Controlled polymerization of higher alkyl methacrylates, e.g. lauryl methacrylate (LMA) and stearyl methacrylate (SMA) has been successfully achieved by atom transfer radical polymerization (ATRP) at ambient temperature using CuCl/N,N,N',N',N double prime-pentamethyldiethylenetriamine (PMDETA)/tricaprylylmethylammonium chloride (Aliquat((R))336) as the catalyst system and ethyl 2-bromoisobutyrate or 2,2,2-trichloroethanol as the initiator. Although the bulk polymerization gives satisfactory control. the latter becomes better when anisole or THF is added into the system. Without AQCl the control was lost. A lame deviation of molecular weight from theory has been observed which has been attributed to the very high-molecular weight of the dead polymers formed during the building-up of the persistent radical. The controlled polymers have been used as macroinitiators for block (di, tri and penta) ATR copolymerization with several methacrylates. (c) 2006 Elsevier Ltd. All rights reserved.