Thermosets Based on Covalent Bond Exchange: Mechanisms, Properties, and Reprocessing

Thermosets are widely used in engineering applications due to their high mechanical strength, thermal stability, and chemical resistance; however, their permanently crosslinked networks also limit repair, reshaping, and recycling. Dynamic covalent chemistry offers a route to addressing these limitations through the incorporation of reversible bond exchange into thermoset networks. A range of dynamic thermosets has been developed based on transesterification, Diels-Alder reactions, imine exchange, disulfide metathesis, boronic ester exchange, and siloxane equilibration, enabling self-healing, reprocessing, welding, and closed-loop recycling. This review examines representative dynamic thermosets in terms of exchange mechanisms, network topology evolution, and macroscopic response. By correlating molecular exchange processes with network-level mechanics and macroscopic performance, this review identifies design principles for dynamic thermosets with improved sustainability and processing compatibility.