Abstract: | Styrene, methyl acrylate, and N,N-dimethylacrylamide were copolymerized with small proportions of p-nitrophenyl acrylate or p-nitrophenyl esters of CH2?CHCONH(CH2)nCOOH (n = 1,3,5). The aminolysis of these copolymers in dioxane and chlorobenzene solution was compared with the corresponding reaction of low molecular weight analogs. The ratio of the reactivity of the polymer substituent and its analog was found to be insensitive to the nature of the amine but strongly dependent on the nature of the polymer backbone. Poly(dimethylacrylamide) chains carrying active ester substituents were in some cases much more reactive than their analogs due to the activating effect of the dimethylamide groups. In the case of the p-nitrophenyl acrylate–styrene copolymer, the aminolysis exhibited a dispersion of the rate constant due to its sensitivity to stereoisomerism in the vicinity of the active ester, but no similar effects were observed with the other copolymers. |