油化学
Online ISSN : 1884-2003
ISSN-L : 0513-398X
18 巻 , 12 号
選択された号の論文の16件中1~16を表示しています
  • 角田 光雄
    1969 年 18 巻 12 号 p. 839-848
    発行日: 1969/12/20
    公開日: 2009/10/20
    ジャーナル フリー
  • 新谷 〓, 丸山 武紀, 今村 正男, 松本 太郎
    1969 年 18 巻 12 号 p. 849-853
    発行日: 1969/12/20
    公開日: 2009/10/20
    ジャーナル フリー
    Seven samples of liquid soybean oil, #135 (I.V. 136.2) and 6 kinds of its serially hardened oil including #120 (I.V. 119.8), #100 (100.6), #80 (83.1), #60 (56.5), #30 (31.1) and #0 (1.7); and another seven samples of #135 oil admixed with fully hardened soybean oil #0 by ratio of 95, 90, 75, 10 and 5%, were submitted to continuous cooling and heating differential thermal analyses (DTA) from -90° to +80°C.
    1) Cooling DTA of the unhardened soybean oil (#135) showed three small exothermic peaks in the temperature range below 0°C. These peaks subsequently transited to the higher temperature side with higher degree of hardening, and the peaks transit to temperature above 0°C from #80 and above, the shapes becoming simpler.
    2) Continuous heating DTA resulted in three endothermic peaks in unhardened #135, the peaks being sharper than those in the case of cooling DTA. These became larger with higher degree of hardening, and the final melting peak transited to the higher temperature side. The peaks were sharper than in the case of cooling DTA.
    3) Cooling DTA of liquid soybean oil mixed with 90 and 95% of fully hardened soybean oil showed only one large exothermic peak at 4546°C, but those mixed with 2575% of hardened oil showed two exothermic peaks.
    4) Continuous heating DTA of the liquid oil mixed with 90 or 95% of fully hardened oil showed the exothermic peaks generally observed on heating DTA, different from those in the cooling DTA. Liquid oils mixed with less than 90% of hardened oil showed the peaks of liquid oil in the low temperature area. A phase diagram is obtained by plotting these endothermic peaks against the mixing ratio of hardened oil.
  • 宮川 正美
    1969 年 18 巻 12 号 p. 854-857
    発行日: 1969/12/20
    公開日: 2009/10/20
    ジャーナル フリー
    Ethyl and isobutyl acetates were pyrolyzed at various temperatures from 450 to 700°C, by which the variations of products with increase in the temperature were studied. The production increased in the amount with rise of the temperature, which tendency is common to the acetic esters carrying β-hydrogen, independently upon the number of β-hydrogen. The principal products from ethyl acetate were acetic acid, ethylene, acetone, carbon dioxide, methane and carbon monoxide. Those from isobutyl acetate were acetic acid, isobutylene, acetone, carbon dioxide, methane, carbon monoxide and a C5-compound. The production of acetic acid, ethylene and isobutylene increased with the rise of the temperature, whereas that of the other products mentioned above was almost temperature-independent. It may be attributed that the pyrolysis of ethyl acetate is an elimination reaction of ethylene, and that of isobutyl acetate is accompanied by other reactions in addition to an isobutylene elimination.
  • 竹原 喜久男, 岡嶋 成晃, 池田 功, 阿河 利男, 小森 三郎
    1969 年 18 巻 12 号 p. 858-862
    発行日: 1969/12/20
    公開日: 2009/10/20
    ジャーナル フリー
    We have previously reported the preparation of higher tert-amin from fatty ester and tert-amine. This report deals the preparation of unsaturated higher amine by similar method from unsaturated fatty ester.
    Ethyl oleate and triethylamine were reacted at the condition of hydrogenolysis, obtaining unsaturated higher tert-amine, Hydrogenolysis of unsaturated fatty ester Cu-Cr-O catalyst gives saturated alcohol, but in the presence of amine, C-C double bond maintained about 50%. And the presence of Cd salt as a co-catalyst increased the survival of unsaturation of the product up to 60% approx.
    The reaction condition that gave the best yield of 86% for the tert-amine was as follows.
    Mole ratio of ethyloleate ; triethylamine=1 : 5
    Weight % of the catalyst to sample ester : 20%
    Cadmium acetate wt% to sample ester : 4%
    Initial hydrogen pressure : 100kg/cm2
    Reaction temperature : 300°C
    Reaction time : 3hr
    In the case sperm oil, a good result was obtained in 80% yield of unsaturated amine with approx. 90% of survival unsaturation under higher initial pressure, 150kg/cm.
