Polystyrene-Based Vitrimers: Inexpensive and Recyclable Thermosets

We report a straightforward and scalable method for the generation of polystyrene-based vinylogous urethane vitrimers using conventional radical polymerization. The copolymerization of the commercially available and inexpensive monomers styrene and (2-acetoacetoxy)­ethyl methacrylate produced β-ketoester-functional network precursors on a multigram scale, which could be cross-linked with diamines to yield thermally robust vitrimer materials. Vitrimers were (re)­processed over three destruction/compression cycles with acid catalysis to overcome the effects of backbone entanglements. Lastly, the viscoelastic properties were investigated, revealing a higher activation energy for viscous flow (E_a) compared with previously prepared methacrylate-based analogs.