Free radical formation in three-component photoinitiating systems

N,N'-diethylthiacarbocyanine iodide (Cy) with two different compounds acting as co-initiators were used in the three-component photoinitiating systems for free radical polymerization of acrylate monomer. The steady state and time-resolved techniques were used to study the fluorescence quenching by co-initiators, as well as laser flash photolysis to investigate an electron transfer process, that occurs in these photoinitiating system (PIS). To investigate the key factors involved with visible-light activated radical polymerizations involving three-component photoinitiators, we used thermodynamic feasibility and kinetic considerations to study photopolymerizations initiated with thiacarbocyanine dye as a photosensitizer. The Rehm-Weller equation was used to verify the thermodynamic feasibility for electron transfer reaction. Experiments show, that the main interaction between the dye and both co-initiators occurs through its excited singlet state. It was concluded, that the key kinetic factors for efficient visible-light activated initiation process are summarized in two ways: (1) to retard back electron transfer and recombination reaction steps and (2) to use a secondary reaction step to consuming dye-based radical and regenerating the original photosensitizer. Basing on the study, it is known that, there are two possible mechanisms of generation of free radicals, which can start polymerization involving photoreducible series mechanism and parallel series mechanism (photoreducible-photooxidizable series mechanism). (C) 2012 Elsevier Ltd. All rights reserved.