Modification of Na+-montmorillonite with mono- and bis(polyfluoroalkyl) phthalates

Layered natural aluminosilicate, Na⁺-montmorillonite, was modified with mono- and bis(polyfluoroalkyl) phthalates. The polyfluorinated esters as Na⁺-montmorillonite modifiers exhibit high organophilizing and hydrophobizing activity, as demonstrated by thermal analysis and IR spectroscopy. A change in the interlayer spacing in the clay was determined by X-ray diffraction. The capability of the modifier for intercalation into the layered structure of the clay depends on the degree of telomerization of the perfluoroalkyl residue.     

Alteration of biotite by suspended montmorillonite

Summary Alteration of biotite flakes which were placed in suspensions of Na⁺ — and Mg⁺⁺-montmorillonite for different contact periods at two different temperatures, were followed using X-ray and petrographic microscope.The biotite seemed to alter to a mineral of the vermiculite type. Na⁺-montmorillonite changed the biotite more than Mg⁺⁺-montmorillonite at 21°C. At 50°C, however, no changes of the biotite flakes could be observed using Na⁺-montmorillonite in contrast to the case when Mg⁺⁺-montmorillonite was used. A good correlation between X-ray measurements and optical observations was found.With 3 figures and 3 tables     

Hybrid nanocomposites based on guanidine methacrylate monomer and polymer and layered aluminosilicates: Synthesis, structure, and properties

Hybrid nanostructures (organomodified montmorillonite) have been synthesized on the basis of activated Na⁺-montmorillonite and new water-soluble ionogenic Na⁺-montmorillonite monomers containing quaternary ammonium guanidine cations. The structure and properties of poly(guanidine methacrylate) nanocomposites have been studied. It has been shown that these compounds efficiently adsorb heavy metals and exhibit a prolonged biocide effect due to the presence of quaternary ammonium guanidine cations.     

Preparation, characterization and electrochemical corrosion studies on environmentally friendly waterborne polyurethane/Na-MMT clay nanocomposite coatings

In this study, we present the first practical evaluation for the corrosion protection effect of waterborne polyurethane (WPU)/Na⁺-montmorillonite (Na⁺-MMT) clay nanocomposite coating. Typically, a series of waterborne polyurethane (WPU)/Na⁺-montmorillonite (Na⁺-MMT) clay nanocomposite materials have been successfully prepared by effectively dispersing the inorganic nanolayers of commercially purified Na⁺-MMT clay in WPU matrix through direct aqueous solution dispersion technique. First of all, WPU was prepared by polymerizing PCL, DMPA and H₁₂MDI, followed by characterized by nuclear magnetic resonance (¹H NMR), Fourier transform infrared (FTIR) and gel permeation chromatography (GPC). Subsequently, the as-prepared PU/Na⁺-MMT clay nanocomposite (Na⁺-PCN) materials were subsequently characterized by FTIR, X-ray diffraction (XRD) patterns and transmission electron microscopy (TEM).PCN materials in the form of coating at low Na⁺-MMT clay loading up to 3 wt% coated on the cold-rolled steel (CRS) coupons were found to exhibit superior corrosion protection effect over those of neat WPU based on a series of electrochemical measurements of corrosion potential, polarization resistance, corrosion current and impedance in 5 wt% aqueous NaCl electrolyte. Effects of the material composition on the gas permeability, thermal stability and optical clarity of neat WPU along with a series of Na⁺-PCN materials, in the form of coating and free-standing film, were also studies by gas permeability analyzer (GPA), thermogravimetric (TGA), differential scanning calorimetry (DSC) and ultraviolet UV-visible transmission spectroscopy, respectively. As control experiments, a series of PU/organo-MMT nanocomposite (denoted by organo-PCN) materials were also prepared for comparative studies.     

Features of reactions of phthalic anhydride with polyfluorinated alcohols

Polyifluoroalkyl mono- and diesters of phthalic acid were obtained by the reaction of phthalic anhydride with polyfluorinated alcohols. The structure of the polyfluoroalkyl phthalates was studied using IR and ¹H, ¹³C NMR spectroscopy. The nature of the associative interactions between cyclohexanone and polyfluorinated alcohols was revealed.     

