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

作　　者：Yue-Xi Zhan Li Zhang Chun Feng Jian-Bo Tan 

机构地区：[1]Department of Polymeric Materials and Engineering,School of Materials and Energy,Guangdong University of Technology,Guangzhou 510006,China [2]Guangdong Provincial Key Laboratory of Functional Soft Condensed Matter,Guangzhou 510006,China [3]Shanghai Key Laboratory of Advanced Polymeric Materials,School of Materials Science and Engineering,East China University of Science and Technology,Shanghai 200237,China

出　　处：《Chinese Journal of Polymer Science》2025年第3期429-438,共10页高分子科学(英文版)

基　　金：financially supported by the National Natural Science Foundation of China(Nos.22171055 and 52222301);the Guangdong Natural Science Foundation for Distinguished Young Scholar(No.2022B1515020078);the Science and Technology Program of Guangzhou(No.2024A04J2821)。

摘　　要：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 macroCTAs 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.

关 键 词：Polymerization-induced self-assembly RAFT polymerization Block copolymer nanoparticles Branched structure 

分 类 号：O63[理学—高分子化学]