Sequence Control in Sulphur-Containing Ring-Opening Co- and Terpolymerisations

Sulphur-containing polymers uniquely expand the catalogue of accessible material properties compared to current commodity materials, yet their synthesis remains underdeveloped. Combining sulphur- and oxygen-containing monomers in ring-opening copolymerisation leads to a reshuffling reaction of the sulphur centres, which has been challenging to control - a central task for reliably tailoring properties. However, very recent methodologies have emerged that not only suppress but also utilise this phenomenon to precisely access sulphur-containing polymer structures. These structures can exhibit improved degradability, chemical recyclability, refractive indices and crystallinity compared to their all-oxygen analogues. Furthermore, underutilised and even entirely untapped monomer feedstocks can become accessible as a result. This minireview aims to provide a roadmap of the tools currently available to selectively access sulphur-containing co- and terpolymer structures to enable emerging applications that leverage the chemistry of sulphur.