Search

CN-121975102-A - PBAT hydrolysis-resistant photodegradation-resistant macromolecular auxiliary agent

CN121975102ACN 121975102 ACN121975102 ACN 121975102ACN-121975102-A

Abstract

The application relates to the field of polymer material chemistry, and particularly discloses a PBAT hydrolysis-resistant photodegradation-resistant macromolecular auxiliary agent. The PBAT hydrolysis-resistant photodegradation-resistant macromolecular auxiliary agent is prepared from the following raw materials, by weight, 100 parts of a main chain monomer mixture, 60-78 parts of a hydrolysis-resistant side chain monomer, 40-56 parts of a photodegradation-resistant side chain monomer, 0.5-2 parts of an initiator, 0.1-1 part of a catalyst, and 1-5 parts of a terminal blocking agent, wherein the preparation method comprises the steps of S1, synthesizing a main chain prepolymer, S2, grafting a functional side chain, S3, blocking a terminal, namely adding the terminal blocking agent into an obtained grafted copolymer, and then precipitating, filtering and drying to obtain the macromolecular auxiliary agent. The PBAT hydrolysis-resistant photodegradation-resistant macromolecular auxiliary agent can be used for producing PBAT products such as agricultural mulching films, food packaging bags, degradable shopping bags and the like, and has the advantages of lasting hydrolysis-resistant and photodegradation-resistant functions.

Inventors

  • ZHANG JING
  • LI JUAN
  • HUANG SHAOWEN
  • DUAN LI

Assignees

  • 贵州省材料产业技术研究院

Dates

Publication Date
20260505
Application Date
20260228

Claims (10)

  1. 1. The PBAT hydrolysis-resistant photodegradation-resistant macromolecular auxiliary agent is characterized by comprising, by weight, 100 parts of a main chain monomer mixture, 60-78 parts of a photodegradation-resistant side chain monomer, 40-56 parts of an initiator, 0.5-2 parts of a catalyst, 0.1-1 part of a terminal group blocking agent and 1-5 parts of a main chain monomer mixture, wherein the main chain monomer mixture consists of adipic acid, terephthalic acid, 1, 4-butanediol and a polyethylene glycol-polypropylene glycol block copolymer according to a molar ratio of 1:1:1.8:0.2, the photodegradation-resistant side chain monomer comprises alkoxysilane and hindered amine, and the photodegradation-resistant side chain monomer comprises benzophenone or phosphite compounds.
  2. 2. The PBAT hydrolysis-resistant and photodegradation-resistant macromolecular auxiliary agent according to claim 1, wherein the weight ratio of alkoxysilane to hindered amine in the hydrolysis-resistant side chain monomer is 2:1-3, the chain segment molar ratio of polyethylene glycol to polypropylene glycol in the polyethylene glycol-polypropylene glycol block copolymer is 1:2, and the number average molecular weight is 1800-2200g/mol.
  3. 3. The PBAT hydrolysis-resistant photodegradation-resistant macromolecular auxiliary agent according to claim 1, wherein the alkoxysilane is gamma-methacryloxypropyl trimethoxysilane, the hindered amine is 2, 6-tetramethylpiperidinol, the benzophenone is 4-hydroxybenzophenone or a methacrylate derivative thereof, and the phosphite is tris (2, 4-di-t-butylphenyl) phosphite.
  4. 4. The PBAT hydrolysis-resistant photodegradation-resistant macromolecular auxiliary agent according to claim 1, wherein the initiator is ethyl alpha-bromoisobutyrate, and the catalyst is a complex of cuprous bromide and N, N, N ', N ' ', N ' ' -pentamethyldiethylenetriamine.
  5. 5. The PBAT hydrolysis-resistant photodegradation-resistant macromolecular auxiliary agent according to claim 1, wherein said end group blocking agent is acetic anhydride or benzoyl chloride.
  6. 6. The PBAT hydrolysis-resistant photodegradation-resistant macromolecular auxiliary agent according to claim 1, wherein the macromolecular auxiliary agent has a number average molecular weight of 10000-15000 g/mol and a terminal group is a blocked ester group or acyl group.
  7. 7. The PBAT hydrolysis-resistant and photodegradation-resistant macromolecular auxiliary agent according to claim 1, further comprising a hydrophobic siloxane segment, wherein the hydrophobic siloxane segment is polydimethylsiloxane, the number average molecular weight is 400-600 g/mol, and the addition amount is 5-10% of the total weight of the hydrolysis-resistant side chain monomers.
  8. 8. A method for preparing a PBAT hydrolysis-resistant photodegradation-resistant macromolecular auxiliary agent, which is characterized by being used for the PBAT hydrolysis-resistant photodegradation-resistant macromolecular auxiliary agent according to any one of claims 1 to 7, and comprising the following steps: S1, synthesizing a main chain prepolymer, namely mixing adipic acid, terephthalic acid, 1, 4-butanediol and a polyethylene glycol-polypropylene glycol segmented copolymer, carrying out esterification reaction for 2-3 hours at 180-200 ℃ under the protection of nitrogen, then heating to 220-240 ℃, and carrying out polycondensation reaction for 4-5 hours under the condition that the pressure is less than 100Pa to obtain the main chain prepolymer containing hydroxyl end groups; S2, functional side chain grafting, namely dissolving the main chain prepolymer obtained in the step S1 in toluene, adding an initiator and a catalyst, and then dropwise adding a water-resistant Jie Celian monomer and a photodegradation-resistant side chain monomer for polymerization reaction to obtain a graft copolymer; s3, end group blocking, namely adding an end group blocking agent into the graft copolymer obtained in the step S2, reacting for 1-2 hours at 60-80 ℃, and then precipitating, filtering and drying to obtain the macromolecular auxiliary agent.
  9. 9. The preparation method of the PBAT hydrolysis-resistant and photodegradation-resistant macromolecular auxiliary agent according to claim 8, wherein in the step S2, the polymerization reaction temperature is 75-85 ℃ and the time is 7-8 hours, and a chain transfer agent is also added, wherein the chain transfer agent is dodecyl mercaptan, and the addition amount is 0.1-0.5% of the total weight of hydrolysis-resistant side chain monomers.
  10. 10. The preparation method of the PBAT hydrolysis-resistant photodegradation-resistant macromolecular auxiliary agent according to claim 8, wherein in the step S3, the solvent used for precipitation is methanol or ethanol, the drying temperature is 40-60 ℃, and the drying time is 4-6 hours.

