Surface-initiated ring-opening metathesis polymerization of 5-(perfluorohexyl)norbornene on carbon paper electrodes

Surface-Initiated Ring-Opening Metathesis Polymerization (SI-ROMP): History, General Features, and Applications in Surface Engineering with Polymer Brushes

“…The attachment of olefin groups can also be done in a two-step manner, where the thiol molecules with hydroxyl groups (for instance, 4-mercapto-1-butanol) first react with the surface. Then, the hydroxyl-covered gold is reacted with an electrophile containing the olefin anchor, such as norbornenyl dicarbonyl chloride, to attach the olefin anchors onto the surface through condensation with the hydroxyl groups [16,25,26]. This method avoids the synthesis of the thiol-modified norbornene as the anchor molecule.…”

“…Their anchoring molecule is shown in Figure 5(a), which contains a catechol (ortho-dihydroxybenzene) group, that is found to bind coordinatively onto the surface of titanium dioxide [82,83]. SI-ROMP was also reported to be performed on cellulose fibers [24], graphene oxide [23], and carbon paper electrodes [25]. The similarity shared by the SI-ROMP on these three substrates is the shared use of an electrophilic norbornene carbonyl chloride (Figures 5(b) and 5(c)) as the anchoring molecule, targeting the hydroxyl moieties on the surfaces of the substrates.…”

“…In the IR analysis of surface-tethered polynorbornene, researchers observed the expected peaks resembling the structures and functionalities of the polynorbornene film, including the peaks of cyclic methylene C-H stretching, tertiary C-H stretching, and C=CH out-ofplane bending and stretching [19,35]. IR is also suitable for polymers containing unique functional groups, such as the C-F bond in polyfluoronorbornenes [21,25] and the carbonyl groups on poly(oxanorbornene-succinimide) [29]. X- 7 International Journal of Polymer Science ray Photoelectronic Spectroscopy (XPS) is used in determining the elemental compositions and structures of the topmost several nanometers of the polymer films [18,21,22,29].…”

Covalent modification of graphene oxide with polynorbornene by surface-initiated ring-opening metathesis polymerization

“…In 1999, Grubbs et al [37] first reported the surface-initiated ROMP (SI-ROMP) of norbornene derivative from gold surface with Grubbs 1st generation catalyst. Subsequently, many reports displayed the successful SI-ROMP from various surface including silicon wafers [38], silica nanoparticles [39], carbon nanotubes [40], carbon paper [41], cellulose fibers [42], montmorillonite clay [43] and other substrates [44], suggesting that ROMP is an important polymerization strategy for the synthesis of a variety of polycycloolefins, such as polynorbornene (PNb), as non-polar polyolefins that can be introduced onto polar materials to effectively tailor the performance of substrates. Our research group recently reported the successful preparation of the surface-bound PNb films from Si/SiO 2 substrates by SI-ROMP, and described a strategy to prevent the degradation during the epoxidation of grafted PNb chains just by solvent effect under mild conditions [45].…”

Surface-Initiated Ring-Opening Metathesis Polymerization in the Vapor Phase: An Efficient Method for Grafting Cyclic Olefins with Low Strain Energies

“…The straightforward process and rapid kinetics render SiROMP an attractive tool to tune surface properties of a number of substrates including Au, 12–17 SiO 2 , 18–21 Si, 22 and carbon. 23 While olefin metathesis is established for synthesis of polyalkenamers in the bulk using a wide variety of cyclic olefins, previous studies on surface functionalization using ROMP have been limited to norbornene (Nbn) and its derivatives. Polynorbornene films were grafted under relatively mild conditions, producing polymer films from nano- to micrometer thick depending on the catalyst type, polymerization temperature and time, and monomer concentration.…”