Atom transfer radical polymerization.

Current status and future perspectives in atom transfer radical polymerization (ATRP) are presented. Special emphasis is placed on mechanistic understanding of ATRP, recent synthetic and process development, and new controlled polymer architectures enabled by ATRP. New hybrid materials based on organic/inorganic systems and natural/synthetic polymers are presented. Some current and forthcoming applications are described.

Atom Transfer Radical Polymerization (ATRP): Current Status and Future Perspectives

Chemical Reviews is published by the American Chemical Society. 1155 Sixteenth Street N.W., Washington, DC 20036 “Green” Atom Transfer Radical Polymerization: From Process Design to Preparation of Well-Defined Environmentally Friendly Polymeric Materials Nicolay V. Tsarevsky, and Krzysztof Matyjaszewski Chem. Rev., 2007, 107 (6), 2270-2299• DOI: 10.1021/cr050947p • Publication Date (Web): 27 May 2007 Downloaded from http://pubs.acs.org on April 2, 2009

"Green" atom transfer radical polymerization: from process design to preparation of well-defined environmentally friendly polymeric materials.

This Perspective presents recent advances in macromolecular engineering enabled by ATRP. They include the fundamental mechanistic and synthetic features of ATRP with emphasis on various catalytic/initiation systems that use parts-per-million concentrations of Cu catalysts and can be run in environmentally friendly media, e.g., water. The roles of the major components of ATRP—monomers, initiators, catalysts, and various additives—are explained, and their reactivity and structure are correlated. The effects of media and external stimuli on polymerization rates and control are presented. Some examples of precisely controlled elements of macromolecular architecture, such as chain uniformity, composition, topology, and functionality, are discussed. Syntheses of polymers with complex architecture, various hybrids, and bioconjugates are illustrated. Examples of current and forthcoming applications of ATRP are covered. Future challenges and perspectives for macromolecular engineering by ATRP are discussed.

Macromolecular Engineering by Atom Transfer Radical Polymerization

Controlled/Living Radical Polymerization

Atom transfer radical polymerization (ATRP) has been successfully carried out in supercritical carbon dioxide (scCO2) for the polymerization of fluorinated (meth)acrylates. In particular, well-controlled polymerizations have been obtained with the use of a fluoroalkyl-substituted 2,2‘-bipyridine ligand. Block copolymers comprised of fluorinated (meth)acrylates and poly(MMA) (MMA = methyl methacrylate) or poly(DMAEMA) (DMAEMA = 2-(dimethylamino)ethyl methacrylate) were produced in scCO2 by ATRP. In addition, the dispersion polymerization of MMA using ATRP in scCO2 in the presence of a fluorinated polymeric surfactant stabilizer was successfully carried out to yield poly(MMA) latex particles with controlled molecular weight and a narrow molecular weight distribution.

Terri Johnson

Papers

Atom Transfer Radical Polymerization in Supercritical Carbon Dioxide

Controlled radical polymerization methods for the synthesis of non-ionic surfactants for CO2

Synthesis of hydrophilic hydrocarbon/fluorocarbon block copolymers using controlled free radical techniques

Molecularly engineered surfactants for CO2