| Abstract: | The living/controlled radical polymerization of styrene was investigated with a new initiating system, DCDPS/FeCl3/PPh3, in which diethyl 2,3‐dicyano‐2,3‐diphenylsuccinate (DCDPS) was a hexa‐substituted ethane thermal iniferter. The polymerization mechanism belonged to a reverse atom transfer radical polymerization (ATRP) process. The polymerization was controlled closely in bulk (at 100 °C) or in solution (at 110 °C) with a high molecular weight and quite narrow polydispersity (Mw/Mn = 1.18 ∼ 1.28). End‐group analysis results by 1H NMR spectroscopy showed that the polymer was ω‐functionalized by a chlorine atom, which also was confirmed by the result of a chain‐extension reaction in the presence of a FeCl2/PPh3 or CuCl/bipy (2,2′‐bipyridine) catalyst via a conventional ATRP process. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 101–107, 2000 |
