James Spanswick

Controlled/living radical polymerization

Until a little more than a decade ago, controlled/living radical polymerization (CRP) would have been an oxymoron. Full control over all aspects of radical polymerization was deemed well-nigh impossible because radical termination reactions occur at diffusion-controlled rates. However, there are now several procedures for controlling radical polymerization, and corporations are introducing products based on CRP into numerous high-value markets. This review briefly summarizes the evolution of CRP, describes some of the materials that can now be prepared, and highlights some of the commercialization efforts currently underway.

Copper-Mediated Atom Transfer Radical Polymerization

This chapter summarizes the evolution and the current status of copper-mediated atom transfer radical polymerization (ATRP). All the different procedures developed for initiation of an ATRP are discussed sequentially ending with the latest more environmentally benign procedures that only require ppm levels of catalyst. This is followed by a discussion of the role of each component added to the reaction, or formed in situ from the added components, on the kinetics of the controlled polymerization. Procedures for control over polymer composition, topology, and site-specific functionality including preparation of gradient copolymers, hybrid materials, molecular brushes, and star polymers are detailed followed by exemplification of the preparation of functional materials targeting specific applications including nanostructured carbons, surfactants, dispersants, functionalized surfaces, and materials for bioapplications.

Atom Transfer Radical Polymerization (ATRP)

This chapter summarizes the evolution and current status of atom transfer radical polymerization (ATRP). All the different procedures developed for initiation of copper mediated ATRP are discussed sequentially, ending with the latest more environmentally benign procedures that only require ppm levels of catalyst. This is followed by a discussion of the role of each component added to the reaction, or formed in situ from the added components, on the kinetics of the controlled polymerization. This discussion includes clarification that the role of Cu(0) in an ATRP is that of a supplemental activator and reducing agent (SARA ATRP). Procedures for control over polymer composition, topology and site specific functionality including preparation of gradient copolymers, hybrid materials, molecular brushes, star polymers are detailed followed by exemplification of the preparation of functional materials targeting specific applications including nanostructured carbons, surfactants, dispersants, functionalized surfaces, and materials for bio-applications.