新型表面活性剂在洗衣液中的应用

洗衣液市场的快速增长促进了其技术的不断进步与产品创新。从洗衣液技术发展趋势的角度讨论了脂肪酸甲酯磺酸盐(MES)、仲烷基磺酸盐(SAS)、异构醇聚氧乙烯醚、脂肪醇聚氧乙烯-聚氧丙烯醚以及脂肪酸甲酯乙氧基化物等新型表面活性剂在洗衣液中的应用和发展前景。     

Foam enhancement by short-chain hydrophobe alcohol ethoxylates in light-duty liquids

This study examined linear alcohol ethoxylates as foam-enhancing agents in light-duty liquids. The ethoxylates were formulated as supplementary surfactants to an anionic main surfactant system. The relationship between ethoxylate structure and performance was elucidated, comparisons were made between ethoxylates and other recognized foam-enhancing agents, and a representative light-duty liquid formula was optimized. Performance evaluation focused on manual plate washing capacity but also included agitation foam volume, surface activity, cloud and clear temperatures, viscosity and grease cutting. Shortchain alcohol ethoxylates with a high degree of ethoxylation (such as C₈ with 70% or 7 moles of ethylene oxide) gave optimum performance that was comparable to or better than acknowledged foam-enhancing agents. The substitution of an alcohol ethoxylate for a fatty acid ethanolamide in the test formulation resulted in substantially lower formulation viscosity.     

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.     

U.S. detergent/surfactant trends— 1980s1

The U.S. surfactant market is large, mature, and likely to grow at a rate of 2-3% over the next 10 years. The household, personal care and industrial markets will maintain roughly the same market shares of the total that they have held historically. Within the household market, there should be a continued trend toward the use of alcohol-based surfactants at the expense of linear alkylbenzene sulfonates (LAS). Several factors point to greater usage of nonionics in the future: popularity of heavy-duty liquids and detergents containing enzymes and fabric softeners, a trend to lower laundry wash temperatures and decreasing dependence on phosphate builders. In personal care end uses, alpha olefin sulfonates are expected to show growth due to cost performance advantages in liquid soaps and shampoos. The industrial surfactant market will remain highly segmented and will grow at ca. 3% annually, mainly as a result of overall industrial expansion. Ample capacity and anticipated feedstock availability at acceptable prices will allow producers of synthetic surfactants to satisfy demand through the rest of the decade. Research will lead to formulations aimed at cooler laundry washing conditions and increased enzyme usage. Enhanced oil recovery may involve new surfactants, but large-scale consumption will not begin before the end of the decade. 1 Presented March 24, 1983, to the European Committee of Organic Surfactants and Their Intermediates (CESIO), Bruges, Belgium.     

Use of certain alcohol ethoxylates to maintain protease stability in the presence of anionic surfactants

Anionic surfactants, including linear alkylbenzene sulfonate (LAS), are known to decrease the stability of detergent proteases, possibly by hastening autoproteolytic processes. Thus, protease shelf life in enzyme-containing, heavy-duty liquid laundry detergents (HDL) is typically maintained by adding stabilizers, by limiting the level of interfering anionics, or by utilizing more compatible anionics, such as alcohol ethoxysulfates (AES). This study examines the stability of Savinase^® detergent protease in HDL formulations based on LAS and containing different alcohol ethoxylates (AE) for protection against protease inactivation. Dose response curves demonstrated that all commonly used anionic surfactants except AES promote loss of protease activity. In HDL formulations with equal percentage compositions of LAS and AE, the structure of the selected AE was found to have a profound influence on protease stability. Inclusion of AE with chain length ≥C₁₄ and ethoxylate levels >70% resulted in greater protease stability. HDL containing LAS and these protective AE could be formulated to achieve protease stability matching those of simulated commercial products. Unlike polyhydric stabilizers, the AE by themselves confer no additional stability to the protease. It is more likely that the stabilizing effect of the “protective” AE is due to decreased availability of LAS to the protease.     

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。     

Optimization of nonionic/anionic surfactant blends for enhanced oily soil removal

Previously reported results for alcohol ethoxylate surfactants have shown that optimum removal of both nonpolar and sebum- like liquid soils from polyester/cotton fabric occurs at the phase inversion temperature (PIT) of the surfactant- water- soil system. A similar correlation between phase inversion and optimum detergency has been identified for detergent systems containing mixtures of nonionic and anionic surfactants such as alcohol ethoxylates and alcohol ethoxysulfates. Experimental techniques other than direct detergency studies are described which allow determination of the optimum nonionic/ anionic surfactant ratio for removal of a particular soil at a specified temperature. In addition, implications of these results for development of temperature- insensitive detergent formulations containing alcohol ethoxylates are discussed.     

