The Determination of the Effective HLB of Nonionic Surfactants by a Phenol Titration I: Relation to Cloud Point

The qualitative similarities in two various methods of the HLB (Hydrophile-Lipophile Balance) determination based on the cloud point and so called phenol index measurements are demonstrated. The effects of polyoxyethylene chain length, surfactant concentration and the presence of additives on the cloud point and phenol index values have been compared. The results are interpreted as the change of the effective HLB of polyoxyethylene nonionic surfactants.     

The effect of glycols on the hydrophile-lipophile balance and the micelle formation of nonionic surfactants

The empirical hydrophile-liophile balance (HLB) value of nonionic surfactants is an important parameter used to predict performance as, e.g., emulsifiers, solubilizers and wetting agents. However, the HLB value is based on an original molecular structure and does not take into account all the factors affecting the performance of nonionics, such as presence of additives, type of solvent, temperature, degree of hydration, structural modifications of the surfactant molecule and decomposition of surfactants. On a performance basis, where these factors come into play, a given nonionic surfactant may exhibit a multiplicity of apparent HLB values. Accordingly, we recently introduced the term “effective HLB value” which is a performance value which incorporates into the HLB the parameters listed above. The HLB value thus becomes a variable depending on the physical and chemical conditions at the time of the measurement. In this work, we investigated the effect of adding glycols and diglycols on the HLB using 3 different methods: cloud point, phenol index and critical micelle concentration (cmc). We found that this type of additive increases the cloud point, phenol index, cmc and the “effective HLB” of a polyoxyethylated nonionic surfactant. The effectiveness of the glycols in causing these increases was in the following order; dipropylene glycol > 1,4-butanediol > 1,2-propanediol > diethylene glycol > ethylene glycol. The solvent effect of glycols and diglycols on the hydrophobic and hydrophilic portions of the surfactant molecule are discussed. On the hydrocarbon part of the surfactant molecule, the solvents cause a weakening of the hydrophobic bond and an increase in the cmc. On the polyoxyethylene part of the molecule, the solvent may cause either an increase or a decrease in the cmc. The effect on the hydro-philic portion is related to hydrogen bonding exhibited by the additives. The results obtained again suggest that the effective HLB value, which is a measure of the HLB under operative conditions, may be of greater practical significance than calculated HLB.     

不同因素对CTAB/TX-100微乳液相图的影响

用ε-β"鱼状"相图法研究了阳离子表面活性剂十六烷基三甲基溴化铵(CTAB)与非离子表面活性剂辛基苯酚聚氧乙烯(10)醚(TX-100)以不同摩尔比复配形成的CTAB/TX-100/醇/油/NaCl水溶液微乳液体系的相行为和增溶性能.结果表明,随着醇浓度的增加,体系由水包油型(O/W)(winsor Ⅰ or (2-)...     

聚醚型非离子表面活性剂的浊点及其影响因素

总结了非离子表面活性剂浓度、外加聚合物、离子表面活性剂、无机电解质、助表面活性剂等对聚醚型非离子表面活性剂水溶液浊点的影响规律 ,发现聚合物由于其结构和分子量不同对浊点的影响也不同 ,一般可使浊点降低 ;加入离子表面活性剂可以和非离子表面活性剂形成混合胶束 ,从而使浊点升高 ;无机盐由于存在盐析和盐溶两种不同效应而对浊点的影响比较复杂 ;醇和有机酸等助表面活性剂根据其碳链的长短不同而影响浊点。这些规律对非离子表面活性剂的研究和应用有一定的指导意义。     

柴油微乳状液及微小乳状液的制备

以HLB值选择乳化剂 ,制备出了柴油O/W微小乳状液及W /O微乳状液 ,系统地考察了复合乳化剂的HLB值、种类、组成、乳化温度、极性添加剂对两种乳状液的形成及粒径的影响     

