Phenoxy resin-based vinylogous urethane covalent adaptable networks

This work presents a post-polymerization approach to the preparation of vitrimers, exploiting the transamination of vinylogous urethane in linear phenoxy resins. Phenoxy vitrimers are obtained by a two-steps synthesis from a commercial phenoxy resin via partial conversion of hydroxyl groups to acetoacetates (AcAc), followed by network formation by reaction with m-xylylendiamine as crosslinker. Three different vitrimers with variable crosslinking density are obtained by tuning the density of AcAc moieties along the phenoxy resin scaffold (5%, 10% and 15% conversion of hydroxyl groups). The conversion of linear polymers to dynamic crosslinked net-works is confirmed by dynamic mechanical thermal analyzer and rheology measurements, followed by stress relaxation tests to investigate the kinetics of bond exchanges. Tensile tests as a function of reprocessing cycles reveal an increase of the maximum elongation and stress at break and prove the good recyclability of the vit-rimers. Enhanced adhesive properties compared to pristine phenoxy resins are demonstrated, including the possibility to thermally re-join the assembly after its mechanical failure. Finally, the solvent-free preparation of vitrimers is explored at 5% crosslinking density via melt reactive blending, providing a valuable alternative to the less environmentally sustainable synthesis in solution.