distortion temperature is 43 ℃; initial decomposition temperature of333℃。
Example 45
31.2g of dimethyl 2, 5-furandicarboxylate, 6.44g of 2-hydroxy-N- (4-hydroxybutyl) valeramide, 36.0g of 1, 4-butanediol and tetrabutyl titanate as catalyst accounting for 0.1wt% of the mass of the reactants are added into a polymerization device, transesterification is carried out for 4 hours at 175 ℃ under nitrogen atmosphere, pre-polycondensation is carried out for 0.5 hour at 200 ℃ under 200Pa, then reaction is carried out for 2.5 hours at 210 ℃ under 49Pa, and finally material is taken under nitrogen.
The intrinsic viscosity [ eta ] of the copolyester obtained]0.9dL/g, and a tensile strength of 64MPa; elongation at break of 201%; CO 2 Permeability coefficient of 2.10E-15[ cm ] 3 ·cm/(cm 2 ·s·Pa)]；O 2 Permeability coefficient of 2.17E-15[ cm ] 3 ·cm/(cm 2 ·s·Pa)]The method comprises the steps of carrying out a first treatment on the surface of the The heat distortion temperature is 46 ℃; the initial decomposition temperature was 331 ℃.
Example 46
31.2g of dimethyl 2, 5-furandicarboxylate and 2.58g of 1 N, 4 Adding N-heavy (2-hydroxymethyl) cyclohexane amide, 38.7g of 1, 4-butanediol and tetrabutyl titanate which is a catalyst accounting for 0.1 weight percent of the total mass of reactants into a polymerization device, carrying out transesterification reaction for 4 hours at 180 ℃ under nitrogen atmosphere, carrying out pre-polycondensation for 1.0 hour at 200 ℃ under 200Pa, then carrying out reaction for 2.5 hours at 210 ℃ under 57Pa, and finally taking materials under nitrogen.
The intrinsic viscosity [ eta ] of the copolyester obtained]1.1dL/g, and a tensile strength of 62MPa; elongation at break 340%; CO 2 Permeability coefficient of 1.50E-15[ cm ] 3 ·cm/(cm 2 ·s·Pa)]；O 2 Permeability coefficient of 1.57E-15[ cm ] 3 ·cm/(cm 2 ·s·Pa)]The method comprises the steps of carrying out a first treatment on the surface of the The heat distortion temperature is 41 ℃; the initial decomposition temperature was 340 ℃.
Example 47
31.2g of dimethyl 2, 5-furandicarboxylate and 5.16g of 1 N, 4 Adding N-heavy (2-hydroxymethyl) cyclohexane amide, 37.8g of 1, 4-butanediol and tetrabutyl titanate which is catalyst and is 0.1 weight percent of the total mass of reactants into a polymerization device, carrying out transesterification reaction for 4 hours at 180 ℃ under nitrogen atmosphere, and carrying out pre-treatment at 200 ℃ and 200Pa Polycondensation is carried out for 0.5 hour, then the reaction is carried out for 3 hours at 210 ℃ under 49Pa, and finally the material is taken out under nitrogen.
The intrinsic viscosity [ eta ] of the copolyester obtained]1.0dL/g, and a tensile strength of 68MPa; elongation at break of 286%; CO 2 Permeability coefficient of 1.72E-15[ cm ] 3 ·cm/(cm 2 ·s·Pa)]；O 2 The permeability coefficient is 1.95E-15[ cm ] 3 ·cm/(cm 2 ·s·Pa)]The method comprises the steps of carrying out a first treatment on the surface of the The heat distortion temperature is 46 ℃; the initial decomposition temperature was 336 ℃.
Example 48
31.2g of dimethyl 2, 5-furandicarboxylate and 10.32g of 1 N, 4 Adding N-heavy (2-hydroxymethyl) cyclohexane amide, 36.0g of 1, 4-butanediol and tetrabutyl titanate which is a catalyst accounting for 0.1 weight percent of the total mass of reactants into a polymerization device, carrying out transesterification reaction for 4 hours at 180 ℃ under nitrogen atmosphere, carrying out pre-polycondensation for 0.5 hour at 200 ℃ under 210Pa, then carrying out reaction for 2 hours at 210 ℃ under 56Pa, and finally taking materials under nitrogen.
The intrinsic viscosity [ eta ] of the copolyester obtained]1.0dL/g, and a tensile strength of 75MPa; elongation at break 213%; CO 2 Permeability coefficient of 2.17E-15[ cm ] 3 ·cm/(cm 2 ·s·Pa)]；O 2 Permeability coefficient of 2.25E-15[ cm ] 3 ·cm/(cm 2 ·s·Pa)]The method comprises the steps of carrying out a first treatment on the surface of the The heat distortion temperature is 49 ℃; the initial decomposition temperature was 330 ℃.
Example 49
31.2g of dimethyl 2, 5-furandicarboxylate and 5.04g 1 N, 4 Adding N-heavy (2-hydroxymethyl) benzamide, 37.8g of 1, 4-butanediol and tetrabutyl titanate which is a catalyst accounting for 0.1 weight percent of the total mass of reactants into a polymerization device, carrying out transesterification reaction for 4 hours at 180 ℃ under nitrogen atmosphere, carrying out pre-polycondensation for 0.5 hour at 200 ℃ and 200Pa, then carrying out reaction for 2 hours at 210 ℃ and 54Pa, and finally taking materials under nitrogen.
