油化学
Online ISSN : 1884-2003
ISSN-L : 0513-398X
29 巻, 1 号
選択された号の論文の11件中1~11を表示しています
  • 平田 博文
    1980 年 29 巻 1 号 p. 2-14
    発行日: 1980/01/20
    公開日: 2009/11/10
    ジャーナル フリー
  • 西口 毅, 後藤 晋一, 杉崎 勝久, 福住 一雄
    1980 年 29 巻 1 号 p. 15-19
    発行日: 1980/01/20
    公開日: 2009/11/10
    ジャーナル フリー
    リノール酸メチル (ML), サフラワー油, あまに油からの1, 4-シクロヘキサジエン (CHD) の生成が, WCl6-SnBun4系触媒を用いた無溶媒下及びクロロベンゼン中でのオレフィンメタセシス反応において, 検討された。WCl6を主触媒としたMLの反応において, 助触媒の活性は, 最適条件下でSnBun4>SnMe4>AlEt3>SnEt4の順であった。80℃, 3hの反応において, 最適反応条件下のオレフィン/WCl6比は約30, SnBun4/WCl6比は6~8と, ほぼみなしうる。最適条件下におけるオレフィン/触媒比がこのように低いことは, 油脂のエステル基が触媒の活性を低下させていることを示唆している。CHDの存在はオレイン酸メチルの自己メタセシスにおける平衡には影響を及ぼさなかった。このことから, CHDは一度生成すると, もはやメタセシス反応を受けず, 他の生成物間の平衡には関与しないと推定される。最適条件下におけるCHDの収率は, MLの無溶媒下での反応では17%, MLのクロロベンゼン中の反応では24%, サフラワー油の無溶媒下での反応では22%, あまに油の無溶媒下での反応では44%, あまに油のクロロベンゼン中での反応では56%であった。この結果はリノレン酸残基は, リノール酸残基よりも, CHDを与えやすいことを示している。MLの反応で, 触媒を一度に加えず段階的に加えることは, CHDの収率を向上させることが確かめられた。
  • 木村 誓, 柏谷 景昌, 村井 幸一
    1980 年 29 巻 1 号 p. 20-22
    発行日: 1980/01/20
    公開日: 2009/11/10
    ジャーナル フリー
    In order to develop a useful application of α-olefins, investigation was undertaken to synthesize branched fatty acids by the reaction with water and carbon monoxide generated in situ using sulfuric acid and formic acid with a view to employing these branched acid for solvent extraction of metal.
    The highest yield of the branched acid was obtained when 1mol of α-olefin was reacted with 12mol of sulfuric acid and 2mol of formic acid (85%) at 25°C. for 2h.
    The solvent extraction of metal such as Cu, Pb, Cd and Zn was conducted using the branched acids derived from 1-hexene, 1-octene, and 1-decene. Experimental results showed that these branched acids exhibited excellent extractability superior to those of straight chain fatty acids such as capric acid.
  • 立松 良一, 尾嵜 新平, 長瀬 俊治, 犬飼 鑑
    1980 年 29 巻 1 号 p. 23-29
    発行日: 1980/01/20
    公開日: 2010/02/19
    ジャーナル フリー
    Fluorinated nonionic surfactants : CF3 (CF2) 5CH2O (C2H4O) pH, CF3 (CF2) 5CH2CH2O (C2H4O) pH, and CF3 (CF2) 7CH2CH2O (C2H4O) p'H (p=1, 3, 5, 10, 20, p'=1, 3) were prepared by the addition of ethylene oxide (EO) to long-chain fluoroalcohols in the presence of a base or an acid catalyst and their physicochemical properties were clarified.
    Cloud points of aqueous solutions of those adducts were found to be higher with increase in the number of oxyethylene units. For the same number of oxyethylene units, these cloud points decreased with increase in the carbon chain length of the starting alcohols. Among those adducts, CF3 (CF2) 5-CH2O (C2H4O) pH showed the best surface activities; especially the 10mol EO adduct had a strong emul-sifying power toward xylene, and the 20mol EO adduct exhibited a good foaming property. Aqueous solutions of these adducts generally had low surface tension, and CF3 (CF2) 5CH2O (C2H4O) 3H showed the lowest aqueous surface tension (15.4dyn/cm) of the adducts. The cmc values for the fluorinated surfactants increased with increase in the number of oxyethylene units.
    These results were compared with those reported previously, and discussion was made on the characteristics of the surface activities of the fluoroalcohol- EO adducts.
  • その凝集作用とその他の性質
    芹田 元, 大谷 規隆, 木村 誓
    1980 年 29 巻 1 号 p. 30-35
    発行日: 1980/01/20
    公開日: 2009/11/10
    ジャーナル フリー
    Polyurethaneamine (PUA) was prepared from N-methyldiethanolamine and hexamethylenediiso-cyanate. A variety of quaternary ammonium salts of PUA (cationic polymer) were prepared from PUA and alkyl bromides of various chain length (C2C12) with a view of obtaining good flocculants. In alkylating PUA with alkyl bromides, it was found that alkylation occured to urethane-N as well as quaternization reaction, and using low molecule of urethane as model compound prepared from ethanol and hexamethylenediisocyanate, alkylation to urethane-N was ascertained by the reaction of urethane and dodecyl bromide. The flocculation ability for aqueous suspension of kaoline was investigated in the relation to the structure of cationic polymers by measuring the sedimentation velocity, sedimentation volume, and turbidity. Cationic polymer obtained from PUA and the higher alkyl bromide showed good flocculation effect. The suitable range of degree of quaternization was 4060%. Cationic polymer was most effective for flocculation with increase of acidity. The most clarity of supernatant gave 40ppm turbidity at the dosage of 50ppm using cationic polymer (degree of quaternization 84.4%) obtained from PUA and dodecyl bromide. Interraction (metachromasia) between methyl orange and cationic site of a number of cationic polymers were examined, and cationic polymers with the higher degree of quaternization derived from the higher alkyl bromides and PUA were shown large metachro-masia. Cationic polymers derived from the higher alkyl bromides showed good flocculating ability which are not inferior that of typical commercial products.
