The polymerization of n-butyl methacrylate was investigated using the Atom Transfer Radical Polymerization technique with CuBr and CuCl/N

N

N'

N"

N"-pentamethyldiethylenetriamine catalytic systems. Various combinations of catalyst systems and initiators were utilized in order to optimize the polymerization conditions and to obtain well-defined polymers (i.e. controlled molecular weights and low polydispersities). It has been found that the optimal initiator for this system is a chlorine-based initiator

when the catalyst used is a Cu(I)salt in conjunction with the N

N

N'

N"

N"-pentamethyldiethylenetriamine ligand. Bromine-based initiators tend to result in large amounts of initial termination

leading to polymers with less than ideal chain end functionality

even if CuCl is used as the Cu(I) species to invoke the halogen exchange. Additionally

the effects of the polymerization temperature

copper(I)species and the initiator structure were determined.