Ethylene oxide oligomer distribution in nonionic surfactants via high performance liquid chromatography (HPLC)

A high performance liquid chromatography (HPLC) method using adsorption columns combined with linear gradient elution has been developed for the determination of ethylene oxide (EO) distribution in nonionic surfactants. The quantitative ethoxylate adduct distribution in single-carbon-number and mixed-carbon-number primary alcohol-based samples can be obtained. The HPLC method is also applicable for determining the molar EO distributions in diverse ethylene oxide adduct compounds such as alkylphenol ethoxylates, branched alcohol ethoxylates and secondary alcohol ethoxylates. Nonionic surfactant samples containing adducts up to 25 mol have been successfully separated and the individual adducts quantitated.     

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.     

Synergism and Performance Optimization in Liquid Detergents Containing Binary Mixtures of Anionic–Nonionic, and Anionic–Cationic Surfactants

In this paper evaluation of surface active and application properties in liquid detergent formulations containing binary mixtures of anionic–nonionic, and anionic–cationic surfactants is discussed. Surfactants used include: linear alkylbenzene sulfonate (LAS), alcohol ether sulfate (AES-2EO), alcohol ethoxylate (AE-7EO), lauryl dimethyl amine oxide, and alkyl hydroxyethyl dimethyl ammonium chloride (AHDAC). Surface active parameters relating to the effectiveness and efficiency of surface tension reduction were determined from the surface tension data. Non-ideal solution theory was used to determine the degree of interactions between the two surfactants, and the conditions under which a mixture of two surfactants show synergism in surface active properties. Our data indicated that synergism in mixed surfactants increases with the degree of charge difference between the surfactants. In both mixed micelle and mixed monolayer formation, the degree of interactions between the two surfactants in the mixture increased in the following order: LAS/AE < AES-2EO/amine oxide < AES-2EO/AHDAC. This synergistic behavior as presented in this paper leads to unique application properties and improved performance in terms of foam volume, and soil removal which has applications in formulation of dishwashing liquids, and laundry detergents.     

Degradation of Recalcitrant Surfactants in Wastewater by Ozonation and Advanced Oxidation Processes: A Review

Surfactants are used in varieties of industrial cleansing processes as well as in consumer products. Spent surfactants normally enter domestic or industrial wastewater and are treated biologically. However, some of them are resistant to biodegradation and are released into the environment. Thus, the toxicity and environmental persistence of these surfactants are emerging concerns. Based on extensive review of the literature, ozonation and advanced oxidation using various combinations of ozone, hydrogen peroxide, ultraviolet light irradiation, and iron salts were found effective in degrading recalcitrant surfactants, including linear alkylbenzene sulfonates, alkylphenol ethoxylates, and quaternary ammonium surfactants. Biodegradability of these surfactants was improved after the treatment to some extent in the aqueous solution as well as in real wastewaters.     

一种高效浓缩洗衣液的研制

初步研究了脂肪醇聚氧乙烯醚硫酸钠(AES)、醇醚羧酸盐(AEC_9)、改性油脂、烷基糖苷(APG)及异构醇聚氧乙烯醚等5种表面活性剂在浓缩洗衣液中的应用,通过对去污力、泡沫性能、水溶分散性和酶活稳定性等的测试,将此几种表面活性剂与其他助剂复配,得到一种低泡、高效浓缩洗衣液。测试结果表明,自制浓缩洗衣液稳定,去污力强、可达到4倍浓缩的效果,水溶分散性好,无凝胶出现,酶活稳定性达87.1%。     

Sulfates of ethoxylated tridecyl alcohol in dishwashing formulations

Summary The foam stability of several light-duty liquid dishwashing formulations containing sulfated ethoxylates of tridecyl alcohol, lauryl alcohol, and nonylphenol have been compared. The effects of water hardness, sulfating agent, and ethylene oxide/hydrophobe mole ratio have been examined. In very soft water formulations containing alkanolamide and tridecyl alcohol derivatives were shown to be especially effective. At higher water-hardnesses, combinations containing sulfated ethoxylates of tridecyl alcohol and nonylphenol performed best. Optimum ethylene oxide content for the sulfated tridecyl alcohol ethoxylates has been shown to be 4 to 5 moles/mole of alcohol regardless of water hardness or detergent concentration. The alcohol ethoxylates were shown to be more tolerant of stronger sulfating agents with respect to product quality than the alkylphenol ethoxylates. Presented at the fall meeting, American Oil Chemists’ Society, Los Angeles. Calif., Sept. 28–30, 1959.     