  • 藤井 富美子, 奥山 春彦
    1980 年 29 巻 1 号 p. 36-42
    発行日: 1980/01/20
    公開日: 2009/11/10
    ジャーナル フリー
    The moisture regain of textile fibers and the water content in solution equilibrated together with then were determined in the presence of various amounts of water solubilized by 0.1M Aerosol OT in perchloroethylene at 10°C, 20°C and 30°C. Simultaneously, the vapor pressure of solubilized water was measured at each temperature. Rayon, wool, nylon and acryl were used as test fabrics.
    The differential heat of absorption of water vapor (ΔHV) on the fabrics was calculated from the slope of linear plots of logarithm of the vapor pressure against the reciprocal of the absolute tempera-ture at given regains. ΔHV decreased with increase of moisture regain of the fabrics and with increase of solvent relative humidity in the solution. When the fabric and solution were in equilibrium with atmosphere, ΔHV was explained by the sum of the heat of solubilization (ΔHS) and the heat of solvation (ΔHH) of water. The decrease in free energy and the entropy change accompanying the absorption of water on the fabrics were also calculated approximately from the present data. It was concluded that the water was held by the fabrics in two different states; i.e., bound water and free water, near-by 75% solvent relative humidity in nonaqueous solution.
  • 渡辺 昭次, 藤田 力, 須賀 恭一, 磯部 敏男, 三浦 俊郎, 倉持 忠雄
    1980 年 29 巻 1 号 p. 43-48
    発行日: 1980/01/20
    公開日: 2009/11/10
    ジャーナル フリー
    3-Hydroxy acids were synthesised in good yield from ketones and carboxylic acids using lithium naphthalenide in the presence of diethylamine. From cyclohexanone and propionic acid, 2- (1-hydroxy- cyclohexyl) propionic acid (3) was obtained in 98% yield. 3-Hydroxy acids were treated with various acidic reagents to give 3, 4-unsaturated carboxylic acids and γ-butyrolactones. From the reaction of (3) with p-toluenesulphonic acid, 2- (1-cyclohexenyl) propionic acid (4) was obtained (yield 98%) and with 97% sulphuric acid 2- (2-hydroxycyclohexyl) propionic acid lactone (5) was formed (93% yield).
    We have found that an 2, 3-unsaturated δ-lactone or spirolactone could be prepared from the reaction of 3-hydroxy acid with 1, 3, 5-trioxane or paraformaldehyde. When a mixture of the compound (3), 1, 3, 5-trioxane, and sulfuric acid was refluxed in acetic acid, 2- (2-hydroxymethylcyclohexylidene) propionic acid lactone (6) was obtained in 88% yield; interestingly, at 25°C, only 2, 5-dimethyl-4, 6-dioxa-3-oxo spirobicyclohexane (7) was obtained in 71% yield.
    3, 4-Unsaturated acids were condensed with paraformaldehyde in boiling acetic acid containing a small amount of aluminium chloride to afford 2, 3-unsaturated δ-lactones. From 2- (1-cyclohexenyl) octanoic acid (8) and paraformaldehyde, 2- (2-hydroxylmethylcyclohexylidene) octanoic acid lactone (9) was obtained in up to 93% yield.
  • 武田 徳司, 安原 諭, 渡辺 昭二
    1980 年 29 巻 1 号 p. 49-52
    発行日: 1980/01/20
    公開日: 2009/11/10
    ジャーナル フリー
    The synthetic reaction of alkyl chloroacetates (1) with ethylene oxide (EO) in N, N-dimethylacet-amide (DMA) was studied. EO was inserted into the C-Cl bond of t-butyl, hexyl, octyl, 1-methyl-heptyl and decyl chloroacetates to form novel compounds, alkyl 2-chloroethoxyacetates (2), although the insertion of EO into the C-Cl bond of 1-chlorooctane did not occur under the same conditions. Zinc chloride and lithium halide were effective catalysts in the present reaction. Optimum amounts of DMA and of zinc chloride to (1) were equimolar and 1/30-1/10 molar, respectively, and optimum temperature was at 110120°C. The effect of the structure of alkyl group of (1) on the yield of (2) was studied. The branching and increasing of alkyl chain diminished the yield of (2).
  • 根来 健二, 田坂 誠基
    1980 年 29 巻 1 号 p. 53-56
    発行日: 1980/01/20
    公開日: 2009/11/10
    ジャーナル フリー
    Sodium N-cyclohexyl-N-n-alkylaminopropan (or ethane) -1-sulfonates (alkyl : butyl-, hexyl-, octyl-) were prepared, separated, refined, and identified. Studies on some physicochemical properties of these aqueous samples solutions were carried out. From these obtained results, it is concluded that these samples were good as surface active and bufferring agents.
  • 富山 新一
    1980 年 29 巻 1 号 p. 57-59
    発行日: 1980/01/20
    公開日: 2010/02/19
    ジャーナル フリー
  • さんま油の脂肪酸組成/ぶどう種子油の脂肪酸組成/各種油脂の脂肪酸組成 索引
    油脂及び油脂製品試験法部会・ガスクロデータ小委員会
    1980 年 29 巻 1 号 p. 70-73
    発行日: 1980/01/20
    公開日: 2009/11/10
    ジャーナル フリー
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