CN115124699A - Degradable aromatic-aliphatic copolyester material and preparation method and application thereof - Google Patents
Degradable aromatic-aliphatic copolyester material and preparation method and application thereof Download PDFInfo
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- CN115124699A CN115124699A CN202110330774.0A CN202110330774A CN115124699A CN 115124699 A CN115124699 A CN 115124699A CN 202110330774 A CN202110330774 A CN 202110330774A CN 115124699 A CN115124699 A CN 115124699A
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- AXKZIDYFAMKWSA-UHFFFAOYSA-N 1,6-dioxacyclododecane-7,12-dione Chemical compound O=C1CCCCC(=O)OCCCCO1 AXKZIDYFAMKWSA-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
- C08G63/183—Terephthalic acids
-
- 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
- C08G63/181—Acids containing aromatic rings
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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
- C08G63/181—Acids containing aromatic rings
- C08G63/185—Acids containing aromatic rings containing two or more aromatic rings
- C08G63/187—Acids containing aromatic rings containing two or more aromatic rings containing condensed aromatic rings
- C08G63/189—Acids containing aromatic rings containing two or more aromatic rings containing condensed aromatic rings containing a naphthalene ring
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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
- C08G63/66—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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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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
- C08G2230/00—Compositions for preparing biodegradable polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention discloses a degradable aromatic-aliphatic copolyester material and a preparation method and application thereof, wherein the method comprises the following steps: (1) mixing aromatic dibasic acid and dihydric alcohol for esterification reaction to obtain an esterification product; (2) carrying out pre-polycondensation reaction on the esterification product so as to obtain an aromatic prepolymer; (3) and mixing the aromatic prepolymer and aliphatic polyester for ester exchange reaction to obtain the degradable aromatic-aliphatic copolyester material. According to the method, the aliphatic polyester units are randomly inserted into the aromatic copolymerized polymer chain by a copolymerization modification method, so that the degradation performance of the aliphatic polyester is organically combined with the excellent comprehensive performance of the aromatic polyester to obtain the degradable polyester material with high performance and low cost, and the bottleneck problems of poor mechanical property of the degradable polyester material, nondegradable traditional plastics and the like are fundamentally solved.
Description
Technical Field
The invention belongs to the field of degradable materials, and particularly relates to a degradable aromatic-aliphatic copolyester material, and a preparation method and application thereof.
Background
The synthetic polymer material is widely used due to its excellent characteristics such as light weight and corrosion resistance, but due to its chemical stability in natural environment, the waste thereof imposes a great burden on the environment, and the development of a polymer material having biodegradability has great significance for solving the pollution of plastic waste.
At present, the degradable plastics researched and developed globally are dozens of types, wherein the degradable plastics capable of being industrially produced mainly comprise chemically synthesized poly (butylene adipate/terephthalate) (PBAT), polylactic acid (PLA), poly (butylene succinate) (PBS), Polycaprolactone (PCL), Polyglycolide (PGA) and polycarbonate (PPC); polyhydroxy fatty acid ester (PHA) synthesized by microbial fermentation, natural high molecular starch blend starch/PBS, starch/PLA and the like.
The degradable material has various types and advantages, but the development of the degradable material is always restricted by the defects of limited high manufacturing cost, limited comprehensive mechanical property and the like, the average selling price of the degradable material is generally 1.5-4 times of that of the traditional plastic, mainly because the production process of the degradable plastic is complicated, the required monomer process is monopolized abroad, the price is high, the production cost is invisibly increased, and the large-scale application of the degradable material is limited; on the other hand, from the viewpoint of material molecular structure and properties, the degradable material is usually aliphatic polyester or polycarbonate material, which makes the thermal properties of the polymer general, the glass transition temperature low, and the comprehensive mechanical properties poor, so that it is difficult to replace the traditional plastics in practical application. For example, although aliphatic polyester PLA has good hardness, gloss, and good food and human safety, its disadvantages, such as hard and brittle texture, insufficient elasticity and flexibility, poor heat resistance, limited strength and modulus, etc., are significant, and therefore modification of PLA homopolymer is usually required to meet the use requirements. In addition, PBAT is an aromatic polyester material which has good industrial prospect and market prospect at present, has good ductility and elongation at break, good heat resistance and impact resistance, and excellent biodegradability, but the production difficulty of PBAT mainly lies in that the process is complex, the byproduct is tetrahydrofuran, and the requirements on the production process flow and production equipment are high. And other degradable polyester materials such as PGA, PHA, PCL and the like are limited by monomers or process flows, so that the product price is high, and industrial production and large-scale popularization and use are more difficult.
Besides the degradable homopolymer material, the novel polymer can be prepared by blending modification, so that the defects of poor homopolymer performance and the like can be obviously overcome. For example, the natural polymer starch-based degradable material widely used in the packaging industry at present has the advantages that the cost of the final degradable material product can be greatly reduced by blending starch in a certain proportion, but due to the compatibility problem of a blending system, the starch-based material is easy to age and become brittle, and has poor mechanical property and water resistance.
Disclosure of Invention
The present invention is directed to solving, at least to some extent, one of the technical problems in the related art. Therefore, one purpose of the invention is to provide a degradable aromatic-aliphatic copolyester material and a preparation method and application thereof, wherein an aliphatic polyester unit is randomly inserted into an aromatic copolymerization polymer chain by a copolymerization modification method, so that the degradation performance of aliphatic polyester and the excellent comprehensive performance of aromatic polyester are organically combined to obtain a high-performance low-cost degradable polyester material, and the bottleneck problems of poor mechanical property of the degradable polyester material, non-degradability of traditional plastics and the like are fundamentally solved.
In one aspect of the present invention, a method of preparing a degradable aromatic-aliphatic copolyester material is presented. According to an embodiment of the invention, the method comprises:
(1) mixing aromatic dibasic acid and dihydric alcohol for reaction so as to obtain an esterification product;
(2) carrying out pre-polycondensation reaction on the esterification product so as to obtain an aromatic prepolymer;
(3) mixing the aromatic prepolymer and aliphatic polyester for transesterification reaction to obtain the degradable aromatic-aliphatic copolyester material.
