New amphoteric surfactants containing a phosphoric acid group: II. Binary system of amphoteric/anionic surfactant of sodium 2-(N-2-hydroxytetradecyl-N-methylamino)ethyl hydrogen phosphate

We studied behaviors of the binary system of 2-(N-2-hydroxytetradecyl-N-methylamino)ethyl hydrogen phosphate (C₁₄-HMP) and sodium dodecyl sulfate (SDS) in aqueous solution. We found that C₁₄-HMP reduced the ability of SDS to denature protein, to inhibit enzyme activity and to decrease transepidermal water loss. These phenomena were considered to be due to the interaction between the cationic group in the zwitterionic structure of C₁₄-HMP and the anionic group of sulfate in SDS molecule. These behaviors suggest that C₁₄-HMP has a potential to reduce skin irritation when applied to personal care products such as cleaners and shampoos having anionic surfactants.     

New amphoteric surfactants containing the 2-perfluoroalkyl 2-hydroxy ethyl group and an amino acid residue

Amphoteric perfluoroalkylated surfactants containing a hydroxyl group were prepared by the addition of 2-perfluoroalkyl-1,2-epoxy ethane to a starting (L,D or L) amino acid (glycine, alanine, β-alanine, serine, 2-amino butyric acid, norvaline, norleucine, methionine, sarcosine, aspartic acid, glutamic acid).     

New amphoteric surfactants containing a 2-hydroxyalkyl group: I preparation and properties of N-(2-hydroxyethyl)-N-(2-hydroxyalkyl)-β-alanines

A series of new amphoteric surfactants, sodium salts of N-(2-hydroxyethyl)-N-(2-hydroxyalkyl)-β-alanines (Na-HAA) was prepared by adding methyl acrylate to N-(2-hydroxyalkyl)-ethanolamine and subsequent saponification. Neutralization with HCl gave N-(2-hydroxyethyl)-N-(2-hydroxyalkyl)-β-alanines, and the addition of ethylene oxide to Na-HAA gave oxyethylated drivatives. The structures of these compounds prepared were confirmed by infrared spectra, proton magnetic resonance spectra, elementary analyses, etc. Solubility in water, surface tension, foaming power, and critical micelle concentration were determined.     

New amphoteric surfactants containing a 2-hydroxyalkyl group: II. the dependence of physicochemical properties on the pH value for N-(2-hydroxyethyl)-N-(2-hydroxyalkyl)-β-alanines

The dependence of physicochemical properties on the pH of micellar solutions for N-(2-hydroxyethyl)-N-(2-hydroxyalkyl)-β alanines (HAA) was studied by means of a differential titration method (DTM), Fourier transform infrared (FTIR) spectra, and measurements of critical micelle concentration, surface tension, and foaming power. The aspect of the dissociation of HAA was pursued by DTM. The mutual transformation among cationic, zwitterionic, and anionic forms with the change of pH range was confirmed by FTIR spectroscopy. The micelle formation energy was determined at each pH value. Further, the dependence of surface active properties on the pH value for the adducts of ethylene oxide to Na-HAA was also investigated.     

New amphoteric surfactants containing a 2-hydroxyalkyl group: IV. Performance of amphoteric surfactant/soap blends

The performance of new amphoteric surfactants,N-(2-hydroxyethyl)-N-(2-hydroxyalkyl)-β-alanines (HAA) and their oxyethylated derivatives (HAA-nEO) was studied in blends with a fatty acid soap. The solubility, foaming power and fabric detergency were measured for blends of (Na-HAA or Na-HAA-nEO)/soap. Furthermore, lime soap dispersing power, toxicity to fish and biodegradability for HAA or HAA-nEO homologs were examined and evaluated. The blend of tallow soap and not less than 10% of C_12–14-Na-HAA exhibited better solubility behavior than tallow soap or tallow/coconut oil soap alone. Fabric detergency was improved by blending Na-HAA with soap. Soil deposition in Na-HAA/soap or Na-HAA/soap/Na₂CO₃ solution was measured. On the basis of the results for: (a) the measurements of redeposition; (b) interfacial tension between oil and water and (c) contact angle between oil and fabric in water, it was presumed that since Na-HAA adsorbed more or less in preference to soap on the surface of fabric in water, soil redeposition would be prevented in the Na-HAA/soap detergent solution.     

