油化学
Online ISSN : 1884-2003
ISSN-L : 0513-398X
10 巻 , 4 号
選択された号の論文の14件中1~14を表示しています
  • 滋野 吉広
    1961 年 10 巻 4 号 p. 193-199
    発行日: 1961/04/20
    公開日: 2009/10/09
    ジャーナル フリー
  • 1961 年 10 巻 4 号 p. 199
    発行日: 1961/04/20
    公開日: 2009/10/09
    ジャーナル フリー
  • 山本 襄, 宮川 高明
    1961 年 10 巻 4 号 p. 200-205
    発行日: 1961/04/20
    公開日: 2010/01/27
    ジャーナル フリー
    For the quantitative analysis of fatty acid composition of fatty oils, the application of paper-chromatography using hydrogenation on papers was examined, in addition to the usual reversed phase paperchromatography consisted of hydrocarbon as the stationary phase and acetonitril acetic acid as the mobil solvent. Complete hydrogenation on papers was achieved after 2 hr at 30, using palladium black as catalyst. By applying this analytical method, the composition of fatty acids of wheat germ oil and of skipper oil was determined as follows.
    Wheat germ oil : C16F0 : 12.3%, C18F0 : 3.7%, C18F1 : 20.6%, C18F2 : 45.6%, C18F3 : 12.3%, C20F0 : 5.4%.
    Skipper oil : C14F0 : 8.6%, C16F0 : 14.6%, C16F1 : 3.8%, C18F0 : 1.6%, C18F1 : 8.7%, C18F2, : 6.8%. C18F3 : 1.2%, C20F1 : 15.7%, C20F4, 5 : 7.1%, C22F1 : 17.2% C22F5, 6 : 14.7%
  • 伊沢 康司, 徳升 健次, 木村 和三郎
    1961 年 10 巻 4 号 p. 205-208
    発行日: 1961/04/20
    公開日: 2009/10/09
    ジャーナル フリー
    For the rapid and accurate determination of anionics, a new volumetric method, “4-Amino-4'-Chlorobiphenyl Hydrochloride Diazotitration Method” has been developed.
    The active component of anionics is precipitated in dilute acidic aqueous solution with 4-amino-4'-chlorobiphenyl hydrochloride (ACBH), and the excess of ACBH in the filtrate is titrated back with sodium nitrite standard solution by diazotitration, using potassium-iodide-starch paper until it turns blue.
    The experimental results with various anionics showed that the new method was quite satisfactory. Higher mole-ratio of ACBH to anionics than 6 resulted too high analytical values. Potassium-iodide-starch paper showed clearer end point of diazotitration than p-dimethyl-aminobenzaldehyde test paper in this new method.
  • 今井 怡知朗, 若林 他家男, 吉野 道夫, 小宮 林
    1961 年 10 巻 4 号 p. 208-215
    発行日: 1961/04/20
    公開日: 2009/10/09
    ジャーナル フリー
    The optimum condition for synthesis of higher alkyl ketene dimer and its purity reduction with time elapse were studied.
  • 福島 正敏, 下飼 勝次郎
    1961 年 10 巻 4 号 p. 215-222
    発行日: 1961/04/20
    公開日: 2009/10/09
    ジャーナル フリー
    The reductive condensation reaction of C6C18 saturated fatty acid methyl esters by means of metallic sodium was studied for the purpose of analysis in reaction systems. The yields of reduction and Claisen condensation products, such as acyloins, α-diketones, α-glycols, fatty alcohols, and β-ketoesters could be determined.
    From the fairly high yields of acyloins, principal reaction of this system is to form acyloins when used esters of more than six carbon atoms. The yields of reductive condensation products were obtained in maximum at some chain length. The formation of fatty alcohols as well as the generation of hydrogen was found to increase with chain length, while those of fatty acids and β-ketoesters decreased.
    From these results about the action of metallic sodium in tolueme, the reactions stated above in the presence of the bases were classitied into two initial mechanisms, namely base addition to the carboyl group and proton removal from the α-carbon aton.
    The mechanism of the reaction system was discussed.
  • 若林 他家男, 吉野 道夫, 亀沢 和良, 池田 哲夫
    1961 年 10 巻 4 号 p. 222-228
    発行日: 1961/04/20
    公開日: 2009/10/09
    ジャーナル フリー
    The effects of some catalysts on disproportionation of tall rosin were investigated for comparison.
    As a result, Cu-Cr catalyst had only a little effect on disproportionation, but Pd-carbon catalyst, leaving a little unsaponifiable matter, was very effective to main reaction. Active carbons were also useful to main reaction, and carbon activated by ZnCl2 was more effective than the carbon activated by steam.
    Zn compounds play a sub-catalytic effect, especially, carbon activated by ZnCl2 was effective to disproportionation, but it has a drawback nature producing more unsaponifiable matter by side reaction. Tall rosin was distilled fractionally, and fractions were disproportionated with active carbon activated by ZnCl2. The formation of unsaponifiable matter was nearly equal for each fractions.
