Overview of RAFT Polymerization

Multiblock copolymer synthesisviaRAFT emulsion polymerization

“…The history, mechanism and application of the RAFT process have been described in numerous reviews and we only note some of the more recent here. 15,[43][44][45][46][47] RAFT polymerization, involving so-called macromonomer RAFT agents, was first reported in 1995 as a new form of controlled-growth radical polymerization for forming low dispersity (multi)block copolymers by (semi-batch) polymerization. [48][49][50] The more popular form of RAFT polymerization using carbonothioylsulfanyl compounds (more commonly called thiocarbonylthio compounds, but this nomenclature is deprecated by IUPAC) as RAFT agents was announced in 1998.…”

“…15,[43][44][45][46][47] RAFT polymerization, involving so-called macromonomer RAFT agents, was first reported in 1995 as a new form of controlled-growth radical polymerization for forming low dispersity (multi)block copolymers by (semi-batch) polymerization. [48][49][50] The more popular form of RAFT polymerization using carbonothioylsulfanyl compounds (more commonly called thiocarbonylthio compounds, but this nomenclature is deprecated by IUPAC) as RAFT agents was announced in 1998. 13,15 The public announcement was preceded by patent submissions by CSIRO/DuPont 51,52 and Rhodia.…”

“…53 A review on the historical development of RAFT has been published. 50 IUPAC defines RAFT polymerization as a ''degeneratetransfer radical polymerization in which chain activation and chain deactivation involve a degenerative chain-transfer process, which occurs by a two-step addition-fragmentation mechanism''. 54,55 Degenerate-transfer radical polymerization is then a ''reversible-deactivation polymerization in which the deactivation of the active species involves degenerative chain transfer'', 56 and degenerative (or degenerate) chain transfer is a ''chain-transfer reaction that generates a new chain carrier and a new chain-transfer agent with the same reactivity as the original chain carrier and chain-transfer agent''.…”

“…The RAFT agent 1 and macroRAFT agent 2 (refer Scheme 2) are reactively symmetrical. The group X is usually sulfur (in carbonothioylsulfanyl RAFT agents), 13 but carbon (in macromonomer RAFT agents or sulfur-free RAFT) [48][49][50]57 and other examples have been reported. The RAFT agent Z substituent is generally called an activating group and determines the reactivity of the CQS or CQC bond towards radical addition alongside the stability of the intermediates.…”

High-throughput concurrent synthesis of core-crosslinked star-polydimethylsiloxane using an arm-first approach

“…Most recent efforts make use of reversible deactivation radical polymerisation (RDRP), 9,10 which includes nitroxide-mediated polymerisation (NMP), [11][12][13] atom-transfer radical polymerisation (ATRP), 14,15 reversible addition-fragmentation chain-transfer (RAFT) polymerisation, 4,[16][17][18][19][20][21][22] and combinations thereof. [23][24][25] RAFT polymerisation [26][27][28] has been used to produce low molar mass dispersity stars through the arm-first method. 29 These include mikto-arm stars, so-called because they comprise of arms which are compositionally diverse.…”