Anionic phosphate surfactants

Conclusions A study of the sodium monoalkyl phosphates and sodium dialkyl phosphates has shown that the dialkyl esters, in general, possess markedly superior surfactant and detergent properties compared to the monoalkyl esters. This is true whether we are comparing equivalent mol wt mono- and diesters or when comparing those made from the same alcohols. The branched chain didecyl ester, in addition to giving aqueous solutions of exceptionally low surface tensions and possessing a very low critical micelle concentration, also performs exceptionally well in built detergents. In fact, our data indicate that its performance characteristics are considerably better than commercial surfactants used today in these types of products.     

脂肪醇类溶剂对青霉素的萃取

研究了不同醇类及醇酯混合体系对青霉素的萃取. 在pH=4的条件下脂肪醇及醇酯混合体系的萃取能力均高于乙酸丁酯. 具有相同碳原子数、带支链的脂肪醇对青霉素的萃取能力比直链醇强,平衡后的有机相水含量下降. 红外光谱分析表明：乙酸丁酯的加入使脂肪醇羟基谱带变宽且明显向高波数方向位移,能阻止醇的多聚,使羟基活性增强. 激光拉曼光谱结果证明：青霉素是以反相微乳液的形式进入脂肪醇相的;支链的存在使体系的有序性和极性都明显增加.     

Crystal growth inhibition of tetrahydrofuran hydrate with bis- and polyquaternary ammonium salts

Small quaternary ammonium salts, particularly with butyl or pentyl groups, have been shown previously to be good Structure II tetrahydrofuran hydrate crystal growth inhibitors. This ability has been exploited in their use as synergists for certain kinetic hydrate inhibitor polymers, and in the design of commercial gas hydrate anti-agglomerants. We have now investigated the effect of bis- and polyquaternary ammonium salts, in which all the nitrogen atoms are in the backbone of the molecule, on the crystal growth of tetrahydrofuran hydrates. The results are compared with those of monomeric quaternary compounds previously reported. The new compounds tested contain 2 to over 100 quaternary centres with various structural geometries including linear and branched polymers. The size of the alkyl groups on the nitrogen atoms was varied and contained from 2 to 6 carbon atoms. Improved performance over monoquaternary ammonium salts was obtained with both bis-quaternary and polyquaternary ammonium products. The optimal distance between the nitrogen atoms in bis-quaternary ammonium salts for best THF hydrate inhibition appears to be with a chain of 6–8 aliphatic carbon atoms.     

Preparation and Surface Activity of Phosphated Alkyl Oligoglucosides

A family of phosphated alkyl oligoglucoside surfactants was prepared by reacting alkyl oligoglucosides with phosphorus oxychloride. The alkyl oligoglucosides were obtained by an usual method in which the glucose is reacted with a fatty alcohol containing 10–18 carbon atoms. These novel phosphated surfactants have been found to exhibit good surface tension, foaming and wetting power. The critical micelle concentration was found to increase with the length of hydrocarbon chain of the surfactant. The surface excess concentration and the interfacial area per surfactant molecule are reported. These phosphated surfactants also exhibit a good performance to improve the whiteness and wetting of cotton fabrics in a hydrogen oxide bleaching system, and they are also found to be more biodegradable than conventional surfactants.     

Chemical reactions at lipid-gas interfaces: II. Insolubilizing reactions induced by an electrical discharge

Reactions caused by corona discharges (passing through atmospheres of methane, hydrogen or argon) striking the surfaces of aqueous solutions containing long chain fatty acid salts resulted in the formation of solid and insoluble products. These results show that the fatty acid ions were oriented on the aqueous surfaces in such a way that the hydrocarbon chains projected out of the surfaces. Surface layers of long chain alcohols reacted similarly but short and branched chain compounds were not polymerized under the experimental conditions that were used. When methane or hydrogen was used as the discharge gas, reactions occurred along the hydrocarbon chains of the compounds so that the products consisted of networks of many short hydrocarbon chains. These reactions were probably caused by the penetration of hydrogen atoms into the surface layers. Joining of terminal methyl groups of the hydrocarbon chains was the main reaction observed when argon was used as the discharge gas.     

