A simplified electrochemically mediated ATRP synthesis of PEO-b-PMMA copolymers

• Amphiphilic diblock copolymers were synthesized by eATRP and seATRP.
• ATRP of MMA was well controlled with low concentration of CuIIBr2/TPMA complex.
• Results of kinetic studies confirmed controlled process of polymerization.

Poly(ethylene oxide)-block-poly(methyl methacrylate) amphiphilic copolymers were prepared via electrochemically mediated atom transfer radical polymerization (eATRP) utilizing only 50 ppm of CuII complex, rather than previously reported concentrations of catalyst of ca. 1,000–30,000 ppm. The copolymers were also prepared via a simplified electrochemically mediated ATRP (seATRP) procedure utilizing an aluminum wire sacrificial anode as a counter electrode, which was directly immersed into the reaction flask, without the need of its separation. This seATRP system works under both potentiostatic and galvanostatic conditions. In each case the polymerization results showed similar molecular weight evolution while maintaining a narrow molecular weight distribution throughout the reactions. The successful chain extension and formation of block copolymers confirmed the living nature of the poly(alkyl methacrylates) prepared by eATRP and seATRP.

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