MACROMOLECULAR ENGINEERING VIA LIVING FREE-RADICAL POLYMERIZATIONS

The use of nitroxide-mediated 'living' free radical procedures as a sy nthetic tool for obtaining polymers with well defined and complex macr omolecular architectures is discussed. The preparation of linear home, block, and random co-polymers by 'living' free radical procedures hav e been demonstrated for a variety of systems and results in a signific ant increase in control over the macromolecular structure when compare d 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 stabil ity of a wide range of unimolecular alkoxyamine initiators will also b e demonstrated and their use in the preparation of complex macromolecu lar architectures such as hyperbranched polymers and hybrid dendritic- linear polymers illustrated.