油化学
Online ISSN : 1884-2003
ISSN-L : 0513-398X
24 巻 , 4 号
選択された号の論文の13件中1~13を表示しています
  • 佐々木 恒孝
    1975 年 24 巻 4 号 p. 207-215
    発行日: 1975/04/20
    公開日: 2009/11/10
    ジャーナル フリー
  • Osamu SUZUKI, Tetsutaro HASHIMOTO
    1975 年 24 巻 4 号 p. 216-222
    発行日: 1975/04/20
    公開日: 2009/11/10
    ジャーナル フリー
    The photochemical reactions of conjugated fatty acid methyl esters, that is, methyl α-eleostearate, methyl cis-9, trans-11-and trans-9, trans-11-octadecadienoates, under various conditions were studied. The formation of dimers was rapid from these conjugated fatty esters in either CCl4 or CHCl3. However, the dimers produced were found to be chlorinated. Accordingly, the photo-dimerization in halomethanes was recognized to be a kind of telomerization, where the halomethane itself took part in the reaction.
    In the greater part of the photochemical reactions in organic solvents other than halomethanes, the cis-trans isomerization reaction was observed. Especially, the cis, trans-conjugated fatty ester was converted into only trans, trans-conjugated isomer in heptane without forming the dimer. Then, both the photo-dimerization and the isomerization of the conjugated fatty esters in heptane were suggested to be carried out by the conversion of the conjugated fatty esters into their electronically excited molecules by irradiation.
    Futhermore, the effective wave length of light on the photochemical reactions of the conjugated esters was also examined by monochromatic radiation.
  • 丸銭 詔司
    1975 年 24 巻 4 号 p. 223-228
    発行日: 1975/04/20
    公開日: 2009/11/10
    ジャーナル フリー
    Using the model of the perfect solutions or the regular solutions, mathematical equations were derived for the approximation of the entropy of mixing of triglyceride oils, or fatty oil that is the solution of multicomponent of triglyceride species.
    The molar entropy of mixing of triglyceride oils entirely depends upon the triglyceride structures; namely, the equations derived for mono acid structure (sO), 1-random-2-random-3-random (sP), 1, 3-random-2-random (sQ) and 1, 2, 3-random (sR) are respectively as follows;
    sO=-RnΣJwJlnwJ
    sP=-RinΣJxJ, ilnxJ, i
    sQ=-R {nΣJ (3wJ-xJ, 2) ln (3wJ-xJ, 2/2) +nΣJxJ, 2lnxJ, 2}
    sR=-3RnΣJwJlnwJ
    where R is the gas constant, wJ and xJ, i are mole fractions of acid radical AJ (J=1, 2, …, n) in total fatty acid composition and in i- (i=1, 2, 3) position respectively.
    The increase of entropy of mixing and the free energy change as the regular solution in mixing of different kinds of triglyceride oils were also calculated by assuming that the structure of these oils is 1-random-2-random-3-random distribution.
  • 石井 節, 山根 浩一, 加藤 仁司, 国弘 和雄
    1975 年 24 巻 4 号 p. 229-232
    発行日: 1975/04/20
    公開日: 2009/11/10
    ジャーナル フリー
    The carbon chain distribution of lipophilic group of alkane sulfonate was determined by gas chromatography in the form of mercapto derivative.
    At first, alkane sulfonate is converted to corresponding sulfonyl chloride by the reaction with thionyl chloride, and reduced to mercapto derivative by hydrochloric acid-zinc powder. This derivative is steam-distilled and extracted with dichloromethane for gas chromatographic analysis.
    A 1m×3mm i.d. glass column, packed with 3% Silicone OV-17 on 60 to 80 mesh Chromosorb W, is employed for gas chromatographic separation.
    The peaks are very sharp and separated enough to determine the carbon chain distribution. The relative ratio of peak area corresponds to original carbon chain distribution.
    The position isomers of alkane sulfonate are well-separated by using a capillary column.
    Improvement of reproducibility and accuracy was accomplished, and this method was applied to commercial sodium alkane sulfonate.
  • 星加 安之, 角脇 〓, 小島 一郎, 小池 一美, 吉本 健二
    1975 年 24 巻 4 号 p. 233-236
    発行日: 1975/04/20
    公開日: 2009/11/10
    ジャーナル フリー
    Two proposed sample preparation method were applied for the gas chromatographic analysis of sulfur compounds and aliphatic amines in the exhaust gas from a fish meal dryer and cooker.
    At least eleven sulfur compounds from a fish meal dryer and at least seven sulfur compounds from a cooker were identified including hydrogen sulfide and methylmercaptan by the use of direct cold trap method with liquid oxygen, and by flame photometric detector.
    The detected concentrations of representative sulfur compounds in the exhaust gas from the fish meal dryer are as follows; carbonyl sulfide 0.08ppm, hydrogen sulfide 0.91ppm, carbon disulfide 0.03ppm, methylmercaptan 0.32ppm, n-propyl mercaptan 0.40ppm, dimethyl disulfide 0.17ppm.
