Crystallization‐Driven Controlled 2D Self‐Assemblies via Aqueous RAFT Emulsion Polymerization

Aqueous emulsion polymerization is a robust technique for preparing nanoparticles of block copolymers; however, it typically yields spherical nanoassemblies. The scale preparation of nanoassemblies with nonspherical high‐order morphologies is a challenge, particularly 2D core–shell nanosheets. In this study, the polymerization‐induced self‐assembly (PISA) and crystallization‐driven self‐assembly (CDSA) are combined to demonstrate the preparation of 2D nanosheets and their aggregates via aqueous reversible addition‐fragmentation chain transfer (RAFT) emulsion polymerization. First, the crucial crystallizable component for CDSA, hydroxyethyl methacrylate polycaprolactone (HPCL) macromonomer is synthesized by ring opening polymerization (ROP). Subsequently, the RAFT emulsion polymerization of HPCL is conducted to generate crystallizable nanomicelles by a grafting‐through approach. This PISA process simultaneously prepared spherical latices and bottlebrush block copolymers comprising poly(N′,N′‐dimethylacrylamide)‐block‐poly(hydroxyethyl methacrylate polycaprolactone) (PDMA‐b‐PHPCL). The latexes are now served as seeds for inducing the formation of 2D hexagonal nanosheets, bundle‐shaped and flower‐like aggregation via the CDSA of PHPCL segments and unreacted HPCL during cooling. Electron microscope analysis trace the morphology evolution of these 2D nanoparticles and reveal that an appropriate crystallized component of PHPCL blocks play a pivotal role in forming a hierarchical structure. This work demonstrates significant potential for large‐scale production of 2D nanoassemblies through RAFT emulsion polymerization. By incorporating a novel crystallization nucleation driving force, the aqueous reversible addition‐fragmentation chain transfer (RAFT) emulsion polymerization has successfully combined polymerization‐induced self‐assembly (PISA) and crystallization‐driven self‐assembly (CDSA), facilitating the fabrication of 2D nanoassemblies and aggregates of bottlebrush block copolymers composed of poly(N′,N′‐dimethylacrylamide)‐block‐poly(hydroxyethyl methacrylate polycaprolactone) (PDMA‐b‐PHPCL) and macromonomers. These nanoassemblies include hexagonal nanosheets, bundle‐shaped nanoparticles as well as flower‐like micellar clusters.