The intrinsic viscosity [ eta ] of the copolyester obtained]1.1dL/g, and a tensile strength of 63MPa; elongation at break of 256%; CO 2 Permeability coefficient of 1.35E-15[ cm ] 3 ·cm/(cm 2 ·s·Pa)]；O 2 Permeability coefficient of 1.42E-15[ cm ] 3 ·cm/(cm 2 ·s·Pa)]The method comprises the steps of carrying out a first treatment on the surface of the The heat distortion temperature is 42 ℃; the initial decomposition temperature was 341 ℃.
Example 50
31.2g of dimethyl 2, 5-furandicarboxylate and 10.88g of 1 N, 4 Adding N-heavy (2-hydroxymethyl) benzamide, 36.0g of 1, 4-butanediol and tetrabutyl titanate which is a catalyst accounting for 0.1 weight percent of the total mass of reactants into a polymerization device, carrying out transesterification reaction for 4 hours at 180 ℃ under nitrogen atmosphere, carrying out pre-polycondensation for 0.9 hour at 195 ℃ under 210Pa, then carrying out reaction for 3 hours at 210 ℃ under 60Pa, and finally taking materials under nitrogen.
The intrinsic viscosity [ eta ] of the copolyester obtained]1.0dL/g, and a tensile strength of 72MPa; elongation at break was 197%; CO 2 Permeability coefficient of 1.63E-15[ cm ] 3 ·cm/(cm 2 ·s·Pa)]；O 2 Permeability coefficient of 1.72E-15[ cm ] 3 ·cm/(cm 2 ·s·Pa)]The method comprises the steps of carrying out a first treatment on the surface of the The heat distortion temperature is 46 ℃; the initial decomposition temperature was 335 ℃.
Example 51
36.82g of dimethyl 2, 5-furandicarboxylate, 31.72g of 1, 4-butanediol, 9.34g of diethylene glycol and tetrabutyl titanate which is a catalyst accounting for 0.1 weight percent of the total mass of reactants are added into a polymerization device, transesterification reaction is carried out for 4 hours at 175 ℃ under nitrogen atmosphere, pre-polycondensation is carried out for 1.0 hour at 190 ℃ under 230Pa, then reaction is carried out for 3 hours at 220 ℃ under 58Pa, and finally material is taken under nitrogen.
Intrinsic viscosity [ eta ] of intrinsic viscosity of the obtained copolyester]1.3dL/g, and the tensile strength is 65MPa; elongation at break 300%; CO 2 Permeability coefficient of 9.00E-16[ cm ] 3 ·cm/(cm 2 ·s·Pa)]；O 2 Permeability coefficient of 1.12E-15[ cm ] 3 ·cm/(cm 2 ·s·Pa)]The method comprises the steps of carrying out a first treatment on the surface of the The heat distortion temperature is 46 ℃; the initial decomposition temperature was 362 ℃.
Example 52
36.82g of dimethyl 2, 5-furandicarboxylate, 23.79g of 1, 4-butanediol, 18.68g of diethylene glycol and tetrabutyl titanate as catalyst in an amount of 0.1% by weight based on the total mass of the reactants were charged into the polymerization apparatus, and the reaction mixture was discharged after transesterification and polycondensation in accordance with the procedure and conditions given in example 44.
The intrinsic viscosity [ eta ] of the copolyester obtained]1.2dL/g, and the tensile strength is 80MPa; elongation at break of 275%; CO 2 Permeability coefficient of 8.25E-16[ cm ] 3 ·cm/(cm 2 ·s·Pa)]；O 2 Permeability coefficient of 9.75E-16[ cm ] 3 ·cm/(cm 2 ·s·Pa)]The method comprises the steps of carrying out a first treatment on the surface of the The heat distortion temperature is 47 ℃; the initial decomposition temperature was 365 ℃.
Example 53
36.82g of dimethyl 2, 5-furandicarboxylate, 21.81g of 1, 4-butanediol, 21.02g of diethylene glycol and tetrabutyl titanate as catalyst in an amount of 0.1% by weight based on the total mass of the reactants were fed into the polymerization apparatus, and the reaction mixture was discharged after transesterification and polycondensation in accordance with the procedure and conditions given in example 44.
The intrinsic viscosity [ eta ] of the copolyester obtained]1.0dL/g, and a tensile strength of 78MPa; elongation at break 160%; CO 2 Permeability coefficient of 8.03E-16[ cm ] 3 ·cm/(cm 2 ·s·Pa)]；O 2 Permeability coefficient of 8.23E-16[ cm ] 3 ·cm/(cm 2 ·s·Pa)]The method comprises the steps of carrying out a first treatment on the surface of the The heat distortion temperature is 45 ℃; the initial decomposition temperature was 369 ℃.
Example 54
36.82g of dimethyl 2, 5-furandicarboxylate, 7.93g of 1, 4-butanediol, 37.36g of diethylene glycol and tetrabutyl titanate as catalyst in an amount of 0.1% by weight based on the total mass of the reactants were charged into the polymerization apparatus, and the reaction mixture was discharged after transesterification and polycondensation in accordance with the procedure and conditions given in example 44.
The intrinsic viscosity [ eta ] of the copolyester obtained]0.6dL/g, and a tensile strength of 75MPa; elongation at break 50%; CO 2 Permeability coefficient of 7.50E-16[ cm ] 3 ·cm/(cm 2 ·s·Pa)]；O 2 Permeability coefficient of 7.50E-16[ cm ] 3 ·cm/(cm 2 ·s·Pa)]The method comprises the steps of carrying out a first treatment on the surface of the The heat distortion temperature is 42 ℃; the initial decomposition temperature was 375 ℃.
