Atom-transfer radical polymerization polymers

L.K. Breland and R.F. Storey, Polyisobutylene-based miktoarm star polymers via a combination of carbocationic and atom transfer radical polymerizations, Polymer, 49(5) 1154-1163, March 2008. 

Tsujii Y, Ejaz M, Yamamoto S, Fukuda T, Shigeto K, Mibu K, et al. Fabrication of patterned high-density polymer graft surfaces II. Amplification of EB-pattemed initiator monolayer by surface-initiated atom transfer radical polymerization. Polymer 2002 43(13) 3837—41. 

Desai SM, Solanky SS, Mandale AB, Rathore K, Singh RP. Controlled grafting of N-iso-propylacrylamide brushes onto self-standing isotactic polypropylene thin films surface initiated atom transfer radical polymerization. Polymer 2003 44(25) 7645—9. 

Shen D, Huang Y (2004) The synthesis of CDA-g-PMMA copolymers through atom transfer radical polymerization. Polymer 45 7091-7097... 

R. F. Storey, A. D. Scheuer, B. C. Achord, Amphiphilic poly(acrylic add-b-styrene-b-isobutylene-b-styrene-b-acrylic add) pentablock copolymers from a combination of quasiliving carbocationic and atom transfer radical polymerization. Polymer 200S. 46, 2141-2152. 

Greszta, D., Matyjaszewski, K., and Pakula, T. (1997). Gradient copol mers of st5rene and acrylonitrile via atom transfer radical polymerization. Polym. Prepr., 33(1) 709-710. 

Parnell, A. J., Martin, S. J., Dang, C. C., Geoghegan, M., Jones, R. A. L., Crook, C. J., et al. (2009). Synthesis, characterization and sweUing behaviour of poly(methacrylic acid) brushes synthesized using atom transfer radical polymerization. Polymer, 50, 1005-1014. 

Li, L., Ke, Z. J., Yan, G. R, Wu, J. Y. (2008), Polyimide films with antibacterial surfaces from surface-initiated atom-transfer radical polymerization. Polymer International, 57, 1275-80. 

Wu, Y., Shi, Y.,andFu,Z.F. (2005b) Synthesisofheteroarmstar-shaped(poly styrene)(n)-[poly(ethylactylale)](m) via atom transfer radical polymerization. Polymer, 46,12722. 

Lim, K.T., Lee, M.Y., Moon, M.J. et al. (2002) Synthesis and properties of semifluorinated block copolymers containing poly(ethylene oxide) and poly(fluorooctyl methacrylate) via atom transfer radical polymerization. Polymer, 43,7043-7049. 

M.A. Gauthier, M. Ayer, J. Kowal, F.R. Wurm, H.-R. Klok, Arginine-specific protein modification using a-oxo-aldehyde functional polymers prepared by atom transfer radical polymerization. Polym. Chem., 2 (7) 1490-1498, 2011. 

Liang YZ, Li ZC, Chen GQ, Li FM (1999) Synthesis of well-defined poly (2-beta-D-glucopyranosyloxy)ethyl acrylate by atom transfer radical polymerization. Polym Int... 

Mayes A M, Acar M H and Gonzalez-Leon J A (2003) Toward commodity plastics by molecular design, Ahstr 285 ACS Natl Meet, New Orleans, LA, USA PMSE-035. Ga5mor S G, Balchandani P, Kulfan A, Podwika M and Matyjaszewski K (1997) Architectural control in acrylic polymers by atom transfer radical polymerization, Polym Prepr ACS 38 496-497. 

Chen R, Maclaughlin S, Botton G, Zhu S (2009) Preparation of Ni-g-polymer cOTe-shell nanoparticles by surface-initiated atom transfer radical polymerization. Polymer 50(18) 4293 298... 

Khezri K, Haddadi-Asl V, Roghani-Mamaqani H, Salami-Kalajahi M (2012) Nanoclay-encapsulated polystyrene microspheres by reverse atom transfer radical polymerization. Polym Comp 33 990-998... 

In 2003, the van Hest group produced elastin-based side-chain polymers [123]. This research was motivated by the demonstration of the occurrence of an inverse temperature transition in a single repeat of VPGVG [124]. A methacrylate-functionalized VPGVG was synthesized and used as a monomer to perform atom transfer radical polymerization (ATRP) to produce homopolymers (Fig. 16b) or... 

