Prediction of cloth wetting times from diffusion constants of alcohol ethoxylate mixtures

Commercial alcohol ethoxylates are composed of a distribution of ethoxymers, and the width of the distribution can affect some performance properties such as cloth wetting. For example, if the distribution is peaked at the fastest wetting ethoxymer, wetting time decreases. One can predict if further peaking will significantly improve wetting performance if the relationship between ethoxymer distribution peaking and wetting can be determined. As a first step in predicting how cloth wetting time changes with peaking of the ethoxymer distribution, the cloth wetting time of a binary mixture of octaethylene glycol monododecyl ether (C12−8) and hexaethylene glycol monotetradecyl ether (C14−6) was studied. Wetting time was inversely dependent on the average diffusion constant of the mixture, which is predicted from the diffusion constants of the ethoxymers in the mixture and the mixture composition. Diffusion constants of the ethoxymers are derived from dynamic surface tension measurements. Therefore, it is possible to predict the relative cloth wetting time for any alcohol ethoxylate distribution by knowing the diffusion constant of each ethoxymer in the distribution and the distribution composition.     

Studies on viscosity build‐up properties of sodium alcohol ether sulphates

Narrow and broad range distributed ethoxylates of linear C₁₂–C₁₄ alcohols were synthesised using a calcium‐based unconventional catalyst and NaOH, respectively. Their composition was determined by gas chromatography. Sulphates were synthesised in the traditional way by reaction of ethoxylates with sulphur trioxide in a film reactor and neutralised with sodium hydroxide. Products were characterized by the ethoxylate homologue distributions and acid value of the intermediate sulphuric acid derivatives. Viscosity build‐up properties of the narrow and broad range distributed ethoxylates‐based sodium alcohol ether sulphates were studied. Effects of ethoxylate homologue distribution were compared with those of average ethoxylation grade and sulphation degree. It was shown that the acid number of the obtained sulphates, ethoxylate homologue distribution, average polyaddition degree and sodium chloride content influenced remarkably the thickening ability of ethoxylates. Furthermore, it was found that the limited content of the longer ethoxylate chains in narrow range distributed alcohol ethoxylates is responsible for enhanced viscosity build‐up properties of their sodium sulphate derivatives. The following empirical relationship was obtained: log η = (2.99 ± 1.25) + (3.78 ± 0.86) × 10⁻²V − (1.48± 0.15)N_av − (2.69 ± 0.7) × 10⁻²A_N + (0303 ± 0.058) × C_surf + (0.832 ± 0.041) × C_NaCl where η is the viscosity in cP, V is the distribution coefficient, N_av is the average oxyethylation degree, A_N is the acid number of alcohol ether sulphuric acid and C_surf and C_NaCl are concentrations (wt%) of the studied surfactants and sodium chloride, respectively. © 1999 Society of Chemical Industry     

Degradation of a Fluorine‐Free Perfluorooctane Sulfonate Substitute in Chromium Plating Solutions

Hexavalent chromium solutions for decorative chromium plating in which perfluorooctane sulfonate (PFOS) was replaced by the fluorine‐free oleylamine ethoxylate were investigated. This substitute is degraded under the highly oxidative conditions of chromium plating processes and thus has to be replenished. In both an industrial plant and laboratory experiments the lead anode was found to undergo increased corrosion when oleylamine ethoxylate is used. This lead then precipitates as PbCrO₄. The weight loss of the Pb anode was investigated for the use of PFOS and oleylamine ethoxylate as surfactants. It was shown in laboratory experiments that organic substances accumulate in chromium plating solutions with this alternative surfactant. By ion chromatography combined with mass spectrometric detection, dicarboxylates and amino dicarboxylates were identified. However, no negative impact on process safety and product quality could be determined when oleylamine ethoxylate was used. Monitoring of dissolved organic carbon is proposed as a means of assessing a chromium plating solution for organic contamination.     

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.     

