CN115124705A

CN115124705A - Degradable copolyester material and preparation method and application thereof

Info

Publication number: CN115124705A
Application number: CN202110330700.7A
Authority: CN
Inventors: 许越超; 潘斐; 姚杰; 袁翔
Original assignee: CR Chemical Materials Technology Inc
Current assignee: CR Chemical Materials Technology Inc
Priority date: 2021-03-26
Filing date: 2021-03-26
Publication date: 2022-09-30

Abstract

The invention discloses a degradable copolyester material and a preparation method and application thereof, wherein the method comprises the following steps: (1) mixing aromatic dibasic acid, dihydric alcohol and a catalyst for esterification reaction to obtain an esterification product; (2) and mixing the esterification product with itaconic acid, polyether and a polymerization inhibitor to carry out pre-polycondensation reaction, so as to obtain the degradable copolyester material. The method ensures that the finally obtained material has excellent mechanical property and thermal property, introduces itaconic acid containing unsaturated double bonds into aliphatic polyester, and also introduces polyether, so that the biodegradability of copolyester is obviously improved, unsaturated double bonds with reaction activity are reserved in the molecular chain of the copolyester, the copolyester material can further carry out crosslinking reaction and functional reaction, the crosslinking copolyester and the functional copolyester material are prepared, the types and functions of the copolyester are greatly enriched, the added value of the final product is improved, and the application field of the material is expanded.

Description

Degradable copolyester material and preparation method and application thereof

Technical Field

The invention belongs to the field of degradable materials, and particularly relates to a degradable copolyester material and a preparation method and application thereof.

Background

Since the invention of high polymer materials, due to excellent properties and light weight, the high polymer materials can be widely used in various fields such as production and living of people, statistics show that people have produced nearly billions of tons of high polymer materials, but most of the materials are non-degradable materials, can exist in natural environment for hundreds or thousands of years, and cause serious pollution to the natural environment along with the increase of high polymer waste, so that the development of the high polymer materials with biodegradability has great significance for solving the pollution of plastic waste.

Currently, there are dozens of degradable plastics developed globally, wherein the degradable plastics capable of being industrially produced mainly include chemically synthesized poly (butylene adipate/terephthalate) (PBAT), poly (lactic 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. But due to the similar molecular structure, the biodegradable material still has the defects of insufficient mechanical property, common thermal property, high raw material cost, harsh degradation process and the like in practical application and production. Therefore, the development of degradable materials with controllable degradation and mild conditions is imperative.

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 object of the present invention is to provide a degradable copolyester material, a preparation method and an application thereof, wherein an aliphatic polyester unit is inserted into a polymer chain by a copolymerization modification method, such that mechanical properties and thermal properties of the finally obtained material are excellent, itaconic acid containing unsaturated double bonds is introduced into aliphatic polyester, and polyether is also introduced, such that biodegradable properties of copolyester are significantly improved, and unsaturated double bonds having reactivity are retained in a molecular chain of the copolyester, such that the copolyester material can further undergo a crosslinking reaction and a functionalization reaction, such that the crosslinked copolyester and the functionalized copolyester material are prepared, such that types and functions of copolyester are greatly enriched, additional values of the final product are improved, and application fields of the material are expanded.

In one aspect of the present invention, a method of preparing a degradable copolyester material is provided. According to an embodiment of the invention, the method comprises:

(1) mixing aromatic dibasic acid, dihydric alcohol and a catalyst for esterification reaction to obtain an esterification product;

(2) and mixing the esterification product with itaconic acid, polyether and a polymerization inhibitor to carry out pre-polycondensation reaction, so as to obtain the degradable copolyester material.

According to the method for preparing the degradable copolyester material, the aromatic dibasic acid, the dihydric alcohol and the catalyst 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, then the esterification product is mixed with the itaconic acid, the polyether and the polymerization inhibitor for pre-polycondensation reaction, namely, the aliphatic polyester unit is randomly inserted into a polymer chain by a copolymerization modification method, the mechanical property and the thermal property of the finally obtained material are excellent because the chain segment of the aromatic polyester contains a rigid benzene ring structure, the itaconic acid containing unsaturated double bonds is introduced into the aliphatic polyester, the unsaturated double bonds and ortho carbonyl groups form a conjugated structure, so that the degradation property of the copolyester is improved, the polyether is also introduced, and the biodegradable property of the copolyester is further improved, and unsaturated double bonds with reactivity are reserved in the molecular chain of the copolyester, so that the copolyester material can further perform crosslinking reaction and functional reaction to prepare the crosslinked copolyester and the functional copolyester material, the types and functions of the copolyester are greatly enriched, the additional value of a final product is improved, and the application field of the material is expanded.

