油化学
Online ISSN : 1884-2003
ISSN-L : 0513-398X
12 巻 , 6 号
選択された号の論文の10件中1~10を表示しています
  • 岩本 浩明
    1963 年 12 巻 6 号 p. 323-328
    発行日: 1963/06/20
    公開日: 2009/10/09
    ジャーナル フリー
  • 金丸 二郎
    1963 年 12 巻 6 号 p. 329-334
    発行日: 1963/06/20
    公開日: 2009/10/09
    ジャーナル フリー
  • 平岡 道夫, 高瀬 武伸, 御園生 晃
    1963 年 12 巻 6 号 p. 335-342
    発行日: 1963/06/20
    公開日: 2009/10/09
    ジャーナル フリー
    Butadiene was dimerized with sodium dispersion in THF, in the presence of catalytic amounts of o-diphenylbenzene, at various temperatures between -70 and -10°C. The reaction mixture was treated with carbon dioxide and resulting carboxylic acids were separated.
    The composition of the reaction products were determined by gas chromatography. The results showed that the conversions and the composition of the carboxylic acids were depended remarkably on the dimerization temperature. The conversion to the carboxylic acids obtained to butadiene was 95%, in which C10-dicarboxylic acids were contained about 85%, at-70°C. But these values decreased with increase in the dimerization temperature, and the amounts of monocarboxylic acids, in which C9-acids were predominant, and of polybutadienes of lower molecular weights increased. The composition of the position isomers of the carboxylic acids caused by 1, 4- and 1, 2-addition of butadiene were also depended on the dimerization temperature. The amounts of n-carboxylic acids increased with decrease of the temperature.
    The mechanisms of above reactions were discussed.
  • 平岡 道夫, 永井 昭, 小林 康国, 御園生 晃
    1963 年 12 巻 6 号 p. 343-347
    発行日: 1963/06/20
    公開日: 2009/10/09
    ジャーナル フリー
    C12- and C14-diols were synthesized by the addition reaction of ethylene oxide and propylene oxide to disodio-octadienes which were prepared by the additive dimerization of butadiene with sodium dispersion in the presence of catalytic amounts of o-diphenylbenzene in THF at -70°C. Crude unsaturated C12- and C14-diols were obtained at the yield of 90% and 88% respectively.
    The compositions of the diols were determined by gas chromatography. As a result C12- and C14-diols were consisted of three position isomers caused by 1, 2-1, 2-; 1, 2-1, 4- and 1, 4-1, 4-addition of butadiene and the small amounts of alcohols derived from monomer-, dimer- and trimer-monovalent anion of butadiene were formed as the byproducts. Polyalkyleneglycols or polyoxyalkylene glycol ethers were not detected. The terminal hydroxyl groups of C14 diols were mainly secondary OH.
  • 福住 一雄, 伊東 祐隆, 籏智 俊彦
    1963 年 12 巻 6 号 p. 348-351
    発行日: 1963/06/20
    公開日: 2009/10/09
    ジャーナル フリー
    Methyl esters of cuttle-fish oil fatty acids were segregated by urea-complex procedure, then distilled in vacuum and chromatographed to obtain methyl docosapolyenoate. Methyl pentaenoate and hexaenoate were not strictly separated. Autoxidation of this sample was performed in the dark at 0 to 2°C. Initial reaction products in the autoxidation of methyl docosapolyenoate were separated by the countercurrent distribution method, and then their ultraviolet and infrared spectra were determined. One of them showed the peroxide value (m equiv./kg) at 1.13 × 104, which is the highest value for lipid. From this value and infrared spectra, etc., dihydroperoxide may exist. Unsaturated carbonyl groups are little from the result of the ultraviolet spectra. By investigating the conjugation of these peroxide concentrates, and the infrared absorptions of α-methylene group and-OOH group etc., it was concluded that the peroxide concentrates probably contain the-OOH group at their α-methylene position. In the most promoted autoxidation fraction, the amount of conjugated diene is at about less than 0.5 per molecule, and cis-trans and trans-trans conjugated dienes exist. There is little conjugated triene in it. In the less autoxidized fraction, the amount of conjugated diene is larger, but conjugated triene are not found. In both fraction, conjugated tetraene and higher are not found. There are considerably many double bonds left as cis nonconjugated form.