New amphoteric surfactant containing a 2-hydroxyalkyl group: III. Performance of binary systems of amphoteric/anionic surfactants

The performance of new amphoteric surfactants, N-(2-hydroxyethyl)-N-(2-hydroxyalkyl)-β-alanines (HAA), and their oxyethylated derivatives (HAA-nEO) was studied in blends with conventional anionic surfactants. Viscosity, ultraviolet (UV) spectroscopy, surface tension, foaming power, dye solubilization and detergency were measured for the blends of various compositions. The interaction between HAA and sodium linear alkylbenzene sulfonate (LAS) was discussed with respect to the deviation of molar extinction coefficient in the UV spectra. A complex formation was assumed. A notable change in viscosity of 1.0% aqueous solutions was observed at pH 8.0 for the compositions of HAA/LAS (3:1) and HAA/sodium lauryl sulfate (4:1). The binary systems exhibited excellent detergency and other surface active properties, and indicated synergistic effects at a certain weight ratio. Human and rabbit skin irritation also was evaluated.     

New amphoteric surfactants containing a 2-hydroxyalkyl group VIII. Synthesis and surface activities for amphoteric oligomeric or polymeric surfactants of β-alanine type

A series of amphoteric oligomeric and polymeric surfactants of poly(iminoethylene) (PIE) containing both a 2-hydroxyalkyl group (C₁₂-HA or C₁₄-HA) and a 2-carboxyethyl (CE) group as N-substituents was studied as follows: PIE having 1,000 or 20,000 molecular weight was treated with 1,2-epoxydodecane or 1,2-epoxytetradecane and subsequently methyl acrylate. The adducts were saponified to obtain amphoteric oligomeric surfactants (AO) or amphoteric polymeric surfactants (AP), poly{[N-(2-carboxyethyl)-N′-(2-hydroxyalkyl)]iminoethylene}. Various adducts of which the ratios of CE/HA for one unit of iminoethylene group are 2, 3.5, 8, 17 and 89 were synthesized. Surface activities such as surface tension, solubilization of orange OT, and foaming power, and physicochemical properties such as turbidity, isoelectric point, and the dissociation constant, were studied. Particular attention was paid to the dependence of solubilization, viscosity and turbidity on pH value.     

Syntheses of 2-(N-alkyl-N,N-dimethylammonio)ethyl hydrogen phosphates and their physicochemical properties

A series of new amphoteric surfactants, having a quaternary ammonium group and a phosphoric acid group, 2-(N-alkyl-N,N-dimethylammonio)ethyl hydrogen phosphates (alkyl: dodecyl, tetradecyl, hexadecyl), were prepared by introducing a phosphoric acid group into N-alkyl-N,N-dimethyl-(N-2-hydroxyethyl) ammoniumiodide, followed by neutralization with sodium hydroxide and removal of inorganic salts. By the evaluation of the physicochemical properties, it was found that the phosphobetaines behave like “nonionic” surfactant in the zwitterionic region, having very small CMC values in comparison with sodium 2-(N-alkyl-N-methylamino)ethyl hydrogen phosphates. Additionally, similar trends were also observed in the experiments from the point of the effect of electrolyte and temperature on CMC, respectively. It should be considered that the hydrophobicity of the surfactant molecule is increased by the electronic interaction between the quaternary ammonium group and a phosphoric acid group. On the other hand, the phosphobetaines gave the smaller values of the occupied area per molecule at the air/water interface than sodium 2-(N-alkyl-N-methylamino)ethyl hydrogen phosphates. Therefore, it is clear that the phosphobetaines have higher surface-active properties than the amphoteric surfactants.     

