Solvent effect on radical polymerization of phenyl methacrylate

Abstract

The radical polymerization of phenyl methacrylate has been studied in various aromatic solvents at 30 and 60°C, and the solvent effects on the polymerization rate were observed. In order to make clear the cause of the solvent effect, propagation rate constants (kp) and termination rate constants (k%) were determined by the intermittent illumination method. Values kp increased in this order of solvents: Benzene < fluorobenzene < chlorobenzene < anisole < bromobenzene < benzonitrile. The variation of kv value for phenyl methacrylate with solvents was compared with that for vinyl benzoate. The cause of the solvent effect is discussed in terms of monomer solvation, polar effect of the propagating radical, chain transfer, and donor-acceptor complex between the propagating radical and solvents. The variation of kv value with solvents is best explained by the formation of a donor-acceptor complex, and is correlated with delocalization stabilization for the complex formation. © 1977 The Society of Polymer Science, Japan.