Example 55
36.82g of dimethyl 2, 5-furandicarboxylate, 0.4g of 1, 4-butanediol, 46.22g of diethylene glycol and tetrabutyl titanate as catalyst in an amount of 0.1% by weight based on the total mass of the reactants were charged into the polymerization apparatus, and the reaction mixture was discharged after transesterification and polycondensation in accordance with the procedure and conditions given in example 44.
The intrinsic viscosity [ eta ] of the copolyester obtained]0.5dL/g, and a tensile strength of 65MPa; elongation at break 3.9%; CO 2 Permeability coefficient of 1.50E-15[ cm ] 3 ·cm/(cm 2 ·s·Pa)]；O 2 Permeability coefficient of 1.57E-15[ cm ] 3 ·cm/(cm 2 ·s·Pa)]The method comprises the steps of carrying out a first treatment on the surface of the The heat distortion temperature is 38 ℃; the initial decomposition temperature was 380 ℃.
Recovery example 1
Crushing the used waste aliphatic-aromatic copolyester to 20 meshes, adding 0.5g of crushed copolyester into a reaction solvent consisting of 30mL of ethanol and 120mL of water, adding 6g of sodium hydroxide, and reacting at 80 ℃ for 120min; after the reaction is finished, the pH=2 of the reaction solution is adjusted, degradation products can be separated out from the reaction solution, the solid degradation products and the reaction solution are collected, the residual reaction solution in the solid degradation products is removed by washing with ethanol solvent, and then the reaction solution is dried to obtain dry degradation products. The degradation rate of the polyester was 100%, and the yield of the degradation product was 89%.
Recovery example 2
Crushing the used waste aliphatic-aromatic copolyester to 60 meshes, adding 15g of crushed copolyester into a reaction solvent consisting of 90mL of ethanol and 60mL of water, adding 10g of potassium hydroxide, and reacting at 80 ℃ for 120min; after the reaction is finished, the pH=1 of the reaction solution is regulated, degradation products can be separated out from the reaction solution, the solid degradation products and the reaction solution are collected, the residual reaction solution in the solid degradation products is removed by washing with ethanol solvent, and then the reaction solution is dried to obtain dry degradation products. The degradation rate of the polyester was 100%, and the yield of the degradation product was 90%.
Recovery example 3
Crushing the used waste aliphatic-aromatic copolyester to 10 meshes, adding 6g of crushed copolyester into a reaction solvent consisting of 100mL of ethanol and 50mL of water, adding 10g of potassium pyrophosphate, and reacting for 240min at 50 ℃; after the reaction is finished, the pH=6 of the reaction solution is adjusted, degradation products can be separated out from the reaction solution, the solid degradation products and the reaction solution are collected, the residual reaction solution in the solid degradation products is removed by washing with ethanol solvent, and then the reaction solution is dried to obtain dry degradation products. The degradation rate of the polyester was 100%, and the yield of the degradation product was 91%.
Recovery example 4
Crushing the used waste aliphatic-aromatic copolyester to 20 meshes, adding 18g of crushed copolyester into a reaction solvent consisting of 50mL of 1, 4-butanediol, 50mL of diethylene glycol and 50mL of water, simultaneously adding 6g of sodium hydroxide, and reacting at 60 ℃ for 120min; after the reaction is finished, the pH=2 of the reaction solution is adjusted, degradation products can be separated out from the reaction solution, the solid degradation products and the reaction solution are collected, the residual reaction solution in the solid degradation products is removed by washing with ethanol solvent, and then the reaction solution is dried to obtain dry degradation products. The degradation rate of the polyester is 100%.
Recovery example 5
Crushing the used waste aliphatic-aromatic copolyester to 60 meshes, adding 6g of crushed copolyester into a reaction solvent consisting of 50mL of 1, 4-butanediol, 50mL of diethylene glycol and 50mL of water, simultaneously adding 10g of potassium hydroxide, and reacting for 20min at 80 ℃; after the reaction is finished, the pH=2 of the reaction solution is adjusted, degradation products can be separated out from the reaction solution, the solid degradation products and the reaction solution are collected, the residual reaction solution in the solid degradation products is removed by washing with ethanol solvent, and then the reaction solution is dried to obtain dry degradation products. The degradation rate of the polyester was 100%, and the yield of the degradation product was 93%.
Recovery example 6
Crushing the used waste aliphatic-aromatic copolyester into 10 meshes, adding 6g of crushed copolyester into a reaction solvent consisting of 45mL of 1, 4-butanediol, 45mL of diethylene glycol and 60mL of water, adding 10g of potassium pyrophosphate, and reacting at 50 ℃ for 120min; after the reaction is finished, the pH=2 of the reaction solution is adjusted, degradation products can be separated out from the reaction solution, the solid degradation products and the reaction solution are collected, the residual reaction solution in the solid degradation products is removed by washing with ethanol solvent, and then the reaction solution is dried to obtain dry degradation products. The degradation rate of the polyester was 100%, and the yield of the degradation product was 94%.
Recovery example 7
Crushing the used waste aliphatic-aromatic copolyester into 10 meshes, adding 20g of crushed copolyester into a reaction solvent consisting of 60mL of methanol and 90mL of water, adding 10g of potassium pyrophosphate, and reacting at 70 ℃ for 120min; after the reaction is finished, the pH=2 of the reaction solution is adjusted, degradation products can be separated out from the reaction solution, the solid degradation products and the reaction solution are collected, the residual reaction solution in the solid degradation products is removed by washing with ethanol solvent, and then the reaction solution is dried to obtain dry degradation products. The degradation rate of the polyester was 100%, and the yield of the degradation product was 91%.
