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

Abstract

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.