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<p>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 intrinsically 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 <i>via</i> 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 (λ). 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 conformational regulation.</p>

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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

  • 期刊论文

  • 发表日期：

    2026年5月15日

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  • 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

摘要

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 intrinsically 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 (λ). 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 conformational regulation.