Formation and Self-assembly of Amphiphilic Block Copolymers with Dynamic Covalent Bonds

Zhao-lei Zhang; Hao Tang; Xian-deng Qiu; Zi-xuan Zhang; Shu-yue Fang; Rong Wang

doi:10.11777/j.issn1000-3304.2026.26088

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Formation and Self-assembly of Amphiphilic Block Copolymers with Dynamic Covalent Bonds

Research Article | 更新时间：2026-07-30

- Formation and Self-assembly of Amphiphilic Block Copolymers with Dynamic Covalent Bonds
- Acta Polymerica Sinica Vol. 57, Issue 8, Pages: 1656-1666(2026)
- 作者机构：
  
  南京大学化学化工学院高分子科学与工程系配位化学全国重点实验室高性能高分子材料教育部重点实验室南京 210023
- 作者简介：
  
  Rong Wang, E-mail: wangrong@nju.edu.cn
- 基金信息：
- DOI：10.11777/j.issn1000-3304.2026.26088
  CLC：
- CSTR：32057.14.GFZXB.2026.7612
- Received：24 March 2026，
  
  Accepted：21 April 2026，
  
  Online First：26 June 2026，
  
  Published：20 August 2026
- 稿件说明：
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张兆磊, 汤浩, 邱先灯, 张子瑄, 方舒越, 汪蓉. 具有动态共价键的两亲性嵌段共聚物的形成与自组装. 高分子学报, 2026, 57(8), 1656-1666.

Zhang, Z. L.; Tang, H.; Qiu, X. D.; Zhang, Z. X.; Fang, S. Y.; Wang, R. Formation and self-assembly of amphiphilic block copolymers with dynamic covalent bonds. Acta Polymerica Sinica (in Chinese), 2026, 57(8), 1656-1666.
张兆磊, 汤浩, 邱先灯, 张子瑄, 方舒越, 汪蓉. 具有动态共价键的两亲性嵌段共聚物的形成与自组装. 高分子学报, 2026, 57(8), 1656-1666. DOI： 10.11777/j.issn1000-3304.2026.26088. CSTR： 32057.14.GFZXB.2026.7612.

Zhang, Z. L.; Tang, H.; Qiu, X. D.; Zhang, Z. X.; Fang, S. Y.; Wang, R. Formation and self-assembly of amphiphilic block copolymers with dynamic covalent bonds. Acta Polymerica Sinica (in Chinese), 2026, 57(8), 1656-1666. DOI： 10.11777/j.issn1000-3304.2026.26088. CSTR： 32057.14.GFZXB.2026.7612.

摘要

采用耗散粒子动力学(dissipative particle dynamics，DPD)模拟方法研究了具有动态共价键的两亲性嵌段共聚物的自组装行为. 结果表明，在动态共价键的存在下，通过调控疏水作用和嵌段间的相互作用，得到了多室囊泡、囊泡、大复合胶束和球形胶束等形态. 疏水相互作用是自组装的主要驱动力，嵌段间的相互作用可以调节界面曲率，进一步控制聚集体形态；随嵌段间排斥作用增强，聚集体从大复合胶束依次演变为多室囊泡、囊泡及胶束. 在动力学方面，体系浓度对动态键成键率呈现非单调影响，低浓度下反应受扩散控制，成键率随浓度增加而升高；当浓度进一步升高时，排斥体积效应和空间受限增强，反而抑制后续成键，从而表现出成键的最优浓度区间. 此外，对比了游离链与预连接嵌段2种初始模型的组装路径，发现初始拓扑连接性会显著影响体系的组装演化过程；与游离链体系相比，预连接嵌段体系中单室囊泡的形成区域明显扩大. 上述结果为动态共价键调控的高分子聚集体形态设计提供了理论依据.

Abstract

Dissipative particle dynamics (DPD) simulations were employed to investigate the self-assembly behavior of amphiphilic block copolymers with dynamic covalent bonds. The results showed that in the presence of dynamic covalent bonds

multicompartment vesicles

vesicles

large compound micelles

and spherical micelles can be obtained by tuning the hydrophobic interaction and the interaction between blocks. Hydrophobic interactions served as the primary driving force for self-assembly

whereas the interaction between blocks regulated the interfacial curvature

thereby further controlling the aggregate morphology. With increasing repulsion between the blocks

the aggregate morphology underwent a sequential transition from large compound micelles to multicompartment vesicles

vesicles

and micelles. From a kinetic perspective

the system concentration exerted a non-monotonic effect on the bond fraction of the dynamic bonds. At low concentrations

the reaction was diffusion-controlled

and the bond fraction increased with increasing concentration. When the concentration further increased

the enhanced excluded-volume effects and spatial confinement suppressed subsequent bond formation

resulting in an optimal concentration window for bond formation. In addition

a comparison of the assembly pathways between the free-chain and pre-connected block models revealed that the initial topological connectivity significantly affects the assembly evolution process. Compared with the free-chain system

the region for single-compartment vesicle formation was markedly enlarged in the preconnected block system. These results provide a theoretical basis for the morphological design of polymer aggregates regulated by dynamic covalent bonds.

关键词

Keywords

references

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