On-Demand Release of Secondary Amine Bases for the Activation of Catalysts and Crosslinkers

Abstract

Dynamic covalent (DCv) ureas have been used abundantly to design self-healing materials. We demonstrate that apart from self-healing materials, the species present in the equilibrium of DCv ureas can be employed as responsive organocatalysts. Easily controllable stimuli like heat or addition of water shift the equilibrium towards isocyanate and free base which can function as an in situ released reagent. We demonstrate this application of DCv ureas with two examples. Firstly, we use the liberated base to catalytically activate a latent organocatalyst for acylhydrazone formation. Secondly, this base can be employed in an equimolar manner to trigger the release of nitrile-N-oxides from chlorooximes, which react with acrylate-terminated polymers to form an isoxazoline polymer gel.