Structural and electrical properties of doped polypyrrole and its composite with montmorillonite clay

Polypyrrole is synthesized and doped with Dodecylbenzenesulphonic acid. The doped Polypyrrole with Dodecylbenzenesulphonic acid is intercalated into the layers of Montmorillonite clay successfully by in situ polymerization. The structural properties of synthesized doped Polypyrrole and intercalated doped Polypyrrole were studied by XRD analysis. The crystallinity of intercalated doped Polypyrrole into the layers of Montmorillonite clay is confirmed by means of X-rays diffraction studies, which is more than the doped Polypyrrole. Enhanced d-spacing of Montmorillonite confirmed that doped Polypyrrole is interclated into the layers of Montmorillonite clay at nanoscale. The scanning electron micrographs also confirm the formation of dual phase of platelet as well as of flaky structure of intercalated doped Polypyrrole. Temperature dependant conductivity showed three dimensional variable ranges hopping model. Activation energy, density of states and hopping length are calculated and found to be influenced by intercalating Doped Polypyrole into the layers of Montmorillonite clay.     

The reaction of N-tosyl imines with heteroaromatic compounds: a new access to triheteroarylmethanes

Useful triheteroarylmethanes were prepared by the double Friedel-Crafts reaction of a wide variety of aromatic N-tosyl imines with furan, thiophene, and pyrrole in the presence of Cu(OTf)₂ and Montmorillonite K-10 clay catalysts.     

Montmorillonite clay-catalyzed hetero-Diels-Alder reaction of 2,3-dimethyl-1,3-butadiene with benzaldehydes

Montmorillonite K10 clay was found to catalyze the hetero-Diels-Alder reaction of 2,3-dimethyl-1,3-butadiene with o-anisaldehyde and other benzaldehyde derivatives; a transition state involving chelation of the clay’s metal ions with the dienophile’s heteroatoms is proposed.     

Thermal analysis of montmorillonite-aminotriazole interactions

In the present investigation, DTA and TG techniques were used to study the thermal behaviour of montmorillonite treated with solutions of the pesticide aminotriazole (AMT), in nitrogen flow. These techniques have been complemented by mass spectrometry of the evolved gases (EGA-MS). AMT is adsorbed in the interlamellar space of montmorillonite as a cation. Results obtained in this study show that this provokes a shift of the dehydroxylation peak of montmorillonite to lower temperatures than those of the untreated clay. Montmorillonite protects the adsorbedAMT, delaying its first decomposition step, and catalysesAMT final decomposition at lower temperatures. The DTA curve of montmorillonite-AMT mechanical mixture differs from the sum of those of the clay mineral and the pesticide heated individually. Montmorillonite dehydroxylation occurs at lower temperature, indicating a complex formation betweenAMT and the mineral during the heating process. However the DTA of the mixture is different from that of the complex previously studied, indicating that in the complex obtained by heating the physical mixtureAMT is adsorbed as neutral molecule or as a product of its decomposition.     

Inclusion of aramid chains into the layered silicates through solution intercalation route

Aramid–organoclay nanocomposites were fabricated through solution intercalation technique. Montmorillonite was modified with p-amino benzoic acid in order to have compatibility with the matrix. The effect of clay dispersion and the interaction between clay and polyamide chains on the properties of nanocomposites were investigated using X-ray diffraction (XRD), transmission electron microscopy (TEM), tensile testing of thin films, differential scanning calorimetry (DSC), thermogravimetric analysis (TGA) and water uptake measurements. Excessive clay dispersion was achieved even on the addition of high proportions of clay. The structural investigations confirmed the formation of delaminated nanostructures at low clay contents and disordered intercalated morphology at higher clay loadings. The tensile behavior and thermal stability significantly amplified while permeability reduced with increasing dispersibility of organoclay in the polyamide matrix.     

Montmorillonite clay-catalyzed cyclotrimerization and oxidation of aliphatic aldehydes

A temperature-dependent equilibrium is observed for the cyclotrimerization of aliphatic aldehydes in the presence of Montmorillonite K10 clay, while aerobic oxidation of aliphatic aldehydes to the corresponding carboxylic acids is favored at room temperature in the presence of Montmorillonite KSF clay.     

