Preparation of well-defined poly[ethylene oxide-b-(sodium 2-acrylamido-2-methyl-1-propanesulfonate)] diblock copolymers by water-based atom transfer radical polymerization

Well-defined poly[(ethylene oxide)-block-(sodium 2-acrylamido-2-methyl-1-propane sulfonate)] diblock copolymers [P(EOm-b-AMPSn)], have been obtained by water-based ATRP using a-methoxy-?-(2-methylbromoisobutyrate) poly(ethylene oxide)s (MeO-P[EO]m-BriB with m ranging from 12 to 113) and CuBr?·?2Bpy (Bpy for 2,2'-bipyridyl) as macroinitiator and catalytic complex, respectively. Compared to direct polymerization in water, it has been demonstrated that the water/methanol (3:1, v/v) mixture is better suited for predicting the final number-average molar mass from the initial monomer-to-macroinitiator molar ratio and achieving a quite narrow polydispersity, even at high monomer conversion (?˜?1.4 at 80% conversion). The effect of temperature, solvent mixture composition and addition of NaCl salt on the polymerization rate and extent of control over the copolymer molecular parameters have been highlighted as well.