Atom transfer radical polymerization grafting

W. Feng, J.L. Brash, S. Zhu, Non-biofouling materials prepared by atom transfer radical polymerization grafting of 2-methacryloloxy-ethyl phosphorylcholine separate effects of graft density and chain length on protein repulsion. Biomaterials 27 (2006) 847-855. 

Fig. 4 Synthesis process of preparing polymeric organic phase hy surface-initiated atom transfer radical polymerization (grafting-from method).

Chen R, Feng W, Zhu S, Botton G, Ong B, Wu Y (2006) Surface-initiated atom transfer radical polymerization grafting of poly(2,2,2-trifiuoroethyl methacrylate) from flat silicon wafer surfaces. J Polym Sci A Polym Chem 44(3) 1252-1262... 

Feng W, Brash JL, Zhu S (2005) Atom transfer radical polymerization grafting of 2-methacryloyloxyethyl phosphorylcholine fm nrai-biofouling surfaces. Polym Preprints... 

Gong R, Maclaughlin S, Zhu S (2008) Surface modification of active metals through atom transfer radical polymerization grafting of acrylics. Appi Surf Sci 254(21) 6802-6809... 

Ejaz, M., Yamamoto, S., Ohno, K., Tsujii, Y. and Fukuda, T. (1998) Controlled graft polymerization of methyl methacrylate on silicon substrate by the combined use of the Langmuir-Blodgett and atom transfer radical polymerization techniques. Macromolecules, 31, 5934-5936. 

In this review, synthesis of block copolymer brushes will be Hmited to the grafting-from method. Hussemann and coworkers [35] were one of the first groups to report copolymer brushes. They prepared the brushes on siUcate substrates using surface-initiated TEMPO-mediated radical polymerization. However, the copolymer brushes were not diblock copolymer brushes in a strict definition. The first block was PS, while the second block was a 1 1 random copolymer of styrene/MMA. Another early report was that of Maty-jaszewski and coworkers [36] who reported the synthesis of poly(styrene-h-ferf-butyl acrylate) brushes by atom transfer radical polymerization (ATRP). 

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... 

SIP-driven polymer brush library fabrication leverages the fact that the polymerization initiation species are permanently bound to the substrate. Since the initiators are tethered, controlled delivery of monomer solution to different areas of the substrate results in a grafted polymer library. In NIST work, initiators bound via chlorosilane SAMs to silicon substrates were suitable for conducting controlled atom transfer radical polymerization (ATRP) [53] and traditional UV free radical polymerization [54, 55]. Suitable monomers are delivered in solution to the surface via microfluidic channels, which enables control over both the monomer solution composition and the time in which the solution is in contact with the initiating groups. After the polymerization is complete, the microchannel is removed from the substrate (or vice versa). This fabrication scheme, termed microchannel confined SIP ([t-SIP), is shown in Fig. 10. In these illustrations, and in the examples discussed below, the microchannels above the substrate are approximately 1 cm wide, 5 cm long, and 300-500 [tm high. 

Mecerreyes D, Atthoff B, Boduch KA, Trollsas M, Hedrick JL (1999) Unimolecular combination of an atom transfer radical polymerization initiator and a lactone monomer as a route to new graft copolymers. Macromolecules 16 5175-5182... 

Worthy of special remark is surface grafting via a novel technique of polymer synthesis, atom-transfer radical polymerization (ATRP), the usefulness of which has received much recognition due to the control of the molecular... 

Scheme 1.11 Grafting of polymers via atom transfer radical polymerization (ATRP) using an ester linkage to oxidized MWCNTs. Formation of MWCNT-COCI, reaction with...

Figure 2.5. Schematic of grafting of PMMA chains from the surface of nanotubes using atom transfer radical polymerization. Reproduced from reference 30 with permission from American Chemical Society.

S. Hohnberg, P. Holmlund, C.E. Wilen, T. KaUio, G. Sundhohn, and F. Sundhohn. Synthesis of proton-conducting membranes by the utilization of preirradiation grafting and atom transfer radical polymerization techniques. Journal of Polymer Science Part A Polymer Chemistry 40, 591-600 2002. 

Controlled free-radical polymerization (CFRP) has been used successfully to produce block, graft, and other controlled architecture copolymers within the last decade for a variety of free radically polymerizable monomers. The main techniques include reversible addition fragmentation and transfer (RAFT) polymerization, stable free-radical polymerization (SFRP) mediated by nitroxide/alkoxyamine based radicals, atom transfer radical polymerization (ATRP), diphenyl ethylene (DPE) mediated polymerization, and novel precipitation/emulsion polymerization based methods like free-radical retrograde precipitation polymerization (FRRPP). ... 

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