The atom transfer radical polymerization (ATRP) of n-docosyl acrylate (DA) was studied at 80 degrees C in N,N-dimethylformamide using the carbon tetrabromide/ FeCl3/2,2'-bipyridine (bpy) initiator system in the presence of 2,2'-azobisisobutyronitrile (AIBN) as the source of reducing agent. The rate of polymerization exhibits first-order kinetics with respect to the monomer. The linear relationship between the molecular weight of the resulting poly(n-docosyl acrylate) with conversion and the narrow polydispersity of the polymers indicates the living characteristics of the polymerization reaction. The significant effect of AIBN on the ATRP of DA was studied keeping [FeCl3]/[bpy] constant. A probable reaction mechanism for the polymerization system is postulated to explain the observed results. (C) 2005 Wiley Periodicals, Inc.