Facile Synthesis of Tertiary Amine Pendant Polymers by Cu0-Mediated ATRP under Aqueous Conditions

Cu0-mediated atom transfer radical polymerization (ATRP) in aqueous media is extended to tertiary amine-pendant methacrylate polymers with poly([2-dimethylamino]ethyl methacrylate) (PDMAEMA) serving as a model polymer. By increasing the concentration of deactivating CuII species, reducing the reaction temperature, and increasing the supporting halide concentration to 1 M, polymers with well-defined molecular weight distributions (MWDs) are achieved in under 4 h. MWDs show good agreement with theoretical values, with polydispersity indices (Đ) as low as 1.14. Furthermore, this reaction system shows a remarkable tolerance to dissolved oxygen, with little to no deleterious effects observed for polymerizations run without degassing prior to initiation. Syntheses at a mildly acidic pH of 3.5 demonstrate excellent retention of active end groups as demonstrated by chain extensions at near-quantitative conversion and extend the system to 2-(diethylamino)ethyl methacrylate (DEAEMA) and 2-(diisopropyl)ethyl methacrylate (DPAEMA). This work presents a new aqueous method for the rapid and facile synthesis of tertiary amine-pendant polymers with well-defined MWDs.