Preparation and properties of double- or triple- chain surfactants with two sulfonate groups derived fromN- Acyldiethanolamines

Bis(sulfonate) types of amphipathic compounds with three long- chain alkyl groups were prepared by the reaction ofN- (long- chain acyl)diethanolamine diglycidyl ethers with long- chain fatty alcohols, followed by the reaction with propanesultone. The diglycidyl ethers were easily obtained from the correspondingN- acyldiethanolamines and epichlorohydrin in the presence of a phasetransfer catalyst. The same types of compounds with two longchain alkyl groups were also prepared from Nacetyldiethanolamine according to similar procedures. All these new double- or triple- chain surfactants were soluble in water and showed much better micelle forming and ability to lower surface tension than general types of single- chain surfactants with one sulfonate group. The critical micelle concentration (CMC) and γ_CMC values of the triple- chain compounds were still much smaller than those of the corresponding double- chain compounds with two common alkyl groups. The efficiency of adsorption at the water/air interface (pC₂₀) of these surfactants was very high. Their foaming properties, wetting ability toward a felt chip, and lime- soap dispersing ability were measured. To whom correspondence should be addressed at Department of Applied Chemistry, Faculty of Engineering, Osaka University, Yamadaoka 2-1, Suita, Osaka 565, Japan.     

Surface-active properties of novel cationic surfactants with two alkyl chains and two ammonio groups

A series ofbis-quaternary ammonium salts was easily prepared by the reaction of a long-chaintert-alkylamine with epichlorohydrin, and their surface-active properties were measured. The prepared amphipathic compounds had good water solubility and showed characteristic surface-active properties, particularly, extremely excellent foaming ability and foam stability for some specific compounds, such as the compound with a dodecyl and a tetradecyl group as the lipophilic chains. Their critical micelle concentration, which decreased with increased alkyl chainlength, is two orders of magnitude lower compared with the conventionalmono-quaternary ammonium salts. In comparison with surface-active properties ofbis-quaternary ammonium salts, prepared from various organic dichlorides, there are little differences based on the kind of connecting group in the surface-active properties except for foaming.     

Synthesis and properties of geminis with two alkyl and two phosphate headgroups

Amphipathic compounds having two phosphate groups and two long‐chain alkyl groups were prepared by a two‐step process: (a) preparation of monoalkyl phosphate from pyrophosphoric acid and dodecanol, (b) preparation of bis‐phosphoric acid from monoalkyl phosphate, (CH₃)₄NOH and 1,6‐dibromo hexane by using acetonitrile as solvent. The experimental results showed that a 5 : 10 : 2.5 molar ratio of reactants (alkyl phosphate/(CH₃)₄NOH/1,6‐dibromo hexane) and 3 h duration was the optimum for the reaction. The structure of the synthesized product was verified by analytical methods, viz. FT‐IR and ¹H‐NMR. The surface‐active and performance properties like foaming, wetting and anionic content of the disodium salt of bis‐phosphoric acid were also evaluated. The synthesized anionic gemini surfactants possessed maximum anionic content, i.e. 73.4%, and showed better water solubility, foaming and wetting ability than conventional monoalkyl phosphates.     

Preparation and surface active properties of amphipathic compounds with two sulfate groups and two lipophilic alkyl chains

These compounds with various connecting groups between the two lipophilic groups were prepared by the reaction of glycol diglycidyl ethers with long-chain alcohols, followed by sulfation with chlorosulfonic acid or with a mixture of chlorosulfonic acid and acetic acid. The Krafft point of all these new amphipathic compounds was below 0°C, and they had good water solubility. These compounds were superior in surface active properties to general anionic surfactants with one lipophilic chain and one hydrophilic group, such as sodium dodecylsulfate. The effect of the structure of the connecting group on CMC, γ_CMC, foaming properties and wetting ability was investigated. They also showed excellent lime-soap dispersing ability.     

Preparation, surface-active and antielectrostatic properties of multiple quaternary ammonium salts

A series of new cationic surfactants, bis-quaternary ammonium salts and tris-ammonium salts, were prepared from N,N-dimethyldodecylamine and a product of the reaction of epichlorohydrin with ethyl-, propyl-, butyl-, pentyl-, hexyl-, and octylamine (in the xase of bis-ammonium salts) or the hydrochloride of diethyl-, dipropyl-, dibutyl-, or dihexylamine (in the case of tris-ammonium salts). The obtained multiple salts were examined with respect to their surface-active properties: Critical micelle concentrations (CMC), effectiveness of surface tension reductions (γ_CMC), and adsorption efficiencies (pC₂₀) were measured. All these surfactants showed good water solubility and low CMC of more than one order of magnitude lower than those of corresponding monoalkylammonium salts. They also showed good foaming properties, but worse wetting capability. The obtained multiple salts showed excellent antielectrostatic properties.     

