直链烷基苯磺酸异丙胺盐的性能及其在餐具洗涤剂中的应用研究

对直链烷基苯磺酸异丙胺盐(HIPN)的表面张力、润湿力、乳化力、发泡能力等基本性能进行研究,并与洗涤剂常用阴离子表面活性剂直链烷基苯磺酸钠(LAS)、脂肪醇聚氧乙烯醚硫酸钠(AES)和α-烯基磺酸钠(AOS)进行了对比,研究了HIPN在手洗餐具洗涤剂配方中的表现。结果表明,在餐具洗涤剂中HIPN具有优异的增稠性能,能全部代替或者部分代替LAS和AES,实现和AOS复配的低成本无二烷配方。     

New household detergent based on AOS

The synthetic detergent industry is one of the fastest growing industries in Japan. Its production, together with soap, is estimated to be almost 2 billion pounds in 1970. In addition to this increased production, quality modification in terms of biodegradability is now being undertaken. Alpha olefin sulfonate (AOS) has been known since the 1930’s, but only within the last two years has it been highlighted for commercial interest as a detergent material due to progress in sulfonation technology as well as commercial availability of alpha olefins. To make use of AOS as an active ingredient for formulation of heavy duty household granules, several properties of AOS itself or of the built detergent were studied in comparison with linear alkylate sulfonate (LAS), alkylbenzene sulfonate (ABS) and alcohol sulfate (AS). AOS was proved to be a potentially economical detergent material having as good performance and better biological properties than LAS or AS and better biodegradability than LAS. It has been marketed since 1967 in Japan as the first AOS-based household heavy duty granular detergent. It has been accepted by the housewives as the most efficient detergent and has become the best selling brand. Presented at the AOCS-AACC Joint Meeting, Washington, D.C., April 1, 1968.     

常规SO3磺化类表面活性剂现状及发展趋势

介绍了几类常规SO₃磺化类表面活性剂的现状。重点阐述了国内烷基苯磺酸盐(LAS)、脂肪醇醚硫酸盐(AES)、烯基磺酸盐(AOS)和脂肪醇硫酸盐(AS)几类常规磺化产品产销量情况以及发展趋势。     

The workhorse surfactants: LAS,alcohol sulfates,and ether sulfates

Relative market volumes are discussed illustrating why LAS, alcohol sulfates, alcohol ether sulfates, and branched chain alkylene benzene sulfonates are called “workhorse” surfactants. Typical heavy duty powder, heavy duty liquid, and light duty liquid formulations from around the world are given for each material. Low mole ether sulfates for heavy duty powders are discussed as to chemical constituency and performance. Comparisions of LAS to paraffin sulfonates and olefin sulfonates are given for light duty liquid formulations. Shampoo performance advantages of alcohol sulfates over olefin sulfates are illustrated.     

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.     

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.     

AOS — An anionic surfactant system: Its manufacture,composition, properties,and potential application

Several sulfonation parameters, believed to be critical to the manufacture of good quality a-olefin sulfonate (AOS), are related to product color and conversion. The interfacial properties for single carbon number AOS and the major components comprising AOS are investigated. Results, based on surface activity, indicate that AOS in the molecular weight range from C₁₄ through C₁₈ should be of value in formulating efficient cleaning agents. The data show that AOS is more effective for lowering Crisco®/solution interfacial energy than the more commonly used surfactants. The alkene-1-sulfonate component of AOS was found to be most effective in lowering interfacial energy with the hydroxyalkane-1-sulfonate component being significantly less effective but still more effective than alcohol ether sulfate or linear alkylbenzene sulfonate of comparable molecular weight. Hand dishwashing efficacy was found greatest for the hydroxyalkane-1-sulfonate component of AOS, but combinations of hydroxyalkane-1-sulfonates and alkene-1-sulfonates were shown to be synergistic for laundering applications. The presence of the -OH group in the hydroxyalkane sulfonate structure was shown to increase solubility and lower surface activity significantly more than the presence of unsaturation in the alkene sulfonate. Long, single branching in the a-olefin sulfonate and random internal olefin sulfonate are shown to reduce drastically the surface activity. The hydroxyalkane and alkene-1-sulfonates were rapidly biodegraded. Disulfonates and long, singly branched sulfonate were more slowly degraded. Both 1,3-sultones and 1,4-sultones were found to biodegrade rapidly.     

