Synthesis and thiol–ene photopolymerization of (meth)allyl‐terminated polysulfides

Thiol‐terminated polysulfides (PS) are cured by mixing with an oxidant, resulting in limited shelf‐ and/or pot‐life, depending on whether formulated as a one‐ or two‐component system. Mixtures of thiol‐ and alkene‐terminated polysulfides offer the potential for an on‐demand curing process through thiol–ene photopolymerization. Thiol end groups of commercial polysulfides, PS‐1 (1000 g/mol) and PS‐2 (3000 g/mol), were converted to alkene by reaction with (meth)allyl bromide. Photopolymerizations were performed by irradiating films of equimolar thiol:ene mixtures at 320–500 nm (30 mW/cm²) in the presence of 5 wt % 2,2‐dimethoxy‐2‐phenyl‐acetophenone (DMPA). Reaction kinetics were measured using real‐time FTIR by monitoring absorbances at 3075 cm^?1 (alkene) or 2550 cm^?1 (thiol). In the absence of any reactive diluent, mixtures of thiol and alkene polysulfides failed to gel notwithstanding high reaction conversion (>90%). Partial or total replacement of the thiol polysulfide component with pentaerythritol tetrakis(3‐mercaptopropionate) (PETMP) yielded solid elastomeric films and ultimate reaction conversions of 80–96% after 5 min irradiation. Crosshatch adhesion measured on glass, aluminum, and steel was very poor (0B) for (meth)allyl PS‐1/PETMP and poor (2B) for (meth)allyl PS‐2/PETMP without adhesion promoters. (3‐Mercaptopropyl)trimethoxysilane (1 wt %) significantly improved adhesion of (meth)allyl PS‐2/PETMP on all substrates (4B) but yielded no improvement for (meth)allyl‐terminated PS‐1/PETMP. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 45523.