Compatibility of nonionic surfactants with membrane materials and their cleaning performance

Membranes applied in industrial processes, such as for the desalination of seawater as well as for dairy and beverage industry are subjected to fouling resulting in a decline of their performance. In order to regain the flux of the membranes, cleaning procedures are conducted, whereby inorganic scale is often removed with acids and organic matter with surfactants under alkaline conditions. Currently, either ionic surfactants or alkylphenol ethoxylates are utilised to clean membranes of organic matter. Other nonionic surfactants (i.e. fatty alcohol ethoxylates) are not applied, due to the assumption that they irreversibly adhere to the membrane surface and thereby clog the pores. At BASF we have studied the adsorption of a wide range of nonionic surfactants to membrane materials. It was shown, that the affinity of nonionic surfactants critically depends on their structure. Linear alkyl ethoxylates irreversibly adsorb to the membrane surfaces, whereas branched alkyl ethoxylates do not. In a second step, we tested the cleaning performance of nonionic surfactants. Similar to the results for adsorption, a structure-performance relationship was discovered where several branched alkyl ethoxylates showed excellent cleaning results. In a third step, combinations of nonionic surfactants, chelating agents and enzymes were tested in terms of cleaning efficiency. All tested combinations showed excellent cleaning performance on bacterial fouling layers.     

Effects of the ethylene oxide distribution on nonionic surfactant properties

Detergent-range primary alcohols are readily converted into nonionic surfactants by reaction with ethylene oxide. Optimum performance properties for these surfactants generally are attained by varying the number of moles of ethylene oxide reacted with each mole of alcohol or by altering the structure of the primary alcohol. However, variations in the ethoxylate-adduct distribution also affect surfactant properties in such a way that products with relatively narrow distributions possess features which are highly desirable in many household and industrial applications. For a given cloud point narrow-range ethoxylates have lower molecular weights and therefore lower pour points than broad-range surfactants. Because narrow-range ethoxylates contain less unreacted alcohol and other water-insoluble species, they are capable of forming aqueous solutions with much lower cloud points than their broad-range counterparts. Aqueous solutions of narrow-range products have lower viscosities, exhibit lower gel temperatures and remain fluid over a wider concentration range than solutions of broad-range surfactans. While the foams obtained with narrow-range surfactants in the Ross-Miles test are higher initially, they are less stable than those produced by conventional nonionic surfactants. Draves wetting data show that narrow-range products wet cotton substrates more efficiently than normal-distribution materials. Narrow-range ethoxylates exhibit higher aqueous surface tension and higher polyester adhesion tension values than their broad-range counterparts. In addition, narrow-range surfactants reduce the interfacial tension against paraffin oil more efficiently and more effectively than broad-range products. These results, along with laboratory detergency data, suggest that the use of narrow-range ethoxylates may lead to cleaning systems with improved performance and/or physical properties.     

Ozonation of Anionic and Non-ionic Surfactants in Aqueous Solutions: Impact on Aquatic Toxicity

The objective of this study was to investigate the influence of ozonation of anionic and non-ionic surfactants on their aquatic toxicity. Toxicity values of various commercially important anionic and non-ionic surfactants have been determined using the luminescent bacterium Vibrio fischeri. Surface tension measurements were made to study the interfacial activity. The behavior depends on the chemical structure. Some intermediate ozonation products were found to be more toxic than the base surfactant and others were found to be less. Surfactants with aromatic rings such as linear alkyl benzene sulfonates, or surfactants with glycosidic groups such as alkylpolyglucosides, exhibit a lower toxicity after ozonation. On the other hand, ether groups present in the fatty-alcohol ethoxylates and ether carboxylic derivative surfactants, and carboxylic acid derivates present in the ether carboxylic derivative surfactants lead to increasing toxicity after ozonation. Surfactants with ether groups probably formed short-chain polyethoxylated compounds and carboxylic acids, which are possibly responsible for the surface-tension decrease that promotes the toxicity increase.     

