Abstract

AbstractThe rates of epoxidation of polybutadiene homopolymers and styrene–butadiene triblock copolymers with monoperoxyphthalic acid were measured at four temperatures in homogeneous solution. Dioxane and mixed solvents with chloroform were used as reaction media. Activation energy values were also calculated for polymers different in microstructure and styrene content. Viscometry in a modified viscometer was performed and combined with kinetic measurement to monitor the conformational change during epoxidation. Cis‐content in polybutadiene and styrene content in SBS exhibit only slight effect on epoxidation in dioxane. The addition of chloroform promotes the reaction rate remarkably and enlarges the difference between polymers. Explanations were given including the solvent effect on reduced viscosity, which was used to correlate the conformational change of polymer chains. NMR and GPC analysis confirmed the absence of ring opening and degradation during epoxidation up to 54% epoxy group content.

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