Radiation‐induced polymerization of glass‐forming systems. V. Initial polymerization rate in binary glass‐forming systems

Abstract

AbstractThe radiation‐induced polymerization of binary systems consisting of glass‐forming monomer and glass‐forming solvent in supercooled phase was studied. The initial polymerization rates were markedly affected by Tg (glass transition temperature) and Tv of the system (30–50°C higher than Tg), which turned to be functions of the composition. The composition and temperature dependence of initial polymerization rate in binary glass‐forming systems were much affected by homogeneity of the polymerization system and the Tg of the glass‐forming solvent. The composition and temperature dependences in the glycidyl methacrylate–triacetin system as a typical homogeneous polymerization system were studied in detail, and the polymerizations of hydroxyethyl methacrylate–triacetin and hydroxyethyl methacrylate–isoamyl acetate systems were studied for the heterogeneous polymerization systems; the former illustrates the combination of lower Tg monomer and higher Tg solvent and the latter typifies a system consisting of higher Tg monomer and lower Tg solvent. All experimental results for the composition and temperature dependence of initial polymerization rate in binary glass‐forming systems could be explained by considering the product of the effect of the physical effect relating to Tv and Tg of the system and the effect of composition in normal solution polymerization at higher temperature, which was also the product of a dilution effect and a chemical or physical acceleration effect.