油化学
Online ISSN : 1884-2003
ISSN-L : 0513-398X
10 巻 , 1 号
選択された号の論文の10件中1~10を表示しています
  • 小森 三郎
    1961 年 10 巻 1 号 p. 2-5
    発行日: 1961/01/20
    公開日: 2009/10/09
    ジャーナル フリー
  • 福島 正敏, 下飼 勝次郎
    1961 年 10 巻 1 号 p. 6-11
    発行日: 1961/01/20
    公開日: 2009/10/09
    ジャーナル フリー
    The C12C36 sym. α-glycols were prepared from acyloins by catalytic hydrogenation with Raney nickel. The properties of α-glycols were studied.
    Melting point of the α-glycol is higher than that of the corresponding acyloin or α-diketone and decreases with chain length. Two hydroxyl groups can be quantitatively acetylated by acetic anhydride, and reacted with 3, 5-dinitrobenzoyl chloride to give the crystalline 3, 5-dinitrobenzoate. From mp and optical rotation of fractional crystals, α-glycols obtained by catalytic hydrogenation seem to consist of meso or racemic form. In the acetic acidical solution α-glycols are quantitatively oxidized with periodic acid as well as ethylene glycol, and in the 99% alcoholic solution the oxidation by periodic acid is quite the same as acyloins. When heated to 200°C, these α-glycols are hard to change into ketones by dehydration.
    α-Glycols show the broad absorption band in the range of 2.293.01μ assigned to associated hydroxyl groups, and complicated bands of C-O stretching in the range of 810μ.
  • 小西 〓, 石束 哲男
    1961 年 10 巻 1 号 p. 11-18
    発行日: 1961/01/20
    公開日: 2009/10/09
    ジャーナル フリー
    We prepared sulfate of higher alcohol which contained alkylated polyvinyl compounds, and also prepared polyvinylated nonionic surfactants from polyoxyethylen series nonionics, which had alcoholic hydroxyl group as in alchols, polyvinylated soap and polyvinylated diethanolamide from polyvinylated fatty acids which obtained by solution polymerisation of vinyl acetate in fatty acid. The properties of the products were measured.
  • 小森 三郎, 滋野 吉広, 山本 慧介, 池田 弘治
    1961 年 10 巻 1 号 p. 18-24
    発行日: 1961/01/20
    公開日: 2009/10/09
    ジャーナル フリー
    In the previous paper, we reported that the maleinized fatty esters are the useful primary plasticizers for polyvinyl chloride. On this paper, we attempted to improve the properties of these plasticizers by epoxidation. The epoxidation of maleinized oleic esters was rather difficult than that of oleic ester by the steric effect of maleic ester. Thus, we could not get the epoxide having high content of oxirane oxygen. However, the PVC film plasticized by the epoxides obtained (oxirane oxygen content 0.20.4%) showed better properties than the film plasticized by the raw maleinized fatty esters in color, clearness and thermal stability.
  • 野田 万次郎, 平山 修
    1961 年 10 巻 1 号 p. 24-28
    発行日: 1961/01/20
    公開日: 2010/01/27
    ジャーナル フリー
    A simple and rapid method for the separation and identification of fatty acids and glycerides has been developed by using circular paper chromatography. Petroleum hydrocarbon, dodecylbenzene, and tetralin were used as the stationary solvents. As the developing solvents, 90% acetic acid and methanol-acetic acid, both saturated with a stationary solvent, were suitable for the separations of fatty acids and of glycerides respectively. The fatty acids were detected on paper by successive treatment with 0.5% lead acetate, water, and ammonium sulfide solution. The selective detection of unsaturated acids by spraying with a 2% solution of iodine in ethanol was also applied. The separation of various “critical partners” of fatty acids was achieved by the method of double development, involving the first low-temperature development with petroleum ether under dry ice and the second reversed-phase development with the usual solvent systems at room temperature. The unsaturated glycerides were chromatographed as their mercuric acetate addition compounds, and were detected by spraying with a 0.2% solution of diphenylcarbazone in ethanol or by soaking in a Sudan black solution. The clear-cut separations of fatty acids and glycerides into their homologs can be attained by these circular chromatographic techniques, since the separation of unsaturated triglycerides mainly depends on their unsaturation and that of mono-, di-, and triglycerides mainly depends on the number of their free hydroxyl groups. This method was successfully applied to the analysis of various fats, fatty acids, and their products, and was confirmed to be of great value as a simple, rapid, and practical method for their analysis.
  • 永野 義彰, 田中 武英
    1961 年 10 巻 1 号 p. 29-32
    発行日: 1961/01/20
    公開日: 2009/10/09
    ジャーナル フリー
    It was known that unsaturated fatty acids were very sensitive to oxygen, but little studies on the thermal isomerization were made. We investigated the effect of thermal change of methyl-linoleate.
    The isomerization was conducted by passing nitrogen containing 1, 5 and 10 vol% of oxygen into pure cis methyl-linoleate at the rate of 3l/hr at 100 and 200°C. The obtained results are summarized as follows :
    1) In the presence of oxygen, cis methyl-linoleate isomerizes rapidly, even at low temperature, to trans-trans conjugated or trans non-conjugated one.
    2) The increase of oxygen content is only effective to increase the speed of isomerization.
