AbstractPolymers with tertiary amino groups were obtained by reaction of chloromethylated polystyrene (CMPS) with 3‐alkylaminopropionitriles (2a — e). The resulting polymers3a — ewere characterized by elemental analyses, IR and1H NMR spectra. Kinetic investigation showed that the reaction is characterized by two rate constants, the rate change taking place at a conversion of 45–50%. Viscosimetric studies of the hydrochlorides of polymers3a — ein water and methanol showed that they behave as polyelectrolytes only in methanol. The abnormal behaviour of water solutions was explained by hydrolysis reaction. To prove the conclusions on the molecular structures of3a — eand the reactivity of CMPS, a study of the reaction of benzyl chloride with the same amines wa