A green and efficient deoximation using H_2O_2 catalyzed by montmorillonite-K10 supported CoCl_2

Oximes were oxidized to the corresponding carbonyl compounds in good to high yields by environmentally friendly and green oxidant,H_2O_2 catalyzed by montmorillonite K-10 supported cobalt(Ⅱ) chloride.     

Synthesis of polyurethane/clay intercalated nanocomposites

 A kind of polyurethane/organophilic montmorillonite (PU/OMT) nanocomposite based on polyether, OMT, phenylmethane diisocyante and diglycol was synthesized and characterized by X-ray diffraction (XRD) and high-resolution electron microscopy (HREM). A polyether/OMT hybrid was first prepared in a nanocomposite form as confirmed by XRD. It was shown that there is a multilayered structure consisting of alternating PU chains stacked with the layers of the silicate layers in the microstructure of the PU/OMT nanocomposite as confirmed by study of the XRD patterns and the HREM images. The contents of the hard segment of PU and OMT had an effect on the basal spacing of the PU/OMT nanocomposite. Received: 29 August 2000 Accepted: 16 February 2001     

Characterization of homoionic Fe-type montmorillonite: Potential chemical species of iron contaminant

Fe²⁺-montmorillonite with Fe²⁺ ions occupying cation exchange sites is an ideal transformation product in bentonite buffer material. In our previous study on preparation and characterization of Fe²⁺-montmorillonite, the montmorillonite sample that adsorbed Fe²⁺ ions on almost all of the cation exchange sites was prepared using a FeCl₂ solution under an inert gas condition [N. Kozai, Y. Adachi, S. Kawamura, K. Inada, T. Kozaki, S. Sato, H. Ohashi, T. Ohnuki, T. Banba, J. Nucl. Sci. Technol. 38 (2001) 1141]. In view of the unstable nature of iron(II) chemical species, this study attempted to determine the potential contaminant iron chemical species in the sample. Nondestructive elemental analysis revealed that a small amount of chloride ions remained dispersed throughout the clay particles. The chloride ion retention may be due to the adsorption of FeCl⁺ ion pairs in the initial FeCl₂ solution and the subsequent containment of the Cl⁻ ions that are dissociated from the FeCl⁺ ion pairs during excess salt removal treatment. Two explanations are advanced for the second process: the slow release of the remaining Cl⁻ ions from the collapsed interlayer of the montmorillonite, and the transformation of a minor fraction of the remaining FeCl⁺ ion pairs to iron(III) hydroxide chloride complexes having low solubility.     

Thermal degradation of poly(lactic acid) measured by thermogravimetry coupled to Fourier transform infrared spectroscopy

Thermogravimetric (TG), differential thermal analysis (DTA) and thermal degradation kinetics, FTIR and X-ray diffraction (XRD) analysis of synthesized glycine–montmorillonite (Gly–MMT) and montmorillonite bound dipeptide (Gly–Gly–MMT) along with pure Na–MMT samples have been performed. TG analysis at the temperature range 25–250 °C showed a mass loss for pure Na–MMT, Gly–MMT and Gly–Gly–MMT of about 8.0%, 4.0% and 2.0%, respectively. DTA curves show the endothermic reaction at 136, 211 and 678 °C in pure Na–MMT whereas Gly–MMT shows the exothermic reaction at 322 and 404 °C and that of Gly–Gly–MMT at 371 °C. The activation energies of the first order thermal degradation reaction were found to be 1.64 and 9.78 kJ mol⁻¹ for Gly–MMT and Gly–Gly–MMT, respectively. FTIR analyses indicate that the intercalated compounds decomposed at the temperature more than 250 °C in Gly–MMT and at 250 °C in Gly–Gly–MMT.     

Solid State Deoximation with Clay SupportedAmmonium Chlorochromate: Regenerationof Carbonyl Compounds Using Microwavesin a Solventless System

Summary.  Ammonium chlorochromate adsorbed on montmorillonite K-10 rapidly regenerates carbonyl compounds from their corresponding oximes under microwave irradiation and solvent-free conditions. Received October 11, 1999. Accepted (revised) November 15, 1999     

Paraquat release control using intercalated montmorillonite compounds

A representative herbicide, paraquat (PQ; 1,1′-dimethyl-(4,4′-bipyridium) dichloride) was intercalated into montmorillonite by solution and solid state reaction methods. In a typical solution process paraquat aqueous solution was mixed with montmorillonite (Kunipia-F) aqueous suspension, which resulted in a paraquat-montmorillonite layer complex with a basal spacing of 1.3 nm. A paraquat-montmorillonite complex was also easily prepared by solid state reaction method. The mixture of paraquat and Na-montmorillonite was ground under ambient temperature. The basal spacing of the mixture increased to 1.3 nm after grinding for 30 min. In order to achieve the pH dependent releasing of intercalated PQ molecules, the PQ-montmorillonite complex was coated with cellulose acetate phthalate. The polymer modified PQ-montmorillonite complex exhibited a strongly suppressed PQ releasing in the acidic pH domain, while an enhanced PQ releasing at the neutral pH range, respectively.     

Montmorillonite K-10-catalyzed intramolecular rearrangement of vinylidenecyclopropanes

A series of naphthalene, indene, and 6aH-benzo[c]fluorene derivatives are synthesized by intramolecular rearrangement of vinylidenecyclopropanes using a heterogeneous solid acid catalyst, montmorillonite K-10, under mild reaction conditions in good to excellent yields. The solid acidic catalyst, montmorillonite K-10, can be recovered and reused.     

Fire retardancy and biodegradability of poly(methyl methacrylate)/montmorillonite nanocomposite

The poly(methyl methacrylate) (PMMA)/montmorillonite (MMT) nanocomposite was prepared by emulsifier-free emulsion technique and its structure and properties were characterized with infra red, X-ray diffraction, transmission electron microscopy, thermogravimetric analysis, and cone calorimetry. The highly exfoliated MMT layers with dimension 1-2 nm in thickness were randomly dispersed in the polymer matrix containing MMT lower than 5% w/v, whereas the intercalated structure was predominant with MMT content higher than 5% w/v. Consequently, the fine dispersion of the MMT and the strong interactions between PMMA and MMT created significant improvement of the thermo-stability and fire retardancy of the nanocomposite. The combustion behavior has been evaluated using oxygen consumption cone calorimetry. In addition, a scheme was proposed to describe fire retardancy of PMMA and MMT as well as the correlation between the interaction and structure in polymer/clay systems. The biodegradability of the nanocomposite fire-retardant was tested for its better commercialization.     

Replication and Evolution in Inorganic Systems

Using layer silicates as models, the principle of replication, i.e. the spontaneous self-multiplication of a carrier of information, can be shown to be a general property of certain macromolecular systems. Errors in replication and feedback together with environmental influences may lead to mutants with higher or lower replication rates, thus enabling evolution. In the light of these findings, the question of whether or not chemical evolution resulted directly in the nucleic acid/protein system, i.e. the genetic principle common to all living systems known up to now, has to be answered. It seems conceivable that as a first step a much simpler replicating system was formed: such a system might then have undergone an evolution of replicating systems, resulting in the final nucleic acid/protein system.