Living/controlled radical polymerization of styrene with a new initiating system: DCDPS/FeCl3/PPh3

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.