Synergistic Dual-Cure Reactions for the Fabrication of Thermosets by Chemical Heating.

Large composite structures, such as those used in wind energy applications, rely on the bulk polymerization of thermosets on an impressively large scale. To accomplish this, traditional thermoset polymerizations require both elevated temperatures (>100 °C) and extended cure durations (>5 h) for complete conversion, necessitating the use of oversize ovens or heated molds. In turn, these requirements lead to energy-intensive polymerizations, incurring high manufacturing costs and process emissions. In this study, we develop thermoset polymerizations that can be initiated at room temperature through a transformative "chemical heating" concept, in which the exothermic energy of a secondary reaction is used to facilitate the heating of a primary thermoset polymerization. By leveraging a redox-initiated methacrylate free radical polymerization as a source of exothermic chemical energy, we can achieve peak reaction temperatures >140 °C to initiate the polymerization of epoxy-anhydride thermosets without external heating. Furthermore, by employing Trojan horse methacrylate monomers to induce mixing between methacrylate and epoxy-anhydride domains, we achieve the synthesis of homogeneous hybrid polymeric materials with competitive thermomechanical properties and tunability. Herein, we establish a proof-of-concept for our innovative chemical heating method and advocate for its industrial integration for more energy-efficient and streamlined manufacturing of wind blades and large composite parts more broadly.