Kinetic study of amination of chloromethylated polystyrene with hydroxyalkylic tertiary amines

The kinetics of the amination of chloromethylated polystyrene with two hydroxyalkylic tertiary amines (1-dimethyl-amino-3-propanol and 1-dimethylamino-2-propanol) in dimethylacetamide and dioxane was studied. The amination of benzyl chloride with the two amines in dimethylacetamide was followed. It was found that the amination of chloromethylated polystyrene is a two-step reaction taking place with different rates. The rate constants k₁ and k₂ were calculated for the two stages, and a self-accelerating effect of the reaction was noticed. Also, the influence of the position of the hydroxyl group versus the tertiary nitrogen was investigated. The increase of the dielectric constant of the solvent favorably influences the reaction rate.