油化学
Online ISSN : 1884-2003
ISSN-L : 0513-398X
24 巻 , 10 号
選択された号の論文の14件中1~14を表示しています
  • 彦田 毅
    1975 年 24 巻 10 号 p. 639-644
    発行日: 1975/10/20
    公開日: 2009/11/10
    ジャーナル フリー
  • 中村 尚武, 渡辺 明
    1975 年 24 巻 10 号 p. 645-648
    発行日: 1975/10/20
    公開日: 2009/11/10
    ジャーナル フリー
    The structures and transition behaviors of the linear long chain primary bromides of even carbon atoms from 1-bromodocosane to 1-bromooctacosane were studied by X-ray powder diffraction method at various temperatures from ordinary temperature to their melting points, and the solid state transition mechanism of the compounds was discussed.
    Crystal structures at room temperature of all the bromides studied here belong to monoclinic system. On the assumption that the c-axis of the unit cell is parallel to the chain axes of the molecules, the lattice constants a (5.51Å), b (7.44Å) and β (117°) are found to be the same within the experimental erorr for all the bromides. The values of the lattice constant c increase with the increasing carbon number of the bromides, 62.4Å for 1-bromodocosane, 67.7Å for 1-bromotetracosane, 72.4Å for 1-bromohexacosane and 78.0Å for 1-bromooctacosane. The c values indicate an arrangement of double layer of molecules.
    Crystal structures of 1-bromodocosane and 1-bromotetracosane at higher temperatures belong to hexagonal system. The basal planes have the same size in both compounds. The lattice constant c of 1-bromodocosane and 1-bromotetracosane are 63.5Å and 67.8Å, respectively. The structures of 1-bromohexacosane and 1-bromooctacosane belong to monoclinic system. Assuming that the crystal axis c is parallel to the molecular chain axes, the lattice constants a, b, c and β in these compounds can be determind as follows; a=4.92Å, b=8.20Å, c=72.3Å and β=98° for 1-bromohexacosane, a=5.12Å, b=8.22Å, c=77.6Å and β=104° for 1-bromooctacosane.
    The mechanism of the solid state phase transition of 1-bromodocosane and 1-bromotetracosane can be interpreted as follows. At their transition points the lattice constants a and b change and the c axis of the crystal is thought to become perpendicular to the basal plane. This transition phenomenon refer to the rotational transition as a molecular rotation around the chain axis. A similar mechanism of the transition could be applied for 1-bromohexacosane and 1-bromooctacosane.
  • 丸銭 詔司, 村瀬 行信
    1975 年 24 巻 10 号 p. 649-653
    発行日: 1975/10/20
    公開日: 2010/02/19
    ジャーナル フリー
    The homogeneous hydrogenation of cottonseed oil in n-hexane by using binary catalyst system of Ziegler type, nickel acetylacetonate [Ni (acac) 2] and triethylaluminium (Et3Al), was performed at low temperatures down to -20°C where saturated or less soluble glycerides were crystallized out of the reacting solution. No one has who heretofore been known explored such a reaction process and it might be called hydrogenation with simultaneous crystallization or H.S.C. in abbreviation to distinguish it from the usual hydrogenation process.
    In this paper, various chemical and physical properties of cake and filtrate fractions produced by the H.S.C. process were examined. Futhermore the cake fractions mentioned above were subjected to the acetone solvent fractionation to produce the fat as filtrate having properties like hard butter which is characterized by the particularly sharp melting point of about body temperature. As the result, the total yield of the desired product was around 60% when the solvent fractionation was properly combined with the H.S.C. at lower temperature.
  • 藤原 義人, 畑 忠太, 松原 義治
    1975 年 24 巻 10 号 p. 654-658
    発行日: 1975/10/20
    公開日: 2009/11/10
    ジャーナル フリー
    Acyclic terpenes and alicyclic alcohols were isomerized and dehydrogenated with catalyst systems composed of copper and zinc over a temperature range from 160 to 262°C under a reduced pressure.
    Geranial, neral, citronellal, dihydrocitronellal, myrcene, and homoperillyl alcohol were obtained by the isomerization and dehydrogenation of geraniol [1], nerol [2], citronellol [3], dihydrocitronellol [4], 2- (10) -pinene [5], and nopol [6], respectively.
    In addition, dehydrogenation of alcohols, such as cyclopentanol [7], cyclohexanol [8], 2-methylcyclohexanol [9], and cyclooctanol [10] gave corresponding alicyclic oxo-compound in almost quantitative yields.
    The most suitable conditions for the reactions mentioned above were proposed in the light of the experimental results.
