油化学
Online ISSN : 1884-2003
ISSN-L : 0513-398X
24 巻 , 6 号
選択された号の論文の11件中1~11を表示しています
  • 森 昭
    1975 年 24 巻 6 号 p. 347-356
    発行日: 1975/06/20
    公開日: 2009/11/10
    ジャーナル フリー
  • Ryoichi MAEJIMA
    1975 年 24 巻 6 号 p. 357-362
    発行日: 1975/06/20
    公開日: 2009/11/10
    ジャーナル フリー
    Highly purified β-1-monoglycerides from Nihon Glycerides Co. Ltd. was used for taking powder X-ray patterns of them. The results are as follows :
    1) Nearly hexagonal packing which was proposed in the previous paper1) explaining the existence of the short spacings for the β-1-monoglycerides of Riken Vitamin Co. Ltd. has also been applied to the short spacings of the specimens used in this paper, and the best fits are obtained between observed short spacings and calculated ones.
    2) Especial attention has been given to the extraordinary strong X-ray intensity of every (00 n+5) spacing, then the model which is constructed to describe the mass distribution of the chain molecule along its axis has been proposed by assuming that the two glycerol radicals in a double molecule are arranged in alignment with the acid chain, and the intensity ratios of (00 n+4), (00 n+5) and (00 n+6) are calculated based upon the model. The calculated intensity ratios are in fair accord with the observed ones, considering that the length of the gap between two successive double molecules increases slightly with carbon number.
  • 和泉 学, 佐藤 誠, 庄子 栄
    1975 年 24 巻 6 号 p. 363-366
    発行日: 1975/06/20
    公開日: 2009/11/10
    ジャーナル フリー
    Some aliphatic nitrogen compounds have the properties of reacting with or being absorbed strongly to metals, metal salts etc., due to the action of the unshared electron pair on nitrogen atom in the molecule. If the structural balance of the hydrophilic and the hydrophobic groups in the molecule is suitable, an interesting application of the compounds may be expected. With the aim to obtain such compounds, aminolysis of cuttlefish oil (CFO) with ethylenediamine (ED), 2-aminoethanol (AE) or diethanolamine (DEA) was studied. As a results, the desirable conditions for manufacturing N-monoacyl derivatives were proposed.
    N-monoacyl ethylenediamine……mole ratio of CFO : ED=1 : 6, reaction temperature 200°C, reaction time 1 hour.
    N-monoacyl-2-aminoethanol……mole ratio of CFO : AE : sodium methoxide=1 : 6 : 1.4×10-3 or 1 : 3 : 7×10-4, reaction temperature 112° or 142°C, reaction time 35 minutes.
    N-acyl diethanolamine……mole ratio of CFO : DEA : sodium methoxide=1 : 6 : 7×10-3, reaction temperature 150°C, reaction time 35 minutes.
  • 高木 徹, 山崎 恵
    1975 年 24 巻 6 号 p. 367-370
    発行日: 1975/06/20
    公開日: 2009/11/10
    ジャーナル フリー
    The methods for the rapid analysis of commercial hexane in edible oils are presented. Precolumn attachments are used to protect the analytical column from the contamination with the nonvolatile oils. Analysis is carried out by the direct injection of the oils into the precolumn or by the insertion of the precolumn containing the oils. The minimum limits of the determination are about 0.5 and 0.05ppm respectively using FID detectors under the conditions of these experiments. The detection of commercial hexane can be confirmed by the retention time and the relative ratio of the peak area in GC analysis, and the mass spectrum in GC-Mass analysis.
  • 戸谷 永生, 松尾 登
    1975 年 24 巻 6 号 p. 371-376
    発行日: 1975/06/20
    公開日: 2010/02/19
    ジャーナル フリー
    A mixture of cyclic monomers were prepared from photo-isomerised tung oil under the condition of 295°C, 15min in a stainless autoclave. The mixture was separated by an inverted dry column packed with AgNO3-silica gel into 5, 6-disubstituted 1, 3-cyclohexadiene (A), 1, 6-disubstituted-1, 3-cyclohexadiene (B), 1, 2-disubstituted-1, 3-cyclohexadiene (C), 1, 6-disubstituted-1-cyclohexene (D) and o-substituted aromatic compounds (E). Then, these cyclic monomers were studied chemically and instrumentally in reference to the literature.
    It was found that the cyclic monomers first produced from the tung oil were A, and then A were isomerised by heating at 240°C to C via B.
    Further, C showed disproportionation reaction i.e., C changed into D and E by heating at 250°C for 5hr.
  • 高木 徹, 市川 和昭, 浜口 哲夫, 福住 一雄, 青山 正博
    1975 年 24 巻 6 号 p. 377-380
    発行日: 1975/06/20
    公開日: 2009/11/10
    ジャーナル フリー
    The homogeneous olefin metathesis of 2-heptene with a catalyst system of WCl6-Bu4Sn was investigated. The optimum ratios of Bu4Sn to WCl6 were in the wide range of 1.02.0, and the Friedel-Crafts products were less than 3% when the ratios were more than 1.0. The addition of ether to the reaction medium has a relatively little influence on the catalyst activity. Bu3SnCl and Bu2SnCl2 were not effective as the cocatalyst and the decrease of the conversion with the excess amount of Bu4Sn was not significant. It therefore seems likely that Bu4Sn can provide only one alkyl group for the substitution of WCl6 and the substitution attains equilibrium in the first step of the catalyst formation.
