Waterborne Methacrylate-Based Vitrimers.

We demonstrate waterborne, unimolecularly dissolved vitrimer prepolymer systems that can be transferred into a vitrimer material using catalytic transesterification. The one-component prepolymer system can be processed via film casting and subsequent heat-induced cross-linking. A variation of the density of side chain hydroxy groups over ester and amide groups in the methacrylate/methacrylamide backbone, as well as of the Lewis acid catalyst loading, allow control of the extent of cross-linking and exchange rates. The increase of the amount of both catalyst and hydroxy groups leads to an acceleration of the relaxation times and a decrease of the activation energy of the transesterification reactions. The system features elastomeric properties, and the tensile properties are maintained after two recycling steps. Thus far, vitrimers have been limited largely to hydrophobic polymers; this system is a step forward toward waterborne, one-component materials, and we demonstrate its use in waterborne bioinspired nanocomposites.