Every chemical reaction occurs only when a molecule is provided the necessary activation energy. When activation energy is provided in the form of light then the reaction is known as photochemical reaction. The spectrum of solar light is mostly spread across the visible and near infrared ranges with a small part in the near ultraviolet. Apart from that handling visible light compare to UV light is very easy and safe and it can be potentially applied on an industrial scale.1 The use of light in controlled radical polymerization also brings several distinct advantages, including temporal and spatial control over chain growth, easy preparation of well-defined polymers at room temperature and minimization of possible higher temperature side reactions. Although extensive efforts have been made in this area, it is still crucial to explore an effective light-induced controlled radical polymerization method in synthetic polymer chemistry. The commonly used light-induced CRP methods are adapted from thermal counterparts including iniferter, nitroxide-mediated radical polymerization, atom transfer radical polymerization (ATRP), cobalt-mediated radical polymerization, organoiodine-mediated radical polymerization, organotellurium-mediated radical polymerization and reversible addition-fragmentation chain transfer polymerization etc. Among them, light-induced ATRP has been studied extensively because of the broad range of monomers and mild polymerization conditions. The light-induced ATRP is based on photoredox reactions of copper catalysts under various radiation sources with or without various photoinitiators.2-4 Many UV and visible light free radical photoinitiators were reported to be powerful promoters for light-induced ATRP. The infinitely available, easily handled and environmentally friendly visible light makes it attractive for polymer chemists to promote it for CRP methods. Recently, visible light-induced ATRP of vinyl monomers using type I and type II photoinitiators in the presence of copper(II) catalyst5, iridium based photoredox catalyst, dimanganese decacarbonyl/copper(II) catalyst6 and mesoporous graphitic carbon nitride/copper(II) catalyst systems7have been developed. In this presentation, the synthetic possibilities for visible-light induced ATRPs and their mechanistic insights are discussed. Figure 1. General mechanism for visible light induced ATRP(1) Yagci, Y.; Jockusch, S.; Turro, N. J. Macromolecules 2010  , 43, 6245.(2) Tasdelen, M. A.; Uygun, M.; Yagci, Y. Macromolecular Rapid Communications 2011  , 32, 58.(3) Tasdelen, M. A.; Uygun, M.; Yagci, Y. Macromolecular Chemistry and Physics 2011  , 212, 2036.(4) Ciftci, M.; Tasdelen, M. A.; Li, W.; Matyjaszewski, K.; Yagci, Y. Macromolecules 2013  , 46, 9537.(5) Tasdelen, M. A.; Ciftci, M.; Yagci, Y. Macromolecular Chemistry and Physics 2012  , 213, 1391.(6) Ciftci, M.; Tasdelen, M. A.; Yagci, Y. Polymer Chemistry 2014  , 5, 600.(7) Dadashi-Silab, S.; Tasdelen, M. A.; Kiskan, B.; Wang, X.; Antonietti, M.; Yagci, Y. Macromolecular Chemistry and Physics 2014  , n/a.

Visible light-induced atom transfer radical polymerization for macromolecular syntheses

248th National Meeting (2014)

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