Iniferter concept and living radical polymerization

Abstract

Iniferters are initiators that induce radical polymerization that proceeds via initiation, propagation, primary radical termination, and transfer to initiator. Because bimolecular termination and other transfer reactions are negligible, these polymerizations are performed by the insertion of the monomer molecules into the iniferter bond, leading to polymers with two iniferter fragments at the chain ends. The use of well‐designed iniferters would give polymers or oligomers bearing controlled end groups. If the end groups of the polymers obtained by a suitable iniferter serve further as a polymeric iniferter, these polymerizations proceed by a living radical polymerization mechanism in a homogeneous system. In these cases, the iniferters (CS bond) are considered a dormant species of the initiating and propagating radicals. In this article, I describe the history, ideas, and some characteristics of iniferters and living radical polymerization with some iniferters that contain dithiocarbamate groups as photoiniferters and several compounds as thermal iniferters. From the viewpoint of controlled polymer synthesis, iniferters can be classified into several types: thermal or photoiniferters; monomeric, polymeric, or gel iniferters; monofunctional, difunctional, trifunctional, or polyfunctional iniferters; monomer or macromonomer iniferters; and so forth. These lead to the synthesis of various monofunctional, telechelic, block, graft, star, and crosslinked polymers. The relations between this work and other recent studies are discussed. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 2121–2136, 2000

Living Radical Polymerization by the RAFT Process

“…In these polymerizations, radicals may be generated directly from the RAFT agent and these may be responsible for initiation. It was suggested by Pan and coworkers that the mechanism for molecular weight control in UV [143] and γ-initiated [147] processes might involve reversible coupling and be similar to that proposed by Otsu et al [151] to describe the chemistry of dithiocarbamate photoiniferters. However, Quinn et al [142,145] have demonstrated that the living behaviour observed in these polymerizations can be attributed to the standard RAFT mechanism (Scheme 6).…”

Atom transfer radical polymerization in aqueous dispersed media

“…This is the reason why controlled/living radical polymerization (CRP) procedures immediately received a large attention since their debut [1][2][3][4][5]. In the past two decades, various CRP techniques, especially nitroxide mediated polymerization (NMP) [6,7], atom transfer radical polymerization (ATRP) [8][9][10][11] and degenerative transfer systems [12] such as reversible addition-fragmentation chain transfer (RAFT) polymerization [13,14], have been introduced, defined and refined.…”

Photochemically Initiated Single Polymer Immobilization

“…This has been further enhanced by the recent development of new and powerful synthetic methodologies that allow the preparation of polymers with welldefined structures as well as dimensions. [3][4][5][6] Because the structure directly affects the final properties of the material, a significant outcome of the structural diversity of polymers is the wide range of associated properties that are tuneable and can be tailored by rational design.…”