Recovery example 8
Crushing the used waste aliphatic-aromatic copolyester to 60 meshes, adding 25g of crushed copolyester into a reaction solvent consisting of 80mL of methanol and 70mL of water, adding 10g of potassium hydroxide, and reacting at 60 ℃ for 120min; after the reaction is finished, the pH=2 of the reaction solution is adjusted, degradation products can be separated out from the reaction solution, the solid degradation products and the reaction solution are collected, the residual reaction solution in the solid degradation products is removed by washing with ethanol solvent, and then the reaction solution is dried to obtain dry degradation products. The degradation rate of the polyester is 100%, and the yield of the degradation product is 95%.
Recovery example 9
Crushing the used waste aliphatic-aromatic copolyester to 20 meshes, adding 6g of crushed copolyester into a reaction solvent consisting of 60mL of methanol and 90mL of water, adding 6g of sodium hydroxide, and reacting at 60 ℃ for 120min; after the reaction is finished, the pH=2 of the reaction solution is adjusted, degradation products can be separated out from the reaction solution, the solid degradation products and the reaction solution are collected, the residual reaction solution in the solid degradation products is removed by washing with ethanol solvent, and then the reaction solution is dried to obtain dry degradation products. The degradation rate of the polyester is 100%, and the yield of the degradation product is 95%.
Recovery example 10
Crushing the used waste copolyester containing the fat structure to 20 meshes, adding 15g of the crushed copolyester into a reaction solvent consisting of 80mL of methanol and 70mL of water, adding 6g of sodium hydroxide, and reacting at 70 ℃ for 120min; after the reaction is finished, standing the reaction solution at 10 ℃ for 2 hours, filtering to obtain sodium salt of degradation product, dissolving the sodium salt in deionized water, adjusting the pH=2 of the solution, separating out the degradation product from the reaction solution, collecting solid degradation product and the reaction solution, washing the solid degradation product with ethanol solvent to remove residual reaction solution, and drying the solid degradation product to obtain the dry degradation product. The degradation rate of the polyester was 100%, and the yield of the degradation product was 93%.
Recovery example 11
Crushing the used waste copolyester containing the fat structure to 60 meshes, adding 8g of the crushed copolyester into a reaction solvent consisting of 100mL of methanol and 50mL of water, adding 10g of potassium hydroxide, and reacting at 80 ℃ for 120min; after the reaction is finished, standing the reaction solution at 9 ℃ for 2 hours, filtering to obtain potassium salt of degradation products, dissolving the potassium salt in deionized water, adjusting the pH=2 of the solution, separating out the degradation products from the reaction solution, collecting solid degradation products and the reaction solution, washing the solid degradation products with ethanol solvent to remove residual reaction solution, and drying the solid degradation products to obtain the dried degradation products. The degradation rate of the polyester was 100%, and the yield of the degradation product was 90%.
Recovery example 12
Crushing the used waste copolyester containing the fat structure to 10 meshes, adding 15g of the crushed copolyester into a reaction solvent consisting of 80mL of methanol and 70mL of water, adding 20g of potassium pyrophosphate, and reacting for 120min at 70 ℃; after the reaction is finished, standing the reaction solution at 7 ℃ for 2 hours, filtering to obtain potassium salt of degradation products, dissolving the potassium salt in deionized water, adjusting the pH=2 of the solution, separating out the degradation products from the reaction solution, collecting solid degradation products and the reaction solution, washing the solid degradation products with ethanol solvent to remove residual reaction solution, and drying the solid degradation products to obtain the dried degradation products. The degradation rate of the polyester was 100%, and the yield of the degradation product was 91%.
Recovery example 13
Crushing the used waste copolyester containing the fat structure to 10 meshes, adding 8g of the crushed copolyester into a reaction solvent consisting of 60mL of ethanol and 90mL of water, adding 20g of potassium pyrophosphate, and reacting for 120min at 70 ℃; after the reaction is finished, standing the reaction solution at 8 ℃ for 2 hours, filtering to obtain potassium salt of degradation products, dissolving the potassium salt in deionized water, adjusting the pH=4 of the solution, separating out the degradation products from the reaction solution, collecting solid degradation products and the reaction solution, washing the solid degradation products with ethanol solvent to remove residual reaction solution, and drying the solid degradation products to obtain the dried degradation products. The degradation rate of the polyester was 100%, and the yield of the degradation product was 89%.
Recovery example 14
Crushing the used waste copolyester containing the fat structure to 60 meshes, adding 15g of the crushed copolyester into a reaction solvent consisting of 100mL of ethanol and 50mL of water, adding 20g of potassium hydroxide, and reacting at 70 ℃ for 120min; after the reaction is finished, standing the reaction solution at the temperature of 4 ℃ for 2 hours, filtering to obtain potassium salt of degradation products, dissolving the potassium salt in deionized water, adjusting the pH value of the solution to be=5, separating out the degradation products from the reaction solution, collecting solid degradation products and the reaction solution, washing the solid degradation products with ethanol solvent to remove residual reaction solution, and drying the solid degradation products to obtain the dried degradation products. The degradation rate of the polyester was 100%, and the yield of the degradation product was 92%.
Recovery example 15
Crushing the used waste copolyester containing the fat structure to 20 meshes, adding 6g of crushed copolyester into a reaction solvent consisting of 120mL of ethanol and 30mL of water, adding 6g of sodium hydroxide, and reacting at 80 ℃ for 120min; after the reaction is finished, standing the reaction solution at the temperature of 1 ℃ for 2 hours, filtering to obtain sodium salt of degradation products, dissolving the sodium salt in deionized water, adjusting the pH=2 of the solution, separating out the degradation products from the reaction solution, collecting solid degradation products and the reaction solution, washing the solid degradation products with ethanol solvent to remove residual reaction solution, and drying the solid degradation products to obtain the dried degradation products. The degradation rate of the polyester was 100%, and the yield of the degradation product was 93%.
