RAFT polymerization for advanced morphological control: from individual polymer chains to bulk materials

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.