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.     

Reduction in pluming during the spray drying of a nonionic-based heavy duty powder

The plume observed during the spray drying of a nonionic-based heavy duty powder has been attributed to volatilization/recondensation of unethoxylated alcohols and other components in the alcohol ethoxylate. These “volatile components” comprise only 24–40% of the total spray tower emissions, but they are responsible for 85–95% of the observed opacity. Therefore, the relationship between observed opacity of the plume and particulate loading is not valid for the exhaust air from a spray tower producing nonionic-based powdered detergents. Alcohol ethoxylates are not decomposed to any measurable amount in a typical spray-dryer operation. The relative pluming tendency of alcohol ethoxylates depends exclusively on their relative vapor pressure. The vapor pressure of an alcohol ethoxylate is a function of the hydrophobe composition (starting alcohol) and the degree of ethoxylation which determines the level of unethoxylated alcohols. A new generation of alcohol ethoxylates with 60% less unethoxylated alcohol for a given ethoxylation level has been introduced recently. These Novel™ alcohol ethoxylates result in drastically improved pluming characteristics.     

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.     

Effect of hydrophobe structure on performance of alcohol ethoxylates

Alcohol ethoxylates are versatile surfactants because both the hydrophobic and the hydrophilic moieties can be varied readily to change performance. Many studies have focused on the effect of changes in the average length of the hydrophobe and the nature of the hydrophile. Less frequently studied, however, has been the effect on performance of hydrophobe structure, yet this can be varied easily by changing the alcohol feedstock used to make the alcohol ethoxylate. This study compares the performance of alcohol ethoxylates derived from oleochemical alcohol and oxo-alcohols derived from kerosene, butylene, or coal by the Fischer-Tropsch process. Two aspects of hydrophobe structure were found to be important for performance of alcohol ethoxylates: the overall linearity of the parent alcohol and the degree of substitution at the C2 carbon. As the linearity of the parent alcohol increases, the critical micelle concentration (CMC) decreases and the surface tension at the CMC increases. Increasing substitution at the C2 carbon increases the amount of unethoxylated alcohol in the ethoxylate but decreases the inverse cloud point temperature, wetting time, and foam stability in the absence of soil.     

Biodegradation of nonionic surfactants

This paper discusses the biodegradability of alcohol-based nonionics measured by the recommended legislative test procedures and how the results obtained are affected by the chemical structure of the surfactant, and thus provides guidance on the selection of materials. More detailed studies on the biodegradation of alcohol ethoxylates during the activated sludge sewage treatment process are also reported. Examination of a wide range of alcohol ethoxylates in the legislative tests shows that the majority of those nonionics of practical importance will be extensively biodegraded. Although the mathematical model used to design the treatability test is very simple and has frequently come under criticism, the predictions seem to be upheld and the results obtained appear to provide a reliable guide to what is likely to happen in practice. The sludge residence time, which has long been regarded as of particular importance by those involved in the field of sewage treatment, is clearly demonstrated to be a highly significant factor whose influence should be taken into account in any detailed laboratory study of treatability. The study of alcohol ethoxylates indicates that extensive primary biodegradation will occur even in overloaded treatment plants where sludge retention times (SRT) are likely to be short. The effect of temperature on the biodegradation is small and suggests that effective treatment will be achieved in such plants even at the lower temperatures experienced during winter. Ultimate biodegradation of alcohol ethoxylates was shown to be extensive under practical conditions and levels of “polyethylene glycol” intermediates discharged to surface waters will be low. Although alcohol ethoxylates are rapidly and extensively absorbed on activated sludge, this does not play a significant role in the removal process which is essentially one of biodegradation.     

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.     

The prediction of ethylene oxide distributions in mixed alcohol ethoxylates

Supercritical fluid Chromatographic analyses of ethoxylates of 2- ethylhexanol in the pure state and in mixtures were used to determine relative propagation- to- initiation ethoxylation rate constants. Earlier work with normal octanol was verified in that ethylene oxide distributions were found to be unaffected by the presence of other alcohols in the ethoxylation of mixed alcohols. An apparent decrease in the relative ethoxylation rates with increasing number of ethylene oxide monomers in ethoxylates is attributed to truncation of the measured distributions and is eliminated by adding small amounts of higher ethoxylates to the distribution. The Weibull- Tornquist effect of decreasing relative rate constants as the overall average ethylene oxide- to- alcohol ratio increases was again observed. Rate constants of the ethoxylation of 2- ethylhexanol and its ethylene oxide adducts relative to the ethoxylation of normal octanol were determined from the analysis of ethoxylates of their mixtures. A computer model using averaged relative rate constants was developed that effectively predicts the ethylene oxide distributions in ethoxylates of alcohol mixtures. To whom correspondence should be addressed at Exxon Chemical Company, Intermediates Technology Division, P.O. Box 241, Baton Rouge, LA 70821     

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.     

