Synthesis of nitroxide-containing block copolymers for the formation of organic cathodes

This contribution describes the polymerization of 2,2,6,6-tetramethylpiperidin-4-yl methacrylate by atom transfer radical polymerization (ATRP). Different catalytic systems are compared. The CuCl/4,40 -dinonyl-2,20 -dipyridyl catalytic system allows a good control over the polymerization and provides polymers with a polydispersity index below 1.2. The successful polymerization of styrene from PTMPM-Cl macroinitiators by ATRP is then demonstrated. Successful quantitative oxidation of PTMPM-b-PS block copolymers leads to poly(2,2,6,6-tetramethyl- piperidinyloxy-4-yl-methacrylate)-b-poly(styrene) (PTMA-b-PS). The cyclic voltammogram of PTMA-b-PS indicates a reversible redox reaction at 3.6 V (vs. Liþ/Li). Such block copolymers open new opportunities for the formation of functional organic cathode materials.