Expanding the supramolecular polymer LEGO system: Nitroxide‐mediated living free‐radical polymerization as a tool for mono‐ and telechelic polystyrenes

Abstract Nitroxide‐mediated, controlled living radical polymerization was employed to introduce terpyridine ligands at one or two chain ends of polystyrene. For this purpose, a unimolecular initiator bearing both a terpyridine ligand as well as a mediating nitroxide was synthesized and used for the controlled polymerization of styrene. Moreover, a maleimide‐functionalized terpyridine was prepared in order to synthesize telechelic polymers, utilizing nitroxide substitution reactions. Kinetic studies of the polymerization of styrene were carried out. In all polymerizations, special attention was focused on the retention of end‐group functionality, in light of the effects of autoinitiation and autopolymerization. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4016–4027, 2004