国外除草剂助剂品种开发动向

简要介绍了国外除草剂助剂品种开发趋势和几种新助剂品种的结构类型及其特性。     

The effect of “peaking” the ethylene oxide distribution on the performance of alcohol ethoxylates and ether sulfates

In comparison to conventional ethoxylates, a “peaked” ethoxylate has less unethoxylated alcohol, is more soluble, and has a higher concentration of the more desired homologs. A “peaked” ethoxylate therefore has a lower odor, is easier to formulate into liquids, and can perform better in terms of detergency and wetting performance. Since “peaked” ethoxylates have less unethoxylated alcohol, less alcohol sulfate is formed during sulfation. Decreasing the content of alcohol sulfate increases the capacity to salt-thicken and can potentially improve skin mildness.     

Effect of surfactant structure on stability of enzymes formulated into laundry liquids

The effect of surfactant structure on enzyme stability in heavy duty laundry liquids was investigated. Surfactants studied were alcohol ethoxylates and anionic surfactants having varying hydrophobic and hydrophilic types and chain lengths. Enzymes used were proteases and amylases. The results showed these enzymes were considerably more stable when formulated into laundry liquids containing alcohol ethoxylates and ethoxysulfates than when formulated with alcohol sulfates and surfactants containing sulfonate groups such as linear alkylbenzene sulfonates and alpha olefin sulfonates. Enzyme stabilizer systems were only partially effective in reducing the enzymedeactivating influence of sulfonate-containing surfactants. Presented at the AOCS meeting in Dallas, May, 1984.     

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.     

Viscosity,pour point,and chain length relations for the alcohol ethoxylates

Because pour points of surfactant alcohol ethoxylates are important and tedious to determine experimentally, it is desirable to have methods for calculating pour points from other properties, e.g., viscosities (1). To facilitate calculating pour points, several types of equation were developed that relate (a) chain lengths of the alcohol ethoxylates to pour points, (b) chain lengths to viscosities, and (c) viscosities to pour points.     

Methyl ester ethoxylates

Conventional ethoxylation of fatty methyl esters, or other fatty-fatty esters or diesters, produces poor yields of the desired ethoxylated ester. A proprietary ethoxylation catalyst, currently in use to produce “peaked” or “narrow-range” alcohol ethoxylates, has been found to successfully insert ethylene oxide into the ester linkage of fatty esters. The mechanism for this insertion likely involves an ethoxylation-transesterification step in the ethoxylation process. Physical, performance, and environmental/human safety properties were evaluated. Results, in general, show that methyl ester ethoxylates behave similarly to alcohol ethoxylates with the exception of having a lower foam profile and being less irritating. Presented at the Annual Meeting of the American Oil Chemists’ Society, Indianapolis, Indiana.     

传统醇醚的生产工艺技术提升

从产品合成、生产装置、催化剂类型、产品EO分布和游离醇含量以及下游衍生应用等方面介绍了近些年我国传统醇醚工艺技术的升级与进步。     

Partially saponified triglyceride ethoxylates

Various triglycerides (coconut oil, palm kernel oil, tallow) were ethoxylated with a proprietary catalyst (calcium/aluminum alkoxide complex partially neutralized in an alcohol ethoxylate base) to obtain triglyceride ethoxylates. Triglyceride ethoxylates were then partially saponified with sodium hydroxide to form mixtures of mono-, di-, and triglyceride ethoxylates, fatty acid soap, and glycerol ethoxylate. These mixtures were characterized in terms of physical properties, surface activity, and mildness. Partially saponified triglyceride ethoxylates were found to be unexpectedly mild and capable of imparting mildness to other surfactants. Presented at the Annual Meeting of the American Oil Chemists' Society, Orlando, Florida, May 10, 1999.     

Effect of homolog distribution on the toxicity of alcohol ethoxylates

Previous work established a high correlation between the potential environmental toxicity of oxyethylenated nonionic surfactants and the average degree of ethoxylation. For this reason, it was considered of interest to determine whether a narrow- or broad-range homolog distribution of polydisperse commercial alcohol ethoxylates would influence toxicity. Ethoxylated fatty alcohols, both linear and branched, were synthesized with sodium hydroxide or an unconventional calcium-based catalyst. Toxicity tests were run onDaphnia magna and luminescent marine bacteria. Toxicity of ethoxylated alcohols as a function of type of ethoxylate homolog distribution (narrow or broad) and average degree of polyaddition is analogous for both test species. However, narrow-range ethoxylates show lower toxicity values than conventional ethoxylates. Differences in toxicity values between broad- and narrow-range ethoxylates depend on the degree of ethoxylation.     

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.     

脂肪酸甲酯乙氧基化物的物化性能研究

对不同烷链和不同EO加合数的脂肪酸甲酯乙氧基化物的物化性能进行了测试,并对FMEE在洗衣粉中替代AEO9进行了初步研究。结果表明,与脂肪醇乙氧基化物相比,FMEE泡沫低,水溶速度快,对油脂增溶能力强,用棕榈油甲酯乙氧基化物替代AEO9在洗衣粉中应用可改善去污性能并降低成本。     

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。