  • 鈴木 修, 橋本 哲太郎
    1969 年 18 巻 12 号 p. 862-867
    発行日: 1969/12/20
    公開日: 2009/10/20
    ジャーナル フリー
    When an equimolar mixture of methyl linoleate and methyl trans-9, trans-11-octadecadienoate was heated at 230 or 250°C, the linoleate did not react with the conjugated octadecadienoate ; but when the same mixture was heated at 270° or 290°C, the linoleate formed a small amount of addition compound with the conjugated octadecadienoate. In all cases, however, the conjugated octadecadienoate underwent dimerization.
    From the results of reaction rate measurements at 270 and 290°C, it has been found that the dienophilic activity of the linoleate is about one-tenth as large as that of the conjugated octadecadienoate.
  • 鈴木 修, 橋本 哲太郎
    1969 年 18 巻 12 号 p. 867-873
    発行日: 1969/12/20
    公開日: 2009/10/20
    ジャーナル フリー
    Anthraquinone has been recognized as an effective catalyst for the thermal dimerization and the formation of conjugated isomers of methyl linoleate. From the results of analysis of kinetic data obtained, the mechanism of thermal dimerization of methyl Linoleate in the presence of anthraquinone is proposed as follows : The anthraquinone draws off a hydrogen atom from methyl linoleate molecule thus forming the radicals, which in turn produce either dimer by the radical-addition reaction or conjugated isomers of methyl linoleate. Then, the conjugated isomers and the linoleate dimerize by the Diels-Alder reaction, where the trans, trans-conjugated isomer acts as diene, and the trans, trans-, the cis, trans-conjugated isomer or the linoleate act as dienophile. Besides these reactions, the formation of octadecenoate also occurs.
  • 鈴木 修, 橋本 哲太郎
    1969 年 18 巻 12 号 p. 874-878
    発行日: 1969/12/20
    公開日: 2009/10/20
    ジャーナル フリー
    The mechanism of thermal dimerization of methyl linoleate has been studied by a kinetic method. Based on the results of analysis of kinetic data obtained, the following reaction mechanism is proposed : This involves three steps. The first is the draw off of an isolated α-methylenic hydrogen atom from the methyl linoleate molecule by a second molecule, where the linoleate reacts in both as a hydrogen donor and as a hydrogen accepter. This will give rise to two radicals, octadecadienoate radicals R·1 and octadecenoate radicals (R·2). The second step is the formation of cis, trans-conjugated isomers of methyl linoleate and the isomerization of the cis, trans-isomers into the trans, trans-form. The cis, trans-isomers are formed by a chain reaction in which R·1 of the conjugated form draws off a hydrogen atom from the linoleate molecule to form the conjugated isomer and a new R·1 radical. The final step is the dimer-formation by (1) addition reactions between R·1 and R·2 and by (2) the Diels-Alder reactions of the conjugated isomers and the linoleate, where the trans, trans-isomer acts as diene and the trans, trans-, the cis, trans-isomer or the linoleate act as dienophile. Besides these reactions, the formation of octadecenoate by the interaction of R·2 with the linoleate also occurs.
  • 須賀恭一 , 渡辺昭次 , 藤田力 , 国吉正之
    1969 年 18 巻 12 号 p. 878-881
    発行日: 1969/12/20
    公開日: 2009/10/20
    ジャーナル フリー
    The reaction of styrene derivatives with lithium naphthalene was studied. 2, 3-Dimethyl-1, 4-diphenyl butane was obtained from ω-methyl styrene and allyl benzene, 1, 4-diphenyl-2-butene from ω-bromostyrene, 2, 3-diphenyl adipic acid from cinnamic acid, 1, 1, 4, 4-tetraphenyl butane from 1, 1-diphenyl ethylene, and 1, 4-diphenyl butane from phenylacetylene. Reactions of lithium naphthalene with 1, 2-disubstituted ethylenes gave the reduction products.
  • 岡本 能樹, 新田 勉, 桜井 洸
    1969 年 18 巻 12 号 p. 882-885
    発行日: 1969/12/20
    公開日: 2009/10/20
    ジャーナル フリー
    α, β-Unsaturated alkenephosphonic acids, having even number carbon atoms from 6 to 14, were prepared by dehydrochlorination of β-chloroalkanephosphonic acids, which were obtained by the reaction of α-olefin and phosphorus pentachloride.