Advanced environmentally friendly anticorrosive materials prepared from water-based polyacrylate/Na-MMT clay nanocomposite latexes

A series of novel advanced environmentally friendly anticorrosive materials have been successfully prepared by effectively dispersing nanolayers of Na⁺-montmorillonite (Na⁺-MMT) clay into water-based polyacrylate latex (i.e., vinyl acrylic terpolymers). First of all, a polyacrylate latex was synthesized through co-polymerizing organic monomers of MMA, BMA and styrene (St) using conventional emulsion polymerization technique with SDS, 1-pentanol and KPS as surfactant, co-surfactant and initiator, respectively. Subsequently, the commercial purified hydrophilic Na⁺-MMT was effectively dispersing into the polyacrylate latex through the direct solution dispersion technique.The as-prepared neat polyacrylate and the series of water-based polyacrylate/Na⁺-MMT clay nanocomposite (Na⁺-PCN) materials were subsequently characterized by FTIR spectroscopy, XRD, TEM and GPC. The water-based Na⁺-PCN materials loaded with low content of Na⁺-MMT when in the form of coating on the cold rolled steel (CRS) coupons was found to be remarkably superior in anticorrosion efficiency over those of neat polyacrylate based on a series of electrochemical measurements of corrosion potential, polarization resistance, corrosion current, and impedance spectroscopy in saline. Effect of material composition on the molecular barrier, optical clarity and thermal stability were also studied by molecular permeability analysis, ultraviolet-visible transmission spectra, differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA), respectively. Organo-PCN materials were also prepared as a control experiment for comparative studies.     

Hydrophobic and organophilic properties of polyfluoroalkyl-oligo-ɛ-caproamide as a Na+-montmorillonite modifier

A high organophylic and hydrophobic activity of the polyfluoroalkyl-oligo-?-caproamide as a modifier of Na⁺-montmorillonite was revealed using the methods of derivatography and IR spectroscopy. The effect of the degree of oligomerization of polyfluoroalkyl-oligo-?-caproamide and telomerization of the polyfluoroalkyl residue on the ability to intercalate into the layered structure of the clay was demonstrated.     

Preparation and characterization of poly(o-methoxyaniline)/Na-MMT clay nanocomposite via emulsion polymerization: Electrochemical studies of corrosion protection

A series of poly(o-methoxyaniline) (PMA)/Na⁺-montmorillonite (MMT) clay nanocomposite (Na⁺-PCN) materials have been successfully prepared by in situ emulsion polymerization in the presence of inorganic nanolayers of hydrophilic Na⁺-MMT clay with DBSA and APS as surfactant and initiator, respectively. The as-synthesized Na⁺-PCN materials were characterized by Fourier-transformation infrared (FTIR) spectroscopy, wide-angle powder X-ray diffraction (XRD) and transmission electron microscopy (TEM).Na⁺-PCN materials in the form of coatings with low loading of Na⁺-MMT clay (e.g., 5 wt.%, CLMA5) on cold rolled steel (CRS) were found much superior in corrosion protection over those of neat PMA based on a series of electrochemical measurements of corrosion potential, polarization resistance, corrosion current and impedance spectroscopy in 5 wt.% aqueous NaCl electrolyte. The molecular weight of PMA extracted from Na⁺-PCN materials and net PMA were determined by gel permeation chromatography (GPC) with NMP as eluant. Effects of material composition on the optical properties, electrical conductivity, thermal stability and surface morphology of neat PMA and/or a series of Na⁺-PCN materials, in the form of solution, powder-pressed pellet and fine powder, were also studied by ultraviolet-visible spectra, four-point probe technique, thermogravimetric analysis (TGA) and scanning electron microscopy (SEM), respectively.     

Metal ions exchanged montmorillonite as catalyst for alkylation of benzene with 1-dodecene

Summary About 8.5% of benzene was alkylated with 1-dodecene in the presence of Na⁺-montmorillonite. When the reaction was carried out with montmorillonite exchanged with Mn²⁺, Cu²⁺, Ni²⁺, Zn²⁺ and Fe²⁺ ions as catalyst (M²⁺/mont.), 91 to 95% of 1-dodecene was remarkably converted to a mixture of linear monoalkylbenzenes.     

