Research on the High-Value Transformation of Plant Oils: Toward High-Performance Recycled and Degradable Thermosetting Polymers

To address the challenge of achieving multisite functionalization of inert C═C bonds in plant oils while preserving the triglyceride scaffold to develop high-performance and recyclable thermosets, a universal strategy is proposed based on thiol–ene click chemistry and dynamic thiocarbamate networks. Pentaerythritol tetrakis(mercaptoacetate) is employed to introduce multiple thiol groups onto the double bonds without disrupting the triglyceride structure. Subsequent polymerization with isocyanate monomers yields tunable thermosets, with tensile strength ranging from ∼10 to 40 MPa and elongation at break from ∼5% to ∼1300%. The dynamic thiocarbamate bonds enable solid-state reprocessability (68%–101% recovery) and self-healing (75%–94% healing efficiency). A sunlight-driven synthesis is developed as a green alternative to UV initiation, producing resins with comparable performance. The retained triglyceride motifs also allow enzymatic degradation, with over 40% mass loss within 30 days. This work provides a versatile platform for upcycling plant oils into high-performance polymers with mechanical robustness, recyclability, and end-of-life degradability, enabling a closed-loop lifecycle.