Polymerisation‐Induced Self‐Assembly of Graft Copolymers

We report the polymerisation‐induced self‐assembly of poly(lauryl methacrylate)‐graft‐poly(benzyl methacrylate) copolymers during reversible addition‐fragmentation chain transfer (RAFT) grafting from polymerisation in a backbone‐selective solvent. Electron microscopy images suggest the phase separation of grafts to result in a network of spherical particles, due to the ability of the branched architecture to freeze chain entanglements and to bridge core domains. Small‐angle X‐ray scattering data suggest the architecture promotes the formation of multicore micelles, the core morphology of which transitions from spheres to worms, vesicles, and inverted micelles with increasing volume fraction of the grafts. A time‐resolved SAXS study is presented to illustrate the formation of the inverted phase during a polymerisation. The grafted architecture gives access to unusual morphologies and provides exciting new handles for controlling the polymer structure and material properties.