复合型碱土金属乙氧基化窄分布催化剂及其性能研究

研制出复合型碱土金属乙氧基化催化剂（简称ＦＨ型）。通过辛基酚和月桂醇的乙氧基化反应考察了其催化活性和产品的分子量分布。结果表明，这种催化剂的催化活性高，合成乙氧基化产物分子量分布窄，色泽好。     

Influence of ethoxylate chain length for synperonic NPX surfactants on the film formation behaviour of methylmethacrylate-2-ethylhexyl acrylate copolymer latexes: II. A dielectric investigation

A real time dielectric relaxation investigation covering the frequency range from 10⁻² to ∼10⁵ Hz, on the film forming process in methylmethacrylate-2-ethylhexyl acrylate latex copolymers stabilised with nonylphenol ethoxylate is presented. The three systems investigated have essentially identical latex compositions and the only difference between these materials is the length of the ethoxylate chain in the nonylphenol ethoxylate stabiliser. The dielectric relaxation measurements allow changes in the dipolar nature of the medium to be monitored as the process of film formation and coalescence occur. Combining the dielectric data with other observations of the coalescence process reported in part 1 has allowed identification of various stages in the film formation process. It is evident that the formation of a micro-crystalline phase between the emulsion particles by the longer chain ethoxylate molecules, inhibits the coalescence process. Moreover, the stabiliser can also be seen to play a role in determining the dynamics of the molecules in the latex and a critical role in the overall coalescence process. A schematic model describing the various stages of coalescence is presented.     

凝胶渗透色谱法测脂肪醇聚氧乙烯醚产品的相对分子质量分布

应用高效液相色谱技术 ,采用凝胶色谱柱 ,用示差折光检测器 ,对 AEO产品进行了分析 ,测出了产物的相对分子质量 ,并得到分布图 ,成功地实现了对产品的质量控制和中间控制     

壬基环己醇聚氧乙烯醚硫酸盐的合成及性能

壬基酚聚氧乙烯醚硫酸钠因具有水生毒性而亟需开发其替代物。壬基环己醇聚氧乙烯醚由于其安全性较高,且理化性能与壬基酚聚氧乙烯醚的接近,是壬基酚聚氧乙烯醚潜在的替代物。本文以壬基环己醇聚氧乙烯醚为原料,氯磺酸为硫酸酯化试剂,合成了壬基环己醇聚氧乙烯醚硫酸钠,其中壬基环己醇聚氧乙烯醚（5）硫酸钠和壬基环己醇聚氧乙烯醚（9）硫酸钠（5, 9分别为其环氧乙烷加成数）的酯化率分别可达90.91% 和91.06%。壬基环己醇聚氧乙烯醚（5）硫酸钠水溶液与脂肪醇聚氧乙烯醚（3）硫酸钠（AES）具有相近的表界面活性。合成产物壬基环己醇聚氧乙烯醚硫酸钠具有和壬基环己醇聚氧乙烯醚相当的润湿及泡沫性能,比AES更好的润湿、泡沫及乳化性能。     

Quantitative determination of ethylene oxide oligomer distribution in ethoxylated alkylphenol carboxymethyl ether salts by thin-layer chromatography

A two-dimensional thin-layer chromatographic (TLC) method was used to separate a mixture of ethoxylated alkylphenol carboxymethyl ether salts and unconverted ethoxylated alkylphenol ether with the first eluent, which was then developed at right angles with EtOAc/HOAc/H₂O as the second eluent to resolve the individual ethylene oxide oligomer adducts. Scanning densitometry was used for quantitation. The surfactant's degree of conversion, average ethoxylate number and its distribution were simultaneously determined on a single TLC plate.     

马来酸壬基酚聚氧乙烯醚双酯HLB值的计算和验证

通过多种方法计算了马来酸壬基酚聚氧乙烯醚正烷醇双酯的HLB值,并采用水数法进行了测定,对比分析了实验值与理论计算值。结果表明:马来酸壬基酚聚氧乙烯醚正烷醇双酯的HLB值可采用R值、溶解度参数以及Griffin公式来计算;对于用实验法难以测定其HLB值的马来酸壬基酚聚氧乙烯醚正烷醇双酯磺酸盐而言,其HLB值可采用R值来判断。     

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.     

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.     

Anionic surfactants: lauric products

Lauryl sulfate and lauryl ether sulfate obtained by the sulfation of lauryl alcohol and lauryl alcohol ethoxylate are representative of anionic surfactants and are used as a formable detergent or an emulsifier. For the sulfation of lauryl alcohol and lauryl alcohol ethoxylate, SO₃ gas, it was found that the quality of products was significantly influenced by the reaction conditions. In order to obtain good quality products we developed a new technology by using a new type of reactor called a “climbing film reactor,” in which SO₃ gas and liquid raw material flow ascendingly.     

