Living radical polymerization, brushe

Tsujii, Y, Ohno, K., Yamamoto, S., Goto, A. and Fukuda, T. (2006) Structure and properties of high-density polymer brushes prepared by surface-initiated living radical polymerization. Adv. Polym. Sci., 197, 1-45. 

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. 

Keywords Graft polymerization Living radical polymerization Polymer brush ... 

Structure and Properties of High-Density Polymer Brushes Prepared by Surface-Initiated Living Radical Polymerization... 

A dense polymer brush is obtained using the grafting from techniques. Surface-initiated polymerization in conjunction with a living polymerization technique is one of the most useful synthetic routes for the precise design and functionalization of the surfaces of various solid materials with well-defined polymers and copolymers. Above all, surface-initiated living radical polymerization (LRP) is particularly promising due to its simplicity and versatility and it has been applied for the synthesis of Au NPs. 

Polymer brushes can be obtained by metal-mediated living radical polymerization from the initiator moiety confined to the surface of a substrate via spacers. The surface-initiated living polymerization can control the thickness and the density of brushes the former is regulated by brush s chain length and... 

Yu WH, Kang ET, Neoh KG. Controlled grafting of comb copolymer brushes on poly-(tetrafluoroethylene) films by surface-initiated living radical polymerizations. Langmuir 2005 21(l) 450-6. 

Size-Exclusion Effect and Protein Repellency of Concentrated Polymer Brushes Prepared by Surface-Initiated Living Radical Polymerization Chiaki Yoshikawa, Atsushi Goto, Norio Ishizuka, Kazuki Nakanishi, Akio Kishida, Yoshinobu Tsujii, Takeshi Fukuda ... 

Y. Tsujii, T. Fukuda, Synthesis of gold nanoparticles coated with well-definecl, high-density polymer brushes by surface-initiated living radical polymerization, Macromalecules 2002, 35, 8989 8993 ... 

Haddleton and Ohno reported on maltodextrin modified polymers via copper(I)-mediated living radical polymerization [125]. Comblike structures based on polystyrene with amylose entities were synthesized by Kobayashi et al. [126] and bottle-brush-like structures by Kakuchi and coworkers [127]. 

POE 13] PoELMA J.E., Fors B.P., Meyers G.F. et al, Fabrication of complex three-dimensional polymer brush nanostructures through light-mediated living radical polymerization , Angewandte Chemie International Edition, vol. 52, pp. 6844-6848, 2013. 

Grafting polymer brush by living radical polymerization. Length and density of resultant graft polymer brush are extremely uni-form and dense. 

To overcome these problems, a surface-initialed living radical polymerization technique is used for preparing polymer brush surfaces, where precisely controlled polymer chains are densely tethered. The technique also can be used to construct block copolymer on the surfaces by sequentially grafting another polymer via the active polymer-end groups of a first-grafted polymer brush. As a typical surface-initiated Uving radical polymerization, atom transfer radical polymerization (ATRP) and reversible addition-fragmentafion chain transfer radical (RAFT) polymerization are... 

Zoppe, J., Habibi, Y., Rojas, O.J., Venditti, R.A., Johansson, L.-S., Efimenko, K., Osterberg, M., Laine, J. 2010. Poly(N-lsopropylacrylamide) Brushes Grafted from Cellulose Nanocrystals via Surface-Initiated Single-Electron Transfer Living Radical Polymerization. Biomacromolecules 11 2683-2691. 

The use of SAMs and polymer brushes for biological applications is well reviewed in the literature. Hence, this chapter focuses mainly on a "concentrated" polymer brush prepared by surface-initiated living radical polymerization (Sl-LRP) [7]. 

Concentrated Polymer Brush Prepared by SI-LRP 11.2.1 Living Radical Polymerization (LRP)... 

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