1. Soybean oils, having the peroxide value of 10 and 290 respectively, were heated at 250°C under a stream of nitrogen. Volatile substances coming therefrom were caught in a trap cooled by dry ice-acetone, and then identified by gas chromatography. There were very little decomposition products from the soybean oil of the peroxide value of 10, most of which was hydrocarbons, contaminated with a small amount of carbonyls. As for the hydrocarbons, contents of olefins were higher than saturated hydrocarbons. In the case of the soybean oil of the peroxide value of 290, decomposition occurred mostly at an earlier stage of heating. The amount of decomposition products was much higher than that of the soybean oil of lower peroxide value. The gas chromatogram of the decomposition products at an earlier stage of heating was similar to that of thermal oxidation, and had large peaks due to n-pentane, propionic aldehyde and capronic aldehyde. The gas chromatogram of the decomposition products of the higher peroxide value soybean oil at later stage of heating was similar to that of the lower peroxide value soybean oil. 2. Volatile substances produced by heating safflower oil and olive oil in a stream of air at 250°C were identified by gas chromatography. As a result, some sorts of hydrocarbons and carbonyls were found in these volatile products, and their quantitative proportions were found to differ in accordance with the kind and quantity of fatty acids composing these oils-safflower, olive and soybean oil. 3. The quantitative proportions of these compounds in the volatile decomposition products obtained from these vegetable oils by heating at 250°C suggest that the decomposition of vegetable oil by heating at such high temperatures as 250°C is accompanied firstly by the formation of hydroperoxides and then followed by their cleavages on either side of the carbon atom containing the hydroperoxide group.
Decompositon products obtained from methyl oleate by heating in a stream of air at 200°C were indentified mainly by gas chromatography. Volatile decomposition products were collected in two traps cooled by ice-water and dry ice-acetone, respectively. Decomposition products remaining in methyl oleate were separated with 1N-Na2CO3 and Girard-T reagent into various fractions on the basis of their reactivities. Each fraction thus obtained was gas-chromatographed by using silicon grease or glycol succinate column. The results showed that major parts of the decomposition products were composed of water, C8, C9 aldehydes, semialdehyde methyl esters, C7, C8 hydrocarbons and methyl esters of fatty acid, and that the existence of several fatty acids, monomethyl esters of dibasic acids and alocohols was positively identified. The quantitative proportions of these decomposition products suggest that at such high temperature as 200°C, decomposition of methyl oleate will occur in accordance with the mechanism of so-called autoxidation and some of these decomposition product will be further oxidized.
Methyl pentachloro stearate was stabilized by epoxidized soybean oil and butyl ester of epoxidized soybean fatty acid, and properties of PVC compounds containing them were examined. Stability of methyl pentachloro stearate was improved by the addition of epoxidized soybean oil and butyl ester of epoxidized soybean fatty acid, but mechanical strength and electrical resistivity of the PVC compounds became inferior. Permanency of plasticized sheets in hot air and oil was improved by the addition of epoxidized soybean oil, but it became inferior by the addition of butyl ester of epoxidized soybean fatty acid. Low temperature flexibility and efficiency of the plasticizer was improved markedly by the addition of butyl ester of epoxidized soybean fatty acid. The stabilized methyl pentachloro stearate appears to be of broad utility applicable to a wide range of vinyl processing techniques.
The ultraviolet absorption spectra were investigated for the substances absorbed from the rice bran oil by several types of ion exchange resins sach as -OH, -Cl and -HCO3 type of Amberlite IRA-401, -OH type of Amberlite IRA-410 and IR-4B, and -H and -Na type of Amberlite IR-120. From these spectral analysis, the existence of some components which have the maximum absoption near (1) 350mμ, (2) 290mμ, (3) 230mμ and 280mμ was presumed.
Separation of the special components contained in thuja oil was successfully carried out by the usual ion exchanger and their behaviors were investigated. The results showed that most part of the special components was absorbed by the strongly basic anion exchange resin and that the ultra violet and infrared absorption spectra of a certain component of them was analogous to those of pure hinokitiol. From the fact that hinokitiol in the oil are easily absorbed by the commercial ion exchange resin such as Amberlite ITA-401 (OH form), it may be possible to recover them from the thuja oil.
