Sequential Ring-opening Copolymerization of Bio-based <italic style="font-style: italic">γ</italic>-Methyl-<italic style="font-style: italic">ε</italic>- caprolactone and 6-Oxabicyclo[3.2.1]octan-7-one toward Thermoplastic Elastomers and Their Closed-loop Recycling

Dian-gang Liu; Li-ying Wang; Hong Chang; Hai-ning Niu; Ya-han Deng; Yu-fei Kan; Yong Shen

doi:10.11777/j.issn1000-3304.2026.26080

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Sequential Ring-opening Copolymerization of Bio-based γ-Methyl-ε- caprolactone and 6-Oxabicyclo[3.2.1]octan-7-one toward Thermoplastic Elastomers and Their Closed-loop Recycling

Research Article | 更新时间：2026-07-30

- Sequential Ring-opening Copolymerization of Bio-based γ-Methyl-ε- caprolactone and 6-Oxabicyclo[3.2.1]octan-7-one toward Thermoplastic Elastomers and Their Closed-loop Recycling
- Acta Polymerica Sinica Vol. 57, Issue 8, Pages: 1689-1698(2026)
- 作者机构：
  
  青岛科技大学化工学院高性能有机光学聚合物与先进制造技术全国重点实验室青岛 266042
- 作者简介：
  
  Yu-fei Kan, E-mail: kanyufei@qust.edu.cn
  Yong Shen, E-mail: shenyong@qust.edu.cn
- 基金信息：
- DOI：10.11777/j.issn1000-3304.2026.26080
  CLC：
- CSTR：32057.14.GFZXB.2026.7611
- Received：17 March 2026，
  
  Accepted：21 April 2026，
  
  Online First：18 June 2026，
  
  Published：20 August 2026
- 稿件说明：
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刘典刚, 王丽颖, 常鸿, 牛海宁, 邓亚涵, 阚雨菲, 沈勇. 生物基γ-甲基-ε-己内酯与6-氧杂双环[3.2.1]辛烷-7-酮顺序开环共聚制备热塑性弹性体及其闭环回收. 高分子学报, 2026, 57(8), 1689-1698.

Liu, D. G., Wang, L. Y., Chang, H., Niu, H. N., Deng, Y. H., Kan, Y. F., Shen, Y. Sequential ring-opening copolymerization of bio-based γ-methyl-ε-caprolactone and 6-oxabicyclo[3.2.1]octan-7-one toward thermoplastic elastomers and their closed-loop recycling. Acta Polymerica Sinica (in Chinese), 2026, 57(8), 1689-1698.
刘典刚, 王丽颖, 常鸿, 牛海宁, 邓亚涵, 阚雨菲, 沈勇. 生物基γ-甲基-ε-己内酯与6-氧杂双环[3.2.1]辛烷-7-酮顺序开环共聚制备热塑性弹性体及其闭环回收. 高分子学报, 2026, 57(8), 1689-1698. DOI： 10.11777/j.issn1000-3304.2026.26080. CSTR： 32057.14.GFZXB.2026.7611.

Liu, D. G., Wang, L. Y., Chang, H., Niu, H. N., Deng, Y. H., Kan, Y. F., Shen, Y. Sequential ring-opening copolymerization of bio-based γ-methyl-ε-caprolactone and 6-oxabicyclo[3.2.1]octan-7-one toward thermoplastic elastomers and their closed-loop recycling. Acta Polymerica Sinica (in Chinese), 2026, 57(8), 1689-1698. DOI： 10.11777/j.issn1000-3304.2026.26080. CSTR： 32057.14.GFZXB.2026.7611.

摘要

针对当前聚苯乙烯型热塑性弹性体难以回收、废弃后易造成环境污染的挑战，发展可化学循环的热塑性弹性体，是有望实现对此类传统材料部分替代，解决塑料污染的重要途径之一. 本工作以生物基

-甲基-

-己内酯和6-氧杂双环[3.2.1

]

辛烷-7-酮为原料，利用有机碱/脲二元催化体系实现其顺序开环共聚，成功制备得到系列三嵌段共聚物. 系统研究了分子量和硬段摩尔分数对所得共聚物热学和力学性质的影响. 当硬段摩尔分数为43%时，三嵌段共聚物表现出热塑性弹性体性质，具有较高的断裂强度、断裂伸长率和回弹性. 以氢氧化钠为催化剂，三嵌段共聚物在本体条件下可以解聚回收得到原始单体，单体再聚合后可以得到与原始材料力学性能相当的热塑性弹性体.

Abstract

Developing chemically recyclable thermoplastic elastomers (TPEs) from bio-renewable feedstocks to replace widely used polystyrene-based TPEs is a promising strategy for addressing the end-of-life issue of plastics. In this study

a series of triblock copolymers was successfully prepared by the sequential ring-opening copolymerization of bio-based

-methyl-

-caprolactone and 6-oxabicyclo[3.2.1

]

octan-7-one in the presence of a binary catalytic system composed of an organobase (

Bu-P

) and urea (U1). The obtained copolymers were carefully examined using

H-

C-

and 2D DOSY-NMR spectra. All the triblock copolymers had a 5% weight-loss temperature above 342 ℃

indicating their excellent thermal stability. The microphase separation between the soft and hard segments was confirmed by differential scanning calorimetry (DSC) and small-angle X-ray scattering (SAXS) measurements. The thermal and mechanical properties of these triblock copolymers can be adjusted by changing the molar fraction of the hard segment (

hard

)

and molecular weight (

). The tensile strength of these copolymers increased with increasing

hard

and molecular weight. Specifically

a triblock copolymer (TPE-4) with a

hard

of 43% and

of 130 kDa exhibited good thermoplastic elastomer properties

with a high tensile strength of 27.5 MPa and an elongation at break of 1100%. Meanwhile

TPE-4 also exhibited excellent elastic recovery of 78.2%

good resilience of 58.2%

and low residual strain of 13.7%. Furthermore

the prepared triblock copolymers can be depolymerized in bulk at 180 ℃ using sodium hydroxide as the catalyst. The monomers can be easily recovered by vacuum distillation

with a yield of up to 85%. The recovered monomers can be re-polymerized to afford triblock copolymers with molecular weights and mechanical properties comparable to those of the original TPE material. This study offers a simple strategy for preparing high-performance

closed-loop recyclable TPEs from bio-renewable feedstocks.

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Keywords

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Sequential Ring-opening Copolymerization of Bio-based γ-Methyl-ε- caprolactone and 6-Oxabicyclo[3.2.1]octan-7-one toward Thermoplastic Elastomers and Their Closed-loop Recycling

DOI：10.11777/j.issn1000-3304.2026.26080

摘要

Abstract

关键词

Keywords

references