Macromolecular engineering via 'living' free radical polymerizations

Abstract

The use of nitroxide-mediated 'living' free radical procedures as a synthetic tool for obtaining polymers with well defined and complex macromolecular architectures is discussed. The preparation of linear homo, block, and random co-polymers by 'living' free radical procedures have been demonstrated for a variety of systems and results in a significant increase in control over the macromolecular structure when compared to traditional free radical polymerization. The factors which affect the success of this novel synthetic approach will be reviewed and the advantages of 'living' free radical polymerization over other living polymerization techniques discussed. The synthesis and chemical stability of a wide range of unimolecular alkoxyamine initiators will also be demonstrated and their use in the preparation of complex macromolecular architectures such as hyperbranched polymers and hybrid dendritic-linear polymers illustrated.