Interaction of nonionic detergents and swelling clays

Summary The 25° sorption isotherms of a polyoxyethylated n-dodecanol with 14 ethylene oxide units (C₁₂EO₁₄) on sodium and calcium montmorillonite were determined. Sorption complexes of the two clays were also prepared with C₁₂EO₃₀, n-dodecanol, polyethylene glycol and polypropylene glycol. X-ray powder diagrams show that the sorbed organic molecules are intercalated with their chains parallel to the montmorillonite lamellae, in layers one or two molecules thick. Sodium montmorillonite sorbs C₁₂ EO₁₄ and C₁₂EO₃₀ in excess of close-packed double layers: the excess detergent is occluded in interstices and absorbs moisture at 85% relative humidity to the same extent as the bulk detergents. The double layer complexes are not swelled by water; the single layer complexes sorb a single layer of water molecules at 85% relative humidity.Apparent densities of the sorbed organic molecules decrease with increasing EO content while bulk densities increase. This is explained in terms of chain flexibility and polarity.

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Zusammenfassung Die 25°-Absorptions-Isothermen von polyoxyäthyliertem n-Dodekanol mit 14Äthylenoxyd-Einheiten(C₁₂EO₁₄) an Na- und Ca-Montmorillonit wurden bestimmt. Sorptions-Komplexe der 2 Tone wurden ebenfalls mit nDodekanol, Polyäthylenglykol und Polypropylenglykol präpariert. Pulverdiagramme zeigen, daß die sorbierten organischen Moleküle mit ihren Ketten parallel zu den Montmorillonitlamellen eingelagert sind, in Schichten 1 oder 2 Moleküle dick. Na-Montmorillonit sorbiert C₁₂EO₁₄ und C₁₂EO₃₀ im Überschuß zur dichtgepackten Doppelschicht. Der Überschuß ist in Hohlräumen eingelagert und absorbiert Wasser bei 85° relativer Feuchtigkeit im selben Ausmaß wie die reinen Detergentien. Die Doppelschichtkomplexe werden nicht durch Wasser gequollen. Die Einschichtkomplexe sorbieren eine Monoschicht von Wasser-Molekülen bei 85° relativer Luftfeuchtigkeit.Scheinbare Dichten der sorbierten organischen Moleküle nehmen mit steigendem Äthylenoxydgehalt ab, während die Dichten der reinen Substanz ansteigen. Dies läßt sich auf Grund der Kettenbeweglichkeit und Polarität erklären.

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Presented at the 145^th Meeting of the American Chemical Society, New York, N. Y., September 1963.     

Colorimetric determination of anionic detergents

Many types of anionic detergents can be determined colorimetrically by the action of the detergent on a protein-bromcresol purple complex. The amount of free dye liberated from the complex is proportional to the amount of detergent added between certain limits.     

Kinetics of ion-exchange on montmorillonite clays

The kinetics for the exchange of Li⁺, K⁺, Rb⁺, and Cs⁺ for Na⁺ as the exchangeable cation on bentonite and montmorillonite K10 and KSF have been studied using conductimetric stoppedflow. Dilute aqueous suspensions of the clays, of particle sizes of a few micrometers, were used, so that diffusion was fast and the rate-determining step was the substitution of one cation by another on the lattice surface. The kinetics were treated in terms of relaxation from equilibrium. Relaxation times ranged from 100 to 250 ms, and forward rate constants from 30 to 500 M^?1 s^?1. The reactions had very low activation enthalpies (7–25 kJ mol^?1) and were only slow enough to be studied by the stopped-flow technique because of the large negative entropies of activation (?120 to ?170 J K^?1 mol^?1). © 1993 John Wiley & Sons, Inc.     

蒙脱土催化的有机化学反应

本文从合成有机化学角度, 按反应类型综述了蒙脱土类催化剂近年来在有机化学反应中的应用。这些结果表明这类催化剂比传统的催化剂在产率、选择性等多方面有更高的效率。     

Effect of sonication on the particle size of montmorillonite clays

This paper reports on the effect of sonication on SAz-1 and SWy-1 montmorillonite suspensions. Changes in the size of the particles of these materials and modifications of their properties have been investigated. The variation of the particle size has been analyzed by DLS (dynamic light scattering). In all cases the clay particles show a bimodal distribution. Sonication resulted in a decrease of the larger modal diameter, as well as a reduction of its volume percentage. Simultaneously, the proportion of the smallest particles increases. After 60 min of sonication, SAz-1 presented a very broad particle size distribution with a modal diameter of 283 nm. On the other hand, the SWy-1 sonicated for 60 min presents a bimodal distribution of particles at 140 and 454 nm. Changes in the properties of the clay suspensions due to sonication were evaluated spectroscopically from dye-clay interactions, using Methylene Blue. The acidic sites present in the interlamellar region, which are responsible for dye protonation, disappeared after sonication of the clay. The changes in the size of the scattering particles and the lack of acidic sites after sonication suggest that sonication induces delamination of the clay particles.     

