| Abstract: | Well‐defined polystyrenes with an α‐C(CH3)2(CN) and an ω‐chlorine atom end‐groups, and narrow polydispersity (Mn = 3000–4000 g mol?1, Mw/Mn = 1.3–1.4) have been synthesized by a radical polymerization process using 2,2′‐azobisisobutyronitrile(AIBN)/FeCl3/PPh3 initiation system. When the ratio of St]0:AIBN]0:FeCl3]0:PPh3]0 is 200:1:4:12 at 110 °C, the radical polymerization is ‘living’, but the molecular weight of the polymers is not well‐controlled. The polymerization mechanism belongs to a reverse atom transfer radical polymerization (ATRP). Because the polymer obtained is end‐functionalized by a chlorine atom, it can then be used as a macroinitiator to perform a chain extension polymerization in the presence of CuCl/2,2′‐bipyridine catalyst system via a conventional ATRP process. The presence of a chlorine atom as an end‐group was determined by 1H NMR spectroscopy. © 2000 Society of Chemical Industry |