Analysis of cationic and amphoteric surfactants: IV. structural analysis of the amphoteric surfactants obtained by the reaction of 1-(2-Hydroxyethyl)-2-alkyl-2-imidazoline with ethyl acrylate

Structural analysis of amphoteric surfactants obtained by the reaction of l-(2-hydroxyethyl)-2-alkyl-2-imidazoline (HEAI) with ethyl acrylate or β-propiolactone has been investigated. These amphoteric surfactants were hydrolyzed under aqueous alkaline media, followed by acid hydrolysis to afford fatty acids and diamine derivatives. By the analysis of the resulting fatty acids, it has been found that ethyl acrylate adds to the carbon atom alpha to an imidazoline ring in the absence of solvent. On the other hand, the resulting diamine derivatives were identified by the isolation and their syntheses, and were quantitatively analyzed by gas chromatography. Based upon the results of their analyses, it has been demonstrated that the reaction products can be divided into three types. In addition, on reaction of HEAI with β-propiolactone, it was found that quaternization at the nitrogen atom of 3-position occurred selectively.     

Analysis of cationic and amphoteric surfactants: V. structural analysis of the amphoteric surfactants obtained by the reaction of 1-(2-Hydroxyethyl)-2-alkyl-2-imidazoline with sodium monochloroacetate

Structural analysis of the amphoteric surfactants obtained by the reaction of l-(2-hydroxyethyl)-2-alkyl-2-imidazoline (HEAI) with sodium monochloroacetate has been carried out. These amphoteric surfactants were hydrolyzed under aqueous alkaline media, followed by acid hydrolysis to afford fatty acid and diamine derivatives. The resulting diamine derivatives were identified by the isolation and their syntheses, and were quantitatively analyzed by gas chromatography. Based upon the results of these analyses, it has been found that the reaction products can be divided into two typical types. The reaction products have simpler compositions than those of ethyl acrylate. However, these amphoteric surfactants are characterized by the presence of appreciable amounts of hydrolysis products of amides, soap and free diamine derivative XI.     

Syntheses of 2-(N-2-hydroxyalkyl-N,N-dimethylammonio)ethyl hydrogen phosphates and their physicochemical and antimicrobial properties

A series of new phosphate type of amphoterics having a 2-hydroxyalkyl group as a hydrocarbon chain, 2-(N-2-hydroxyalkyl-N,N-dimethylammonio)ethyl hydrogen phosphates (alkyl[R]:dodecyl, tetradecyl, hexadecyl), was synthesized and their physicochemical properties—isoelectric point, critical micelle concentration (CMCs), occupied area/molecule at interface and the change of free energy of micellization—and antimicrobial properties were investigated in comparison with those of sodium 2-(N-alkyl-N-methylamino)ethyl hydrogen phosphates. It was found that the CMCs and the occupied areas were observed to decrease due to a phosphobetaine moiety and a 2-hydroxyethyl group. Solution properties of the binary system of SDS/2-(N-2-hydroxytetradecyl-N,N-dimethylammonio)ethyl hydrogen phosphate in aqueous solutions were studied in terms of surface tension and pH value. On the other hand, it was observed that the Minimum inhibitory concentration (MICs) of 2-(N-2-hydroxyhexadecyl-N,N-dimethylammonio)ethyl hydrogen phosphate against fungi were smaller than those of chlorhexidine digluconate.     

Syntheses of sodium 2-(N-alkyl-N-methylamino)ethanephosphates and their physicochemical properties

A series of new amphoteric surfactants, sodium salts of 2-(N-alkyl-N-methylamino)ethanephosphates (alkyl: n-dodecyl, n-tetradecyl and n-hexadecyl) were prepared by reacting alkylbromides with N-methylaminoethanol, followed by addition of phosphoric acid groups and neutralization with sodium hydroxide. The structures of these compounds were confirmed by spectroscopy and elemental analysis. Physical properties such as Krafft point, isoelectric point, critical micelle concentration, occupation area of molecule at surface, foaming power and the effect of pH on surface activity were evaluated. These surfactants were found to exhibit zwitterionic characteristics in the pH range from approximately 5 to 9 and demonstrated good surface-active properties over a wide pH range (pH 4~10). Large occupation areas of the molecule at a surface in comparison with sodium dodecyl sulfate was noted as a characteristic feature of these surfactants.     

