Abstract
Kinetic data on the radical polymerization of methyl methacrylate are treated in terms of termination rate equations based on Stokes law and the reptation model. The values of k/kp2 obtained are independent of initiation rate, where k corresponds to the rate constant of the diffusion-controlled reaction between segment radicals and kp is the propagation rate constant. When x (conversion) is less than 0.5, an equation as k/kp2∝exp (−1.1/Vf) (Vf, free volume) is obtained. When x>0.5, k/kp2 deviates from such an equation. This deviation may show that the propagation rate decreases with increasing in x, since this rate becomes diffusion-controlled.
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Ito, K. Evaluation of Termination Rate by the Free Volume Thoery in Radical Polymerization. Polym J 13, 727–731 (1981). https://doi.org/10.1295/polymj.13.727
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DOI: https://doi.org/10.1295/polymj.13.727