  • 福住 一雄, 安藤 逸平
    1963 年 12 巻 6 号 p. 351-354
    発行日: 1963/06/20
    公開日: 2009/10/09
    ジャーナル フリー
    Highly purified methyl docosahexaenoate was prepared from cuttle-fish oil. Autoxidation of this product was performed in the dark at 33 to 35°C. Peroxide concentrates from autoxidized methyl docosahexaenoate (I) were obtained by the countercurrent distribution method. The peroxide value (m equiv./kg) of (I) was 1.33 × 104, which is the highest value for lipid. By investigating the peroxide value and infrared spectra, etc., it was suggested that at least dihydroperoxide is contained. The amount of conjugated diene is about lees than 0.5 per molecule and a higher conjugated polyene than triene can not be found, through the ultraviolet spectra of (I). It was presumed that (I) might contain the-OOH group at α-methylene position from investigation of the degree of α-methylene group absorption in the infrared spectra and that of conjugation, etc., The absorptions attributed to aldehydes were slightly noticeable. Trans-trans conjugated diene increased. Considerable numbers of cis nonconjugated forms remained. It was concluded that polymers were generated in respectable amount.
  • 鈴木 義仁, 武内 次夫
    1963 年 12 巻 6 号 p. 354-358
    発行日: 1963/06/20
    公開日: 2009/10/09
    ジャーナル フリー
    The refined rape-seid oil was oxidized with dried air at 96°C, for 1224 hr. The volatile carbonyl compounds evolved were caught in two traps of 2, 4-dinitrophenylhydrazine solution. Hydrazone compounds were then passed through alumina column with benzene to collect only mono-carbonyl compounds. C6- and C8-unsaturated carbonyl compounds in this monocarbonyl compounds were separated with preparative paper-chromatography and re-crystalized. The constituents of these compounds were investigated by U. V., I.R.-spectra and paper-chromatography of oxidation product with ozone. As a result;
    1) The constituents of C6-unsaturated carbonyl compounds were CΔ : 26, CΔ : 36 and CΔ2 : 46.
    2) The costituents of C8-unsaturated carbonyl compounds were CΔ : 28, CΔ2 : 48 and trace CΔ : 58.
  • 上野 誠一, 浜田 茂
    1963 年 12 巻 6 号 p. 358-364
    発行日: 1963/06/20
    公開日: 2009/10/09
    ジャーナル フリー
    (A) Hiroshima Rape Seed Oil.
    The seeds of Brassica pektnesis R. or Hiroshima rape, indigeneous in Hiroshima district of Japan, were blackish brown in colour, and contained 36.6% of yellow colored oil. The oil had the following charactenstics : d154 0.9078, n20D 1.4698, A. V. 3.06, S. V. 173.2, I. V. (wijs) 104.4, unsaponifiable matter 1.38%.
    The fatty acids were compcsed of 57.8% of solid acids (mainly myristic, palmitic, and behenic), and 41.7% of liquid acids (mainly tsuzuic, zoomaric, oleic, gadoleic, and an acid having different constitution of ordinary erucic acid). Phytosterol was isolated from the unsaponifiable matter.
    (B) Chinese milk-vetch seed oil.
    The Chinese milk-vetch seed oil obtained from Astragalus sinicus, L. was investigated and properties of the oil were as follows, oil content 5 90%, n20D.
    1 4719, A V 15 7, S V 193 7, I V (wijs) 129. 6, and unsaponifiable matter 5 04%.
    The fatty acids of oil consisted of 25. 44% of saturated acids and 73. 68% of unsaturated. The saturated acids chiefly consisted of stearic, and C14, C16, C20, C24 acids The chief composition of liquid fatty acids was oleic, linoleic, and linolenic Phytosterol was detected from unsaponifiable matter
  • 山本 隆, 角田 清治, 難波 義郎
    1963 年 12 巻 6 号 p. 365-371
    発行日: 1963/06/20
    公開日: 2009/10/09
    ジャーナル フリー
    The “Pickling” of steel or iron comprises removal of metal oxide on the surface by immersion in an acid. It has been found that the addition of cationic surface active agents (CSA) which have been called “Inhibitor” to acid decreases the rate of corrosion.
    In order to study the relationship between chemical construction of CSA and corrosion inhibitive property, various CSA were tested.
    CSA containing I-anion, was superior to others in inhibitive characteristics and luster after acid-cleaning. This comes from the action of HI formed by the double decomposion. of CAS and acid for cleaning. Same results were obtained in case using CSA together with HI.
    There has been no CSA that was effective in H3PO4, but the addition of HI when used together with CSA was greatly effective.
    Chemical construction of cationic parts of CSA did not so affect as were anionic parts.
  • 野中 正夫
    1963 年 12 巻 6 号 p. 371
    発行日: 1963/06/20
    公開日: 2009/10/09
    ジャーナル フリー
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