In addition, the method for preparing the degradable copolyester material according to the above embodiment of the invention may also 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, diphenic acid, phthalic acid, isophthalic acid, furandicarboxylic acid, terephthalate, phthalate, bibenzoate, isophthalate, furandicarboxylate, 2, 6-naphthalenedicarboxylic acid, and 2, 6-naphthalenedicarboxylate, preferably terephthalic 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: (1.2-1.6).

In some embodiments of the invention, in step (1), the amount of the catalyst is 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 240-260 ℃ and the time is 2-3 h.

In some embodiments of the present invention, in the step (2), the addition amount of the itaconic acid is 0.5 to 10%, preferably 1 to 5% of the total mass of all raw materials. Thus, the cross-linked copolyester and the functionalized copolyester material can be prepared.

In some embodiments of the invention, in the step (2), the amount of the polymerization inhibitor added is 0.01-1% of the mass of the itaconic acid. Thus, the double bond addition reaction in the polymer can be effectively suppressed.

In some embodiments of the invention, the polymerization inhibitor comprises at least one of hydroquinone, p-benzoquinone, bishydroxyanisole, diethylhydroxylamine, o-nitrophenol, 2-tert-butylhydroquinone, 2, 4-dinitrophenol, and N, N' -di-sec-phenylenediamine, preferably o-nitrophenol. Thus, the double bond addition reaction in the polymer can be effectively suppressed.

In some embodiments of the present invention, in the step (2), the polyether is added in an amount of 0.2 to 2 times the mass of the glycol. Therefore, the biodegradability of the copolyester material can be improved.

In some embodiments of the invention, the polyether comprises at least one of polyethylene glycol, polypropylene glycol, polybutylene glycol, polypentylene glycol, and polyhexamethylene glycol. Therefore, the biodegradability of the copolyester material can be improved.

In some embodiments of the present invention, in step (2), the viscosity of the degradable copolyester material is 0.4dL/g to 0.6 dL/g.

In a second aspect of the present invention, a degradable copolyester material is provided. According to the embodiment of the invention, the degradable copolyester material is prepared by the method. Therefore, the degradable material realizes the organic combination of the degradation performance of the polyether and the itaconic acid and the excellent comprehensive performance of the aromatic polyester, has the advantages of high performance and low cost, and keeps unsaturated double bonds with reaction activity in a molecular chain of the copolyester, so that the copolyester material can further carry out crosslinking reaction and functional reaction to prepare the crosslinked copolyester and the functional copolyester material, thereby greatly enriching the types and functions of the copolyester, improving the added value of final products and expanding the application field of the material.

In a third aspect of the present invention, a packaging material is presented. According to an embodiment of the invention, the packaging material is prepared from the degradable copolyester material. Therefore, by adopting the degradable material with the advantages of high performance and low cost to prepare the packaging material, the performance of the packaging material can be improved, the cost of the packaging material can be reduced, and the packaging 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 chart of a method for preparing a degradable copolyester material according to an embodiment of the invention.

Detailed Description

The following detailed description of the embodiments of the 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 copolyester material is provided. According to an embodiment of the invention, with reference to fig. 1, the method comprises:

s100: mixing aromatic dibasic acid, dihydric alcohol and catalyst for esterification

In the step, aromatic dibasic acid, dihydric alcohol and a catalyst are mixed for esterification reaction, the mixture is stirred for reaction for 2-3 hours at the temperature of 240-260 ℃ to obtain an esterification product, and water as a byproduct is removed, wherein the aromatic dibasic acid comprises at least one of terephthalic acid, diphenyldicarboxylic acid, phthalic acid, isophthalic acid, furandicarboxylic acid, terephthalic acid ester, phthalic acid ester, biphenyldicarboxylic acid ester, isophthalic acid ester, furandicarboxylic acid ester, 2, 6-naphthalenedicarboxylic acid and 2, 6-naphthalenedicarboxylic acid, preferably terephthalic acid, and the aromatic polyester has a rigid benzene ring structure in a chain segment, so that the mechanical property and the thermal property of the material are excellent, and meanwhile, the aromatic dibasic acid material is low in cost, cheap and easily available in raw materials and is not limited by suppliers. 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: (1.2-1.6). 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 amount of the catalyst is 1-3% of the total mass of all raw materials, and the catalyst includes but is not limited to at least one of antimony-based catalyst, titanium-based catalyst and tin-based catalyst. It is to be noted that "all raw materials" in the present application include aromatic dibasic acids, glycols, itaconic acid, polyethers, and polymerization inhibitors.