According to the method for preparing the degradable aromatic-aliphatic copolyester material, the aromatic dibasic acid and the dihydric alcohol are mixed for esterification reaction, the aromatic dibasic acid and the dihydric alcohol are cheap and easy to obtain and are not limited by suppliers, so that the raw material cost is reduced, the esterification product is subjected to pre-polycondensation reaction, and then the aromatic prepolymer and the aliphatic polyester are mixed for ester exchange reaction, namely, the aliphatic polyester unit is randomly inserted into an aromatic copolymerization polymer chain by a copolymerization modification method, the aromatic polyester has a rigid benzene ring structure in a chain segment, so that the finally obtained material has excellent mechanical property and thermal property, the aliphatic polyester has excellent degradation property, the degradation property of the aliphatic polyester is organically combined with the excellent comprehensive property of the aromatic polyester, and the degradable polyester material with high performance and low cost is obtained, the invention can solve the bottleneck problems of bad mechanical property of degradable polyester material and non-degradability of traditional plastics, and the reaction process of the invention does not need to use any solvent, and only generates water as non-toxic and harmless by-product.
In addition, the method for preparing a degradable aromatic-aliphatic copolyester material according to the above embodiment of the present invention may further have the following additional technical features:
in some embodiments of the present invention, in step (1), the aromatic dibasic acid comprises at least one of terephthalic acid, phthalic acid, isophthalic acid, furandicarboxylic acid, terephthalic acid ester, phthalic acid ester, isophthalic acid ester, furandicarboxylic acid ester, 2, 6-naphthalenedicarboxylic acid, and 2, 6-naphthalenedicarboxylic acid ester, preferably at least one of terephthalic acid and 2, 6-naphthalenedicarboxylic acid. Therefore, the mechanical property and the thermal property of the polyester material can be obviously improved.
In some embodiments of the invention, in step (1), the glycol comprises at least one of ethylene glycol, 1, 3-propanediol, 1, 4-butanediol, and 1, 6-hexanediol, preferably ethylene glycol.
In some embodiments of the present invention, in step (1), the aromatic dibasic acid and the glycol are in a molar ratio of 1: (1.1-2), preferably 1: (1.2-1.8).
In some embodiments of the present invention, in step (1), the aromatic dibasic acid and the dihydric alcohol are mixed and reacted under the action of a catalyst, wherein the amount of the catalyst is 1% to 5%, preferably 1% to 3%, of the total mass of all raw materials.
In some embodiments of the invention, in the step (1), the temperature of the esterification reaction is 230-260 ℃ and the time is 1-3 h.
In some embodiments of the invention, in step (2), the aromatic prepolymer has a viscosity of 0.3dL/g to 0.5 dL/g. Therefore, the mechanical property and the thermal property of the polyester material can be obviously improved.
In some embodiments of the invention, in the step (2), the temperature of the pre-polycondensation reaction is 260-270 ℃ and the time is 1-3 h.
In some embodiments of the invention, in step (3), the aliphatic polyester comprises at least one of lactic acid, glycolic acid, hydroxypropionic acid, hydroxybutyric acid, glycolic acid, butyrolactone, caprolactone, polylactic acid, polyglycolic acid, polybutrolactone, and polycaprolactone, preferably at least one of lactic acid and polylactic acid.
In some embodiments of the present invention, in the step (3), the feeding molar ratio of the aromatic dibasic acid to the aliphatic polyester is (1-99): (1-99), preferably (10-90): (10-90).
In some embodiments of the invention, in the step (3), the temperature of the transesterification reaction is 265 ℃ to 275 ℃ for 1 to 3 hours.
In a second aspect of the present invention, a degradable aromatic-aliphatic copolyester material is provided. According to the embodiment of the invention, the degradable aromatic-aliphatic copolyester material is prepared by adopting the method. Therefore, the degradable material realizes the organic combination of the degradation performance of aliphatic polyester and the excellent comprehensive performance of aromatic polyester, has the advantages of high performance and low cost, and fundamentally solves the bottleneck problems of poor mechanical property of the degradable polyester material, non-degradability of traditional plastics and the like.
In a third aspect of the present invention, a packaging material is presented. According to an embodiment of the present invention, the packaging material is prepared by using the degradable aromatic-aliphatic copolyester material. Therefore, the degradable material with the advantages of high performance and low cost is adopted to prepare the packaging material, so that the cost of the packaging material can be reduced while the performance of the packaging material is improved, and the degradable material is beneficial to industrial production and large-scale popularization and use.
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Drawings
The above and/or additional aspects and advantages of the present invention will become apparent and readily appreciated from the following description of the embodiments, taken in conjunction with the accompanying drawings of which:
FIG. 1 is a schematic flow diagram of a method for preparing a degradable aromatic-aliphatic copolyester material according to an embodiment of the present invention;
FIG. 2 is a hydrogen nuclear magnetic spectrum of the copolyester obtained in example 1;
FIG. 3 is a DSC spectrum of the copolyester obtained in example 1.
Detailed Description
The following detailed description of the embodiments of the present invention is intended to be illustrative, and not to be construed as limiting the invention.
In one aspect of the present invention, a method of preparing a degradable aromatic-aliphatic copolyester material is presented. According to an embodiment of the invention, with reference to fig. 1, the method comprises:
s100: mixing aromatic dibasic acid and dihydric alcohol for esterification reaction
In the step, aromatic dibasic acid and dihydric alcohol are mixed, and are stirred and reacted for 1-3 h at the temperature of 230-260 ℃ to obtain an esterification product, and water as a byproduct is removed, wherein the aromatic dibasic acid comprises but is not limited to at least one of terephthalic acid, phthalic acid, isophthalic acid, furan dicarboxylic acid, terephthalate, phthalate, isophthalate, furan dicarboxylate, 2, 6-naphthalenedicarboxylic acid and 2, 6-naphthalenedicarboxylate, preferably at least one of terephthalic acid and 2, 6-naphthalenedicarboxylic acid, and the segment of the aromatic polyester contains a rigid benzene ring structure, so that the material has excellent mechanical property and thermal property, and meanwhile, the aromatic dibasic acid material is low in cost, cheap and easily available in raw materials and is not limited by suppliers. In addition, the 2, 6-naphthalenedicarboxylic acid and 2, 6-naphthalenedicarboxylate have naphthalene rings with higher rigidity in molecular chains, and the naphthalene ring structure enables the material to have higher physical and mechanical properties, gas barrier property, chemical stability, heat resistance, ultraviolet resistance, radiation resistance and other properties, so that the 2, 6-naphthalenedicarboxylic acid unit is introduced into the molecular chains, the overall comprehensive performance of the copolymer is further improved, and the final material has wider application prospects. Further, the above-mentioned dihydric alcohol includes, but is not limited to, at least one of ethylene glycol, 1, 3-propanediol, 1, 4-butanediol and 1, 6-hexanediol, preferably ethylene glycol.