    By the addition of adequate amount of phosphorus trichloride into the reaction mixture, the yield of by-product, 1, 2-dichloroalkane, was suppressed and β-chloroalkanephosphonic acid could be obtained in high yield (93%).
    Dehydrochlorination of β-chloroalkanephosphonic acid could be conducted with morpholine, dimethylaniline and aniline (pKa<8.35), and α, β-unsaturated alkene-phosphonic acids were obtained, but with cyclohexylamine and triethylamine (pKa>10.6), the rupture of C-P bond occurred and α-olefin was obtained instead of alkenephosphonic acid.
  • 梅原 和夫, 加藤 陽一
    1969 年 18 巻 12 号 p. 886-890
    発行日: 1969/12/20
    公開日: 2009/10/20
    ジャーナル フリー
    The inhibitive properties of sodium or amine salts of monobasic and dibasic acids for mild steel specimens have been examined in humidity cabinet at 40°C or 50°C and relative humidity 95100%
    The monobasic and dibasic acids used were monocarboxylic, dicarboxylic, alkylphosphoric, dialkylthiophosphoric, n-octylphosphonic and n-octylmalonic acids, etc. About the almost same length of carbon chain, the sodium salts of dibasic acids with polar group at both ends have most inhibitive efficiency and those of no branched monobasic acids have more efficiency than those of dibasic acids with two polar groups near one end or those of branched monocarboxylic acids. It seems that the inhibitors with the chain length of about 8 carbon atoms are most effective among the homologous series. The influence of pH in sample solution on corrosion greatly increased with increase of pH, especially more than pH 10.
    Results of indoor exposure test for mild steel indicate that sodium salts of n-octylphosphonic and n-octylphosphonic acid have good inhibitive property, and do not correlate always with results of humidity cabinet test.
  • 河端 治, 武田 勉, 加藤 久武, 小森 三郎
    1969 年 18 巻 12 号 p. 891-896
    発行日: 1969/12/20
    公開日: 2009/10/20
    ジャーナル フリー
    In recent years, n-paraffins and n-olefins have been attracted interest as the lipophilic group of surfactants. And secondary chloroalkanes became easy to obtain from these materials by commercial process.
    The method of preparation of cationics from primary chloroalkanes with pyridine have been commercially carried out from past time and is being practiced currently. But the method of preparation of cationics from secondary chloroalkanes with lower amines did not come into operation, because the reation was difficult, and olefins were formed as by-product. The authors attempted the reaction between secondary chloroalkanes and alkanolamines and found that N-β-oxyethyl-2-amino alkanes can be prepared quite easily by a new one-step process. Chloroalkanes were insoluble in alkanolamines, but these materials reacted easily under the condition of heterogenous agitating system by homomixer. Good yield of N-β-oxyethyl-2-amino alkanes were obtained under the condition; 1 atm., 150160°C, without catalyst, without solvent. After reaction, the purification of the product was very easy because the reaction product was separated almost quantitatively from the lower phase of excess ethanolamines and these salts of hydrochloride. The hydrochloride produced by the dehydrochlorination, reacted with excess ethanolamines selectively. Ethanolamines were reproduced easily from these salts of hydrochloride by the addition of sodium hydroxide.
    The reaction rate was retarded by increased chain length of chloroalkanes, and the yield decreased according with shift of the substituted position of chlorine to the center.
    From these results, it was concluded that 2-chloroalkanes prepared from α-olefins are most suitable source materials in this reaction.
  • 亀山 栄一, 峰岸 裕, 桑村 常彦
    1969 年 18 巻 12 号 p. 897-900
    発行日: 1969/12/20
    公開日: 2010/02/12
    ジャーナル フリー
    Some higher homologues of N-trimethylaminoalkanimide (CH3) 3N-NCOR (I) (R : C11C17) were prepared from fatty acid hydrazides and their surface active properties were examined. Also, the availability of (I) for reactive surfactants was studied, since the pyrolysis of aminimides have been known to give the corresponding isocyanates.
