Safflower oil was heated in the presence of 5, 2.5, and 1wt% of magnesium iodide at 220, 200, 180, 160, and 140°C. The fatty acid compositions of reaction products were determined by means of GLC and UV methods. Isomerization proceeded extensively at high tempreature and with high catalyst concentration. The amount of conjugated diene formed reached the miximum and then decreased. On the same time, a large amount of substance which has the same retention time as methyl oleate formed. The maximum amount of the substance was 52.3% at 160°C for 4hr with 5% magnesium iodide. As the results of GLC, GC-MS, and oxidative ozonolysis, the substance is a mixture of positional isomers of octadecenoic acid of which double bonds are mainly trans form. The components formed by side reactions such as decomposition, polymerization, and so on, were analyzed by means of GC-MS method. The results show the presence of 9- (o-propyl phenyl) nonanoic acid, 8-phenyl octanoic acid, alkyl iodides, alkyl bezenes, and n-alkanes. The similarity of the substances formed in the thermal reaction with magnesium iodides to those with iodine reported in our former work suggests that free iodine liberated from magnesium iodide in the thermal reaction will play mainly role of catalyst.
Lard contaminated with fish oil (final concentration 40%) was heated at 180°C under the condition of specific surface area 0.132cm2/g, and the effect of tocopherol on its thermal deterioration was studied. Thermal deterioration of the contaminated lard was retarded by the addition of tocopherol at high concentration. During the course of thermal deterioration, highly unsaturated fatty acids decomposed rapidly, and the thermal decomposition was suppressed to some extent by the addition of tocopherol at high concentration. When tocopherol was added to fresh lard at the concentration of 0.04%, high stability of the lard in autoxidation was found, but the heated lard (180°C, 16 hours) reached maximum stability by the addition of tocopherol at the concentration of 0.4%. On the other hand, the stability of the contaminated lard did not increase by the addition of tocopherol. In the course of thermal treatment, tocopherol in the contaminated lard decomposed more slowly than that in fresh lard. The higher the initial concentration of tocopherol became, the larger grew its amount remaining in lard after heating.
Determination of long chain quaternary ammonium salts in the mixtures of cationic and nonionic surfactants was attempted. The quaternary ammonium salt reacted with potassium dichromate in an aqueous solution to give a precipitate composed of 2 mole quaternary ammonium and 1 mole dichromate ion. The precipitate, separated by filteration, was dissolved in methanol and the absorbance of the methanol solution was measured at 355mμ. Sufficient results were obtained for the determination of all used cationic surfactants-lauryl-, cetyl-, stearyl-trimethylammonium chlorides, myristyl-, cetyl-benzyldimethylammonium chlorides, lauryl-, and cetyl-pyridinium chlorides. The cationic surfactants could be determined in the presence of a large amount of polyethylene glycols (molecular weights (6008000)). The determination was not disturbed by the additions of non-ionic surfactants and inorganic salts until ten times as large in quantity as the cationic surfactant.
Removal of sodium dodecylbenzene sulfonate (DBS) with Fenton's reagent was done in not too much dilute solution. It was observed that DBS was removed mainly by adsorption on ferric hydroxide floc at relatively higher concentration of ferrous salt, but oxidative decomposition of DBS was dominant at lower concentration of ferrous salt. When the pH after reaction was about 3, DBS was removed most effectively. Further, heat of reaction between DBS and Fenton's reagent was measured in dilute solution by using a microcalorimeter, and also heat of reaction of ferrous sulfate with hydrogen peroxide was measured by the same method. Effect of pH on the heat of reaction was remarkable for the former reaction, and heat evolved was maximum at the optimum pH for removal of DBS. Also for the latter reaction, dependence of pH on the heat of reaction was pronounced and heat of reaction increased with decrease in pH. Generally, the pH dropped as reaction proceeded. For the former reaction, however, abnormally higher value of pH was observed in the optimum pH range for evolution of heat, and it was found that maximum rise of pH measured in the above range, maximum heat of reaction, and minimum hour required to get to the peak of curve for calorie evolved were realized when the almost same initial pH was used. Concerning the above two reactions, the effect of pH on the heat of reaction and the change of pH at elapse of reaction etc. were discussed.
An attempt has been made to prepare surfactants containing oxazoline ring such as 2-alkyl-2-oxazoline organic salt and N-alkyl-4, 4-dimethyl-2-oxazolinium bromide. 2-Alkyl-2-oxazoline was formed by the ring closure of N-β-chloroethyl fatty amide made by condensing a fatty acid (C10-C14) with etanolamine followed by chlorination and 4, 4-dimethyl-2-oxazoline was prepared from formic acid and 2-amino-2-methyl-1-propanol. From the experimental results it was found rhat the organic salts of oxazoline were generally superior in surface tension lowering ability and wetting power, but inferior in foaming power and emulsifying power to the oxazolinium salts.
The effect of ethylene glycol (E.G.) on solubilization of water in perchloroethylene of Aerosol OT was investigated. The amount of solubilization was determined by means of turbidity. The main results obtained were as follows : 1) By adding E.G. in water, the maximum amount of solubilization increased linearly with increase of the concentration of the surfactant as well as in case of water. 2) The maximum amount of solubilization of E.G.-water system increased with increase of the amount of E.G. in water.
The processors of oil and fat are in need of a quick determination method of iodine value of oils and fats especially in case of checking the degree of unsaturation of them in the hydrogenation process. Hoffman and Green modified the Wijs' method by employing mercuric acetate as catalyst and made it possible to determine the iodine value of a sample in ten minutes or so. Mercuric acetate, however, cannot be empolyed now because the reaction solution is hard to meet the regulation of water pollution and its disposal has become difficult. Authors have investigated other methods of quick determination of iodine value especially for the oils in the hydrogenation process and have found after all the Wijs' method could be appropriate by only shortening the reaction time to three minutes for the oils of the iodine value less than about 100. This quick Wijs' method gives almost equivalent value of Hoffman's although it tends to give less value than that of the Wijs' method.
A testing method for biodegradability of nonionic surfactant has recently been legislated by Japanese Industrial Standards Committee. As the method is, however, concerned only with the disappearance of surface activities, a comparison of results of several kinds of tests is preferred in oder to evaluate the complete degradability. As a part of the evaluation work the authors conducted river die-away tests of some commercial nonionic surfactants using the river water taken from the upper, the middle and the lower reaches of Tama River, in which biodegradabilities were followed by three analytical methods, i.e. (A) foam, (B) CTAS and (C) COD (Cr). It was found that nonylphenol ethoxylate was not degraded at all in clean water of the upper reaches and was degraded slowly in highly polluted water of the middle or lower reaches as compared with primary or secondary alcohol ethoxylate. In view of COD (Cr), only a part corresponding to the ethoxyl chain of nonylphenol ethoxylate was seemed to be degraded even in the water of the lower reaches, while alcohol ethoxylates were seemed to be degraded completely in all cases.
The reaction of benzene with 5-oxo-6-methyl-1-heptene (II) in the presence of aluminium trichloride gave 2-methyl-6-phenyl-3-heptanone (IV) in yield of 40%. Similarly, sesquiterpene-like compounds were prepared from various aromatic hydrocarbons and the compound (II).
A gas chromatography of the wax esters in sperm whale head oil on APOLAR 10C column has characterized them according to their carbon number and number of double bonds. The analytical results obtained by the new technique were confirmed by comparison with those obtained by GC using the nonpolar column OV-17.