Star multiple block copolymer of poly(4-vinylpyridine)-block-polystyrene (s-P4VP-b-PS) is synthesized via initial synthesis of linear poly(4-vinylpyridine)-block-polystyrene (l-P4VP-b-PS) by dispersion RAFT polymerization to form l-P4VP-b-PS nano-assemblies and then cross-linking within the l-P4VP-b-PS nano-assemblies. The synthesized s-P4VP-b-PS has a high molecular weight and exists 25-47 nm nanospheres in the common solvent of N,N-dimethylformamide. The self-assembly of s-P4VP-b-PS in two block selective solvents, e.g., toluene and methanol, is investigated, and great difference from l-P4VP-b-PS is demonstrated. In methanol, s-P4VP-b-PS forms core-corona nanospheres. In toluene, s-P4VP-b-PS forms dispersed nanoparticles or nanoparticle clusters dependent on polymer concentration. In the s-P4VP-b-PS nanoparticle clusters, poly(4-vinylpyridine) forms dispersed nano-domains, the size of which is firmly dependent on the degree of polymerization of the P4VP block. It is thought that the great difference between s-P4VP-b-PS and l-P4VP-b-PS will arouse new interest on self-assembly of block copolymers.

聚（4-乙烯基吡啶）-嵌段-聚苯乙烯（s-P4VP- b -PS ）的星形多嵌段共聚物是通过线性聚（4-乙烯基吡啶）-嵌段-聚苯乙烯（1-P4VP- b -PS ）的初始合成而合成的通过分散RAFT聚合形成1-P4VP- b -PS纳米组件，然后在1-P4VP- b -PS纳米组件内交联。合成的s-P4VP- b -PS具有高分子量，并且在N，N-二甲基甲酰胺的普通溶剂中存在25-47nm的纳米球。s-P4VP- b -PS在两种嵌段选择性溶剂中的自组装，例如研究了甲苯和甲醇，并证明了与1-P4VP- b -PS的巨大差异。在甲醇中，s-P4VP- b -PS形成核心电晕纳米球。在甲苯中，取决于聚合物浓度，s-P4VP- b -PS形成分散的纳米颗粒或纳米颗粒簇。在s-P4VP- b -PS纳米颗粒簇中，聚（4-乙烯基吡啶）形成分散的纳米域，其大小牢固地取决于P4VP嵌段的聚合度。据认为，S-P4VP-之间的巨大差异b -PS和L-P4VP- b -PS会激起新的兴趣自组装嵌段共聚物。