Recovery example 16
Crushing the used waste copolyester containing the fat structure to 20 meshes, adding 8g of the crushed copolyester into a reaction solvent consisting of 80mL of 1, 4-butanediol and 70mL of water, simultaneously adding 6g of sodium hydroxide, and reacting for 120min at 60 ℃; after the reaction is finished, standing the reaction solution at the temperature of 2 ℃ for 2 hours, filtering to obtain sodium salt of degradation products, dissolving the sodium salt in deionized water, adjusting the pH value of the solution to be=3, separating out the degradation products from the reaction solution, collecting solid degradation products and the reaction solution, washing the solid degradation products with ethanol solvent to remove residual reaction solution, and drying the solid degradation products to obtain the dried degradation products. The degradation rate of the polyester was 100%, and the yield of the degradation product was 90%.
Recovery example 17
Crushing the used waste copolyester containing the fat structure to 60 meshes, adding 6g of crushed copolyester into a reaction solvent consisting of 50mL of 1, 4-butanediol, 50mL of methanol and 50mL of water, simultaneously adding 10g of potassium hydroxide, and reacting for 120min at 50 ℃; after the reaction is finished, standing the reaction solution at 3 ℃ for 2 hours, filtering to obtain potassium salt of degradation products, dissolving the potassium salt in deionized water, adjusting the pH=2 of the solution, separating out the degradation products from the reaction solution, collecting solid degradation products and the reaction solution, washing the solid degradation products with ethanol solvent to remove residual reaction solution, and drying the solid degradation products to obtain the dried degradation products. The degradation rate of the polyester was 100%, and the yield of the degradation product was 92%.
Recovery example 18
Crushing the used waste copolyester containing the fat structure to 60 meshes, adding 30g of the crushed copolyester into a reaction solvent consisting of 50mL of 1, 4-butanediol, 50mL of methanol and 50mL of water, simultaneously adding 20g of potassium pyrophosphate, and reacting at 80 ℃ for 160min; after the reaction is finished, standing the reaction solution at 9 ℃ for 2 hours, filtering to obtain potassium salt of degradation products, dissolving the potassium salt in deionized water, adjusting the pH value of the solution to be=5, separating out the degradation products from the reaction solution, collecting solid degradation products and the reaction solution, washing the solid degradation products with ethanol solvent to remove residual reaction solution, and drying the solid degradation products to obtain the dried degradation products. The degradation rate of the polyester is 100%, and the yield of the degradation product is 95%.
Recovery example 19
Crushing the used waste copolyester containing the fat structure to 20 meshes, adding 6g of the crushed copolyester into a reaction solvent consisting of 45mL of 1, 4-butanediol, 45mL of 1, 4-cyclohexanedimethanol and 60mL of water, simultaneously adding 6g of sodium hydroxide, and reacting for 140min at 80 ℃; after the reaction is finished, standing the reaction solution at 10 ℃ for 2 hours, filtering to obtain sodium salt of degradation product, dissolving the sodium salt in deionized water, adjusting the pH=2 of the solution, separating out the degradation product from the reaction solution, collecting solid degradation product and the reaction solution, washing the solid degradation product with ethanol solvent to remove residual reaction solution, and drying the solid degradation product to obtain the dry degradation product. The degradation rate of the polyester was 100%, and the yield of the degradation product was 94%.
Recovery example 20
Crushing the used waste copolyester containing the fat structure to 60 meshes, adding 25g of the crushed copolyester into a reaction solvent consisting of 40mL of 1, 4-butanediol, 40mL of 1, 4-cyclohexanedimethanol and 70mL of water, simultaneously adding 10g of potassium hydroxide, and reacting at 70 ℃ for 120min; after the reaction is finished, standing the reaction solution at the temperature of 5 ℃ for 2 hours, filtering to obtain potassium salt of degradation products, dissolving the potassium salt in deionized water, adjusting the pH=2 of the solution, separating out the degradation products from the reaction solution, collecting solid degradation products and the reaction solution, washing the solid degradation products with ethanol solvent to remove residual reaction solution, and drying the solid degradation products to obtain the dried degradation products. The degradation rate of the polyester was 100%, and the yield of the degradation product was 93%.
Recovery example 21
Crushing the used waste copolyester containing the fat structure to 60 meshes, adding 10g of the crushed copolyester into a reaction solvent consisting of 50mL of 1, 4-butanediol, 50mL of 1, 4-cyclohexanedimethanol and 50mL of water, adding 30g of potassium pyrophosphate, and reacting at 80 ℃ for 120min; after the reaction is finished, standing the reaction solution at 6 ℃ for 2 hours, filtering to obtain potassium salt of degradation products, dissolving the potassium salt in deionized water, adjusting the pH=4 of the solution, separating out the degradation products from the reaction solution, collecting solid degradation products and the reaction solution, washing the solid degradation products with ethanol solvent to remove residual reaction solution, and drying the solid degradation products to obtain the dried degradation products. The degradation rate of the polyester was 100%, and the yield of the degradation product was 91%.
