Dynamic Sulfur-Rich Polymers from Elemental Sulfur and Epoxides

Sulfur-containing dynamic polymers had attracted significant attention due to their unique chemical structures with high reversibility. Utilizating sulfur, an inexpensive industrial waste product, to synthesize dynamic polysulfide polymers through reverse vulcanization has been a notable approach. However, this method required high temperatures and resulted in the release of unpleasant oders. In this study, we presented a robust method for the preparation of sulfur-rich polymers with dynamic polysulfide bonds from elemental sulfur and inexpensive epoxide monomers via a one-pot strategy at the mild room temperature. Different types of polysulfide molecules and polymers were synthesized by reacting various epoxide compounds with sulfur, along with the investigation of their structures and dynamic behaviors. It was noteworthy that the obatined polymers prepared from m-(2,3-epoxypropoxy)-N,N-bis(2,3-epoxypropyl)aniline and elemental sulfur exhibit multiple dynamic behaviors, including polysulfide metathesis and polysulfide-thiol exchange, enabling their rapid stress relaxation, self-healing, reprocessing and degradable properties of the cross-linked polymer. More importantly, the hydroxyl groups at the side chains from epoxide ring opening exhibited potential transesterification. This work provided a facile strategy for designing dynamic sulfur-rich polymers via a mild synthesis route.