Controlled/Living Radical Polymerization
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) . 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.