S200: mixing the esterification product with itaconic acid, polyether and polymerization inhibitor to carry out pre-polycondensation reaction

In the step, the obtained esterification product is mixed with itaconic acid, polyether and a polymerization inhibitor, the reaction temperature is slowly raised to 260-270 ℃ for pre-polycondensation reaction for 2-3 h to obtain a degradable copolyester material with the viscosity of 0.4-0.6 dL/g, after the reaction is finished, the degradable copolyester material is cooled to room temperature, the obtained copolyester is dissolved in a small amount of dichloromethane to obtain a clear and transparent polymer solution, and the polymer solution is poured into a large amount of methanol for precipitation, filtration and drying to obtain the final copolyester material. The inventor finds that itaconic acid containing unsaturated double bond is introduced into aliphatic polyester, the unsaturated double bond and ortho carbonyl form a conjugated structure, so that the degradation performance of copolyester is improved, meanwhile, polyether is introduced to further improve the biodegradability of the copolyester, but because the double bond of the itaconic acid has certain self-polymerization activity at high temperature, a polymerization inhibitor is added to inhibit the double bond addition reaction so as to keep the double bond, therefore, the polymerization inhibitor is added to avoid unnecessary reaction, so that unsaturated double bonds with reaction activity are reserved in the molecular chain of the final copolyester, the copolyester material can further generate crosslinking reaction and functionalization reaction to prepare the crosslinked copolyester and the functionalized copolyester material, so that the variety and the function of the copolyester are greatly enriched, the additional value of a final product is improved, and the application field of the material is expanded.

Further, the addition amount of the itaconic acid accounts for 0.5-10%, preferably 1-5% of the total mass of all raw materials. The inventor finds that when the addition amount of itaconic acid is too large, itaconic acid is easily self-polymerized in the polymerization process, so that a large amount of double bond addition byproducts are generated, and the selectivity and the yield of the final target copolyester are influenced; and when the itaconic acid is added too little, the itaconic acid has no obvious effect and can not play an effective degradation role. Meanwhile, the adding amount of the polymerization inhibitor is 0.01-1% of the mass of the itaconic acid, and is preferably 0.1%, wherein the polymerization inhibitor comprises but is not limited to at least one of hydroquinone, p-benzoquinone, dihydroxy anisole, diethyl hydroxylamine, o-nitrophenol, 2-tert-butyl hydroquinone, 2, 4-dinitrophenol and N, N' -di-sec-butyl phenylenediamine, and is preferably o-nitrophenol. Meanwhile, the addition amount of the polyether is 0.2-2 times, preferably 0.5 times of the mass of the dihydric alcohol. The inventor finds that if the addition amount of the polyether is too much, the glass transition temperature of the final copolyester is greatly reduced, and the requirements of application scenes cannot be met; if the addition amount of the polyether is too small, the hydrophilicity is not improved enough to promote the degradation capability of the copolyester, and the synergistic effect with the degradation function of the itaconic acid cannot be generated. Wherein the polyether includes, but is not limited to, at least one of polyethylene glycol, polypropylene glycol, polybutylene glycol, polypentylene glycol, and polyhexamethylene glycol. The inventor finds that the polyether has excellent hydrophilicity and excellent flexibility, so that the molecular chain of the copolyester has better flexibility, the processing formability of the copolyester is good, and products with different shapes can be developed conveniently.