Recovery example 22
Crushing the used waste copolyester containing the fat structure to 60 meshes, adding 25g of the crushed copolyester into 150mL of reaction liquid collected after recovery experiments, adding 10g of potassium hydroxide, and reacting at 70 ℃ for 120min; after the reaction is finished, standing the reaction solution at the temperature of 5 ℃ for 2 hours, filtering to obtain potassium salt of degradation products, dissolving the potassium salt in deionized water, adjusting the pH=2 of the solution, separating out the degradation products from the reaction solution, collecting solid degradation products and the reaction solution, washing the solid degradation products with ethanol solvent to remove residual reaction solution, and drying the solid degradation products to obtain the dried degradation products. The degradation rate of the polyester was 100%, and the yield of the degradation product was 92%.
Recovery example 23
Crushing the used waste copolyester containing the fat structure to 60 meshes, adding 10g of the crushed copolyester into 150mL of reaction liquid collected after a recovery experiment, adding 30g of potassium pyrophosphate, and reacting for 120min at 80 ℃; after the reaction is finished, standing the reaction solution at 6 ℃ for 2 hours, filtering to obtain potassium salt of degradation products, dissolving the potassium salt in deionized water, adjusting the pH=4 of the solution, separating out the degradation products from the reaction solution, collecting solid degradation products and the reaction solution, washing the solid degradation products with ethanol solvent to remove residual reaction solution, and drying the solid degradation products to obtain the dried degradation products. The degradation rate of the polyester was 100%, and the yield of the degradation product was 93%.
Recovery example 24
Crushing the used waste aliphatic-aromatic copolyester to 60 meshes, adding 25g of crushed copolyester into 150mL of reaction liquid collected after recovery experiments, adding 10g of potassium hydroxide, and reacting at 60 ℃ for 120min; after the reaction is finished, the pH=2 of the reaction solution is adjusted, degradation products can be separated out from the reaction solution, the solid degradation products and the reaction solution are collected, the residual reaction solution in the solid degradation products is removed by washing with ethanol solvent, and then the reaction solution is dried to obtain dry degradation products. The degradation rate of the polyester is 100%, and the yield of the degradation product is 95%.

Claims (8)

1. A fat, fat-aromatic copolyester which can be rapidly recovered in a closed loop under mild conditions, characterized in that the copolyester is composed of structural units represented by the following I, III, V or I, III, VI or I, III, IV, VII or I, III, VIII or I, III, ix or II, III, IV or II, III, V or II, III, VI or II, III, IV, VII or II, III, VIII or II, III, ix:
Figure 94591DEST_PATH_IMAGE001
[I]
wherein R is 1 Is C 2 -C 10 Is used for the preparation of an alkylene group,
Figure 141044DEST_PATH_IMAGE002
[II]
Figure 204946DEST_PATH_IMAGE003
[III]
wherein R is 2 Is C 2 -C 10 Is used for the preparation of an alkylene group,
Figure 577022DEST_PATH_IMAGE004
[IV]
wherein R is 3 Is C 2 -C 10 The alkylene groups of (C) may be the same or different,
Figure 693751DEST_PATH_IMAGE005
[V]
wherein R is 4 Is C 1 -C 10 Is used for the preparation of an alkylene group,
Figure 809475DEST_PATH_IMAGE006
[VI]
wherein R is 5 Is C 1 -C 10 The alkylene groups of (C) may be the same or different,
Figure 196725DEST_PATH_IMAGE007
[VII]
wherein R is 6 Is C 1 -C 10 The alkylene groups of (C) may be the same or different,
Figure 739702DEST_PATH_IMAGE008
[VIII]
Figure 343727DEST_PATH_IMAGE009
[Ⅸ]
wherein R is 7 、R 8 And R is 9 Each of the following groups:
Figure 997562DEST_PATH_IMAGE010
[IV]the number of structural units of [ III ]]1 to 99% of the number of structural units [ II ]]The number of structural units: [ III+IV]The number of structural units of (1); [ V]The number of structural units of [ I ]]1 to 99% of the number of structural units [ III ]]The number of structural units: [ I+V]The number of structural units of (1); [ V]The number of structural units of [ III ]]1 to 99% of the number of structural units [ I ]]The number of structural units: [ III+V]The number of structural units of (1); [ V]The number of structural units of [ III ] ]1 to 99% of the number of structural units [ II ]]The number of structural units: [ III+V]The number of structural units of (1); [ VIII ]]The number of structural units of [ I ]]1 to 99% of the number of structural units [ III ]]The number of structural units: [ VIII+I ]]The number of structural units of (1);[VIII]the number of structural units of [ II ]]1 to 99% of the number of structural units [ III ]]The number of structural units: [ VIII+II ]]The number of structural units of (1); [ VI ]]The number of structural units of [ III ]]1 to 99% of the number of structural units [ I ]]The number of structural units: [ III+VI ]]The number of structural units of (1); [ IV+VII ]]The number of structural units of [ III ]]1 to 99% of the number of structural units [ I ]]The number of structural units: [ III+IV+VII ]]The number of structural units of (1); [ IX ] A]The number of structural units of [ III ]]1 to 99% of the number of structural units [ I ]]The number of structural units: [ III+IX ]]The number of structural units of (1); [ V]The number of structural units of [ II ]]1 to 99% of the number of structural units [ III ]]The number of structural units: [ II+V]The number of structural units of (1); [ VI ]]The number of structural units of [ III ]]1 to 99% of the number of structural units [ II ]]The number of structural units: [ III+VI ]]The number of structural units of (1); [ IV+VII ]]The number of structural units of [ III ]]1 to 99% of the number of structural units [ II ]]The number of structural units: [ III+IV+VII ] ]The number of structural units of (1); [ IX ] A]The number of structural units of [ III ]]1 to 99% of the number of structural units [ II ]]The number of structural units: [ III+IX ]]The number of structural units of (1); the chain segment formed by each structural unit is formed by arbitrary connection and combination of carboxyl and hydroxyl functional groups, and the characteristic viscosity number [ eta ] of the copolyester]0.5 to 2.8 dL/g; the tensile strength is 40.0-80.0 MPa; the elongation at break is 3.9-600.0%; CO 2 The permeability coefficient is 7.50E-16-2.25E-15 cm 3 ·cm/ (cm 2 ·s·Pa)]；O 2 The permeability coefficient is 7.50E-16-3.00E-15 cm 3 ·cm/ (cm 2 ·s·Pa)]The method comprises the steps of carrying out a first treatment on the surface of the The heat distortion temperature is 38-95 ℃; the initial decomposition temperature is 325-380 ℃.
