The Menschutkin reaction of three poly(tertiary aminostyrene)s: poly( N,-N-dimethyl-4-vinylphenylamine) (PPA), poly(N,N-dimethyl-4-vinylbenzylamine) (PBA), and poly( N,N-dimethyl-4-vinylphenethylamine) (PPTA) was investigated. These three polymers having narrow molecular weight distributions were prepared via anionic living polymerization. PPA reacted homogeneously with n-butyl bromide in N,N-dimethylformamide (DMF). PBA and PPTA also reacted homogeneously with n-butyl bromide in a mixture of DMF/methanol (75/25 v/v %). GPC measurement of the quaternized polymers was carried out using a mixture of water/acetonitrile (80/20 v/ v %) containing 0.5 M acetic acid and 0.3 M sodium sulfate (pH Γ
2.9) as an eluant in order to suppress adsorption of the quaternized water soluble polymers on GPC gel. Results of GPC measurement indicate that the polymer chains of the three poly(tertiary aminostyrene)s are neither severed nor crosslinked in the process of quaternization. Temperature dependence and reaction time dependence on the degree of quaternization (DQ) were studied for PPT, PBA, and PPTA. By altering reaction time and temperature, the DQ values of the three poly(tertiary aminostyrene)s could be controlled in the range from 0% to nearly 100%. Quaternization reactivity of the amino groups in the three polymers was found to decrease in the order, PPTA, PBA, and PPA. The differences in reactivity are thought to be attributable to the electron density on the nitrogen atom of the N,N-dimethylamino group, and steric hindrance in the vicinity of the nitrogen atom.