    From the cooker; carbonyl sulfide 0.03ppm, hydrogen sulfide 4.2ppm, carbon disulfide 0.02ppm, methyl mercaptan 5.2ppm, and dimethyl disulfide 0.09ppm were detected.
    The major component of the exhaust gas from the fish meal dryer was hydrogen sulfide, and that from the cooker was methyl mercaptan.
    From analysis of aliphatic amines, only trimethyl amine was detected by the use of direct cold trap method with liquid oxygen and chemical trap method with 0.1 N-hydrochloric acid aqueous solution, and by flame ionization detector.
    In latter case the trapped sample was decomposed with 40% sodium hydroxide aqueous solution, followed by the cold trap method.
    The detected concentrations of trimethylamine are as follows; 0.42ppm, for the exhaust gas from fish meal dryer and 1.0ppm for the exhaust gas from cooker.
    In this method of analysis, a 5.8ppm of ethanol was also detected.
    The concentrations ratio of trimethylamine versus hydrogen sulfide in fish meal dryer was about 0.5 : 1, and in cooker about 0.2 : 1.
  • 峰岸 裕, 相上 紘二, 荒井 明彦
    1975 年 24 巻 4 号 p. 237-240
    発行日: 1975/04/20
    公開日: 2009/11/10
    ジャーナル フリー
    The substitution effects of α-alkyl chain on the physical properties of fatty acid and sodium salt were studied.
    The introduction of alkyl chain into α-position brought about a depression of melting point of fatty acid, a depression of Krafft point, an expansion of area per molecule and a decrease of c.m.c. of its sodium salt.
    These substitution effects of α-alkyl chain increased as the carbon number of α-alkyl chain increased and with decrease of main alkyl chain.
    In the case of c.m.c., there existed linearity between the carbon number of α-alkyl chain and logarism of c.m.c., it was therefore found from calculation that one carbon of α-alkyl chain corresponded with 0.3 to 0.4 carbon of main alkyl chain.
  • 高橋 秀男, 桑村 常彦
    1975 年 24 巻 4 号 p. 241-245
    発行日: 1975/04/20
    公開日: 2010/02/19
    ジャーナル フリー
    Branched higher aliphatic aldehydes obtained through oxo-synthesis have been treated with polyoxyethylene glycols using an acid catalyst to give acetal type nonionics : R (CH2) 2CH (R) CH [O (C2H4O) m/2H] 2 (OAG series) and RCH2CH=C (R) CH [O (C2H4O) m/2H2] 2 (OAGΔ series), R : -CHMeCH2CMe3. Cloud point (Cp), aqueous surface tension (γ), cmc and some gross effects of OAG and OAGΔ were compared with those of nonionics containing comparable hydrophobe : R (CH2) 2CH (R) CH2O (C2H4O) mH (iso series) and CH3 (CH2) 17O (C2H4O) mH (S series).
    At the same HLB values based on the Davies' group number, Cp of OAG and OAGΔ were lower than those of iso series. The cmc values increased in the order S<iso<OAGΔ<OAG. The order of the increase in γ lowering ability was S<<OAGΔ<OAG≤iso, and wetting powers also increased in this order. OAG and OAGΔ showed low foaming properties and excellent emulsifying powers. Suspending powers and detergencies of OAG and OAGΔ were almost comparable to those of iso series. OAG and OAGΔ were fairly stable in neutral or weakly basic aqueous solution, but easily hydrolyzed under acidic conditions. These facts reveal the possibility of their controlled surface activities depending on the pH of aqueous solution used, to afford some industrial applications.
  • 平田 博文, 今枝 健一, 田中 洋, 福住 一雄
    1975 年 24 巻 4 号 p. 246-252
    発行日: 1975/04/20
    公開日: 2009/11/10
    ジャーナル フリー
    The rate of acetic acid catalyzed elimination reaction of 1- (m-nitrophenyl) -2- (2-quinolyl) ethyl acetate [1m] to give trans-2- (m-nitrostyryl) quinoline [2m] is correlated with the electron donability of solvents, ΔνD, rather than with the dilectric constant of solvents, D, because of hydrogen bonding complex between acetic acid and solvent.
    Addition of solvents having lone pair of oxygen and/or nitrogen atom (nitrile, carbonyl, ether, alcohol, amide, sulphoxide or amine) caused a decrease in rate for the dichloroacetic acid catalyzed elimination of [1m] in benzene at 40°C. From the drop in rate, the equilibrium constant K of the formation of hydrogen bonding complex between dichloroacetic acid and lone pair of oxygen and/or nitrogen atom in benzene was estimated. A good linear free energy relation was observed between the equilibrium constant K and the electron donability of solvents, SX, which is very important. From the above linear correlation, it is found that the basicity of oxygen atom of alcohols is as strong as that of dioxane (or ethers). A molecule of a strong amine (e.g., triethyl amine) interacted with more than one molecule of dichloroacetic acid in benzene or in toluene at 40°C, which suggests a 1 : 2 complex.
  • 河田 和雄, 磯部 次男, 渡辺 昭一郎
    1975 年 24 巻 4 号 p. 253-256
    発行日: 1975/04/20
    公開日: 2009/11/10
    ジャーナル フリー
    Triesters containing a ether linkage were synthesized and their utilization as plasticizer was examined.