Synthesis of water‐soluble thermosensitive polymers having phosphonium groups from methacryloyloxyethyl trialkyl phosphonium chlorides–N‐isopropylacrylamide copolymers and their functions

Water‐soluble thermosensitive polymers having phosphonium groups were synthesized by the copolymerization of N‐isopropylacrylamide (NIPAAm) with methacryloyloxyethyl trialkyl phosphonium chlorides (METRs) having varying alkyl lengths. The relative viscosities of the copolymer solutions increased with increasing content of phosphonium groups in the copolymers and decreased with increasing chain length of alkyl chains in the phosphonium groups. However, the copolymers of METR with octyl groups in phosphonium groups (METO) and NIPAAm became water insoluble with increasing contents of METO moieties in the copolymers. The transmittance at 660 nm of the copolymer solutions above the lower critical solution temperature (LCST) decreased gradually with increasing temperature and decreased with increasing chain length of alkyl chains in the phosphonium groups. The transmittance at 660 nm of the copolymer solutions above the LCST was greatly affected by the addition of neutral salts such as KCl. The copolymers of METR with ethyl groups in phosphonium groups and NIPAAm and those of METR with butyl groups in phosphonium groups and NIPAAm had high flocculating abilities against bacterial suspensions. The METO–NIPAAm copolymer was found to have a high antibacterial activity. The flocculating ability and the antibacterial activity of the copolymers were affected by not only the content of phosphonium groups but also the alkyl chain length in the phosphonium groups in the copolymers. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 386–393, 2003     

Surface activities,biodegradability and antimicrobial properties of glucosamine derivatives containing alkyl chains

Three series of D-glucosamine derivatives containing an alkyl chain with 8 to 14 atoms, methyl 2-acylamino-2-deoxy-D-glucopyranosides,n-alkyl 2-acetylamino-2-deoxy-D-glucopyranosides andn-alkyl 2-amino-2-deoxy-D-glucopyranoside hydrochlorides, were synthesized, and their surface properties (such as surface tension, critical micelle concentration (CMC), dynamic surface tension and foaming properties), biodegradability and antimicrobial activities were evaluated.n-Alkyl 2-amino-2-deoxy-D-glucopyranoside hydrochlorides containing C8 to C12 carbon chains showed surface activities, a CMC and excellent foaming properties. The α-anomers showed a slightly lower CMC than the β-anomers, indicating less hydrophilicity of the α-anomers. On the other hand, glucosamine derivatives containing amide groups showed poor surface activities in water due to their lower solubilities in water. All glucosamine derivatives containing alkyl chains were biodegraded as well as conventional ethoxylated nonionics by activated sludge from the municipal sewage treatment plant. Methyl 2-acylamino-2-deoxy-D-glucopyranosides andn-alkyl 2-amino-2-deoxy-D-glucopyranoside hydrochlorides showed a broader spectrum of antimicrobial activity than the correspondingn-alkyl glucopyranosides. Among them the C12 derivatives showed the best results.     

Solution Properties of Alkyl β-D-Maltosides

Alkyl β-D-maltosides are an important class of sugar-based nonionic surfactants and have been widely studied. Nevertheless, it is still necessary to investigate further their amphiphilic structure-surface property relationships. In this article, we reported a series of properties of synthetic alkyl β-D-maltosides ( 6a – 6i , n = 6–18) including their hydrophilic–lipophilic balance (HLB) number, water solubility, hygroscopicity, moisture-retention capacity, foaming ability, surface tension, thermotropic phase behavior, and skin irritation. Their HLB number and water solubility decreased with increasing alkyl chain length. Hexyl β-D-maltoside exhibited the strongest hygroscopicity and moisture-retention capacity. Decyl β-D-maltoside and dodecyl β-D-maltoside possessed excellent foaming power and foaming stability. Furthermore, the critical micelle concentration (CMC) of alkyl β-D-maltoside ( 6a – 6g , n = 6–14) and their surface tension at CMC decreased with increasing alkyl chain length. At last, alkyl β-D-maltosides ( 6a – 6g ) should be considered as safe surfactants by the skin irritation assessment.     