Precipitation of anionic surfactants in the presence of sodium oleate and calcium ions

Precipitation of anionic surfactants, linear alkylbenzene sulfonate (LAS) and alpha olefin sulfonate (AOS), by calcium ions was studied in the presence of sodium oleate. Lather stability was determined by the Ross-Miles method, precipitation was followed by measuring the optical density (OD), and equilibrium surface tension (EST) and Fourier transform infrared (FTIR) spectroscopy were used to characterize the nature of the precipitate formed. For the 5 mM LAS-0.7 mM oleate system, lather was unstable, and the OD was high in the 2–5°FH region of calcium hardness, while at higher calcium hardness levels, lather was stable and the turbidity of solutions decreased. On the other hand, in the 5 mM AOS-0.7 mM oleate system, lather was unstable throughout the calcium hardness region studied (0–20°FH). Also, the turbidity build-up was much higher in the AOS system than in the LAS system. Analysis of the precipitates formed in these systems by FTIR spectroscopy indicated that the precipitate from the AOS system had an additional band at 1190 cm⁻¹, corresponding to the sulfonate group. These results, together with the EST data, confirm that the precipitate formed in the LAS system between 2–5°FH calcium is calcium oleate, and that formed in the AOS system is likely to be calcium (AOS) oleate. It is tempting to hypothesize that the similarity of AOS and oleate in chainlength could be responsible for the coprecipitation of AOS and oleate with calcium, whereas LAS, which has a larger headgroup with a benzene ring and two smaller chains (average length is C8) is unlikely to precipitate with the oleate.     

新型表面活性剂、助剂与碱性蛋白酶的相互作用

研究了洗涤剂组分中表面活性剂(MEE、AEC、甜菜碱、AEO9、AOS、LAS)溶液和助剂(高稳定层状二硅酸钠、3型AN助剂、亚微米4A沸石、4A沸石)溶液对碱性蛋白酶(黄海黄杆菌YS-9412-130低温碱性蛋白酶、Properase450E、Savinase4.0T)的影响作用。40min时表面活性剂溶液中酶的存活率在70%以上,助剂中酶的存活率在85%以上,并对以上结果提出可能的作用机理解释。     

α-烯烃磺酸盐在液体洗涤剂中的应用

介绍了采用气相三氧化硫法生产的α-烯烃磺酸钠在液体洗涤剂配方中的应用。通过正交设计说明,影响黏度的最重要因素是氯化钠的质量分数。考察了不同碳数AOS对液体洗涤剂黏度的影响以及AOS与AES复配后液体洗涤剂去污力、调黏度和泡沫性能的区别,综合应用实验结果表明,AOS适合用于液体洗涤剂中。     

Separation and quantitative determination of active ingredients in detergent formulations

During the past few years, the increasing complexity of detergent formulations has required the analytical detergent chemists to devise many new and complicated separation schemes. This paper describes a method which allows the separation and quantitative determination of linear alkylbenzene sulfonate (LAS), ethoxylated alcohol sulfate (AES), alcohol sulfate (AS), free nonionic and amine oxide in detergent formulations. A combination of ion exchange, chemical separations, and gas chromatography is used in the described method. In addition to quantitating the types of “active” material listed, the ethylene oxide content of the ethoxylated alcohol sulfate and the homolog distribution of the alcohol hydrophobe in both the ethoxylated alcohol sulfate and the alcohol sulfate are obtained. This separation scheme is applicable to either liquid or powdered detergent formulations.     

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.     

