RAFT or Reversible Addition–Fragmentation chain Transfer is a form of living radical polymerization. RAFT polymerization was discovered at CSIRO in 1998.1 It soon became the focus of intensive research, since the method allows synthetic tailoring of macromolecules with complex architectures including block, graft, comb, and star structures with predetermined molecular weight.2 RAFT polymerization is applicable to a very wide range of monomers under a large number of experimental conditions, including the preparation of water-soluble materials.3
The RAFT process involves conventional free radical polymerization of a substituted monomer in the presence of a suitable chain transfer agent (RAFT agent or CTA). Commonly used RAFT agents include thiocarbonylthio compounds such as dithioesters,1 dithiocarbamates,4,5 trithiocarbonates,6 and xanthates,7 which mediate the polymerization via a reversible chain-transfer process. Use of a proper RAFT agent allows synthesis of polymers with low polydispersity index (PDI) and high functionality as shown below in
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