On‐Demand Deconstructable Thermosets Through Cleavable Comonomer and Thermolatent Base Synergy

Abstract

ABSTRACT Thermosets provide superior chemical and mechanical properties critical for high‐performance applications, but their permanent crosslinked networks severely limit recyclability and end‐of‐life (EOL) management. Traditional approaches relying on cleavable comonomers enable degradation only through slow diffusion of acidic or basic solutions, hindering practical implementation. Here, on‐demand deconstructable thermosets are developed by incorporating stimuli‐responsive thermolatent bases alongside cleavable comonomers prior to polymerization. These latent species remain inert during thermal or photoinitiated curing, including vat photopolymerization 3D printing, preserving classical thermoset performance. Upon near‐infrared photothermal or thermal activation (>100°C), rapid network deconstruction yields soluble branched oligomers, enabling efficient chemical recycling without aggressive solvents during service life. This strategy is demonstrated using thermolatent 1,5,7‐triazabicyclo[4.4.0]dec‐5‐ene derivatives with radical copolymerization of dibenzo[ c , e ]oxepine‐5‐thione with styrene/acrylic monomers, as well as ring‐opening metathesis polymerization of dicyclopentadiene with silyl ether‐containing cyclic olefins. The approach offers programmable degradation for sustainable high‐performance thermosets.