Sulfo Acid Research Articles

Sulfo ethyl cellulose/Nafion composite for high‐temperature proton exchange membrane

AbstractThis study investigated the potential enhancement of proton conductivity in Nafion membranes through the incorporation of sulfo ethyl cellulose (SEC) at varying weight ratios (5 and 10 wt.%). Results indicated that increasing the weight ratio of SEC led to improvements in water absorption, activation energy, and proton conductivity within the composite membranes. Specifically, the composite membrane exhibited a significant increase in proton conductivity, reaching up to 170 mS cm−1, in contrast to the pristine Nafion membrane which recorded 40.08 mS cm−1, particularly at temperatures exceeding 120°C. At the sub‐molecular level, Fourier transfer inferred spectroscopy (FTIR) analysis of Nafion/SEC membranes unveiled cross‐linking interactions occurring between the sulfo acid groups of Nafion chains and the hydroxyls within the SEC matrix. Moreover, X‐ray diffraction (XRD) findings of the composite membranes were instrumental in identifying crystalline phases, orientation, and structural features. The results indicated variations in atomic radius and alterations in lattice parameters at the nanoscale, induced by heightened surface forces resulting from the inclusion of SEC in the Nafion matrix. This phenomenon leads to a reduction in crystallite size, accompanied by an increase in peak broadening and surface area within the composite membranes. Such changes signify a clear interaction between SEC and Nafion, as confirmed by both scanning electron microscopy and thermal gravimetry analyses. Taken together, these findings strongly indicate that the cross‐linked composite membranes utilizing SEC‐Nafion hold significant promise as proton exchange membranes.

Substituted (сycloalkylcarbonylthioureido)aryl-(benzyl-)carboxylic(sulfonic) acids: synthesis, antimicrobial and growth-regulating activity

Acylisothiocyanates are a promising class of organic compounds that are present in the plant world and can be used in the synthesis of disubstituted thioureas and various heterocycles. These derivatives are characterized by growth-regulating, antibacterial, fungicidal, cytotoxicity, and other activities. Modification of acylisothiocyanates by fragments of substituted aminoarylcarboxylic (sulfo) acids is promising, as some of them (anthranilic, p-aminobenzoic acids) are precursors for the auxins and other natural compounds synthesis. Their combined activity is also an important aspect. Namely the simultaneous manifestation of both fungicidal and restrictive activity. Based on this, the synthesis of new substituted (cycloalkylcarbonylthioureido)aryl-(benzyl-)carboxylic (sulfonic) acids is relevant as promising regulators of plant growth with antibacterial activity.
 The aim of this work is to search for effective compounds with growth-regulating and antimicrobial activity among substituted (cycloalkylcarbonylthioureido)aryl-(benzyl-)carboxylic (sulfonic) acids.
 Materials and methods. Methods of organic synthesis, physical and physical-chemical methods of analysis of organic compounds (IR, NMR 1H-spectroscopy, chromato-mass spectrometry, elemental analysis). Antimicrobial activity studies were performed on standard strains of bacteria and fungi (S. aureus ATCC 25923, E. coli ATCC 25922, P. aeruginosa ATCC 27853 and C. albicans ATCC 885-653). The effect of synthesized compounds on growth rates was evaluated on wheat (variety Grom).
 Results. An “in situ” method for the synthesis of substituted (cycloalkylcarbonylthioureido)aryl-(benzyl-)carboxylic (sulfonic) acids was proposed. It was shown that the latter could be easily synthesized by the sequential interaction of cyclopropanecarbonyl chloride, ammonium isothiocyanate, and aminoaryl-(benzyl-)carboxylic, sulfanilic acids or sulfamide. Data of 1H NMR spectra showed the peculiarities of the structure of the synthesized compounds, namely the presence of singlet signals of protons of urea, thioamide and carboxyl groups, multiple signals of methine and methylene protons of cyclopropane fragment. It was found that the synthesized compounds showed moderate antimicrobial activity against S. aureus and P. aeruginosa (MIC 50 μg/ml, MBC 100 μg/ml) and significant antifungal activity against C. albicans (MIC 25–50 μg/ml, MFC 25–50 μg/ml). A number of compounds were identified as effective regulators of wheat growth and exceed the natural analogue – heteroauxin (3-indolylacetic acid) in terms of auxin-like activity.
 Conclusions. A one-step method for the synthesis of substituted (cyclopropanecarbonylthioureido)aryl-(benzyl-)carboxylic (sulfonic) acids was developed. The physical-chemical properties of the synthesized compounds were studied using a set of methods (IR, 1H NMR spectroscopy, chromato-mass spectrometry, elemental analysis) and the features of the structure were discussed. The synthesized compounds reveal moderate antimicrobial, high antifungal activity, and growth-promoting activity.

