Atom-transfer radical polymerization modification

Singh N, Chen Z, Tomer N, Wickramasinghe SR, Soice N, Husson SM. Modification of regenerated cellulose ultrafiltration membranes by surface-initiated atom transfer radical polymerization. J Membr Sci 2008 311(1—2) 225-34. 

Lindqvist J, Mahnstrom E. Surface modification of natural substrates by atom transfer radical polymerization. J Appl Polym Sci 2006 100(5) 4155—62. 

Singha et al. reported DA cross-linked products [158] using furan-modified polymethacrylate (PFMA) as the polymeric precursor, which was prepared through atom transfer radical polymerization (ATRP) and free-radical polymerization (FRP). Furthermore, the self-healing behavior of a triblock copolymer (PFMA-co-MMA) prepared by ATRP was demonstrated by means of scanning electron microscopy (SEM). With the modification, an almost fully recovered surface from knife-cut samples has been observed [159]. Chen et al. also reported the DA polymer product of PFMA-BM possessing thermal reversibility, whereas the homopolymer was prepared from anionic polymerization [160]. 

Fig. 6.39 Modification of a macroporous silicon scaffold with initiator-terminated self-assembled monolayers (a) and then immersed in the atom transfer radical polymerization (ATRP) solution where the surface-initiated copolymerization of sulfopropyl methacrylate (SPM) and monomethoxy oligo-(ethylene glycol) methacrylate (MeOEGMA) was carried out (b). Also depicted are the chemical structures of the copolymer bmsh (n = 0.87, m = 0.13, x = 5) and the surface-confined ATRP initiator (Reproduced from [494] with permission)...

Recently, surface modification techniques for polymer chains have progressed a great deal with the development of a new polymer synthesis method. In particular, surface-initiated atom transfer radical polymerization (SI-ATRP) is one of the most effective modification methods for preparing a well-defined dense polymer brush structure, or polymer brush, on solid substrates. Thus, a self-oscillating polymer brush prepared by SI-ATRP can be expected to create a novel self-oscillating surface with autonomous function, which will lead to potential applications in transporting systems for nanomaterials of flow control in microfluidics. 

Matrab, T., Chancolon, ]., L hermite, M.M, Rouzaud, J.-N., Deniau, G., Boudou, J.P, Chehimi, M.M., and Delamar, M. (2006) Atom transfer radical polymerization (ATRP) initiated by aryl diazonium salts a new route for surfiice modification of multiwalled carbon nanotubes by tethered polymers chains. Colloid. Surf., A, 287 (1-3), 217-221. 

Xiao, D. Zhang, H. Wirth, M., Chemical Modification of the Surface of Poly(dimethylsiloxane) by Atom-Transfer Radical Polymerization of Acrylamide. Langmuir 2002,18, 9971-9976. 

As mentioned above, the cleavage of Si-Si-bonds in polysilanes upon irradiation with UV-light is very efficient and results in the formation of silicon radicals. These radicals react with olefins to initiate radical polymerizations. Especially the polymerization of methylmethacrylate and styrene with a variety of polysilanes as photoinitiators has been studied in detail [104]. The advantage of this kind of initiation is the possibility to prepare polysilane-polyolefin hybrids [105]. All modifications of radical polymerizations, such as the atom transfer radical polymerization (ATRP), are possible with polysilanes as photoinitiators [106]. 

Zhang, F., Xu, F.J., Kang, E.T., Neoh, K.G. 2006. Modification of Titanium via Surface-Initiated Atom Transfer Radical Polymerization (ATRP). 

Liu, Y.-L., Chen, W.-H. 2007. Modification of Multiwall Carbon Nanotubes with Initiators and Macroinitiators of Atom Transfer Radical Polymerization. 

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. 

The group of Lei Tao has reported several approaches that realize a polymer-izadmi and sequential post-modification in one pot. For example, simultaneous copper(l)-catalyzed azide-alkyne cycloadditiOTi, enzymatic transesterification, and atom transfer radical polymerization (ATRP) were successfully conducted [15]. 

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