The efficiency of titanocene as photoinitiator in the polymerization of dental formulations

A comparative kinetic study of the polymerization of tetraethyleneglycol dimethacrylate (TEEGDM) under visible light irradiation was carried out in order to determine the effectiveness of titanocene as photoinitiator in this process. The pair camphorquinone/dimethylaminoethyl methacrylate, CQ/DMAEMA (0.5/0.5%, by weight), was used as a reference photoinitiatior system. The reactions were carried out both in the presence and absence of oxygen (in N2) and with variable and constant titanocene concentration and incident light intensity. It was observed that in both atmospheres the polymerization reaction commenced rapidly and its initial rate was comparable with that obtained in the presence of the classic initiation system. However, after reacting for a few seconds this process suffered abrupt deactivation, this tendency being more noticeable at low titanocene concentrations. To explain the observed kinetic behavior, the study of the photofragmentation of titanocene upon irradiation with visible light in both atmospheres was carried out. The quantum yield calculated in the presence of O2 (fr = 8 at 465 nm) suggests the existence of a chain reaction with participation of oxygen, and this explains, in turn, the high value of the initial rate of polymerization and also the rapid disappearance of the photoinitiator. In an inert atmosphere the photofragmentation occurs in a conventional way, this being a very effective process with quantum yield of 0.7 at 465 nm. However, it seems that only a small part of the active species acts as initiating radicals and these are not sufficient to achieve the appropriate monomer conversion.