  • 中里 敏
    1961 年 10 巻 4 号 p. 228-232
    発行日: 1961/04/20
    公開日: 2009/10/09
    ジャーナル フリー
    In the previous paper, preparation of the mixed methyl esters, consisted of fatty and rosin esters, was discussed. In this paper, these esters were converted into mixed alcohols, consisted of fatty and rosin alcohol, by Bouvealt-Blanc reaction. The kind, amount of reduced alcohol, amount of sodium in the reduction and the distillation of produced crude alcohol were discussed.
    Tertiary butyl alcohol was most suitable for reduction in the case of all esters. Because saponification value of the esters containing rosin ester can not be accurately determined, theoretical requirement for sodium and reducing alcohol could not be calculated. However, excess sodium and reducing alcohol seems to increase the yield of mixed alcohol. Against author's expectation, these esters have a saponifying tendencies, when excess sodium is present. Methyl ester from distilled tall oil is less saponifiable than that from crude tall oil in the reduction reaction. When distilled the crude alcohols produced, under reduced pressure, fatty alcohols are distilled out firstly and the rosin alcohol subsequently. Distillation residue is considered to be a polymerized rosin esters, the rotation property of which is extremely changed owing to the isomerization caused by heating.
  • 高橋 越民, 西川 貞道, 舟山 浩二
    1961 年 10 巻 4 号 p. 232-236
    発行日: 1961/04/20
    公開日: 2009/10/09
    ジャーナル フリー
    In the previous report, the antistatic capacity of the surfactant which has ionic and nonionic (polyoxyethylene) radicals in one molecule was studied. Author expected some advantage of this compound type surfactant at lower humidity, considering from Valko's work whereby salt and nonionic surfactant were applied together to get a synergistic result. The result obtained was negative.
    In the present report, the antistatic effect which will arise from a simultaneous application of ionic surfactant and nonionic surfactant to a synthetic fabric was studied. The applicated ratio of both surfactants was 1 : 1, in order to compare with the compound type surfactant above mentioned. Individual application of each surfactant was investigated in parallel. Electric resistance of treated fabrics was plotted against R.H. (25, 45, 65%) to investigate. The hygroscopicity of the surfactant was plotted against R, H. (25, 45, 65%), too. I n this experiment, author expected superiority of simultaneous application of both surfactants to individual application at lower humidity.
    Conclusion : At the simultaneous application of ionic surfactant and nonionic surfactant, and at the individual application of ionic surfactant, electric resistance-R.H. relation curve shows steeper inclination than that of individual application of nonionic surfactant; both curves cross.
    Hygroscopicity-R.H. relation curve also takes same tendency, however, no crossing occurs. Hence, the hygroscopicity is not all factors of antistatic capacity, Author's expectation above mentioned has also failed in this case.
  • 山田 実
    1961 年 10 巻 4 号 p. 236-239
    発行日: 1961/04/20
    公開日: 2009/10/09
    ジャーナル フリー
    The lipid of a marine plankton, Neomysis nakazawai Ii, was examined.
    The ether extract was obtained from the sun-dried material of the plankton collected at Funka Bay, Hokkaido. The lipid content was 6.5% of dry matter and its characteristics were as follows : n20D 1.4845, S.V. 163.6, I.V. 181.3, A.V. 132.2, and unsaponifiable matter 10.62%.
    The fatty acids of this lipid were consisted of 23.0% of saturated acids (C14 5.4%, C16 13.9%, C18 and C>18 3.7%) and 77.0% of unsaturated acids (C14 1.3%, C16 8.9%, C18 15.8%, C20 33.5%, C22 17.5%). Saturated acids were mainly consisted of C18. Unsaturated acids contained large amount of C20 and C22. These results.indicate that this lipid has the same fatty acid composition as that of marine type.
  • 小池 基生, 阿部 竜雄
    1961 年 10 巻 4 号 p. 240-247
    発行日: 1961/04/20
    公開日: 2009/10/09
    ジャーナル フリー
    To study the influences of the polar groups of rust inhibitors upon the results of different corrosion tests, seven sorts of corrosion tests were carried out with sorbitan partial esters added in lubricating oils. The sorbitan partial esters used in these tests were six sorts of esters composed of mono and tri esters of lauric, stearic and oleic acids.
    The anti-corrosion properties of sorbitan partial esters were best shown in the shed storage test;and in the humidity cabinet test, the reaction test by potassium ferricyanide, and the salt water immersion test also, they were shown with fairly good effect. While in the sulfuric acid immersion test, the non-ferrous metal immersion test and the heat stability test, they did not present good results.
    It follows that sorbitan partial esters may be suitable for the additives to usual rust preventive oils, yet unsuitable when used in an acid atmosphere or in such a circumstance as is subject to oxidization at high temperature. They are liable to cause the discoloration of non-ferrous metal ; especially they badly corrode lead.
