Structural Difference in the Core-forming Block Reshapes RAFT-mediated Polymerization-induced Self-assembly

Yue-Xi Zhan; Li Zhang; Chun Feng; Jian-Bo Tan

doi:10.1007/s10118-025-3275-0

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Structural Difference in the Core-forming Block Reshapes RAFT-mediated Polymerization-induced Self-assembly

RESEARCH ARTICLE | Updated：2025-02-25

- Structural Difference in the Core-forming Block Reshapes RAFT-mediated Polymerization-induced Self-assembly
- Chinese Journal of Polymer Science Vol. 43, Issue 3, Pages: 429-438(2025)
- Affiliations：
  
  a.Department of Polymeric Materials and Engineering, School of Materials and Energy, Guangdong University of Technology, Guangzhou 510006, China
  b.Guangdong Provincial Key Laboratory of Functional Soft Condensed Matter, Guangzhou 510006, China
  c.Shanghai Key Laboratory of Advanced Polymeric Materials, School of Materials Science and Engineering, East China University of Science and Technology, Shanghai 200237, China
- Author bio：
  
  cfeng@ecust.edu.cn (C.F.)
  tanjianbo@gdut.edu.cn (J.B.T.)
- Funds：
- DOI：10.1007/s10118-025-3275-0
  CLC：
- Received：28 October 2024，
  
  Revised：2024-11-16，
  
  Accepted：21 November 2024，
  
  Online First：20 January 2025，
  
  Published：01 March 2025
- Accepted：
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Zhan, Y. X.; Zhang, L.; Feng, C.; Tan, J. B. Structural difference in the core-forming block reshapes RAFT-mediated polymerization-induced self-assembly. Chinese J. Polym. Sci. 2025, 43, 429–438

Yue-Xi Zhan, Li Zhang, Chun Feng, et al. Structural Difference in the Core-forming Block Reshapes RAFT-mediated Polymerization-induced Self-assembly[J]. Chinese Journal of Polymer Science, 2025, 43(3): 429-438.
Zhan, Y. X.; Zhang, L.; Feng, C.; Tan, J. B. Structural difference in the core-forming block reshapes RAFT-mediated polymerization-induced self-assembly. Chinese J. Polym. Sci. 2025, 43, 429–438 DOI： 10.1007/s10118-025-3275-0.

Yue-Xi Zhan, Li Zhang, Chun Feng, et al. Structural Difference in the Core-forming Block Reshapes RAFT-mediated Polymerization-induced Self-assembly[J]. Chinese Journal of Polymer Science, 2025, 43(3): 429-438. DOI： 10.1007/s10118-025-3275-0.

摘要

Effects of the core-forming structure on polymerization-induced self-assembly as well as the morphology of block copolymer nanoparticles are investigated. It was found that the branched core-forming structure favored the formation of lower-order morphologies while the brush-like core-forming block favored the formation of higher-order morphologies.

Abstract

Polymerization-induced self-assembly (PISA) has become one of the most versatile approaches for scalable preparation of linear block copolymer nanoparticles with various morphologies. However

the controlled introduction of branching into the core-forming block and the effect on the morphologies of block copolymer nanoparticles under PISA conditions have rarely been explored. Herein

a series of multifunctional macromolecular chain transfer agents (macro-CTAs) were first synthesized by a two-step green light-activated photoiniferter polymerization using two types of chain transfer monomers (CTMs). These macro-CTAs were then used to mediate reversible addition-fragmentation chain transfer (RAFT) dispersion polymerization of styrene (St) to prepare block copolymers with different core-forming block structures and the assemblies. The effect of the core-forming block structure on the morphology of block copolymer nanoparticles was investigated in detail. Transmission electron microscopy (TEM) analysis indicated that the brush-like core-forming block structure facilitated the formation of higher-order morphologies

while the branched core-forming block structure favored the formation of lower-order morphologies. Moreover

it was found that using macro-CTAs with a shorter length also promoted the formation of higher-order morphologies. Finally

structures of block copolymers and the assemblies were further controlled by changing the structure of macro-CTA or using a binary mixture of two different macro-CTAs. We expect that this work not only sheds light on the synthesis of block copolymer nanoparticles but also provide important mechanistic insights into PISA of nonlinear block copolymers.

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references

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