Treating a large quantity of different kinds of rice bran in large tubes of thin steel plate, an examination was made on the effect of lipase on the hydrolytic velocity of fatty matter, on the variation of oil content and on its transformation due to the lapse of reaction time by measuring different kinds of constants and by fractional distillation. Of the fatty acids that constitute rice bran oil, an investigation was conducted to determine which fatty acid was selectively hydrolyzed. As a result it was found that the diameter of steel tubes and the location showed no difference on effect as was in the case of our fundamental research. As reaction time lasts longer free fatty acid content increases, but the amount of unsaponifiable matter, iodine value and peroxide value remain at almost definite values, and only a small amount of hydroxy acid is produced. When free fatty acid content is 75%, acetyl value becomes 4550, but when free fatty acid content is more or less than 75%, acetyl value decreases. It is presumed from this tendency of increase and decrease of acetyl value that the hydrolytic mechanism of fatty matter by lipase comes about by stepwise. In the case of the first step of reaction, an experimental formula exists between free fatty acid content and specific gravity or refractive index. In the case of the latter step of reaction wherein free fatty acid decreases after increasing once, however, no experimental formula exists. This comes from the formation of ethyl ester. As a result of analysis, by distillation under reduced pressure, the composition of the fatty matter after 140 hours' reaction time, the presence of ethyl ester was confirmed. It is considered that from the carbohydrate that co-exists in rice bran, ethanol is formed by alcohol fermentation, which in turn, produces ethyl ester by the synthetic action of lipase. No ethyl ester existed, however, in a sample oil after 7080 hours' reaction. The oil content decreases initially about 0.10.2% but after that there is a tendency of a slight increase. Of the fatty acids that constitute rice bran oil, those that are to be subjected to selective hydrolysis by lipase are palmitic, oleic and linolic acids in order.
Oxidation patterns of cottonseed oil, methyl oleate and methyl linoleate with aeration at a rate of 300ml/min/100g of lipid at various temperatures ranging from 0 to 180°C for 24hr were investigated by measuring refractive index, viscosity, loss in weight, iodine value, and the content of total trans isomers (not only trans oleate, but cis-trans conjugated, trans-trans conjugated, and trans-trans nonconjugated linoleates). Cis-trans conjugated linoleate was not found in any oxidized lipids. Total trans isomers content in the oxidized cotton seed oil, methyl oleate and methyl linoleate has appreciably increased for the lipid oxidized at or above 90, 120 and 60°C respectively, compared with those treated below the critical temperatures. Besides these contents were approximately constant in the lipids oxidized above their critical oxidation temperatures of 90, 120, 60°C, respectively. As an exception, total trans isomers content of methyl linoleate oxidized at 180°C becomes appreciably small.
In the previous report, the thermal change of methyl cis-linoleate and methyl cis-linolenate were investigated, and it was found that trans-trans conjugated isomer and cis-trans conjugated isomer were obtained respectively in the first stage and that the product accumulated in the final stage was trans non-conjugated isomer in both cases. In this report, the process of isomerization was investigated quantitatively by the ultraviolet and infrared absorption spectrometric methods. The thermal change of four pure isomers of methyl linoleate, -cis non-conjugated, cis-trans conjugated, trans-trans conjugated and trans non-conjugated isomers-, was carried out. The obtained results are summarized as follows : 1) From cis non-conjugated isomer, little amount of trans-trans conjugated isomer and finally trans non-conjugated one was resulted. 2) Cis-trans conjugated one rapidly isomerizes to trans-trans conjugated one until it accumulates about 57%, and the latter isomerizes to trans non-conjugated one gradually. 3) Trans-trans conjugated one slowly isomerizes to trans non-conjugated one. 4) Trans non-conjugated one does not change to any other isomers. In all cases, it was proved that trans non-conjugated isomer was accumulated in the thermal change. However, in the thermal change, the dimerization was also found simultaneously. In case of change of trans non-conjugated one at 300°C for 5hr, the amount of dimer was about 25%.
