Ein Beitrag zur Dünnschichtchromatographie von Aniontensiden

A Contribution to the Thin-Layer Chromatography of Anionic Surfactants Anionic surfactants and some nonionic surfactants are chromatographed on silica gel plates with tetrahydrofuran + acetone (1 + 9 v/v) as solvent, sprayed with a solution of pinacryptol yellow and examinated under ultraviolet light at 366 nm. The surfactants appear as coloured fluorescent spots on a pale blue background. The relative air humidity has a major influence, i. e. the water content of the silica gel layer, which can be fixed by preconditioning of the plate by the vapour of the solvent. A complete separation of alkane-/olefinesulfonate, cumene/xylene-/toluenesulfonate, alkylbenzenesulfonate, α-sulfofatty acid methylester, fatty alcohol sulfate, fatty alcohol ether sulfate, fatty acid diethanolamide, fatty acid monoethanolamide and soap can be attained. Thin-layer chromatograms of a range of mixtures fatty alcohol sulfate/fatty alcohol ether sulfate and several fatty alcohol ether sulfates with increasing content of ethylen oxide are discussed.     

Microaerophilic biodegradation of tallow-based anionic detergents in river water

Nine anionic detergents from five general classes (alcohol sulfates, ether alcohol sulfates, sulfated alkanolamides, α-sulfo esters and alkylbenzenesul-fonates) were rapidly screened for biodegradability under aerobic and microaerophilic conditions in river water at 25 and 35 C. In decreasing order, the ease of biodegradation under microaerophilic conditions at 35 C was as follows: alcohol sulfates, sulfated alkanolamides, α-sulfo fatty acid esters and ether alcohol sulfates. Linear alkylbenzenesulfonate did not degrade. Presented at the AOCS Meeting, New Orleans, April 1970.     

Neuere Entwicklungen auf dem Gebiet fettchemischer Tenside

New Developments in the Field of Oleochemical Surfactants A large area of application for fats and oils in the technical field is the manufacture of surfactants. The oleochemical industry has long been making intensive efforts to gain a still greater share of the world's surfactant production for oleochemical surfactants. There are some promising conditions to reach this goal. New developments in the field of anionic and nonionic surfactants are summarized in an overview. There will be discussed fatty alcohol sulfates (especially tallow alcohol sulfate), α-sulfo-fatty acid methylesters, acyl cyanamides, non-terminal fatty acid methylester sulfonates (by sulfoxidation of saturated fatty acid methylesters and by SO₃-sulfonation of unsaturated fatty acid esters), oleic acid sulfonates, alkyl- and alkenyl ether sulfonates, hydroxy alkyl ether sulfates, alkyl glucosides, fatty alcohol polyethyleneglycol alkyl ethers and -hydroxyalkyl ethers and narrow range fatty alcohol ethoxylates. The development work on new oleochemical surfactants which has been described permits the conclusion that in future oleochemical surfactants will further increase their share of world surfactant production.     

Ozonation Impact on Degradation and Toxicity of Non-Ionic Surfactants

Aqueous solutions of five selected non-ionic surfactants: Triton (i-octylphenolethoxylates), Tergitol (2,6,8-trimethyl-4-nonanoloxethylates), Symperonic (n-nonylphenol-oxethylates) and Brij (fatty alcohol ethoxylates) were investigated in this study. Using the bioluminescent bacteria Vibrio fischeri the toxicity of the surfactants solutions were determined. An attempt was made to relate rather low biodegradability of nonionic surfactant solutions measured by the BOD₅/COD ratio (ranging from 1 to 17%) to their toxicity. The ozonation process was carried out in a 1.5 dm³ stirred cell reactor equipped with two ozone detectors. The following parameters were analyzed: pH, COD, BOD₅, DOC, TOC, polarography as well as UV spectrum. The positive effect of ozonation, represented by decay of UV absorption, was visible in almost complete destruction of the surfactants, with exception of Triton X-705 (only 65% degradation after absorption of 2000 mgO₃/dm³). The most striking results were obtained in toxicity tests for ozonated solutions of the non-ionic surfactants – an increase of the bacterial growth inhibition (1.5 to 4 times increase in toxicity due to ozonation). The obtained results were discussed taking into account the literature and our own experimental data on mechanisms of ozonation and biodegradation of non-ionic surfactants of the Triton-type and similar chemical structures.     

