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CN-122011356-A - Biodegradable anti-aging agent and preparation method and application thereof

CN122011356ACN 122011356 ACN122011356 ACN 122011356ACN-122011356-A

Abstract

The invention discloses a biodegradable anti-aging agent, a preparation method and application thereof, and belongs to the field of biodegradable high polymer materials. The invention takes dibasic acid, dihydric alcohol and acid compound or ester derivative thereof containing hindered phenol structure as raw materials, prepares macromolecular anti-aging agent through esterification, polycondensation reaction and esterification or transesterification reaction, realizes high dispersibility and migration resistance, and the anti-aging agent is directly mixed with biodegradable resin to be subjected to melt molding such as blow molding film forming, extrusion casting and the like, thereby simplifying the hot working process, reducing the loss of mechanical and ageing resistance of the material, and the phenolic hydroxyl can capture free radicals, remarkably improve the ageing resistance of the biodegradable material and prolong the service life of the material. The anti-aging biodegradable material prepared by the invention can be applied to film products, and is particularly suitable for high-performance degradable mulch films and environment-friendly packaging materials.

Inventors

  • FU YE
  • KANG YUHANG
  • WENG YUNXUAN

Assignees

  • 北京工商大学

Dates

Publication Date
20260512
Application Date
20260303

Claims (10)

  1. 1. A biodegradable anti-aging agent comprises the reaction product of a dibasic acid, a dihydric alcohol and a modifier, wherein the modifier is selected from at least one of acid compounds or ester derivatives thereof with hindered phenol structures.
  2. 2. The biodegradable anti-aging agent according to claim 1, characterized in that, The dibasic acid is at least one selected from aromatic dibasic acid and aliphatic dibasic acid, preferably, the aromatic dibasic acid is terephthalic acid, and/or the aliphatic dibasic acid is at least one selected from succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and sebacic acid, and/or, The dihydric alcohol is at least one selected from aliphatic dihydric alcohol, preferably at least one selected from ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, heptanediol, octanediol, nonanediol, decanediol, and/or, The modifier is selected from at least one of gallic acid, agilawood acid, ferulic acid, sinapic acid, p-coumaric acid, diphenolic acid, p-hydroxyphenylpropionic acid, 3, 5-di-tert-butyl-4-hydroxyphenylacetic acid, 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid or ester derivatives of the above compounds.
  3. 3. A method for producing the biodegradable antioxidant according to claim 1 or 2, comprising the step of reacting a component containing a dibasic acid and a dibasic alcohol with a modifier after an esterification reaction and a polycondensation reaction.
  4. 4. The method for preparing the biodegradable anti-aging agent according to claim 3, characterized in that the method for preparing the biodegradable anti-aging agent specifically comprises the following steps: (1) The components including dibasic acid and dihydric alcohol are subjected to esterification reaction under the action of a catalyst C1; (2) Carrying out polycondensation reaction on the product obtained after the esterification reaction in the step (1) to obtain hydroxyl-terminated copolyester; (3) And (3) reacting the hydroxyl-terminated copolyester obtained in the step (2) with a modifier under the action of a catalyst C2 to obtain the biodegradation anti-aging agent.
  5. 5. The method for preparing a biodegradable anti-aging agent according to claim 4, characterized in that, The molar ratio of the dihydric alcohol to the dibasic acid is (1-2): 1, preferably (1.2-1.6): 1, and/or, The catalyst C1 and the catalyst C2 are the same or different and are independently selected from at least one of titanium-based catalyst, germanium-based catalyst, tin-based catalyst and guanidine-based catalyst, preferably at least one of titanium dioxide, titanate-based catalyst, antimony trioxide, antimony acetate, ethylene glycol antimony, dicyandiamide, creatinine acetate guanidine, glycollic acid creatinine guanidine and dicyandiamide, and/or, The molar amount of the modifier is 0.005 to 2.0mol%, preferably 0.015 to 0.5mol%, based on the total molar amount of the dibasic acid.
  6. 6. The method for preparing a biodegradable anti-aging agent according to claim 4, characterized in that, The esterification reaction is carried out in a protective gas atmosphere at 120-220 ℃ for 1-5 hours and/or, The conditions of the polycondensation reaction are 220-260 ℃, the pressure is less than 50 Pa, the time is 0.2-6 hours, and/or, The reaction in the step (3) is carried out in a protective gas atmosphere at 120-220 ℃ for 0.2-1 h.
  7. 7. An aging-resistant biodegradable material comprising a polymer and an anti-aging agent, wherein the anti-aging agent is the biodegradable anti-aging agent according to claim 1 or 2 or the biodegradable anti-aging agent obtained by the preparation method according to any one of claims 3 to 6.
  8. 8. The aging-resistant biodegradable material according to claim 7, characterized in that, The polymer is selected from at least one of biodegradable aromatic-aliphatic copolyester and biodegradable aliphatic copolyester, preferably at least one of polybutylene terephthalate-adipate, polybutylene terephthalate-succinate, polybutylene succinate-adipate and polybutylene succinate, and/or, The weight percentage of the anti-aging agent is 5-50wt%, preferably 10-30wt%, based on 100wt% of the total weight of the anti-aging biodegradable material.
  9. 9. A method for producing the aging-resistant biodegradable material according to claim 7 or 8, comprising the step of mixing the components including the polymer and the aging inhibitor and then performing melt processing.
  10. 10. The method for preparing an aging-resistant biodegradable material according to claim 9, wherein the temperature of the melt processing is 120-190 ℃.

