Clickable initiators, monomers and polymers in controlled radical polymerizations – a prospective combination in polymer science

Abstract

Preparation of multifunctional and well-defined macromolecules requires a smart selection of the most suitable controlled polymerization technique in combination with appropriate click reactions. In this review, we provide an overview on the use of various ''clickable'' initiators and monomers as well as on the postpolymerization modifications that have been widely used to construct clickable macromolecules. As such, this contribution will aid polymer chemists to select a suitable combination of CRP and click methodologies to design the target structures.

Living Radical Polymerization by the RAFT Process – A Third Update

“…Several reviews on combined use of RDRP and 'click chemistry' have appeared. [66][67][68][69][70][71][72] The 'clickable' functionality may be present on the Z or R groups of the RAFT agent (see elsewhere in this review) or in the monomers. These monomers can be incorporated in blocks as a precursor to a polymer brush or copolymerized to provide sites for the attachment of functionality or for crosslinking.…”

“…[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'.…”

“…[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. Some of those that include significant mention of RAFT polymerization include reviews on RDRP, [63] mechanism and reagent design, [11,64,65] click chemistry, [66][67][68][69][70][71][72] synthesis of telechelics, [73] the polymerization of carbazole-containing monomers, [74] N-vinyl-1,2,3-triazoles, [75] N-vinyl heterocycles, [76] fluoro-monomers, [77] and glycomonomers, [78][79][80] synthesis of metallopolymers, [81] conjugated block copolymers, [82] dye-functionalized polymers, [83] stimuliresponsive polymers, [84,85] complex architectures, [86,87] polyolefin blocks, [88] biopolymer-polymer conjugates and bioapplications, [59,[89][90][91][92][93] polysaccharide modification, [94,95] polymerization in heterogeneous media, [96,97] microwave-assisted polymerization, [65,98,99] industrial prospects for RDRP, [100,…”

PNIPAM grafted surfaces through ATRP and RAFT polymerization: Chemistry and bioadhesion

“…Various techniques are commonly used for grafting polymers to surfaces, both for "grafting to" or "grafting from" strategies [47,53,54]. Among these techniques, the most used, i.e.…”

Synthesis of Terpolymers by Click Reactions

“…[1][2][3] More recently, click reactions [4] including the copper-catalyzed azide-alkyne cycloaddition (CuAAC), Diels-Alder, and thiol-ene reactions widely adapted to polymer chemistry have emerged as powerful tools for the preparation of well-defined polymers with different architectures. [5][6][7][8][9][10][11][12][13][14][15][16][17][18][19] The use of click reactions has been extremely productive when combined with living polymerization techniques, such as ring-opening polymerization (ROP), ring-opening metathesis polymerization (ROMP), and living radical polymerizations (LRP) techniques which include atom-transfer radical polymerization (ATRP), reversible addition fragmentation chain-transfer polymerization (RAFT), and nitroxide-mediated radical polymerization (NMP), because end-functionalities of polymeric precursors generated by LRP techniques can be easily converted to suitable groups needed for click reactions. [5][6][7][8][9][10][11][12][13][14][15][16][17][18][19] Among the various architectures, block copolymers play a key role in polymer science, which are produced by the covalent bonding of two or more thermodynamically incompatible polymeric chains, and lead to a rich variety of microstructures both in bulk and in solution.…”