Recent Advancement in Precise Engineering of Block Copolymer Microparticles via Confined Assembly in Emulsion Droplets

Abstract

The self-assembly of block copolymers (BCPs) within three-dimensional (3D) emulsion droplets has emerged as a highly versatile and robust platform for fabricating polymer microparticles with precisely controlled shapes and internal nanostructures. This review comprehensively summarizes recent advancements in this field, with a particular focus on the key factors and sophisticated strategies that govern the specific nanostructures of BCP microparticles formed via confined self-assembly. A detailed discussion is presented on the strategic manipulation of critical assembly parameters, such as the BCP volume fraction, solvent selectivity, surfactant, incorporation of small-molecular additives, evaporation kinetics, crystallization-induced assembly, and post-assembly processes. The distinctive properties arising from these tailored architectures are highlighted, with a focus on their applications in high-performance gas sensors, catalysts, drug delivery, and photonic crystals. The review concludes by addressing the remaining challenges and future research directions for the precise fabrication of multifunctional 3D microparticles, thereby guiding future innovations in advanced polymeric materials through emulsion-confined assembly.