Chain Rigidity as a Key Regulator on Grafting Density and Dispersity of Polymer Brushes: Insights from Coarse-Grained Molecular Dynamics Simulations

Zheng-Jie Zhang; Wei-Shao Xu; Li-Jun Ma; Ying-Xiang Li; Yu-Qi Guo; Guo-Jie Zhang; Zhong-Yan Zhang; Yan Wang; Hong Liu

doi:10.1007/s10118-026-3605-x

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Chain Rigidity as a Key Regulator on Grafting Density and Dispersity of Polymer Brushes: Insights from Coarse-Grained Molecular Dynamics Simulations

RESEARCH ARTICLE | Updated：2026-07-01

- Chain Rigidity as a Key Regulator on Grafting Density and Dispersity of Polymer Brushes: Insights from Coarse-Grained Molecular Dynamics Simulations
- Chain Rigidity as a Key Regulator on Grafting Density and Dispersity of Polymer Brushes: Insights from Coarse-Grained Molecular Dynamics Simulations
- Chinese Journal of Polymer Science 2026年44卷第7期页码：2305-2321
- Affiliations：
  
  a.Key Laboratory of Theoretical Chemistry of Environment Ministry of Education, School of Environment, South China Normal University, Guangzhou 510006, China
  b.School of Chemistry, South China Normal University, Guangzhou 510006, China
  c.Institute of Systems and Physical Biology, Shenzhen Bay Laboratory, Shenzhen 518132, China
  d.Dongguan HEC Tech R & D Co., Ltd., Dongguan 523871, China
  e.Department of Chemical Engineering, School of Chemistry and Chemical Engineering, Guangzhou University, Guangzhou 510006, China
  f.Department of Chemical and Material Engineering, Lyuliang University, Lvliang 033001, China
- Author bio：
  
  zhangzhongyan@szbl.ac.cn (Z.Y.Z.)
  wangyan.cn@m.scnu.edu.cn (Y.W.)
  hongliu@m.scnu.edu.cn (H.L.)
- Funds：
  
  This work was financially supported by the National Natural Science Foundation of China (Nos. 22473046, 22273027, 22373024, 22503036, 22573021 and 22403059), and the Natural Science Foundation of Guangdong Province (No. 2025A1515010731). Hong Liu gratefully acknowledges support from the Alexander von Humboldt Foundation.;The authors declare no interest conflict.Electronic supplementary information (ESI) is available free of charge in the online version of this article at http://doi.org/10.1007/s10118-026-3605-x.The data that support the findings of this study are available from the corresponding author upon reasonable request. The author’s contact information: hongliu@m.scnu.edu.cn.
- DOI：10.1007/s10118-026-3605-x
  中图分类号：
- 收稿：2025-12-31，
  
  录用：2026-01-30，
  
  网络首发：2026-05-15，
  
  纸质出版：2026-07-05
- Accepted：
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Zhang, Z. J.; Xu, W. S.; Ma, L. J.; Li, Y. X.; Guo, Y. Q.; Zhang, G. J.; Zhang, Z. Y.; Wang, Y.; Liu, H. Chain rigidity as a key regulator on grafting density and dispersity of polymer brushes: insights from coarse-grained molecular dynamics simulations. Chinese J. Polym. Sci. 2026, 44, 2305–2321

Zheng-Jie Zhang, Wei-Shao Xu, Li-Jun Ma, et al. Chain Rigidity as a Key Regulator on Grafting Density and Dispersity of Polymer Brushes: Insights from Coarse-Grained Molecular Dynamics Simulations[J]. Chinese Journal of Polymer Science, 2026, 44(7): 2305-2321.
Zhang, Z. J.; Xu, W. S.; Ma, L. J.; Li, Y. X.; Guo, Y. Q.; Zhang, G. J.; Zhang, Z. Y.; Wang, Y.; Liu, H. Chain rigidity as a key regulator on grafting density and dispersity of polymer brushes: insights from coarse-grained molecular dynamics simulations. Chinese J. Polym. Sci. 2026, 44, 2305–2321 DOI： 10.1007/s10118-026-3605-x.

Zheng-Jie Zhang, Wei-Shao Xu, Li-Jun Ma, et al. Chain Rigidity as a Key Regulator on Grafting Density and Dispersity of Polymer Brushes: Insights from Coarse-Grained Molecular Dynamics Simulations[J]. Chinese Journal of Polymer Science, 2026, 44(7): 2305-2321. DOI： 10.1007/s10118-026-3605-x.

摘要

This study investigates how polymer chain rigidity affects grafting density. In "grafting-to

" rigidity influences chain diffusion and grafting probability

while in "grafting-from

" it controls active site accessibility.

Abstract

Polymer brush-based surface modification plays a crucial role in tailoring material properties across a wide range of applications

from biomedicine to electronics. Grafting density and dispersity are key parameters governing the performance of polymer brushes; however

the influence of polymer chain rigidity on these characteristics remains insufficiently understood. Polymer chain rigidity is intr

insically determined by chemical structure and can be further modulated by intramolecular and intermolecular interactions

solvent quality

external fields

and topological constraints. In this work

we focus on isolating the role of chain rigidity by controlling it through intramolecular bond-angle interactions in coarse-grained molecular dynamics simulations with an implicit solvent description

allowing a systematic investigation of its role in polymer brush fabrication

via

both “grafting-to” and “grafting-from” strategies using a stochastic reaction model. For the grafting-to strategy

a moderate increase in chain rigidity enhances grafting density

whereas excessive rigidity restricts chain mobility

thereby hindering grafting efficiency. We further examine the effects of polymer chain length

solution concentration

and surface grafting site density

revealing that grafting kinetics are governed by the cooperative interplay of these factors. To optimize grafting density in binary polymer brushes of flexible and rigid chains using the “grafting-to” strategy

we compare three grafting approaches—flexible-first/rigid-second (F/R)

rigid-first/flexible-second (R/F)

and simultaneous grafting

by varying the initial ratio of rigid chains (

). The results show that simultaneous grafting with a high fraction of rigid chains yields the highest grafting density

providing a pathway for optimizing the fabrication of high-density polymer brushes. In contrast

for the grafting-from strategy

with the rigidity range investigated in this study

increasing chain rigidity promotes more extended chain conformations

reduces the spatial shielding of surface initiation sites

and leads to polymer brushes with higher grafting density and lower dispersity. Overall

this study elucidates the mechanistic role of polymer chain rigidity in brush formation and provides theoretical guidance for the rational design and controlled fabrication of high-performance surface-modified materials through confo

rmational regulation.

关键词

Keywords

references

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