New three‐component photoinitiating systems consisting of a cyanine dye, borate salt, and a 1,3,5‐triazine derivative were investigated by measuring their photoinitiation activities and through fluorescence quenching experiments. Polymerization kinetic studies based on the microcalorimetric method revealed a significant increase in polymerization rate when the concentration of n‐butyltriphenylborate salt or the 1,3,5‐triazine derivative were increased. The photo‐induced electron transfer process between electron donor and electron acceptor was studied by means of fluorescence quenching and SrEt change of the fluorescence intensity. The experiments performed documented that an increase of the n‐butyltriphenylborate salt concentration dramatically increases the rate of dye fluorescence quenching, whereas the increasing of the 1,3,5‐triazine derivative concentration slows down the consumption of the dye. We conclude that the primary photochemical reaction involves an electron transfer from the n‐butyltriphenylborate anion to the excited singlet state of the dye, followed by the reaction of the 1,3,5‐triazine derivative with the resulting dye radical to regenerate the original dye. This reaction simultaneously produces a triazinyl radical anion derived from the 1,3,5‐triazine, which undergoes the carbon‐halogen bond cleavage yielding radicals active in initiation of a free radical polymerization chain. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3626–3636, 2007

2-Ethyl-2-(hydroxymethyl)-1,3-propanediol triacrylate was polymerized in the presence of squarylium dye and various onium salts.

a 1,3-Bis(p-bromophenylamino)squaraine which functions as an electron-transfer photosensitizer for a wide range of diphenyliodonium salts radical photoinitiators of triacrylate polymerization under UV-blue light irradiation is presented. The functionality of the photosensitizer is determined by the presence of a suitable co-initiator. For this purpose, several different diphenyliodonium salts were used as a source of active species for radical polymerization. The reactivity of the new iodonium salts was studied with ultraviolet-blue light initiated radical polymerization by photo-DSC using squaraine dye as a sensitizer.The iodonium salts functionated as radical initiators bearing different substitution patterns. Electron transfer from the excited state of the sensitizer to the iodonium salt results in initiating radicals. The ability to initiate free radical polymerization of TMPTA by iodonium salts studied is similar. Most of the iodonium salts exhibit no large differences regarding the reactivity in initiation of TMPTA polymerization.However, an introduction of a nitro group in the para position of the phenyl ring of the co-initiator results in a significant increase in the rate of polymerization and degree of monomer conversion. The dye-sensitized photoreaction mechanism of the SQ/I system was also confirmed.