Enhanced thermal stability and structural characteristics of different MMT-Clay/epoxy-nanocomposite materials

Epoxy-clay nanocomposites, HDTMA-BDGE, HDTMA-BPDG, HDTMA-BBDG, HDTMA-TGDDM and HDTPP-BDGE were synthesized using hexadecylammonium clay and hexadecylphosphonium clay, respectively. The Montmorillonite (MMT) clay was modified with quaternary ammonium salt and with triphenylphosphonium salt which was intercalated into the interlayer region of MMT-Clay. The epoxy-clay systems were cured by using diaminodiphenylsulphone as a curing agent. The X-ray diffraction patterns obtained for the systems confirmed the nanodispersion of MMT-Clay in the epoxy networks. The ammonium clay-modified systems displayed appreciable mechanical and glass-transition temperature properties while, the phosphonium clay-modified system exhibited highest thermal resistance properties compared with unmodified epoxy systems. The T_g decrease observed in all the clay-modified epoxy systems, may be compromised with their advantage of requiring the filler content very low (5wt%), when compared to the conventional epoxy systems whose filler quantity is normally required from 25 to 30 wt%.     

Reactions on solid supports part I: Novel preparation of α-formyl pyrroles from α-methylpyrroles by oxidation with thallium (III) nitrate on clay

Treatment of α-methylpyrroles with thallium (III) nitrate/Montmorillonite clay affords the corresponding α-formylpyrroles in excellent yields.     

Reactions on solid supports part II: a convenient method for synthesis of pyrromethanes using a montmorillonite clay as catalyst

α-Acetoxymethylpyrroles couple with α-free pyrroles in presence of Montmorillonite clay to form unsymmetrical pyrromethanes in excellent yields. Symmetrical pyrromethanes were also prepared in a similar manner by clay catalysed self-condensation of α-acetoxymethylpyrroles.     

Alternate Syntheses Of Pyrromethanes And Porphyrins Using Acid-Modified Montmorillonite K-10 Clay

A variety of porphyrins and pyrromethanes are prepared using Montmorillonite clay mixed with a variety of acids (p-TsOH, BF₃ Et₂O).The ease of use of the naturally occurring clay as a co-catalyst makes it an attractive reagent for use in synthesis.     

Preparation and thermal stability of boron-containing phenolic resin/clay nanocomposites

In order to further improve thermal stability of the phenolic resins, we combined boron and clay with phenolic resins to prepare nanocomposites (BH-B, BP-B, and BE-B series). Boron-containing phenolic resin/clay (montmorillonite) nanocomposites were prepared using in situ polymerization of resol-type phenolic resins. Montmorillonite (MMT) was modified by benzyldimethylhexadecylammonium chloride (BH), benzyldimethyphenylammonium chloride (BP), and benzyltriethylammonium chloride (BE). X-ray diffraction measurements and transmission electron microscope (TEM) observations showed that clay platelets were partially exfoliated after complete curing of the phenolic resins. Thermogravimetric analysis showed that thermal decomposition temperatures (T_d) and residual weight at 790 °C of cured boron-containing nanocomposites were much higher than the corresponding nanocomposites without boron. For example, the rise in decomposition temperature of BE-B10% is about 42 °C (from 520 to 566 °C), whereas the increase in char yields is 6.4% (from 66.2% to 72.6%). However, the boron-containing composites were more prone to absorb moisture (ca. 9-14%) than boron-free ones (ca. 3-4%), which was attributed to unreacted or partially reacted boric acid during preparation process.     

Montmorillonite K10 clay-catalyzed synthesis of homoallylic silyl ethers: an efficient and environmentally friendly Hosomi-Sakurai reaction

Aromatic aldehydes react with allyltrimethylsilane in the presence of activated Montmorillonite K10 clay to give homoallylic silyl ethers in good to excellent yields.     

Acylation of aromatic alcohols and phenols over InCl3/montmorillonite K-10 catalysts

Montmorillonite K-10 clay supported InCl₃ is a highly active catalyst for the acylation of aromatic alcohols and phenols with different acyl chlorides. This catalyst can be reused in reactions a number of times without very significant loss of catalytic activity     

Montmorillonite K10 Clay Catalysed Friedel-Crafts Aralkylation in Room Temperature: Synthesis of Functionalised Linear Aryl-Alkyl-Aryl Systems

The Montmorillonite K10 clay catalysed Friedel-Crafts aralkylation of compound 2 with a number of aromatic hydrocarbons furnished functionalised linear Aryl-Alkyl-Aryl systems in good yield. A comparative study of this reaction was carried out with mont-K10 and Fe³⁺-Mont-K10.     