Use of nanoporous Na+-montmorillonite sulfonic acid (SANM) as an eco-benign, efficient and reusable solid acid catalyst for the one-pot synthesis of 14-aryl-14-H-dibenzo[a,j]xanthenes and 1,8-dioxo-dodecahydroxanthene derivatives

Nanoporous Na⁺-montmorillonite sulfonic acid was found to be an efficient and green catalyst for the synthesis of various 14-aryl-14H-dibenzo[a,j]xanthenes and 1,8-dioxo-dodecahydroxanthene derivatives by the reaction of aldehydes with 2-naphthol and 1,3-cyclohexanedione, respectively. This novel synthetic method has the advantages of high yields, short reaction times and recyclability of the catalyst, simplicity and easy workup compared to the conventional methods reported in the literature.     

Synthesis, characterisation and mass spectrometric fragmentation of O-(chlorodifluoroacylated) alcohols

An indirect and uncatalysed esterification of chlorodifluoroacetic acid with polyfluoro and hydrocarbon alcohols has been developed. The method which involves the reaction between sodium chlorodifluoroacetate and alcohols in dimethylformamide (DMF) is particularly facile with polyfluorinated alcohols resulting in esters in 71-85% yield. The esters have been characterised on the basis of ¹H and ¹⁹F NMR and mass spectral data. The electron impact (EI) mass spectrometric fragmentation of these polyfluorinated esters have shown some interesting features which have been substantiated by using tandem mass spectrometry.     

K+-montmorillonite: its electric double layer extension and point of zero charge by diffusion potential

The dependence of the counterion transference number on the distance from the charged surface, that is, on the water (solution) thickness, is used for an approximation of the extension of the electric double layer (edl) in K⁺-montmorillonite.The extension of edl in K⁺-montmorillonite in 10^–2–10^–3 M KCl solutions is approximately 3.7k ^–1, wherek ^–1 is the Debye length.The dependence of the counterion transference number on the pH of water (solution) is used for estimating the point of zero charge (pzc) of K⁺-montmorillonite; the estimated pzc=1.     

Acidic ionic liquid immobilized on nanoporous Na<Superscript>+</Superscript>-montmorillonite as an efficient and reusable catalyst for the formylation of amines and alcohols

In this work, nanoporous sodium montmorillonite clay (Na⁺-MMT) was used as a support for the immobilization of 1-methyl-3-(trimethoxysilylpropyl)-imidazolium hydrogen sulfate. The Na⁺-MMT chemical modification ([Na⁺-MMT-[pmim]HSO₄) was confirmed by a variety of techniques including Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), thermogravimetric analysis (TGA), scanning electron microscopy and potentiometric titration. The catalytic performance of this immobilized acidic ionic liquid was probed for the N-formylation of a variety of amines using formic acid under solvent-free conditions. This reagent is also useful for the formylation of benzylic alcohols. The procedure gave the products in excellent yields in very short reaction times. Also, this catalyst can be reused ten times without loss of its catalytic activity.     

Fe3+-Montmorillonite K10: an Efficient Catalyst for Selective Amidation of Alcohols with Nitriles Under Non-Aqueous Condition

An efficient method for preparation of secondary amides by reaction of alcohols with nitriles is described using a catalytic amount of Fe³⁺-montmorillonite K10.     

Synthesis and Biological Activity of 4-Chloromethyl-substituted 1,3,2-Dioxaphosphorinanes Phosphates and Amidophosphates

A series of 2-N and 2-O-substituted 2-oxo-4-chloromethyl-1,3,2-dioxaphosphorinanes were prepared by reaction of amines and alcohols with 2-oxo-2-chloro-4-chloromethyl-1,3,2-dioxaphosphorinane. The structure of compounds obtained was proved by means of ¹H and ^{1 3}C NMR spectroscopy. Some cyclic amidocyclophosphates possessed biological activity as inhibitors of mitotic fission and of Na⁺/H⁺ exchange.     

