Covalent Adaptable Networks with Rapid UV Response Based on Reversible Thiol-Ene Reactions in Silicone Elastomers

PhotoCAN silicone elastomers, based on the thiol-ene reaction, exhibit rapid and reversible changes in dynamic modulus at room temperature when illuminated by UV. By combining results from magic angle spinning solid-state NMR as well as EPR and rheometry measurements, both under UV, it is concluded that the mechanical response can be attributed to a combination of dissociative, associative, and oxidation reactions. The cleavage of the C-S bonds under UV in the presence of an excess of thiyl radicals is identified as the reversible dissociative reaction responsible for abrupt drops in the storage modulus. A slower but concurrent reaction is a termination process involving thiyl radicals to form disulfide bonds. A kinetic model is developed that successfully relates the rates of the underlying reaction mechanisms to changes in the storage modulus. The results provide a basis for designing new, ambient temperature photoresponsive covalently adaptive network materials.