椰子油脂乙氧基化物在餐具洗涤剂中的应用

通过对椰子油脂乙氧基化物（COE）与阴离子表面活性剂直链烷基苯磺酸钠（LAS）及脂肪醇聚氧乙烯醚硫酸钠（AES）等的复配实验,研究了复配体系的黏度、去污力和泡沫性能。实验结果表明,COE与AES、LAS有优异的协同效能,COE适合做餐具洗涤剂中的主表面活性剂。     

无机盐对表面活性剂去污力影响的研究

用去污实验机测定了直链烷基苯磺酸钠(LAS)、脂肪醇聚氧乙烯醚硫酸钠、α-烯基磺酸钠、脂肪酸甲酯磺酸钠等阴离子表面活性剂的去污力,考察了无机盐对去污力的影响。结果表明,三聚磷酸钠使这几种表面活性剂的去污值增加了29.11%~121.26%,磷酸三钠使LAS的去污值增加了128.25%;三聚磷酸钠、δ-层状结晶二硅酸钠、4A沸石等软水剂增强去污力的效果最好,碳酸钠和硅酸钠等碱性助剂次之;硫酸钠、氯化钠、磷酸二氢钠和十水四硼酸二钠不适合用作洗涤剂的助洗剂。     

Performance of alpha olefin sulfonates derived from ziegler olefins in light duty liquid detergents

Single carbon number olefins derived from Ziegler technology were sulfonated in a continuous fallingfilm SO₃ reactor. The resulting alpha olefin sulfonate (AOS) was evaluated in a dishwashing test at several water hardnesses. Statistical analysis of the data led to the selection of compositions suitable for hand dishwash applications. AOS, prepared by sulfonating a blend of C₁₄ and C₁₆ olefins, was evaluated for hand dishwashing efficiency in a ternary mixture consisting of AOS, an alcohol ether sulfate and monoethanolamide. Regression equations calculated from the data permit the prediction of performance levels for all practical combinations of the three ingredients. The effect of unreacted olefin on AOS dishwash performance was also determined. With a binary blend of AOS and monoethanolamide it was shown that up to 5% free oil (based on AOS active) could be tolerated without significant deleterious effect.     

Aquatic environmental monitoring of detergent surfactants

Since 1998, Japan Soap and Detergent Association has been continuously evaluating the concentrations of four surfactants used in household detergents and fabric conditioners in river surface water: linear alkylbenzene sulfonate (LAS), polyoxyethylene alkyl ether (AE), alkyldimethylamine oxide (AO) and dialkyl dimethylammonium chloride (DADMAC) in Japanese urban rivers, in order to assess the risks of surfactants on aquatic organisms. Surfactant concentrations in the river water in June and September were found to be lower than those in March and December, the season where water temperature is lower, suggesting that the rates of biodegradation in environmental water differ depending on the water temperature. All the measured surfactant concentrations were below the reported predicted no-effect concentration (PNEC) and have been decreasing year by year; suggesting that surfactant risk on aquatic organisms in Japanese rivers is low under current conditions.     

Environmental life-cycle inventory of detergent-grade surfactant sourcing and production

Life-cycle inventories were compiled to characterize natural resource requirements and environmental emissions associated with the sourcing and production of selected, detergent-grade surfactants and surfactant feedstocks. Petrochemical surfactant types examined were linear alkylbenzene sulfonate, alcohol sulfate (AS), alcohol ethoxylate (AE) and alcohol ethoxylate sulfate (AES). Oleochemical surfactants derived from palm oil, palm kernel oil and inedible tallow were AS, AE, AES and (for palm oil and tallow) methyl ester sulfonate. It was determined that natural resource requirements were primarily related to the source of feedstock and secondarily to surfactant type. Likewise, the composition and mass of atmospheric, aqueous and solid emissions were principally determined by feedstock source. Energy requirements varied as a function of both feedstock and surfactant type. The inventories do not support fundamental shifts in surfactant usage or feedstock sourcing on the basis of environmental concerns, as no single surfactant or feedstock was identified as superior across all resource and emissions criteria examined. The data provide baselines for evaluating opportunities for resource optimization, pollution prevention and waste minimization within each production technology surveyed.     

