The Adsorption of Hydroxyl Mixed Ether Nonionic Polymeric Surfactants at Air/Water and Solid/Water Interfaces: Influence of Surfactant Molecular Structure

This paper reports the adsorption of four nonionic Hydroxyl Mixed Ether (HME) polymeric surfactants at air/water and solid/water interfaces. The characteristics of these nonionic surfactants, including surface tension, critical micelle concentration (CMC) and adsorption onto saponite and Teflon are investigated. At the air/water interface, the surface activity of the HME-surfactants decreases with an increasing degree of ethoxylation. The surface tension results indicate that CMC, surface tension at CMC (γ_CMC), and the minimum surface area per adsorbed HME-surfactant molecule (A _min) all increased with the degree of ethoxylation for surfactants with similar hydrocarbon chain lengths. Additionally, a strong adsorption onto the saponite (synthetic clay) was measured and found dependent on both the degree of ethoxylation and the hydrocarbon chain length. This adsorption was also observed by atomic force microscopy (AFM). On the other hand, the adsorption of HME-surfactants on Teflon was independent of the hydrocarbon chain length.     

Polymeric surfactants for enhanced oil recovery. Part II—the hlb-cmc relationship of ethoxylated alkylphenol-formaldehyde polymeric surfactants

The natural log of critical micelle concentration (CMC) values obtained from the natural log discontinuities in surface tension-concentration relationships, through the least-squares regression analysis, were plotted against the respective hydrophile-lipophile balance (HLB) values of four groups of ethoxylated octylphenol-, dodecylphenol-, tetradecylphenol- and hexadecylphenol-formal-dehyde polymeric surfactants. The obtained HLB-CMC relationship for the investigated compounds can be represented satisfactorily by the linearized equation In (CMC) = a—b (HLB). Values of the two constants a (intercept) and b (slope) for 16 of these compounds were determined at 28, 38, 48 and 58°C, using the least-squares regression analysis of data. The study revealed that both a and b values increase with increasing number of carbon atoms in the ethoxylates of polymeric compounds having a linear alkyl chain. The influence of branching is reflected in the values of a and b of the compounds having a branched dodecyl chain. The most striking feature of the obtained equation is that the CMC decreases with increasing HLB (negative slope). This observation is contrary to what is generally expected for both ionic and nonionic surfactants.     

On the measurement of critical micelle concentrations of pure and technical-grade nonionic surfactants

The critical micelle concentrations (CMC) of nine commercial nonionic surfactants (Tween 20, 22, 40, 60, and 80; Triton X-100; Brij 35, 58, and 78) and two pure nonionics [C₁₂(EO)₅ and C₁₂(EO)₈] were determined by surface tension and dye micellization methods. Commercially available nonionic surfactants (technical grade) usually contain impurities and have a broad molecular weight distribution owing to the degree of ethoxylation. It was shown that the surface tension method (Wilhelmy plate) is very sensitive to the presence of impurities. Much lower CMC values were obtained with the surface tension method than with the dye micellization method (up to 6.5 times for Tween 22). In the presence of highly surfaceactive impurities, the air/liquid interface is already saturated at concentrations well below the true CMC, leading to a wrong interpretation of the break in the curve of surface tension (γ) vs. concentration of nonionic surfactant (log C). The actual onset of micellization happens at higher concentrations, as measured by the dye micellization method. Furthermore, it was shown that when a commercial surfactant sample (Tween 20) is subjected to foam fractionation, thereby removing species with higher surface activity, the sample yields almost the same CMC values as measured by surface tension and dye micellization methods. It was found that for monodisperse pure nonionic surfactants, both CMC determination methods yield the same results. Therefore, this study indicates that precaution should be taken when determining the CMC of commercial nonionic surfactants by the surface tension method, as it indicates the surface concentration of all surface-active species at the surface only, whereas the dye method indicates the presence of micelles in the bulk solution.     

Polymeric surfactants for enhanced oil recovery. Part III—interfacial tension features of ethoxylated alkylphenol-formaldehyde nonionic surfactants

