Recyclable and Repairable Dynamic Polysulfide Polymer from Elementary Sulfur and Thiol

Ke-xiang Chen; Chuan-zhen Zhang; Wen-bo Fan; Zi-yan Zhang; Xiao-yu Li; Chen-hui Cui; Yin-zhou Guo; Zhi-yuan He; Xiao-qing Ming; Yan-feng Zhang

doi:10.11777/j.issn1000-3304.2025.25206

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Recyclable and Repairable Dynamic Polysulfide Polymer from Elementary Sulfur and Thiol

Research Article | 更新时间：2025-12-18

- Recyclable and Repairable Dynamic Polysulfide Polymer from Elementary Sulfur and Thiol
- Acta Polymerica Sinica Vol. 56, Issue 12, Pages: 2396-2405(2025)
- 作者机构：
  
  西安交通大学化学学院氟氮化工新材料全国重点实验室西安市可持续高分子重点实验室西安 710049
- 作者简介：
  
  Yan-feng Zhang, E-mail: yanfengzhang@mail.xjtu.edu.cn
- 基金信息：
- DOI：10.11777/j.issn1000-3304.2025.25206
  CLC：
- CSTR：32057.14.GFZXB.2025.7476
- Received：27 August 2025，
  
  Accepted：26 September 2025，
  
  Published Online：01 December 2025，
  
  Published：20 December 2025
- 稿件说明：
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陈可祥, 张传真, 樊文博, 张子言, 李小雨, 崔晨晖, 郭寅周, 何之源, 明小庆, 张彦峰. 基于硫磺和硫醇反应的可回收、可修复动态多硫高分子. 高分子学报, 2025, 56(12), 2396-2405

Chen, K. X.; Zhang, C. Z.; Fan, W. B.; Zhang, Z. Y.; Li, X. Y.; Cui, C. H.; Guo, Y. Z.; He, Z. Y.; Ming, X. Q.; Zhang, Y. F. Recyclable and repairable dynamic polysulfide polymer from elementary sulfur and thiol. Acta Polymerica Sinica, 2025, 56(12), 2396-2405
陈可祥, 张传真, 樊文博, 张子言, 李小雨, 崔晨晖, 郭寅周, 何之源, 明小庆, 张彦峰. 基于硫磺和硫醇反应的可回收、可修复动态多硫高分子. 高分子学报, 2025, 56(12), 2396-2405 DOI： 10.11777/j.issn1000-3304.2025.25206. CSTR： 32057.14.GFZXB.2025.7476.

Chen, K. X.; Zhang, C. Z.; Fan, W. B.; Zhang, Z. Y.; Li, X. Y.; Cui, C. H.; Guo, Y. Z.; He, Z. Y.; Ming, X. Q.; Zhang, Y. F. Recyclable and repairable dynamic polysulfide polymer from elementary sulfur and thiol. Acta Polymerica Sinica, 2025, 56(12), 2396-2405 DOI： 10.11777/j.issn1000-3304.2025.25206. CSTR： 32057.14.GFZXB.2025.7476.

摘要

交联聚合物综合性能优异、应用广泛，但高度稳定的三维交联结构使其难以修复和回收. 动态多硫键是一种具有较快交换速率的动态共价键，将其引入交联聚合物构建动态多硫高分子，可赋予其快速修复、快速回收等性能. 本工作开发了一种有机碱催化硫醇与硫磺反应形成含动态多硫键交联高分子的策略，通过核磁氢谱研究了模型分子的化学结构与多硫键复分解反应，通过拉曼光谱、X射线衍射、拉伸、应力松弛研究了含有动态多硫键高分子的基本性能. 结果显示，多硫键成功引入并且展现出良好的动态交换能力. 基于多硫键复分解反应，交联聚合物表现出优异的修复、重塑性能；并且多硫交联聚合物可以被过量硫醇降解，再利用硫醇与异氰酸酯的反应将降解产物升级为聚硫氨酯. 此外，动态多硫聚合物可以在硫化钠溶液中温和降解. 这一简单而高效动态化学设计理念，为开发新型可回收、可修复绿色智能材料提供了新的思路.

Abstract

Cross-linked polymers exhibit excellent properties and have broad applications. However

owing to their highly stable three-dimensional cross-linked structures

cross-linked polymers exhibit poor repair and recycling behavior. Dynamic polysulfide bond is a type of dynamic covalent bond with a relatively fast exchange rate. Incorporating it into cross-linked polymers to construct dynamic polysulfide polymers can endow the material with properties such as rapid self-healing and recyclability. In this study

we developed a strategy to synthesize cross-linked polymers containing dynamic polysulfide bonds

via

an organic base-catalyzed reaction between thiols and elemental sulfur. The chemical structures of the mo

del molecules and their polysulfide metathesis behaviors were investigated using

H-NMR. The fundamental properties of polysulfide-containing polymers were studied using Raman spectroscopy

XRD

tensile test

and stress relaxation. The results showed that polysulfide bonds were successfully incorporated and exhibited good dynamic exchange behavior. Based on polysulfide metathesis

the cross-linked polymers exhibited excellent self-healing and reprocessing behavior. Furthermore

polysulfide polymers could be degraded by excess thiols and upcycled into polythiourethanes

via

the reaction between thiols and isocyanates. Additionally

the dynamic polysulfide polymers could be gently degraded in a sodium sulfide solution. This simple and efficient dynamic chemical design concept provides new ideas and inspiration for the development of new recyclable

repairable

eco-friendly

and smart materials.

关键词

Keywords

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