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CN-121975097-A - Controllable degradation polyglycolic acid copolymer and preparation method thereof

CN121975097ACN 121975097 ACN121975097 ACN 121975097ACN-121975097-A

Abstract

The invention discloses A controllable degradable polyglycolic acid copolymer and A preparation method thereof, which belong to the technical field of intrinsic hydrolytic degradation modification of high molecular compounds and biodegradable polyesters obtained by reactions except carbon-carbon unsaturated bonds, wherein the polyglycolic acid copolymer is A-B or A-B-A or B-A-B block copolymer, the block A is A cyclic ester polymer chain segment, and the block B is A polyglycolic acid chain segment. Ring-opening polymerizing cyclic ester monomer or glycolide, catalyst and initiator to obtain prepolymer, ring-opening polymerizing prepolymer, glycolide or cyclic ester monomer and catalyst to obtain controllable degradable polyglycolic acid copolymer, and purifying and drying. The hydrophobic monomer is introduced to play a role in inhibiting the hydrolytic degradation of polyglycolic acid, the introduced amount of the monomer and the degradation of the hydrophobic chain length regulating material are regulated, the intrinsic modification has no obvious negative effect on the processing property and mechanical property of the polyester material, and the elongation at break of the material is greatly improved.

Inventors

  • WANG YUZHONG
  • OuYang Xueping
  • WU GANG
  • CHEN SILI
  • TIAN GUOQIANG
  • ZHANG JIE

Assignees

  • 四川大学

Dates

Publication Date
20260505
Application Date
20260205

Claims (9)

  1. 1. A controllably degradable polyglycolic acid copolymer, wherein the polyglycolic acid copolymer is an A-B or A-B-A or B-A-B block copolymer, wherein block A is A cyclic ester polymer segment and block B is A polyglycolic acid segment.
  2. 2. A process for the preparation of a controllably degradable polyglycolic acid copolymer according to claim 1, comprising the steps of: step 1, ring-opening polymerization is carried out on a cyclic ester monomer or glycolide, a catalyst and an initiator under the condition of protective atmosphere to obtain a prepolymer, and the prepolymer is purified and dried; step 2, ring-opening polymerizing prepolymer, glycolide or cyclic ester monomer and catalyst under protective atmosphere, and obtaining controllable degradable polyglycolic acid copolymer after full reaction; And 3, purifying and drying the controllably degradable polyglycolic acid copolymer.
  3. 3. The controllably degradable polyglycolic acid copolymer and the preparation method as defined in claim 2, wherein in step1, the initiator comprises a monohydric alcohol or a dihydric alcohol, the monohydric alcohol comprises one of benzyl alcohol, 1-amyl alcohol, 1-octanol and lauryl alcohol, and the dihydric alcohol comprises one of 1, 4-butanediol, 1, 6-hexanediol and ethylene glycol.
  4. 4. The controllably degradable polyglycolic acid copolymer and the preparation method as defined in claim 2, wherein in the step 1, the molar ratio of the initiator to the cyclic ester monomer or glycolide is 1:10-200.
  5. 5. The controllably degradable polyglycolic acid copolymer and the preparation process as defined in claim 2, wherein the cyclic ester monomer comprises one or two or more of glycolide, p-dioxanone, butyrolactone, valerolactone, epsilon-caprolactone, delta-caprolactone, heptolactone, octanolide, decanolide, ethylene glycol brassylate, cyclopentadecanolide.
  6. 6. The controllable degradable polyglycolic acid copolymer and the preparation method as claimed in claim 2, wherein in the step 1, the reaction temperature of the ring-opening polymerization is 80 ℃ to 150 ℃ and the reaction time is 4h to 72 h.
  7. 7. The controllably degradable polyglycolic acid copolymer and the preparation method as defined in claim 2, wherein the catalyst in step 1 and step 2 comprises a metal organic catalyst or an organic base catalyst; the metal organic catalyst comprises one of aluminum isopropoxide, stannous octoate, bismuth subsalicylate, anhydrous zinc acetate, tris (trimethylsilyl) lanthanum amide and zinc isopropoxide; The organic base catalyst comprises one of 1,5, 7-triazabicyclo [4, 0] dec-5-ene, 1, 8-diazabicyclo [5,4,0] undec-7, 7-methyl-1, 5, 7-triazabicyclo [4.4.0] dec-5-ene; In the step 1, the molar ratio of the catalyst to the cyclic ester monomer or glycolide is 1:10-20000; in the step 2, the molar ratio of the catalyst to the glycolide or cyclic ester monomer is 1:10-20000.
  8. 8. The controllable degradable polyglycolic acid copolymer and the preparation method as claimed in claim 2, wherein in the step 2, the reaction temperature of the ring-opening polymerization is 150 ℃ to 230 ℃ and the reaction time is 0.1 to 6 hours.
  9. 9. The controllably degradable polyglycolic acid copolymer and the preparation method as claimed in claim 2, wherein in the step 2, the monomer segments except the glycolic acid segment account for 3% -50% of the total mass of the polyglycolic acid copolymer.