Electrocapillary potentiometric determination of anionic surfactants in detergents

Summary An attempt has been made to use electrocapillarity for potentiometric determinations of anionic surfactants. A sitting mercury drop indicator electrode was successfully used for these titrations. Anionic surfactants should be titrated in a solution of defined ionic strength (0.8% sodium sulphate) at any pH between 3 and 10. A cationic surfactant (Hyamine 1622) should be used as the titrant. Pure anionic surfactants, technical grade anionic surfactants and anionic surfactants in model detergents have all been successfully titrated.

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Elektrokapillare Potentiometrie anionischer Tenside

Zusammenfassung Der Elektrokapillareffekt wurde zur potentiometrischen Bestimmung anionischer Tenside auszunutzen versucht. Als Indikatorelektrode wurde mit Erfolg eine J-förmige Hg-Elektrode (Elektrode mit aufsitzendem Hg-Tropfen) benutzt. Die Titration anionischer Tenside wird in einer Lösung bestimmter Ionenstärke (0,8% Natriumsulfat) und im pH-Bereich 3–10 durchgeführt. Als Titrant verwendet man dazu ein kationisches Tensid (Hyamin 1622). Reine anionische Tenside, technische anionische Tenside und anionische Tenside in einem Modellwaschmittel wurden titriert.

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Presented at the 8th International Microchemical Symposium, Graz, August 25–30, 1980.     

Layer-by-layer composite of anionic and cationic clays by metathesis

An alternately stacked layer-by-layer composite of oppositely charged layered solids was obtained by solvothermal treatment of the monolayer colloidal dispersions of dodecylsulfate intercalated nickel aluminum LDH and cetyl trimethylammonium intercalated smectite in 1-octanol. This composite shows altered thermal decomposition behavior compared to the parent solids. On heating the LDH component of the composite decomposes to NiO, while the layer structure of the cationic clay is retained up to 800°C.     

Thermal characterization of montmorillonite clays saturated with various cations

Emanation thermal analysis (ETA), thermogravimetry and high temperature XRD were used to characterize the thermal behavior during dehydration of natural Na montmorillonite (Upton Wyoming, USA) and homoionic montmorillonite (MMT) samples saturated with different cations, i.e. Li⁺, Cs⁺, NH₄⁺, Mg²⁺ and Al³⁺. ETA results characterized radon mobility and microstructure changes that accompanied the mass loss of the samples due to dehydration on heating in air. A collapse of interlayer space between the silicate sheets after water release from the MMT samples was characterized by a decrease of the radon release rate, ΔE. Decreases in c-axis basal spacing (d ₀₀₁) values determined from XRD patterns for the different montmorillonite samples follow the sequence:

Acid activated montmorillonite and vermiculite clays as dehydration and cracking catalysts

Treatment of montmorillonite and vermiculite with hydrochloric acid results in an overall increase in acidity and acidic sites. IR and DSC studies of base adsorbed catalysts have revealed the heterogeneity of surface acidity on the activated catalysts. Clay catalysts have been found to dehydrate 1-butanol to 1-butene, which directly isomerizes tocis- andtrans-2-butenes, confirming the presence of Lewis and Brönsted acid sites. Cumene cracking studies using the clay catalyst also confirm the presence of Brönsted acid sites. The temperature and concentration of acid have been found to have a significant influence on the catalytic activity.     

Adsorption of polyethylene glycol from aqueous solution on montmorillonite clays

Adsorption rates and capacities of polyethylene glycol (PEG) were investigated for five montmorillonite clays. The adsorption of PEG for all the montmorillonite clays was rapid, and equilibrium was attained within 30 min. The adsorption isotherms of PEG for all the montmorillonites conformed to the Freundlich equation. The adsorption heats were 7.3 and 11.6 kJ · mol^–1(mw.:2000), and 8.7 and 14.2 kJ · mol^–1(mw.:20000) for the montmorillonite and the bentonite II-Ca, respectively. Adsorption capacities for all the clay samples approached constants for the molecular weight of PEG over 2000, though they increased with the increase of molecular weight under 2000. The adsorption capacities were slightly influenced by a nearly neutral pH. The montmorillonite clays which had different interlayer cations showed quite different adsorption capacities. The bentonite II-Ca, the acid clay, and the activated clay showed large adsorption capacities that were 30–50 % of that of an activated carbon.     

水滑石类阴离子黏土的合成及催化应用研究进展

水滑石类阴离子黏土具有一些独特的性能,作为催化材料应用广泛。本文就水滑石类阴离子黏土的合成现状进行了概述,对其各种不同的合成方法进行了比较。给出了它作为碱催化剂、氧化还原催化剂以及催化剂载体的应用实例,共引用文献60篇。     

Morphological and thermal properties of ABS/montmorillonite nanocomposites using two different ABS polymers and four different montmorillonite clays