In a second aspect of the present invention, a degradable copolyester material is provided. According to the embodiment of the invention, the degradable copolyester material is prepared by adopting the method. Therefore, the degradable material realizes the organic combination of the degradation performance of the polyether and the itaconic acid and the excellent comprehensive performance of the aromatic polyester, has the advantages of high performance and low cost, and the molecular chain of the copolyester keeps unsaturated double bonds with reaction activity, so that the copolyester material can further carry out crosslinking reaction and functional reaction to prepare the crosslinked copolyester and the functional copolyester material, thereby greatly enriching the variety and the function of the copolyester, improving the added value of the final product and expanding the application field of the material. It should be noted that the features and advantages described above for the method of preparing a degradable copolyester material are also applicable to the degradable 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 invention, the packaging material is prepared from the degradable 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 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 those 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) and 128g of antimony catalyst antimony acetate into a 20L reaction kettle, uniformly stirring, 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, releasing the pressure to atmospheric pressure, opening the kettle, adding 150g of itaconic acid, 1200g of polyethylene glycol and 0.15g of o-nitrophenol, then heating to 270 ℃ for condensation prepolymerization reaction, wherein the reaction time is 3 hours, monitoring the torque change in the polymerization process, discharging, dissolving, precipitating, filtering and drying after the reaction is finished to obtain the final copolyester material, and the test results are shown in Table 1.

Example 2

Adding 4922g of terephthalic acid (PTA), 2467g of Ethylene Glycol (EG) and 128g of antimony catalyst antimony acetate into a 20L reaction kettle, uniformly stirring, 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, releasing the pressure to atmospheric pressure, opening the kettle, adding 225g of itaconic acid, 1200g of polyethylene glycol and 0.22g of o-nitrophenol, then heating to 270 ℃ for condensation prepolymerization reaction, wherein the reaction time is 3 hours, monitoring the torque change in the polymerization process, discharging, dissolving, precipitating, filtering and drying after the reaction is finished to obtain the final copolyester material, and the test results are shown in Table 1.

Example 3

Adding 4922g of terephthalic acid (PTA), 2467g of Ethylene Glycol (EG) and 128g of antimony catalyst antimony acetate into a 20L reaction kettle, uniformly stirring, heating to 260 ℃, carrying out esterification reaction under a pressurized condition, carrying out reaction for 3 hours, monitoring the water yield of the esterification reaction in the reaction process, releasing the pressure to atmospheric pressure after the reaction is finished, opening the kettle, adding 300g of itaconic acid, 1200g of polyethylene glycol and 0.3g of o-nitrophenol, then heating to 270 ℃ for condensation prepolymerization reaction, carrying out reaction for 3 hours, monitoring torque change in the polymerization process, discharging, dissolving, precipitating, filtering and drying after the reaction is finished, thus obtaining the final copolyester material, wherein the test results are shown in Table 1.

Example 4

4922g of terephthalic acid (PTA), 2467g of Ethylene Glycol (EG) and 128g of antimony acetate serving as an antimony catalyst are added into a 20L reaction kettle, the mixture is stirred uniformly and then heated to 260 ℃ for esterification reaction under the pressure condition, and the reaction time is 3 hours. Monitoring the water yield of the esterification reaction in the reaction process, after the reaction is finished, releasing the pressure to atmospheric pressure, opening the kettle, adding 370g of itaconic acid, 1200g of polyethylene glycol and 0.37g of o-nitrophenol, then raising the temperature to 270 ℃ for condensation prepolymerization reaction, wherein the reaction time is 3 hours, the torque change is monitored in the polymerization process, and after the reaction is finished, discharging, dissolving, precipitating, filtering and drying are carried out to obtain the final copolyester material, and the test results are shown in table 1.

Example 5

8200g of biphenyldicarboxylate, 3200g of 1, 3-propanediol and 180g of titanium catalyst butyl titanate are added into a 20L reaction kettle, the mixture is uniformly stirred and then heated to 260 ℃ for esterification reaction under the pressure condition, and the reaction time is 3 hours. Monitoring the water yield of the esterification reaction in the reaction process, after the reaction is finished, releasing the pressure to atmospheric pressure, opening the kettle, adding 370g of itaconic acid, 1200g of polyethylene glycol and 0.5g of dihydroxy anisole, then raising the temperature to 270 ℃ for condensation prepolymerization reaction, monitoring the torque change in the polymerization process for 3 hours, discharging, dissolving, precipitating, filtering and drying after the reaction is finished, thus obtaining the final copolyester material, wherein the test results are shown in Table 1.

Example 6

8200g of biphenyldicarboxylate, 4000g of 1, 4-butanediol and 240g of tin catalyst stannous octoate are added into a 20L reaction kettle, the temperature is raised to 260 ℃ after uniform stirring, 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 pressure is relieved to atmospheric pressure, 370g of itaconic acid, 1200g of polyethylene glycol and 0.6g of N, N' -di-sec-butylbenzene diamine are added into the kettle, then the temperature is raised to 270 ℃ for condensation prepolymerization reaction, the reaction time is 3 hours, torque change is monitored in the polymerization process, and after the reaction is finished, discharging, dissolving, precipitating, filtering and drying are carried out to obtain the final copolyester material, wherein the test results are shown in Table 1.

