Unlocking the Potential of Polythioesters

As the demand for sustainable polymers increases, most research efforts have focused on polyesters, which can be bioderived and biodegradable. Yet analogous polythioesters, where one of the oxygen atoms has been replaced by a sulfur atom, remain a relatively untapped source of potential. The incorporation of sulfur allows the polymer to exhibit a wide range of favorable properties, such as thermal resistance, degradability, and high refractive index. Polythioester synthesis represents a frontier in research, holding the promise of paving the way for eco‐friendly alternatives to conventional polyesters. Moreover, polythioester research can also open avenues to the development of sustainable and recyclable materials. In the last 25 years, many methods to synthesize polythioesters have been developed. However, to date no industrial synthesis of polythioesters has been developed due to challenges of costs, yields, and the toxicity of the by‐products. This review will summarize the recent advances in polythioester synthesis, covering step‐growth polymerization, ring‐opening polymerization (ROP), and biosynthesis. Crucially, the benefits and challenges of the processes will be highlighted, paying particular attention to their sustainability, with the aim of encouraging further exploration and research into the fast‐growing field of polythioesters. Polythioesters have introduced numerous innovative perspectives to polymer chemistry since their ground‐breaking synthesis in 1951. As the sulfur‐containing analogues of polyesters, polythioesters hold considerable promise as sustainable materials. However, the potential of polythioesters has yet to be fully harnessed, and challenges persist in achieving industrial‐scale production. This review examines recent advancements, aiming to encourage further exploration into sustainable polythioester materials.