Thermal Initiators as Additives for Photopolymerization of Methacrylates upon Blue Light

Free radical polymerization is often performed by thermal initiation but also more and more by light-assisted polymerization processes. This second approach allows the polymerization to be carried out under mild conditions (under air, upon blue light exposure, under low light intensity). The aim and the originality of the present paper is to perform photopolymerization in the presence of a thermal initiator, i.e., we can take advantage of the exothermicity of the photopolymerization process to decompose the thermal initiator, leading to enhanced polymerization rates. The performance of the photoinitiating system is discussed in the present study based on real-time Fourier-transform infrared spectroscopy measurements (following the C=C bond content evolution vs. time) and by thermal imaging experiments. Mechanisms of the new system proposed in this work are also fully detailed using cyclic voltammetry, electron spin resonance (ESR) spin trapping, and UV-visible absorption properties.