Copper-based ATRP (atom transfer radical polymerization) catalytic systems with polydentate nitrogen ligands such as bpy and aliphatic polyamines is among most efficient controlled/living radical polymerization systems (CRP).^1,2 New ATRP initiating systems allow to decrease level of Cu-catalyst to a few ppm with preserved control.³ ATRP of (meth)acrylates, styrenes, acrylamides, acrylonitrile and other vinyl monomers provides polymers with low polydispersities and molecular weights in a range 200>Mn>20,000,000. Polymers can be formed quantitatively in bulk, in solution and in emulsions. Block, graft, star, hyperbranched, gradient and periodic copolymers as well as molecular brushes have been prepared.² The (co)polymers made by ATRP have many potential applications as components of coatings, elastomers, adhesives, surfactants, dispersants, lubricants, additives, but also as specialty materials in biomedical and electronic areas and will affect the market of ~$20 billion/year.⁴ Examples of design, synthesis, characterization and applications of nanostructured multicomponent polymeric materials enabled by various CRPs will be presented.

(1) Matyjaszewski, K., Davis, T. P., Eds. Handbook of Radical Polymerization; Wiley, Hoboken 2002;

(2) Wang, J. S., Matyjaszewski, K. J. Am. Chem. Soc. 1995, 117, 5614; Matyjaszewski, K., Xia, J. Chem. Rev. 2001, 101, 2921; Matyjaszewski, K. et al. US 5,763,548; US 5,789,487; US 5,807,937; US 5,945,491; (3) Matyjaszewski, K. et al. Proc. Nat. Acad. Sci. 2006, 103, 15309; Angew. Chem. 2006, 45, 4482; J. Am. Chem. Soc. 2006, 128, 10521; (4) Matyjaszewski, K.; Spanswick, J., Materials Today 2005, 8, 26; Matyjaszewski, K.; Gnanou, Y.; Leibler, L., Macromolecular Engineering, Wiley-VCH, Weinheim 2007