Pulse radiolysis studies on the polymerization of acrylates and methacrylates

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EB (electron beam) initiated polymerization of methyl acrylate (MA) and methyl methacrylate (MMA) in dilute cyclohexane solution was investigated by pulse radiolysis with kinetic spectroscopic detection. The maximum in the absorption spectrum of the methacryl radical was shifted somewhat lower wavelength as compared to the acryl radical ( λ max = 287 nm in MA and λ max = 292 nm in MMA solution). From the decay curves rate parameters of termination (2 k t) were calculated. The decay depart from the simple second order kinetics when measured at high concentrations and the decay curves can be fitted only by combination of two second order decays. The deviation from the simple second order kinetics at high doses was attributed to termination with primary radicals.