Example 7

8200g of biphenyldicarboxylate, 4000g of 1, 4-butanediol and 240g of antimony catalyst ethylene glycol antimony are added into a 20L reaction kettle, the mixture is uniformly stirred and then heated to 260 ℃, and esterification reaction is carried out under the pressure condition for 3 hours. Monitoring the water yield of the esterification reaction in the reaction process, after the reaction is finished, releasing the pressure to the atmospheric pressure, opening the kettle, adding 370g of itaconic acid, 1200g of polyethylene glycol and 0.37g of o-nitrophenol, then increasing the temperature to 270 ℃ to carry out condensation prepolymerization reaction, reacting for 3 hours, monitoring torque change in the polymerization process, discharging, dissolving, precipitating, filtering and drying after the reaction is finished to obtain the final copolyester material, wherein the test result is shown in table 1.

Example 8

Adding 5600g of 2, 6-naphthalenedicarboxylic acid, 3450g of ethylene glycol and 240g of antimony catalyst ethylene glycol antimony into a 20L reaction kettle, uniformly stirring, 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, releasing the pressure to atmospheric pressure after the reaction is finished, opening the kettle, adding 370g of itaconic acid, 1200g of polyethylene glycol and 0.37g of o-nitrophenol, then heating to 270 ℃ for condensation prepolymerization reaction, wherein the reaction time is 3 hours, monitoring the torque change in the polymerization process, discharging, dissolving, precipitating, filtering and drying after the reaction is finished to obtain the final copolyester material, and the test results are shown in Table 1.

Example 9

4922g of terephthalic acid (PTA), 2467g of Ethylene Glycol (EG) and 128g of antimony acetate serving as an antimony catalyst are added into a 20L reaction kettle, the mixture is stirred uniformly and then heated to 260 ℃ for esterification reaction under the pressure condition, and the reaction time is 3 hours. Monitoring the water yield of the esterification reaction in the reaction process, after the reaction is finished, releasing the pressure to atmospheric pressure, opening the kettle, adding 740g of itaconic acid, 1200g of polyethylene glycol and 0.37g of o-nitrophenol, then raising the temperature to 270 ℃ for condensation prepolymerization reaction, wherein the reaction time is 3 hours, the torque change is monitored in the polymerization process, and after the reaction is finished, discharging, dissolving, precipitating, filtering and drying are carried out to obtain the final copolyester material, and the test results are shown in table 1.

Example 10

4922g of terephthalic acid (PTA), 2467g of Ethylene Glycol (EG) and 128g of antimony catalyst antimony acetate are added into a 20L reaction kettle, the mixture is stirred uniformly, then the temperature is raised to 260 ℃, and esterification reaction is carried out under the pressure condition, and the reaction time is 3 hours. Monitoring the water yield of the esterification reaction in the reaction process, after the reaction is finished, releasing the pressure to atmospheric pressure, opening the kettle, adding 370g of itaconic acid, 2400g of polyethylene glycol and 0.37g of o-nitrophenol, then raising the temperature to 270 ℃ to carry out condensation prepolymerization reaction, wherein the reaction time is 3 hours, the torque change is monitored in the polymerization process, and after the reaction is finished, discharging, dissolving, precipitating, filtering and drying are carried out to obtain the final copolyester material, and the test result is shown in table 1.

Example 11

Adding 4922g of terephthalic acid (PTA), 4600g of hexanediol (EG) and 128g of antimony acetate serving as an antimony catalyst into a 20L reaction kettle, uniformly stirring, 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, releasing the pressure to atmospheric pressure, opening the kettle, adding 150g of itaconic acid, 1200g of polyethylene glycol and 0.15g of o-nitrophenol, then heating to 270 ℃ for condensation prepolymerization reaction, wherein the reaction time is 3 hours, monitoring the torque change in the polymerization process, discharging, dissolving, precipitating, filtering and drying after the reaction is finished to obtain the final copolyester material, and the test results are shown in Table 1.

