Near-infrared photopolymerization: Initiation process assisted by self-quenching and triplet–triplet annihilation of excited cyanine dyes

The mechanism of radical polymerization photoinitiated by a near-infrared absorbing indotricarbocyanine (HITC) was investigated using an indirect kinetics method based on the photobleaching dynamics of the dye. Despite similar photophysical features in glycerol and in pentaerythritol triacrylate monomer, HITC undergoes a very fast photobleaching in the acrylate resin which leads to photopolymerization at high power regime. The addition of an amine induces the decrease of photopolymerization threshold by a factor 5 with unexpected dye regeneration. These effects were correlated to the reactivity of the reduced and oxidized forms of HITC produced via triplet–triplet annihilation and ground state quenching processes.