Description

Biodegradable anti-aging agent and preparation method and application thereof Technical Field The invention belongs to the technical field of biodegradable materials, and particularly relates to a biodegradable anti-aging agent, a preparation method and application thereof. Background The biodegradable material is used for replacing the plastic which is difficult to recycle in a disposable scene to reduce environmental leakage, and is an effective means for preventing and controlling the plastic pollution problem. However, the biodegradable material often has the problem of insufficient ageing resistance, and especially under the complex environmental conditions of continuous sunlight, alternating temperature and humidity and the like, the mechanical strength and the structural integrity of the biodegradable material are easy to be rapidly reduced, and the durability and the reliability of the material function are influenced. At present, the technical method for improving the ageing resistance of the biodegradable material mainly comprises the steps of adding an anti-ageing agent, such as a method for preparing ageing-resistant biodegradable copolyester by adding a cross-linking agent, a catalyst, a stabilizer, an anti-hydrolysis agent and an antioxidant, so that the humidity-heat ageing resistance of the material is obviously improved, and the shelf life of a product is prolonged, a PBAT composite material for an anti-photoaging hydrolysis-resistant agricultural film is disclosed in Chinese patent CN117050481A, wherein a powder chain extender 6902 is adopted to extend the chain while short polymer groups are prevented from being introduced, and the purpose of absorbing water is achieved through water molecule-polyglycerol exchange in zeolite powder. However, the technical means for improving the ageing resistance of the biodegradable copolyester in the above patent are mainly focused on modification processing links, and an anti-ageing agent is added to slow down ageing, but the mechanical properties and long-term durability of the material are often reduced due to compatibility and migration problems, and even potential problems of biological safety and environmental safety exist. Therefore, development of an anti-aging agent which can remarkably improve the aging resistance of biodegradable materials and maintain good mechanical properties is needed, and the materials are popularized and applied on a large scale. Disclosure of Invention Aiming at the defects existing in the prior art, the invention provides a biodegradable anti-aging agent and a preparation method thereof, wherein the macromolecular anti-aging agent with a hindered phenol structure is prepared through esterification reaction, polycondensation reaction and reaction with a modifier (esterification reaction or transesterification reaction), so that the high dispersibility and migration resistance of the anti-aging agent are realized. The invention also aims to provide an anti-aging biodegradable material, which is prepared by directly mixing an anti-aging agent with biodegradable resin for molding and processing, simplifies the hot processing process, has simple production process and can be produced in a large-scale industrialized manner. The aim of the invention is achieved by the following technical scheme: The first aspect of the present invention provides a biodegradable antioxidant comprising a reaction product of a dibasic acid, a dibasic alcohol and a modifier selected from at least one of an acid compound having a hindered phenol structure or an ester derivative thereof. According to the invention, the biodegradable anti-aging agent comprises: the dibasic acid is at least one selected from aromatic dibasic acid and aliphatic dibasic acid, preferably, the aromatic dibasic acid is terephthalic acid, and/or the aliphatic dibasic acid is at least one selected from succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and sebacic acid, and/or, The dihydric alcohol is at least one selected from aliphatic dihydric alcohol, preferably at least one selected from ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, heptanediol, octanediol, nonanediol, decanediol, and/or, The modifier may be a common acid compound with a hindered phenol structure or an ester derivative thereof, preferably the modifier is selected from at least one of gallic acid, agilawood acid, ferulic acid, sinapic acid, p-coumaric acid, diphenolic acid, p-hydroxyphenylpropionic acid, 3, 5-di-tert-butyl-4-hydroxyphenylacetic acid, 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid, or an ester derivative of the above compound, wherein the ester derivative is an esterification product of the above acid compound with a hindered phenol structure and an aliphatic alcohol, preferably an esterification product of the above acid compound with a hindered phenol structure and at least one of methanol, ethanol, propanol, and butan