The monolayer behavior and transfer characteristics of phospholipids at the air/water interface

The monolayer behavior of phospholipids at the air/water interface and their transfer characteristics on the: solid substrates have been investigated with a constant-perimeter type Langmuir trough. From the surface pressure-area (Π-A) isotherm, evaluated were the cross-sectional area of an oriented molecule, phase transition, and the miscibility of mixed monolayers. The monolayer state depends on the chain length and its mobility, and by adding proper salts, the monolayers were stabilized. The miscibility of mixed monolayers was also discussed with collapse pressure and excess area. The monolayers of all lipids were transferred into only one layer on hydrophobic substrates, and up to two layers on hydrophobic substrates. The multilayer formation of dipalmitoylphosphatidic acid (I)PPA) was significantly affected by the subphase pH and the addition of multivalent salts. As a transfer promoter. DPPA or octadecylamine (ODA) was used as a component in a mixture with lipid materials, and their mixed monolayers resulted in good transfer characteristics. The transferred mass and film thickness of DPPA, determined by using a quartz crystal microbalance (QCM) and by an ellipsometry respectively, were proportional to the number of transfer. The lattice spacing of DPPA was 20.3 Å per layer by ellipsometry, and 22.78 Å per layer by X-ray diffraction. These indicated that the transferred multilayers had well-defined layered structures of Y-type.     

Preparation, surface-active properties, and antimicrobial activities of bis(alkylammonium) dichlorides having a butenylen or a butynylene spacer

A series of new cationic gemini surfactants, bis(alkylammonium) dichlorides having a butenylene or a butynylene spacer, were prepared almost quantitatively by the reaction of a long-chain alkyldimethylamine with a highly reactive allylic or propargylic dichloride, and their surface-active properties were measured. All of them showed good water solubility and quite low critical micelle concentrations, which were more than one order of magnitude lower than those of the corresponding mono(alkylammonium) salts. They also showed quite high foaming ability and foam stability when they have an appropriate hydrophile-lipophile balance. Many of them showed almost the same antimicrobial activities against the eumycetes Aspergillus sp. and Candida albicans as commercial germicides such as benzalkonium chloride and chlorhexidine gluconate.     

Surface active N-acylglutamate: II. Physicochemical properties of long chain N-acylglutamic acids and their sodium salts

The physicochemical properties of long chain N-acylglutamic acids (AGA) and their sodium salts (AGS_n) are described. The solubility, Krafft point, pH value, critical micelle concentration, surface tension and foaming power were measured. The properties of the optically active AGA or AGS_n differed from those of the corresponding racemates, especially in solubility. The monosodium salts generally had high Krafft points, but monosodium N-oleoylglutamate had a low Krafft point. The monosodium salts hydrolyzed in the diluted aqueous solution to liberate the AGA. The aqueous solutions of the monosodium salts had low surface tensions and good foaming properties. The disodium salts were highly soluble in water, while surface tensions and foaming properties were inferior to those of the corresponding monosodium salts.     

Synthesis,Surface Activity,and Biological Activities of Phosphonium and Metronidazole Salts

A series of phosphonium amphiphilic compounds was synthesized. Cationic parts of molecules contain triphenylphosphonium moieties. Lipophilic parts of compounds are represented by straight alkyl chain or the alkyl chains which are ornamented by benzyl or metronidazole. The physicochemical properties of phosphonium amphiphilic compounds were investigated by the measurements of surface tension and conductivity. The critical micelle concentration (cmc), the surface tension value at the cmc (γ_cmc), the surface area at the surface saturation per head group (A_cmc) were determined. The lowest cmc value was determined for phosphonium salts with straight dodecyl alkyl chain. Its value was 1.5 × 10⁻³ mol dm⁻³. Surface tension at the cmc decreases with the addition of bulky moieties (benzyl, radical from metronidazol) at the end of alkyl chains. Biological activities of compounds were studied on human erythrocytes and strains of Acanthamoeba lugdunensis and Acanthamoeba quina. Dodecyltriphenylphosphonium bromide showed the highest activity against Acanthamoeba. To the best of our knowledge, it is the first compound of the group of phosphonium amphiphiles, which exhibited high activity against Acanthamoeba. The determined structure–activity relationship indicated nonspecific trophocidal and hemolytic activity that depends on physicochemical properties of the studied compounds.     