Star polymers are a class of polymers with interesting rheological and physical properties. The tetra-functionalized adamantane cores (adamantyls) have been employed as initiators in the atom transfer radical polymerization (ATRP) method applied to styrene and various acrylate monomers (see Fig. 21). 

Figure 21. Atom transfer radical polymerization (ATRP) synthetic route to tetrafunctional initiators of a star polymer with adamantyl (adamantane core). Taken from Ref. [91] with permission.

Pyun, J., Kowalewski, T. and Matyjaszewski, K. (2003) Synthesis of polymer brushes using atom transfer radical polymerization. Macromol. Rapid Commun., 24, 1043-1059. 

Novel catalytic systems, initially used for atom transfer radical additions in organic chemistry, have been employed in polymer science and referred to as atom transfer radical polymerization, ATRP [62-65]. Among the different systems developed, two have been widely used. The first involves the use of ruthenium catalysts [e.g. RuCl2(PPh3)2] in the presence of CC14 as the initiator and aluminum alkoxides as the activators. The second employs the catalytic system CuX/bpy (X = halogen) in the presence of alkyl halides as the initiators. Bpy is a 4,4/-dialkyl-substituted bipyridine, which acts as the catalyst s ligand. 

Atom transfer radical polymerization, ATRP, is a controlled radical process which affords polymers of narrow molecular weight distributions. Strictly this is not a coordinative polymerization, but its dependency upon suitable coordination complexes warrants a brief discussion here. 

Matyjaszewski, K. Miller, P. J. Kickelbick, G. Nakagawa, Y. Diamanti, S. Pacis, C. Organic-Inorganic Hybrid Polymers from Atom Transfer Radical Polymerization and Poly(dimethylsiloxane). In Silicones and Silicone-Modified Materials Clarson, S. J., Fitzgerald, J. J., Owen, M. J., Smith, S. D., Eds. ACS Symposium Series 729 American Chemical Society Washington, DC, 2000 pp 270-283. 

P. Zhou, G. Q. Chen, H. Hong, F.S. Du, Z.C. Li, F. M. Li, Synthesis of C60-endbonded polymers with designed molecular weights and narrow molecular weight distributions via atom transfer radical polymerization, Macromolecules, vol. 33, pp. 1948-1954, 2000. 

Qin, S., et al., Polymer brushes on single-walled carbon nanotubes by atom transfer radical polymerization ofn-butyl methacrylate. Journal of the American Chemical Society, 2003. 126(1) p. 170-176. 

While in most of the reports on SIP free radical polymerization is utihzed, the restricted synthetic possibihties and lack of control of the polymerization in terms of the achievable variation of the polymer brush architecture limited its use. The alternatives for the preparation of weU-defined brush systems were hving ionic polymerizations. Recently, controlled radical polymerization techniques has been developed and almost immediately apphed in SIP to prepare stracturally weU-de-fined brush systems. This includes living radical polymerization using nitroxide species such as 2,2,6,6-tetramethyl-4-piperidin-l-oxyl (TEMPO) [285], reversible addition fragmentation chain transfer (RAFT) polymerization mainly utilizing dithio-carbamates as iniferters (iniferter describes a molecule that functions as an initiator, chain transfer agent and terminator during polymerization) [286], as well as atom transfer radical polymerization (ATRP) were the free radical is formed by a reversible reduction-oxidation process of added metal complexes [287]. All techniques rely on the principle to drastically reduce the number of free radicals by the formation of a dormant species in equilibrium to an active free radical. By this the characteristic side reactions of free radicals are effectively suppressed. 

Fig. 9 Schematic representation of controiled topoiogies, compositions, and functionalities of polymers and molecular composites prepared by atom transfer radical polymerization (ATRP). (Reproduced with permission from [42])...

Dynamic formation of graft polymers was synthesized by means of the radical crossover reaction of alkoxyamines by using the complementarity between nitroxide radical and styryl radical (Fig. 8.13) [40]. Copolymer 48 having alkoxyamine units on its side chain was synthesized via atom transfer radical polymerization (ATRP) of TEMPO-based alkoxyamine monomer 47 and MMA at 50°C (Scheme 8.9). The TEMPO-based alkoxyamine-terminated polystyrene 49 was prepared through the conventional nitroxide-mediated free radical polymerization (NMP) procedure [5,41], The mixture of copolymers 48 and 49 was heated in anisole... 

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