Statistical, Gradient and Segmented Copolymers by Controlled/Living Radical Polymerizations

This review is focused on controlled/living radical polymerization methods for the preparation of various copolymers. A brief introduction to the subject of radical polymerization, and early attempts to control it, is followed by a detailed examination of the literautre on controlled/living radical copolymerizations from the mid-90's until 2001. The topics covered include statistical/gradient, block, graft, and star copolymers and the polymerization methods used to produce them. These copolymers were prepared using three major controlled radical methods (either nitroxide mediated polymerization, atom transfer radical polymerization or degenerative transfer) and a combination of polymerization techniques, including transformation chemistry or the simultaneous/dual living polymerizations, to achieve the desired chain architecture or topology. An evaluation of the current state of the field is also presented.