There are reports on the decomposition of peroxides from fats and esters of common fatty acids, but few papers reported on that of peroxides from esters of highly unsaturated acids. Methyl esters of highly unsaturated acids (saponification value, 172.0; iodine value, 350.9) from cuttlefish oil were oxidized by blowing dried air at 35°C in the scattered sunlight to obtain peroxides with peroxide value (m eq./kg) at 3.00 × 103. This product was decomposed under the conditions of adding no substances, iron soap, or copper soap in the nitrogen atmosphere in the dark, at 35°C. Peroxide value, and ultraviolet and infrared spectra showed that the accelerating effect on the decomposition of peroxides by iron and copper soaps did not appear when the peroxide value was high, but the effect appeared after decompositions considerably performed. As the peroxide value decreased, the amount of conjugated diene decreased, and conjugated triene and higher did not appear in any case. As peroxides decomposed, the-OOH group changed into the-OH group, the α-methylene groups decreased, the formation of aldehydes increased, and the numbers of cis nonconjugated forms did not vary so much. Every effect becomes generally most remarkable, if copper soap is added. The numbers of the double bonds did not increase or decrease prominently.
Reports on the separation of polymers obtained from autoxidized fats and esters of usual fatty acids have been published, but there are probably no papers on polymers obtained from autoxidized esters of highly unsaturated acids. Methyl esters of highly unsaturated acids (saponification value : 177.3, iodine value : 322.5) from cuttlefish oil were oxidized by blowing dried air at 35°C in the scattered sunlight to prepare the product with peroxide value (m eq./kg) of 2.73 ×103. This was extracted by a mixed solvent, n-hexane and diethyl ether, and separated into 15 fractions by increasing the mixing ratio of diethyl ether from 0 to 75%. The extracted fractions, 3 (I), 11 (II), and 13 (III) correspond to monomer, dimer, and trimer and for which the ultraviolet and infrared absorption spectra were determined. (I), (II), and (III) contained considerable conjugated dienes, and no conjugated triene or higher. These products had the absorption band arising from the-OOH group in which high-frequency shifts were slightly seen. In this case the scission products, such as aldehydes, may be produced. Trans-trans conjugated diene presents in (II) and (III). The absorption band of cis nonconjugated forms decreasases in (II) and (III).
In batchwise rectification of linseed oil fatty acids, yields of the distillate were observed to lower as the pressure increased. Fatty acid of high N.V. was obtained by acidifying after saponification of the rectification residue, and about 60% of the distillate was recovered by redistillation. In vacuum heating under reflux condition of fatty acids, depression rates of N.V. were observed to become greater as the pressure or temperature rose, where by the rate is much greater in linseed oil fatty acids than in stearic acid. The lesser loss of both S.V. and I.V. in this case meant the formation of fatty acid anhydrides.caused by the dehydration of carboxyl groups. Furthermore, following results were obtained by introducing various gases into linseed fatty acids under aforesaid conditions. The depression rates of N.V. were about the same among nitrogen, air and little amount of steam. On the other hand, using much more steam showed tendency of decreasing loss in N.V. and the loss became lesser under no agitating condition.
The components of the volatile decomposition products of soybean oil by thermal oxidation were studied at different stages of deterioration. Soybean oil was previously heated at 240°C for 2, 4, 6 and 10 hr, respectively, and was differentiated according to changes in their chemical properties or degree in deterioration. The Soybean oils thus differentiated were then heated at 240°C under stream of air for 1 hr, and the volatile decomposition products coming therefrom were collected in two traps cooled by ice-water and dryiceacetone for identification by gas chromatography. The gas-chromatograms showed that these decomposition products consist of many sorts of aldehydes and hydrocarbons, and that there were slight differences in the quantitative proportions of these compounds given off from soybean oils according with the varying degrees in deterioration. The contents of olefinic hydrocarbons and C4, C5, C6 aldehydes increased and pentane decreased in the volatile products from soybean oil at an advanced stage of thermal oxidation. It seemed that the differences in the quantitative proportions of the volatile products from soybean oils at different stages of thermal oxidation were related differences in the contents of linoleic and linolenic acids in these oils.
Authors investigated to find the relations between the foaming tendencies and the chemical properties of soybean oil used for deep fat frying. Soybean oil was heated at 200°C for 10 hr and the changes in their chemical properties such as acid value, peroxide value, iodine value, carbonyl value, hydroxyl value and epoxyl value were determined. Also, the contents of dimer and secondary product fractions in fatty acids obtained from the soybean oil at the different stages of thermal oxidation were measured by using silica-gel column chromatography. To observe the foaming tendencies, water soaked pieces of filter paper were used. The above experiments indicated that the foaming tendencies of oil were much related to the content of polar fraction as the degree of polymerization. Chemical properties and thin layer chromatogram of polar fractions obtained from fatty acids of foaming oil showed that these polar fractions contain polyhydroxyl acids and especially much dihydroxyl acids.
Quaternary ammonium salts, C12H25N+ (CH3)2C2H4OH, A- containing various anion ; i.e., F-, Cl-, Br-, I-, 1/2 SO4--, ClO4-, H2PO4, NO3-, CH3 COO-, CCl3COO-, C11H23COO-, 1/2 (COO-) 2, _??_-COO- and CH3-_??_-SO3- and quaternary ammonium chloride having various chemical constitutions were synthesized by the reaction of corresponding amine salts with ethylene oxide. Their foaming, dispersion and bacteria-static properties were tested. The foaming properties were affected little by cationic parts, but affected more by anions, and quaternary ammonium perchlorate, benzoate and paratoluenesulfonate were superior to others. Quaternary ammonium salts containing_??_-COO- and CH3-_??_-SO3-as anion and benzene and ether-linkage in cationic parts such as C8H17-_??_-OC2H4OC2H4N+ (CH3)2 C2H4OH, Cl- showed good dispersion properties. The bacteria-static properties were affected little by the kinds of anions as constitution of cationic parts.