  • 司 英隆, 斎藤 鐘次郎
    1975 年 24 巻 10 号 p. 659-664
    発行日: 1975/10/20
    公開日: 2009/11/10
    ジャーナル フリー
    Alkylation of methyl=methylthiomethyl=sulfoxide (formaldehyde dimethyl mercaptal S-oxide : FAMSO [1]) with alkyl halides was carried out effectively in tetrahydrofuran (THF) with sodium naphthalene as condensing agent. From n-hexyl bromide, heptylaldehyde dimethyl mercaptal S-oxide [2a] was obtained in 70% yield as main product, and from benzyl bromide, phenyl acetaldehyde dimethyl mercaptal S-oxide [2b] was obtained in 82% yield. Several by-products separated were identified to be methyl hexyl sulfoxide [5], n-dodecane [6], methyl-1-heptenyl sulfoxide ([3a], [3b]), methyl benzyl sulfoxide [8], dibenzyl [9], methyl styryl sulfoxide ([3c], [3d]).
    When the aldehyde dimethyl mercaptal S-oxide [2] was distilled under reduced pressure at 160°C, methyl vinyl sulfide [3] was obtained in quantitative yield. From compound [2a], methyl-1-heptenyl sulfide ([3a], [3b]) was obtained in 97% yield, and from compound [2b], methyl styryl sulfide ([3c], [3d]) was obtained in 96% yield. The by-products in the pyrolysis of compound [2a] were identified to be n-heptylaldehyde [4], S-methyl heptane thioate [12], α-methylthio heptylaldehyde [13], H2O [10], dimethyl disulfide [11].
  • 辻 和郎, 堀内 康子, 寺井 咲子, 小西 一生
    1975 年 24 巻 10 号 p. 665-670
    発行日: 1975/10/20
    公開日: 2009/11/10
    ジャーナル フリー
    The microdetermination of anionic surface-active agents was carried out based on the fact that anionic surfactants generally inhibit the enzyme reaction, and moreover trace amounts of cationic, nonionic and amphoteric surfactants were determined by using the phenomena that these surfactants apparently suppress the inhibition of enzyme activity by anionic surfactants.
    Substrate, 1-naphthyl acetate, was allowed to react with enzyme cholinesterase and the change in absorbance due to formation of 1-naphthol was automatically recorded at 324nm. Surfactants inhibit the enzymatic hydrolysis and cause decreases in the slopes of the absorbance-time curves. Using the degree of the inhibition abilities, the surfactant concentrations were determined. Using this method 20 to 200ppm of sodium linear dodecylbenzenesulfonate could be determined. When enzyme was previously incubated with sodium linear dodecylbenzenesulfonate and then the substrate solution was added to the mixed solution, 10 to 45ppm of the surfactant could be determined.
    When 50ppm of sodium linear pentadecylbenzenesulfonate was previously added to substrate solution as an inhibitor, cationic, nonionic, and amphoteric surfactants diminish the inhibition and the absorbance increases. By this method the determination of 2 to 20ppm of dodecyl trimethyl ammonium chloride, 6 to 100ppm of polyoxyethylene dodecyl ether, 10 to 300ppm of polyoxyethylene octyl phenyl ether and 30 to 100ppm of dodecyl betaine has become feasible.
  • 関口 一, 大場 健吉, 増田 光輝, 杉山 豊樹
    1975 年 24 巻 10 号 p. 671-674
    発行日: 1975/10/20
    公開日: 2009/11/10
    ジャーナル フリー
    To investigate the role of adsorption and the subsequent biodegradation of α-olefin sulfonate (AOS) in a sewage treatment system, the adsorption of AOS onto three cultures was observed at three pH conditions of 3.5, 7.2 and 8.5. The tested microorganisms were Pseudomonas surfactassimilas, gram-negative Escherichia coli (F-1) and gram-positive Bacillus subtilis (PCI). Out of those three, only Pseudomonas surfactassimilas has the surfactant degrading ability.
    The adsorption tests showed no significant difference in terms of adsorbing behavior between surfactant degrading and non-degrading bacteria as well as between gram-positive and gram-negative bacteria. In all cases of three bacteria, the adsorption took place according to a Freundlich adsorption isotherm and higher adsorption was observed at low pH of 3.5.
    Only in the case of surfactant degrading Pseudomonas surfactassimilas, the initial reduction of AOS by physical adsorption was followed by the successive reduction due to the biodegradation; and re-added AOS was subject to the similar adsorption and subsequent biodegradation again.
    These phenomena indicate that the removal of surfactant in a sewage treatment process is made not by a single step, but by the combination of two successive steps of the adsorption and the subsequent biodegradation.
  • 関口 一, 大場 健吉, 増田 光輝, 杉山 豊樹
    1975 年 24 巻 10 号 p. 675-679
    発行日: 1975/10/20
    公開日: 2009/11/10
    ジャーナル フリー
    Major components of α-olefin sulfonate (AOS) are alkene sulfonates and hydroxyalkane sulfonates.
    The relative biodegradation rate of alkene selfonate and hydroxyalkane sulfonate was measured to investigate the biodegradation process of AOS by activated sludge, by the use of a gas chromatographic analysis after having converted the residual sulfonates to sulfonyl chloride derivatives.
