Transforming Element Sulfur to High Performance Closed-Loop Recyclable Polymer via Proton Transfer Enabled Anionic Hybrid Copolymerization.

The utilization of sulfur has been a global issue. Copolymerization of element sulfur (S) with other monomers is a promising route to convert it to useful materials but is limited by the comonomers. Here, we report anionic hybrid copolymerization of S with acrylate and epoxide at room temperature, where S does not copolymerize with epoxide in the absence of acrylate. Yet, the proton transfer from the methyne in acrylate to the oxygen anion enables the ring-opening of the cyclic comonomer and hence the copolymerization. The cyclic comonomers can be expanded to lactone and cyclic carbonate. Specifically, the copolymer of S with bisphenl A diglycidyl ether and diacrylate displays mechanical properties comparable to those of most common plastics, namely, it has ultimate tensile strength as high as 60.8 MPa and Young's modulus up to 680 MPa. It also exhibits high UV resistance and good transparency. Particularly, it has excellent UV-induced self-healing, reprocessability and closed-loop recyclability due to the abundant dynamic S-S bonds and ester groups. This study provides an efficient strategy to turn element sulfur into closed-loop recyclable polymer with high mechanical and optical performances.