Preparation and properties of sodium alkyl sulfoacetates

The preparation and properties for a homologous series of sodium salts of alkyl sulfoacetates, containing 10, 12, 14 and 16 carbon atoms are described. The sodium salts of alkyl sulfoacetates were prepared from monochloroacetic acid, sodium sulfite and corresponding higher alcohol. The Krafft point, c.m.c. value, surface tension, solubilizing power, emulsifying power, foaming power, and calcium ion stability and resistance to acid hydrolysis were measured as the properties of these compounds. The c.m.c. values at 40 C obtained by electrical conductivity were related to the alkyl carbon number (N) of the compounds by log c.m.c.=4.852–0.301 N. Solubilizing power, emulsifying power and foaming power increased with the number of carbon atoms of alkyl chain in the surfactant. But the calcium ion stability and resistance to the acid hydrolysis decreased with an increase in the length of the hydrophobic portion.     

Preparation,Surface-Active Properties and Antimicrobial Activities of Bis(Ester Quaternary Ammonium) Salts

New cationic surfactants, bis-quaternary ammonium salts, were prepared from N,N-dimethylaminoalkyl esters of saturated fatty acids and products of the reactions of epichlorohydrin with primary amines: pentyl-, hexyl- and octylamine. The bis (ester–ammonium) salts obtained were examined in respect to their surface-active properties: critical micelle concentration (CMC), effectiveness of surface tension reduction (γ_CMC), and adsorption efficiency (pC₂₀). All these surfactants showed good water solubility and low critical micelle concentrations of more than two orders of magnitude lower than these of corresponding mono-alkylammonium salts. They also showed good wetting capability, but worse foaming properties. All the surfactants tested were nontoxic to gram-negative bacteria, but some of them inhibited the growth of gram-positive bacteria and yeast.

Synthesis and Properties of Alkoxyethyl β‐d‐Xylopyranoside

In order to improve the water solubility of sugar‐based surfactants, alkyl β‐d‐ xylopyranosides, novel sugar‐based surfactants, 1,2‐trans alkoxyethyl β‐d‐ xylopyranosides, with alkyl chain length n = 6–12 were stereoselectively prepared by the trichloroacetimidate method. Their properties including hydrophilic–lipophilic balance (HLB) number, water solubility, surface tension, emulsification, foamability, thermotropic liquid crystal, and hygroscopicity were investigated. The results indicated that their HLB number decreased with increase of alkyl chain, the water solubility improved since the hydrophilic oxyethene (─OCH₂CH₂─) fragment was introduced. The dissolution process was entropy driven at 25–45 °C for alkyl chain length n = 6–10. Octyloxyethyl β‐d‐ xylopyranoside had the best foaming ability. Nonyloxyethyl β‐d‐ xylopyranoside had the best foam stability and the emulsifying ability was better in toluene/water system than in rapeseed oil/water system. The surface tension of in aqueous solution dropped to 27.8 mN m^?1 at the critical micelle concentration, and it also showed the most distinct thermotropic liquid phases with cross pattern texture upon heating and the fan schlieren texture on cooling. Hexyloxyethyl β‐d‐ xylopyranoside possessed the strongest hygroscopicity. Based on the effective improvement of water solubility, the prepared alkoxyethyl β‐d‐ xylopyranosides showed excellent surface activity and are expected to develop their practical application as a class of novel sugar‐based surfactants.     

Effect of length of hydroxyalkyl groups in the clay modifier on the properties of thermoplastic polyurethane/clay nanocomposites