Biodegradability and aquatic toxicity of glycoside surfactants and a nonionic alcohol ethoxylate

The environmental properties of three glycoside surfactants and one alcohol ethoxylate were examined by standardized laboratory methods. All of the surfactants biodegraded extensively in aerobic screening tests and may be assumed to approach 100% removal in aerobic wastewater treatment plants, except in cases of high loadings or otherwise exceptional conditions. Anaerobic biodegradability tests showed that an ethyl glycoside monoester (EGE) and a linear alkyl polyglycoside (APG) were both mineralized (>70%) under methanogenic conditions. In contrast, a branched APG resisted anaerobic degradation, while the alcohol ethoxylate was partially mineralized by anaerobic bacteria. The EGE surfactant was most rapidly mineralized in aerobic and anaerobic biodegradability tests. None of the surfactants inhibited respiration in activated sludge at the highest concentration tested (200 mg/L). Tests with aquatic organisms showed increasing toxicity in the following order: branched APG<EGE<linear APG<alcohol ethoxylate. Negligible aquatic toxicity was observed for the branched APG, while the alcohol ethoxylate was highly toxic to examined organisms. This evaluation demonstrates that considerable variation in biodegradability and toxicity responses can be seen within structurally related glucose-based surfactants.     

Darstellung und Eigenschaften von Fettsäurepolyglykolestersulfaten

Production and Properties of Fatty Acid Polyglycol Ester Sulfates Fatty alcohol oxethylates, produced by reaction of fatty alcohols from hydrogenated fatty acid methyl esters with ethylene oxide, are the basic material for an important class of anionic tensides, the fatty alcohol ether sulfates. The fatty acid polyglycol ester sulfates are a very interesting alternative to the fatty alcohol ether sulfates. The former are available by saving hydrogenation, in principle directly by fatty acid oxethylation or interesterification of fatty acids with polyglycols, followed by sulfatation. We report about the production of fatty acid ester sulfates by sulfatation of the fatty acid polyglycol monoesters by sulfurtrioxide or chlorosulfonic acid. By means of the results of physicochemical measurements and process trials it is discussed how far fatty acid polyglycol monoester sulfates are suited as alternative tenside raw material fatty alcohol ether sulfates.     

Challenges to a mature industry: Marketing and economics of oleochemicals in Western Europe

Basic oleochemicals are produced by splitting and further reactions of oils and fats: fatty acids, glycerine, fatty acid methyl esters, fatty alcohols and amines. The last two are included in the list of oleochemical raw materials, primarily because of their importance in the preparations of further derivatives. The wide range of derivatives of oleochemical raw materials such as fatty alcohol ethoxylates, fatty alcohol sulfates, fatty alcohol ether sulfates, quaternary ammonium compounds and soaps are summarized. Oleochemicals such as fatty alcohols and glycerine from oils and fats have equivalents on the basis of petrochemicals. Using the customary terminology, petrochemical products are referred to as “synthetics.” The are included in the present discussion because in the application of oleochemical raw materials the origin of the material is often less important than the structure. Oleochemistry can be regarded as a mature branch of chemistry, with many applications for its products, but with few completely new fields. The challenge and the opportunities for oleochemistry today lie in the changing economic and ecological conditions. Availability and price development of oils and fats are discussed with particular reference to European conditions, for these are the prerequisites if oleochemicals are to be competitive and are to improve their chances in the marketplace. The importance and development of the oleochemical raw material fatty acids, fatty acid methyl esters, glycerine, fatty alcohols and amines are considered on the basis of historical data. In considering future developments of oleochemicals, the capacity, demand and the possible influence of petrochemistry or crude oil is discussed. The highly developed oleochemical raw materials industry is a flexible supplier of medium-to long-chain fatty alkyl groups. These facts, together with the well organized supply lines for raw materials and the considerable potential of these renewable raw materials, could provide the necessary conditions for the oleochemical raw materials industry to fulfil its future tasks on a larger scale. This could arise, for example, due to the partial substitution of petrochemical surfactants, if this should become necessary as a result of developments in the price and availability of crude oil, or on grounds of ecological factors.     

The effect of tallow-based detergents on anaerobic digestion

Eight anionic detergents from three general classes (alcohol sulfates,a-sulfo fatty acid esters and alkylbenzenesulfonates were tested for biodegradability under anaerobic conditions of sludge digestion. The alcohol sulfates were found to be readily and completely degraded. Thea-sulfo fatty acid esters did not degrade but had no adverse effect on bacteriological digestion while the alkylbenzenesulfonates used for control purposes did not degrade and disrupted the normal digestion process. Preliminary lysimeter studies showed that sodium isopropyla-sulfostearate is completely degraded, linear alkylbenzenesulfonate 83%, and ABS 35%. Presented at the AOCS meeting, Chicago, 1964. E. Utiliz. Res. Devel. Div., ARS, USDA.     

