CHAPTER 4: Design and Physicochemical Characterization of Novel Organic–Inorganic Hybrids from Natural Aluminosilicate Nanotubes

Surface functionalization of tubular nano-clays of imogolite and halloysite using the selective binding of organophosphonic acids and organosilane compounds, and the use of the surface modified nanotubes in polymer hybrids were studied. Surface modification of imogolite with alkyl phosphonic acid salt through the specific interaction of phosphonic acid and the exterior alumina sites of imogolite was presented. SI-ATRP was performed with the selectively adsorbed phosphonic acid functionalized ATRP-initiator to prepare polymer brushes on the imogolite surface. Selective modification of halloysite nanotube exterior and inner surfaces was demonstrated. Aqueous phosphonic acid binds to alumina sites at the tube lumen to make the lumen hydrophobic. Subsequent modification with organosilane affords bifunctionalized halloysites with both the lumen and exterior surface modified. Loading of hydrophobic organic compound to the modified lumen was confirmed. SI-ATRP was performed through the selectively adsorbed DOPA-functionalized ATRP-initiator to prepare polymer brushes on the nanotube lumen. Also, surface modified halloysite was applied for preparation of novel intelligent polyurethane nanocomposites with improved thermal stability and mechanical properties.