Polymer brushes ring-opening polymerization

Thermoresponsive polymer brushes on 20 nm colloidal gold formed through ATRP of W-isopropyl acrylamide in aqueous media End-functionalized 3D self-assembled monolayers (SAMs) on GNPs by living cationic ring-opening polymerization reaction directly on GNP surfaces... 

Most work on REMP was done with COE (8) or cyclooctadiene (COD) (9) but functionalized monomers can also be used. A dendronized macro-monomer 10 (Figure 1.4) has been used under REMP conditions, leading to the formation of cyclic nanostructures with a diameter of 35-40 nm [40]. Recently, a REMP-derived cyclic macro-initiator derived from monomer 11 was used to prepare cyclic brush copolymers by combining REMP with triazabicyclodecene-catalyzed ring-opening polymerization of a cyclic ester [41]. Furthermore, REMP processes were developed for the synthesis of functional cyclic polymers, cyclic polymer brushes, and cyclic gels [42, 43]. 

Lu H, Wang J, Lin Y, Oieng J (2009) One-pot synthesis of brush-like polymers via integrated ring-opening metathesis polymerization and polymerization of amino acid N-carboxyanhy-drides. J Am Oiem Soc 131 13582-13583... 

Besides the polymerization techniques discussed above, other polymerization methods have been used for the preparation of surface grafts. Recently, ring-opening metathesis polymerization (ROMP) became popular. This polymerization type will be discussed by Buchmeiser in Chapter 8. Recently, interesting accounts have appeared on solventiess polymerization techniques applying (living) ROMP on surfaces to prepare structured brush surfaces of conjugated polymers [331, 332]. 

Samanta, S. Locklin, J. Formation of photochromic spiropyran polymer brushes via surface-initiated, ring-opening metathesis polymerization reversible photocontrol of wetting behavior and solvent dependent morphology changes. Langmuir 2008,24,9558-9565. 

Fig. 4. The protocol for polymer brushes by SIP ring opening metathesis polymerization (ROMP), with initiators attached to Au nanoparticles. From Ref 39.

In direct write lithography, a tip can be used to pattern a surface and prepare polymeric nanostructures. Polymerization is initiated by the tip and a pattern is formed. Polymer brush nanostructures can be synthesized using ring opening metathesis polymerization (ROMP). Edge distances of less than 100 nm are possible, and control over feature size, shape, and interfeature distance is achievable. 

Schematic illustration of the two strategies used in the preparation of ferrocene-functionalized polymer brushes (a) hydroxyl groups of the PHEMA brushes activated by CDl, followed by coupling with FCNH2 and (b) epoxy groups of the PGMA brushes underwent direct ring-opening reaction with FcNHj. (Reprinted with permission from Wu et al. 2009. Electrochemical Biosensing Using Amplification-by-Polymerization. Analytical Chemistry 81 (16) 7015-7021, copyright (2(X)9) American Chemical Society.)...

Graphical representation of the preparation of ferrocene-functionalized polymer brush arrays via SI-ROMP by DPN. (Reproduced from Liu et al. 2(X)3. Surface and site-specific ring-opening metathesis polymerization initiated by dip-pen nanolithography. Angewandte Chemie-lnternational Edition 42 (39) 4785-4789 with permission from Wiley.)... 

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