Вплив модифікатора на селективність реакції хлорування етилену до 1,2-дихлоретану в промислових умовах

Досліджено вплив стабілізатора (модифікатора) каталітичного комплексу – натрієвої солі перфторованої сульфокислоти – на каталітичну систему [FeCl3– NaCl] у промисловому процесі прямого рідиннофазного хлорування етилену до 1,2-дихлоретану на діючій установці хлорування етилену виробництва хлористого вінілу ТОВ "Карпатнафтохім", м. Калуш, Івано-Франківської області. Встановлено, що введення до складу каталізатора натрієвої солі перфторованої сульфокислоти в кількості 1-4 % від маси хлориду натрію не призводить до помітних змін у процесі розчинення, а зростання кількості стабілізатора каталітичного комплексу від 4 до 10 % скорочує тривалість розчинення з 2 до 1 год, веде до зростання концентрації хлориду натрію до проектних значень у каталітичному розчині та до збільшення селективності утворення цільового продукту до 99,3 %, при цьому кількість побічних продуктів – в основному 1,1,2-трихлоретану – зменшується в 1,8 раза. Показано, що експериментальні результати, отримані в лабораторії, корелюють із результатами, отриманими у промислових умовах. Після припинення подачі модифікатора технологічні показники процесу погіршуються, концентрація йонів натрію зменшується з 50 до 6-8 ррм, а селективність утворення 1,2-дихлоретану – до 98,5 %. Використання натрієвої солі перфторовної сульфо-кислоти у промисловому процесі можливе без будь-яких змін у технологічній схемі діючого виробництва 1,2-дихлоретану. Експериментально визначена оптимальна концентрація натрієвої солі перфторованої сульфокислоти, яка становить 8-10 % від маси хлориду натрію. Результати випробовувань модифікатора каталітичної системи процесу прямого рідинно-фазного хлорування етилену показали ефективність його роботи у промислових умовах і дали змогу отримати фактичний економічний ефект.

Synthesis and spectral luminescent properties of 4,4´,4´´,4´´´-tetra(tert-butyl)-5,5´,5´´,5´´´-tetrakis(phenylsulfanyl)phthalocyanines and their sulfo acids

Magnesium and zinc complexes of 4,4´,4´´,4´´´-tetra(tert-butyl)-5,5´,5´´,5´´´-tetra kis-(phenylsulfanyl)phthalocyanine were synthesized. The corresponding sulfo acids were prepared by sulfochlorination and further hydrolysis. Spectral luminescent properties of the synthesized phthalocyanine derivatives were studied. Introduction of sulfo groups resulted in a bathochromic shift of Q-band in the spectra recorded in DMF and pyridine regardless of the metal nature as well as in a hypsochromic shift in sulfuric acid.

Computer simulation of the hydration of sulfocation exchanger containing imino acid

The mechanism of formation of hydrate structures in the system sulfo exchanger-imino acid was suggested. The mutual position of fixed ion, imino acid, and water molecules was determined in cation exchanger. The conclusion was made on the presence of water molecule between the functional group of sorbent and counterion of imino acid. It was demonstrated that the mechanism of sorption of proline and hydroxyproline is performed by the break of bond between water molecules and protonation of carboxylic group of imino acid.

