Radical polymerization of styrene in presence of poly(2,2,6,6-tetramethylpiperidine-N-oxyl-4-yl methacrylate) - formation of polymer brushes

The radical polymerization of styrene in presence of poly(2,2,6,6-tetramethylpiperidine-N-oxyl-4-yl methacrylate) (PTMA) is described. PTMA is a well-known polymer for organic radical batteries. Tetramethylpiperidine-N-oxyl (TEMPO) is the common reagent for nitroxide-mediated controlled radical polymerization (NMP). PTMA, as macromolecular counterpart of TEMPO, was found to lead to a partly controlled polymerization process. During the polymerization, large amounts of the graft copolymer PTMA-g-PS are formed via the grafting-to approach. No indication for insoluble gel formation at high conversion rates is observed. The isolated graft copolymers were characterized by dynamic light scattering and revealed hydrodynamic radii in the range of 30-50 nm. The polymerization in presence of PTMA offers a convenient way to the multigram-scale synthesis of bottle-brush polymers. (C) 2017 Elsevier Ltd. All rights reserved.