Synthesis and physico‐chemical properties of novel dialkyl diphosphate gemini surfactants based on octadecanol

A series of dialkyl diphosphate gemini surfactants has been synthesized using C₁₈ as hydrophobic chains and phosphate as head groups. Three flexible spacers have been used. In the present study, an attempt has also been made to synthesize mono octadecyl phosphate (MOP) at 35°C, which was used as an intermediate in the synthesis of geminis. This long chain of MOP has been effectively converted to gemini surfactants and subsequently converted to their disodium salts. The effect of reaction variables like temperature, duration, molar ratios of reactants, catalyst and spacer on the yield of dialkyl diphosphate gemini surfactant has also been reported. The MOP, gemini surfactants and disodium salt of gemini surfactants were characterized using FT‐IR and ¹H‐NMR. Surface active and physico‐chemical properties of synthesized gemini surfactants and their monomer were also determined. The results revealed that the yield of dialkyl diphosphate gemini surfactants ranged from 80 to 90%. Among all synthesized dialkyl diphosphate gemini surfactants D, S‐1,6‐GSOD had maximum anionic content, i.e. 80.7%, showed highest foaming ability and superior dispersing ability, whereas D, S‐1,8‐GSOD showed low cmc values, i.e. 0.00012 mM/L; minimum surface tension and interfacial tension, i.e. 39.1 and 36.3 mN/m, respectively.     

A study of the surface activity of tertiary alcohol sulfates

A number of tertiary alcohols were prepared by the action of a series of Grignard reagents on ethyl oleate. The tertiary alcohols were converted to alkyl sulfates by reaction with sodium chlorosulfonate. The surface active properties of the prepared sodium alkyl sulfates were studied in relation to the length of the branched chain and the bulkiness of the charged head of the surfactants.     

Synthesis and properties of new cationic surfactants. II. Odd homologous members

In connection with our previous work on the synthesis and study of new pyrimidinium cationic surfactants, some new members of the N-alkyl-pyrimidinium salts homologous series were prepared. The above compounds contain long-chain alkyl groups of 7, 9, 11, 13, 15, 16, 17 and 18 carbon atoms. The series of these compounds having an alkyl chain of C₇–C₁₈ has been completed, and a correlation between their constitution and some properties has been made. The structural assignment of these compounds was made on the basis of the elemental analysis and IR, NMR, MS spectroscopic data. Surface tension, water solubility and antimicrobial activities were determined for these surfactants. The wet fastness of direct dyed cotton fabrics after-treated with these cationics also was studied.     

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.     

Synthesis and Characterization of Novel Surfactants 1,2,3-tri(2-oxypropylsulfonate-3-alkylether-propoxy) Propanes

A series of trimeric sulfonate surfactants 1,2,3-tri(2-oxypropylsulfonate-3-alkylether-propoxy) propanes were prepared by the reaction of glycerin triglycidyl ether with long-chain alcohols, followed by sulfonation with 1,3-propane sultone. Glycerin triglycidyl ether was synthesized by the reaction of epichlorohydrin with glycerin. The chemical structures of the prepared compounds were confirmed by FTIR, ¹H NMR and element analysis. Their solution properties were characterized by use of the method of equilibrium and dynamic surface tension, steady-state fluorescence spectroscopy of pyrene and fluorescence quenching. With the increasing length of the carbon chain, the values of their CMC initially decreased. All these trimeric sulfonate surfactants had good water solubility. These compounds were superior in surface active properties to the reference surfactant SDS. The efficiency of adsorption at the water/air interface (pC₂₀) of these surfactants was very high. It is found that the shorter hydrocarbon chain length of the trimeric sulfonate surfactants, the faster the rate of decrease of surface tension, and the bigger the aggregation number of the trimeric sulfonate surfactants.     

A comparison by warburg respirometry and die-away studies of the degradability of select nonionic surface-active agents

The relative biodegradability of several classes of nonionic surfactants have been determined by Shake Flask, Die-Away and Warburg Respirometer tests. Analytical techniques used to follow the degradation processes involved the measurement of loss of surfactant properties (surface tension or foamability), colorimetric determinations and oxygen uptake studies. Nonionic products prepared from naturally occurring or synthesized straight chain hydrophobes were shown to exhibit based upon branched chain materials. A good correlation of data by the various analytical techniques was obtained on the straight chain based products.     