Clay Catalysis: Synthesis of Organosulphur Synthons

Abstract

The Montmorillonite KSF catalyses the synthesis of a large variety of organic sulphur compounds from carbonyl compounds: dithianes, thioacetals, thioketals, thiochromanes.

Clay minerals are known to cataiyse a variety of organic reactions(1). In these reaction, the clay catalyst acts as a solid Bronsted acid. One of the most acidic, Montmorillonite manufactured by Sud Chemie, is the KSF catalyst. Clay is inexpensive and offers several advantages to the classic acid: a strong acidity (Ho = ?8 to ?9), no corrosive action, selectivity and easy work-up.

We report here, that KSF clay is a convenient catalyst for the synthesis of useful thio-organic reagents : dithianes, thioketals, trithioorthoformiates, thiochromanes. The condensations of the thiol with the carbonyl compounds were completed in refluxing toluene in presence of KSF with the azeotropic separation of water. Generally the pure compound was obtained in these reactions and the work-up very simple.     

Regioselective synthesis of C-prenylated flavonoids via intramolecular [1,3] or [1,5] shift reaction catalyzed by acidic clays

Prenyl side chain and dihydropyrano skeleton exists in many natural and synthetic biologically active flavonoids. A highly efficient and regioselective method for the synthesis of C-prenylated flavonoids via intramolecular [1,3] or [1,5] shift reaction of 5-O-prenylflavonoids catalyzed by Florisil or Montmorillonite clays is described. Florisil catalyzes intramolecular [1,5] shift reaction of 5-O-prenylflavonoids to obtain 8-C-prenylated flavonoids exclusively, Montmorillonite K10 exhibits the superior selectivity to promote intramolecular [1,3] shift reaction to obtain 6-C-prenylated flavonoids compared with Florisil and Montmorillonite KSF. This method provides a practical process to regioselective synthesize biologically important C-prenylated flavonoids in good yields using commercially available and inexpensive catalyst under mild conditions.     

Montmorillonite K-10 Clay Catalysed Glycosidation of 1-O-Acetyl-2,3-dideoxy-dl-pent-2-enopyrano-4-ulose

The O-glycosidation reaction of 1-O-acetyl-2,3-dideoxy-DL-pent-2-enopyran - 4 -ulose catalysed by the environmentally accepted and inexpensive industrial catalyst Montmorillonite K-10 clay with variety of alcohols in high yield is reported.     

Friedel-Crafts alkylation of a cage enone: synthesis of aralkyl substituted tetracyclo[5.3.1.0.0]undeca-9,11-diones and the formation of fascinating novel cage compounds with pyrrole and thiophene using Montmorillonite K-10

The intrinsic catalytic properties of Montmorillonite K-10 clay have been utilized for Friedel-Crafts alkylation of the polycyclic caged enone 1 using different carbo and heterocyclic aromatic systems leading to novel compounds. Carbon-carbon bond formation between the aromatic compounds and the cage system has led to three different types of products.     

TG characterization of organically modified montmorillonite

Montmorillonite was modified with octadecyltrimethylammonium chloride, under different reaction conditions, as evidenced by TG and XRD. TG curves presented two degradation peaks (295 and 395°C). At low salt concentrations, only the 395°C-degradation appeared, which increased with reaction time to the limit of 9 g of salt/100 g of clay. The second peak presented a limit at 17/100 m/m of salt/clay ratio. XRD analysis confirmed clay organic modification as the basal distance increased, showing greater reaction time effect than the salt mass effect, and with only one d-spacing. This suggested that an intercalation complex was formed but also that octadecyltrimethylammonium was adsorbed on the external surfaces of clay particles. This revised version was published online in August 2006 with corrections to the Cover Date.     

Polyethylene and polypropylene nanocomposites based upon an oligomerically modified clay

Montmorillonite clay was modified with an oligomeric surfactant, which was then melt blended with polyethylene and polypropylene in a Brabender mixer. The morphology was characterized by X-ray diffraction and transmission electron microscopy, while thermal stability was evaluated from thermogravimetric analysis and the fire properties by cone calorimetry. The nanocomposites are best described as mixed immiscible/intercalated/delaminated systems and the reduction in peak heat release rate is about 40% at 5% inorganic clay loading.