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Reversible Addition Fragmentation chain Transfer (RAFT) has emerged as one of the most important methods for controlling radical polymerization. RAFT has been shown to be robust and versatile and applicable to the majority of monomers subject to radical polymerization. However, selection of the appropriate RAFT agent for the monomers in tandem with the proper reaction conditions is crucial for successful polymerization.
Zhang, L. et al. Multiblock poly(4-vinylpyridine) and its copolymer prepared with cyclic trithiocarbonate as a reversible addition-fragmentation transfer agent. J. Polym. Sci. A 45, 2617–2623 (2007).
Reversible Addition-Fragmentation chain Transfer or RAFT polymerization is one of several kinds of Reversible-deactivation radical polymerization. It makes use of a chain transfer agent in the form of a thiocarbonylthio compound (or similar, from here on referred to as a RAFT agent, see Figure 1) to afford control over the generated molecular weight and polydispersity during a free-radical polymerization.
In addition to structural biomaterials and device components, polymers may also be used for the controlled delivery of therapeutic agents. While a diverse range of polymers may be generated by numerous polymerization reactions, radical polymerization is among the most robust and widely applicable methods. The biggest drawback to conventional radical polymerization (i. e. large dispersity and poor control over molecular mass) is addressed by the use of living radical polymerization techniques such as Nitroxide Mediated Polymerization (NMP)  and , Atom Transfer Reduction Polymerization (ATRP)  and , and Reversible Addition Fragmentation chain Transfer.
Cyclic polymers with alternating monomer sequences are synthesized for the first time by the ring-closure strategy. In this approach, well-defined telechelic alternating polymers are synthesized by reversible addition–fragmentation chain transfer polymerization through copolymerizing electron acceptor monomer of N-benzylmaleimide and donor monomer of styrene. The corresponding cyclic alternating polymers are then produced by the UV-induced Diels–Alder click reaction to ring-close the linear alternating polymer precursors.
A new system for controlling radical polymerization based on nitroxides as stable free radicals is developed by Solomon, Rizzardo and Cacioli in 1986. They synthesized methyl acrylate oligomers via reversible capping of growing radical chain by using 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO) as a stable free radical. The reversible capping of growing chains defined the first mechanism of three general routes to controlled/ “living” radical polymerization. This route was named as “Stable Free Radical Polymerization (SFRP)” by its discovers. Three main types of techniques have been developed over the years: 1) stable free radical polymerization (SFRP) with nitroxide-mediated radical polymerization (NMP), 2) atom transfer radical polymerization (ATRP) and 3) reversible addition-fragmentation transfer.