Abstract: | The atom transfer radical polymerizations of styrene were successfully carried out in bulk and solution, respectively, at 115 °C, with a novel photoiniferter reagent, (1‐naphthyl)methyl N,N‐diethyldithiocarbamate (NMDC), as an initiator in the presence of copper (I) bromide and N,N,N′,N″,N″‐pentamethyldiethylenetriamine. The results showed that NMDC was an effective initiator with high initiation efficiency for ATRP of St. The polymerization rate was first‐order with respect to the monomer concentration and the molecular weights of the obtained polystyrene (PS) increased linearly with the monomer conversion, with very narrow molecular weight distributions (Mw/Mn = 1.07–1.29). The functionalized naphthalene‐labeled PS bearing N,N‐(diethylamino)dithiocarbamoyl group which was confirmed by 1H NMR analysis, and chain extension of the PS exhibited fluorescence and ultraviolet absorption in chloroform (CHCl3). © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 510–518, 2006 |