Sulfonate-carboxylate systems

Mixed Carboxylate-Sulfonate Systems. Decanolc and octanoic acids were selected as carboxylic acids in view of their intermediate chain lengths. Some initial experiments using a short-chain carboxylic acid (isobutyric acid) were not very promising, apparently because only a fraction of the acid would partition to the drop surface. 

Proton acids can be used as catalysts when the reagent is a carboxylic acid. The mixed carboxylic sulfonic anhydrides RCOOSO2CF3 are extremely reactive acylating agents and can smoothly acylate benzene without a catalyst.265 With active substrates (e.g., aryl ethers, fused-ring systems, thiophenes), Friedel-Crafts acylation can be carried out with very small amounts of catalyst, often just a trace, or even sometimes with no catalyst at all. Ferric chloride, iodine, zinc chloride, and iron are the most common catalysts when the reactions is carried out in this manner.266... 

Chemically, the triarylmethane dyes are monomethine dyes with three terminal aryl systems of wind] one or more arc substituted with primary, secondary, or tertiary amino groups or hydroxyl groups in the para position to the methine carbon atom. Additional substituents such as carboxyl, sulfonic acid, halogen, alkyl, and alkoxy groups may be present on the aromatic rings. The number, nature, and position of these substituents determine both the hue or color of the dye and the application class to which the dye belongs. 

A number of experimental techniques by measurements of physical properties (interfacial tension, surface tension, osmotic pressure, conductivity, density change) applicable in aqueous systems suffer frequently from insufficient sensitivity at low CMC values in hydrocarbon solvents. Some surfactants in hydrocarbon solvents do not give an identifiable CMC the conventional properties of the hydrocarbon solvent solutions of surfactant compounds can be interpreted as a continuous aggregation from which the apparent aggregation number can be calculated. Other, quite successful, techniques (light scattering, solubilization, fluorescence indicator) were applied to a number of CMCs, e.g., alkylammonium salts, carboxylates, sulfonates and sodium bis(2-ethylhexyl)succinate (AOT) in hydrocarbon solvents, see Table 3.1 (Eicke, 1980 Kertes, 1977 Kertes and Gutman, 1976 Luisi and Straub, 1984 Preston, 1948). 

The effects of pH on microemulsions have been Investigated by Qutubuddin et al. (4,5) who have reported a model pH-dependent microemulsion using oleic acid and 2-pentanol. It has been shown that the effect of salinity on phase behavior can be counterbalanced by pH adjustment under appropriate conditions. Added electrolyte makes the surfactant system hydrophobic while an increase in pH can make it hydrophilic by ionizing more surfactant. Based on the phase behavior of pH-dependent systems, a novel concept of counterbalancing salinity effects with pH is being proposed. The proposed scheme for reducing the sensitivity of ultralow interfacial tension (IFT) to salinity is to add some carboxylate or similar surfactant to a sulfonate system, and adjust the pH. The pK and the concentration of the added surfactant are variables that may be... 

The molar ratio of cosurfactant to active sulfonate is 5.8 for 5 gm/dl TRS 10-410 - 3 gm/dl IBA mixture. The molar ratio of deca-noic acid to active sulfonate was chosen to be 1.67. A sufficient amount of IBA was added to the aqueous solution to keep the molar ratio of IBA to total surfactant (carboxylate plus sulfonate) the same as in the carboxylate-free system. Smaller amounts of cosurfactant resulted in unfavorable precipitation. Based on the aqueous phase, the final composition was 5 gm/dl TRS 10-410, 8 gm/dl IBA and 2 gm/dl decanolc acid. The salinity was varied between 0.8 and 8 gm/dl NaCl for this surfactant composition. 

Effect of Temperature on the Solution Behavior of Carhoxylate and Sulfonate lonomers. Based on the results above, a substantial difference in the solution behavior of carhoxylate and sulfonate ionomers might be expected as a function of temperature. Figure 10 illustrates the effect of temperature on the solution viscosity of carboxylated and sulfonated ionomers at very low sulfonate and carhoxylate content. At low polymer concentrations it is seen that the sulfonate system manifests a higher viscosity level in 1% hexanol/xylene solution. This is consistent with the dilute solution viscosity behavior. More importantly, at high polymer concentrations it is seen from Figure 10 that the 5% S-PS curve actually goes through a maximum, while the carhoxylate system decreases mono-tonically. These results are apparently attributable to the weaker ionic association in the carhoxylate case as compared to the sulfonate system. 