  • 永山 升三, 奥村 統, 谷口 勝美, 安達 郁男
    1975 年 24 巻 6 号 p. 381-384
    発行日: 1975/06/20
    公開日: 2009/11/10
    ジャーナル フリー
    The sulfation reactions of long chain alkyl primary alcohols having sulfur in the β-position by various sulfating agents were studied. 2-Alkylsulfinylethanol was reacted with strong sulfating agents, i.e., chlorosulfonic acid or sulfur trioxide to give 2-alkylsulfinylethyl sulfate in 6373% yield, whereas 2-alkylmercaptoethanol was not sulfated with such strong acids but sulfated with weak acids, i.e., sulfamic acid-dimethyl formamide or sulfamic acid-urea complex to give 2-alkylmercaptoethyl sulfate in 7387% yield. 2-Alkylsulfonylethanol was also reacted with weak sulfating agents to give 2-alkylsulfonylethyl sulfate in high yield but in lower yield with strong sulfating agents.
    The stabilities toward hydrolysis of sodium 2-alkylmercapto, sulfinyl, sulfonylethyl sulfates were compared with those of sodium alkyl sulfates. Under acidic conditions, these alkyl sulfates having S, SO and SO2 groups in the β-position behaved almost similaly to alkyl sulfates, but under basic conditions, they were rapidly hydrolyzed to mainly alkyl vinyl sulfide, sulfoxide and sulfone respectively along with small amounts of the corresponding alcohols.
  • 加藤 仁司, 藤田 学, 国弘 和雄
    1975 年 24 巻 6 号 p. 385-388
    発行日: 1975/06/20
    公開日: 2010/02/19
    ジャーナル フリー
    A gas chromatographic method for the determination of sodium nitrilotriacetate (NTA) and sodium citrate (SC) in granular detergent was investigated.
    NTA and SC were directly converted into their n-propyl esters under a continuous flow of dry hydrogen chloride gas, without any previous acidification. The optimum reaction time was found to be 2 hours at the reflux temperature of n-propyl alcohol. These volatile derivatives were separated and determined on a silicone OV-17 column (1m×3mm i.d.), with n-propyl myristate as an internal standard.
    NTA and SC were quantitatively rceovered from a standard detergent in the range of usual formulations. This method allows a rapid simultaneous determination of NTA and SC in granular detergents.
  • 高野 敏, 八木 典子, 国弘 和雄
    1975 年 24 巻 6 号 p. 389-394
    発行日: 1975/06/20
    公開日: 2010/02/19
    ジャーナル フリー
    A selective and sensitive chromatographic method for the determination of trace amounts of alkyl benzenesulfonates (ABS) has been developed.
    ABS in water was satisfactorily recovered by the use of Amberlite XAD-2 resin, a stylene-divinylbenzene porous polymer. Further, Amberlite XAD-2 was useful for the separation of ABS and other admixtures in contaminated water.
    The samples treated with Amberlite XAD-2 were concentrated and then determined either by methylene blue spectrophotometric method after acid hydrolysis or by high performance liquid chromatography (HPLC).
    Silicagel was used as a stationary phase in HPLC and the samples dissolved in methanol were determined by stepwise elution method at 225nm, The peak of ABS was very sharp and separated enough from other admixtures in contaminated water. The detection limit of ABS was 0.1μg.
    A good reproducibility on the determination of ABS in river water was obtained by both methods, but HPLC method showed much better selectivity and sensitivity in comparison with methylene blue spectrophotometric method. Therefore, HPLC method is applicable for the determination of trace amounts of ABS in contaminated water.
  • 永山 升三, 奥村 統, 阪谷 武信, 橋本 茂, 野田 誠二
    1975 年 24 巻 6 号 p. 395-399
    発行日: 1975/06/20
    公開日: 2009/11/10
    ジャーナル フリー
    The mechanism of the formation of sodium salt of α-sulfo fatty acid methyl esters (α-SFMeNa) and disodium α-sulfo fatty acids (α-SFNa2) by sulfonation of methyl esters of fatty acids (FMe) with sulfur trioxide (SO3) was investigated.
    Methyl propionate and methyl stearate were sulfonated by dropwise addition of SO3 in carbon tetrachloride at -20°C, and the structure of the initial sulfonation product (I) was elucidated by the NMR analysis. The product (I) was FMe-SO3 adduct which was stable at -20°C, but when it was warmed to room temperature another SO3 attacked at α-hydrogen to give α-sulfonated FMe-SO3 adduct. This intermediate was neutralized with NaOH to give α-SFNa2 of which detergency and solubility were extremely poor. However, this intermediate was heated to 60°C and then neutralized to give α-SFMeNa which was known as an anionic surfactant with excellent biodegradability and detergency.
    In a continuous thin film sulfonator, the higher the molar ratio of SO3 to FMe and the higher the reaction temperature were, the higher conversion ratio was obtained. However, the rate of the elimination reaction of the intermediate to α-SFMe was so slow that no more than 84% conversion ratio was obtained. Consequently, to gain the highest yields, the post reactor in which the inter-mediate was kept for a longer period at higher temperatures was necessary.
  • 宮嶋 孝一郎
    1975 年 24 巻 6 号 p. 400-408
    発行日: 1975/06/20
    公開日: 2009/11/10
    ジャーナル フリー
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