Meanwhile, the molar ratio of the aromatic dibasic acid to the dihydric alcohol is 1: (1.1-2), preferably 1: (1.2-1.8). The inventor finds that if the ratio of the two is too low, the glycol is consumed along with the reaction, the reaction can be incomplete, and the final yield of the polymer is reduced; if the ratio of the two is too high, the DEG content in the product is too high, and the thermal property of the obtained product is reduced. Further, the aromatic dibasic acid and the dihydric alcohol are mixed to carry out esterification reaction under the action of a catalyst, wherein the dosage of the catalyst is 1-5%, preferably 1-3% of the total mass of all raw materials, and the catalyst comprises but is not limited to at least one of an antimony catalyst, a titanium catalyst and a tin catalyst, preferably the antimony catalyst. In this application, "all raw materials" include aromatic dibasic acids, glycols, and aliphatic polyesters.
S200: the esterification product is subjected to pre-polycondensation reaction
In the step, the reaction temperature is slowly raised, and the esterification product is subjected to pre-polycondensation reaction for 1-3 h at the temperature of 260-270 ℃ to obtain the aromatic prepolymer with the viscosity of 0.3 dL/g-0.5 dL/g. The inventor finds that if the viscosity of the aromatic prepolymer is too low, the subsequent transesterification reaction by-product is too much, and the final polymer yield is influenced; if the viscosity of the resulting aromatic prepolymer is too high (greater than 0.5dL/g), the transesterification reaction may be incomplete and a proportion of the blend may be present in the product.
S300: mixing aromatic prepolymer and aliphatic polyester for ester exchange reaction
In the step, the obtained aromatic prepolymer and aliphatic polyester are mixed together with stirring and slowly heated to perform transesterification reaction at 265-275 ℃ for 1-3 hours, preferably 2 hours, so as to obtain the degradable aromatic-aliphatic copolyester material, wherein the aliphatic polyester comprises but is not limited to at least one of lactic acid, glycolic acid, hydroxypropionic acid, hydroxybutyric acid, glycolic acid, butyrolactone, caprolactone, polylactic acid, polyglycolic acid, polybutyrolactone and polycaprolactone, and preferably comprises at least one of lactic acid and polylactic acid. Furthermore, the feeding molar ratio of the aromatic dibasic acid to the aliphatic polyester is (1-99): (1-99), preferably (10-90): (10-90).
Specifically, the aromatic dibasic acid contains a benzene ring rigid structure, so that the aromatic dibasic acid not only can provide higher glass transition temperature and use temperature for a final product, but also can provide excellent mechanical property for materials and provide higher tensile strength for copolyester; the dihydric alcohol and the aliphatic polyester enhance the flexibility of a high molecular chain, and are determined by balancing poor solubility, poor processing performance and the like caused by excessive aromatic units, and the introduction of the aliphatic polyester unit can inhibit crystallization, thereby obtaining a copolyester material with better transparency. More importantly, with the increase of the content of the aliphatic polyester, the final material can have certain degradation performance, and the requirement of environmental protection is met, so that the organic combination of aromatic dibasic acid, dihydric alcohol and aliphatic units is realized, the thermal performance, the processing performance, the mechanical performance and the degradation performance of the copolyester are synergistically improved, and the performance of the final material can be freely switched and regulated by regulating the proportion of each unit and the distribution condition in a high molecular chain, so that a wider application scene is met. Meanwhile, the introduction of the lactic acid unit can reduce the glass transition temperature of the copolymer, and the application range of the copolyester is limited, so that the naphthalene dicarboxylic acid unit with higher glass transition temperature is innovatively introduced while the lactic acid unit is adopted, so that the influence of thermal property reduction brought by lactic acid is offset, and the copolyester material with more excellent and balanced comprehensive properties is prepared. Compared with the traditional PBAT copolyester material, the process is more environment-friendly, and does not produce tetrahydrofuran as a byproduct, so that the equipment cost and the operation difficulty are greatly reduced, and the environment-friendly and green requirements of the whole process from the process to the final polyester product are met.
Taking terephthalic acid, ethylene glycol and lactic acid as examples, the reaction equation is as follows:
in a second aspect of the present invention, the present invention provides a degradable aromatic-aliphatic copolyester material. According to the embodiment of the invention, the degradable aromatic-aliphatic copolyester material is prepared by adopting the method. Therefore, the degradable material realizes the organic combination of the degradation performance of aliphatic polyester and the excellent comprehensive performance of aromatic polyester, has the advantages of high performance and low cost, and fundamentally solves the bottleneck problems of poor mechanical property of the degradable polyester material, non-degradability of the traditional plastic and the like. It should be noted that the features and advantages described above for the method for preparing the degradable aromatic-aliphatic copolyester material are also applicable to the degradable aromatic-aliphatic copolyester material, and are not described herein again.
In a third aspect of the present invention, a packaging material is presented. According to an embodiment of the present invention, the packaging material is prepared by using the degradable aromatic-aliphatic copolyester material. Therefore, the degradable material with the advantages of high performance and low cost is adopted to prepare the packaging material, so that the cost of the packaging material can be reduced while the performance of the packaging material is improved, and the degradable material is beneficial to industrial production and large-scale popularization and use. Specifically, the packaging material is a disposable food packaging bag, a disposable medical packaging bag and the like. It should be noted that the features and advantages described above for the degradable aromatic-aliphatic copolyester material and the preparation method thereof are also applicable to the packaging material, and are not described herein again.
The following embodiments of the present invention are described in detail, and it should be noted that the following embodiments are exemplary only, and are not to be construed as limiting the present invention. In addition, all reagents used in the following examples are commercially available or can be synthesized according to methods herein or known, and are readily available to one skilled in the art for reaction conditions not listed, if not explicitly stated.
