The synthesis of glycerine by the hydrolysis of epichlorohydrin with sodium hydroxide solution was studied. The factor which mostly affects the yield of glycerine is the concentration of sodium hydroxide, and the lower its concentration the higher the yield is. Moreover, the reaction temperature, the dropping method … whether to drop epichlorohydrin or sodium hydroxide solution to the reaction solution ……, and the dropping velocity were found other factors affecting the yield. The maximum yield was 85% for 1% sodium hydroxide solution. As it is necessary to use low concentration solution of sodium hydroxide for elevating the yield, the concentration of glycerine produced is accordingly low. Therefore, sodium hydroxide may not be economical for industrial glycerine synthesis in case epichlorohydrin hydrolysis. In addition, the side reaction in this synthesis is considered as the polymerisation of glycidol.
The authors could confirm the separation of unsaturated alcohols from saturated alcohols on thinlayer chromatography (TLC) by making adduct with mercuric acetate. Experiments were carried out with three groups of samples, mercuric acetate-adducted oleylal cohol and stearylalcohol, the adducted oleyl acetate and stearyl acetate, and the adducted sperm whale alcohols, by using Silica gel G as the adsorbent, and bezene, toluene, xylene and other solvents as the developing agents. Benzene, toluene and xylene were better developers than other solvents tested. Acetylated alcohols gave better separation of saturated and unsaturated alcohols than that of untreated ones. Silica gel G was found as suitable adsorbent for the purpose.
Beta-eleostearic acid and its methyl ester were oxidized with peracetic, perbenzoic or monoperphthalic acid at temperature below 30°C. The oxidation products were viscous, and their specific gravities were more than 1. It was considered that epoxy compound is not present in the oxidation products from the data of infra-red spectra and the result of hydrogenation with lithium aluminium hydride, although the products reacted with hydrogen bromide under the condition of Durbetaki's oxyrane oxygen determination method. From the data of infra-red and ultraviolet spectra and from the acid, saponification and hydroxyl values, the oxidation products were estimated as hydroxy-acyloxy compounds. Conjugated diene was found in some of products oxidized with perbenzoic or monoperphthalic acid, and conjugated triene was found in some of products oxidized with monoperphthalic acid from the data of infra-red and ultraviolet spectra. It was estimated that reactivity of peracids with eleostearic acid or its methyl ester was in the order; peracetic>perbenzoic>monoperphthalic acids.
1. The object of this study is to elucidate the foam-forming properties and the chemical properties of oxidative-polymerized fractions in foaming oils, the contents of which caused durable foaming of oil by frying. 2. 100g of linseed oil, soybean oil and olive oil were heated at 200°C for about 4, 8 and 13hrs. in 300cc beakers respectively. At intervals of 30 minutes, a piece of potato was dipped in the oil to observe the oil foaming. Thus we could obtain (1) samples, one half part of the surface was covered by foams when a piece of potato was dipped in them and (2) samples, whole surface of which covered by foams, for each of the oils. We defined them as “the half-foaming oils” for the former and as “whole-foaming oils” for the latter. These foaming oils were fractionated by the column chromatographic methods into 3 fractions. Silicagel treated with n-hexane containing 5% of i-propyl ether served as the absorbent. Foaming oil samples were eluted with 15% i-propyl ether in hexane to yield the first fraction (F1); with 60% i-propyl ether in n-hexane to yield the 2nd fraction (F2) and ethyl ether to yield the third fraction (F3). The chemical properties such as the carbonyl value, acid value, hydroxyl value and mean molecular weight of F1, F2 and F3 were measured for various oils. The F2 and F3 thus fractionated from thermally oxidized linseed oil and olive oil were added to the original oils in various contents, then the foaming properties of these oils were measured. The measurement of foaming tendencies was carried out by gas pumping method, as reported in our former paper. 3. Experimental data showed that there was small variation in the foam-forming properties and in chemical properties of F3 fractionated from either of “half-foaming oil” and “whole-foaming oil” originated from the same oil. The properties of F2 fractionated from various oils also resembled to each other. And foam-forming properties of F2 were weaker than that of F3. The F1 fractionated from various oils showed no forming property.
Bömer numbers were measured by acetone method to know the effects of addition of other animal fats to pure lards, which were obtained from the abdomen and the back of Middle Yorkshire hogs in Ibaragi Prefecture. The various semples had been prepared by mixing above two kinds of pure lards and the mixture of : them with beef tallow, mutton tallow, horse fat, bear fat and hydrogenated lard respectively in various ratios. 1) The Bömer numbers of the lard-mixtures and the back-lard with 20% of beef tallow or 20% of mutton tallow respectively, fall below 73, but the value remains above 73 when 20% of beef tallow is mixed in the abdomen-lard. Addition of these fats over this amount results in increased yield of the precipitated glyceride with lowering of the Bömer number. 2) Content of 60% of horse fat or bear fat in lard-mixtures results in the Bonier number of 74.5.and 76.0, respectively, accompanied by the remarkable lowering of the amount of the precipitated glyceride. Addition of a large amount than the above results in no glyceride to be precipitated out. 3) Bömer number falls to below 70 when 20% of hydrogenated lard is contained. Addition of 40% gives a Bömer number of 65, indicating great effect of hydrogenated lard on the Bömer number. The yield of the precipitated glyceride increases rapidly with increase in the amount of hydrogenated lard added.
Author investigated the surface activities of the polyoxyethylene ethers which have the oxyethylene chains of definite lengths. Mono, di, tri, tetra and penta oxyethylene ethers of lauryl, cetyl, oleyl alcohols and nonylphenol, synthesized in our labolatory, were dissolved or suspended in water and the surface tension of the solutions was measured by using du Nouy's surface tension meter. With the exception of cetyl ethers and mono and di oxyethylene lauryl ethers, the surface tensionconcentration curves of the solutions showed same characteristics as those of ordinary surface active agents. Namely, change in the surface tension is little at higher concentration, while it increases rapidly as the concentration decreases for the range below c.m.c. Furthermore, it was observed that the surface tension of the solutions of paired ethers containing lauryl-oleyl, oleyl-nonylphenyl, and nonylphenyl-lauryl, having tetraoxyethylene chain respectively, was in a range between those of individuals of the pair ethers. Exploratory experiments were also carried out with other combinations and the effect was studied.