Description

PBAT hydrolysis-resistant photodegradation-resistant macromolecular auxiliary agent Technical Field The application relates to the technical field of polymer material chemistry, in particular to a PBAT hydrolysis-resistant photodegradation-resistant macromolecular auxiliary agent. Background In the production process of PBAT related products, a small molecular hydrolysis inhibitor and a light stabilizer are generally introduced into a polymer matrix in a physical blending mode to enhance the durability of materials, and the method involves mechanically mixing an auxiliary agent with PBAT resin in a processing stage (such as melt extrusion or banburying) to ensure uniform dispersion, so that the hydrolysis inhibitor can inhibit a degradation reaction induced by moisture, and the light stabilizer can absorb or scatter ultraviolet radiation to effectively improve the long-term stability of the product in a damp-heat or illumination environment. Related PBAT related products usually introduce small molecule hydrolysis resistance agents and light stabilizers in a physical blending manner to improve the durability of the products, but due to poor compatibility and lack of firm chemical bonding between the small molecule auxiliary agents and a PBAT matrix, migration and precipitation easily occur in the processing or using process, so that the products cannot provide durable and effective protection for PBAT products in the environments of damp heat, ultraviolet irradiation and the like. Disclosure of Invention In order to solve the problem that a related PBAT related product cannot provide durable and effective protection for a PBAT product in the environments of damp heat, ultraviolet irradiation and the like due to the fact that a small-molecule hydrolysis-resistant agent and a light stabilizer are generally introduced in a physical blending mode to improve the durability of the related PBAT related product, the application provides a PBAT hydrolysis-resistant photodegradation-resistant macromolecular auxiliary agent. In a first aspect, the application provides a PBAT hydrolysis-resistant photodegradation-resistant macromolecular auxiliary agent, which adopts the following technical scheme: The PBAT hydrolysis-resistant photodegradation-resistant macromolecular auxiliary agent is prepared from the following raw materials, by weight, 100 parts of a main chain monomer mixture, 60-78 parts of a hydrolysis-resistant side chain monomer, 40-56 parts of a photodegradation-resistant side chain monomer, 0.5-2 parts of an initiator, 0.1-1 part of a catalyst and 1-5 parts of a terminal blocking agent, wherein the main chain monomer mixture consists of adipic acid, terephthalic acid, 1, 4-butanediol and a polyethylene glycol-polypropylene glycol segmented copolymer according to a molar ratio of 1:1:1.8:0.2, the hydrolysis-resistant side chain monomer comprises alkoxysilane and hindered amine, and the photodegradation-resistant side chain monomer comprises benzophenone or phosphite compounds. By adopting the technical scheme, adipic acid, terephthalic acid and butanediol which are combined according to a certain molar ratio form a main chain structure similar to a PBAT matrix, a foundation is provided for subsequent compatibility, simultaneously, an introduced polyethylene glycol-polypropylene glycol segmented copolymer chain segment provides flexibility and a reaction site, an anti-water Jie Celian monomer and an anti-photodegradation side chain monomer are respectively introduced onto the main chain through subsequent graft polymerization reaction, wherein silanol groups formed after alkoxy silane hydrolysis can be crosslinked to form a hydrophobic protective layer, hindered amine can capture acidic substances generated by hydrolysis, the two synergistic effects inhibit ester bond rupture, the synergistic mechanism can improve the hydrolysis resistance of the material, benzophenone compounds absorb ultraviolet light and convert the ultraviolet light into harmless heat energy, phosphite compounds serve as a hydroperoxide decomposer, the photo-oxidative degradation process of the polymer is delayed, and simultaneously, the use amount of an initiator and a catalyst ensures that the graft polymerization reaction has controllable activity characteristics, and an end blocking agent eliminates unstable terminal functional groups through end blocking reaction, so that the thermal stability of a macromolecular auxiliary agent is improved. Preferably, in the hydrolysis-resistant side chain monomer, the weight ratio of the alkoxy silane to the hindered amine is 2:1-3, and in the polyethylene glycol-polypropylene glycol segmented copolymer, the chain segment molar ratio of the polyethylene glycol to the polypropylene glycol is 1:2, and the number average molecular weight is 1800-2200g/mol. By adopting the technical scheme, the weight ratio of the alkoxy silane to the hindered amine is controlled, the compact siloxane network is forme