Hard surface detergency

In a study of hard surface detergency using glyceryl trioleate, oleic acid, and octanoic acid soils with three types of anionic and three types of nonionic syndets, only potassium laurate showed maximum detergency at the CMC (critical micelle concentration), with the potassium laurateoctanoic acid system being an exception. In general glyceryl trioleate and oleic soil removal (180°F.) at the CMC was low, not over 40%; octanoic acid detergency at the CMC was substantially higher, 65 to 83%. Considerable differences in removal of the various soils by the same surfactants were found. A generalization was observed in the detergency of glyceryl trioleate soil—soil removal increased sharply on passing the CMC with increasing concentration until approximately 90% detergency was reached, at which point soil removal began to level off and approach 100% with a much smaller slope. Visual observations of the cleaning processes suggested a partial answer for the differences in soil removal. Removal or glyceryl trioleate soil by both anionic and nonionic syndets appeared to be due chiefly to a displacement action caused by preferential wetting of the basis metal. Removal of octanoic acid by the nonionic surfactants in a diffusing cloud of small particles seemed to be due to solubilization followed by emulsification and precipitation of the acid soil. Several relationships were discovered in two series of analogs (polyethenoxyethers of nonyl phenol and tridecyl alcohol). It was found that the ratio of the HLB (hydrophile-lipophile balance) values of two analogs was approximately equal to the fifth root of the ratio of their CMC values. The correlation held for analogs varying by as much as 15 moles ethylene oxide. A linear relationship was also found between HLB value and the reciprocal of the ethylene oxide mole ratio for the polyethenoxyethers of nonyl phenol.     

Cloud Point and Emulsion Inversion Point

The effects of some hydrophilic additives on the cloud point and, emulsion inversion point have been studied. Hydrophilic additives cause an increase in the effective HLB of the surfactants as was indicated by raise of the cloud point and decrease of the emulsion inversion point value, depending on the nature of additive, its concentration and polyoxyethylene chain length. In conclusion it may be stated and emphasized that it is necessary to take into account the HLB value correction in order to select an emulsifier blend for a given system.     

Deinking of water-based ink printing from plastic film using nonionic surfactants

When plastic film packaging is processed for reuse, residual ink colors the polymer and makes the polymer less stiff, weaker, and denser than the original material. These problems can be avoided if the printing is removed from the plastic film surface. In this study, a commercial polyethylene film with water-based ink printing was deinked (the ink was removed) using nonionic surfactants under a variety of conditions, and the effect of some parameters related to the deinking process were quantified and optimized. Nonylphenol polyethoxylate, ethoxylated alcohol at a pH of 10, and ethoxylated amine at either acidic, neutral, or basic pH level were identified to be effective at deinking. The hydrophiliclipophilic balance (HLB) value and the cloud point are useful parameters for characterizing the effectiveness of nonionic surfactants. For optimal deinking, the HLB of the nonionic surfactants should be as small as possible or the cloud point as low as possible without the deinking temperature substantially exceeding the cloud point. Information related to scaleup of the process was also developed. Soaking plastic film in surfactant solution prior to mechanical agitation significantly decreased the needed agitation time to achieve a given level of deinking. Deinking decreases as the plastic/solution ratio (consistency) increases, and cutting plastic film into smaller pieces improves the deinking at moderate consistency. Increasing agitation speed also enhances the deinking. Experiments performed with pilot-sized paper deinking apparatuses demonstrated that deinking of plastic film using surfactants is technically feasible. Presented at the 88th AOCS Annual Meeting & Expo, May 11–14, 1997, Seattle, Washington.     

含水乙醇汽油体系相稳定剂的研究

通过向乙醇汽油中加入相稳定剂的方法,获得稳定的含水乙醇汽油体系,从而降低其成本,促进乙醇汽油在我国的推广应用。对4种非离子表面活性剂:月桂醇聚氧乙烯醚(AEO-3)、壬基酚聚氧乙烯醚(NP-4)、辛基酚聚氧乙烯醚(OP-4,OP-6)的相稳定效果进行研究。结果表明:对E15,E20和E25乙醇汽油,相稳定剂用量(体积分数)大于3%时,AEO-3的相稳定效果最优;对E5,E10乙醇汽油,随各表面活性剂的HLB值逐渐增大,相稳定效果依次增强。温度一定,体系的最大增溶水量与表面活性剂用量、乙醇配比均成正比。     

Application of NMR for the determination of HLB values of nonionic surfactants

Hydrophilic lipophilic balance (HLB) values for various commercial nonionic surfactants have been determined by means of high resolution NMR. The results are in good agreement with given HLB values. The method is rapid, nondestructive and requires only small samples.     