    The aqueous solution of (I) was neutral and showed very low conductivities. Behavior of (I) in aqueous solution was generally similar to nonionic surfactants, as well as N-fattyalkyl-dimethylaminoacetimides R (CH3) 2N-NCOCH3 (II). The surface tension of (I) above cmc was about 30 dyne/cm, a little lower than that of corresponding (II), and cmc of (I) was slightly higher than that of (II).
    Cotton clothes treated by stearoyl homologue of (I) showed excellent durable water-repellency. It is a characteristic of (I) as water-repellent agent that no color change of the treated clothes was virtually observed during the curing at higher temperature (150170°C).
    Interfacial tension, penetrating power and foaming power of (I) were measured and compared with those of polyoxyethylene nonionics.
  • 小森 三郎, 小松 満男, 池田 功
    1969 年 18 巻 12 号 p. 901-908
    発行日: 1969/12/20
    公開日: 2010/02/12
    ジャーナル フリー
    Among α-olefins which came into massproduction recently, longer ones containing 1218 carbons have been widely employed as raw materials for surface active agents, but middle sized ones containing 410 carbons, unavoidable byproducts, are not sufficiently utilized yet. Using these middle-sized α-olefins, the authors synthesized 64 kinds of nonionic samples as follows.
    _??_
    Thus synthesized nonionics have excellent penetrating ability and those containing 10 or 12 carbons in R and R' were better penetrants than Aerosol type one and were far better than nonionic penetrant from lauryl alcohol on sale. They also showed low foamability.
    The correlation between the structure of the nonionics and their penetrating ability was discussed in detail. Logarithmic plots of sinking time of testing cloth vs. molar concentration indicated an almost straight line, whose gradient was dependent on the number of carbons contained in R and R', and not upon the length of hydrophilic oxyethylene group.
    Authors made another attempt in discussing the effects of the position of hydrophilic group attached and of branching in lipophiles, and it was recognized that their penetrating ability is much influenced by these factors.
  • 鈴木 信弘, 三橋 達雄
    1969 年 18 巻 12 号 p. 909-911
    発行日: 1969/12/20
    公開日: 2009/10/20
    ジャーナル フリー
    Studies on the lipid compositions in the horny tissues have not been undertaken except on the crystal lens of tunny (Thunnus thynnus orientalis) and the scales of Kinmedai (Beryx splendeus Lows) studied by authors.
    This investigation was attempted to analyse the lipid components of the tendon of Sardine-whale as to the fatty acids and unsaponifiable matters. The lipids were obtained by extracting the tendon with ether, then treated with n-hexane. The yield was 2.3% to fresh tissue. The weight and the properties were as follows ; reddish brown liquid, n20D 1.4791, I.V. 92.8, A.V. 5.2 and unsaponifiable matters 3.78%.
    The fatty acid contents analysed by means of gas chromatography were as follows ; C12 : 0=0.8, C14 : 0=5.7, C16 : 0=8.5, C18 : 0=5.2, C20 : 0=18.6, C12 : 1=1.3, C14 : 1=2.1, C14 : 2=0.4, C16 : 1=6.7, C16 : 2=0.8, C18 : 1=14.1, C18 : 2=3.8, C18 : 3=3.9, C20 : 1=16.3, C20 : 2=1.8, C22 : 1=10.0.
    The fatty acid compositions obtained by means of spectrometric analysis were as follows ; F2=3.6 (conjd. 1.30), F3=1.5 (conjd. 0.05), F4=1.3 (conjd. 0.03), F5=0.4, F6=0.6.
    The unsaponifiable matters were orange liquid containing 76.0% sterol (by Digitonin method). The main sterol of those is believed as cholesterol and the other sterol is Δ5.7 sterol (8.5%). The balance of the unsaponifiable matters seems higher alcohol and hydrocarbon.
  • 須賀 恭一, 渡辺 昭次, 宮重 昂, 森山 勝
    1969 年 18 巻 12 号 p. 911-914
    発行日: 1969/12/20
    公開日: 2009/10/20
    ジャーナル フリー
    Various metallic salts of monoalkyl phosphates were prepared. The effect of these salts on the critical antiwear load of gear oil were studied. Zinc salt of mono-oleylphosphate, and zinc, barium and tin salts of mono-2-ethylhexylphosphate showed excellent properties on antiwear test using Soda four ball machine.
  • 鈴木 修
    1969 年 18 巻 12 号 p. 915-918
    発行日: 1969/12/20
    公開日: 2009/10/20
    ジャーナル フリー
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