Solvent Effect on Radical Polymerization of Vinyl Acetate

Abstract

Absolute rate constants of vinyl acetate (VAC) polymerization have been measured by using the intermittent illumination method in various aromatic solvents and ethyl acetate at 30°. It was shown that the solvent effect was mainly ascribed to the variation in propagation rate constants (kp) with solvents rather than that in termination rate constants (kt). The kp increased in the order: benzonitrile < ethyl benzoate < anisole < chlorobenzene < fluorobenzene < benzene < ethyl acetate. This order is almost the same as that for vinyl benzoate (VBZ) previously reported. There was about an eightyfold difference between the largest and the smallest values. This large variation in kp is explained neither by copolymerization through solvents nor the chain transfer to solvents, but by a reversible complex formation between the propagating radical and aromatic solvents. The kp was determined in mixed solvents of ethyl benzoate and ethyl acetate, decreasing with increasing content of ethyl benzoate. This result supports the idea of a reversible complex. The stability constants (Ks) of the complex were estimated on the assumption that the complexed radical was in a dormant state and inactive in the polymerization. The correlation between Ks or kp and the calculated delocalization stabilization energy for the complex was found, and supported the explanation for the solvent effect.