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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. [ABSTRACT FROM AUTHOR]

Photopolymerization processes, and especially those carried out under visible light, are more and more widespread for their multiple advantages compared to thermal processes. In the present paper, new 1,8-naphthalimide derivatives are proposed as photoinitiators for free-radical polymerization upon visible light exposure using light-emitting diodes (LEDs) at 395, 405, and 470 nm. These photoinitiators are used in combination with both iodonium salts and phosphine. The synthesis of these compounds as well as their excellent polymerization initiation ability for methacrylate monomers are presented in this article. A full picture of the involved chemical mechanisms is also provided thanks to photolysis, radical characterization, and redox measurements. [ABSTRACT FROM AUTHOR]