Catalyst-Free Vitrimers from Vinyl Polymers

Cross-linked networks feature exceptional chemical and mechanical resilience but consequently lack recyclability. Vitrimers have emerged as a class of materials that feature the robustness of thermosets and the recyclability of thermoplastics without compromising network integrity. Most examples of vitrimers have involved new polymers with exchangeable bonds within their backbones. In pursuit of a more universal, commercially viable route, we propose a method utilizing commercially available and inexpensive reagents to prepare vitrimers from vinyl monomer-derived prepolymers that contain cross-linkable β-ketoester functional groups. Controlled radical copolymerization of methyl methracrylate and (2-acetoacetoxy)ethyl methacrylate afforded linear prepolymers that were converted into vitrimers in a single step by treatment with a trifunctional amine. These materials displayed the characteristic features and reprocessability of vitrimers over as many as six (re)processing cycles. Critically, the networks prepared through this process largely retain the chemical and thermal properties of their linear counterparts, suggesting this method holds significant utility as a user-friendly and commercially relevant approach to the rational design of vitrimers with diverse properties.