稠油乳化降黏开采用表面活性剂的筛选

介绍了稠油乳化降黏及筛选适合特定油品的理想稠油乳化降黏剂（目标活性剂）的基本原则和方法。综述了稠油乳化降黏用表面活性剂的类型及其常用的非离子型表面活性剂的主要类型。依据目标活性剂的两大必要性能特征参数（HLB值和PT），概述了用HLB值法及PIT法筛选目标活性剂的方法。结合现场实践提出了筛选目标活性剂的具体实验方法和步骤。     

The Characteristic Curvature of Ionic Surfactants

Characterizing the hydrophilic-lipophilic nature of a surfactant molecule has been a challenge for colloid scientists and technologists. The hydrophilic-lipophilic balance (HLB), the packing factor, the phase inversion temperature (PIT) and the natural curvature of the surfactant are all terms that seek to address this issue. In this article we build on the hydrophilic–lipophilic difference concept (HLD) (Salager et al. Langmuir, 16, 5534–5539, 2000) to develop a methodology to determine a characteristic curvature (Cc) for ionic surfactants based on the phase behavior of mixed ionic surfactant microemulsions. In essence, the method consists of evaluating the shift in optimal electrolyte concentration as a function of the mole fraction of the test surfactant in a mixture with a reference surfactant, sodium dihexyl sulfosuccinate (SDHS) and applying the appropriate HLD equation for ionic surfactant mixtures to determine Cc. The values of Cc were determined for a range of surfactants, including sodium dodecyl sulfate (SDS), sodium dodecyl benzene sulfonate (SDBS), sodium naphthenate, and others. The method was also extrapolated to nonionic additives and hydrophilic linkers. It was observed that the calculated values of Cc were similar to those predicted by group contribution models, however the proposed method can be used even for complex surfactant mixtures. Finally, when Cc values were compared to apparent packing factor and HLB values, it was found that Cc is correlated with the apparent packing factor of ionic surfactants, and that Cc correlates with the HLB value for nonionic amphiphiles. The physical interpretation of Cc, and its potential application in the Net-Average Curvature equation of state for oil-surfactant-water systems is discussed.

表面活性剂HLB值对炭黑色浆分散稳定性的影响

考察了表面活性剂的亲水疏水平衡值(HLB)及添加量对色浆中炭黑润湿、分散及稳定性的影响,借助等效润湿接触角法、润湿热法、分散函数、稳定函数法和理想化模型法等对色浆体系稳定性进行了评价,并对稳定机理进行了分析. 结果表明,无论是引入单一型表面活性剂还是复配型表面活性剂,只有当体系的HLB值与炭黑的HLB值接近时,才能达到良好的润湿、分散与稳定效果;复配表面活性剂对炭黑分散效果优于单一型表面活性剂;阴离子与非离子表面活性剂复配的分散效果明显优于非离子与非离子表面活性剂复配;添加5.0wt%表面活性剂时体系分散稳定性最佳;基于吸附层理论与结合力理论较好地解释了表面活性剂存在最佳HLB值和添加量的原因.     

Making homogeneous and fine droplet O/W emulsions using nonionic surfactants

In many emulsion systems, creaming occurs during the first stage of emulsion breakdown. To reduce the rate of creaming, emulsions having small and uniform droplets are desirable. In this work, types and HLB of nonionic surfactants, emulsification methods, and combinations of oils and nonionic surfactants were investigated in order to make stable and homogeneous emulsions. Emulsification was attained by dissolving the surfactants in the oil phases. The addition speed and volume of water to the oil phases were important factors affecting the emulsion droplet size. The change of the solute state in the process of emulsification was observed stage by stage, and the mechanism of emulsification was elucidated. Homogeneous emulsions were formed in the HLB region, showing liquid crystalline and gel phases in the emulsifying process. The addition speed of water to the oil phase was very important in forming the liquid crystalline and gel phases. Polyoxyethylene(n)sorbitan monostearate could emulsify three kinds of oils (hydrocarbon, fatty acid ester and triglyceride). Polyoxyethylene(n)alkyl ether could emulsify hydrocarbon and fatty acid ester. Polyoxyethylene(n)-monostearate could emulsify only hydrocarbon. Surfactants with proper HLB which were soluble in the oil phase and in the presence of a very small amount of water formed a stable emulsion. The solubility state of oil and surfactant was the key to making a fine emulsion.     