    Some monoesters were obtained from 1-chloro-3- (2-hydroxyethoxy) -propanol-2 and potassium hexanoate, octanoate, decanoate, laurate, myristate, palmitate or stearate and then they were acylated with acetyl, benzoyl or n-hexanoyl chloride to yield triesters, including diacetates, dibenzoates and dihexanoates, respectively.
    The triesters were evaluated on the plasticizing effect, through comparison of the effects on the properties of polyvinyl chloride (PVC), with those of dioctyl phthalate (DOP). PVC containing diacetates were considerably inferior than the control (containing only DOP) only in heat stability. With dibenzoates, heat stability was appreciably improved, however, low temperature flexibility lowered. On the other hand, PVC containing dihexanoates showed almost the same degree of heat stability as the control did and were superior than the control in low temperature flexibility. The number of carbon atoms contained in the fatty acid molecules used did not appreciably influence the plasticizing effect.
  • 黒田 善十郎
    1975 年 24 巻 4 号 p. 257-260
    発行日: 1975/04/20
    公開日: 2010/02/19
    ジャーナル フリー
    The heating method which has been widely used commercially for deodorizing oils is condensing Dowtherm or high pressure steam heating. Direct fired heating has been kept away because of danger of overheating.
    If oil is heated in the direct-fired tubular furnace, the heat balance at any cross section of the radiant tube gives
    RD=h (tw-tb) Di (1)
    or
    tw=tb+ (R/h) (D/Di) (2)
    The overheating of oil must occur at the point where tw is too high. Eq. (2) indicates that tw depends on tb and R/h, if the inside and outside diameters of the tube are given.
    Consider a tubular furnace, employing 3/8 in. (2mm thick wall) heating tube, which absorbs heat at the rate of 20, 000kcal/m2hr. Let oil be heated by direct firing in this furnace up to 250°C. The maximum value of tw is calculated as follows.
    Since, in ordinary case, tw will get to the highest at the outlet of the heating tube where tb is the highest, tb=250°C. D=0.0173m, Di=0.0133m for 3/8 in. tube and h=1, 500kcal/m2hr°C.
    The radiant rate is non-uniform at various points around the circumference of the tube. The radiant flux distribution on the tube circumference has the maximum value at the point facing just opposite to the heat source. For the common tubular furnace in which bare tubes are arranged in a single row in front of a refractory wall, the ratio of the maximum point flux to the average flux on the tube surface is πD/lF12. It varies with l/D as shown in Table-1. Assuming l/D is 2.0, the maximum flux is 1.78 times of the average flux, and the maximum radiant rate is also 1.78 times of the average.
    Substitution in Eq. (2) gives the maximum value of tw=250+ (20, 000×1.78/1, 500) (0.0173/0.0133) =281°C.
    This temperature is not so high that it seems the effect is not injurious to the product. It suggests that the direct fired tubular furnace can be used to heat oils without danger of overheating.
    The author modified a usual semicontinuous deodorizer having a capacity of 18 tons oil per 24 hour day to test the direct fired heating system on a commercial scale. Fig.-1 shows a flowsheet of the modified deodorizer with an external tubular furnace instead of Dowtherm heating system. The modified plant was operated satisfactorily with refined cottonseed oil for over 300hr including a 200-hr continuous run. Both commercially and laboratory-deodorized samples were tested for initial flavor and AOM. An example of the test results is shown in Table-2.
    The direct firing system has been demonstrated on a commercial scale to be able to heat oils for deodorization without overheating if the tubular furnace is properly designed.
  • Yuhei UZU
    1975 年 24 巻 4 号 p. 261-264
    発行日: 1975/04/20
    公開日: 2009/11/10
    ジャーナル フリー
    Equilibrium phase transition temperatures have been determined by using a differential scanning calorimeter for lithium stearate in a series of hydrocarbons, including a re-examination of the phase behavior in mineral oil. A correlation was found between phase transition temperatures and the molecular weights of the hydrocarbons, just as obtained by Cox for the systems of lithium stearate-mineral oil. Moreover, the difference of the crystal habits of the soap fibers in hydrocarbons has been observed with the scanning electron microscope.
  • 佐藤 〓, 木瀬 秀夫, 妹尾 学, 浅原 照三
    1975 年 24 巻 4 号 p. 265-267
    発行日: 1975/04/20
    公開日: 2009/11/10
    ジャーナル フリー
    Lavandulyl methyl ether was prepared by the following reactions : The addition of chloromethyl methyl ether to prenyl chloride in the presence of stannic chloride afforded 1, 3-dichloro-2-methoxymethyl-3-methylbutane, which was then treated in DMF to give the dehydrochlorination product, 2-methyl-3-methoxymethyl-4-chlorobutene-1. The Grignard reaction of the butene derivative with methallyl chloride gave lavandulyl methyl ether. The total yield of lavandulyl methyl ether was 3540% based on isoprene.
  • 富山 新一
    1975 年 24 巻 4 号 p. 271-274
    発行日: 1975/04/20
    公開日: 2009/11/10
    ジャーナル フリー
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