Some physicochemical properties of poly (ethyl acrylate) emulsions containing carboxyl groups

Conductometric and potentiometric titration behavior of emulsions of ethyl acrylate copolymers with acrylic acid and methacrylic acid was investigated. On the conductometric titration curves of the emulsions of the copolymers with more than 5 mole-% of the acids, two equivalence points, based on the copolymerized acids, were observed, but only one equivalence point was observed on potentiometric titration. Almost all of the copolymerized acids could be detected by both titration methods. The change in optical density of the dilute emulsions with their pH was measured. The particles of these emulsions were studied under an electron microscope. These results showed that, when the pH of the emulsions was raised, the surface layers of the particles began to dissolve and their cores started to swell near the pH of their first equivalence points. When the pH was again lowered the dissolved polymers coagulated, tiny particles were formed, and the swollen cores were dehydrated. The surface layers thickened with increasing amount of the copolymerized acid. These behaviors were very similar in the emulsions of the copolymers with acrylic acid and methacrylic acid. The quantity of water-soluble polymers formed in the course of the emulsion copolymerization was approximately 3–4% or slightly more. This quantity depended only slightly upon the amount and type of the copolymerized acid. The acid contents of the water-soluble polymers were higher in cases of the copolymers with acrylic acid than in those with methacrylic acid. No relationship with the amount of copolymerized acid was established.     

New amphoteric surfactants derived from lysine. I. Preparation and properties of Nε-acyllysine derivatives-acyllysine derivatives

New amphoteric surfactants were prepared from N^ε-acyllysine which was obtained by the thermal dehydration of a higher fatty acid salt of lysine and was not soluble in water. N^α,N^α-dimethyl-N^ε-acyllysine was prepared by the catalytic reductive condensation of N^ε-acyllysine ester with formaldehyde in good yield. N^α,N^α,N^α-trimethyl-N^ε-acyllysine was obtained from the reaction of N^α,N^α-dimethyl-N^ε-acyllysine ester with methyl iodide. Confirmation of the structure of these derivatives was obtained by spectrometric and spectroscopic analyses. The solubility of N^ε-acyllysine was improved significantly by the introduction of N^α-methyl groups. Physicochemical and surface active properties of the derivatives were investigated in terms of isoelectric points, dissolution temperatures, surface tensions, critical micelle concentrations (cmc), foaming properties and wetting powers. N^α,N^α,N^α-trimethyl-N^ε-acyllysine had lower dissolution temperatures than N^α,N^α-dimethyl-N^ε-acyllysine. The latter showed lower surface tensions than the former at cmc. N^α,N^α-dimethyl-N^ε-lauroyllysine was best in wetting power and foaming property.     

牙膏级磷酸氢钙生产中湿法磷酸脱氟工艺

针对湿法磷酸中氟的存在形式，试验了活性氧化硅和氯化钾预脱氟，再用石灰乳二段中和深度脱氟的工艺，生产出合格的牙膏级磷酸氢钙，联产饲料级磷酸氢钙。原料酸中94％以上的五氧化二磷进入牙膏级和饲料级磷酸氢钙，其中约30％的五氧化二磷进入牙膏级磷酸氢钙的生产，进入肥料级的只有6％以下。该工艺大幅度提高了五氧化二磷的回收率。     

Soap-based detergent formulations: XVIII. Effect of structure variations on surface-active properties of sulfur containing amphoteric surfactants