Alpha olefin sulfonates from a commercial SO3-Air reactor

Alpha olefin sulfonate (AOS) can be made by SO₃-air sulfonation of straight chain alpha olefins followed by saponification of the neutralized product. The sulfonation step forms unsaturated sulfonic acids, sultones and sultone sulfonic acids. Hydrolysis of the various sultones yields a mixture of unsaturated and hydroxy sulfonates. Sulfonation of commercial mixtures of straight chain alpha olefins in a large-scale SO₃ falling film unit has given AOS of 1.5–3.0% oil based on active content and tristimulus color of about 40% saturation (2% solution) which is readily bleachable with 1–3% NaOCl to about 10–15% saturation. Performance of AOS made from C₁₅−C₁₈ alpha olefin is comparable to that of the high-foaming C₁₁−C₁₄ LAS in both detergency and dishwashing foam. It is superior to similar products made from internal straight chain olefins. The product shows a low order of toxicity and biodegrad-ability slightly better than that of LAS. A C₁₅−C₁₆ AOS blend is especially attractive in liquid detergent formulations. Presented at the AOCS Meeting, Los Angeles, April 1966.     

Performance and Efficiency of Anionic Dishwashing Liquids with Amphoteric and Nonionic Surfactants

Performance and efficiency of anionic [sodium lauryl ether sulfate (SLES) and sodium α-olefin sulfonate (AOS)] and amphoteric [cocamidopropyl betaine (CAB)] as well as nonionic [cocodiethanol amide (DEA), various ethoxylated alcohols (C₁₂–C₁₅–7EO, C₁₀–7EO and C₉–C₁₁–7EO) and lauramine oxide (AO)] surfactants in various dishwashing liquid mixed micelle systems have been studied at different temperatures (17.0, 23.0 and 42.0 °C). The investigated parameters were critical micelle concentration (CMC), surface tension (γ), cleaning performance and, foaming, biodegradability and irritability of anionic (SLES/AOS) and anionic/amphoteric/nonionic (SLES/AOS/CAB/AO) as well as anionic/nonionic (SLES/AOS/DEA/AO, SLES/AOS/C₁₂-C₁₅-7EO/AO, SLES/AOS/C₁₀–7EO/AO and SLES/AOS/C₉–C₁₁–7EO/AO) dishwashing surfactant mixtures. In comparison to the starting binary SLES/AOS surfactant mixture, addition of various nonionic surfactants promoted CMC and γ lowering, enhanced cleaning performance and foaming, but did not significantly affect biodegradability and irritability of dishwashing formulations. The anionic/nonionic formulation SLES/AOS/C₉–C₁₁–7EO/AO shows both the lowest CMC and γ as well as the best cleaning performance, compared to the other examined dishwashing formulations. However, the results in this study reveal that synergistic behavior of anionic/nonionic SLES/AOS/ethoxylated alcohols/AO formulations significantly improves dishwashing performance and efficiency at both low and regular dishwashing temperatures (17.0 and 42.0 °C) and lead to better application properties.     

Studies on replacement of phosphate builders in laundry detergents using radiolabeled soils

The fabric detergency performance of systems containing different types of surfactants and several builders of reduced phosphate content has been compared using a radiolabeled sebum-clay soil. Use of this soil allows quantitative measurement of both sebum and clay removal from soiled swatches, generally cotton and permanent press Dacron-cotton. One study compared alkylbenzene sulfonate (LAS), alcohol sulfate (AS), alcohol ethoxysulfate (AEOS) and alcohol ethoxylate (AEO) as surfactants in formulations containing from 0–45% sodium tripolyphosphate (STPP). Especially under hard water conditions, the AEO and AEOS considerably out-perform the LAS and AS at equal use concentrations and are less sensitive to phosphate reduction. Tests with cotton swatches soiled with five different carbon black-oil mixtures generally rank the surfactants in the same order, although individual responses of the cloths vary considerably. A further study compares the effect of replacing STPP with sodium nitrilotriacetate (NTA) in formulations containing varying amounts of AEO or LAS. Detergency improves significantly with increasing surfactant concentration, particularly with AEO, and declines as builder strength is reduced. AEO exceeds LAS considerably in performance under the test conditions even at relatively high concentrations of LAS. Another study compares the performance of AEO and LAS at equal concentrations in formulations containing a variety of builders. AEO is generally superior to LAS in removing both sebum and clay soils and is less sensitive to builders and water hardness. The builders generally rank in this order: STPP > NTA = citrate > carbonate > sulfate. Presented at the AOCS Short Course, “Update on Detergents and Raw Materials,” Lake Placid, N.Y., June 1971.