Controlled/living radical polymerization: Features, developments, and perspectives

Keywords: Fragmentation Chain-Transfer ; Self-Assembled Monolayers ; Walled Carbon Nanotubes ; Well-Defined Polymer ; Nitroxide-Mediated Polymerization ; Block-Copolymer Brushes ; Poly(Methyl Methacrylate) Brushes ; Transfer Raft Polymerization ; Quartz-Crystal Microbalance ; Poly(Acrylic Acid) Brushes Reference EPFL-REVIEW-148464doi:10.1021/cr900045aView record in Web of Science Record created on 2010-04-23, modified on 2017-05-10

Polymer Brushes via Surface-Initiated Controlled Radical Polymerization: Synthesis, Characterization, Properties, and Applications

Polymer brushes: surface-immobilized macromolecules

Chemical Reviews is published by the American Chemical Society. 1155 Sixteenth Street N.W., Washington, DC 20036 “Green” Atom Transfer Radical Polymerization: From Process Design to Preparation of Well-Defined Environmentally Friendly Polymeric Materials Nicolay V. Tsarevsky, and Krzysztof Matyjaszewski Chem. Rev., 2007, 107 (6), 2270-2299• DOI: 10.1021/cr050947p • Publication Date (Web): 27 May 2007 Downloaded from http://pubs.acs.org on April 2, 2009

"Green" atom transfer radical polymerization: from process design to preparation of well-defined environmentally friendly polymeric materials.

Among the living radical polymerization techniques, reversible addition–fragmentation chain transfer (RAFT) and macromolecular design via the interchange of xanthates (MADIX) polymerizations appear to be the most versatile processes in terms of the reaction conditions, the variety of monomers for which polymerization can be controlled, tolerance to functionalities, and the range of polymeric architectures that can be produced. This review highlights the progress made in RAFT/MADIX polymerization since the first report in 1998. It addresses, in turn, the mechanism and kinetics of the process, examines the various components of the system, including the synthesis paths of the thiocarbonyl-thio compounds used as chain-transfer agents, and the conditions of polymerization, and gives an account of the wide range of monomers that have been successfully polymerized to date, as well as the various polymeric architectures that have been produced. In the last section, this review describes the future challenges that the process will face and shows its opening to a wider scientific community as a synthetic tool for the production of functional macromolecules and materials. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43:5347–5393, 2005

https://www.onlinelibrary.wiley.com/doi/pdf/10.1002/pola.20986

Macromolecular design via réversible addition-fragmentation chain transfer (RAFT)/Xanthates (MADIX) polymerization

A model for living radical polymerization

The bulk polymerization of methyl methacrylate (MMA) with 1,2-disubstituted tetraphenylethanes, tetraphenylsuccinodinitrile (TPSN), tetra(p-methoxyphenyl)succinodinitrile (TMPSN), and pentaphenylethane (PPE), was investigated. These compounds were found to serve as thermal iniferters to induce living radical polymerization via a mechanism close to the model proposed previously (see Eq. 2). However, the living nature was not so high, because undesirable side reactions occurred. The oligomer with molecular weight of 2500 was isolated from the reaction mixture of MMA with TPSN, which was found to cause further polymerization of MMA. From the polymerization of styrene (St) with the polymers obtained by these iniferters, the block copolymers were produced.

Radical polymerization of methyl methacrylate with some 1,2-disubstituted tetraphenylethanes as thermal iniferters

To clarify the mechanism of living radical polymerization of methyl methacrylate (MMA) with tetraphenylsuccinodinitrile (TPSN) as a thermal iniferter, a model compound for the end group of the poly(MMA) produced, methyl 2,2-dimethyl-3,3-diphenyl-3-cyanopropionate (2), was synthesized and found to initiate a living radical polymerization of MMA, indicating that the hexa-substituted C-C bond in 2 dissociated into radicals. The poly(MMA) thus obtained further initiated the radical polymerization of styrene (St) to give a block copolymer.

Toshinori Tazaki

Papers

A model for living radical polymerization

Radical polymerization of methyl methacrylate with some 1,2-disubstituted tetraphenylethanes as thermal iniferters

Radical polymerization of methyl methacrylate with methyl 2,2-dimethyl-3,3-diphenyl-3-cyanopropionate as a thermal iniferter

Living Radical Polymerization of Methyl Methacrylate with Tetraphenylsuccinodinitrile as a Thermal Iniferter

Living Radical Polymerization with Reduced Nickel-Halide Systems as Redox Iniferters