Waldo C. Ault

Spectrophotometric determination of small proportions of polyunsaturated constituents in fatty materials

SummaryExisting ultraviolet spectrophotometric methods have been modified for application primarily to the detection and estimation of low proportions of conjugated and nonconjugated unsaturated constituents in fats, oils, and soaps. The method is applicable also to fatty materials having high proportions of these constituents.Modifications include corrections for absorption by interfering substances, use of alkaline glycerol as an isomerization medium in the analytical procedure, and correction of absorption data on the isomerized product for absorption by conjugated constituents in the material before isomerization.The presence of small proportions of highly unsaturated conjugated and nonconjugated compounds is established in lards, tallows, tallow soaps, and highly purified esters and acids. Tall oil fatty acids are shown to contain approximately 10% of conjugated diene acids and a small amount of linolenic acid.

Fractionation of lard and tallow by systematic crystallization

SummaryLard and edible tallow were subjected to a series of fractional crystallizations from acetone at temperatures from 20° to -45°C. Six recrystallized precipitate fractions and a filtrate residue were obtained from each fat. In addition to determining the more common physical and chemical characteristics, fatty acid composition of each fraction was calculated from spectrophotometric data, iodine value, and thiocyanogen value. The consistent results obtained throughout by the spectrophotometric method of fatty acid analysis lend further confirmation to the reliability of this method for composition studies of natural fats. The approximate amounts of tri-saturated, di-saturated, mono-saturated, and tri-unsaturated glycerides of the lard and tallow were estimated from the analysis of each fraction on the assumption that not more than two of these classes of glycerides were present in any one fraction. The tallow contains much higher proportions of tri-saturated and di-saturated glycerides and correspondingly lower proportions of the mono-saturated and tri-unsaturated glycerides than does lard. The amount of tri-unsaturated glycerides in lard was found to be significantly greater than meager information in the literature would indicate. The data indicate that the general pattern of glyceride formation in animals such as the pig and cow is probably of random character.

Sodium salts of alkyl esters ofa-sulfo fatty acids. Wetting, lime soap dispersion, and related properties

A series of esters of the general formula RCH(SO3Na)-CO2R′ of 14–19 carbon atoms prepared by the α-sulfonation of propionic, butyric, pelargonic, lauric, myristic, palmitie, and stearic acids and esterification with normal primary alcohols were compared for critical micelle concentration, surface and interfacial tension, Ca++ stability, wetting properties, foam height, detergency, and lime soap dispersing properties. Comparison of position isomers showed that as the hydrophilic portion moved from the center toward either end, cmc and wetting efficiency decreased, surface and interfacial tension increased, and Ca++ stability and lime soap dispersing properties improved.A coconut oil fatty acid forerun sulfonated with SO3 vapor and esterified with 2-ethylhexanol gave a product with useful wetting properties in soft and hard water.

Fatty acid monoesters of l-ascorbic and d-isoascorbic acids as antioxidants for fats and oils

Summary1. The fatty acid monoesters of l-ascorbic and d-isoascorbic acids have been tested for antioxygenic activity in different fats and oils under various conditions and in combination with other inhibitors.2. Traces of soap were found to have a deleterious effect on the stability of fats. This deleterious effect can be counteracted by the use of fat-soluble ascorbyl monoesters.3. The ascorbyl monoesters used in combination with either α-tocopherol or phospholipids, or both, show a marked synergistic antioxidant effect.4. Possible explanations are given for certain synergistic phenomena that have been observed.

Urethane foams from animal fats. IV. Rigid foams from epoxidized glycerides

Liquid polyols have been prepared from epoxidized glyceryl trioleate, glyceryl monooleate, lard oil, neatsfoot oil, and soybean oil by hydration with 24% fluoboric acid. Upon adjustment of the equivalent weight to 100 with triisopropanolamine, the polyols were foamed by reaction with a prepolymer made from oxypropylated sorbitol and tolylene diisocyanate. The resulting rigid foams had densities between 1.66 and 2.34 lbs/ft3 and compressive strengths ranging from 23 to 39 psi (10% compression).The same polyols were used in one-step systems with PAPI as the isocyanate. In general, foam properties were comparable with those obtained from the prepolymer systems.

