油化学
Online ISSN : 1884-2003
ISSN-L : 0513-398X
25 巻 , 2 号
選択された号の論文の9件中1~9を表示しています
  • 皆川 源信
    1976 年 25 巻 2 号 p. 67-74
    発行日: 1976/02/20
    公開日: 2009/11/10
    ジャーナル フリー
  • Yasuo SUHARA
    1976 年 25 巻 2 号 p. 75-78
    発行日: 1976/02/20
    公開日: 2009/11/10
    ジャーナル フリー
    The photo-induced addition of acetic acid to ethylene gave butyric acid. Small amounts of hexanoic, octanoic, 2-ethylbutyric, and 2-ethylhexanoic acids, and neutral substances were also formed. The presence of a small amount of di-tert. butyl peroxide was effective to form butyric acid. Main neutral substances were dibutyl and di (2-ethylhexyl) phthalates.
    A straight-chain saturated fatty acid was also obtained in an excellent conversion of a 1-olefin by the photo-induced addition of acetic acid to the 1-olefin [acetic acid : 1-olefin, 200 : 1 (mol)]. It was assumed that a ketone and an ester (s) were present in the by-products.
  • 斎藤 衛郎, 金田 尚志
    1976 年 25 巻 2 号 p. 79-86
    発行日: 1976/02/20
    公開日: 2009/11/10
    ジャーナル フリー
    It is known that polymerized oils heated in the inert gas showed toxicity to rats. The toxic components in those oils were presumed to be the monomeric cyclic fatty acids. But little knowledge has been obtained on the exact structure of them. A series of studies was performed to know more detailed structure and biological properties of these cyclic fatty acids.
    Linseed oil heated in the nitrogen atomosphere was converted to methyl esters and subjected to distillation under reduced pressure. The distillate was treated with urea and fractionated into urea adduct and non-adduct-forming fractions. The latter was found to be toxic in a mouse bioassy. This fraction was converted to Bromo-Mercuri-Methoxy (BMM) adducts and chromatographed by silicic acid. After fractionation, the methoxy and bromo mercury groups were eliminated and recovered the original esters. The toxic study indicated that the fraction eluted with petroleum ether : dioxane (90 : 10) (Fr. III.) was found to be the most toxic to mice. In order to concentrate the toxic substances, BMM adducts were reformed from Fr. III and rechromatographed by successive elution with dioxane in petroleum ether in the ratio of 2 : 98 (Fr. III-A), 5 : 95 (Fr. III-B) and 10 : 90 (Fr.III-C). The results indicated that the Fr. III-B was the most toxic followed by the Fr. III-A and Fr. II-C. Subsequent analysis with the aid of GC-MS indicated that these toxic compounds had the skelton of methyl 7- (2'-n-propyl-cyclohexyl) nonancate and methyl 6- (2'-n- butylcyclohexyl) octanoate and containing two double bonds. In an attempt to determine the positions of the double bonds, the main components were collected by preparative GLC and were converted to TMS derivatives to be subjected to GC-MS analysis. The results revealed the presence of four positional isomers from (I) to (IV) in the most toxic fraction.
  • 石上 裕, 楢崎 英男
    1976 年 25 巻 2 号 p. 87-89
    発行日: 1976/02/20
    公開日: 2009/11/10
    ジャーナル フリー
    To investigate the solution behavior of the polysoap (potassium salt of the alternating malefic anhydride and cetylvinyl ether copolymer, MW=6.0×105) which has the tendency of intermolecular association in water, ageing effect of the solution on the Zimm plot and of the reduced viscosity was examined. After heating at 70 °C for a day, the Zimm plot of the polysoap solution showed an unusual shape and the corresponding MW was 1×106, whereas following the four day storage at 70°C the established type of Zimm plot was obtaind and the MW was 5.9×105. This phenomena may be attributed to the disentanglement of the dissolved polysoap molecules which were entangled mechanically in the loops of other molecules. This may be a kind of disruption of the intermolecular aggregates of the polysoap, and then thermodynamically stable aggregates seem to be formed at equilibrium corresponding to the hydrophobic and hydrophilic balance of the polysoap. Also, it was noteworthy that the reduced viscosity greatly depended upon the previous thermal history of the polysoap solution. When the polysoap was dried up from the solution examined above and the reduced viscosity was measured again after heating, both the reduced viscosity and the pH of the solutions were lower than those of the initial solutions. This may be interpreted by the contraction of the polysoap because the polysoap increased its own hydrophobic property as the result of the partial hydrolysis of its carboxylate groups under the influence of atmospheric carbon dioxide.
    From the result, it is plausible that the features of polysoap (solubilization, dispersion and so on) depend upon the thermal history of the aqueous solutions.
  • 石上 裕
    1976 年 25 巻 2 号 p. 90-95
    発行日: 1976/02/20
    公開日: 2009/11/10
    ジャーナル フリー
    To investigate the solution behavior of the polysoap (potassium salt of alternating maleic anhydride and cetylvinyl ether copolymer), the interaction between polysoap and monosoap (potassium laurate (KL) and caprylate) in aqueous solutions was studied by determination of the amount of KL bound onto the polysoap, and by the light scattering measurement of aqueous polysoap solutions containing constant concentrations of monosoaps or potassium acetate.
