Vitrimers are a subclass of covalent adaptable networks, which introduce reshapeability and recyclability in thermoset materials while maintaining a high degree of chemical resistance and dimensional stability. Vitrimer materials based on vinylogous urethane (VU) chemistry have drawn a lot of attention in this area. Classically, these are obtained by the polycondensation polymerization of acetoacetate and amine monomers. Unfortunately, this also releases water, often leading to porosity defects in the initially obtained non-reprocessed crosslinked materials. Here, we demonstrate that alkyne esters (AE) can be used as alternative building blocks for VU vitrimers by a polyaddition polymerization with amines, leading to water-free formulations and straightforward access to defect-free cured VU vitrimer materials.The bond formation and dynamic bond exchange was also studied by small molecule reactions, further rationalized by a computational (DFT) approach. The resulting water-free VU vitrimers display similar material properties compared to vitrimers based on acetoacetates, although also some differences are seen, which can be related to a minor amide-bond forming side reaction. Furthermore, using this novel AE approach, polyaddition curing of VU epoxy vitrimers can easily be prepared in a one-pot three-component method, combining AE, amine and epoxy monomers. This study shows that AE monomers can be used as an easy drop-in method to obtain processable epoxy materials with tunable viscoelastic properties, where the viscous flow behavior can in principle be fully tuned by varying the monomers' ratios and compositions.

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