Activated Phenyl Ester Vitrimers

Abstract Aromatic esters are amongst the oldest known chemical motifs that allow for thermal (re)processing of thermosetting polymers. Moreover, phenyl esters are generally known as activated esters that do not require a catalyst to undergo acyl transfer reactions. Even though dynamic aromatic esters find applications in commercialized thermoset formulations, all‐aromatic esters have found limited use so far in the design of covalent adaptable networks (CAN) as a result of their high glass transition temperature (T g ) and specific curing process. Here, a strategy to include partly aromatic esters as dynamic cross‐links inside low T g (−40 °C) thermosetting formulations, using aliphatic esters derived from para‐hydroxybenzoic acid, which serves as a highly activated phenol or as a reactive “phenylogous anhydride” is reported. A small molecule study shows that the activated phenyl ester bonds can readily exchange with free phenol moieties at 200 °C under catalyst‐free conditions, while the addition of a catalyst allows for a faster exchange. Robust and hydrophobic polymer networks are conveniently prepared via rapid thiol‐ene UV‐curing of unsaturated phenol esters. The obtained networks show high thermal stability (350 °C), fast processability, good water resistance, and low creep up to 120 °C, thus showing good promise as a platform for CAN.