Dual-Factor-Controlled Dynamic Precursors Enable On-Demand Thermoset Degradation and Recycling

Thermosets are well known for their advantages such as high stability and chemical resistance. However, developing sustainable thermosets with degradability and recyclability faces several principal challenges, including reconciling the desired characteristics during service with the recycling and reprocessing properties required at the end of life, establishing efficient methods for large-scale synthesis, and aligning with current manufacturing process. Here a general strategy is presented for the on-demand degradation and recycling of thermosets under mild conditions utilizing dynamic precursors with dual-factor-controlled reversibility. Specifically, dynamic triazine crosslinkers are introduced through dynamic nucleophilic aromatic substitution (S_NAr) into the precursor polyols used in polyurethane (PU) synthesis. Upon removal of the catalyst and alcohol, the reversibility of S_NAr is deactivated, allowing for the use of standard PU polymerization techniques such as injection molding, casting, and foaming. The resulting cyanurate-crosslinked PUs maintain high stability and diverse mechanical properties of traditional crosslinked PUs, yet offer the advantage of easy on-demand depolymerization for recycling by activating the reversibility of S_NAr under specific but mild conditions-a combination of base, alcohol, and mild heat. It is envisioned that this approach, involving the pre-installation of dual-factor-controlled dynamic crosslinkers, can be broadly applied to current thermosetting plastic manufacturing processes, introducing enhanced sustainability.