Influence of Pressure on the Co-nonsolvency Effect of Homopolymer in Solutions: A Molecular Dynamics Simulation Study

Zhi-Yuan Wang; Xing-Ye Li; Zheng Wang; Yu-Hua Yin; Run Jiang; Peng-Fei Zhang; Bao-Hui Li

doi:10.1007/s10118-025-3400-0

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Influence of Pressure on the Co-nonsolvency Effect of Homopolymer in Solutions: A Molecular Dynamics Simulation Study

RESEARCH ARTICLE | Updated：2025-09-26

- Influence of Pressure on the Co-nonsolvency Effect of Homopolymer in Solutions: A Molecular Dynamics Simulation Study
- Influence of Pressure on the Co-nonsolvency Effect of Homopolymer in Solutions: A Molecular Dynamics Simulation Study
- 高分子科学（英文） 2025年43卷第10期页码：1929-1938
- Affiliations：
  
  a.Key Laboratory of Weak-Light Nonlinear Photonics, Ministry of Education, School of Physics, Nankai University, Tianjin 300071, China
  b.State Key Laboratory of Advanced Fiber Materials, Center for Advanced Low-Dimension Materials, College of Materials Science and Engineering, Donghua University, Shanghai 201620, China
- Author bio：
  
  pfzhangphy@dhu.edu.cn (P.F.Z.)
  baohui@nankai.edu.cn (B.H.L.)
- Funds：
  
  B. Li acknowledges the financial support provided by the National Natural Science Foundation of China (Nos. 22173051, 21829301 and 21774066), PCSIRT (IRT1257), and the College Discipline Innovation and Intelligence Introduction Program (111 Project (B16027), the International Cooperation Base (No. 2016D01025), Tianjin International Joint Research and Development Center). P. Zhang acknowledges the financial support provided by NSFC (No. 22473024).
- DOI：10.1007/s10118-025-3400-0
  中图分类号：
- 收稿：2025-04-30，
  
  修回：2025-06-14，
  
  录用：2025-06-18，
  
  网络首发：2025-09-02，
  
  纸质出版：2025-10-05
- Accepted：
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Wang, Z. Y.; Li, X. Y.; Wang, Z.; Yin, Y. H.; Jiang, R.; Zhang, P. F.; Li, B. H. Influence of pressure on the co-nonsolvency effect of homopolymer in solutions: a molecular dynamics simulation study. Chinese J. Polym. Sci. 2025, 43, 1929–1938

Zhi-Yuan Wang, Xing-Ye Li, Zheng Wang, et al. Influence of Pressure on the Co-nonsolvency Effect of Homopolymer in Solutions: A Molecular Dynamics Simulation Study[J]. Chinese Journal of Polymer Science, 2025, 43(10): 1929-1938.
Wang, Z. Y.; Li, X. Y.; Wang, Z.; Yin, Y. H.; Jiang, R.; Zhang, P. F.; Li, B. H. Influence of pressure on the co-nonsolvency effect of homopolymer in solutions: a molecular dynamics simulation study. Chinese J. Polym. Sci. 2025, 43, 1929–1938 DOI： 10.1007/s10118-025-3400-0.

Zhi-Yuan Wang, Xing-Ye Li, Zheng Wang, et al. Influence of Pressure on the Co-nonsolvency Effect of Homopolymer in Solutions: A Molecular Dynamics Simulation Study[J]. Chinese Journal of Polymer Science, 2025, 43(10): 1929-1938. DOI： 10.1007/s10118-025-3400-0.

摘要

In a mixed solvent

the polymer chains form spherical aggregates at low pressures owing to the co-nonsolvency effect. Increasing the pressure caused the polymer chains to transform from an aggregated state to a dispersed state.

Abstract

Stimuli-responsive polymers capable of rapidly altering their chain conformation in response to external stimuli exhibit broad application prospects. Experiments have shown that pressure plays a pivotal role in regulating the microscopic chain conformation of polymers in mixed solvents

and one notable finding is that increasing the pressure can lead to the vanishing of the co-nonsolvency effect. However

the mechanisms underlying this phenomenon remain unclear. In this study

we systematically investigated the influence of pressure on the co-nonsolvency effect of single-chain and multi-chain homopolymers in binary mixed good-solvent systems using molecular dynamics simulations. Our results show that the co-nonsolvency-induced chain conformation transition and aggregation behavior significantly depend on pressure in all single-chain and multi-chain systems. In single-chain systems

at low pressures

the polymer chain maintains a collapsed state over a wide range of co-solvent fractions (

-range) owing to the co-nonsolvency effect. As the pressure increases

the

-range of the collapsed state gradually narrows

accompanied by a progressive expansion of the chain. In multichain systems

polymer chains assemble into approximately spherical aggregates over a broad

-range at low pressures owing to the co-nonsolvency effect. Increasing the pressure reduces the

-range for forming aggregates and leads to the formation of loose aggregates or even to a state of dispersed chains at some

-range. These findings indicate that increasing the pressure can weaken or even offset the co-nonsolvency effect in some

-range

which is in good agreement with the experimental observations. Quantitative analysis of the radial density distributions and radial distribution functions reveals that

with increasing pressure

(1) the densities of both polymers and co-solvent mol

ecules within aggregates decrease

while that of the solvent molecule increases; and (2) the effective interactions between the polymer and the co-solvent weaken

whereas those between the polymer and solvent strengthen. This enhances the incorporation of solvent molecules within the chains

thereby weakening or even suppressing the chain aggregation. Our study not only elucidates the regulatory mechanism of pressure on the microscopic chain conformations and aggregation behaviors of polymers

but also may provide theoretical guidance for designing smart polymeric materials based on mixed solvents.

关键词

Keywords

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