Abstract
Abstract : Changes in the fluorescence intensity and spectral characteristics of a fluorescent probe and FTIR spectroscopy have been used to follow the polymerization of polyolmethacrylates initiated by polymeric photoinitiators and a coinitiator. Polymerization photo initiated by a polymeric photoinitiator forms more a rigid polymer and forms gels more rapidly than do monomeric initiator analogs. The use of varied sequences of initiating radiation supports the conclusion that the primary radicals formed during photoreduction of the visible photoinitiators are much less reactive in the case of the polymeric photoinitiator system. This causes a change from bimolecular termination to a unimolecular termination process. Fluorescence probe studies of the long-term postirradiation process were supplemented by FrIR studies which showed that the C=C conversion occurs before relaxation of free volume. (MM) (
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