Vinylogous Urea-Urethane Vitrimers: Accelerating and Inhibiting Network Dynamics through Hydrogen Bonding.

Vinylogous urethane (VU O ) based polymer networks are widely used as catalyst-free vitrimers that show rapid covalent bond exchange at elevated temperatures. In solution, vinylogous ureas (VU N ) undergo much faster bond exchange than VU O and are highly dynamic at room temperature. However, this difference in reactivity is not observed in their respective dynamic polymer networks, as VU O and VU N vitrimers prepared herein with very similar macromolecular architectures show comparable stress relaxation and creep behavior. However, by using mixtures of VU O and VU N linkages within the same network, the dynamic reactions can be accelerated by an order of magnitude. The results can be rationalized by the effect of intermolecular hydrogen bonding, which is absent in VU O vitrimers, but is very pronounced for vinylogous urea moieties. At low concentrations of VU N , these hydrogen bonds act as catalysts for covalent bond exchange, while at high concentration, they provide a pervasive vinylogous urea - urethane (VU) network of strong non-covalent interactions, giving rise to phase separation and inhibiting polymer chain dynamics. This offers a straightforward design principle for dynamic polymer materials, showing at the same time the possible additive and synergistic effects of supramolecular and dynamic covalent polymer networks.