窄分布脂肪醇聚氧乙烯醚硫酸钠的性能研究

分别对工业化的常规脂肪醇聚氧乙烯醚(AEO_2)和窄分布AEO_2进行气相色谱分析,并对以2种AEO_2为原料生产的脂肪醇聚氧乙烯醚硫酸钠(AES)的表面活性、泡沫性能、乳化性能、润湿性能以及倾点等进行研究。通过对2种AEO_2的气相色谱分析发现,窄分布AEO_2中游离脂肪醇含量更低,EO加合数为1~4的组分含量更高。将2种AES产品的性能进行对比后发现,窄分布AES在倾点、盐增稠能力、泡沫性能、润湿力等方面较常规AES具有一定的优势。     

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.     

Solvent-free high active matter alcohol ethoxysulfate/alcohol ethoxylate blends: Preparation and effect of surfactant structure on rheological properties

Blends of alcohol ethoxysulfates (AES) and alcohol ethoxylates (AE) at high active matter content (90%) have been prepared. These blends contain no solvents other than water and have sufficiently low viscosities enabling the pumping of them from storage vessels to mix tanks. In addition, they may be diluted into aqueous solutions with less gel formation tendencies than shown by AE or AES alone. Specific AE/AES blend ratios, alkyl and polyoxyethylene chain lengths are important selection parameters for achieving desired rheological properties. This paper was presented at the 79th American Oil Chemists’ Society Annual Meeting, May 1988, Phoenix, Arizona.     

窄分布脂肪醇聚氧乙烯醚的合成研究

在KOH和窄分布专用均相催化剂作用下,分别合成了2种不同平均EO加合度的AEO。根据合成过程中EO的消耗量计算得到理论平均EO加合度,气相色谱法分析了产品组成分布,对常规及窄分布AEO的EO分布、平均EO加合度对分子量分布的影响等进行了研究。结果表明,窄分布AEO气相色谱图中C_(12)(EO)_7的峰面积很小,基本看不到C_(14)(EO)_7的峰;对于常规及窄分布AEO,AEO2组分中游离脂肪醇质量分数低于AEO_(1.85),EO加合度为1～4组分的总质量分数则高于AEO1.85;窄分布AEO组分中游离脂肪醇和EO加合度大于4组分的质量分数明显低于常规AEO,而EO加合度为1～4组分的质量分数明显高于常规AEO,分子量分布呈泊松分布,表现出明显的窄分布特点。     

国内外AE／AES生产现状及市场分析

介绍国内外脂肪醇聚氧乙烯醚(AE)和脂肪醇聚氧乙烯醚硫酸盐(AES)的生产现状及供需情况.2003年全球AE的总产能为391.7万t/a,总产量为155.8万t,总消费量为148.3万t;AES的总产能为377.5万t/a,产量约为300万t,消费量约为90万t.2004年我国AE的产能已超过50万t/a,但产量只有15万t,消费量为30.5万t;AES的总产能为37.95万t/a,产量为14万t,市场需求约10万t.最后补充介绍乙氧基化的技术进展.     

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.     

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.     

Quantitation of alcohol ethoxylate surfactants in environmental samples by electrospray mass spectrometry

This report describes a method for obtaining the concentrations of the total and individual alcohol ethoxylate (AE) species in sewage treatment plant (STP) effluents by using electrospray liquid chromatography/mass spectrometry (LC/MS). This is a more advantageous method for quantitative analysis of AE in environmental matrices as compared with a previous thermospray LC/MS method. This new method is more sensitive, uses less solvents, utilizes a deuterated internal standard blend [C₁₃D₂₇O(CH₂CH₂O) _n H, where n varies from 0 to 21 with an average of n=9], which corresponds more closely to the AE, and it is a more robust instrumental technique. In this report, we document the results for validation of the electrospray LC/MS method by spike recovery of AE from STP effluent and influent samples.     

