Synthesis and Properties of Chemically Recyclable Triblock Copolyester

Jia-wei Wang; Chen-lin Pan; Jin-lin He; Pei-hong Ni

doi:10.11777/j.issn1000-3304.2025.25117

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Synthesis and Properties of Chemically Recyclable Triblock Copolyester

Research Article | 更新时间：2026-05-11

- Synthesis and Properties of Chemically Recyclable Triblock Copolyester
  增强出版
- Acta Polymerica Sinica Vol. 56, Issue 11, Pages: 1965-1975(2025)
- 作者机构：
  
  苏州大学材料与化学化工学部新型功能高分子材料国家地方联合工程实验室先进功能高分子材料省高校重点实验室苏州市大分子设计与精密合成重点实验室苏州 215123
- 作者简介：
  
  Jin-lin He, E-mail: jlhe@suda.edu.cn
- 基金信息：
- DOI：10.11777/j.issn1000-3304.2025.25117
  CLC：
- CSTR：32057.14.GFZXB.2025.7450
- Received：07 May 2025，
  
  Accepted：14 July 2025，
  
  Online First：26 September 2025，
  
  Published：20 November 2025
- 稿件说明：
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王佳伟, 潘晨琳, 何金林, 倪沛红. 可化学回收三嵌段共聚酯的合成与性能研究. 高分子学报, 2025, 56(11), 1965-1975

Wang, J. W.; Pan, C. L.; He, J. L.; Ni, P. H. Synthesis and properties of chemically recyclable triblock copolyester. Acta Polymerica Sinica, 2025, 56(11), 1965-1975
王佳伟, 潘晨琳, 何金林, 倪沛红. 可化学回收三嵌段共聚酯的合成与性能研究. 高分子学报, 2025, 56(11), 1965-1975 DOI： 10.11777/j.issn1000-3304.2025.25117. CSTR： 32057.14.GFZXB.2025.7450.

Wang, J. W.; Pan, C. L.; He, J. L.; Ni, P. H. Synthesis and properties of chemically recyclable triblock copolyester. Acta Polymerica Sinica, 2025, 56(11), 1965-1975 DOI： 10.11777/j.issn1000-3304.2025.25117. CSTR： 32057.14.GFZXB.2025.7450.

摘要

首先使用Bayer-Villiger反应制备得到3

4-二氢-2

-苯并[

]

二氧杂环丙烷-2-酮(BDXO)单体，再利用两端含羟基的聚(

-己内酯) (PCL)引发BDXO的开环聚合(ROP)反应，得到三嵌段共聚酯PBDXO-

-PCL-

-PBDXO (简称BCB). 采用体积排除色谱(SEC)和核磁共振波谱(NMR)表征聚合物的化学结构、分子量及分子量分布(

)，结果表明共聚物的分子量可调、分子量分布较窄. 通过改变体系中PBDXO链段和PCL链段的摩尔比，可调控BCB共聚酯的热性能和机械性能. 热重分析(TGA)结果表明聚合物发生了阶段性的分解过程，示差扫描量热法(DSC)表明在PCL软段占主体时，材料表现出结晶性能，而当PBDXO硬段含量超过一半时，材料的结晶性能消失. 力学性能测试表明，BCB共聚酯的结晶性对其力学性能产生了影响. 通过SEC和扫描电子显微镜(SEM)表征共聚酯的降解性能，实验结果表明，BCB共聚酯在碱性条件下具有良好的降解性能，利用

H-NMR和SEC表征BCB的化学回收性质，PBDXO硬段可以通过真空热解回收为单体，而PCL软段则基本保留.

Abstract

This work reports the preparation and characterization of the triblock c

opolyester PBDXO-

-PCL-

-PBDXO

as well as the studies on its degradation and recycling properties. Firstly

a lactone-derived monomer 3

4-dihydro-2

-benzo[

]

dioxepin-2-one (BDXO) was prepared by the Bayer-Villiger oxidation reaction. Then

the ring-opening polymerization (ROP) of BDXO was initiated by hydroxyl-terminated poly(

-caprolactone) (PCL) to obtain the triblock copolyester PBDXO-

-PCL-

-PBDXO (abbreviated as BCB) with PBDXO as the hard segments while PCL as the soft segment. By changing the ratio of BDXO monomer to PCL macroinitiator

the thermal and mechanical properties of the BCB copolyesters can be regulated. Size exclusion chromatography (SEC) and nuclear magnetic resonance (NMR) were used to characterize the chemical structure

molecular weight and molecular weight distribution (

) of the polymers. The results showed that the polymers present a single-peak distribution and relatively low dispersities. Thermogravimetric analysis (TGA)

differential scanning calorimetry (DSC) and tensile testing were employed to systematically characterize the thermal and mechanical properties of copolyesters. These results indicated that when the soft segment of the copolyester is dominant

with the increase of the hard segments

the rapid decomposition temperature of the copolyester showed an upward trend. When the molar ratio of the soft segment to the hard segments in the copolyester changes

the strength and the elongation at break also exhibited corresponding changes. The degradation properties of the copolyester were characterized by SEC and scanning electron microscopy (SEM). With the increasing time

the weight of BCB copolyester decreased

and SEC results at different degradation time points indicated a downward trend in its weight-average molecular weight

along with a broadening of the molecular weight distribution. In the recycling experiment of BCB

the signal of

PBDXO in the

H-NMR test results has almost disappeared

and the SEC curve of the recycled PCL showed a broadening of the molecular weight distribution. This work reports the synthesis of a chemically recyclable triblock copolyester

which can be recycled through vacuum pyrolysis to obtain the monomer from hard segment

while the soft segment can be almost retained.

关键词

Keywords

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