Combining RAFT Radical Polymerization and Click/Highly Efficient Coupling Chemistries: A Powerful Strategy for the Preparation of Novel Materials

Abstract

This paper highlights the powerful combination of reversible addition-fragmentation chain transfer (RAFT) radical polymerization and various click/coupling chemistries. This is not an exhaustive review but rather an overview demonstrating the impressive possibilities that the "marriage" of these two synthetic approaches offers in modern macromolecular design and synthesis.

Living Radical Polymerization by the RAFT Process – A Third Update

“…Chernikova et al [118] used an EPR spin trapping method to measure addition and fragmentation rate constants for the reaction between a t-butyl radical and t-butyl dithiobenzoate (38). Their data analysis indicates a high value for K of ,10 8 M À1 (208C).…”

“…[38,[66][67][68] The RAFT process can be used to synthesize polymers with clickable moieties at the chain ends through the use of RAFT agents with appropriate functionality on 'Z' or 'R'.…”

“…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.…”

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)…”

Surface-initiated reversible addition–fragmentation chain transfer polymerization from “clickable” polypropylene surface modified by iodine plasma activation

“…It could be applied for the grafting of RAFT agents onto polymer surfaces through a plasma activation. Grafting RAFT agents onto a surface gives the opportunity to polymerize a wide range of monomers when choosing the adapted transfer agent, giving finally brushes at the surface [9]. In the case of RAFT polymerization, the choice of the RAFT agent for a given monomer is of peculiar importance for the success of the controlled radical polymerization.…”