1. Harengula zunasi oil. Yellowish brown oil was obtained at yield of 6.95% from Harengula (Bleeker), the characteristics of which were as follows : d154 0.9233, n20D 1.4758, A.V. 12.3, S.V. 192.4, I.V. (Wijs) 168.1 Unsaponifiables 1.34%. Solid acids were chiefly composed of C16 acid with range of C14-C22. Liquid acids contained considerable amount of C18, F2 acid and were composed of C12-C22 acids of F1, F2, F3 and higher unsaturated acids. Unsaponifiable matter, a pale yellow lamina, had mp 129131°C and I.V. 129.4, and existence of considerable amount of cholesterol was recognized. 2. Saurida oil. Sauride argeyrophanes (Richardson) contained 0.73% of body oil. The characteristics of the oil and those obtained from the fish organs were as follows : d154n20D A.V. S.V. I.V. (Wijs) Unsap. matter Color Body oil 0.9391 1.4828 19.0 192.2 195.4 4.13 Reddish brown Entrails 0.9304 1.4875 106.9 159.6 183.5 17.09 Dark brown Liver 0.9240 1.4790 73.8 182.3 167.5 9.15 Reddish brwon Solid acids of body oil contained most of C16-C18 acids, and C14 and C20 acids also existed. Liquid acids were composed of F1, F2, F3 and higher unsaturated acids. Unsaponifiable matter of the oil had the following characteristics : Yield% I.V. mp (°C) Color reaction with conc. H2SO4 Body oil 4.18 114.2 124128 Reddish brown (-) Entrails oil 17.08 116.8 124128 Reddish brown (+) Liver oil 9.15 128.6 Reddish brown (+) Cholesterol seemed to be main component of the matter. 3. Half-beak oil. The oil prepared from Tylosurus gigantcus (Temminck & Schlegel) had the following characteristics : Yield% d154n20D S.V. I.V. (Wijs) Unsaponifiables % 0.69 0.9235 1.4817 158.0 160.4 12.79 Solid acids contained most of C16 and C18 acids, and C14 and C20 acids also existed. Liquid acids were composed of F1, F2, F3 and higher unsaturated acids. Unsaponifiable matter had I.V. 116.7 and mp 134.2138.5°C, and cholesterol seemed to be main component.
Alkylbenzenesulfonates, which have been widely used for industrial and household detergents, contain ortho-para isomer, and it is difficult to separate them each other. In this paper, their separation by the solubility difference of their lead salt in 95% ethanol and their properties were studied with the following results. 1. By infrared spectra and dipole moments, it was confirmed that soluble lead salt was rich in ortho compound and insoluble lead salt was rich in para, but their purities were not determined. There was no difference between their NMR spectra. 2. Solubilizing power and solubility in absolute ethanol of o-DBSNa were much greater than those of p-DBSNa, but there was very slightly difference between their surface tensions, wetting powers and foaming powers. 3. Regarding the actions on micro-organisms (bacteriostatic action and biological degradation), there was no difference between ortho-para isomer of branched alkylbenzenesulfonate.
In suspension polymerization of vinyl chloride a emulsion which contains polyvinyl chloride powder is formed, because polyvinyl chloride is insoluble in vinyl chloride monomer and it is separated out. In order to investigated mechanism of formation of this emulsion, authors observed the phase inversion of emulsion which involves benzene and vinyl chloride monomer as oil phase, polyvinyl chloride power as solid phase, and various surface active agents as suspending agents. Type of emulsion is changed from water in oil (W/O) to oil in water (O/W), as wettability of polyvinyl chloride powder to the oil phase varies with content of suspending agent. Nonionic and anionic synthetic surface active agents have a wider range for the W/O type formation and have a lower stability of emulsion than the high polymeric surface active agents. Also, authors recognized that these phenomenons are reproduced in the suspension polymerization of vinyl chloride whereby the same surface active agents are used as suspending agenst.