Detergent raw material trends in western europe

Household detergent sales during 1975 in Western Europe totaled more than $4 billion and are expected to continue to grow at approximately 3 to 4 percent annual increments during next decade. There is a trend toward more uniform formulations, but factors affecting future market growth include washing practices and conditions that vary from nation to nation. Demand for surfactants is dominated by LAS, accounting for 80 percent of total synthetic actives used in laundry detergent, with increasing use of linear alcohol ethoxylates. Environmental considera-tions, cost, and energy savings are factors in a trend toward less use of phosphate, compensated by greater use of LAS or ethoxylate or both to maintain clean-ing performance. New investment in detergent raw materials is more likely for detergent alcohols and alpha olefin derivatives, and not in LAB. The Soap and Detergent Association 1977 Annual Meeting and Industry Convention, Boca Raton, FL.     

Amine oxide/alcohol ethoxylate blends: Zero-phosphate,high-performance,hard-surface cleaners

Several instances of synergistic interaction have been identified between amine oxides and alcohol ethoxylates in various surfactant formulations. The purpose of this study was to examine whether these benefits could be observed within the framework of generic hard-surface cleaning formulations. Comparative evaluations were also carried out to determine the performance characteristics of low- and zero-phosphate systems in which alkyldimethylamine oxides and linear alcohol ethoxylates are used. Best cleaning was observed with 1:1 mixtures of the subject surfactants, but substantial improvements over alcohol ethoxylate alone also were noted with formulations that contained lower ratios of amine oxide. These systems displayed good cleaning performance when tested on vinyl floor tiles soiled with an oily/particulate soil. Presented at the 85th AOCS Annual Meeting & Expo, May 10, 1994, Atlanta, Georgia.     

Phase inversion of polyacrylamide‐based inverse‐emulsions: Influence of inverting‐surfactant type and concentration

The phase inversion of polymeric water‐in‐oil emulsions has been systematically studied by employing nonylphenol and alcohol ethoxylates with various chemistries as well as physical chemical characteristics. A combination of thermodynamics, phase diagrams, and rheometry were used to investigate the behavior of the inverting surfactants as well as the inverted, acrylamide‐based, cationic emulsions. Polymeric inverse‐emulsions containing the inverting surfactant showed no evidence of low‐shear thinning, though they did thin as hydrodynamic forces increased (0.01 to 100 s^?1) prior to reaching a chemistry‐ and concentration‐independent plateau, as is typical for emulsions. The viscosity of emulsions containing inverting surfactants reached a minimum at 1.2% of the “emulsion breaker”. The efficiency of inversion was optimized at 2 wt % of nonylphenols, expressed as a percentage of the total emulsion mass, and increased with the degree of ethoxylation. Interestingly, the viscosity of the polymer inverted in water was maximized at an inverting‐surfactant level corresponding to the CMC of the pure surfactant in water. The alcohol ethoxylates required a higher concentration for inversion (3 wt %), though they provided a higher ultimate inverse viscosity of the polymeric emulsion in water. Therefore, while the inversion process was less efficient with alcohol ethoxylates, the ultimate dilution solution properties of the polyelectrolytes liberated were improved relative to the nonylphenols. Overall, the process of adding a water‐in‐oil emulsion, containing an emulsion breaker, to an excess of water involves a catastrophic inversion mechanism. To be effective under such circumstances, an inverting surfactant should have a partition coefficient between the aqueous an organic phases greatly exceeding unity as well as a hydrophilic–lipophilic balance (HLB) above 12. Effectiveness increases linearly with the partition coefficient. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3567–3584, 2007     

Fettalkoholethoxylate mit eingeengter Homologenverteilung - Entwicklung neuer Alkoxylierungskatalysatoren

Fatty Alcohol Ethoxylates with Narrow Range Homologue-Distribution - Development of New Catalysts for Alkoxylation Fatty alcohol ethoxylates are most important within the group of nonionic surfactants. They are manufactured by acid or basic catalyzed reaction of fatty alcohols with ethylenoxide. The product composition, particularly the homologue distribution, depends on the nature of catalyst. Basic catalysts, which are widely used in technical processes, yield products with a broad range homologue distribution. Three new catalysts for alkoxylation are presented, which yield fatty alcohol ethoxylates with narrow-range homologue distribution. These narrow-range ethoxylates exhibit new interesting properties.