Abstract
<jats:p>The development of sustainable polymers with material properties competitive with petroleum-derived polymers is a major goal, albeit an ambitious challenge for polymer science. Here, we demonstrate that radical ring-opening polymerization (rROP), previously unable to produce aliphatic poly(thioesters), becomes feasible through the rigorous selection of an appropriate initiation system. This system generates non-stabilized radicals suitable for the polymerization of unsubstituted thionolactones, enabling the homopolymerization of a wide variety of monomers, potentially derived from biomass. This approach proves to be both effective and robust for designing fully degradable sustainable polymers from renewable resources. It operates under optimal industrial conditions: temperatures between 100 and 120°C, ambient atmosphere, and without constraints related to impurities. Moreover, this method extends to the production of poly(thiocarbamates) and poly(thiocarbonate) via radical polymerization, thereby paving the way for a multitude of potential applications.</jats:p>