MMA (methyl methacrylate) was polymerized in different ATRP systems using the different ligands of HMTETA (1, 1, 4, 7, 10, 10, hexamethyltriethylenetetraamine), TMEDA (N,N,N',N'-Tetramethylethylenediamine) with copper salts (CuBr/CuBr2) and EBriB was used as an initiator in toluene at a reaction temperature of 80 degrees C. Both conventional and a low catalyst to initiator ratios ranging from 1/1 to 0.01/1 were compared in this study. All four of the ATRP methods, such as normal, reverse, AGET and ATRP using a high oxidation state metal complex without any additives, were evaluated at different conditions. The ATRP using a high oxidation state metal system in the absence of a conventional radical initiator like AIBN, which is used in reverse ATRP or reducing agents such as Sn (EH)(2) in AGET ATRP was a better controlled system in terms of both the catalytic activity and controllability (PDI similar to 1.2). (C) 2009 Elsevier Ltd. All rights reserved.