RAFT Polymerization for Advanced Morphological Control: From Individual Polymer Chains to Bulk Materials

Abstract Control of the morphology of polymer systems is achieved through reversible‐deactivation radical polymerization techniques such as Reversible Addition‐Fragmentation chain Transfer (RAFT). Advanced RAFT techniques offer much more than just “living” polymerization — the RAFT toolkit now enables morphological control of polymer systems across many decades of length‐scale. Morphological control is explored at the molecular‐level in the context of syntheses where individual monomer unit insertion provides sequence‐defined polymers (single unit monomer insertion, SUMI). By being able to define polymer architectures, the synthesis of bespoke shapes and sizes of nanostructures becomes possible by leveraging self‐assembly (polymerization induced self‐assembly, PISA). Finally, it is seen that macroscopic materials can be produced with nanoscale detail, based on phase‐separated nanostructures (polymerization induced microphase separation, PIMS) and microscale detail based on 3D‐printing technologies. RAFT control of morphology is seen to cross from molecular level to additive manufacturing length‐scales, with complete morphological control over all length‐scales.