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Polyglycolic acid-based biodegradable random copolymer and preparation method thereof

A random copolymer, biodegradable technology, applied in the field of biodegradable materials, can solve the problems of poor thermal stability, ineffective thermal stability and toughening modification, large amount of comonomer, etc., and achieve high crystallinity , excellent biodegradability, and low comonomer content

Active Publication Date: 2022-01-14
ZHEJIANG UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0008] The purpose of the present invention is to solve the problem of poor thermal stability of PGA materials, the modification method in the prior art has the problems of quoting a large amount of comonomers, and the thermal stability and toughening modification effects are not obvious, and provides a polyglycolic acid-based, containing a small amount of A method for preparing a high-performance biodegradable random copolymer of a comonomer, which can obtain a random copolymer with high thermal stability and good toughness, and the random copolymer retains the biodegradable and high barrier properties of PGA itself High strength, high strength and other advantages, excellent comprehensive performance, broad application prospects

Method used

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  • Polyglycolic acid-based biodegradable random copolymer and preparation method thereof
  • Polyglycolic acid-based biodegradable random copolymer and preparation method thereof
  • Polyglycolic acid-based biodegradable random copolymer and preparation method thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0079] Embodiment 1 polycondensation method PGC 8.6 —Single melt crystallization peak, narrow crystallization temperature range

[0080] (1) Add 166g of glycolic acid, 16g of ε-caprolactone, 0.32g of organotin and 0.32g of camphorsulfonic acid catalyst into a 250mL reaction flask, and hydrolyze in situ under stirring, normal pressure, reaction temperature of 190°C, and reflux temperature of 100°C -Esterification reaction for 9h to obtain the precursor.

[0081] (2) Prepolymerize the precursor obtained in step (1) for 2 hours under stirring, 25kPa reaction pressure, 190°C reaction temperature, and 50°C reflux temperature to obtain an intermediate.

[0082] (3) Add 0.14g antioxidant 1010, 0.07g antioxidant 626 to the intermediate obtained in step (2), and add 0.32g organic tin and 0.32g camphorsulfonic acid catalyst, place stirring, 80Pa reaction pressure, The polycondensation reaction was carried out at a reaction temperature of 200°C and a reflux temperature of 70°C for 5 ho...

Embodiment 2

[0083] Embodiment 2 polycondensation method PGC 26.2 — degree of randomness 1.08

[0084] (1) Add 140 g of glycolic acid, 70 g of ε-caprolactone, and 0.37 g of an organotin catalyst into a 250 mL reaction flask, and perform an in-situ hydrolysis-esterification reaction under stirring, normal pressure, 190° C. reaction temperature, and 100° C. reflux temperature for 6 h, get the precursor.

[0085] (2) Prepolymerize the precursor obtained in step (1) for 3 hours under stirring, 50 kPa reaction pressure, 190° C. reaction temperature, and 65° C. reflux temperature to obtain an intermediate.

[0086] (3) Add 0.17g antioxidant 1010, 0.085g antioxidant 626 to the intermediate obtained in step (2), and add 0.37g organotin catalyst, place stirring, 23Pa reaction pressure, 200 ℃ reaction temperature, 65 Under the reflux temperature of ℃, the polycondensation reaction was carried out for 8 hours, and the high-performance biodegradable random copolymer based on glycolic acid was obtain...

Embodiment 3

[0087] Embodiment 3 polycondensation method PGC 10.5 — High performance product 1

[0088] (1) Add 160g of glycolic acid, 21g of ε-caprolactone, 0.32g of organotin and 0.32g of camphorsulfonic acid catalyst into a 250mL reaction flask, and hydrolyze in situ under stirring, normal pressure, reaction temperature of 170°C, and reflux temperature of 100°C -Esterification reaction 10h, obtain precursor.

[0089] (2) Prepolymerize the precursor obtained in step (1) for 2 hours under stirring, 25kPa reaction pressure, 190°C reaction temperature, and 50°C reflux temperature to obtain an intermediate.

[0090] (3) Add 0.14g antioxidant 1010, 0.07g antioxidant 626 to the intermediate obtained in step (2), and add 0.32g organic tin and 0.32g camphorsulfonic acid catalyst, place stirring, 80Pa reaction pressure, The polycondensation reaction was carried out at a reaction temperature of 200°C and a reflux temperature of 76°C for 6 hours to obtain the high-performance biodegradable random...

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Abstract

The invention relates to the technical field of biodegradable materials, and discloses a polyglycolic acid-based biodegradable random copolymer and a preparation method thereof, wherein the copolymer comprises 71-95 mol% of a first repetitive unit and 5-29 mol% of a second repetitive unit; the structure of the first repetitive unit is represented by a formula I, and the structure of the second repetitive unit is represented by any one of formulas II-1-II-3; and a first monomer and a second monomer are subjected to esterification, prepolymerization and polycondensation to obtain the polyglycolic acid copolymer, and the copolymer not only has high thermal stability and good toughness, but also has the advantages of biodegradability, high barrier property, high strength and the like, and is excellent in comprehensive performance and wide in application prospect.

Description

technical field [0001] The invention relates to the technical field of biodegradable materials, in particular to a biodegradable random copolymer based on polyglycolic acid and a preparation method thereof. Background technique [0002] While the rapid development of traditional polymer materials has brought many conveniences to people's production and life, it has also caused a series of environmental problems represented by "white pollution". In this context, biodegradable materials have received extensive attention and rapid development. Unlike low-end applications such as shopping bags and express packaging, high-end applications such as agricultural mulch and food and drug packaging materials require biodegradable materials not only to have sufficient thermal and mechanical properties, but also to have excellent gas barrier properties. At present, biodegradable materials that have been industrially produced generally have the problem of incompatibility in thermal, mech...

Claims

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Application Information

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IPC IPC(8): C08G63/06C08G63/08C08G63/78
CPCC08G63/06C08G63/08C08G63/78
Inventor 吴林波秦鹏凯李伯耿
Owner ZHEJIANG UNIV
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