Natural Na-montmorillonite was cation exchanged for the ammonium cations of various ω-amino acids [H3N+(CH2)n−1 COOH, n = 2, 3, 4, 5, 6, 8, 11, 12, and 18]. X-ray diffraction (XRD) results suggested that the chain axes of ω-amino acids with a carbon number of eight or less were parallel to the silicate layers, and that the chain axes of those with a carbon number of 11 or more were slanted to the layers. The cation-exchanged montmorillonites form intercalated compounds with ∊-caprolactam at 25 °C. The montmorillonites intercalated with both ω-amino acid and ∊-caprolactam were studied by XRD measurement at room temperature and 100 °C. We propose a model where amino acid molecules were arranged perpendicular to silicate layers and ∊-caprolactam molecules filled the space between them. When the ∊-caprolactam was melted at 100 °C, the basal spacing for the montmorillonite increased, in which the carbon number exceeds 11. This phenomenon will be applicable to obtaining the nylon 6-clay hybrid, a molecular composite of nylon 6 and montmorillonite.
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