Example 1
Adding 4922g of terephthalic acid (PTA), 2467g of Ethylene Glycol (EG), 81.5g of isophthalic acid (IPA) and 128g of antimony catalyst ethylene glycol antimony into a 20L reaction kettle, stirring uniformly, heating to 260 ℃, carrying out esterification reaction under a pressurized condition, wherein the reaction time is 3 hours, monitoring the water yield of the esterification reaction in the reaction process, after the reaction is finished, heating to 270 ℃ for condensation prepolymerization reaction, carrying out the condensation prepolymerization reaction for 3 hours, monitoring the torque change in the prepolymerization process, after the reaction is finished (the viscosity of the obtained aromatic prepolymer is 0.4dL/g, adding 2182g of PLA (polylactic acid) slices, keeping the temperature at 270 ℃ in a molten state, continuing the ester exchange reaction, carrying out the reaction for 2 hours, discharging, granulating and drying after the reaction is finished, and the performance test result is shown in Table 1. the hydrogen spectrogram of the copolyester obtained by the method is known, wherein the molar ratio of aromatic group to aliphatic group is about 69: 31, meanwhile, the DSC spectrogram of the obtained copolyester shows that the copolyester does not contain a melting point, is an amorphous polymer and indicates that the two components are in a copolymerization state but not in a blending state.
Example 2
A20L reaction vessel was charged with 5414g of terephthalic acid (PTA), 2714g of Ethylene Glycol (EG), 89.6g of isophthalic acid (IPA) and 128g of antimony catalyst ethylene glycol antimony, stirred uniformly, heated to 260 ℃ and subjected to esterification reaction under pressure for 3 hours. Monitoring the water yield of esterification reaction in the reaction process, after the reaction is finished, heating to 270 ℃ for condensation prepolymerization reaction, wherein the reaction time is 3 hours, monitoring the torque change in the prepolymerization process, after the reaction is finished (the viscosity of the obtained aromatic prepolymer is 0.35dL/g, adding 1600g of PLA (polylactic acid) slices, keeping the temperature at 270 ℃ in a molten state, continuously carrying out ester exchange reaction, reacting for 2 hours, discharging, granulating and drying after the reaction is finished, and the test result is shown in table 1.
Example 3
5906g of terephthalic acid (PTA), 2960g of Ethylene Glycol (EG), 97.6g of isophthalic acid (IPA) and 128g of antimony catalyst ethylene glycol antimony are added into a 20L reaction kettle, the mixture is stirred uniformly, the temperature is raised to 260 ℃ and the esterification reaction is carried out under the pressure condition, the reaction time is 3 hours, the water yield of the esterification reaction is monitored in the reaction process, the temperature is raised to 270 ℃ after the reaction is finished, the condensation prepolymerization reaction is carried out, the reaction time is 3 hours, the torque change is monitored in the prepolymerization process, after the reaction is finished (the viscosity of the obtained aromatic prepolymer is 0.37dL/g, 1097g of PLA (polylactic acid) slices are added, the temperature is kept in a 270 ℃ molten state, the ester exchange reaction is carried out continuously, the reaction time is 2 hours, the discharge, the grain cutting and the drying are carried out after the reaction is finished, the test result is shown in Table 1, the hydrogen spectrogram of the copolyester obtained by the method is known, wherein the molar ratio of aromatic group to aliphatic group is about 80:20, meanwhile, as can be seen from the DSC spectrum of the obtained copolyester, the copolyester only has one melting point of about 223 ℃ and is between the melting points of the PTA homopolymer and the PLA homopolymer, which indicates that the two components are in a copolymerization state rather than a blending state, and the crystallization temperature of the copolymer is about 132 ℃.
Example 4
6400g of terephthalic acid (PTA), 3206g of Ethylene Glycol (EG), 105.6g of isophthalic acid (IPA) and 128g of antimony catalyst ethylene glycol antimony are added into a 20L reaction kettle, stirred uniformly, heated to 260 ℃ and subjected to esterification reaction under the condition of pressurization for 3 hours. Monitoring the water yield of esterification reaction in the reaction process, after the reaction is finished, raising the temperature to 270 ℃ for condensation prepolymerization reaction, wherein the reaction time is 3 hours, monitoring the torque change in the prepolymerization process, after the reaction is finished (the viscosity of the obtained aromatic prepolymer is 0.41dL/g, adding 694g of PLA (polylactic acid) slices, keeping the temperature at 270 ℃ in a molten state, continuing to perform ester exchange reaction for 2 hours, discharging, cutting into granules and drying after the reaction is finished, and the test result is shown in Table 1. the hydrogen nuclear magnetic spectrum diagram of the obtained copolyester is shown in figure 2, wherein the molar ratio of aromatic and aliphatic is about 83:17, which is marked as PET83-co-PLA17, figure 3 is the DSC spectrum diagram of the obtained copolyester PET83-co-PLA17, the copolyester only has a melting point of about 230 ℃, and is between the melting points of the PET homopolymer and the PLA homopolymer, which indicates that the two components are in a copolymerization state and not in a blending state, the crystallization temperature of the copolymer was about 140 ℃.
Example 5
Terephthalic Acid (PTA)6910g, Ethylene Glycol (EG)3450g, isophthalic acid (IPA)113.6g and antimony catalyst ethylene glycol antimony 128g were added to a 20L reactor, stirred uniformly, heated to 260 deg.C, and subjected to esterification reaction under pressure for 3 hours. Monitoring the water yield of the esterification reaction in the reaction process, after the reaction is finished, heating to 270 ℃ for condensation prepolymerization reaction for 3 hours, monitoring the torque change in the prepolymerization process, after the reaction is finished (the viscosity of the obtained aromatic prepolymer is 0.42dL/g, 333g of PLA (polylactic acid) slices are added, the temperature is kept at 270 ℃ in a molten state, the ester exchange reaction is continuously carried out, the reaction time is 2 hours, discharging, granulating and drying after the reaction is finished, and the test result is shown in table 1, the hydrogen nuclear magnetic spectrum of the copolyester obtained by the method can be known, wherein the molar ratio of aromatic to aliphatic is about 92:8, and the DSC spectrum of the copolyester shows that the copolyester has only one melting point of about 247 ℃, and is between the melting points of the PTA homopolymer and the PLA homopolymer, indicating that the two components are in a copolymerized state rather than in a blended state, and the crystallization temperature of the copolymer is about 151 ℃.
