Effect of electrostatic field on the polymer chain in the quaternized reaction of polyvinylpyridine with alkyl halides

Abstract

Abstract In order to discuss the electrostatic‐field effect on a polymer reaction, the quaternization of poly‐4‐vinylpyridine–benzyl chloride (system I) was compared to that of poly‐γ‐chloromethylstyrene–γ‐picoline (system II). In these two systems, the reaction initially proceeded according to the simple second‐order kinetics. However, after the degree of quaternization exceeded 20–30 mole‐%, a deviation from simple second‐order kinetics occurred. In system I negative deviation occurred, while in system II positive deviation occurred. These phenomena occurred even though the solvent or the initial concentrations of the reactants were changed. The reasons for these phenomena are given below. In system I, the quaternized pyridine nitrogens prevented the benzyl chloride from approaching the unquaternized pyridine nitrogens. However, in system II the free γ‐picoline was attracted by the quaternized chloro‐γ‐methyl site. Furthermore, the point at which the deviation occurred was determined by the degree of chloromethylation. All these results suggest that the effect of an electrostatic field must be presumed in these two systems.