Near-Infrared Light-Induced Deep Curing of Thiol–Epoxy Networks Based on Upconversion Photochemistry

Thiol–epoxy photopolymerization offers exceptional advantages for high-performance protective coatings, yet efficiently curing thick formulations remains a significant challenge due to the limited penetration depth of conventional UV light. Herein, we report a novel near-infrared (NIR) light-activated photopolymerization system for deep-curing applications, strategically integrating upconversion nanoparticles (UCNPs) as NIR-to-UV converters, isopropylthioxanthone (ITX) as a photosensitizer, and a liquid N-phenylglycine-based photobase generator (NPG-TBD) with enhanced resin solubility. Upon 980 nm NIR irradiation, photogenerated TBD efficiently catalyzes thiol–epoxy polymerization through an anionic mechanism, enabling uniform network formation with epoxy and thiol functional group conversions greater than 90% throughout samples exceeding 2.5 cm in thickness. The resulting coatings exhibit excellent mechanical properties including 3H pencil hardness, strong adhesion (0 grade), and good flexibility (2 mm), significantly outperforming conventional UV systems limited to approximately 1.5 mm. Additionally, the cured materials demonstrate multifunctional characteristics including distinctive upconversion luminescence and dual-responsive shape memory behavior. This approach addresses critical limitations in deep-photocuring technology while offering significant potential for applications in protective coatings for marine infrastructure, chemical storage facilities, and smart materials requiring both substantial barrier properties and programmable responsiveness.