Example 6
6525g of terephthalic acid (PTA), 780g of 2, 6-naphthalenedicarboxylic acid (NDA), 3450g of Ethylene Glycol (EG), 113.6g of isophthalic acid (IPA) and 128g of antimony catalyst ethylene glycol antimony are added into a 20L reaction kettle, the mixture is uniformly stirred, the temperature is raised to 260 ℃ and the esterification reaction is carried out under the condition of pressurization, the reaction time is 3 hours, the water yield of the esterification reaction is monitored in the reaction process, after the reaction is finished, the temperature is raised to 270 ℃ and the condensation prepolymerization reaction is carried out, the reaction time is 3 hours, the torque change is monitored in the prepolymerization process (the viscosity of the aromatic prepolymer is 0.39dL/g), 333g of PLA (polylactic acid) slices are added after the reaction is finished, the ester exchange reaction is continuously carried out under the condition of 270 ℃, the reaction time is 2 hours, the discharging, grain cutting and drying are carried out after the reaction is finished, and the test results are shown in Table 1. The hydrogen nuclear magnetic spectrum of the obtained copolyester is known, wherein the molar ratio of aromatic to aliphatic is about 90:10, and the DSC spectrum of the obtained copolyester is also known, the melting point of the copolyester is about 260 ℃ and is between the melting points of PTA homopolymer and PLA homopolymer, which indicates that the two components are in a copolymerization state rather than a blending state, and the crystallization temperature of the copolymer is about 166 ℃.
Example 7
Adding 6100g of terephthalic acid (PTA), 1500g of 2, 6-naphthalenedicarboxylic acid (NDA), 3450g of Ethylene Glycol (EG), 113.6g of isophthalic acid (IPA) and 128g of antimony catalyst ethylene glycol antimony into a 20L reaction kettle, uniformly stirring, heating to 260 ℃, carrying out esterification reaction under a pressure condition, carrying out reaction for 3 hours, monitoring the water yield of the esterification reaction in the reaction process, after the reaction is finished, heating to 270 ℃, carrying out condensation prepolymerization reaction, carrying out reaction for 3 hours, monitoring torque change in the prepolymerization process, after the reaction is finished (the viscosity of the obtained aromatic prepolymer is 0.36dL/g), adding 333g of PLA (polylactic acid) slices, keeping the temperature at 270 ℃ in a molten state, continuing the ester exchange reaction, carrying out the reaction for 2 hours, discharging, granulating and drying after the reaction is finished, and the test results are shown in Table 1. The hydrogen nuclear magnetic spectrum of the obtained copolyester is known, wherein the molar ratio of aromatic to aliphatic is about 88:12, and the DSC spectrum of the obtained copolyester is also known, the melting point of the copolyester is about 261 ℃ and is between the melting points of PTA homopolymer and PLA homopolymer, which indicates that the two components are in a copolymerization state rather than a blending state, and the crystallization temperature of the copolymer is about 162 ℃.
Example 8
6525g of phthalic acid, 620g of furandicarboxylic acid, 4250g of 1, 3-propanediol and 128g of antimony catalyst ethylene glycol antimony are added into a 20L reaction kettle, the mixture is stirred uniformly and heated to 260 ℃ for esterification reaction under a pressurized condition, the reaction time is 3 hours, the water yield of the esterification reaction is monitored in the reaction process, after the reaction is finished, the temperature is raised to 265 ℃ for condensation prepolymerization reaction, the reaction time is 2 hours, the torque change is monitored in the prepolymerization process, after the reaction is finished (the viscosity of the obtained aromatic prepolymer is 0.37dL/g), 280g of polyglycolic acid slices are added, the temperature is kept in a 270 ℃ molten state, ester exchange reaction is continued, the reaction time is 2 hours, and after the reaction is finished, discharging, granulating and drying are carried out, and the test results are shown in Table 1. From the hydrogen nuclear magnetic spectrum of the obtained copolyester, the mole ratio of aromatic and aliphatic is about 91:9, and from the DSC spectrum of the obtained copolyester, the melting point of the copolyester is about 258 ℃, and is between the melting points of the poly phthalic acid, the poly furan dicarboxylic acid homopolymer and the poly glycolic acid homopolymer, which indicates that the two components are in a copolymerization state and not in a blending state, and the crystallization temperature of the copolymer is about 140 ℃.
Example 9
6700g of terephthalate, 140g of isophthalate, 4800g of 1, 4-butanediol and 180g of tin catalyst stannous octoate are added into a 20L reaction kettle, the mixture is uniformly stirred and heated to 250 ℃ to carry out esterification reaction under a pressurized condition for 3 hours, the water yield of the esterification reaction is monitored in the reaction process, after the reaction is finished, the temperature is raised to 265 ℃ to carry out condensation prepolymerization reaction for 2 hours, the torque change is monitored in the prepolymerization process, 340g of polyhydroxypropionate slices are added after the reaction is finished (the viscosity of the obtained aromatic prepolymer is 0.39dL/g), the temperature is kept at 270 ℃ in a molten state, ester exchange reaction is continuously carried out, the reaction time is 2 hours, discharging, granulating and drying are carried out after the reaction is finished, and the test results are shown in Table 1. The hydrogen nuclear magnetic spectrum of the obtained copolyester is known to have aromatic and aliphatic molar ratio of about 89:11, and the DSC spectrum of the obtained copolyester shows that the copolyester has only one melting point of about 254 ℃ and is between the melting points of the poly (terephthalic acid) homopolymer and the poly (hydroxy propionate) homopolymer, which indicates that the two components are in a copolymerization state rather than a blending state, and the crystallization temperature of the copolymer is about 144 ℃.
