chapter  17
48 Pages

Controlled/Living Radical Polymerization

WithKrzysztof Matyjaszewski, James Spanswick

Conventional free radical polymerization (RP) has many advantages (see Chapters 2-4 discussing specific polymers prepared by radical polymerization). The procedure can be used for the (co)polymerization of a very large range of vinyl monomers under undemanding conditions; requiring the absence of oxygen, but tolerant to water, and can be conducted over a large temperature range (80 to 250 C) [1]. This is why nearly 50% of all commercial synthetic polymers are prepared using radical chemistry providing a spectrum of materials for a range of markets. Many additional vinyl monomers can be copolymerized via a radical route leading to an infinite number of copolymers with properties dependent on the proportion of incorporated comonomers. The major limitation of RP is poor control over some of the key structural elements that allow the preparation of well defined macromolecular architectures such as molecular weight (MW), polydispersity, end functionality, chain architecture and composition.