Produkte der Dimerisierung ungesättigter Fettsäuren VIII: Über die Zusammensetzung der Fraktion der “Intermediates” bei der Fettsäuredimerisierung

Products of Dimerisation Unsaturated Fatty Acids VIII: The Fraction of “Intermediates” Obtained by Dimerisation of Unsaturated Fatty Acids The fraction of “intermediates” which is obtained by dimerisation of unsaturated fatty acid contains straight chain saturated fatty acids with 20-24 carbon atoms as well as methyl branched isomers thereof. The production of these compounds is probably caused by the presence of small amounts of monounsaturated fatty acids with 20-24 carbon atoms in the starting material. The fraction of “intermediates” contains in addition monocarboxylic acids with 36 carbon atoms. These are probably formed after dimerisation by an intramolecular cyclisation reaction under participation of one carboxylic group, followed by hydrogenation of the produced carbonyl group. Finally the formed alcoholic group is eliminated as a water molecule, and the produced double bond is hydrogenated.     

Synthesis,Surface and Antimicrobial Activity of Piperidine-Based Sulfobetaines

A new method for the preparation of new heterocyclic amine surfactants based on sulfobetaines is proposed. Interfacial activities of the surfactants obtained in aqueous solution were studied by surface tension measurements. The critical micelle concentration, surface excess concentration, minimum area per surfactant molecule, and standard Gibbs energy of adsorption were determined. The adsorption properties of these compounds depend significantly on the alkyl chain length. Alkyl chain length also affects biological properties of the new surfactants, determining the minimum inhibitory concentration and size of inhibited growth zone. The compounds have high antimicrobial activity.     

Synthesis and Surface Active Properties of 1,1,1,1-Tetra-(2-oxypropyl Sulfonate-3-alkylether-propoxy)neopentanes

Tetrameric sulfonate surfactants 1,1,1,1-tetra-(2-oxypropyl sulfonate-3-alkylether-propoxy)neopentanes were prepared with raw materials containing epichlorohydrin, pentaerythritol, long-chain alcohols, 1,3-propane sultone and sodium hydroxide by esterification, a ring opening reaction, and a sulfonation reaction. The chemical structures of the prepared compounds were confirmed by FTIR, ¹H-NMR and element analysis. With the increasing length of the carbon chain, the values of their CMC initially decreased. The longer the alkyl chain, the higher the melting point. The Krafft point of all these tetrameric sulfonate surfactants was below 0 °C and they had excellent water solubility. These compounds were superior in surface active properties to general sulfonate surfactants SDS. The efficiency of adsorption at the water/air interface (pC₂₀) of these surfactants was very high. Their foaming properties, their wetting ability of a felt chip, and their lime-soap dispersing ability was investigated.     

Fatty alcohols

“Fatty” or higher alcohols are mostly C₁₁ to C₂₀ monohydric compounds. In probably no other homologous aliphatic series is the current balance between natural and synthetic products so vividly evident. Natural sources, such as plant or animal esters (waxes), can be made to yield straight chain (normal) alcohols with a terminal (primary) hydroxyl, along with varying degrees of unsaturation. In the past, socalled fatty alcohols were prepared commercially by three general processes from fatty acids or methyl esters, occasionally triglycerides. Fatty acids add hydrogen in the carboxyl group to form fatty alcohols when treated with hydrogen under high pressure and suitable metal catalysts. By a similar reaction, fatty alcohols are prepared by the hydrogenation of glycerides or methyl esters. Fatty alcohols are also prepared by the sodium reduction of esters of fatty acids in a lower molecular weight alcohol. The sodium reduction method was ordinarily too expensive; it was displaced early by the other methods; finally most unsaturated alcohols made by this route were largely replaced. Methyl ester reduction continues to provide perhaps 20% of the saturated fatty alcohols, and selective hydrogenation with the use of special catalysts such as copper or cadmium oxides was developed for the production of oleyl alcohol. Synthetic or petroleum technology for long chain alcohols include the Ziegler process, useful for straight chain, even-numbered saturated products. A second is the carbonylation and reduction of olefins affording medium or highly branched chain alcohols. Paraffin oxidation affords mixed primary alcohols. Fatty alcohols undergo the usual reactions of alcohols. They may be reacted with ethylene oxide to yield a series of polymeric polyoxyethylene alcohols or with acetylene under pressure to yield vinyl ethers or with vinyl acetate to give vinyl ethers.     