Example 10
6500g of phthalate, 620g of furan dicarboxylate, 5600g of 1, 6-hexanediol and 180g of tin catalyst stannous octoate are added into a 20L reaction kettle, the mixture is stirred uniformly and heated to 250 ℃ to carry out esterification reaction under a pressurized condition, the reaction time is 3 hours, the water yield of the esterification reaction is monitored in the reaction process, after the reaction is finished, the temperature is raised to 265 ℃ to carry out condensation prepolymerization reaction, the reaction time is 2 hours, the torque change is monitored in the prepolymerization process, 460g of polyhydroxybutyrate slices are added after the reaction is finished (the viscosity of the obtained aromatic prepolymer is 0.38dL/g), the ester exchange reaction is continuously carried out under the condition that the temperature is kept at 270 ℃, the reaction time is 3 hours, and the materials are discharged, cut into particles and dried after the reaction is finished, and the test results are shown in Table 1. The hydrogen nuclear magnetic spectrum of the obtained copolyester is known, wherein the molar ratio of aromatic to aliphatic is about 90:10, and the DSC spectrum of the obtained copolyester is also known, the melting point of the copolyester is about 230 ℃ and is between the melting points of the poly phthalic acid homopolymer and the poly hydroxybutyrate homopolymer, which indicates that the two components are in a copolymerization state rather than a blending state, and the crystallization temperature of the copolymer is about 120.
Example 11
6525g of terephthalate, 920g of 2, 6-naphthalate, 3450g of ethylene glycol and 150g of titanium catalyst butyl titanate are added into a 20L reaction kettle, the mixture is stirred uniformly and then heated to 250 ℃, the esterification reaction is carried out under the pressure condition, the reaction time is 3 hours, the water yield of the esterification reaction is monitored in the reaction process, after the reaction is finished, the temperature is raised to 275 ℃ for condensation prepolymerization reaction, the reaction time is 3 hours, the torque change is monitored in the prepolymerization process, after the reaction is finished (the viscosity of the obtained aromatic prepolymer is 0.42dL/g, 333g of polylactic acid slices are added, the temperature is kept in a 275 ℃ molten state, the ester exchange reaction is continuously carried out, the reaction time is 3 hours, after the reaction is finished, discharging, grain cutting and drying are carried out, the test result is shown in Table 1, and the hydrogen nuclear magnetic spectrum diagram of the copolyester obtained by the method can be known, wherein the molar ratio of aromatic group to aliphatic group is about 88:12, meanwhile, as can be seen from DSC spectra of the obtained copolyester, the copolyester only has one melting point of about 251 ℃ and is between the melting points of the polyethylene terephthalate homopolymer and the polylactic acid homopolymer, which indicates that the two components are in a copolymerization state rather than a blending state, and the crystallization temperature of the copolymer is about 119 ℃.
Example 12
6500g of terephthalic acid ester, 780g of 2, 6-naphthalenedicarboxylic acid, 3450g of ethylene glycol and 180g of titanium catalyst butyl titanate are added into a 20L reaction kettle, the mixture is stirred uniformly and heated to 250 ℃ to carry out esterification reaction under a pressure condition for 3 hours, the water yield of the esterification reaction is monitored in the reaction process, after the reaction is finished, the temperature is raised to 260 ℃ to carry out condensation prepolymerization reaction for 2 hours, the torque change is monitored in the prepolymerization process, after the reaction is finished (the viscosity of the obtained aromatic prepolymer is 0.4dL/g), 500g of butyrolactone slices are added, the temperature is kept at 270 ℃ in a molten state, ester exchange reaction is continuously carried out, the reaction time is 2 hours, after the reaction is finished, discharging, granulating and drying are carried out, and the test results are shown in Table 1. The hydrogen nuclear magnetic spectrum of the copolyester obtained by the method is known, wherein the molar ratio of aromatic to aliphatic is about 90:10, and the DSC spectrum of the copolyester obtained by the method is known, the melting point of the copolyester is about 236 ℃ and is between the melting points of the polyethylene terephthalate homopolymer and the polyethylene butyrolactone homopolymer, the two components are in a copolymerization state rather than a blending state, and the crystallization temperature of the copolyester is about 130 ℃.
Example 13
Adding 6400g of phthalate, 120g of isophthalic acid, 5100g of 1, 6-hexanediol and 120g of titanium catalyst butyl titanate into a 20L reaction kettle, stirring uniformly, heating to 260 ℃, carrying out esterification reaction under a pressurized condition, wherein the reaction time is 3 hours, monitoring the water yield of the esterification reaction in the reaction process, after the reaction is finished, heating to 265 ℃ to carry out condensation prepolymerization reaction, carrying out reaction for 2 hours, monitoring torque change in the prepolymerization process, adding 400g of polycaprolactone slices after the reaction is finished (the viscosity of the obtained aromatic prepolymer is 0.38dL/g), keeping the temperature at 270 ℃ in a molten state, continuing carrying out ester exchange reaction, carrying out reaction for 3 hours, discharging, granulating and drying after the reaction is finished, and testing results are shown in Table 1. The hydrogen nuclear magnetic spectrum of the obtained copolyester shows that the molar ratio of aromatic to aliphatic is about 86:14, and the DSC spectrum of the obtained copolyester shows that the copolyester only has one melting point of about 222 ℃ and is between the melting points of polyethylene terephthalate homopolymer and polycaprolactone homopolymer, which indicates that the two components are in a copolymerization state rather than a blending state, and the crystallization temperature of the copolymer is about 79 ℃.
Example 14
5500g of furan diformate, 180g of isophthalic acid, 4200g of 1, 3-propylene glycol and 150g of titanium catalyst butyl titanate are added into a 20L reaction kettle, the mixture is stirred uniformly and heated to 250 ℃ to carry out esterification reaction under a pressure condition for 3 hours, the water yield of the esterification reaction is monitored in the reaction process, the temperature is raised to 260 ℃ after the reaction is finished to carry out condensation prepolymerization reaction for 3 hours, the torque change is monitored in the prepolymerization process, after the reaction is finished (the viscosity of the obtained aromatic prepolymer is 0.44 dL/g.), 500g of polyethylene alcohol section slices are added, the temperature is kept in a 270 ℃ molten state, ester exchange reaction is carried out continuously, the reaction time is 1 hour, and after the reaction is finished, discharging, granulating and drying are carried out, and the test results are shown in Table 1. The molar ratio of aromatic to aliphatic in the obtained copolyester is about 87:13 as seen by the hydrogen nuclear magnetic spectrum of the obtained copolyester, and the DSC spectrum of the obtained copolyester shows that the copolyester only has a melting point of about 213 ℃ and is between the melting points of the polypropylene furan dicarboxylate homopolymer and the polyglycolic acid homopolymer, which indicates that the two components are in a copolymerized state rather than a blended state, and the crystallization temperature of the copolymer is about 106 ℃.