Natural fatty oils contain a number of minor components which act as catalyst poison. These are phosphatides, oxidized glyceride, proteins and unidentified gummy material. The poisoning effect is reversible, the catalyst can be reactivated. X-ray diffraction data from the copper-chromium-manganese oxide catalyst which had been used in the hydrogenation of unsaturated fatty oils showed cupric oxide largely reduced to metallic copper, whereas cupric chromite combined manganese oxide, the true catalyst, has not been reduced to cuprous chromite. Authors have succeeded in reviving the spent catalyst by removing the poisons adsorbed on the surface of the catalyst, namely by the “wet oxidizing methods”. The activity and selectivity of revived catalyst for hydrogenation of unsaturated fatty oils were found to be the same order which would be used as well the fresh unpoisoned catalyst.
Sodium docosenyl sulfates, ammonium docosenyl sulfates and sodium docosenyl sulfoethyl ethers were synthesized in pure states from Δ11, 12 docosenol and erucylalcohol respectively. Their properies of surface and interfacial tension, foaming, detergency and solubilities into water were tested. As the results, it was recognized that sulfates of C22 monoenic alcohol were practically useful as detergents. Also the newly made high vacuum apparatus having a rotary brush showed a good fractionation efficiency on the purification of the higher fatty alcohol acetates.
As to the applications of organo-phosphor compounds in the field of surfactants, only phosphoric acid ester of higher aliphatic alcohols is used practically as an antistatic agent for textiles. The authors have synthesized several organo-phosphor compounds, which have long aliphatic chain directly connected to the phosphor-atom, and examined their properties as surfactant and also as textile finishing agent. Some positive results were obtained, i.e. all the compounds, synthesized in this report, have relatively poor characters as surfactant, but they are applicable as antistatic finishing agent for synthetic fibers.
Reaction products of tetradecyl ketene dimer and amine compounds were investigated. As the amine compounds, NH3 (I), CH3NH2 (II), C6H5NH2 (III), H2NC2H4OH (IV), NH (C2H4OH) 2 (V) were used. One mol of tetradecyl ketene dimer was reacted with two mols of amine compounds. By reacting (I) in the medium of benzene at 40 to 45°C, 2-tetradecyl-3-keto-octadecanoic-acid amide (mp 118.1118.4°C) was obtained with about 88 percent yield. When reacted in the medium of water, same product was obtained. By reacting (II) in the medium of benzene at 40 to 45°C, 2-tetradecyl-3-keto octadecanoic-acid N-methyl amide (mp 103.0103.5°C) was obtained with theoretical yield. By reacting (III), (IV) and (V) in the medium of ethyl ether, 2-tetradecyl-3-keto-octadecanoic-acid anilide (mp 95.695.8°C), N-monoethanol amide (mp 109.5109.9°C) and diethanol amide (mp 35.435.8°C) were obtained. The yields were about 80, 80 and 75 percent respectively. Reaction products were identified by ultimate analysis and infrared spectrophotometer.
This report deals with monthly investigation of vitamin A in 15 kinds of enriched household margarine (of which 13 are of JAS and the rest of quasi-JAS) kept at room temperature for 12 months, and at the same time, of the correlation with P.O.V. Vitamin A of samples showed 36, 900I.U./450g at maximum, 18, 200 at minimum and 26, 370 on average, well above the level of European and American standard margarine. The average remaining % of vitamin A was 84.4 after 3 months, 76.3 after 6, 71.6 after 9 and 68.6 after 12, showing stable quality. 8 samples considered to contain milk ingredient showed a much better result than those without it with a few exceptions. Even when much mold came out, 53.5% was remaining after 12 months. 7 samples containing lauric oil which is generally 15%, did not show any effect on vitamin A by it. Ester odor, which is caused readily by co-existence of milk ingredient and lauric oil did not show any change in vitamin A. But rancid odor showed considerable reduction of vitamin A. P.O.V. rises after a certain induction period (9 months), but no correlation between increase of P.O.V. and remaining % of vitamin A could be found in comparison with each sample.