Quaternary ammonium amphoteric surfactants have been found in the past to be excellent lime soap dispersing agents and detergents but exhibit unusual solubility behavior. In search of a relationship between chemical structure and surface-active properties, compounds having the following general formula were synthesized: ZN⁺(CH₃)₂(CH₂)_nX⁻, where Z is C₁₂H₂₅-, C₁₄H₂₉-, C₁₆H₃₃-, or C₁₅H₃₁CONHC₃H₆-, n is 2, 3, or 4 and X is SO₃- or OSO₃-. Tertiary amines were converted to sulfobetaines (X=SO₃-) by reaction with (a) butanesultone (n=4), (b) propanesultone (n=3), or (c) sodium 2-bromoethanesulfonate (n=2). An alternate synthesis for the sulfoethylbetaines (n=2) involved the reaction of the tertiary amines with ethylene bromide, followed by treatment with sodium sulfite. All sulfated quaternary ammonium compounds (X=OSO₃-) were synthesized by treatment of the tertiary amine with the appropriate chloroalcohol, followed by sulfation with chlorosulfonic acid. The sulfated quaternary ammonium amphoterics are stable to acid hydrolysis, and alkaline stability improves with increasing bridge chain length. Sulfoethyl amphoterics are less water soluble than sulfobutyl, which in turn are less soluble than sulfopropyl derivatives of the same alkyl chain length. For the most part, the sulfated amphoterics are insoluble but are solubilized by soap. The lime soap dispersing properties improve as the carbon chain bridge length increases for both the sulfates and sulfonates. Formulations of tallow soap, amphoteric surfactant, and sodium silicates gave good detergency in most cases. Presented at the AOCS meeting, Dallas, April 1975.     

Studies on bipolar membranes: Part III: conversion of sodium phosphate to phosphoric acid and sodium hydroxide

The electrodialytic water dissociation process employing bipolar membranes has been used successfully for obtaining acids and alkalies from salts. Earlier reports by us described the preparation of bipolar membranes and their applications in converting sodium sulphate into sulphuric acid and sodium hydroxide; sodium acetate into acetic acid and sodium hydroxide [G.S. Trivedi et al., React. Funct. Polym. 28 (1996) 243; Ibid: 32 (1997) 209]. In this paper as an extension of our earlier published works the experimental results on the conversion of sodium phosphate to phosphoric acid and sodium hydroxide under different experimental conditions are described.     

2-硬脂酰胺乙基乙基取代苯基磷酸酯的合成和生物活性

烷氧基磷酰二氯与取代苯酚、N-硬脂酰乙醇胺反应制备得到了6个新的标题化合物,其结构用核磁、元素分析进行了表征,并对它们的植物生长调节和杀菌活性进行了测定。     

ICP发射光谱仪测定特种一铵和净化磷酸中的SO_4~(2-)

介绍了用ICP-OES电感耦合等离子体原子发射光谱仪对磷化工生产中的原料、中间产品及最终产品中SO42-含量分析的简单方法。该方法不但方便快捷、测定范围宽,而且分析结果准确度和精密度满足要求。     

Efficacy of tri-n-octylamine,tri-n-butyl phosphate and di-(2-ethylhexyl) phosphoric acid for reactive separation of protocatechuic acid

ABSTRACT

Owing to its chemical and pharmacological significances, the efficacy of reactive separation of protocatechuic acid (0.001–0.01 kmol m^?3) from aqueous stream by means of tri-n-octylamine (TOA), di-2-ethylhexyl phosphoric acid (D2EHPA) as well as tri-n-butyl phosphate (TBP) in octanol has been investigated, in terms of extraction efficiency, loading ratio, equilibrium complexation constants, and distribution coefficients. Extraction ability was obtained in the order TOA (91.2%) > TBP (88.64%) > D2EHPA (86.43%). In all cases, 1:1 protocatechuic acid:extractant complex is obtained. Further, diffusion coefficients, number of stages for extraction systems, and relative basicity model were used for relating the efficacy.