两种新型活性染料净洗剂的性能研究

本文研究了两种两性表面活性剂十二烷基二甲基甜菜碱(BS-12)和羟磺基甜菜碱(LHS)分别与不同类型的非离子表面活性剂进行复配后的净洗性能,并对复配体系添加高分子化合物PVP和CMC后的净洗性能进行进一步的研究。初步总结两种不同类型的甜菜碱与高分子添加物的作用规律,并总结归纳出此类表面活性剂与非离子表面活性剂复配的最佳处方。     

Solution properties of homogeneous polyglycerol dodecyl ether nonionic surfactants

The synthesis and solution properties of a homologous series of polyglycerol dodecyl ethers (R₁₂G_n) are described. The phase behavior, surface tension, cloud point and HLB value (hydrophile lipophile balance) of these surfactants in aqueous solutions and in mixed solutions of water/oil have been investigated and compared with values for polyoxyethylene dodecyl ether (R₁₂EO_n). The surface tension measurements showed that R₁₂G_n have sufficiently low values of surface tension and critical micellization concentration (cmc) to serve as useful nonionic surfactants. The mesophases appearing in the R₁₂G_n systems were more stable in a high temperature range than the mesophases of the R₁₂EO_n systems. The cloud point and HLB data indicated that addition of one glycerol group was equivalent to the addition of three oxyethylene units, as far as the hydrophilic property was concerned. The phase diagrams of the R₁₂G_n/dodecane/water systems showed that the solubilizing and emulsifying powers of R₁₂G_n were greater than those of R₁₂EO_n. It is concluded that the polyglycerol chain can be even more useful as the hydrophilic part of nonionic surfactants than the conventional oxyethylene chain.     

非离子系高分子表面活性剂的研究进展

综述了聚乙烯醇类、聚酯类、纤维素基类和糖基类非离子系高分子表面活性剂的进展过程以及这些非离子表面活性剂的制备反应和一些用途；介绍了非离子系高分子表面活性剂不同于低分子表面活性剂的优良表面活性性能和特有性能，讨论了影响这些性能的内在因素和外在因素以及性能和各种内在因素的关系。     

Review: Implementing the hydrophilic–lipophilic deviation model when formulating detergents and other surfactant-related applications

When designing surfactant formulations using ionic and nonionic surfactants, the hydrophile lipophile balance (HLB) is a generalized surfactant characterization parameter that has shown to be useful when designing surfactant formulations, in the case of both ionic and nonionic surfactants (Davies' and Griffin's methods). Microemulsion phase behavior studies have been extensively used to optimize surfactant formulations, but these studies can cover a very wide phase space and can often encounter troublesome non-equilibrium issues such as coacervation. Detailed phase behavior studies can be time-consuming and difficult to apply beyond the specific surfactant-oil system studied. The hydrophilic–lipophilic deviation (HLD) provides a method to help expedite surfactant formulation research by reducing the number of phase behavior studies required to optimize a given formulation. Detergency experiments have indicated that there is an optimal range of HLD for a given fabric surface. This appears to apply to other applications, as well, for example, surfactant formulations used in enhanced oil recovery have been optimized using the HLD method. These studies found that the HLD can reflect total oil recovery, even if the surfactants were derived from different alcohol feedstocks (e.g., HLD of 0 would describe optimum conditions regardless the type of surfactant). Also with additional parameterization, the HLD method can also be applied to non-ideal surfactant mixtures, specifically ionic/nonionic blends. Overall, the HLD framework has shown to be an effective screening tool for a wide range of surfactant-related applications when appropriate experiments, assumptions, and understanding of surfactant and oil interactions are used to generate the HLD parameters.     

丙烯酰胺反相悬浮聚合分散剂的研究

研究了非离子型表面活性剂(Span系列和Tween系列)种类和用量对丙烯酰胺(AM)反相悬浮聚合体系的稳定性及平均粒径的影响,发现由S—65和S—40构成的复合分散剂,且当HLB值为4.5时,分散体系的稳定性最好,产率出现最大值,分散液滴的直径出现最小值。     

质谱分析聚氧乙烯醚类非离子表面活性剂

介绍了聚氧乙烯醚类非离子表面活性剂的质谱,特别是电子轰击持谱（ＥＩ／ＭＳ）的裂分规律,并根据其一系列主要碎片质量和强度来判断其氧乙烯的聚合度及烷基链长。