Molecular Simulations of Dynamic Heterogeneity of Segment Motion and Bond Exchange in Polymer Vitrimers

Lang Shuai; Jiang-Long Li; Jian-Long Wen; Ying-Ying Xu; Shui Yu; Bo-Yu Ding; Yi-Jing Nie

doi:10.1007/s10118-025-3472-x

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Molecular Simulations of Dynamic Heterogeneity of Segment Motion and Bond Exchange in Polymer Vitrimers

RESEARCH ARTICLE | Updated：2026-01-13

- Molecular Simulations of Dynamic Heterogeneity of Segment Motion and Bond Exchange in Polymer Vitrimers
  Enhanced Publication
- Chinese Journal of Polymer Science Vol. 44, Issue 1, Pages: 242-255(2026)
- Affiliations：
  
  Institute of Polymer Materials, School of Materials Science and Engineering, Jiangsu University, Zhenjiang 212013, China
- Author bio：
  
  nieyijing@ujs.edu.cn
- Funds：
- DOI：10.1007/s10118-025-3472-x
  CLC：
- Received：06 September 2025，
  
  Revised：2025-09-23，
  
  Accepted：08 October 2025，
  
  Published Online：04 January 2026，
  
  Published：15 January 2026
- Accepted：
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Shuai, L.; Li, J. L.; Wen, J. L.; Xu, Y. Y.; Yu, S.; Ding, B. Y.; Nie, Y. J. Molecular simulations of dynamic heterogeneity of segment motion and bond exchange in polymer vitrimers. Chinese J. Polym. Sci. 2026, 44, 242–255

Lang Shuai, Jiang-Long Li, Jian-Long Wen, et al. Molecular Simulations of Dynamic Heterogeneity of Segment Motion and Bond Exchange in Polymer Vitrimers[J]. Chinese Journal of Polymer Science, 2026, 44(1): 242-255.
Shuai, L.; Li, J. L.; Wen, J. L.; Xu, Y. Y.; Yu, S.; Ding, B. Y.; Nie, Y. J. Molecular simulations of dynamic heterogeneity of segment motion and bond exchange in polymer vitrimers. Chinese J. Polym. Sci. 2026, 44, 242–255 DOI： 10.1007/s10118-025-3472-x.

Lang Shuai, Jiang-Long Li, Jian-Long Wen, et al. Molecular Simulations of Dynamic Heterogeneity of Segment Motion and Bond Exchange in Polymer Vitrimers[J]. Chinese Journal of Polymer Science, 2026, 44(1): 242-255. DOI： 10.1007/s10118-025-3472-x.

摘要

This study employs molecular dynamics simulations to visually elucidate the dynamic bond exchange processes in vitrimers. It investigates the coupling between bond exchange kinetics and segmental dynamics

as well as the dynamic heterogeneity induced by varying bond exchange rates.

Abstract

Vitrimers belong to a class of polymeric materials capable of bond exchange reactions

showing great promise for environmental protection and sustainable development. However

studies on the coupling mechanism between the bond exchange kinetics and segmental dynamics near the glass transition temperature (

) remain scarce. Herein

we employed molecular dynamics simulations to investigate the dynamic heterogeneity of the segment motion and bond exchange in vitrimers. The simulation result

s revealed that the bond exchange energy barrier exerts a much stronger influence on the bond exchange kinetics than on the segmental dynamics. At lower temperatures

slower segmental relaxation further constraind the bond exchange rate. Additionally

increasing the bond exchange energy barrier markedly enhanced the dynamic heterogeneity of segment motion. A close correlation was observed between heterogeneity and bond exchange. This study elucidated the coupling mechanism between bond exchange and segmental dynamics at the molecular scale

thereby providing a theoretical basis for designing vitrimer materials with tunable dynamic properties.

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references

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