It was found that montmorillonite cation exchanged for 12-aminolauric acid (12-montmorillonite) was swollen by ∊-caprolactam to form a new intercalated compound. Caprolactam was polymerized in the interlayer of montmorillonite, a layer silicate, yielding a nylon 6-clay hybrid (NCH). The silicate layers of montmorillonite were uniformly dispersed in nylon 6. The carboxyl end groups of 12-aminolauric acid in 12-montmorillonite initiated polymerization of ∊-caprolactam, and as 12-montmorillonite content became larger, the molecular weight of nylon was reduced. From the result of end-group analysis, carboxyl end groups were more than amino end groups. The difference between the carboxyl and the amino end groups was attributed to ammonium cations (-NH3+) of nylon molecules, because the difference agreed with the anion site concentration of the montmorillonite in NCH. It is suggested that the ammonium cations in nylon 6 interact with the anions in montmorillonite.

Various nylon 6-clay hybrids, such as molecular composites of nylon 6 and silicate layers of montmorillonite and saponite, NCH's and NCHP's, respectively, have been synthesized. To estimate the mechanical properties of these hybrids, tensile, flexural, impact, and heat distortion tests were carried out. NCH was found superior in strength and modulus and comparable in impact strength to nylon 6. The heat distortion temperature (HDT) of NCH (montmorillonite: 4.7 wt. %) was 152 °C, which was 87 °C higher than that of nylon 6. In NCHP, saponite had a smaller effect on the increase of these mechanical properties. The modulus and HDT of NCH and NCHP increased with an increase in the amount of clay minerals. It was found that these properties were well described by the contribution of the constrained region calculated from the storage and loss modulus at the glass transition temperature. According to the mixing law on elastic modulus, the following expression was obtained between the modulus E at 120 °C and the fraction of the constrained region C, En = Ecn = C, where the values of n and Ec (modulus of the constrained region) were 0.685 and 1.02 GPa, respectively.

Polypropylene (PP)-clay hybrids (PPCH) have been prepared by simple melt-mixing of three components, i.e., PP, maleic anhydride modified polypropylene oligomers (PP-MA), and clays intercalated with stearylammonium. The dispersibility of 10-Å-thick silicate layers of the clays in the hybrids was investigated by using a transmission electron microscope and X-ray diffractometer. It is found that there are two important factors to achieve the exfoliated and homogeneous dispersion of the layers in the hybrids: (1) the intercalation capability of the oligomers in the layers and (2) the miscibility of the oligomers with PP. Almost complete hybrids were obtained in the case where the PP-MA has both intercalation capability and miscibility. The hybrids exhibit higher storage moduli compared to those of PP especially in the temperature range from Tg to 90°C. The highest relative storage modulus at 80°C of the hybrid based on a mica and the miscible PP-MA is as high as 2.0 to that of PP and is 2.4 to that of the PP/PP-MA mixture, which is considered to be the matrix of the PPCH. Also, the effects of the kinds of clays and oligomers on the dynamic moduli are discussed.

It was found that montmorillonite was intercalated with ϵ‐caprolactam. X‐ray diffraction revealed that the chain axes of the ϵ‐caprolactam were parallel to the montmorillonite plates. The intercalated montmorillonite was swollen by molten ϵ‐caprolactam at 200°C. ϵ‐Caprolactam and 6‐aminocaproic acid (accelerator) were polymerized with the intercalated montmorillonite at 260°C for 6 h, yielding a nylon 6‐clay hybrid. X‐ray diffraction and transmission electron micrography revealed that the silicate layers of the hybrid were uniformly dispersed in the nylon 6 matrix. Mechanical properties of the hybrid were improved. The strength and the modulus of the hybrid increased compared with the previously reported nylon 6 clay‐hybrid (NCH) synthesized by montmorillonite intercalated with 12‐aminolauric acid. The heat distortion temperature (HDT) of the hybrid was 164°C, which was 12°C higher than that of NCH. © 1993 John Wiley & Sons, Inc.

Natural Na-montmorillonite was cation exchanged for the ammonium cations of various w-amino acids [H 3 N + (CH 2 ) n -iCOOH, n = 2, 3, 4, 5, 6, 8, 11, 12, and 18]. X-ray diffraction (XRD) results suggested that the chain axes of co -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 e-caprolactam at 25 °C. The montmorillonites intercalated with both co-amino acid and e-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 e-caprolactam molecules filled the space between them. When the e-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.