Atom transfer radical polymerization of lauryl methacrylate (LMA) was carried out in the presence of various ligands using ethyl-2-bromoisobutyrate as initiator and CuBr as catalyst in toluene at 95 degreesC. The ligands used were 2,2'-bipyridyl,4,4'-dimethyl-2,2'-bipyridyl, N,N,M,A,N''-pentamethyidiethylenetriamine (PMDETA) and N-(n-propyl)-2-pyridylmethanimine (PPMI). Controlled polymerization was observed with PMDETA and PPMI ligands and poly(LMA)s with narrow molecular weight distribution (MWD) (M-w/M-n less than or equal to 1.2) were obtained. The first-order time-conversion plot showed the presence of termination in the presence of PMDETA. A linear first-order time-conversion plot with a small induction period (similar to 10 min) was observed in the presence of PPMI ligand. Di-block copolymers of LMA and methylmethacrylate with controlled molecular weight and narrow MWDs were synthesized via sequential monomer addition. (C) 2004 Elsevier Ltd. All rights reserved.