Montmorillonite compounds

Lothenbach B, Furrer G, Schulin R (1997) Immobilization of heavy metals by polynuclear aluminum and montmorillonite compounds. Environ Sci Technol 31 1452-1462 Marklund E, Ohman L-O (1990) Equilibrium and structural studies of silicon(IV) and aluminum(III) in aqueous solution. 24 A potentiometric and Al NMR study of polynuclear aluminum(III) hydroxo complexes with lactic acid. Acta Chem Scand 44 228-234 Matzapetakis M, Raptopoulou CP, Terzis A, Lakatos A, Kiss T, Salifoglou A (1999) Synthesis, structural characterization, and solution behavior of the first mononuclear, aqueous aluminum citrate complex. Inorg Chem 38 618-619... 

Lothenbach B, G. Furrer, and R. Schulin. 1997. Immobilization of heavy metals by polynuclear aluminum and montmorillonite compounds. Environ. Sci. Technol. 31 1452-1462. 

Depending on the nature of the filler distribution within the matrix, the morphology of the nanoeomposites can evolve from the so-called intercalated structure where a regular alternation of the layered silicates and polymer monolayers is observed, to the exfoliated (delaminated) structure where the layered silicates are randomly and homogeneously distributed within the polymer matrix. The easiest and technically most attractive way to produce these types of materials is to knead the polymer in the molten state with a modified layered silicate, such as montmorillonite. Compounding on different machines, such as a Buss ko-kneader or mills, still produces essentially the same morphology in the resulting nanoeomposites. 

Kojima et al. [ 122] report that the polyamide-6/montmorillonite compound (nanocomposite or hybrid) has superior modulus, tensile strength, flexural modulus, and impact strength compared to neat polyamide-6, as well as higher heat distortion temperature. Indeed, with 4.7 wt% montmorillonite, the heat distortion temperature was increased 87 °C over neat polyamide-6 to 152 °C. 

In a 1975 Japanese patent application, Fujiwara and Sakamoto [71 ] of Unitika adsorbed various lactams onto montmorillonite and found swelling of the clay silicate layers and spontaneous polymerization. Similar but more extensive studies were subsequently published and patented byKojima,Okada,Usuki, and their coworkers [72 to 77] from Toyota from the late 1980s. They then examined the structure and properties of these compoimds. In these compounds, the clay is dispersed as individual exfoliated silicate layers. Various other silicate minerals were studied [76], but montmorillonite compounds were found to be superior in mechanical properties. Similar polymerizations were carried out for a polyamic acid to produce a polyimide [77]. Mechanical property enhancements of exfoliated montmoriUonite/polyamide-6 [78,79] are shown in Fig. 7.3. 

Reductive carbonylation of nitro compounds is catalyzed by various Pd catalysts. Phenyl isocyanate (93) is produced by the PdCl2-catalyzed reductive carbonylation (deoxygenation) of nitrobenzene with CO, probably via nitrene formation. Extensive studies have been carried out to develop the phosgene-free commercial process for phenyl isocyanate production from nitroben-zene[76]. Effects of various additives such as phenanthroline have been stu-died[77-79]. The co-catalysts of montmorillonite-bipyridylpalladium acetate and Ru3(CO) 2 are used for the reductive carbonylation oLnitroarenes[80,81]. Extensive studies on the reaction in alcohol to form the A -phenylurethane 94 have also been carried out[82-87]. Reaction of nitrobenzene with CO in the presence of aniline affords diphenylurea (95)[88]. 

MeO)3CH, Montmorillonite Clay K-10, 5 min-15 h, >90% yield.Diethyl ketals have been prepared in satisfactoiy yield by reaction of the carbonyl compound and ethanol in the presence of montmorillonite clay. " ... 

The synthesis of imidazoles is another reaction where the assistance of microwaves has been intensely investigated. Apart from the first synthesis described since 1995 [40-42], recently a combinatorial synthesis of 2,4,5-trisubstituted and 1,2,4,5-tetrasubstituted imidazoles has been described on inorganic solid support imder solvent-free conditions [43]. Different aldehydes and 1,2 dicarbonyl compounds 42 (mainly benzil and analogues) were reacted in the presence of ammonium acetate to give the trisubstituted ring 43. When a primary amine was added to the mixture, the tetrasubstituted imidazoles were obtained (Scheme 13). The reaction was done by adsorption of the reagent on a solid support, such as silica gel, alumina, montmorillonite KIO, bentonite or alumina followed by microwave irradiation for 20 min in an open vial (multimode reactor). The authors observed that when a non-acid support was used, addition of acetic acid was necessary to obtain good yields of the products. 

Considering the formation of saturated five-membered heterocycles with two heteroatoms, it is worth to note the possibility to prepare 1,3-dioxolanes, dithiane, oxathianes 148 [93] and dioxolanones 149 [94] by condensation of the corresponding carbonyl compounds under microwave irradiation in acid medium (Scheme 52). The reaction, which is very useful for the protection of carbonyl compounds or for the preparation of useful synthetic intermediates, has also been carried out under batch conditions over Montmorillonite KIO clay in more than 150 g scale, using a 1 L quartz reactor [95]. 