Example 12

Adding 4922g of terephthalic acid (PTA), 4600g of hexanediol (EG) and 128g of antimony acetate serving as an antimony catalyst into a 20L reaction kettle, uniformly stirring, 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, releasing the pressure to atmospheric pressure, opening the kettle, adding 300g of itaconic acid, 1200g of polyethylene glycol and 0.15g of o-nitrophenol, then heating to 270 ℃ for condensation prepolymerization reaction, wherein the reaction time is 3 hours, monitoring the torque change in the polymerization process, discharging, dissolving, precipitating, filtering and drying after the reaction is finished to obtain the final copolyester material, and the test results are shown in Table 1.

Example 13

Adding 4922g of terephthalic acid (PTA), 4600g of hexanediol (EG) and 128g of antimony acetate serving as an antimony catalyst into a 20L reaction kettle, uniformly stirring, 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, releasing the pressure to atmospheric pressure, opening the kettle, adding 500g of itaconic acid, 1200g of polyethylene glycol and 0.15g of o-nitrophenol, then heating to 270 ℃ for condensation prepolymerization reaction, wherein the reaction time is 3 hours, monitoring the torque change in the polymerization process, discharging, dissolving, precipitating, filtering and drying after the reaction is finished to obtain the final copolyester material, and the test results are shown in Table 1.

Example 14

8200g of biphenyldicarboxylate, 5800g of hexanediol and 180g of titanium catalyst butyl titanate are added into a 20L reaction kettle, stirred uniformly, heated to 260 ℃ and subjected to esterification reaction under the pressure condition, and the reaction time is 3 hours. Monitoring the water yield of the esterification reaction in the reaction process, after the reaction is finished, releasing the pressure to atmospheric pressure, opening the kettle, adding 740g of itaconic acid, 1200g of polytetramethylene glycol and 0.5g of bis (hydroxyanisole), then raising the temperature to 270 ℃ for condensation prepolymerization reaction, monitoring the torque change in the polymerization process for 3 hours, discharging, dissolving, precipitating, filtering and drying after the reaction is finished, thus obtaining the final copolyester material, wherein the test results are shown in Table 1.

Example 15

8200g of biphenyldicarboxylate, 5800g of hexanediol and 180g of titanium catalyst butyl titanate are added into a 20L reaction kettle, stirred uniformly, heated to 260 ℃ and subjected to esterification reaction under the pressure condition, and the reaction time is 3 hours. Monitoring the water yield of the esterification reaction in the reaction process, after the reaction is finished, releasing the pressure to atmospheric pressure, opening the kettle, adding 740g of itaconic acid, 2400g of polytetramethylene glycol and 0.5g of bis (hydroxyanisole), then raising the temperature to 270 ℃ for condensation prepolymerization reaction, monitoring the torque change in the polymerization process for 3 hours, discharging, dissolving, precipitating, filtering and drying after the reaction is finished, thus obtaining the final copolyester material, wherein the test results are shown in table 1.

Example 16

8200g of biphenyldicarboxylate, 5800g of hexanediol and 180g of titanium catalyst butyl titanate are added into a 20L reaction kettle, stirred uniformly, heated to 260 ℃ and subjected to esterification reaction under the pressure condition, and the reaction time is 3 hours. Monitoring the water yield of the esterification reaction in the reaction process, after the reaction is finished, releasing the pressure to atmospheric pressure, opening the kettle, adding 740g of itaconic acid, 3600g of polytetramethylene glycol and 0.5g of bis (hydroxyanisole), then raising the temperature to 270 ℃ for condensation prepolymerization reaction, wherein the reaction time is 3 hours, the torque change is monitored in the polymerization process, and the final copolyester material is obtained by discharging, dissolving, precipitating, filtering and drying after the reaction is finished, and the test result is shown in table 1.

Example 17

Adding 5600g of 2, 6-naphthalenedicarboxylic acid, 3450g of ethylene glycol and 240g of antimony catalyst ethylene glycol antimony into a 20L reaction kettle, uniformly stirring, heating to 260 ℃, carrying out esterification reaction under a pressurized condition, carrying out reaction for 3 hours, monitoring the water yield of the esterification reaction in the reaction process, releasing the pressure to atmospheric pressure after the reaction is finished, opening the kettle, adding 370g of itaconic acid, 2400g of polytetramethylene glycol and 0.37g of o-nitrophenol, then heating to 270 ℃, carrying out condensation prepolymerization reaction, carrying out reaction for 3 hours, monitoring torque change in the polymerization process, discharging, dissolving, precipitating, filtering and drying after the reaction is finished to obtain a final copolyester material, wherein the test results are shown in Table 1.

