IR spectroscopic study of radical polymerization kinetics

IR spectroscopic technique for the study of the kinetics of radical copolymerization of acryl and vinyl monomers was developed. The technique is based on monitoring the conversion curves and determining copolymerization rates in the course of the process separately for each monomer by measuring variations in the intensity of IR absorption bands of reacting C=CH 2 groups. A comparative study of the copolymerization of model monomer pairs using monofunctional and polyfunctional compounds provided data on the role of structural-physical transformations, involved in the formation of cross-linked polymers, on the copolymerization kinetics and on the nonuniformity of distribution of cross-links in the copolymers formed. Nonuniformity in the spatial distribution of reagents caused by the accumulation of side double bonds in the vicinity of the growing macroradical, microphase separation of the components, and a glass transition in the reacting system are shown to have a significant effect on the effective reactivity of monomers in the three-dimensional copolymerization and the structure of polymers formed.