脂肪醇聚氧乙烯醚硫酸盐生物降解和环境安全性评价

表面活性剂对环境的影响主要表现在生物降解性。简要概述了目前大量使用的表面活性剂脂肪醇聚氧乙烯醚硫酸盐（AES）的厌氧、好氧生物降解以及降解途径。阐述了AES在生物机体中的积累对环境、人体和动物的影响,表明AES在给人类生活和工业发展带来帮助的同时,不会对环境和人体健康造成危害。     

聚乙烯醇/脂肪醇聚氧乙烯醚/水双水相体系:双节点曲线图研究

水溶性聚合物与非离子表面活性剂组成的双水相体系因其可生物降解性和无毒性而受到人们的广泛关注.研究了由聚乙烯醇(BP-05、BP-17和BP-24)、脂肪醇聚氧乙烯醚(AE7)和水组成的双水相体系在25、35和45℃下的液-液平衡数据和双节点曲线图.结果表明:由聚乙烯醇(BP-05、BP-17或BP-24)、AE7和水组...     

Effect of temperature on the biodegradation of linear alkylbenzene sulfonate and alcohol ethoxylate

The effect of temperature on the biodegradation of linear alkylbenzene sulfonate (LAS) and alcohol ethoxylate (AE) was evaluated using method OECD 303 A, Confirmatory test (Husmann units). The experiments were performed using an initial surfactant concentration of 10 mg/L and working temperatures of 25, 15, and 9°C, keeping the biodegradation units inside a thermostatic chamber. In all cases, the removal of both surfactants tested, LAS and AE, was higher than 90%, regardless of the temperature used in the test. We observed that longer acclimation periods were needed by the microorganisms at lower temperatures.     

Refractive index of alcohol nonionics

Refractive index is a rapid and consistent method of analysis for alcohols and nonionics from normal alcohols and ethylene oxide. Correlations of refractive index with hydroxyl number of alcohols and nonionics are excellent and measurement error is considerably lower for refractive index. Refractive index affords a measurement of the amount of ethylene oxide in nonionics and can be used as a replacement for the 1% cloud point analysis. The ethylene oxide adduct distribution has no effect on refractive index. Specific adducts, a narrow range of adducts made by acid catalyzed ethoxylation and a broad range of adducts made by base catalyzed ethoxylation give the same refractive index value for any given ethylene oxide content. Applications for the refractive index method for the laboratory and plant are: alcohol blending control, calculation of ethylene oxide requirements for ethoxylation, nonionic control analysis, calculations of hydroxyl number for sulfations. Also, refractive index can help identify laboratory samples, indicate the 1% cloud point and predict the phase character of nonionics.     

Tuning the polydispersity of alcohol ethoxylates for enhanced oily soil removal

Commercially available alkyl alcohol ethoxylates have a broad distribution of ethylene oxide (EO) units and also a somewhat narrower distribution of alkyl chain length. Generally, the purer the surfactant sample (narrower distribution), the better is its detergency performance, and detergency peaks at the phase inversion temperature (PIT) for a given oil. However, in real detergency processes this may not hold true since soils are typically mixtures of several oily components, and temperature variations are significant. Therefore, if a polydispersity index (PDI) of ethoxylates is defined as the ratio of weight average EO moles to number average EO moles in the sample, then it is conceivable that an optimal PDI might be obtained. We compared the detergency of hexadecane for pentaethylene glycol monododecyl alcohol (C₁₂EO₅) samples in a broad PDI range, using an oil-soluble dye. While detergency at 55°C (PIT of hexadecane with C₁₂EO₅) decreases monotonically with increasing creasing PDI, average detergency over a 20°C temperature range around the PIT tends to show a maximum at PDI of ca. 1.1 (narrow-range ethoxylate). Similarly, for a mixture of undecane/hexadecane/tetracosane (30∶50∶20 w/w/w) for which the average PIT is approximately the same as that of hexadecane detergency at 55°C shows a maximum as a function of PDI at a value of ∼1.37 (broad-range ethoxylate). All detergency results are in general agreement with the reverse trends in oil/water interfacial tension and suggest that, having decided the optimal EO moles for a given application based on PIT, one can further improve the performance of alcohol ethoxylates in real detergency processes by tuning their polydispersity.     

