Dendritic Surfactants show evidence for frustrated intercalation: A new organoclay morphology

Mixing a smectite clay with some dendritic surfactants shows that despite the large size of some of these molecules, a property that frustrates complete intercalation into the gallery of the clay, organoclay materials are obtained. X-ray powder diffraction (XPD) reveals no significant increases in lattice spacing as these surfactants are added. Infrared (IR) spectroscopy and thermal gravimetric analysis (TGA) show that interlayer water is preserved. Consistent with an undisturbed interlayer, the amount of organic material in organoclays derived from frustrated surfactants does not exceed 15% of the cationic exchange capacity (CEC) of the composite. Smaller dendritic surfactants do not display frustrated intercalation and instead readily enter into the gallery of the smectic clay yielding traditional organoclay materials. A range of organic compositions (5-50% w/w) that exceed the CEC of the materials are observed. The organic content is corroborated by UV spectroscopy and TGA. XPD reveals increasing lattice spacings with increasing organic content. IR spectroscopy and TGA support an increasingly hydrophobic interlayer. A linear isomer of a frustrated surfactant can intercalate into the gallery (5-33% w/w) yielding morphologies that depend on the amount of surfactant added. These results support the hypothesis that shape, and not only size, is important for producing frustrated intercalation.