Further studies on methanesulfonic acid catalyzed additions to oleic acid

Infrared study of the products of the addition of m-cresol to oleic acid in methanesulfonic acid, revealed the presence of both the m-creasoxy and hydroxytolyl substituted stearic acids. By employing a modified extractive procedure to recover the products of the reaction, followed by chromatography on a Florisil column, a separation of the two types of addition products was effected.The methanesulfonic acid catalyzed addition reaction was extended to include aryl thiols. Among the sulfur analogues of the previously used phenols that were added are: benzenethiol, p-t-butyl-benzenthiol, 2-naphthalenethiol, o-, m-, and p-toluenethiol. The yields of addition products (which were unobtainable in sulfuric acid media) ranged from 37–70%. In contrast with the results obtained when phenolic nuleophiles were employed no evidence for the formation of rearranged addition products has been found. Thioethers were the only products identified.

Sodium alkyl α-sulfopelargonates, C7H15CH(SO3Na)CO2R. Wetting and related properties

A series of sodium alkyl α-sulfopelargonates prepared from sodium α-sulfopelargonic acid and alcohols of from 2 to 12 carbon atoms were examined for surface active properties. Esters with the hydrophilic portion in the middle of the molecule, as in sodium hexyl, heptyl octyl, capryl (or 2-octyl) and 2-ethylhexyl α-sulfopelargonate were very efficient wetting agents with good foaming properties and a c.m.c. of from 2 to 7 millimoles per liter. The presence of the α-sulfo group inhibits hydrolysis of the ester linkage, apparently by steric hindrance. Sodium capryl α-sulfopelargonate, an ester of a secondary alcohol, was particularly stable to acid and alkaline hydrolysis. The esters are easily soluble in water, organic solvents and mineral oil.

The a-sulfonation of pelargonic, stearic, and substituted stearic acids

Direct sulfonation of higher fatty acids with sulfur trioxide or chlorosulfonic acid, without use of solvent, is possible, but the product must then be isolated as the sodium salt. Use of a chlorinated solvent permits isolation of the α-sulfo acid. Sulfonation with dioxane sulfur trioxide in place of sulfur trioxide gave a nearly colorless α-sulfostearic acid.Substituted stearic acids derived from oleic or elaidic acids (phenyl-, 9,10-dichloro-, and 9,10-dihydroxystearic acids) were α-sulfonated with dioxane sulfur trioxide. Solubility, detergent, and surface-active properties were examined and related to structure.The surface-active properties of sodium α-sulfopelargonic acid are not very evident, but the octyl ester, with a much lower critical micelle concentration (0.08% compared to 1.00%), was found to be a very efficient wetting agent.

Arylstearic acids from oleic acid. Variables affecting the yield and properties

SummaryTwenty-six aromatic compounds were compared in the synthesis of arylstearic acids from oleic acid by the Friedel and Crafts reaction. Xylylstearic acid was the arylstearic acid obtained in the highest yield (92.4%) from technical m-xylene and commerical oleic acid. The various side reactions are disussed including the possible conversion of oleic acid into products which on vacuum distillation of the crude arylstearic acid appear as a forerun and as a still residue. Oleic acid of about 98% purity did not improve the yield but resulted in nearly colorless, rather than yellow viscous oils.Crystalline arylstearic acids have for first time been isolated from the reaction products but only in small yields.

URETHANE FOAMS FROM ANIMAL FATS. I. OXYETHYLATED 9, 10-DIHYDROXYSTEARIC ACID.

Threo- anderythro-9,10-dihydroxystearic acids were reacted with 2, 4, 6 and 8 moles of ethylene oxide. The oxyethylated polyols from thethreo acid, adjusted to equivalent weight 100 with triisopropanolamine, were converted to satisfactory rigid foams by mixing with corresponding amts of isocyanate-terminated oxypropylated sorbitol prepolymers of three viscosities. Typical foam properties had maxima for the tetra- or hexaoxyethylene polyol, and most properties paralleled prepolymer viscosity.