Example 15
5350g of furan diformate, 1200g of terephthalic acid, 5200g of 1, 4-butanediol and 180g of titanium catalyst butyl titanate are added into a 20L reaction kettle, the mixture is stirred uniformly and then heated to 260 ℃, the esterification reaction is carried out under a pressurized condition, the reaction time is 3 hours, the water yield of the esterification reaction is monitored in the reaction process, after the reaction is finished, the temperature is raised to 265 ℃ for condensation prepolymerization reaction, the reaction time is 1 hour, the torque change is monitored in the prepolymerization process, 600g of butyrolactone slices are added after the reaction is finished (the viscosity of the obtained aromatic prepolymer is 0.41dL/g), the ester exchange reaction is carried out continuously under the condition that the temperature is kept at 270 ℃, the reaction time is 1 hour, and the mixture is discharged, granulated and dried after the reaction is finished, and the test results are shown in Table 1. From the hydrogen nuclear magnetic spectrum of the copolyester obtained, the molar ratio of aromatic to aliphatic is about 77: 23, and as can be seen from the DSC spectrum of the obtained copolyester, the copolyester has only one melting point of about 198 ℃ and is between the melting points of the polypropylene furan dicarboxylate homopolymer and the polypropylene butyrolactone homopolymer, which shows that the two components are in a copolymerized state rather than a blended state, and the crystallization temperature of the copolymer is about 88 ℃.
Example 16
6800g of terephthalic acid ester, 140g of phthalic acid, 3450g of ethylene glycol and 128g of antimony catalyst ethylene glycol antimony are added into a 20L reaction kettle, after uniform stirring, the temperature is raised to 250 ℃, esterification reaction is carried out under a pressurized condition, the reaction time is 3 hours, the water yield of the esterification reaction is monitored in the reaction process, after the reaction is finished, the temperature is raised to 260 ℃ for condensation prepolymerization reaction, the reaction time is 3 hours, the torque change is monitored in the prepolymerization process, after the reaction is finished (the viscosity of the obtained aromatic prepolymer is 0.46 dL/g., 700g of polycaprolactone slices are added, the temperature is kept in a 265 ℃ molten state, ester exchange reaction is continuously carried out, the reaction time is 3 hours, after the reaction is finished, discharging, cutting into particles and drying are carried out, the test result is shown in table 1, the hydrogen nuclear magnetic spectrum of the copolyester obtained by the method is known, wherein the molar ratio of aromatic group to aliphatic group is about 75:25, meanwhile, as can be seen from the DSC spectrum of the obtained copolyester, the copolyester only has one melting point of about 188 ℃ and is between the melting points of the polyethylene terephthalate and the polycaprolactone homopolymer, which indicates that the two components are in a copolymerization state rather than a blending state, and the crystallization temperature of the copolymer is about 90 ℃.
TABLE 1 Property parameters of the copolyesters obtained in examples 1 to 16
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Moreover, various embodiments or examples and features of various embodiments or examples described in this specification can be combined and combined by one skilled in the art without being mutually inconsistent.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.
Claims (13)
1. A method of preparing a degradable aromatic-aliphatic copolyester material, comprising:
(1) mixing aromatic dibasic acid and dihydric alcohol to carry out esterification reaction so as to obtain an esterification product;
(2) carrying out pre-polycondensation reaction on the esterification product so as to obtain an aromatic prepolymer;
(3) mixing the aromatic prepolymer and aliphatic polyester for transesterification reaction so as to obtain the degradable aromatic-aliphatic copolyester material.
2. The method according to claim 1, wherein in the step (1), the aromatic dibasic acid comprises at least one of terephthalic acid, phthalic acid, isophthalic acid, furandicarboxylic acid, terephthalate, phthalate, isophthalate, furandicarboxylate, 2, 6-naphthalenedicarboxylic acid, and 2, 6-naphthalenedicarboxylate.
3. The method according to claim 1, wherein in step (1), the glycol comprises at least one of ethylene glycol, 1, 3-propanediol, 1, 4-butanediol, and 1, 6-hexanediol.
4. The process according to any one of claims 1 to 3, wherein in step (1), the molar ratio of the aromatic dibasic acid to the glycol is 1: (1.1-2).
5. The method according to claim 4, wherein in the step (1), the aromatic dibasic acid and the diol are mixed under the action of a catalyst to perform esterification, wherein the amount of the catalyst is 1 to 5 percent of the total mass of all raw materials.
6. The method according to claim 1, wherein in the step (1), the temperature of the esterification reaction is 230-260 ℃ and the time is 1-3 h.
7. The method according to claim 1, wherein in step (2), the viscosity of the aromatic prepolymer is 0.3dL/g to 0.5 dL/g.
8. The method according to claim 1 or 7, wherein in the step (2), the temperature of the pre-polycondensation reaction is 260-270 ℃ and the time is 1-3 h.
9. The method of claim 1, wherein in step (3), the aliphatic polyester comprises at least one of lactic acid, glycolic acid, hydroxypropionic acid, hydroxybutyric acid, glycolic acid, butyrolactone, caprolactone, polylactic acid, polyglycolic acid, butyrolactone, and polycaprolactone.
10. The method according to claim 1 or 9, wherein in the step (3), the feeding molar ratio of the aromatic dibasic acid to the aliphatic polyester is (1-99): (1-99).
11. The method according to claim 10, wherein in the step (3), the temperature of the transesterification reaction is 265-275 ℃ and the time is 1-3 h.
12. A degradable aromatic-aliphatic copolyester material, wherein the degradable aromatic-aliphatic copolyester material is prepared by the method of any one of claims 1 to 11.
