Surface-initiated ring-opening metathesis polymerization

Rutenberg, I. et al.. Synthesis of polymer dielectric layers for organic thin film transistors via surface initiated ring opening metathesis polymerization, J. Am. Chem. Soc. 126, 4062M063, 2004. 

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. 

Surface-Initiated Ring-Opening Metathesis Polymerization. 

Feng J, Stoddart SS, Kanchana A, Weerakoon Chen KAW (2007) An efficient approach to surface-initiated ring-opening metathesis polymerization of cyclooctadiene. Langmuir... 

The living character of the ring opening metathesis polymerization described earlier in this review enables a simple preparation of functionalized norbornene-based monoliths. Adding one more in situ derivatization step that involves functional norborn-2-ene and 7-oxanorborn-2-ene monomers that react with the surface-bound initiator, the pores were provided with a number of typical functional groups such as carboxylic acid, tertiary amine, and cyclodextrin [58,59]. 

Norbornene polymerization was initiated selectively on the surface of SWCNTs via a specifically adsorbed pyrene-linked ring-opening metathesis polymerization initiator (Fig. 1.20). The adsorption of the organic precursor was followed by cross-metathesis with a ruthenium alkylidene, resulting in a homogeneous noncovalent poly (norbornene) (PNBE) coating [249]. 

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. 

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.)... 

Emulsion droplets can also serve as soft templates to produce capsules. A range of cross-linking chemistries on the interface of oil-in-water emulsion droplets, whereby introducing various polymer functionalities in the resulting capsules has been employed. These are ring-opening metathesis polymerization [59], interfacial step-growth polymerization [60], metal coordination polymerization also termed miniemulsion periphery polymerization [61], surface-initiated miniemulsion ATRP [62, 63], and inverse miniemulsion periphery RAFT polymerization [64, 65]. 

Figure 10 Schematic depiction of a surface-initiated poiymerization process ieading to a variety of homopoiymer and copoiymer architectures. In the fignre are also described the chemicai structures of typicai initiator-terminated aikanethiolate SAMs for different polymerization techniqnes (1) atom transfer radicai poiymerization, (2) ring-opening metathesis poiymerization, and (3) thermai free...

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