    3) At the first stage of isomerization, the yield of trans-trans conjugated isomer is almost independent of the oxygen content. This can be explained by the assumption that oxygen is consumed by the polymerization or oxidation reactions (such as to -OH, -OOH or = CO).
    4) The formation of trans-trans conjugated isomer reaches to the equilibrium concentration of about 12%. This may due to either the polymerization of the resulting conjugated isomer, or its isomerization to the thermal stable trans non-conjugated isomer.
    5) Although Lundberg reported the formation of cis-trans conjugated isomer in the oxidation of methyl-linoleate, only trans-trans isomer was found in our experiment.
  • 高橋 越民, 西川 貞道, 越村 雅充, 古場 重喜
    1961 年 10 巻 1 号 p. 32-37
    発行日: 1961/01/20
    公開日: 2009/10/09
    ジャーナル フリー
    In the preveous report, the relation between the chemical structure of some anionic surfactants and their antistatic capacities was studied. In this report, the relation between the chemical structure of cationic surfactants derived from long chain amines (primary, secondary, tertiary amine salts and quaternary ammonium salt) and their antistatic capacities was studied.
    Investigated items with the chemical structure were as follows :
    1. Effect of chain length of fatty residue which forms salt with each amine (C0, C2, C6, C12, C18).
    2. Effect of the classification of cationic surfants (primary, secondary, tertiary amine salt and quaternary ammonium salt).
    3. Effect of the number of long chain residue which belongs to N of amine (1, 2, 3).
    4. Effect of the chain length of long chain residue which belongs to N of amine (C12, C18).
    5. Effect of the substitution of primary amine by long chain residue, and effect of the substitution of those long chain residues by methyl residue.
    Item 25 were investigated in relation with item 1.
    Results :
    1. Primary, secondary, tertiary amine salt, even their structures are varied, are seriously inferior compared to the quaternary ammonium salt in antistatic capacity (1081012Ω to 106107Ω).
    2. The number of long chain residues which belong to N of amine roughly rules the type of relation curves, the electric resistance-chain length of salt forming fatty acid.
  • 中里 敏
    1961 年 10 巻 1 号 p. 37-41
    発行日: 1961/01/20
    公開日: 2009/10/09
    ジャーナル フリー
    It was studied that the mixed methyl ester of tall oil is prepared on the similar composition as the original crude tall oil which is the mixture of fatty acids and rosin acids, and the acid value of produced ester is lowered as possible. The author discussed the conditions of following various esterification processes, that is, the oil and methanol mixture are heated with or without catalysts in an autoclave, and the soap of the oil is reacted with methyl iodide or dimethyl sulfate. It was found that ZnCl2, MgO and active clay are effective as catalyst on the autoclave process, and it is required that the oil and methanol are heated at 300°C under 100kg/cm2 pressure in an autoclave without catalyst. When partial methyl esters, which only fatty acids are esterified but rosin acids are neseterified by oridinary eterification, are neutralized by KOH and dissolved in methanol, then they are heated with methyl iodide of three times of theoretical amount, or they are agitated with a mol of dimethyl sulfate at room temperature, the required methyl esters are produced.
  • 工 静男
    1961 年 10 巻 1 号 p. 41-49
    発行日: 1961/01/20
    公開日: 2009/10/09
    ジャーナル フリー
    The mode of combination of the copper-chromium-manganese oxide catalysts by the X-ray diffraction data is as follows; the standard catalyst (KW-1) was consisted of CuO and CuCr2O4 combined with manganese oxide, and KW-6, treated with hot HCl to remove CuO, was also CuCr2O4 combined with manganese oxide. The results were closely checked by the standard gravimetric analysis. The activity and selectivity of KW-6 on the unsaturated bond of unsaturated fatty oils were superior compared to those of CuO+CuCr2O4 (Adkins catalyst) and CuO prepared by the wet method. The results of these facts demonstrate that the CuCr2O4 combined with manganese oxide is the true catalyst for the selective hydrogenetion of unsaturated fatty oils.
  • 今井 怡知朗, 若林 他家男, 道籏 一兵, 吉野 道夫
    1961 年 10 巻 1 号 p. 49-56
    発行日: 1961/01/20
    公開日: 2009/10/09
    ジャーナル フリー
    Reaction of the alkyl ketene dimer and hydroxyl radicals in the presence of catalysts was studied. Tetradecyl ketene dimer was chosen as the alkyl ketene dimer. p-Toluen sulfonic acid, KOH and KHCO3 were used as the catalysts. Primary, sec-, tert-BuOH, ethylene glycol, phenol and H2O were used as the hydroxyl radicals.
    As a result, the reaction products of alkyl ketene dimer with hydroxyl radicals, except H2O, were esters of 2-alkyl-3-keto acid. Basic catalysts gave larger reaction velocity than acidic catalysts to hydroxyl radicals with the exception of phenol. Sec-, tert-BuOH and H2O which were difficult to react by the acidic catalysts, have readily reacted comparatively by using basic catalysts and the ketone was obtained with H2O. The ester of keto acid was obtained by using KHCO3 and by a small quantity of KOH. However, ketone was obtained with KOH by using more than equivalent of the alkyl ketene dimer.
feedback
Top