13. A packaging material prepared from the degradable aromatic-aliphatic copolyester material of claim 12.
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Citations (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59215319A (en) * | 1983-05-24 | 1984-12-05 | Mitsui Petrochem Ind Ltd | Copolyester and its stretching product |
| JP2004285151A (en) * | 2003-03-20 | 2004-10-14 | Toray Ind Inc | Polylactic acid block copolymer, its preparation process, and molded article |
| CN101104680A (en) * | 2007-07-30 | 2008-01-16 | 南昌大学 | Method for preparing degradable copolyester by trinary reactivity blending |
| CN101412804A (en) * | 2008-11-23 | 2009-04-22 | 浙江大学宁波理工学院 | Method for preparing aromatic-aliphatic copolyester |
| CN101684175A (en) * | 2008-09-22 | 2010-03-31 | 中国科学院宁波材料技术与工程研究所 | Biodegradable multi-block polyester copolymer and method for preparing same |
| CN101684173A (en) * | 2008-09-22 | 2010-03-31 | 中国科学院宁波材料技术与工程研究所 | Biodegradable copolyester and method for preparing same |
| CN101717494A (en) * | 2009-11-23 | 2010-06-02 | 中国科学院宁波材料技术与工程研究所 | Biodegradable aromatic-aliphatic copolyester and preparation method thereof |
| CN102485765A (en) * | 2010-12-02 | 2012-06-06 | 上海杰事杰新材料(集团)股份有限公司 | Aliphatic/aromatic copolyester and preparation method thereof |
| CN102718955A (en) * | 2012-07-03 | 2012-10-10 | 常州大学 | Poly(terephthalate glycol ester-CO-glycolate) copolyester and preparation method thereof |
| US20130053461A1 (en) * | 2011-08-30 | 2013-02-28 | Sabic Innovative Plastics Ip B.V. | Method for the preparation of (polybutylene-co-adipate terephthalate) through the in situ phosphorus containing titanium based catalyst |
| US20140148514A1 (en) * | 2012-03-01 | 2014-05-29 | Sabic Innovative Plastics | Poly(alkylene co-adipate terephthalate) prepared from recycled polyethylene terephthalate having low impurity levels |
| CN103980468A (en) * | 2014-06-06 | 2014-08-13 | 南京工业大学 | Furan dicarboxylic acid-lactic acid-diol copolymer and preparation method thereof |
| CN104341585A (en) * | 2014-05-13 | 2015-02-11 | 浙江大学 | Triblock copolymer using furandicarboxylic acid flexible random copolyester as soft block and preparation method thereof |
| KR20150017797A (en) * | 2013-08-07 | 2015-02-23 | 주식회사 휴비스 | Eco-friendly Copolyester Resin and Process of Preparing Same |
| CN111393620A (en) * | 2020-04-22 | 2020-07-10 | 浙江恒澜科技有限公司 | Preparation method of degradable polytrimethylene terephthalate copolyester |
-
2021
- 2021-03-26 CN CN202110330774.0A patent/CN115124699A/en active Pending
Patent Citations (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59215319A (en) * | 1983-05-24 | 1984-12-05 | Mitsui Petrochem Ind Ltd | Copolyester and its stretching product |
| JP2004285151A (en) * | 2003-03-20 | 2004-10-14 | Toray Ind Inc | Polylactic acid block copolymer, its preparation process, and molded article |
| CN101104680A (en) * | 2007-07-30 | 2008-01-16 | 南昌大学 | Method for preparing degradable copolyester by trinary reactivity blending |
| CN101684175A (en) * | 2008-09-22 | 2010-03-31 | 中国科学院宁波材料技术与工程研究所 | Biodegradable multi-block polyester copolymer and method for preparing same |
| CN101684173A (en) * | 2008-09-22 | 2010-03-31 | 中国科学院宁波材料技术与工程研究所 | Biodegradable copolyester and method for preparing same |
| CN101412804A (en) * | 2008-11-23 | 2009-04-22 | 浙江大学宁波理工学院 | Method for preparing aromatic-aliphatic copolyester |
| CN101717494A (en) * | 2009-11-23 | 2010-06-02 | 中国科学院宁波材料技术与工程研究所 | Biodegradable aromatic-aliphatic copolyester and preparation method thereof |
| CN102485765A (en) * | 2010-12-02 | 2012-06-06 | 上海杰事杰新材料(集团)股份有限公司 | Aliphatic/aromatic copolyester and preparation method thereof |
| US20130053461A1 (en) * | 2011-08-30 | 2013-02-28 | Sabic Innovative Plastics Ip B.V. | Method for the preparation of (polybutylene-co-adipate terephthalate) through the in situ phosphorus containing titanium based catalyst |
| US20140148514A1 (en) * | 2012-03-01 | 2014-05-29 | Sabic Innovative Plastics | Poly(alkylene co-adipate terephthalate) prepared from recycled polyethylene terephthalate having low impurity levels |
| CN102718955A (en) * | 2012-07-03 | 2012-10-10 | 常州大学 | Poly(terephthalate glycol ester-CO-glycolate) copolyester and preparation method thereof |
| KR20150017797A (en) * | 2013-08-07 | 2015-02-23 | 주식회사 휴비스 | Eco-friendly Copolyester Resin and Process of Preparing Same |
| CN104341585A (en) * | 2014-05-13 | 2015-02-11 | 浙江大学 | Triblock copolymer using furandicarboxylic acid flexible random copolyester as soft block and preparation method thereof |
| CN103980468A (en) * | 2014-06-06 | 2014-08-13 | 南京工业大学 | Furan dicarboxylic acid-lactic acid-diol copolymer and preparation method thereof |
| CN111393620A (en) * | 2020-04-22 | 2020-07-10 | 浙江恒澜科技有限公司 | Preparation method of degradable polytrimethylene terephthalate copolyester |
Non-Patent Citations (3)
| Title |
|---|
| 冯凯;谢晖;曹祥薇;王晓艳;: "可生物降解脂肪族-芳香族共聚酯的研究进展", 塑料助剂, no. 05 * |
| 巫民建;苏吉英;陈义旺;贺晓慧;周魏华;: "由环己烷二甲醇和低聚乳酸制备脂肪/芳香共聚酯", 应用化学, no. 07 * |
| 祝桂香;陈伟;黄凤兴;吴保军;陈锡荣;张伟;: "生物可降解脂肪族-芳香族共聚酯的研究进展", 石油化工, no. 10 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114805779A (en) * | 2022-05-05 | 2022-07-29 | 浙江大学 | Method for synthesizing aromatic-aliphatic copolyester from aromatic polyester and product thereof |
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