Example 18

Adding 5600g of 2, 6-naphthalenedicarboxylic acid, 3450g of ethylene glycol and 240g of antimony catalyst ethylene glycol antimony into a 20L reaction kettle, uniformly stirring, 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, releasing the pressure to atmospheric pressure, opening the kettle, adding 520g of itaconic acid, 2400g of polytetramethylene glycol and 0.37g of o-nitrophenol, then heating to 270 ℃ for condensation prepolymerization reaction, wherein the reaction time is 3 hours, monitoring the torque change in the polymerization process, discharging, dissolving, precipitating, filtering and drying after the reaction is finished to obtain the final copolyester material, and the test results are shown in Table 1.

Comparative example 1 (without polyether)

4922g of terephthalic acid (PTA), 2467g of Ethylene Glycol (EG) and 128g of antimony acetate serving as an antimony catalyst are added into a 20L reaction kettle, the mixture is stirred uniformly and then heated to 260 ℃ for esterification reaction under the pressure condition, and the reaction time is 3 hours. Monitoring the water yield of the esterification reaction in the reaction process, after the reaction is finished, releasing the pressure to the atmospheric pressure, opening the kettle, adding 150g of itaconic acid and 0.15g of o-nitrophenol, then raising the temperature to 270 ℃ for condensation prepolymerization reaction, wherein the reaction time is 3 hours, the torque change is monitored in the polymerization process, and the final copolyester material is obtained after the reaction is finished by discharging, dissolving, precipitating, filtering and drying, and the test results are shown in table 1.

Comparative example 2 (without itaconic acid)

4922g of terephthalic acid (PTA), 2467g of Ethylene Glycol (EG) and 128g of antimony acetate serving as an antimony catalyst are added into a 20L reaction kettle, the mixture is stirred uniformly and then heated to 260 ℃ for esterification reaction under the pressure condition, and the reaction time is 3 hours. Monitoring the water yield of the esterification reaction in the reaction process, after the reaction is finished, releasing the pressure to atmospheric pressure, opening the kettle, adding 1200g of polyethylene glycol, then raising the temperature to 270 ℃ for condensation prepolymerization reaction, wherein the reaction time is 3 hours, the torque change is monitored in the polymerization process, and after the reaction is finished, discharging, dissolving, precipitating, filtering and drying to obtain the final copolyester material, wherein the test results are shown in table 1.

TABLE 1 Property parameters of copolyesters obtained in examples 1 to 18 and comparative examples 1 to 2

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. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.

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

1. A method for preparing a degradable copolyester material, which is characterized by comprising the following steps:

2. The method according to claim 1, wherein in the step (1), the aromatic dibasic acid comprises at least one of terephthalic acid, diphenyldicarboxylic acid, phthalic acid, isophthalic acid, furandicarboxylic acid, terephthalate, phthalate, bibenzoate, 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: (1.2-1.6).

5. The method according to claim 4, wherein in the step (1), the amount of the catalyst is 1 to 3% of the total mass of all the raw materials.

6. The method according to claim 1, wherein in the step (1), the temperature of the esterification reaction is 240-260 ℃ and the time is 2-3 h.

7. The method of claim 1, wherein in the step (2), the addition amount of the itaconic acid is 0.5-10% of the total mass of all raw materials.

8. The method according to claim 1 or 7, characterized in that in the step (2), the addition amount of the polymerization inhibitor is 0.01-1% of the mass of the itaconic acid;

optionally, the polymerization inhibitor comprises at least one of hydroquinone, p-benzoquinone, bishydroxyanisole, diethylhydroxylamine, o-nitrophenol, 2-tert-butylhydroquinone, 2, 4-dinitrophenol, and N, N' -di-sec-butylbenzenediamine.

9. The method according to claim 1, wherein in the step (2), the polyether is added in an amount of 0.2-2 times of the mass of the diol;

optionally, the polyether includes at least one of polyethylene glycol, polypropylene glycol, polybutylene glycol, polypentanediol, and polyhexamethylene glycol.

10. The method according to claim 1, wherein in step (2), the viscosity of the degradable copolyester material is 0.4dL/g to 0.6 dL/g.

11. A degradable copolyester material, wherein the degradable copolyester material is prepared by the method of any one of claims 1 to 10.

12. A packaging material prepared from the degradable copolyester material of claim 11.