A comparison of surfactants derived from alcohols based on petrochemical and oleochemical sources

Samples of lauryl-range alcohols derived from palm kernel oil, coconut oil and ethylene (Ziegler) were derivatized into alcohol sulfates and alcohol ether sulfates (2 moles of ethylene oxide adduct). Physical properties and performance characteristics for earch surfactant were evaluated both individually and in light-duty liquid (LDL) dish-washing formulations. The slight differences observed in the physical and performance properties of the surfactants and their formulations were assignable to slight differences the individual alcohol, alcohol sulfate and alcohol ether sulfate samples employed in this study. The magnitude and type of variation found in the samples resulted from normal production variation and not from any properties inherent to the nature of the alcohol source. We therefore conclude that alcohol sulfates, alcohol ether sulfates and LDLs formulated from them exhibit identical physical property and performance characteristics, regardless of whether the original alcohol was manufactured from petrochemical or eleochemical sources.     

Analysis of surfactant mixtures. I

Summary Some data on the use of 93% phosphoric acid as a reagent for recovering the hydrophobic portion of surfactants are presented, and their application to the analysis of surfactant mixtures is discussed. Aromatic sulfonates, straight-chain alkyl sulfates, fatty acid amides, and fatty acid esters decomposed to give good yields of the starting hydrophobic materials. Dioctylsulfosuccinate gave a mixture of octyl alcohols and olefins while the ethylene oxide condensates of lauryl alcohol, tridecyl alcohol, and tertiary dodecyl mercaptan gave olefins derived from the starting hydrophobic materials. Diisobutylene phenol-ethylene oxide condensate decomposed to olefins, conjugated olefins, and alcohols formed by rupture of the aromatic ring. The products are characteristic of the hydrophobic oils, and in most cases products from mixtures of surfactants can be separated by known analytical methods.Alpha-sulfo fatty acids or alkane sulfonates do not give recoverable oils by this treatment.     

表面活性剂生物降解性的研究进展

简述了表面活性剂对生态环境的影响及其对生物体存在的毒害性作用;概括了常用的表面活性剂模拟降解的方法及其检测手段;总结了表面活性剂生物降解的一般规律及新型绿色表面活性剂的生物降解性;介绍了表面活性剂降解性能的影响因素,并对今后表面活性剂生物降解性研究的发展方向进行了展望。     

Adsorptivity and rinsability of built detergents using radiotracers. I

Linear, primary alcohol sulfates and linear alkylbenzene sulfonates tagged with radioactive sulfur or, in one case, tritium, were employed to determine adsorptivity and rinsability characteristics. In the rinsability studies it was found that when using scoured cotton as substrate the linear, primary alcohol sulfates leave a slightly lower residue than the sulfonates. Both surfactants almost reach an equilibrium after the first washdry cycle. The surfactants are present on the surface in a reversibly adsorbed state as shown by exchange experiments with unlabelled surfactants. In the adsorption experiments, run under the same conditions as the rinsability experiments, Langmuir-type isotherms are obtained whose equilibrium values are comparable to the rinsability values. The effect of free detergent alcohol concentration on adsorptivity and rinsability in linear, primary alcohol sulfate built detergent formulations was also studied.     

Study of Antioxidative Properties of Some Mono Amino‐Acid‐Type and Dipeptide‐Type Surfactants

Surfactants of tryptophan, tyrosine, and histidine were successfully synthesized. They were then modified to obtain dipeptide‐type surfactants with better solubility in both polar and nonpolar solvents, giving more emphasis to the development of water‐soluble amino‐acid‐type surfactants. All developed materials were designed to have functionality as antioxidants (AOX). The investigation of free radical scavenging capacity at pre‐micellar concentrations revealed greater Trolox equivalent (TE, relative scavenging capacity to Trolox) results for Trp‐type surfactants followed by Tyr‐type and His‐type. As expected, the synthesized surfactants exhibited comparable AOX properties to their parent amino acids. The AOX behavior of these surfactants was also checked in micellar concentrations, and the trend was found to be analogous: Trp‐type > Tyr‐type > His‐type surfactants. However, all of them were acting as better AOX in the micellar state than in the monomeric state. Investigating the synergistic effect found no interaction between the “amino acid–surfactant” pairs or the “surfactant–surfactant” pairs with varying ratios. They showed total AOX activity with respect to that of each material. This work opens up the door to the application of some new oil and water‐soluble amino‐acid‐type surfactants having auspicious AOX activity.     

