Solvent effect on radical polymerization of methyl methacrylate.

Kamachi Mikiharu, Liaw Der Jang, Nozakura Shun-ichi

doi:10.1295/polymj.13.41

The radical polymerization of methyl methacrylate (MMA) in various aromatic solvents was studied under the same conditions as that of phenyl methacrylate (PMA) reported previously. The propagation-rate constants (k_p) and termination-rate constants (k_t) were determined by intermittent illumination methods. The variation in the k_p values for MMA with aromatic solvents had the same trend as that for PMA, although the solvent effect on the former values was somewhat smaller than that on the latter. Variation in k_p values with solvents can be explained by the formation of an electron donor–acceptor complex and is correlated with the delocalization stabilization of the complex formation. The dependence of k_p value on the monomer concentration supports the view that a propagating radical complexed with a solvent is in the dormant state. A study of temperature dependence on k_p and k_t values was also carried out in benzene and activation energy of these values determined to be 5.0±0.8 and 0.38±0.10 kcal mol⁻¹, respectively.

Solvent effect on radical polymerization of methyl methacrylate.

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