Although linear block copolymer assemblies derived from polymerization-induced self-assembly (PISA) have been prepared with a wide variety of structures, examples with hyperbranched block copolymer assemblies have remained elusive. In this work, efficient synthesis and self-assembly of segmented hyperbranched block copolymers (SHBCs) were achieved via reversible addition–fragmentation chain-transfer (RAFT)-mediated dispersion polymerization-induced self-assembly (PISA) using segmented hyperbranched macro-RAFT agents. Two different approaches including the R-RAFT approach and the Z-RAFT approach were employed to synthesize SHBCs with an important structural difference. Using the Z-RAFT approach, the solvophobic block always grows in the inner of SHBCs, allowing the efficient synthesis of colloidally stable SHBC assemblies with a variety of morphologies. Finally, further structural control over SHBCs and morphological control over SHBC assemblies were achieved by combining the R-RAFT approach and the Z-RAFT approach or adding a chain-transfer monomer into the RAFT-mediated PISA. This work not only develops a facile method for the efficient synthesis of SHBCs and SHBC assemblies but also provides important insights into the PISA process of nonlinear block copolymers.

中文翻译：

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使用分段超支化宏观 RAFT 试剂通过 RAFT 介导的分散聚合高效合成和自组装分段超支化嵌段共聚物

尽管源自聚合诱导自组装 (PISA) 的线性嵌段共聚物组装体已制备成具有多种结构，但具有超支化嵌段共聚物组装体的示例仍然难以捉摸。在这项工作中，通过可逆加成-断裂链转移（RAFT）介导的分散聚合诱导自组装（PISA），使用分段超支化大分子RAFT试剂实现了分段超支化嵌段共聚物（SHBC）的高效合成和自组装。 . 两种不同的方法包括 R-RAFT 方法和 Z-RAFT 方法用于合成具有重要结构差异的 SHBC。使用 Z-RAFT 方法，疏溶剂块总是在 SHBC 内部生长，允许有效合成具有多种形态的胶体稳定的 SHBC 组件。最后，通过结合 R-RAFT 方法和 Z-RAFT 方法或在 RAFT 介导的 PISA 中添加链转移单体，实现了对 SHBC 的进一步结构控制和对 SHBC 组件的形态控制。这项工作不仅为高效合成 SHBC 和 SHBC 组件开发了一种简便的方法，而且还为非线性嵌段共聚物的 PISA 过程提供了重要的见解。