ABS/Clay nanocomposites were prepared using two ABS with different Acrylonitrile (AN) contents and four montmorillonite clays; a natural clay (CNa+) and three modified clays, Cloisites 10A, 20A, and 30B. The composites were prepared in a twin‐screw extruder. Results were analyzed considering the effect of clay and ABS type, on the clay dispersion, intercalation and exfoliation, as well as on the storage modulus and thermal stability of the nanocomposites. XRD and TEM confirm that when using an ABS with higher AN content (ABS2), a better dispersion and intercalation–exfoliation can be obtained. Cloisites 20A and 30B, respectively the one with greater initial intergallery spacing, but lower polarity and with smaller inter‐gallery spacing but greater polarity, produce the ABS nanocomposites with the greater intergallery spacing. Both ABS polymers have similar storage modulus and T_g and in both cases, the modulus increases with the 4 wt % clay. This increase is greater with the modified clays and slightly greater with the ABS2. T_g, from tan δ, increases very little with the 4 wt % clay, but again, this is slightly greater with ABS2. TGA and flammability tests show that the dispersed clay enhances the thermal stability and that the ABS with higher AN content produces a greater increase in fire retardancy. Tests also show that the better thermal stability and fire retardancy is obtained with the Cloisites 20A or 30B. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 190–200, 2008     

A novel color removal adsorbent from heterocoagulation of cationic and anionic clays

We report the preparation and characterization of a novel nanocomposite adsorbent for anionic dye removal. The nanocomposite adsorbent was prepared by heterocoagulation of delaminated bentonite and layered double hydroxide (LDH) colloids. The effects of preparation conditions, LDH loading, particle size, and calcination temperature of the modified material on the physicochemical properties of this composite adsorbent have been investigated. The optimal conditions for best Reactive Yellow 2 (RY2) dye removal efficiency are a weight ratio of LDH to bentonite of 1:1, LDH particle size 100 nm, and calcination temperature 673 K. The adsorption equilibrium data can be fitted well by the widely accepted adsorption isotherm models.     

Synthesis of poly(butylene terephtahlate) nanocomposites using anionic clays

The synthesis of poly(butylene terephthalate) (PBT) nanocomposites by in situ polymerisation method using an organo-modified layered doubled hydroxide is described. 4-Sulfobenzoic acid potassium salt, sodium dodecyl sulfate and dimethyl 5-sulfo isophthalate sodium salt were used as intercalating compounds to improve clay exfoliation. The thermal and dynamic mechanical properties of the nanocomposites prepared were investigated and compared to those of montmorillonite-type nanocomposites prepared by similar synthetic route. The nanocomposites obtained, independent of the degree of exfoliation, showed better dynamic mechanical properties respect to PBT homopolymer while improvements in thermal stability were achieved when dimethyl 5-sulfo isophthalate was used as intercalating agent, highlighting the importance of the interactions of ionic groups covalently linked to the polymer with the charged clay platelets.     

The interaction of an anionic gemini surfactant with conventional anionic surfactants

The interaction in two mixtures of an anionic gemini surfactant having N ,N -dialkylamide and carboxylate groups in a molecule, (CH2)2[N(COC11H23)CH(CO2H)CH2(CO2H)]2. 2NaOH (GA), and conventional anionic surfactants have been investigated in 0.1 M NaCl at pH 5.0. The two mixtures are GA/sodium dodecylsulfate (SDS) and GA/sodium N -dodecanoylglutamate (AGS) at a molar fraction of GA, alphaGA = 0.25 . Mixtures of both GA/SDS and GA/AGS exhibit synergism in surface tension reduction effectiveness. The GA/SDS mixture also exhibits synergism in surface tension reduction efficiency and mixed micelle formation, whereas the GA/AGS mixture does not. The interaction in mixed adsorption film formation is stronger than that in mixed micelle formation for the two mixtures. The interaction in the formation of the mixed adsorption film and the mixed micelle for the GA/SDS mixture is stronger in both formations than that for the GA/AGS mixture. The stronger interaction for the GA/SDS mixture may be caused by the combination of the smaller minimum area per molecule at the air/water interface (Amin) of the head groups in the GA molecule and the larger Amin in the SDS molecule.     

Synthesis of co-containing aluminosilicates with a microporous layered columnar structure from montmorillonite clays

The conditions of synthesis of cobalt-containing aluminosilicates with a microporous layered columnar structure from montmorillonite clays were correlated with their texture characteristics. The main factors governing the texture properties of the material were shown to be the montmorillonite content in natural clay, the calcination temperature, and the type of hydrolyzing agent and OH^?: Me ⁿ⁺ ratio during the preparation of the modifying solution.     

Kinetics of the alkylation of phenol with methanol over catalysts derived from hydrotalcite-like anionic clays

Vapor phase alkylation of phenol with methanol was carried out over catalysts derived from a series of hydrotalcite (HT)-like compounds of the form M(II)Al-HT; where M(II)=Mg, Mn, Co, Ni, Cu and Zn with M(II)/Al atomic ratios of2–5. The kinetic parameters such as rate constant (k), apparent activation energy (E_a) and Arrhenius frequency factor (A_o) for the disappearance of phenol were evaluated employing a power law equation assuming pseudo-first order kinetics. The kinetic parameters were found to be in good agreement with phenol conversion. The existence of the compensation effect between E_a and ln A_o was tested.