Zur optimierung der Polymerfraktionierung auf der Grundlage von Lösungsgleichgewichten in Lösungsmittel-Fällungsmittel-Systemen

The phase separation behavior of dilute polydisperse polymer solutions primarily depends on the partial concentration of each polymer component. So the equilibrium data obtained by turbidimetric titration with “calibration” fractions and their mixtures can be used for the construction of a solubility diagram (Claesson-diagram) which generally allows to describe fractionation processes. It can be shown that the characteristic features of precipitation fractionations can well be derived from the solubility diagram. This diagram then offers the possibility for a complete discussion of parameter variation (concentration, step of γ-variation, process-scheme, temperature, solvent/nonsolvent-system) on the efficiency of a fractionation step. On one hand these results correspond – as for the concentration variation – to well known experimentell experiences. On the other hand it is possible for the first time to give definite predictions for the influence of temperature and the solvent/nonsolvent system. The temperature selection can be shown to be inconsiderable for the separation effect. The usual characterization of solvents and nonsolvents as “good” or “poor” is absolutely insufficient, if not misleading, for there is no connection between these properties and the shape of the solubility diagram. Based on the analysis of the single parameters the optimum conditions for the preparation of narrow preparation of narrow precipitation fractions can be derived.     

Gas chromatographic analysis of ester-type surfactants by using mixed anhydride reagent

Polyoxyethylene alkyl ether sulfates, polyoxyethylene alkyl ether phosphates, and polyoxyethylene fatty acid ester-type surfactants have been analyzed by gas chromatography after chemical decomposition by using the mixed anhydride of acetic and p-toluene-sulfonic acids. In this way, the hydrophobic groups of the polyoxyethylene alkyl ether sulfates and polyoxyethylene alkyl ether phosphates can be identified in the form of alkyl acetates, and the alkyl compositions can be determined easily. On the other hand, the hydrophobic groups of the polyoxyethylene fatty acid ester-type surfactants, such as polyoxyethylene fatty acid ester, polyoxyethylene glycerol fatty acid ester, and polyoxyethylene sorbitan fatty acid ester, have been identified after conversion into their corresponding fatty acids. At the same time, the base compounds of the hydrophilic groups have been converted into ethylene glycol diacetate, glycerol triacetate, and isosorbide diacetate, respectively, so these surfactants may be distinguished easily.     

Nichtionogene Tenside für Spezialwaschmittel

Nonionic Surfactants for Special Washing Agents The use of fatty alcoholethoxylates and alkylphenolethoxylates as surfactants for washing agents has considerably increased during the past years. These surfactants show, especially on synthetic fabrics, a superior washing action compared to anion-active surfactants. Owing to superior biodegradability, the ethoxylated primary and secondary alcohols are used in washing and cleansing agents in preference to poorly biodegradable ethoxylated alkylphenols which, in the future, are likely to lose their significance as surfactants for washing agents. At present an extensive use of nonionic surfactants in amounts comparable to anionic surfactants is limited by the relatively high price of the former and the difficulties involved in their processing.     

磺化产品中未磺化物的离子交换色谱测定法

采用DowexPraktCl-和DowexPraktH+阴阳离子交换混合柱 ,甲醇为流动相 ,运用示差折光仪将未磺化物检出并记录。其相对平均误差和精密度分别为 4.0 %和 0 .6 %。该法适用于测定脂肪醇硫酸盐 ,脂肪醇醚硫酸盐 ,烷基苯磺酸等中的未磺化物。     

磺酸盐类表面活性剂的合成和应用现状

本文综述了磺酸盐类表面活性剂的合成路线及其研究现状,并对脂肪醇聚氧乙烯醚磺酸盐表面活性剂、芳基或脂肪醇醚磺酸盐表面活性剂的合成进行了重点介绍。我国应大力开发原料易得、活性高的脂肪醇醚磺酸盐、脂肪酸酯磺酸盐表面活性剂,注重具有新颖结构、独特性能的AOT型和Gemini型表面活性剂的研究以适应更广泛的需求。     

Synthesis and Surface Active Properties of Novel Carbohydrate-based Cationic Surfactants

The synthesis of new cationic carbohydrate surfactants is presented in this paper. The obtained surfactants have structures that are typical for saponins, which contain fatty amide hydrophobic chains and hydrophilic heads with cationic carbohydrate units. Their surface active properties and biodegradability have been studied. For two types, the biodegradability was above 85% and comparable to standard carbohydrate surfactants.     

Development and application of kinetic models for the primary biodegradation of non-ionic surfactants

The growing concern for the environment is promoting the use of surfactant products from renewable sources such as fatty alcohol ethoxylates. The high production and use of these products implies the need to develop models that enable predictions of their behaviour in biodegradation processes. The biodegradation tests were carried out according to the OECD 301 E test for ready biodegradability. In this work, kinetic models of general application to surfactant biodegradation are developed, both for substrates that do not support growth and for those that do, considering a residual substrate concentration as not being biodegraded. The models were applied to three commercial non-ionic surfactants, fatty alcohol ethoxylates with different carbon-chain lengths and degrees of ethoxylation, also analysing the initial surfactant concentration.