Development of a comprehensive free radical photopolymerization model incorporating heat and mass transfer effects in thick films

A comprehensive kinetic model describing photopolymerization is developed which allows variation of temperature, species concentrations, and light intensity through the thickness of a photopolymerized film. Heat and mass transfer effects are included, as is the generation of heat by both reaction and light absorption. In addition to initiation, propagation, and termination mechanisms, both primary radical termination and inhibition are incorporated into the model. The possible presence and diffusion of an inert solvent are also accounted for. Thus, the model is useful for examining complex polymerization kinetics and behavior in industrially and commercially important thick film photopolymerizations, such as the curing of contact lenses, dental restorative materials, photolithographic resists, and optoelectronic coatings. The comprehensive model is used to predict polymerization rate, temperature, and conversion profiles in a variety of systems. The effects of heat generation and the thermal boundary conditions are explored, with the result that heat generation in thick samples leads to greatly increased con-versions approaching 100 percent. Increased temperature in these samples also may lead to the appearance of two rate maxima, with the first due to the temperature increase and the second caused by the autoaccelcration process. The magnitude of the temperature increase, along with the resultant effects, is more pronounced in insulated systems. (C) 2002 Elsevier Science Ltd. All rights reserved.