Enhancement of 1,2-dehydration of alcohols by alkali cations and protons: a model for dehydration of carbohydrates

We have used electronic structure calculations to investigate the 1,2-dehydration of alcohols as a model for water loss during the pyrolysis of carbohydrates found in biomass. Reaction enthalpies and energy barriers have been calculated for neat alcohols, protonated alcohols and alcohols complexed to alkali metal ions (Li⁺ and Na⁺). We have estimated pre-exponential A factors in order to obtain gas phase rate constants. For neat alcohols, the barrier to 1,2-dehydration is about 67 kcal mol⁻¹, which is consistent with the limited experimental data. Protonation and metal complexation significantly reduce this activation barrier and thus, facilitate more rapid reaction. With the addition of alkali metals, the rate of dehydration can increase by a factor of 10⁸ while addition of a proton can lead to an increase of a factor of 10²³.     

Synthesis of halo-fluoro-substituted adamantanes by electrophilic transannular cyclization of bicyclo[3.3.1]nonane dienes

3,7-Dimethylenebicyclo[3.3.1]nonane and its derivatives with a methyl or phenyl substituent in a methylene group react, with N-halosuccinimides NXS (X=Cl, Br, I) in dichloromethane in the presence of tetrabutylammonium dihydrotrifluoride or polyfluorinated alcohols via a transannular cyclization leading to the corresponding 1-fluoro- or 1-polyfluoroalkoxy-3-halomethyladamantanes. The reaction of the dienes with NXS and Bu₄N⁺H₂F₃⁻ conducted in THF, oxetane or ethylene oxide runs through a cascade addition of electrophiles (positively charged halogen atoms) and external nucleophiles (solvent molecules and halide anions) to the starting diene substrate and intermediate adamantyl carbocation.     

Adsorption of methyl green on montmorillonite

Adsorption of the dye methyl green (MG) on Na -montmorillonite (Clay) takes place through a cation exchange mechanism. At low and high MG loads, each MG molecule replaces approximately two and one Na⁺ ions, respectively. Interactions between MG and Clay were studied using visible absorption and FTIR spectroscopies, and the orientation of the adsorbed molecules were determined by infrared linear dichroism and X-ray powder diffraction. The dye molecules are preferentially oriented with their plane parallel to the clay surface. The influence of MG load on the adsorption of two additional organic molecules, benzyl benzoate and benzophenone, was also studied.     

Features of the reaction of polyfluoroalkyl chlorolsulfites with allyl alcohol

Unlike the saturated aliphatic and aromatic alcohols, allyl alcohol under the same conditions reacts with polyfluoroalkyl chlorosulfites to form not ethers, but polyfluorinated alcohols. The exception is polyfluoroalkyl chlorosulfites with the chain length of more than five carbon atoms. Allyl ethers of polyfluorinated alcohols of general formula CH₂=CHCH₂OCH₂(CF₂CF₂)nH (n = 1–3) were obtained, when the reaction proceeded in the presence of potassium carbonate, owing to its participation in a specific orientation of the reaction centers in the resulting intermediate structure, which is easily transformed into allyl ethers of polyfluorinated alcohols.     

Dielectric and conductivity studies of 90 MeV O7+ ion irradiated poly(ethylene oxide)/montmorillonite based ion conductor

In the present work effect of 90 MeV O⁷⁺ ions with five different fluences on poly(ethylene oxide) (PEO)/Na⁺-montmorillonite (MMT) nanocomposites has been investigated. PEO/MMT nanocomposites were synthesized by solution intercalation technique. With the increase in irradiation fluence, gallery spacing of MMT increases in the composite and an exfoliated nanostructure is obtained at the fluence of 5?×?10¹² ions/cm² as revealed by X-ray diffraction results. Highest room temperature ionic conductivity of 4.2?×?10^?6?S?cm^?1 was found for the fluence 5?×?10¹² ions/cm², while the conductivity for unirradiated polymer electrolyte was found to be 7.5?×?10^-8?S?cm^?1. The increase in intercalation of PEO chains inside the galleries of MMT results in the increase in interaction between Na⁺ cation and oxygen heteroatom leading to the increase in ionic conductivity of the composites. Surface morphology and interactions among the various constituents in the nanocomposites at different fluence have been examined by scanning electron microscopy and Fourier transform infrared spectroscopy, respectively. The appearance of peak for each fluence in the loss tangent suggests the presence of relaxing dipoles in the polymer nanocomposite electrolyte films. With the increase in ion fluence the peak shifts towards higher frequency side, suggesting decrease in the relaxation time.