Synthesis, characterization and surface properties of 1-N-l-tryptophan-glycerol-ether surfactants

A novel homologous series of 1-N-l-tryptophanglycerol-ether surfactants was synthesized and characterized. The precursor compounds, 3-alkyloxy-1-chloropropan-2-ols, were prepared from epichlorohydrin and aliphatic alcohols with alkyl chain lengths of 9–16 carbon atoms. Tryptophan was then attached to the monosubstituted glycerol backbone from its α-amino group through an α-NH-C bond. Structural assignment of the new compounds was made on the basis of elemental analysis and spectroscopic data. Critical micelle concentrations of the new surfactants, as well as the negative logs of the surfactant concentrations required to reduce the surface tension of the solvent by 20 mN/m (pC ₂₀) and the interfacial areas occupied by the surfactant molecules, were calculated from aqueous surface tension measurements using the Wilhelmy plate technique.     

The Application of Ozone in the Decomposition of Aqueous Solutions of Nonionic Surfactants

Aqueous solutions of nonionic surfactants are decomposed by ozone. In the experiments compounds differing in chemical structure (i.e., the presence of a benzene ring in the molecule, the type of aliphatic chain [linear or branched] and the length of the polyoxyethylene chain) were used. The research was conducted using solutions of Triton, Tergitol, Symperonic, and Brij surfactants produced by Fluka Chemie Ag. The initial concentrations were chosen to be over and below a critical micelle concentration (CMC). Decomposition was analyzed by polarography, spectrophotometry, total organic carbon (TOC) and chemical oxygen demand (COD) value. It was found that the rate and effectiveness of ozonation depended on the chemical structure of surfactant molecule, chain structure (linear or branched), oxyethylene chain lengthening, and a monomeric or micelle form of the surfactant molecule appearing in the solution.     

Some detersive properties of model straight chain sodium alkylbenzenesulfonates

Model long chain sodium ortho and para alkylbenzenesulfonates having primary, secondary and tertiary carbon atoms attached to the phenyl group have been evaluated for foam, wetting and detergency. The data indicate that the surface active properties of these three classes of compounds which are primarily linear in structure are dependent upon sulfonate position, phenyl position and chain length. Each of these factors contributes to performance. Ortho sulfonates are better wetting agents than para sulfonates but the para compounds generally foam better and appear to have superior detergency properties than their respective ortho isomers. Ortho sulfouate in a detergent composition may have a greater influence on surface active properties than had been heretofore recognized. Presented the AOCS Meeting in Houston, Texas, 1965.     

Surface properties of linear alkyl benzene sulfonates in hard river water

Surface properties of a series of highly purified linear alkyl benzene sulfonates were extensively studied in hard river water. The effects of water hardness, alkyl chain length and position of the phenyl sulfonate group in the molecule on such surface properties as pC₂₀, critical micelle concentration (CMC), γ_CMC, CMC/C₂₀ ratio, and minimum area per molecule at the interface are discussed in detail. The position of phenyl sulfonate group in the molecule was found to have a pronounced effect on the CMC, γ_CMC value, CMC/C₂₀ ratio, and, to the contrary, a relatively small effect on the pC₂₀ value. The linear relationship between pC₂₀ or-log CMC, and m, the number of carbon atoms in the alkyl chain, was found for surfactants with the phenyl sulfonate group either at the terminal position or at the more central position in the molecule. γ_CMC decreases but the CMC value increases, when the position of phenyl sulfonate group moves from the terminal toward a more central position of the molecule, reflecting the “Hartley Effect” resulting from the branched alkyl chain.     

计算脂肪醇沸点的新方法

直接从脂肪醇的分子结构提取4个结构参数:烷基的极化效应指数PEI、碳原子数目Nc、羟基所连接碳原子上的氢原子个数α-H和羟基与支链相对位置差ΔN,与118种脂肪醇的沸点进行相关分析,得到相关模型方程。运用留一法确证模型方程具有较好的稳定性和预测能力。方程所选用的参数计算简单,物理意义明确,能够被广泛使用。