Experimental and theoretical investigations of active center generation and mobility in cationic and free-radical photopolymerizations

Photopolymerization is considered an attractive alternative in many industries to traditional polymerization processes. The advantages of photopolymerization over other types of polymerization include elimination of heat sources, faster cure times, and reduction in the use of volatile organic solvents. Despite these environmental and cost-saving advantages, photopolymerizations have several limitations. Light attenuation can be a problem for systems containing pigments or fillers. The radiation source penetrates only to a shallow depth beneath the surface, limiting the thickness of strongly pigmented or filled coatings and films. Photopolymerization is also generally limited to systems with simple geometries that can be uniformly illuminated. Coatings on three-dimensional substrates, or other systems with complex geometries, are difficult to uniformly cure. These problems can be solved by "shadow cure," which is defined as the reactive diffusion of photoinitiated active centers into regions of a polymer that are unilluminated. In this contribution, the generation and subsequent spatial and temporal evolution of the active center concentrations during illumination are analyzed using the differential equations that govern the light intensity gradient and photoinitiator concentration gradient for polychromatic illumination. Reactive diffusion of the active centers during the post-illumination period is shown to result in cure of unilluminated regions. A kinetic analysis is performed by coupling the active center concentration profiles with the propagation rate equation, yielding predicted cure times for a variety of applications. This analysis is used for the evaluation of cationic shadow cure in pigmented photopolymerization systems, and systems with complex geometries. The extensive characterization of cationic systems is then applied to free-radical photopolymerization to examine the potential of shadow cure for active centers with much shorter lifetimes. An example of a free-radical photopolymerization system is characterized in which the dimensional scales are small enough to utilize the short lifetimes of the active centers. The results presented for both free-radical and cationic shadow cure indicate that the reactive diffusion of photoinitiated active centers may be used for effective cure in unilluminated regions of a photopolymer. This research will potentially allow photopolymerization to be applied in industries where it has never before been utilized.