Seventeen kinds of synthetic surfactants were chromatographed by silica-coated plate and thin-layer chromatograph was proved as a useful method for the analysis of surfactants. Chloroform-methanol-water system was selected for developing. The surfactants gave sharp spots when free components were developed but not for the salts. Anionic surfactants gave peculiar fluorescence by ultraviolet light after spraying of sulfuric acid and heating. α-Sulfo-fatty acid was separated from other sulfonic acids and sulfates. Polyoxyethylene surfactants were separated into major components and polyethylene oxide. Cationic surfactants were detected by Dragendorff reagent and platinum chloride-potassium iodide reagent. These procedures are useful to detect impurities in synthetic surfactants and to check progress of the reaction in the manufacturing process.
Utilization of saturated higher fatty alcohols having more than eighteen carbon atoms is a very important project for fatty oil industry as well as petrochemical industry. Because higher fatty alcohols are produced during Ziegler Process. The reactions between lower alcohol and amines or ammonia are familiar, but the reactions of higher alcohols are very fewly known. Authors attempted to synthesized fatty amines from higher alcohols and lower amines. The reactions were carried out in autoclaves using Cu-Cr-O catalyst. Initial hydrogen pressure at about 15kg/cm2 gave good effects for the reaction. 58% methylstearylamine, 24% dimethylstearylamine and 13% distearylmethylamine were obtained after the reaction between stearyl alcohol and methylamine at 300°C.
Condensation product of oleyl alcohol with paraformaldehyde in acetic acid at the presence of sulfuric acid as the catalyst, were saponified and then fractionated by chromatography and recrystalization and the following substance was obtained. The substance, mp 9394°C, seemed to have tetrahydropyranol-4 structure because of its characteristics (Fig.-3, Table-1) and it was considered as 3-heptyl-4-hydroxy-5-hydroxyoctyltetrahydropyrane (or 3-octyl-4-hydroxy-5-hydroxyheptyltetrahydropyrane). As the catalyst, perchloric acid was most effective and sulfuric acid was also fairly effective (Fig. 1).
Authors observed that the color reversion is very slight in refined and deodorized soybean oil extracted with normal hexane from the 1963 crop of Illinois soybeans. The cause for this may be attributed to a low moisture content of 9.77% (crushed to pass 700 micron sieve and dried to constant weight at 90°C, 30mmHg) of the 1963 crop soybeans which had experienced a draught in the growing and harvesting season. When the 1963 crop soybeans with a low moisture content of 9.77% is moistend with water to a moisture level of 13.814.0% before extraction, the color reversion becomes conspicuous. On the contrary, in case domestic soybeans with a high moisture content of 13.8% is dehydrated down to a level of 10.110.3% before extraction, the maximum value of color reversion falls considerably. Further, we have confirmed that the moisture content of soybeans in the process of cracking and grinding is a more affecting factor for the color reversion of refined and deodorized soybean oil than that in the process of extraction.
The aqueous citric acid solution was added into the vegetable oils (cotton seed oil, soya-been oil) and heated to 180°240°C, and analysed by paper-chromatography with chloroform-acetic acid-water solvent (volume ratio 30 : 15 : 1.2). Authors confirmed that citric acid is decomposed to citraconic anhydride through aconitic and itaconic acids by heating at 180°C for 30min. At 240°C, citric acid was disappeared after 10min heating and only small quantity of citraconic anhydride was detected after 30min heating. No citric acid was detected after 30min heating at the condition of deodorization for oil purification (210°C, 23mmHg, steam blowing). The stabilities were tested by A.O.M. for the oil added with citric acid before and after the deodorization. The A.O.M. stability was higher for the oil added the acid after the deodorization, and when it is added before, it is necessary to restrict the duration time of the deodorization within 30min because citraconic anhydride formed by the decomposition has no antioxidant effect.
Author contemplated to survey the change of carbonyls occurring in the soybean oil at the frying temperature (190°C). The column and thin layer chromatographic methods were employed for separation and identification of the carbonyls. I. The results of frying test were : 1) Before the TSUKARE (weariness of oil) appeared, the major portions of carbonyls were C4, C6 and C10C12 and when the TSUKARE developed, C3, C5 and C7 appeared in the oil. But these mono-carbonyls constituted only 2030% of the total and the remainder were higher carbonyls formed inside glyceride (or polymerized glyceride). 2) At the earlier stage of oxidation, the amount of staturated carbonyls was significantly larger than the unsaturated, but as oxidation developed, the unsaturated content increased in the oil according with progress. II. The results of aeration test were : 1) With the progress of oxidation, the unsaturated carbonyls (C3C7) increased in both scattered out of the oil and remained in the oil. But there seemed that the saturated were enriched in the former and the unsaturated condensed in the latter. 2) The scattered carbonyls consisted of 1623% of the total, and considerable amount of volatile carbonyls (2028%) was detected in the oil. 3) As to the oxidation mechanism for the formation of carbonyl group at the frying temperature, it could be conceived that the carbonyl formation inside the oxidative glyceride is unremittingly competing with the fission reaction of carbon to carbon bond in the oil, and with increase in the TSUKARE, the fission occurres more frequently than the carbonyl-glyceride formation.
In order to make statistical analysis of the melting point of fats in margarine and shortening products in Japan, melting point of products was measured monthly on 18 kinds of household margarine, 14 kinds of bakery margarine, and 14 kinds of shortening. Mean value (x), maximum and minimum values, range (R), and yearly standard deviation (σ) were calculated and these values were found to be the highest in shortening, followed in the order of bakery and household margarines, the values being x 35.55°C, 34.55°C, 33.52°C, R 12.45, 11.24, 10.24°C, and σ 4.13, 3.77, 3.29, respectively. Some of the household margarines, showed hardly any difference in the melting point throughout the year. Salt content, saponification value, iodine value, and thiocyanate value were measured as being responsible for the maximum and minimum values of the melting point, and examinations were also made on the correlation between the melting point and iodine value, linolic acid, and saturated acid.