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.     

Synthesis and Characterization of Sodium Nonylphenol Ethoxylate(10) Sulfoitaconate Esters

Two sodium nonylphenol ethoxylate(10) sulfoitaconate ester surfactants, namely disodium nonylphenol ethoxylate(10) sulfoitaconate monoester (DNE(10)SIM) and sodium nonylphenol ethoxylate(10) sulfoitaconate diester (SNE(10)SID), were synthesized through the esterification and sulfonation reactions with nonylphenol ethoxylate(10) ester, itaconic acid and sodium sulfite as the raw materials. The chemical structures of the prepared surfactants were confirmed by FTIR and ¹H NMR. The surface tension of the synthesized surfactants was measured at 25 °C and the surface active properties were characterized. The DNE(10)SIM had better surface activity. The CMC was 1.77 × 10⁻⁶ mol L⁻¹ and γ_CMC was 35.45 mN m⁻¹. The CMC and γ_CMC for the SNE(10)SID were 5.42 × 10⁻⁵ mol L⁻¹ and 37.67 mN m⁻¹, respectively. Moreover, the emulsification power of SNE(10)SID was better.     

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.     

Surface Properties of an Alcohol Alkoxylate in the Presence of a Cationic Surfactant

Alcohol alkoxylate was prepared via propoxylation of an industrial alcohol ethoxylate. The chemical structure of the prepared compound was confirmed using FT-IR and the physical properties were evaluated by the usual methods according to ASTM. The surface properties of the aqueous solution of alcohol alkoxylate were determined with or without addition of a cationic surfactant in comparison to the corresponding alcohol ethoxylate. The measured parameters were surface tension, CMC, maximum surface excess, minimum surface area and the interaction parameter (β). These data indicate that surface properties changed due to the attractive complex formation in the mixed system.     

Synthesis and characterization of TRITON™ X‐based surfactants with carboxylic or amino groups in the oxyethylene chain end

This paper describes the synthesis and characterization of a series of TRITON™ X‐based surfactants with a predominantly alkyl phenol ethoxylate (APE) backbone and carboxylic or amino chain ends. Three carboxylic acid‐containing TRITON X (or APE)‐derivatives, [OPE2‐COOH], [OPE5‐COOH], and [OPE10‐COOH], were prepared from commercially available octyl phenol ethoxylate (OPE) of different oxyethylene units (i.e., n = 2, 5, and 10) and ethyl bromoacetate via a simple etherification reaction followed by saponification. Two amine‐containing TRITON X ‐derivatives, [NPE10‐NH₂] and [NPE10‐imidazole], were prepared based on modifications of mesylate of nonyl phenol ethoxylate (NPE) of 10 oxyethylene units reacted with ammonia and imidazole, respectively. Depending on their composition and chain length of oxyethylene units used in the reaction, the surfactants show different thermal degradation behaviors. The carboxylic acid‐containing surfactants give no char at high temperatures under air condition. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 162–170, 2007     

月桂酸甲酯乙氧基化物中的聚乙二醇和月桂酸甲酯的同时测定

使用C8键合硅胶色谱柱、示差折光检测器的反相液相色谱法同时测定了月桂酸甲酯乙氧基化物中的聚乙二醇和月桂酸甲酯的含量,通过优化流动相配比实现了月桂酸甲酯乙氧基化物同聚乙二醇和月桂酸甲酯的完全分离,方法简便快速,适用于产品的质量控制和工艺研究。     

椰子油乙氧基化物与阴离子表面活性剂协同效应研究

摘要：对椰子油乙氧基化物-30EO（COE-30）与直链烷基苯磺酸（LAS）、脂肪醇聚氧乙烯醚硫酸钠（AES-2）及脂肪醇聚氧乙烯醚羧酸钠（AEC-5）复配的二元体系进行研究,运用非理想溶液理论计算混合胶束和混合吸附层的组成及二者在混合胶束和混合吸附层中协同作用参数。结果表明,复配体系在混合胶束和混合吸附层显示出较强的协同作用,混合胶束中作用参数|βm|= 2~6,混合吸附层中作用参数|βσ|= 2~6。三个复配体系在形成胶束能力和降低表面张力效率方面存在协同增效作用,同时COE-30/AES-2和COE-30/AEC-5体系在降低表面张力能力方面也存在协同增效作用。