Toward living radical polymerization

Radical polymerization is one of the most widely used processes for the commercial production of high-molecular-weight polymers. The main factors responsible for the preeminent position of radical polymerization are the ability to polymerize a wide array of monomers, tolerance of unprotected functionality in monomer and solvent, and compatibility with a variety of reaction conditions. Radical polymerization is simple to implement and inexpensive in relation to competitive technologies. However, conventional radical polymerization severely limits the degree of control that researchers can assert over molecular-weight distribution, copolymer composition, and macromolecular architecture. This Account focuses on nitroxide-mediated polymerization (NMP) and polymerization with reversible addition-fragmentation chain transfer (RAFT), two of the more successful approaches for controlling radical polymerization. These processes illustrate two distinct mechanisms for conferring living characteristics on radical polymerization: reversible deactivation (in NMP) and reversible or degenerate chain transfer (in RAFT). We devised NMP in the early 1980s and have exploited this method extensively for the synthesis of styrenic and acrylic polymers. The technique has undergone significant evolution since that time. New nitroxides have led to faster polymerization rates at lower temperatures. However, NMP is only applicable to a restricted range of monomers. RAFT was also developed at CSIRO and has proven both more robust and more versatile. It is applicable to the majority of monomers subject to radical polymerization, but the success of the polymerization depends upon the selection of the RAFT agent for the monomers and reaction conditions. We and other groups have proposed guidelines for selection, and the polymerization of most monomers can be well-controlled to provide minimal retardation and a high fraction of living chains by using one of just two RAFT agents. For example, a tertiary cyanoalkyl trithiocarbonate is suited to (meth)acrylate, (meth)acrylamide, and styrenic monomers, while a cyanomethyl xanthate or dithiocarbamate works with vinyl monomers, such as vinyl acetate or N-vinylpyrrolidone. With the appropriate choice of reagents and polymerization conditions, these reactions possess most of the attributes of living polymerization. We have used these methods in the synthesis of well-defined homo-, gradient, diblock, triblock, and star polymers and more complex architectures, including microgels and polymer brushes. Applications of these polymers include novel surfactants, dispersants, coatings and adhesives, biomaterials, membranes, drug-delivery media, electroactive materials, and other nanomaterials.