End Group Reactions of RAFT-Prepared (Co)Polymers

Abstract

This review highlights the chemistry of thiocarbonylthio groups with an emphasis on chemistry conducted at v or a and v chain-ends in copolymers prepared by reversible addition–fragmentation chain-transfer (RAFT) radical polymerization. We begin by giving a general overview of reactions associated with the thiocarbonylthio groups, followed by examples associated with macromolecular thiols

Living Radical Polymerization by the RAFT Process – A Third Update

“…include those on the kinetics and mechanism of RAFT polymerization, [26,27] RAFT agent design and synthesis, [28] the use of RAFT to probe the kinetics of radical polymerization, [29] microwaveassisted RAFT polymerization, [30,31] RAFT polymerization in microemulsion, [32] end-group removal/transformation, [33][34][35][36] the use of RAFT in organic synthesis, [37] the combined use of RAFT polymerization and click chemistry, [38] the synthesis of star polymers and other complex architectures, [39][40][41][42] the synergistic use of RAFT polymerization and ATRP, [43,44] the synthesis of self assembling and/or stimuli-responsive polymers, [45][46][47] and the use of RAFT-synthesized polymers in green chemistry, [48] polymer nanocomposites, [49][50][51] drug delivery and bioapplications, [41,46,47,[52][53][54][55][56][57][58][59][60] and applications in cosmetics [61] and optoelectronics. [62] The process is also given substantial coverage in most recent reviews that, in part, relate to polymer synthesis, living or controlled polymerization or novel architectures.…”

Novel α,α‐Bischolesteryl Functional (Co)Polymers: RAFT Radical Polymerization Synthesis and Preliminary Solution Characterization

“…Additionally, reaction of the polyPFP(M)A parent scaffolds with a small excess of primary amines also results in the aminolysis of the thiocarbonylthio groups at the ω chain ends. This is not unexpected and represents the most common approach for removing such end groups in RAFT‐synthesized (co)polymers . However, to avoid oxidative coupling of the resulting macromolecular thiols, the acyl‐substitution reactions of the polyPFP(M)A precursors were performed in the presence of an acrylamido‐based Michael acceptor (3‐hydroxypropyl acrylamide, N ‐isopropylacrylamide, or N,N ‐diethylacrylamide) resulting in a thiol‐Michael addition reaction following aminolysis of the thiocarbonylthio species.…”

RAFT Polymerization – Then and Now

“…General reviews include those by Moad, Rizzardo and Thang (14,15,(62)(63)(64)(65) Destarac (66), and Barner-Kowollik et al (67). Reviews devoted to RAFT or RAFT polymerization in specific areas include those on the origins of RAFT polymerization (3), the design and synthesis of RAFT agents (48), advances in Switchable RAFT agents (68,69), dithiobenzoate-mediated RAFT polymerization (70), RAFT chemistry using xanthates (4,71), RAFT polymerization of vinyl esters (72), RAFT crosslinking polymerization (73), RAFT polymerization in microemulsion (74), RAFT polymerization induced self-assembly (75,76), the synthesis of block copolymers (77), the synthesis of star polymers and other complex architectures (78)(79)(80)(81), block copolymers based on amino acid-derived monomers (82), end group removal and transformation (83)(84)(85)(86), the synergistic use of RAFT polymerization and ATRP (87), microwave-assisted RAFT polymerization (88,89), silica nanoparticles (90), polymer nanocomposites (91,92), the use of RAFT-synthesized polymers in gene-delivery (93), drug delivery and bioapplications (79,(94)(95)(96)(97)…”