Description

Controllable degradation polyglycolic acid copolymer and preparation method thereof Technical Field The invention belongs to the technical field of intrinsic hydrolytic degradation modification of macromolecular compounds obtained by reactions except carbon-carbon unsaturated bonds and biodegradable polyesters, and particularly relates to a controllable degradable polyglycolic acid copolymer and a preparation method thereof. Background Polyglycolic acid materials have high crystallinity, high thermal stability, extremely high gas barrier properties, and high mechanical strength and rigidity, as well as biodegradability. PGA shows great potential in high temperature and high gas barrier packaging applications due to its diversity and unique properties of synthesis. However, also due to the hydrolyzable nature of polyglycolic acid, it is susceptible to degradation during storage, transport and use for everyday use, resulting in reduced performance and thus affecting the useful life of the product. In order to solve this problem, researchers have mainly used blending and adding hydrolysis-resistant stabilizers, blocking agents, and the like to improve the hydrolysis stability of polyglycolic acid. In the prior art, as CN118344715A, biodegradable polyesters such as polybutylene terephthalate-adipate, polybutylene succinate-adipate and the like and compatilizer are added, so that the hydrolysis resistance of the product is effectively improved, and the shelf life of the product is prolonged. However, polyglycolic acid materials are relatively polar and are difficult to compatibilize with the addition of small amounts of polyester, while the addition of large amounts of blending materials necessarily reduces the strength of the polyglycolic acid-based material. For example, CN114075378B can improve the hydrolysis resistance of polyester and the durability of polyglycolic acid material by adding polycarbodiimide, phosphite ester hydrolysis resistance agent and antioxidant. However, increasing the stability of a material represents a weakening of its degradation properties, and stability and degradation of the material are contradictory. Currently there are few studies on the regulated degradation of polyglycolic acid. Disclosure of Invention It is an object of the present invention to address at least the above problems and/or disadvantages and to provide at least the advantages described below. To achieve these objects and other advantages and in accordance with the purpose of the invention, there is provided A controllably degradable polyglycolic acid copolymer which delays hydrolytic degradation in air, prolongs product shelf life, and simultaneously degrades rapidly in seawater, wherein the polyglycolic acid copolymer is an A-B or A-B-A or B-A-B block copolymer, wherein block A is A cyclic ester polymer segment and block B is A polyglycolic acid segment. A method for preparing a controllably degradable polyglycolic acid copolymer, comprising the steps of: step 1, ring-opening polymerization is carried out on a cyclic ester monomer or glycolide, a catalyst and an initiator under the condition of protective atmosphere to obtain a prepolymer, and the prepolymer is purified and dried; step 2, ring-opening polymerizing prepolymer, glycolide or cyclic ester monomer and catalyst under protective atmosphere, and obtaining controllable degradable polyglycolic acid copolymer after full reaction; And 3, purifying and drying the controllably degradable polyglycolic acid copolymer. Preferably, in the step 1, the initiator comprises monohydric alcohol or dihydric alcohol, the monohydric alcohol comprises one of benzyl alcohol, 1-amyl alcohol, 1-octanol and lauryl alcohol, and the dihydric alcohol comprises one of 1, 4-butanediol, 1, 6-hexanediol and ethylene glycol. Preferably, in the step 1, the molar ratio of the initiator to the cyclic ester monomer or glycolide is 1:10-200. Preferably, the cyclic ester monomer comprises one or two or more of glycolide, p-dioxanone, butyrolactone, valerolactone, epsilon-caprolactone, delta-caprolactone, enantholactone, octanolactone, decalactone, ethylene glycol brassylate and cyclopentadecanolide. Preferably, in the step 1, the reaction temperature of the ring-opening polymerization is 80 ℃ to 150 ℃ and the reaction time is 4 hours to 72 hours. Preferably, the catalyst in the step 1 and the step 2 comprises a metal organic catalyst or an organic base catalyst; the metal organic catalyst comprises one of aluminum isopropoxide, stannous octoate, bismuth subsalicylate, anhydrous zinc acetate, tris (trimethylsilyl) lanthanum amide and zinc isopropoxide; The organic base catalyst comprises one of 1,5, 7-triazabicyclo [4, 0] dec-5-ene, 1, 8-diazabicyclo [5,4,0] undec-7, 7-methyl-1, 5, 7-triazabicyclo [4.4.0] dec-5-ene; In the step 1, the molar ratio of the catalyst to the cyclic ester monomer or glycolide is 1:10-20000; in the step 2, the molar ratio of the catalyst to the glycolide or cyclic