N‐alkoxy pyridinium ion terminated polystyrenes: A facile route to photoinduced block copolymerization

Photoactive N‐alkoxy 4‐phenyl pyridinium and N‐alkoxy isoquinolinium ion terminated polystyrenes with hexafluoroantimonate counter anion were prepared and characterized. For this purpose, mono‐ and dibrominated polystyrenes were prepared by atom transfer radical polymerization (ATRP). The reaction of these polymers with silver hexafluoroantimonate in the presence of 4‐phenylpyridine N‐oxide and isoquinoline N‐oxide in dichloromethane produced desired polymeric salts with the corresponding functionalities. Irradiation of these photoactive polystyrenes produced alkoxy radicals at chain ends capable of initiating free radical polymerization of methyl methacrylate (MMA). This way, depending on the number of functionality, AB or ABA type block copolymers were formed which were characterized with the aid of gel permeation chromatography and ¹H NMR spectroscopy. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 423–428, 2007.