In Situ Synthesis of Polymer−Clay Nanocomposites from Silicate Gels

Polymer-containing silicate gels were hydrothermally crystallized to form layered magnesium silicate hectorite clays containing polymers that are incorporated in situ. Gels consist of silica sol, magnesium hydroxide sol, lithium fluoride, and the polymer of choice. Dilute solutions of gel in water are refluxed for various lengths of time and then isolated via centrifugation, washed, and air-dried. Polymer loadings up to 86% were attained by adding more polymer to the solutions after 2-day reaction times, reacting for another 24 h, and continuing this process prior to isolation. Polyaniline (PANI)− and polyacrylonitrile (PACN)−clay samples contain up to 57% and 76% polymer, respectively, after just one sequential addition at high polymer loading. Series of PANI−, PACN−, poly(vinylpyrrolidone) (PVP)−, and hydroxypropylmethylcellulose (HPMC)−clays also were prepared by several sequential additions of lower polymer loading to the silicate gel during crystallization. Final polymer loadings were determined by thermal analysis. Basal spacings between clay interlayers were measured by X-ray powder diffraction for all samples. Increases in polymer loadings and basal spacings were observed for all the neutral polymers studied, until or unless delamination occured. Delamination was evident for PACN− and PANI−clay nanocomposites. The highest loadings were observed for the PACN−clays, up to 86%. For the cationic polymer polydimethyldiallylammonium chloride, however, the loading could not be increased beyond about 20%. This is due to electrostatic interactions that balance the negatively charged sites on the silicate lattice with those on the cationic polymer chain. Beyond charge compensation, there is no driving force for further incorporation. Charge compensation in the case of the neutral polymers is attained by interlayer lithium(I) cations.