The interfacial tensions (IFT) of four low molecular weight groups of ethoxylated octylphenol-, dodecylphenol-, tetradecylphenol- and hexadecyl-phenol—formaldehyde polymeric surfactants were determined using the spinning drop method. Some noteworthy features of the interfacial behaviour of dilute aqueous solutions of 16 of these compounds and homologous hydrocarbons are discussed. An important feature is that these surfactants behave similarly to monomeric ones in their hydrocarbon scan, that is they have a minimum IFT value against a particular member of a homologous hydrocarbon series. The magnitudes of the tension at minimum (γ_min) values obtained in this study are of the order of ‘ultralow’ (10^?2-10^?3 mNm^?1). The n_min values of these polymeric nonionic surfactants decrease with increasing hydrophilicity, that is decrease with the increase of ethylene oxide units condensed per mole of alkylphenol unit in the polymeric surfactants studied. In this case, the downward shift in n_min is smaller and apparently not linearly related to the number of EO units. Increasing the hydrophobicity of these polymeric nonionics, that is increasing the length of the alkyl chain from C₈ to C₁₆, resulted in an increase in the n_min values obtained. For each of the investigated groups, the lowest γ_min values are obtained with polymeric surfactants having the highest EO content. The optimum low tension performance occurs at the low end of the equivalent alkane carbon number scale (at EACNs below 6). Under the influence of added electrolytes these EACNs were shifted to higher values.     

Synthesis of Some Nonionic Polymeric Surfactants Based on Aminolized PET as Corrosion Inhibitors

The present work deals with the preparation of nonionic polymeric surfactants based on aminolytic degradation of PET by using diethanolamine (DEA) in the presence of Na-acetate as a catalyst to produce bis(4-hydroxyethylene)terephthalamide (B4HETA) monomer. The monomer produced was reacted with stearic acid and poly (ethylene glycol) with different number average molecular weights, namely 600, 2000 and 4000 gmol^?1, to produce nonionic polymeric surfactants having different hydrophile–hydrophobe balances. The molecular weights and polydispersity of the prepared surfactants were determined by the GPC technique. Surface tension as a function of concentration for different solutions of the prepared surfactants was measured at 298, 308, and 318 K to calculate surface and thermodynamic properties of the investigated compounds. Furthermore, corrosion inhibition efficiency of the investigated nonionic polymeric surfactants was thoroughly studied.     

Structural and Physicochemical Properties of a Polymerizable Surfactant Synthesized from <Emphasis Type="Italic">N</Emphasis>-Methylol Acrylamide

A new polymerizable nonionic surfactant with reactive vinyl groups has been synthesized from N‐methylol acrylamide using a two‐step procedure. The structure of the surfactant molecule was characterized by Fourier transform infrared, ¹H nuclear magnetic resonance and mass spectroscopy. The surface active properties alongside its self‐assembly properties were investigated by surface tension, electrical conductivity, and fluorescence spectroscopy measurements. As compared with other nonionic surfactants, this study showed that this polymerizable surfactant possesses slightly a higher critical micelle concentration (CMC) value and the surface tension value at CMC. The obtained CMC values were compatible among measurements, ca. 0.02–0.038 M. The evidence of micelle formation also provided by the zeta potential measurements and the obtained zeta potential values showed that the polymerizable surfactant solutions had limited stability. The hydrolysis stability and solubility of the polymerizable surfactant were also investigated. The solubility results have shown that it was soluble in polar solvents while insoluble in nonpolar solvents both at room temperature and 40 °C. The acidic and basic hydrolysis of the surfactant increased as the temperature increased and the hydrolysis stability was 180 min (basic medium) and 55 min (acidic medium) at 80 °C.     

温度及无机盐对LMEE和SDS混合溶液表面张力的影响

通过表面张力的测定,研究了温度和不同无机盐对月桂酸甲酯乙氧基化物(laurylmethylesterethoxylate,简称LMEE)与十二烷基硫酸钠(SDS)复配物表面张力及临界胶束浓度(CMC)的影响。研究表明:混合体系的CMC在很宽的复配比例内出现最低值,25℃、未加无机盐时可使CMC最低降至3 8×10-5mol/L;温度对复配体系表面张力的影响较小,温度上升复配物的CMC略有降低。3种价态无机盐的加入均可使复配物的CMC有所降低,但与单一表面活性剂相比,温度和无机盐对复配物的CMC影响均不大,说明复配体系的抗温变及抗盐能力均有增强。     

New non-ionic surfactants: Alkyl polyoxyethylene diethers of isomeric dimethylxanthines

Novel isomeric nonionic surfactants of the poly-oxyethylene (POE) ether type possessing terminal dimethylxanthine functions related to caffeine have been prepared using a polyoxyethylene cetyl mono-ether as the starting material. The surface tension pro-perties indicate that, compared to the parent com-pound and its chloride derivative, these derivatives show pronounced changes in the critical micelle con-centration (CMC) and pre-CMC slope but relatively minor changes in the minimum surface tension value. The findings are discussed also in terms of efficiency and effectiveness of surfactants. The evidence indi-cates that the structure of the terminal hydrophilic portion can have a significant effect on interfacial packing. The cloud points of the chloride derivative and the xanthine derivatives were considerably lower than that of the parent ether. Cloud point curves for the ether, the chloride, and the xanthines over the dilute concentration range show similar features.     