Methyltins are less likely than the butyl- and octyl-tins to partition to sediments, soils, and organic carbon. Modelled data for K c suggest much lower capacity for binding to organic carbon than do measured values, often by several orders of magnitude. Measured data have been used in preference to model environmental fate of the compounds. The compounds also bind strongly to clay minerals, montmorillonite in particular. 

Fewer controlled experiments have been carried out for purely aquatic systems. Montmorillonite complexes with benzylamine at concentrations below 200 pg/L decreased the extent of mineralization in lake-water samples, although a similar effect was not noted with benzoate (Snbba-Rao and Alexander 1982). Even in apparently simple systems, general conclusions cannot therefore be drawn even for two structurally similar aromatic compounds, both of which are readily degradable nnder normal circumstances in the dissolved state. 

Bentonite is an impure clay that is formed by weathering of volcanic tuffs. It contains a high content of montmorillonite. Bentonites exhibit properties such as ability to swell, ion exchange, and thixotropy. Properties can be modified by ion exchange, for example, exchange of earth alkali metals to alkali metals. The specific surface can be modified with acid treatment. Organophilic properties can be increased by treatment with quaternary ammonia compounds. 

In a study of adsorption of organic herbicides by montmorillonite, Bailey and colleagues138 found that none of the compounds conformed to the Langmuir adsorption equation. Of the 23 compounds tested, only a few did not conform well to the Freundlich equation. 

Fig. 6.20 Simplified diagram of montmorillonite clay with anionic and cationic organic compounds bonded to it (Ferris, 1998)...

Four billion years ago, the Earth s thin crust consisted of geochemicals (i.e., compounds containing the elements Si, O, Al, Fe, Mg, Ca, K and Na, as well as traces of other elements). Thus, some biogenesis researchers believed that the first replicating material consisted of geochemical material rather than substances containing carbon and other bioelements. Clay minerals in particular were included in experimental and theoretical studies. The most important are kaolinite and montmorillonite the latter was, and still is, used in many experiments carried out to simulate prebiotic reactions. 

A diverse group of organic reactions catalyzed by montmorillonite has been described and some reviews on this subject have been published.19 Examples of those transformations include addition reactions, such as Michael addition of thiols to y./bunsatu rated carbonyl compounds 20 electrophilic aromatic substitutions,19c nucleophilic substitution of alcohols,21 acetal synthesis196 22 and deprotection,23 cyclizations,19b c isomerizations, and rearrangements.196 24... 

A new synthetic route for functionalized polyhydroxyalkyl-pyrimidines starting from unprotected aldoses and based on montmorillonite K-10 catalysis and solvent-free microwave irradiation conditions, has been reported by Yadav et al,m Thus, reaction of D-glucose and D-xylose with semicarbazide or thiosemicarbazide (186) in the presence of montmorillonite K-10, under microwave irradiation, proceeded via domino cycloisomerization, dehydrazination, and dehydration of the intermediate semi- or thiosemicarbazones (187) to afford l,3-oxazin-2-ones or l,3-oxazine-2-thiones (188) in one single step and in yields between 79% and 85% (Scheme 34). Other mineral catalysts tested, such as silica gel and basic alumina, were far less effective for this transformation and only silica gel was active at all, giving low yields (15-28%) of compounds 188a-d. The l,3-oxazin-2-ones(thiones) thus synthesized were subsequently converted into the target pyrimidines by reaction with aromatic... 

SCHEME 35. Montmorillonite K-10-catalyzed cyclodehydration of the l,3-oxazin-2-one and 1,3-oxazin-2-thione derivatives 189 into bicyclic compounds 190. 

A facile method for the oxidation of alcohols to carbonyl compounds has been reported by Varma et al. using montmorillonite K 10 clay-supported iron(III) nitrate (clayfen) under solvent-free conditions [100], This MW-expedited reaction presumably proceeds via the intermediacy of nitrosonium ions. Interestingly, no carboxylic acids are formed in the oxidation of primary alcohols. The simple solvent-free experimental procedure involves mixing of neat substrates with clayfen and a brief exposure of the reaction mixture to irradiation in a MW oven for 15-60 s. This rapid, ma-nipulatively simple, inexpensive and selective procedure avoids the use of excess solvents and toxic oxidants (Scheme 6.30) [100]. Solid state use of clayfen has afforded higher yields and the amounts used are half of that used by Laszlo et al. [17,19]. 

Sodium cyanoborohydride [123], sodium triacetoxyborohydride [124] or NaBH4 coupled with sulfuric acid [125] are common agents used for the reductive amination of carbonyl compounds. These reagents either generate waste or involve the use of corrosive acids. The environmentally friendlier procedures developed by Varma and coworkers have been extended to a solvent-free reductive amination protocol for carbonyl compounds using moist montmorillonite K 10 day supported sodium borohydride that is facilitated by microwave irradiation (Scheme 6.39) [126]. 

The efficiency of type II organoclays in taking up organic pollutants from water is also apparent from the data in Figs. 7 and 8 showing the removal of naphthalene and 17P-estradiol (an endocrine-disrupting compound) by octadecyltrimethylammonium-montmorillonite (Yuan 2004). 

---