Reversing Controlled Radical Polymerisation: Towards Complete Depolymerisation

ended

Controlled radical polymerisation has revolutionised the field of polymer chemistry by allowing access to the synthesis of a wide range of materials with controlled molecular weight, dispersity, architecture and end-group fidelity. Although thousands of papers have reported on optimising the polymerisation parameters, very few reports have focused on reversing controlled radical polymerisation. This is a significant oversight, as controlled depolymerisation has the potential not only to reveal intriguing avenues of research, but also to pave the way for promising applications including innovative polymer characterisation methodologies. The overall vision of DEPO is to develop a universal, quantitative and controlled depolymerisation of polymers (i.e. converting polymers back to the corresponding monomers) synthesised mainly by controlled radical polymerisation. Although this strategy will initially be developed for atom transfer radical polymerisation (ATRP) systems, it will be expanded to include reversible addition-fragmentation chain-transfer (RAFT) and nitroxide-mediated polymerisation (NMP) protocols. Widely-used polymers synthesised by other methods such as polystyrene will also be modified to permit for depolymerisation. Importantly, this approach will operate at room temperature and will be applicable to a range of polymer classes and architectures (block copolymers, stars, etc.). The fundamental outcomes of this research will inform depolymerisation design strategies and will pave the way for additional opportunities such as advanced polymer characterisation.