Experimental Study of CMC Evaluation in Single and Mixed Surfactant Systems, Using the UV–Vis Spectroscopic Method

In this study, the critical micellar concentration (CMC) of anionic, cationic and nonionic surfactants was determined using the UV–Vis spectroscopic method. Sodium lauryl sulfate (SDS) as anionic, hexadecyl-trimethyl-ammonium bromide as cationic, tert-octylphenol ethoxylates TOPEON (with N = 9.5, 7.5 and 35) and lauryl alcohol ethoxylate (23EO) as nonionic surfactants have been used. Concentration of surfactants varies both from below and above the CMC value in the pyrene solution. In addition, the amount of the CMC was determined using the values from the data obtained from the graph of absorbance versus concentration of surfactants. A comparative study was conducted between the results of the present study and the literature which shows a good agreement, in particular for TOPEO9.5 and LAEO23. Furthermore, the CMC value of SDS (as an ionic surfactant) in the presence of nonionic surfactants was also examined. The result reveals that with addition of small amount of nonionic surfactant to the anionic SDS surfactant, a decline in the CMC value of the anionic–nonionic system relative to the CMC of pure anionic surfactant was observed. In addition and for the first time, the effect of UV irradiation on the size of the micelle formations was studied. It was found that UV irradiation causes the formation of smaller micelles which is of prime concern in membrane technology.     

Preparation and Characterization of Amphiphilic Lignin Derivatives as Surfactants

Abstract

Acetic acid lignin (AL), one of the organosolv lignins, was modified by polyoxyethylation using commercially available polyethylene glycol diglycidylethers (PEGDE) having various chain lengths in order to generate novel nonionic polymeric surfactants. AL could be converted to the amphiphile by modifying with PEGDE (PEGDE-AL) having more than 9 of the ethylene oxide (EO) repeating units. Although the surface activities of PEG and AL were very limited, PEGDE-AL did strongly depress surface tension of water, and showed clear critical micelle concentrations (CMC). The CMC value of PEGDE-AL could be comparable to a commercial anionic lignin surfactant, lignosulfonate. The surface activity of AL amphiphile was further improved by modification with monoepoxides, ethoxy-(2-hydroxy)-propoxy-polyethylene glycol glycidylether (EPEGGE). The surface tension of water was depressed by the addition of the EPEGGE-AL to the same level as Triton® X-100, which is a commercial PEG-based nonionic surfactant, although there is still room for improvement in CMC value. The hydrophile–lipophile balance (HLB) of these AL amphiphiles was in the range of 11–14, and significant biodegradation was observed. These results suggest that the AL amphiphiles can be used as emulsifier and detergent.     

Aggregation and Phase Separation Phenomenon of Amitriptyline Hydrochloride Under the Influence of Pharmaceutical Excipients

The interaction between the amphiphilic drug amitriptyline hydrochloride (AMT) and the nonionic surfactants used in drug delivery has been investigated. Herein, we report the micellization behavior of AMT in presence of ethoxylated alkyl phenols in aqueous medium and the clouding phenomenon in the absence and presence of different nonionic surfactants in buffer solution. The values of critical micelle concentration (CMC) of AMT obtained using the conductivity method, decrease as nonionic surfactant concentration increases. With an increase in temperature, the CMC first increases and then decreases. At 303.15 K, the maximum CMC values were obtained with or without nonionic surfactant. The results obtained indicate attractive interactions (synergism) between the two mixing amphiphiles in solution. The experimentally obtained critical micelle concentration (CMC) values are always lower than ideal CMC values. Micellar mole fraction (X₁) values, calculated by different proposed models, show the contribution of nonionic surfactant concentration. At a fixed drug concentration (50 mmol kg^?1) and pH (=6.7) nonionic surfactants show continuous increase in cloud point (CP). Increase in drug concentration and pH, in the presence of fixed amounts of nonionic surfactant, increases and decreases the CP, respectively.     