2. Fat, fat-aromatic copolyesters which can be recovered in a rapid closed loop under mild conditions according to claim 1, [ IV]The number of structural units of [ III ]]8 to 80% of the number of structural units [ II ]]The number of structural units: [ III+IV]The number of structural units of (1); [ V]The number of structural units of [ I ]]8 to 80% of the number of structural units [ III ]]The number of structural units: [ I+V]The number of structural units of (1); [ V]The number of structural units of [ III ]]8 to 80% of the number of structural units [ I ]]The number of structural units: [ III+V]The number of structural units of (1); [ V]The number of structural units of [ III ]]8 to 80% of the number of structural units [ II ]]The number of structural units: [ III+V ]The number of structural units of (1); [ VIII ]]The number of structural units of [ I ]]8 to 80% of the number of structural units [ III ]]The number of structural units: [ VIII+I ]]The number of structural units of (1); [ VIII ]]The number of structural units of [ II ]]8 to 80% of the number of structural units [ III ]]The number of structural units: [ VIII+II ]]The number of structural units of (1); [ VI ]]The number of structural units of [ III ]]8 to 80% of the number of structural units [ I ]]The number of structural units: [ III+VI ]]The number of structural units of (1); [ IV+VII ]]The number of structural units of [ III ]]8 to 80% of the number of structural units [ I ]]The number of structural units: [ III+IV+VII ]]The number of structural units of (1); [ IX ] A]The number of structural units of [ III ]]8 to 80% of the number of structural units [ I ]]The number of structural units: [ III+IX ]]The number of structural units of (1); [ V]The number of structural units of [ II ]]8 to 80% of the number of structural units [ III ]]The number of structural units: [ II+V]The number of structural units of (1); [ VI ]]The number of structural units of [ III ]]8 to 80% of the number of structural units [ II ]]The number of structural units: [ III+VI ]]The number of structural units of (1); [ IV+VII ]]The number of structural units of [ III ]]8 to 80% of the number of structural units [ II ]]The number of structural units: [ III+IV+VII ]]The number of structural units of (1); [ IX ] A]The number of structural units of [ III ] ]8 to 80% of the number of structural units [ II ]]The number of structural units: [ III+IX ]]The number of structural units of (1); the chain segment formed by each structural unit is arbitrarily connected and combined according to carboxyl and hydroxyl functional groups, and the characteristic viscosity number [ eta ] of the copolyester]0.6-2.8 dL/g, and the tensile strength is 45.0-80.0 MPa; the breaking elongation is 50.0-600.0%; CO 2 The permeability coefficient is 7.50E-16-2.25E-15 cm 3 ·cm/ (cm 2 ·s·Pa)]；O 2 The permeability coefficient is 7.50E-16-3.00E-15 cm 3 ·cm/ (cm 2 ·s·Pa)]The method comprises the steps of carrying out a first treatment on the surface of the The heat distortion temperature is 42-90 ℃; the initial decomposition temperature is 330-375 ℃.
3. Fat, fat-aromatic copolyesters which can be recovered in a rapid closed loop under mild conditions according to claim 1, [ IV]The number of structural units of [ III ]]10 to 50% of the number of structural units [ II ]]The number of structural units: [ III+IV]The number of structural units of (1); [ V]The number of structural units of [ I ]]10 to 50% of the number of structural units [ III ]]The number of structural units: [ I+V]The number of structural units of (1); [ V]Is a knot of (2)The number of building blocks is [ III ]]10 to 50% of the number of structural units [ I ]]The number of structural units: [ III+V]The number of structural units of (1); [ V]The number of structural units of [ III ]]10 to 50% of the number of structural units [ II ]]The number of structural units: [ III+V]The number of structural units of (1); [ VIII ]]The number of structural units of [ I ] ]10 to 50% of the number of structural units [ III ]]The number of structural units: [ VIII+I ]]The number of structural units of (1); [ VIII ]]The number of structural units of [ II ]]10 to 50% of the number of structural units [ III ]]The number of structural units: [ VIII+II ]]The number of structural units of (1); [ VI ]]The number of structural units of [ III ]]10 to 50% of the number of structural units [ I ]]The number of structural units: [ III+VI ]]The number of structural units of (1); [ IV+VII ]]The number of structural units of [ III ]]10 to 50% of the number of structural units [ I ]]The number of structural units: [ III+IV+VII ]]The number of structural units of (1); [ IX ] A]The number of structural units of [ III ]]10 to 50% of the number of structural units [ I ]]The number of structural units: [ III+IX ]]The number of structural units of (1); [ V]The number of structural units of [ II ]]10 to 50% of the number of structural units [ III ]]The number of structural units: [ II+V]The number of structural units of (1); [ VI ]]The number of structural units of [ III ]]10 to 50% of the number of structural units [ II ]]The number of structural units: [ III+VI ]]The number of structural units of (1); [ IV+VII ]]The number of structural units of [ III ]]10 to 50% of the number of structural units [ II ]]The number of structural units: [ III+IV+VII ]]The number of structural units of (1); [ IX ] A]The number of structural units of [ III ]]10 to 50% of the number of structural units [ II ] ]The number of structural units: [ III+IX ]]The number of structural units of (1); the chain segment formed by each structural unit is arbitrarily connected and combined according to carboxyl and hydroxyl functional groups, and the characteristic viscosity number [ eta ] of the copolyester]0.7-2.8 dL/g, and the tensile strength is 50.0-80.0 MPa; the elongation at break is 100.0-600.0%; CO 2 The permeability coefficient is 7.50E-16-1.50E-15 cm 3 ·cm/ (cm 2 ·s·Pa)]；O 2 The permeability coefficient is 7.50E-16-2.25E-15 cm 3 ·cm/ (cm 2 ·s·Pa)]The method comprises the steps of carrying out a first treatment on the surface of the The heat distortion temperature is 45-85 ℃; the initial decomposition temperature is 332-370 ℃.