Polyether‐ and polyester‐based thermoplastic polyurethane (TPU) nanocomposites containing the montmorillonite modified with quaternary ammonium salts having a relatively long hydroxyalkyl branch (MMT‐OH) were prepared via solution mixing. Quaternary ammonium salts with dimethyl, octyl, hydroxyundecyl branches were synthesized by the addition reaction of dimethyloctylamine and 11‐bromo‐1‐undecanol and were used for the preparation of MMT‐OH. In this MMT‐OH clay, hydroxyl groups are located at the outer end of the relatively long undecyl branch, which may make the hydroxyl groups more exposed to the matrix polymers compared to the clays with the modifiers having shorter hydroxyalkyl chain such as C30B. Actually, more hydroxyl groups in MMT‐OH's are thought to be exposed outside the modified clay, since MMT‐OH's were observed to be somewhat dispersed in water, while clays with shorter alkyl chains were not. From XRD and TEM results, the silicate layers of MMT‐OH were shown to be very well dispersed in ether‐TPU and ester‐TPU nanocomposites prepared from dimethyl acetamide solution. In the case of ester‐TPU nanocomposites, much better clay dispersion was observed for nanocomposites containing MMT‐OH than the ones with C30B in the TEM images. The tensile properties measurement showed the similar trend. Although MMT‐OH has only one hydroxyl group while C30B has two, above results of better tensile properties and water dispersibility of MMT‐OH than C30B having two hydroxyls indicate that the position of hydroxyls may be a important factor in determining the properties of TPU/clay nanocomposites. Fourier transform infrared spectroscopy analyses showed that the long hydroxyalkyl chain modifiers may provide more hydrogen bonding sites than short hydroxyalkyl chain modifiers. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

The effect of amphiphilic salts on the interface of two immiscible liquids

Calculation of the thermodynamic characteristics of the interface of two immiscible electrolyte solutions (ITIES) was carried out using the self-consistent mean-field theory for adsorption and/or aggregation developed by Scheutjens and Fleer (1). The effect of tetraalkyl-ammonium-halogenid salts on the interfacial tension of 1,2-dichloro-ethane-water system was calculated for different alkyl groups, hence for different amphiphilic salts. For comparison, experimental determination of the interfacial tension was also carried out using a dynamic drop-weight method. It is found that the interfacial tension is significantly reduced due to the presence of the salts and the effect is larger for larger alkyl groups. Qualitative agreement was found between the calculated and the measured data. The model calculations showed also that the concentration of water near the interface may change non-monotonously.     

Synthesis and Properties of Dissymmetric Gemini Surfactants

A series of novel dissymmetric gemini cationics surfactants was synthesized by three-step reactions. The dissymmetric gemini surfactants contain a dodecanoic acid dimethylethylamine ester as the constant cationic part on one side of the hydroxypropyl center and a similar other cationic part, but with a different acid length (from octanoic to palmitic), on the other side. The critical micelle concentration (CMC) and the effectiveness of surface tension reduction (γ _CMC) were determined. The surface tension measurements of dissymmetric gemini surfactants showed good water solubility, and low CMC had great efficiency in lowering the surface tension and a strong adsorption at the air/water interface. The CMC was observed to increase initially with the increase of the ester bond alkyl group. They also showed good foaming properties and wetting capabilites.     

Roles of mono- and di-functional organic salts as plasticizer and/or filler in styrene-based ionomers

The plasticization and/or filler effects of sodium salts of hexanoate (Na6), adipate (Na6Na), dodecanedioate (Na12Na), and dodecylbenzenesulfonate (Na12) on the dynamic mechanical properties of styrene-based ionomers were investigated. When a small amount of Na6, having one carboxylate ionic group at one end of alkyl chain, was added to a styrene-methacrylate ionomer, the salt acted as a very effective plasticizer for the ionomer cluster regions. With increasing salt contents, however, the salts became phase-separated and formed bilayer crystalline domains that acted as filler. In the case of the Na12Na and Na6Na salts, containing two carboxylate ionic groups, one at each end of alkyl chain, they formed phase-separated domains, acting as filler, in the methacrylate ionomers. Na12, possessing one sulfonate ionic group at only one end of a long alkyl chain, acted as a plasticizer in a sulfonated polystyrene ionomer. However, an excess amount of Na12 salt also formed phase-separated domains. It was also found that Na12 showed a filler effect only at much higher salt contents in comparison with Na6.     

Synthesis of Alkyl Monoglucoside Citric Monoester and Properties of Its Sodium Salt

A series of disodium alkyl monoglucoside citric monoesters (AG‐EC) were synthesized with an indirect method using glucosides, lauryl/decyl/octyl alcohol and citric acid. The structure and composition of the synthesized surfactants were defined by Fourier transform infrared spectroscopy (FTIR) and liquid chromatography–mass spectrometry (LC/MS). The surface properties, foaming ability and wetting ability were investigated. AG‐EC surfactants exhibited excellent water solubility which eliminated the defect of long‐chain alkyl glucoside. All three surfactants showed high surface activities. AG12‐EC and AG10‐EC showed remarkable foaming abilities in distilled water and hard water. Aqueous solutions of AG‐EC surfactants spread slowly on a parafilm surface.