Degradable thermosets via orthogonal polymerizations of a single monomer

Crosslinked thermosets are highly durable materials, but overcoming their petrochemical origins and inability to be recycled poses a grand challenge1–3. Many strategies to access crosslinked polymers that are bioderived or degradable-by-design have been proposed, but they require several resource-intensive synthesis and purification steps and are not yet feasible alternatives to conventional consumer materials4–8. Here we present a modular, one-pot synthesis of degradable thermosets from the commercially available, biosourced monomer 2,3-dihydrofuran (DHF)9. In the presence of a ruthenium catalyst and photoacid generator, DHF undergoes slow ring-opening metathesis polymerization to give a soft polymer; then, exposure to light triggers strong acid generation and promotes the cationic polymerization of the same DHF monomer to spatially crosslink and strengthen the material10–12. By manipulating catalyst loading and light exposure, we can access materials with physical properties spanning orders of magnitude and achieve spatially resolved material domains. Importantly, the DHF-based thermosets undergo stimuli-selective degradation and can be recycled to the monomer under mild heating. The use of two distinct polymerization mechanisms on a single functional group allows the synthesis of degradable and recyclable thermoset materials with precisely controlled properties.