Tuning Interfacial Activity of Polymeric Resin–Surfactant/<Emphasis Type="Italic">n</Emphasis>-Alcohol Solution Interactions

Measurements of surface tension were carried out for several aqueous solutions of different amphiphilic systems. This research studied the interaction between two polymeric resins (more structure definition) (PR) and nonyl phenol ethoxylates (NP) with degrees of ethoxylation varying from 10 to 20 ethylene oxide groups. The results show that in mixtures of PR and NP₂₀EO, the adsorption on the surface was lower, with the molecules tending to remain within the liquid. On the other hand, mixtures of PR and NP₁₀EO have resulted in greater surface adsorption. The effect of the added alcohols was to tune the interfacial activity of the PR as function of the PR and alcohol concentrations. The general tendency of the surface tension curves to decrease with increasing PR/alcohol concentration in solutions was not significantly modified with the addition of alcohols; however, the surface tension values changed due to the addition of alcohols and a model is proposed to explain these changes, as they depend on both alcohol chain length and the PR/alcohol concentration. An emulsion stability test was performed on polymeric resins–surfactant systems to determine the correlation between their surface properties. Nonionic surfactants present in these mixtures are mainly responsible for the emulsion stability. It was concluded that mixtures of the less hydrophilic PR (PR_B) with NP₁₀EO have good interfacial properties, including a high interfacial concentration and a low critical micellar concentration.     

Micellization and Adsorption Behaviors of New Reactive Polymerizable Surfactants Based on Modified Nonyl Phenol Ethoxylates

The synthesis and characterization of a series of polymerizable surfactants based on alkyl phenol ethoxylate backbone and carboxylic or anhydride chain ends were investigated. Surface activities of these polymerizable surfactants were investigated to correlate their structure and their performances. The new bifunctional surfmers were prepared by reacting polyoxyethylene 4-nonyl-2-propylene-phenol nonionic reactive surfactants with maleic anhydride. The chemical structure of the prepared surfactants was characterized by ¹³C and ¹H NMR analyses. The surface activities of the modified polymerizable surfactants were measured from the adsorption isotherm measurements which were determined from the relationship between the concentrations and surface tension of surfactants in aqueous medium at different temperatures. Critical micelle concentration (CMC) values were determined for water soluble surfactants. It was found that CMC decreases with the incorporation of the anhydride and acid groups in the chemical structure of polyoxyethylene 4-nonyl -2-propylene-phenol nonionic surfactant. surface-active parameters such as area per molecule at the interface (A _min), surface excess concentration (Γ_max) and the effectiveness of surface tension reduction (π_CMC) were measured from the adsorption isotherms of the modified surfactants. Some thermodynamic data for the adsorption process were calculated and discussed. The data indicated that the new surfmers are more reactive than the simple polyoxyethylene 4-nonyl-2-propylene-phenol and more adsorbed at interfaces. We have performed a preliminary experiment to explore the emulsification efficiency of the newly synthesized reactive surfactants in equal volume oil–water emulsions. Different emulsion types and stabilities were obtained.     

Some Surface Properties of Polysorbates and Cetyl Trimethyl Ammonium Bromine Mixed Systems

Mixed surfactant solutions consisting of cationic/nonionic surfactants were prepared in different compositions of the components in aqueous solution in order to determine the surface properties. The critical micelle concentration (CMC) of aqueous solutions of the individual surfactants cetyl trimethyl ammonium bromide (CTAB) and polysorbate nonionics, and their mixtures are determined at different proportions. The results show that there is synergistic behavior in mixtures at higher mole fraction of nonionic surfactant. The effect of the alkyl chain on the CMC is also determined.     

Preparation and Surface Activities of Modified Soy Protein–Dextrin Surfactants

A series of polymeric surfactants has been prepared through the reaction of soy protein with polyethoxylated stearyl ethers of various hydrophilic chain lengths. These surfactants exhibited surface activity, evaluated using surface tension, foaming, and wetting power that was superior to that of traditional surfactants containing only one hydrophobic moiety and one hydrophilic head group. Changing the ethoxylate (EO) group length had a significant effect on the surface activity. Increasing the EO group length decreased the critical micelle concentration (CMC) and increased the surface tension at the CMC (γ_CMC). The good surface properties of these polysaccharide/protein‐type surfactants suggest that they could be used as emulsifiers to prepare oil‐in‐water emulsions displaying good stability.     

