Polymer brushes nitroxide-mediated

Li J, Chen XR, Chang YC. Preparation of end-grafted polymer brushes by nitroxide-mediated free radical polymerization of vaporized vinyl monomers. Langmuir 2005 21 (21) 9562-7. 

B. Zhao,Synthesis of binary mixed homopolymer brushes by combining atom transfer polymerization and nitroxide-mediated radical polymerization. Polymer 2003, 44, 4079-4083. 

CRP is usually divided into three categories (i) ATRP (ii) reversible radical addition fragmentation chain transfer (RAFT) and (iii) nitroxide-mediated polymerization (NM P). All three techniques permit the polymer molecular weight, the polydispersity, and the polymer architecture to be accurately controlled, and have been used to build up highly dense polymer brushes from inorganic particles. A list of macro-initiators which have been developed recently for this purpose is provided in Table 4.6. 

Currently, there has been only one report in the literature concerning ATRP of 2-(dimethylamino)ethyl acrylate (DMAEA) which involved homogeneous (bulk) polymerization (instead of polymer brush) formation [54]. To the authors knowledge, the only LRP technique applied in the s)mthe-sis of PDMAEA polymer brushes is nitroxide-mediated radical polymerization [55-57]. The first synthesis of PDMAEA brushes from Si substrates by SC-ATRP used a CuCl/CuCl2/Me6TREN/2-bromopropionyl type initiator catalyst system and reaction temperature of 70°C. PDMAEA dry layer thicknesses reached 34 5.9 nm after 72 h. 

Abstract The current chapter gives a general overview on surface-initiated nitroxide-mediated polymerization (SI-NMP). More particularly, the developed strategies to perform an SI-NMP process, the various type of substrates including inorganic and organic supports, and the potential of SI-NMP to prepared advanced materials are discussed. Based on a selected number of literature examples it appears that SI-NMP is a versatile and powerful approach to introduce polymer brushes on surfaces and/or tune polymer surface properties. 

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