Poly(thioether) Vitrimers via Transalkylation of Trialkylsulfonium Salts

Vitrimers are permanently cross-linked organic polymers that can be reshaped, molded, and recycled without loss of network integrity. Herein, we report poly(thioether) networks, prepared through a straightforward thiol-ene photopolymerization, that can be turned into catalyst-free vitrimer materials by partial alkylation of the thioethers (1-10%) to the corresponding trialkylsulfonium salts. Based on a classical S_N2-type substitution, the resulting polyionic networks can be reshaped upon heating via swift transalkylation reactions. This novel exchange reaction for the design of vitrimers was studied both on low MW model compounds as well as on a material level. In addition, we demonstrated the recycling of these networks without significant loss of mechanical properties.