Surfactant properties of low molecular weight phospholipids

Surface tensions, critical micelle concentrations (CMCs), contact angles on hydrophobic polyethylene, and foaming characteristics of phosphatidic acids, phosphatidylcholines, phosphatidylethanolamines, and phosphatidylglycerols were measured to determine their suitability as substitutes for traditional surfactants. These phospholipids have fatty acid chains of 5 to 12 carbon atoms, a range over which they are soluble at room temperature. Their surface tensions decrease with increasing concentrations until their CMCs are reached, above which their plateau surface tensions are as low as 21 mN/m, indicating excellent surface activities. In general, plateau surface tensions decrease with increasing chain length within each phospholipid type. The classical relationship for In CMC vs. chain length is followed with slopes typical of anionic surfactants for phosphatidic acids and phosphatidylglycerols and resembling zwitterionic surfactants for phosphatidylcholines and phosphatidylethanolamines, consistent with the charge on the hydrophilic group. The wetting capabilities of aqueous solutions on polyethylene are good and foam heights and stabilities are high, the latter two properties being comparable to traditional anionic (sodium dodecylsulfate) and nonionic (octylphenol polyethoxylate) surfactants. Some anomalies are observed regarding the effect of chain length on wetting and foaming, probably due to the depletion effect. Many phospholipids slowly degrade in aqueous solution. We conclude that short-chain phospholipids exhibit excellent surfactant properties and may be useful in many applications.     

Simple and Efficient Synthesis and Surfactant Properties of <Emphasis Type="Italic">N</Emphasis>-Alkyl-3-Boronopyridinium Acid Triflates

In this paper, we describe a simple and efficient procedure of original N-alkyl-3-boronopyridinium triflates synthesis and report on the surface properties of these surfactants. Key micellar parameters were obtained, the critical micelle concentrations (CMC values) were determined and compared to conventional ionic surfactants as well as the surface activity of these surfactants (pC ₂₀ value and the surface tension at the CMC). These new boronic functionalized surfactants exhibit a stunning efficiency in their tendency to self-assemble and are significantly more surface active that their conventional analogues. This new family of surfactants represents a new direction in both functionality and performance, and may open perspectives in chemical synthesis and applications.     

Synthesis and surface activity of poly(maleic diester) surfactants

A series of maleic diester monomers have been prepared by esterification of maleic anhydride with a series of n-alkanols and poly(ethylene glycol) with different molecular weights. These monomers were polymerized in acetic anhydride solution in the presence of cumene hydroperoxide as initiator. The synthesized polymers have been characterized by IR and ¹H NMR spectroscopy, and their surface and thermodynamic properties as non-ionic surfactants is investigated. The surface tension as a function of concentration of the surfactant in aqueous solutions was measured at 298, 308, 318 and 328 K. The surface parameters are calculated. The data reveal that the CMC value of the polymeric surfactant is lower than that of the monomeric surfactant. It is also found that the CMC value decreases with increasing temperature and the number of ethylene oxide units in the surfactant molecule. The thermodynamic parameters of micellization and adsorption are also determined. The structural effectiveness of surface tension is discussed in terms of these parameters. © 1999 Society of Chemical Industry     

Synthesis and characterization of polymerizable epoxy resin surfactants

Polymerizable epoxy resin (PER) surfactants have been prepared from the reaction of bisphenol A epoxy resin with acrylic acid, followed by the reaction with polyethylene glycol (PEG) with different molecular weights. The reaction procedures were monitored by chemical titrations, infrared spectroscopy, and NMR. The products show typical surface‐active properties as but much higher water solubility than nonpolymerizable nonionic surfactant OP‐10. With the increase of PEG's molecular weight, the HLB value, the water solubility, and the critical micellar concentration (CMC) of the PER surfactants, the cloud point of the PER surfactant solutions, as well as the solubilization capability of the PER surfactants to organic compounds increase under the experimental conditions. The copolymerization under UV radiation indicated that about 75–80 wt % of PER surfactants participated in the copolymerization with epoxy diacrylate (EdA), except for the PER surfactant with the lowest PEG molecular weight of 1 k. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42598.     

Synthesis and characterization of surfactants <Emphasis Type="Italic">via</Emphasis> epoxidation of tall oil fatty acid

The synthesis and characterization of novel surfactants derived from tall oil fatty acid methyl esters are presented. The tall oil fatty acid methyl esters, which mainly contain methyl oleate, were converted to 9,10-epoxy derivatives and further transformed to the 9 (or 10) polyethylene glycol (PEG) ethers. Compounds with three different monomethylated PEG chain lengths with molecular weights of 350, 550, and 750, corresponding roughly to 7, 11, and 16 ethylene oxide units, were prepared. Surfactants were formed at an 89% overall yield from tall oil fatty acid. Cloud points were 46, 63, and 84°C, respectively, and surface tensions at the CMC (2.0, 1.0, and 0.4 mM, respectively) varied from 33 to 38 mN/m. Equilibrium surface tension and reflectometry measurements were made and results were similar to those of conventional long alkyl chain PEG surfactants. Results of the tensiometry and reflectometry measurements showed that the surfactants aligned better at the air-water interface than conventional surfactants. The adsorption properties for the three surfactants were similar to those of polyoxyethylene glycol alkyl ethers.