4.6 Article

Enhanced Hydrolytic Stability of Siliceous Surfaces Modified with Pendant Dipodal Silanes

Journal

CHEMISTRY-A EUROPEAN JOURNAL
Volume 20, Issue 30, Pages 9442-9450

Publisher

WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.201402757

Keywords

dipodal silanes; hydrolytic stability; silicon; siloxane-silanol equilibria; surface chemistry

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Dipodal silanes possess two silicon atoms that can covalently bond to a surface. They offer a distinct advantage over conventional silanes commonly used for surface modification in terms of maintaining the integrity of surface coatings, adhesive primers, and composites in aqueous environments. New nonfunctional and functional dipodal silanes with structures containing pendant rather than bridged organofunctionality are introduced. The stability of surfaces in aqueous environments prepared from dipodal silanes with hydrophobic alkyl functionality is compared to the stability of similar surfaces prepared from the conventional si-lanes. In strongly acidic and brine environments, surfaces modified with dipodal silanes demonstrate markedly improved resistance to hydrolysis compared to surfaces prepared from conventional silanes. Pendant dipodal silanes exhibit greater stability than bridged dipodal silanes. The apparent equilibrium constant for the formation of silanol species by the hydrolysis of a disiloxane bond was determined as K-c=[SiOH](2)/[Si-O-Si][H2O]= 6 +/- 1x10(-5) and is helpful in understanding the enhanced hydrolytic stability of surfaces modified with dipodal silanes.

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