    The rust preventive properties of sorbitan partial esters vary to a high degree according to the sorts of the fatty acids linked rather than the number of the radicals of the fatty acids. Through all the corrosion tests conducted it was found that the best of all was oleate. This is, it can be said, because laurate and stearate have poor solubility to mineral oils as compared with oleate. It can be further said to be natural that oleate is superior to laurate and stearate because of the better adsorption of the moleculer film of oleate to metal surfaces.
    In measuring displacement energy, laurate showed almost as much minus value as oleate, yet in the humidity cabinet test or in two or three other corrosion tests laurate was inferior to oleate. It can be further understood that this is due to the fact that the chain of oleate is unsaturated and is longer and more hydrophobic than that of laurate.
  • 木村 午朗
    1961 年 10 巻 4 号 p. 248-252
    発行日: 1961/04/20
    公開日: 2009/10/09
    ジャーナル フリー
    An experiment was conducted by storing rice bran in a room for a few mon ths in the summertime. Six weeks after rice cleaning the acid value of fatty matter reached its maximum of 159, then as the days of storage increased the acid value decreased and the oil content increased about 1.5%. The cause was investigated by analyzing each constant of the fatty matter and its composition. As a result it was confirmed that the decrease in acid value is due to the formation of ethyl ester and not to the increase in unsaponifiable matter. It was also confirmed that the optimum temperature for the acid value decrease reaction is 30°C and the optimum pH is 6.46.5 and that the optimum temperature for the acid value decrease reaction of fatty matter of rice bran, to which monohydric aliphatic alcohol being added, is also 30°C.
  • 工 静男, 橋本 利夫
    1961 年 10 巻 4 号 p. 253-255
    発行日: 1961/04/20
    公開日: 2009/10/09
    ジャーナル フリー
    Authors made an investigation on the hydrogenation of unsaturated fatty oils with the copper-chromium-manganese oxide catalyst by adding metallic soaps, ferric oxide and a very small amount of reduced nickel.
    As a results, it was found that the metallic soaps have no retarding effect on the activity of catalyst, but some of them, such as soaps of nickel, zink and copper have degrading effect on the selectivity of catalyst, whereas the soaps of lead, cadmium and sodium, known as the poison of nickel catalyst, had no degrading effect.
    Ferric oxide has retarding effect on both the selectivity and activity of catalyst and a very small amount of reduced nickel has a degrading effect on the selectivity of catalyst.
    Soaps of lead, cadmium and sodium have a tendency of suppressing the formation of trans isomer of oleic acid, whereas reduced nickel possesses the tendency to increase the formation of trans isomer in partially hydrogenated fatty oils.
  • 熊野谿 従
    1961 年 10 巻 4 号 p. 255-258
    発行日: 1961/04/20
    公開日: 2009/10/09
    ジャーナル フリー
    In this paper the author studied on the composition of o-, m- and p-isomers of higher alkylphenols prepared by the reaction of phenol with some kinds of alcohols and an olefin, nonene, in the presence of Japanese acid clay. The reaction conditions were as follows; mol ratio of phenol to alcohol or olefin, 1.5/1.0; the quantity of clay added, 10% by weight for total amount of phenol and alcohol ; reaction time, 1.01.5 hr; reaction temp., 110180°C. Quantitative analysis of isomers was carried out by infrared method, neglecting the quantity of m-isomers.
    Under these conditions diallkyl phenols were scarcely formed. In some cases very small amount of m-isomer was formed but the main products were the mixtures of o- and p-mono-alkylphenols. In alkylatation of phenol with alochols of C6 to C12, almost equal amounts of o-alkylphenol and p-isomer were formed, even in the alkylation of phenols with tert-alkyl group. In the order from cyclohexy-lalcohol to cetylalcohol, the formation of p-isomer increased except that in the case of benzyl alcohol o-isomer was predominant; with nonene, in comparison with alcohols, p-isomer was formed predo-minantly.
    The yields and the o-/p- ratios of produced mono-alkylphenols were as follows; 2-ethylbutylalcohol (55%, 1.0/1.3), 2-ethylhexylalcohol (52%, 1.0/1.4), n-octylalcohol (70%, 1.0/1.2), n-decylalcohol (69%, 1.0/1.1), n-dodecylalcohol (69%, 1.0/1.2), n-cetylalcohol (83%, 1.0/4.3), cyclohexylalcohol (49%, 1.0/1.8), benzylalcohol (78%, 1.5/1.0), nonene (80%, 1.0/10; 90%, 1.0/6.7 in case of mol ratio of phenol to nonene being 4.0; and 70%, 1.0/5.7, using sulfuric acid as a catalyst at 5860°C).
    Two samples of nonionic detergent prepared from ethylene oxide and two kinds of nonylphenols, one prepared and the other bought on the market, showed no difference in the interfacial tention of aq. solution and some other properties, despite some difference of the composition (the former contained 13% of o-isomer, and the lattter only 3.0%).
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