Efficient dual radical/cationic photoinitiator under visible light: a new concept

A new concept based on the photoredox catalysis is proposed for the design of a photoinitiating system able to efficiently generate, in a single catalytic cycle, both a radical and a cation as initiating species. This is exemplified here by the tris(1,10-phenanthroline)ruthenium(II) (Ru(phen)32+) complex in combination with a diphenyl iodonium salt and a silane. Interesting and promising photopolymerization profiles in free radical photopolymerization (FRP) and free radical promoted cationic photopolymerization (FRPCP) are obtained under air and upon xenon lamp exposure and even soft irradiation conditions (fluorescence bulb, sunlight). An acrylate/epoxide blend is also easily polymerized under air using a fluorescent bulb. The mechanisms are investigated by ESR and Laser Flash Photolysis experiments.