    Four α-olefin sulfonates of single carbon chain C15, C16, C17 and C18 were partially biodegraded respectively upto ca. 50% degradation level, and in all cases, it was found that the biodegradation rate of the alkene sulfonate was two times or more rapider than that of the hydroxyalkane sulfonate.
    It was observed that there was little difference in biodegradation rate caused by different carbon chain length of lipophilic group.
    The similar result was also obtained, with 50 to 70% degraded samples of the three C15 to C18 AOS mixtures, which had different disulfonate content.
  • 笠野 雅信, 松原 義治
    1975 年 24 巻 10 号 p. 680-684
    発行日: 1975/10/20
    公開日: 2009/11/10
    ジャーナル フリー
    Sesquiterpenyl ethylene glycol monoethers (containing terpenyl group : longimethylcamphenylyl [8], T-cadinyl [13], α-cadinyl [14] and γ-cadinyl [15]), sesquiterpenyl diethylene glycol monoethers (containing terpenyl group : longimethylcamphenylyl [9], T-cadinyl [16], α-cadinyl [17] and γ-cadinyl [18]), sesquiterpenyl triethylene glycol monoethers (containing terpenyl group : longimethylcamphenylyl [10], T-cadinyl [19] and α-cadinyl [20]) and sesquiterpenyl polyethylene glycol monoethers (containing terpenyl group : longimethylcamphenylyl [11], [12], T-cadinyl [21], [23] and α-cadinyl [22], [24]) were prepared by the reaction of various sesquiterpene hydrocarbons such as longifolene [1] and γ-cadinene [2] with ethylene glycol [3], diethylene glycol [4], triethylene glycol [5] and polyethylene glycol (MW=400 [6] and 600 [7]) in the presence of cation exchange resin at 50°±2°C. These structures were confirmed by physical constants, IR and NMR spectra. Surface activities such as surface tention, foaming property, penetrating power, solubilizing power and emulsifying power of these nonionic surfactants were investigated.
    As a result sesquiterpenyl polyethylene glycol monoethers had lower foaming property than ABS (alkyl benzene sulfonate). Sesquiterpenyl polyethylene glycol monoethers obtained by reaction of sesquiterpene hydrocarbons and polyethylene glycol (MW=400, 600) had far better penetrating power than ABS.
    Antimicrobial activity of these sesquiterpenyl ethylene- and sesquiterpenyl polyethylene-glycol monoethers were investigated.
  • 星加 安之, 角脇 〓, 小島 一郎, 小池 一美, 吉本 健二
    1975 年 24 巻 10 号 p. 685-686
    発行日: 1975/10/20
    公開日: 2009/11/10
    ジャーナル フリー
    Determination of the sulfur compounds in the exhaust gas from a cellophan factory were studied by gas chromatography equipped with liquid oxygen cold trap, and with flame photometric detector.
    The sulfur compounds, i.e., COS. H2S, CS2 were identified with the use of TCEP and TCP columns, and the ranges of the detected concentrations were as follows; COS 8-14ng/0.01l, H2S 26-48, CS2 720->1, 000 in non irradiation, respectively (Table-1).
    Light irradiation of natural sunlight (0.6cal cm-2 min-1, by thermocouple type) effect of the exhaust gas were produced COS (ab. 23ng/0.01l), SO2 (ab. 800ng/0.01l) but not H2S (Table-2).
  • 西田 守衛, 宮岸 重好, 樽谷 隆至, 岡野 政次
    1975 年 24 巻 10 号 p. 687-688
    発行日: 1975/10/20
    公開日: 2009/11/10
    ジャーナル フリー
    Long chain alkylamines were found to behavior as the thermotropic liquid crystals at a certain temperature range, that is, at 2765, 3874, 4777 and 5589°C, respectively, in laurylamine, mirystylamine, cetylamine and stearylamine. These liquid crystals were studied by means of DTA, IR spectroscopy, dielectric constant and microscopic observation. The mixtures of these two amines also were investigated.
  • 菊地 英夫, 須賀 恭一, 渡辺 昭次, 藤田 力
    1975 年 24 巻 10 号 p. 689-690
    発行日: 1975/10/20
    公開日: 2009/11/10
    ジャーナル フリー
    Isomerization of eugenol to isoeugenol was examined by the use of various transition metal complexes. It has been found that PdCl2-nitrile and PdCl2-olefin complexes are excellent catalysts of this reaction.
  • 中川 照真
    1975 年 24 巻 10 号 p. 691-699
    発行日: 1975/10/20
    公開日: 2009/11/10
    ジャーナル フリー
  • Henryk NIEWIADOMSKI, 阿部 芳郎
    1975 年 24 巻 10 号 p. 700-703
    発行日: 1975/10/20
    公開日: 2009/11/10
    ジャーナル フリー
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