    The binding of KL onto the polysoap occurred over the entire concentration range, similarly to the solubilization of oil by polysoap. The amount of KL onto the polysoap increased linearly with polysoap concentration, and was 0.7 mol/basemol polysoap at the 0.4% polysoap solution in the 0.18 M-KOH solution as a solvent.
    Potassium salts of shorter members of fatty acids (≤C8) promoted the intermolecular association between polysoap molecules, instead of the binding onto the polysoap.
    On the other hand, KL interrupted the intermolecular association between polysoap molecules in aqueous solution, because of hydrophobic interaction between the hydrophobic portion of KL and polysoap, and so the complex formation of KL and almost one unit of polysoap may be confirmed.
  • 石上 裕
    1976 年 25 巻 2 号 p. 96-101
    発行日: 1976/02/20
    公開日: 2009/11/10
    ジャーナル フリー
    (1) Interactions between polysoap (potassium salt of alternating maleic anhydride and cetylvinyl ether copolymer) and monosoap (potassium palmitate (KP), laurate (KL), and caprylate (KC)) in aqueous solution, were classified into four groups from the viscosity behavior of the nixed polysoap/ monosoap solutions at constant mixed ratios.
    a) The plots of the observed reduced viscosity vs. polysoap concentration were in straight line and were in parallel to the calculated plots (the summation of the viscosity of the polysoap and the monosoap solution respectively). This would mean the presence of the polysoap/monosoap complexes due to the hydrophobic bonding which had constant compositions and contents.
    b) The observed plots were almost flat, while the calculated ones were sloping. This may be attributed to the contraction of the polysoap molecules subsequent to the fixation of counter ions by polysoap anions, similarly to the effect of the addition of potassium acetate (KA) on the viscosity of the polysoap solution.
    c) The observed plots were situated on remarkably lower levels than the calculated ones (the KL/polysoap systems in the 4/1 (mol/basemol basis) mixed ratio). This seems to correspond that intermolecular aggregates of the polysoap present in the aqueous polysoap solution were degrated by the adsorption of the monosoap to the polysoap owing to the hydrophobic bonding between them.
    d) Distinct maxima occurred in the observed plots (the KC/polysoap systems in the 12/ 1 mixed ratio). It could be considered that the saturated adsorption of KC to the polysoap was attained at the maximum by the hydrophobic bonding between them.
    (2) Hydrophobic interactions between polysoap and monosoap were also confirmed from the carbon black dispersion of the mixed polysoap/monosoap solutions in comparison with the mixed polysoap/KA solutions.
    (3) The hydrophobic interactions between polysoap and monosoap were governed by the number of chemically-attached soap-like groups of the polysoap, and monosoaps interacted in a less degree with smaller polysoaps.
  • 阿部 芳郎, 小山内 州一
    1976 年 25 巻 2 号 p. 102-105
    発行日: 1976/02/20
    公開日: 2009/11/10
    ジャーナル フリー
    N-Substituted aminosulfonic acid derivatives, ROC2H4N (R') (CH2) 1-2SO3M, R=C10H21, C12H25 R'= H, CH3 M=H, Na, containing long chain alkoxy group were synthesized, and their growth inhibitory activities against Gram positive, Gram negative bacilli and some fungi were compared with those of the N-substituted amino acid derivatives. The introduction of the self onic group instead of the carboxylic group to the N- (2-alkoxyethyl) amino methane or ethane carboxylic acid type amphoterics enhanced their antimicrobial activities. The number of methylene groups between amino and self onic groups influenced their antimicrobial properties, and aminomethanesulf onic acid derivatives showed stronger antimicrobial activities than aminoethanesulfonic acid derivatives. Dodecoxy group was more effective on their antimicrobial properties than the decoxy group. The antimicrobial effect of a methyl group introduced into N atom of the N-alkoxyethylaminomethanesulfonic acid was not so clear as that of a methyl group in the N-substituted amino acid type amphoterics. Moreover, aqueous solution of these amphoterics showed better surface activities at any pH environment,
  • 桑村 常彦
    1976 年 25 巻 2 号 p. 106-109
    発行日: 1976/02/20
    公開日: 2009/11/10
    ジャーナル フリー
    A homologous series of 2-hydroxy -3-alkoxypropane sulf onates (HAPS) was prepared by the addition of sulfite to alkyl glycidyl ethers (R : C4C9). The efficiency of HAPS as an additive for promoting mercerization was evaluated by a conventional method of measuring a rate of shrinkage of cotton thread in concentrated alkaline solution (2040%) at 25°C. HAPS having a proper hydrocarbon chain (R : i -C5n-C8), as well as some commercial wetting agents, Tergitol EH, Teepol X, Emal O, exhibited high ability of accelerating shrinkage of cotton fiber due to alkali.
  • 渡辺 昭次, 藤田 力, 須賀 恭一, 斎藤 紀雄
    1976 年 25 巻 2 号 p. 110-112
    発行日: 1976/02/20
    公開日: 2010/02/19
    ジャーナル フリー
    Reaction of vinylmagnesium chloride v ith cyclic carboxylic acids and their methyl esters produces a mixture of vinylketone and divinylcarbinol. For example, from 2-furoic acid, a mixture of 3- (2'-furyl) -3-hydroxy-1, 4-pentadiene, 1- (2'-furyl) -4-penten-1-one, and 1- (2'-furyl) -2-propen-1-one was obtained in good yield.
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