Self-healing, Recyclable and Reprocessable Polyoxime-urethane Elastomer with Multiple Dynamic Hybrid Crosslinks

Rui Wang; Hui-xia Xuan; Hai-liang Chen; Guang-chen Liu; Ying-qian Li; Yong Guan; Qing-bao Guan; Zheng-wei You

doi:10.11777/j.issn1000-3304.2025.25088

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Self-healing, Recyclable and Reprocessable Polyoxime-urethane Elastomer with Multiple Dynamic Hybrid Crosslinks

Research Article | 更新时间：2025-10-29

- Self-healing, Recyclable and Reprocessable Polyoxime-urethane Elastomer with Multiple Dynamic Hybrid Crosslinks
- Acta Polymerica Sinica Vol. 56, Issue 11, Pages: 1976-1986(2025)
- 作者机构：
  
  1.东华大学先进纤维材料全国重点实验室材料科学与工程学院上海 201620
  2.上海工程技术大学化学化工学院医药前沿技术研究院上海 201620
  3.山东一诺威聚氨酯股份有限公司淄博 255086
- 作者简介：
  
  Hui-xia Xuan, E-mail: xyhx@sues.edu.cn
  Qing-bao Guan, E-mail: qbguan@dhu.edu.cn
  Zheng-wei You, E-mail: zyou@dhu.edu.cn
- 基金信息：
- DOI：10.11777/j.issn1000-3304.2025.25088
  CLC：
- CSTR：32057.14.GFZXB.2025.7412
- Received：10 August 2025，
  
  Accepted：14 September 2025，
  
  Published Online：10 October 2025，
  
  Published：20 November 2025
- 稿件说明：
移动端阅览
王瑞, 轩慧霞, 陈海良, 刘广臣, 李英乾, 管永, 管清宝, 游正伟. 多重动态杂化交联构建聚肟氨酯弹性体及其自愈合与可回收再加工性能. 高分子学报, 2025, 56(11), 1976-1986

Wang, R.; Xuan, H. X.; Chen, H. L.; Liu, G. C.; Li, Y. Q.; Guan, Y.; Guan, Q. B.; You, Z. W. Self-healing, recyclable and reprocessable polyoxime-urethane elastomer with multiple dynamic hybrid crosslinks. Acta Polymerica Sinica, 2025, 56(11), 1976-1986
王瑞, 轩慧霞, 陈海良, 刘广臣, 李英乾, 管永, 管清宝, 游正伟. 多重动态杂化交联构建聚肟氨酯弹性体及其自愈合与可回收再加工性能. 高分子学报, 2025, 56(11), 1976-1986 DOI： 10.11777/j.issn1000-3304.2025.25088. CSTR： 32057.14.GFZXB.2025.7412.

Wang, R.; Xuan, H. X.; Chen, H. L.; Liu, G. C.; Li, Y. Q.; Guan, Y.; Guan, Q. B.; You, Z. W. Self-healing, recyclable and reprocessable polyoxime-urethane elastomer with multiple dynamic hybrid crosslinks. Acta Polymerica Sinica, 2025, 56(11), 1976-1986 DOI： 10.11777/j.issn1000-3304.2025.25088. CSTR： 32057.14.GFZXB.2025.7412.

摘要

共价交联聚氨酯因高度稳定的三维共价交联网络结构，使其回收重加工成为一项难题. 本研究通过三重动态交联的设计策略，构建了含有动态肟氨酯键、氢键、可逆Diels-Alder反应基元的可回收再加工、自愈合性能的动态杂化交联聚肟氨酯弹性体DFPU-DA. 通过电子万能试验机、热重分析、动态热机械分析等探究了不同交联程度对弹性体力学，热学和自愈合性能的影响. 结果表明，当呋喃基团与双马来酰亚胺摩尔比为1.0:0.2时，DFPU-DA弹性体具备良好的机械性能(断裂强度为(48.8±1.6) MPa，断裂伸长率达(530±18)%)，经80 ℃热处理12 h后的愈合效率约80%. 通过反复热压重塑评估了该弹性体的回收再加工性能，再利用高温旋转流变仪定量化表征该弹性体的再加工温度. 结果表明DFPU-DA弹性体能够实现多次循环回收，具有良好的再加工性质；通过熔融纺丝和3D打印等技术得到纤维和三维网络图案化结构，具有潜在的应用前景.

Abstract

Thermoset polyurethane exhibits limited recyclability and reprocessability due to their permanent three-dimensional covalent crosslinked network structures. Thermoset polyurethanes incorporating dynamic covalent bonds for recyclability face challenges in balancing mechanical performance and reprocessability within single dynamic network systems. Additionally

conventional molding-based reprocessing methods limit their application in fabricating customized architectures

necessitating integration with advanced manufacturing techniques to enable structural personalization. This study constructs a self-healing

recyclable and reprocessable polyoxime-urethane elastomer (DFPU-DA) through a triple dynamic crosslinking strategy

integrating dynamic oxime-urethane bonds

hydrogen bonds

and reversible Diels-Alder reaction. The influence of crosslinking density on the mechanical properties

thermal stability

and self-healing property of DFPU-DA was investigated using universal tensile testing

thermogravimetric analysis

and dynamic mechanical analysis. Results showed that DFPU-DA exhibited good mechanical properties

achieving a breaking strength of (48.8±1.6) MPa and an elongation at break of (530±18)%

when the molar ratio of furan groups to bismaleimide is 1.0:0.2. The healing efficiency was determined to be approximately 80%

assessed by comparing the elongation at break and fracture strength before and after the healing process. These results indicated that the DFPU-DA elastomer exhibited minimal alterations in its mechanical properties

chemical structure

and thermal decomposition temperature after multiple recycling cycles

demonstrating good reprocessability. Furthermore

DFPU-DA is reprocessed as fiber morphology

via

melt-spinning and three-dimensional grid structure

via

3D printing

verifying its good processability for potential applications.

关键词

Keywords

references

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