Self-Immolative Adaptable Oleic-Acid-Based Thermosets: Modular Design, Degradability, and Light-Driven Reprocessability

Abstract This paper presents a rational molecular design for sustainable thermosets that utilizes biomass feedstocks and provides molecular-level control over both malleability and degradability. An oleic-acid-based degradable core monomer was synthesized via a one-pot process and copolymerized with a polycaprolactone-based functional macromonomer to form a robust transparent network containing active sites for programmable degradation in response to a specific stimulus, releasing predesigned products. With the addition of trace alcohols, the renewable networks became recyclable through covalent bond exchange while maintaining site-specific degradability. Furthermore, incorporating polydopamine-coated ZrO2 nanoparticles reinforced the network, enhancing modulus and radiopacity while imparting light-driven spatiotemporal control. The resulting composite demonstrated rapid underwater healing, shape-preserving reconfiguration, and recyclable yet disposable adhesive performance. This design can be extended to other biomass-derived units or synergistic additives, offering a feasible strategy for sustainable thermosets and highlighting the potential of abundant fatty acids for functional polymeric materials.