Sulfur in oxidation state IV can be used to produce a variety of anionic snUbnates, as depicted in Scheme 1.5. Sodium bisulfite can be used to prepare sulfonates of a,b-unsaturated acids and esters, such as those prepared from maleic anhydride. The mechanism involves Michael addition to the activated double bond by the more nucleophilic sulfur atom, and is conducted in an aqueous two-phase system where, for example, a maleate half acid ester or diester is dispersed and heated under narrowly controlled pH conditions to minimize ester hydrolysis and avoid competitive hydroxide addition to the double bond. The resulting classes of surfactants include sulfosuccinates (which are in fact carboxylate sulfonate disalt surfactants) prepared from the maleic half acid esters of fatty alcohols or alcohol ethoxylates. Diesters of maleic are sulfonated by the same type of process to produce surfactants such as the ubiquitous dioctyl sulfosuccinate (DOSS) from the diester of 2-ethylhexyl alcohol and maleic anhydride. 

These reactions are carried out in aqueous/organic two-phase solvent systems with one of the reagents in an alkali metal salt form. Some examples of the anionic nucleophilic reagents (Y) are hydroxides, halides, cyanides, sulfides, cyanamides, carboxylates, sulfonates, and so forth. In fact, one of the most studied PEG phase transfer catalyzed reaction is the formation of carboxylate esters, such as acetates [159,1601. 

Chem. Descrip. Carboxylate/sulfonate/nonionic functional terpolymer Uses Scale inhibitor, dispersant for cooling water systems dispersant for CaCOj, calcium sulfate, calcium phosphate, and clay iron oxide and zinc stabilizer sludge conditioner for boiler water treatment in refinery plants, chem. plants, drilling oil, steel mills, etc. 

ACID DYES Commercial acid dyes contain one or more sulfonate groups, thereby providing solubility in aqueous media. These dyes are apphed in the presence of organic or mineral acids (pH 2—6). Such acids protonate any available cationic sites on the fiber, thereby making possible bonding between the fiber and the anionic dye molecule. Wool, an animal fiber, is an amphoteric coUoid, possessing both basic and acidic properties because of the amino and carboxylic groups of the protein stmcture. In order to dye such a system, coulombic interactions between the dye molecule and the fiber must take place ie, H2N" -wool-COO + H2N" -wool-COOH. The term acid dye is appHed to those that are capable of such interactions. Acid dyes... 

Ci2-Ci3 ether carboxylic acid with 4.5-6 mol EO and Ci2-C15 ether carboxylic acid with 9 mol EO as cosurfactant improve the use of alkyl-o-xylene-sulfonate as primary surfactant at different salinity while maintaining good oil solubilization [189]. It is possible to optimize the surfactant system in relation to the crude oil reservoir characteristics. 

Results described in the literature have resulted in several patents, such as one for the improvement of the transport of viscous crude oil by microemulsions based on ether carboxylates [195], or combination with ether sulfate and nonionics [196], or several anionics, amphoterics, and nonionics [197] increased oil recovery with ether carboxylates and ethersulfonates [198] increased inversion temperature of the emulsion above the reservoir temperature by ether carboxylates [199], or systems based on ether carboxylate and sulfonate [200] or polyglucosylsorbitol fatty acid ester [201] and eventually cosolvents which are not susceptible for temperature changes. Ether carboxylates also show an improvement when used in a C02 drive process [202] or at recovery by steam flooding [203]. 

The reaction of alcohols with CO was catalyzed by Pd compounds, iodides and/or bromides, and amides (or thioamides). Thus, MeOH was carbonylated in the presence of Pd acetate, NiCl2, tV-methylpyrrolidone, Mel, and Lil to give HOAc. AcOH is prepared by the reaction of MeOH with CO in the presence of a catalyst system comprising a Pd compound, an ionic Br or I compound other than HBr or HI, a sulfone or sulfoxide, and, in some cases, a Ni compound and a phosphine oxide or a phosphinic acid.60 Palladium(II) salts catalyze the carbonylation of methyl iodide in methanol to methyl acetate in the presence of an excess of iodide, even without amine or phosphine co-ligands platinum(II) salts are less effective.61 A novel Pd11 complex (13) is a highly efficient catalyst for the carbonylation of organic alcohols and alkenes to carboxylic acids/esters.62... 

Most studies of micellar systems have been carried out on synthetic surfactants where the polar or ionic head group may be cationic, e.g. an ammonium or pyridinium ion, anionic, e.g. a carboxylate, sulfate or sulfonate ion, non-ionic, e.g. hydroxy-compound, or zwitterionic, e.g. an amine oxide or a carboxylate or sulfonate betaine. Surfactants are often given trivial or trade names, and abbreviations based on either trivial or systematic names are freely used (Fendler and Fendler, 1975). Many commercial surfactants are mixtures so that purity can be a major problem. In addition, some surfactants, e.g. monoalkyl sulfates, decompose slowly in aqueous solution. Some examples of surfactants are given in Table 1, together with values of the critical micelle concentration, cmc. This is the surfactant concentration at the onset of micellization (Mukerjee and Mysels, 1970) and can therefore be taken to be the maximum concentration of monomeric surfactant in a solution (Menger and Portnoy, 1967). Its value is related to the change of free energy on micellization (Fendler and Fendler, 1975 Lindman and Wennerstrom, 1980). 

---