ARGET ATRP of Triblock Copolymers (PMMA-b-PEO-b-PMMA) and Their Microstructure in Aqueous Solution

[Image: see text] Triblock copolymers poly(methyl methacrylate)-b-poly(ethylene oxide)-b-poly(methyl methacrylate) (PMMA-b-PEO-b-PMMA) with designed molecular weight of PMMA and PEO blocks were synthesized via the activator regenerated by electron transfer (ARGET) atom transfer radical polymerization (ATRP) of MMA. The Br-terminated Br–PEO–Br with the molecular weights of 20k and 100k were used as macroinitiators. ARGET ATRP was performed with ppm level amount CuBr(2) as the catalyst and ascorbic acid as the reducing agent to overcome the sensitivity to oxygen in a traditional ATRP. The molecular weight of the PMMA block was manipulated by changing the molar ratio of monomers to the Br–PEO–Br macroinitiators. The synthesis of PMMA-b-PEO-b-PMMA and its structure was confirmed by Fourier transform infrared and (1)H NMR, and the molecular weight of the PMMA block was determined by (1)H NMR. Aqueous solutions of PMMA-b-PEO-b-PMMA were prepared by solvent-exchange, and their microstructures were examined by tensiometry, static light scattering, and transmission electron microscopy. The effects of molecular weight of the PMMA and PEO blocks on the microstructure were elucidated.