Group Interactions in Polyelectrolytes. VIII. The Animation of Chloromethylated Polystyrene with Secondary Amines and the Quaternization of the Aminated Polymer

Abstract The animation of chloromethylated polystyrene (CMPS) and benzyl chloride with diethyl amine, diethanolamine, and di-n-butylamine was investigated kinetically in N,N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), or dioxane. The apparent second-order rate constant decreased as the amination proceeded in the amination of CMPS with diethylamine and di-n-butylamine in DMF as well as in dioxane. Although a similar deceleration was also observed in the amination of CMPS with diethanolamine in DMF and DMSO, acceleration was observed during the course of the amination in dioxane. It is assumed that the deceleration and the acceleration are due to the steric obstruction and to the formation of a hydrogen bond by the neighboring groups in the transition state respectively. The intrinsic rate constants of the amination of CMPS were almost the same as those of benzyl chloride. The rate of the amination with diethanolamine was lower than that of the amination with diethylamine because of the inductive effect of the hydroxyl group. The rate constants in different solvents were in this order; DMSO>DMF>>dioxane. The aminated CMPS with diethanolamine (pK0=7.37) was quaternized with methyl iodide or bromoacetic acid in 50% aq. DMF. The deceleration due to the electrostatic effect of the neighboring groups was observed in the quaternization.