Synthesis of sorption-active polyfunctional derivatives of polycaproamide and polyglycidyl methacrylate graft copolymers

The kinetic and thermodynamic parameters of polymer-analog conversion of the graft copolymer of polycaproamide and polyglycidyl methacrylate with sulfamic acid (initial rate, duration, and effective activation energy) were determined. It was shown that the values of the initial rates correlate well with the concentration of the sulfamic acid reaction solution. The formation of a new derivative of the PCA—PGMA graft copolymer containing functionally active amino and sulfo acid groups was confirmed by the data from chemical and analytical analysis and IR spectroscopy. A method was developed for obtaining a sorption-active fibrous polyampholyte containing functionally active amino and sulfo acid groups with SECHCl = SECNaOH = 0.895 mmole/g.

Poly(arylene oxides) containing sulfo acid groups: Synthesis, properties, and application

Key advances in the synthesis, characterization, and application of poly(arylene oxides) containing sulfo acid groups in main chains of macromolecules and side substituents are surveyed. The main advantages and drawbacks of various approaches to the synthesis of these polymers, such as postsulfonation of poly(arylene oxides), polycondensation with the use of sulfonated monomers, and transformations of polymers containing reactive groups, are analyzed.

The kinetics of cation exchange in network calyxarene-containing polymers: the nanoreactor effect

The kinetics of cation exchange from aqueous solutions of electrolytes in network calyxarene-containing polymers with sulfo acid and phenol ionic groups was studied. It was shown that the interaction of the polymers with aqueous solutions of LiCl, NaCl, AgNO3, LiOH, NaOH, and (CH3)4NOH was controlled by ion diffusion in the polymer phase. The nanoreactor effect, that is, a significant increase in the ion exchange rate in sulfonated calyxarene-containing polymers, was observed. The spherical layer model was used to obtain an analytic dependence of conversion on the interdiffusion coefficient and ion exchange duration in bifunctional cationites.

The properties of water in swollen cross-linked polystyrene sulfo acids

The properties of water in polystyrene sulfo acid gels with various cross-linking degrees were studied by optical volumetry and dynamic desorption porosimetry. The isotherms of water desorption obtained by dynamic desorption porosimetry coincided with isopiestic isotherms, which allowed this method to be recommended for the determination of the amount of water in polymer gels. Joint optical volumetry and dynamic desorption porosimetry studies showed that the interphase boundary in the cross-liked hydrophilic polymer-water system did not coincide with the visible gel boundary, because gels were two-phase systems, which contained water of two types, “free” and “bound.” The influence of the degree of polymer cross-linking on the amounts and properties of water of the two types was studied. It was shown that constants of water distribution in the polymer could be calculated from the dynamic desorption porosimetry data.

Oxidative polymerization of aniline on the surface of insoluble solid poly(sulfo acids) as a method for the preparation of efficient biosorbents

Polyaniline coatings of the cation-exchange resin Dowex and a synthetic composite material based on silica gel surface-modified by a sulfated styrene-divinylbenzene copolymer were prepared by precipitative polymerization of aniline on the surface of the supports. The optimal conditions for the preparation of the polyaniline-containing material providing the formation of a thin polymeric coating on the support surface were determined. Aniline is predominantly consumed to the formation of a uniform polymeric coating about 3 nm thick with an increase in the concentration of sulfo groups on the support surface. The efficiency of using the polyaniline-containing sorbents for the preparative isolation of DNA from plant tissue lysates was demonstrated.

Matrix polymerization of aniline in the presence of polyamides containing sulfo acid groups

The matrix synthesis of polyaniline in the presence of water-soluble aromatic polyamides containing sulfo acid groups has been studied. It has been shown that the nature of polyacid and the concentration of reagents affect the shape and dynamics of a change in absorption spectra. The S-shaped profile of kinetic curves for spectra variation and the experiments on the seed polymerization provide evidence for the autocatalytic character of polymerization. It has been concluded that, depending on the nature of polyacid, polymer complexes form in which polyaniline macromolecules are situated along main chains of polyacid macromolecules (the two-stream structure) or appear as side chains of polyacid macromolecules (the comb-shape structure). In the latter case, polyaniline macromolecules serve as ionic bridges crosslinking polyacid macromolecules, as is confirmed by the viscometric study of solutions in the course of polymerization.

