Unusual exfoliation of layered silicate clays by non-aqueous amine diffusion mechanism

The organic ionic exchange intercalation of smectite clays is conventionally performed in water swelling conditions. Here we report a different mechanism for modifying the smectite clays in alcohol solvents. The modification of sodium montmorillonite with poly(oxyethylene-oxypropylene)-amines (POA-amine) were compared for the differences between in water and in alcohol. In water, the intercalation of hydrophobic poly(oxypropylene)-rich amines in the silicate galleries expands the interlayer spacing up to 10 nm and even to exfoliation (featureless in X-ray diffraction pattern) with over 5 amine equivalents, where as hydrophilic poly(oxyethylene)-rich amines could only intercalate in a low spacing of 1.8 nm. On the other hand, all of the POA-amines in isopropanol afford the exfoliation with over, 3 amine equivalents. The mechanism of this unexpected exfoliation is explained by the thermodynamic formations of an imaginary membrane surrounding the clay units, followed by amine diffusion from the solvent into the clay galleries.