Nitroxide-mediated 'living' free radical polymerisation (LREP) was employed for the first time to prepare graft copolymer by having arylated poly (vinyl chloride) (PVC-Ph) as a backbone and polystyrene (PS) as branches. The graft copolymerization of styrene was initiated by arylated PVC carrying 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO) groups as a macroinitiator. Thus, the arylated PVC was prepared in the mild conditions and these reaction conditions could overcome the problem of gelation and crosslinking in polymers. Then, 1-hydroxy TEMPO was synthesized by the reduction of TEMPO with sodium ascorbate. This functional nitroxyl compound was coupled with brominated arylated PVC (PVC-Ph-Br). The resulting macro-initiator (PVC-Ph-TEMPO) for 'living' free radical polymerization was then heated in the presence of styrene to form graft copolymer. DSC, GPC, (HNMR)-H-1, and FT-IR spectroscopy were employed to investigate the structure of the polymers. Copyright (C) 2007 John Wiley & Sons, Ltd.