Complexation of poly(dimethyl diallyl ammonium chloride) with 1‐anilino‐8‐naphthalene sulfo acid in solution

AbstractComplex formation between poly(dimethyl diallyl ammonium chloride) and 1‐anilino‐8‐naphthalene sulfo acid has been investigated in different solvents by measurements of fluorescence, UV‐spectroscopy and potentiometric titration. The interaction between the polymer and the low molecular weight compound depends on the molar ratio of the components, ionic strength of the solution and the solvent.

Plastic aluminosilicate concrete compositions

In the preparation of aluminosilicate plastic batches it was established that chamotte-clay batches are satisfactorily plasticized by a clay-phosphate slip containing 5–10% added sulfo acids or their salts.

Chemistry of 2-aryl-substituted 3-hydroxypyridines communication 3. Sulfonation of 2-aryl-3-hydroxypyridines

1. A study was made of the sulfonation of the 2-phenyl-, 2-(4′-alkylphenyl)-2-(4′-methoxyphenyl)-, 2-(3′,4′-dimethoxyphenyl)-, and 2-(4′-hydroxyphenyl)-3-hydroxypyridines. 2. In the case of 2-phenyl-3-hydroxypyridine the substitution was directed to the p-position of the phenyl ring, whereas in the p-aryl-substituted 3-hydroxypyridines the sulfo group substitutes in the mposition of the phenyl ring. 3. A comparison of the conditions for the sulfonation of benzene and 2-phenyl-3-hydroxypyridine discloses that the presence of a heterocyclic ring as a substituent in the phenyl ring lowers the reactivity of the latter in sulfonation reactions. 4. The insertion of alkyl groups (with the exception of tert-butyl), methoxy, and hydroxy groups in the phenyl ring facilitates sulfonation. 5. 2-(3′-Hydroxy-4′-alkylphenyl)-3-hydroxypyridines were synthesized by the alkaline fusion of sulfo acids of the 2-(4′-alkylphenyl)-3-hydroxypyridine series.

Extraction of nitrogen bases from fuels by aromatic sulfo acids

1. We have shown that quantitative extraction of nitrogen bases from fuel fractions can be obtained with aqueous solutions of aromatic sulfo acids or the dry acids. The best results are obtained with o-sulfobenzoic and sulfosalicylic acids. 2. Concentrates of nitrogen bases, containing 1–4% nitrogen, have been obtained from gas-oil and kerosene distillates by means of sulfo acids.

Tallow based detergent formulations: Mixtures of alcohol sulfates, salts ofa‐sulfo acids and esters, and soap

AbstractSaturated (I, ROSO3Na) and unsaturated (II, R'OSO3Na) tallow alcohol sulfates, the disodium salt ofa‐sulfonated saturated tallow fatty acids (III, RCH(SO3Na)CO2Na), the sodium salt of the methyl ester ofa‐sulfonated saturated tallow fatty acids (IV, RCH(SO3Na) CO2CH3), and commercial tallow soap flakes (V) were compared, singly and in combinations, as built and unbuilt solutions in soft and hard water, with respect to foam height and detergency, using four different types of standard soiled cotton.Built solutions of combinations of the two most soluble detergents, II and IV, at concentration 0.05% total active ingredient plus 0.20% builder in hard water of 300 ppm, remained perfectly clear on standing for several months. Built solutions containing I or II had the best foaming properties. The presence of soap decreased foam height.Cloths A and B showed the detergency of built solutions to be in the order I=II>IV>III>V, and all combinations containing I or II were superior detergents. With cloth C, detergents ranked in the order I=II=IV>III>V, and many combinations containing I or II with IV were synergistic. Cloth D did not distinguish sharply between detergents in built solutions in hard water.In general, detergent systems containing tallow alcohol sulfates witha‐sulfo esters had the most desirable solubility, wetting, foaming, and detergent properties.

Removal of vanadium from petroleum and petroleum products with aqueous solutions of sulfo acids

1. It was shown that it is possible to remove vanadium from petroleums and petroleum products with aqueous solutions of p-toluenesulfonic acid, o-sulfobenzoic acid, and sulfanilic acid. 2. Vanadium is extracted best from those petroleums and petroleum products in which the vanadium-porphyrin complex is not present.