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The photopolymerization of Vinyl acrylate (VA) has been investigated with respect to the self-initiating efficiency. VA initiated polymerization of conventional acrylates exhibit fast rates of polymerization and high degrees of conversion are obtained. Herein we report a comprehensive real time infrared (RTIR) investigation of the reaction kinetics of the homo- and copolymerization of VA with various comonomers in the absence and presence of photoinitiators. Analysis of the relative polymerization rates of the acrylate C=C bond versus the vinyl ester C=C bond in VA were performed by the use of RTIR and compared to photo-DSC results. The reactivity of the acrylate C=C is much higher than that of the vinyl ester C=C. The increased reactivity is mainly due to the very close proximity of the two different C=C bonds, exhibiting very large differences in electron densities. Modeling studies were compared to real time kinetics and a good correlation was obtained.
