Sustainable Polythioesters via Thio(no)lactones: Monomer Synthesis, Ring‐Opening Polymerization, End‐of‐Life Considerations, and Industrial Perspectives

As the environmental effects of plastics are of ever greater concern, the industry is driven towards more sustainable polymers. Besides sustainability, our fast-developing society imposes the need for highly versatile materials. Whereas aliphatic polyesters (PEs) are widely adopted and studied as next-generation biobased and (bio)degradable materials, their sulfur-containing analogs, polythioesters (PTEs), only recently gained attention. Nevertheless, the introduction of S atoms is known to often enhance thermal, mechanical, electrochemical, and optical properties, offering prospects for broad applicability. Furthermore, thanks to their thioester-based backbone, PTEs are inherently susceptible to degradation, giving them a high sustainability potential. The key route to PTEs is through ring-opening polymerization (ROP) of thio(no)lactones. This Review critically discusses the (potential) sustainability of the most relevant state-of-the-art in every step from sulfur source to end-of-life treatment options of PTEs, obtained through ROP of thio(no)lactones. The benefits and drawbacks of PTEs versus PEs are highlighted, including their industrial perspective.