Thermoswitchable catalysis to inhibit and promote plastic flow in vitrimers

Acid-base catalysis is a common strategy to induce covalent bond exchanges in dynamic polymer networks. Strong acids or strong bases can promote rapid network rearrangements, and are simultaneously preferred catalysts for chemical reactions where maximum efficiency at the lowest possible temperature is aimed for. However, within the context of dynamic polymer networks, the incorporation of highly active catalysts can negatively affect the longer term application potential. Network dynamicity can diminish through catalyst ageing or quenching and highly active catalysts may prematurely activate bond exchanges, leading to dimensional instability and thus low creep resistance of the polymer networks. Herein, we present several examples where we explicitly explored weak acids (carboxylic acids) as catalysts for dynamic bond exchanges, using vinylogous urethanes (VU) as a well-understood protic acid catalysed vitrimer chemistry. Surprisingly, we have found that the sought-after long-term stability offered by a weak acid does not necessarily bring lower activity at high temperature. In fact, the weak acids show a remarkable thermoswitchable catalytic behaviour, going from an inactive hydrogen bonded state to an active state where the polymer matrix is protonated, with a profound impact on the network reactivity and rheology. Carboxylic acids with different electronic or steric environments show clear reactivity trends and their fine-tuning resulted in the most thermally responsive VU vitrimers studied to date. Our findings point out that catalyst choice and design for vitrimers is only poorly informed by catalyst performance in more traditional chemical reactions (in solvent), and that a more tailored catalyst design holds great promise for the field of vitrimers.