十二烷基苄醇聚氧乙烯醚的合成及性能

以十二烷基苯为原料,经氯甲基化、水解及环氧乙基化等步骤得到平均乙氧基(EO)数为9.5的十二烷基苄醇聚氧乙烯醚(LBAEOn)。分别用FTIR和1HNMR表征了产物LBAEOn的结构特征,并用ESI-MS确定了LBAEOn中的EO分布。以表面张力法测得在25℃时LBAEOn的cmc和γcmc分别为1.83×10-6mol.L-1和39.0 mN.m-1;与脂肪醇聚氧乙烯醚(AEO9)和壬基酚聚氧乙烯醚(NPEO10)相比较,除钙皂分散性能大致相当以外,LBAEOn的表面活性较好、发泡力较低、对正辛醇的增溶能力较强和对帆布的润湿性能较差。     

催化氧化制备醇醚羧酸盐及其复配性能研究

以脂肪醇聚氧乙烯醚(AEO9)、氧气和氢氧化钠为原料,在自制的Pd/C催化剂作用下催化氧化制备醇醚羧酸盐(AE9C)阴离子表面活性剂.考察了反应条件对产品收率的影响,并研究了AE9C与双癸基二甲基氯化铵(DDMAC10)复配体系的润湿、乳化和泡沫性能.结果表明较佳的反应条件为:温度70℃、压力0.08 Mpa、反应时间4 h,产品的收率可达85%.AE9C与DDMAC10复配具有较好的协同效应.     

低加成数脂肪醇聚氧乙烯醚的气相色谱分析

采用HP4890毛细管色谱柱、程序升温、FID检测，较好的分离了各种低加成数脂肪醇聚氧乙烯醚（AEO）样品中的各组分；使用GC－MS进行了样品中组分的定性，并经实验研究彩和峰面积归一化法进行了组分的定量，较准确地计算出了各种样品AEO游离脂肪醇质量分数及聚氧乙烯醚的环氧乙烷（EO）加成数分布。方法简便、快速，有较好的准确度和精确度。     

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.     

High-temperature stability of alcohol ethoxylates

The oxidative stability of alcohol ethoxylates during storage and handling is studied. Realistic conditions are modelled by heating in quiescent air. More rigorous, extensively aerated conditions are modelled by thermogravimetry with mass spectrometric detection and differential scanning calorimetry with vapor-phase sampling. In quiescent air, C_12–15 alcohol with an average of 7 moles ethylene oxide (EO) is discolored at 204°C, with some increase in aldehydes, but there is no change in the EO distribution of the sample. Under extensively aerated conditions, increased oxidation occurs above 150°C, with a loss of one EO unit on average, and increases in CO and CO₂ occur in the vapor phase above the sample. High-temperature oxidation under extensive aeration is not affected by an antioxidant or by raising the pH of the sample from 6.4 to 7.5.     

Dissolution of Soap Scum by Surfactant Part I: Effects of Chelant and Type of Soap Scum

The equilibrium solubilities of two model soap scums [calcium stearate and magnesium stearate: Ca(C₁₈)₂ and Mg(C₁₈)₂] were measured in aqueous solutions containing three different types of surfactants: methyl ester sulfonate (MES) as an anionic; alcohol ethoxylate (EO9) as a nonionic; and dimethyldodecylamine oxide (DDAO) as an amphoteric with and without a chelating agent [disodium ethylenediaminetetraacetate (Na₂EDTA)]. The solubility of calcium soap scum was generally higher than that of magnesium soap scum, the exception being some DDAO systems. The use of the DDAO surfactant with the Na₂EDTA chelating agent at high pH gives the highest solubilities of both studied soap scums. The soap scum solubility is on the order of 2,000 times that in water at high pH. The DDAO is the most effective surfactant under all conditions. The MES is more effective than the EO9 at low pH with the opposite trend observed at high pH. The synergism from added chelant is generally greater at higher pH and is greatest for DDAO followed by EO9.     

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。