4. A method for preparing the fat, fat-aromatic copolyester capable of being quickly recycled in a ring closure mode under the mild condition, which is characterized in that under the condition of a conventional catalyst, after esterification reaction of equimolar amount of dibasic acid and dihydric alcohol by adopting a direct esterification method or after transesterification reaction of equimolar amount of dibasic acid esterified substance and dihydric alcohol by adopting an ester exchange method, the method is prepared by polycondensation reaction, and is characterized in that before esterification reaction, before transesterification reaction or before transesterification reaction, a modified monomer accounting for 1-99% of the mole percentage of the dibasic acid or dibasic acid esterified substance is added into a reaction system.
5. The method for preparing the fat, fat-aromatic copolyester capable of being rapidly recycled in a closed loop under mild conditions according to claim 4, wherein the modified monomer used in the method is at least one of the following structural formulas:
Figure 754166DEST_PATH_IMAGE011
Wherein Z is 1 Is C 2 ~C 10 May be the same or different,
Figure 953197DEST_PATH_IMAGE012
wherein Z is 2 Is C 1 ~C 10 Alkoxy radicals of (C), which may be identical or different, Z 3 Is C 2 ~C 10 May be the same or different,
Figure 60830DEST_PATH_IMAGE013
Figure 33203DEST_PATH_IMAGE014
wherein Z is 3 Is C 2 ~C 10 May be the same or different,
Figure 644313DEST_PATH_IMAGE015
wherein Z is 3 Is C 2 ~C 10 May be the same or different,
Figure 545404DEST_PATH_IMAGE016
wherein Z is 2 Is C 1 ~C 10 The alkoxy groups of (2) may be the same or different,
Figure 874754DEST_PATH_IMAGE017
wherein Z is 3 Is C 2 ~C 10 May be the same or different, R 7 、R 8 And R is 9 Is the following group:
Figure 379380DEST_PATH_IMAGE018
。
6. use of a fat, fat-aromatic copolyester which can be rapidly recycled in closed loop under mild conditions according to claim 1, characterised in that the copolyester is used directly as a plastic, fibre, nonwoven, film, medical packaging material, container material or 3D printing material, or as a modified processing aid.
7. A method for recovering fat, fat-aromatic copolyester which can be recovered rapidly and in closed loop under mild conditions as claimed in claim 1, which comprises the following steps:
(1) Distinguishing the used waste copolyester into aliphatic structure copolyester or aliphatic-aromatic copolyester, respectively crushing the aliphatic structure copolyester or the aliphatic-aromatic copolyester into 10-60 meshes, adding the aliphatic structure copolyester or the aliphatic-aromatic copolyester into a mixed solution of an alkaline catalyst and a reaction solvent or a mixed solution of the alkaline catalyst and a recovered reaction liquid, and reacting the aliphatic structure copolyester or the aliphatic-aromatic copolyester at 50-80 ℃ for 20-240 min, wherein the mass-volume ratio of the aliphatic structure copolyester or the aliphatic-aromatic copolyester to the reaction solvent or the recovered reaction liquid is 0.004-0.2W/V, and the mass-volume ratio of the alkaline catalyst to the reaction solvent or the alkaline catalyst to the recovered reaction liquid is 0.04-0.2W/V;
(2) And (3) cooling the reaction solution of the copolyester containing the fat structure obtained in the step (1) to 1-10 ℃, filtering, dissolving the obtained solid product in deionized water, and then adjusting the pH value of the solution to 1-6, or directly adjusting the pH value of the reaction solution of the copolyester containing the fat and the aromatic in the step (1) to 1-6, so that degradation products can be precipitated, degradation products and reaction solution are obtained, the degradation products can be collected and can be reused as raw materials for synthesizing new polyesters, and the collected reaction solution can be used for replacing a reaction solvent for repeated use.
8. The method for recovering fat and fat-aromatic copolyester capable of being recovered rapidly and in a closed loop under mild conditions according to claim 7, wherein the reaction solvent used in the method is at least one of methanol, ethanol, isopropanol, n-propanol, n-butanol, isobutanol, pentanol, hexanol, 1, 4-butanediol, diethylene glycol and 1, 4-cyclohexanedimethanol, or a mixed solution of water and at least one of methanol, ethanol, isopropanol, n-propanol, n-butanol, isobutanol, pentanol, hexanol, 1, 4-butanediol, diethylene glycol and 1, 4-cyclohexanedimethanol, and the volume ratio of the mixed solution is 20-80: 20-80 parts; the basic catalyst is at least one of alkoxide, basic metal salt, basic metal oxide and hydroxide.
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