Continuous cooling and heating differential thermal analyses (DTA) were carried out in a low temperature range, at the rate of 5°C/min, with 14 samples of refined or refined and winterized six kinds of vegetable oil. DTA curves of these oil samples were found to show considerable distinctive features. 1) Cooling DTA curve of cotton-seed oil showed an appreciable exothermic peaks at 7° and -12.5°C, but after wintering, the peak at 7°C disappeared and that at -12.5°C became small. A considerable change was also seen in the heating DTA curve. 2) Cooling DTA curve of rice oil had three exothermic peaks at -19°, -39° and -77°C but after wintering, the peak at -19°C became small. Such a difference was not seen in heating DTA curve. 3) Corn oil, safflower oil and soybean oil all showed different peak temperature in their DTA curves but all had three exothermic peaks. The peak in the lowest temperature side were larger in salad oils of corn and safflower, while the three peaks in the salad oil of soybean transited to the lower temperature side. In heating DTA, curves of corn oil and soybean oil were similar, and there was no difference from those of their salad oil. 4) The cooling DTA curve of rape-seed oil had a large and very sharp exothermic peak at -41°C, and two large endothermic peaks at -20° and -7°C, and a small exothermic peak at -5°C in heating DTA curve. There was no difference the DTA curves of its salad oil.
As a means for discriminating foreign fats in butter, heating differential thermal analysis (DTA) and continuous cooling and heating DTA were carried out. Samples used were three kinds of pure butter fat and two kinds each of coconut oil, palm kernel oil, palm oil and beef tallow, and four kinds of modified butter fat for reference. 1) In heating DTA from 0°C, presence of other fats cannot be discriminated unless mixed in more than 30% in the case of coconut oil, and palm kernel ail, more than 20% in the case of palm oil or beef tallow and 30% in the case of modified butter fat. 2) In continuous cooling and heating DTA, presence of more than 5% of coconut oil and palm kernel oil can be detected but it is not possible to discriminate between coconut oil and palm kernel oil. 3) Presence of even 5% of palm oil and beef tallow can be discriminated, and the detection becom further clear if they are present in more than 10%. However, discrimination between palm oil and beef tallow is not possible. 4) Modified butter fat can be detected if present in more than 510%. Since this fat could not be detected by any other method, DTA would be a rapid and simple method for its detection.
The polymerization of methyl linoleate in the presence of aluminium halides, AlI3, AlBr3, AlCl3 and AlF3 at 300°C was studied. The result shows that only aluminium iodide among the halides promotes the polymerization. The effects of reaction conditions on the polymerization of methyl linoleate with aluminium iodide were studied further. The main results obtained are as follows : (1) The increase of catalyst concentration at 300°C decreases the time required for the polymer content to reach 70%. (2) As the reaction temperature increased in the polymerization with 2mol% aluminium iodide in 250325°C, the amount of polymer formed was increased. (3) The maximum polymer content of the product under the following reaction condition was about 75%, catalyst concentration 2mol%, reaction temperature 325°C, and reaction time 10hr. The dimer separated from polymerization product with aluminium iodide was catalytically dehydro-genated. From the results of analyses of the dehydrogenated dimer and other information, it is considered that the polymerization of methyl linoleate with aluminium iodide catalyst involves mainly the Diels-Alder reaction.
The reaction of propane sultone with sodium salts of higher fatty acids in alcoholic solvents was investigated. it is clear that the following side reactions occur; (1) (I) (2) (II) And these resulted strongly acidic substances (I and II) promote the decomposition of APS (sodium γ-acyloxypropane sulfonate); RCOOCH2CH2CH2SO3Na+H2O→RCOOH+HOCH2CH2CH2SO3Na (3) RCOOCH2CH2CH2SO3Na+CH3OH→RCOOCH3+HOCH2CH2CH2SO3Na (4) Sodium salts of I and II did not promote the reaction (3) or (4). Therefore, APS was not decomposed under neutralization of I and II after a definite reaction time. From the results in methanol, it was made clear that the yield of APS greatly depends on occur-rence of the reactions (2) and (4). In isopropanol and tert-butanol, such decomposition was difficult to occur. Using sodium oleate as the salt of higher fatty acid, the yields of APS in methanol, isopropanol and tert-butanol were 67, 84 and 91%, respectively.
Yellowing phenomena of fabrics which were soiled with various model oily substances were observed. The unsaturated compounds such as squalene, linoleic acid, oleic acid, and triolein cause more yellowing than cholesterol and n-octadecane. On the other hand, soiling with palmitic acid and tripalmitin has a tendency to reduce the yellowing of fabrics. The degree of yellowing is different by the kind of fabrics, however, when they are soiled even with the same sort of oily substances.
The concentration of the free counterion of an ionic surfactant has been measured for the mixed polymer-surfactant solutions, and the degree of ionic dissociation (α) of the surfactant has been calculated from the pNa data of these mixed solutions. The polymers examined were polyvinylpyrrolidone (PVP), polyethylene glycol (PEG) and polyvinylalcohol (PVA), and the surfactant was sodium dodecyl sulfate (NaDS). The value of α increases with increase in mixing ratio of polymer/NaDS (monomer unit mol/mol) and tends to decrease with increase in the molecular weight of polymer. The absolute value of α increases in the order PVP>PEG>PVA, namely in the order of increasing hydrophobic character of the polymer. From these results, authors discussed the mode of binding of NaDS onto these polymers. It was suggested that the surfactant is bound onto PVP or PEG forming aggregates on it in such a manner as micelle formation, but onto PVA the surfactant is bound monomolecularly.
In order to investigate the effect of alkyl chain length and builder on adsorption, the adsorption isotherms of linear alkylbenzene sulfonate from aqueous solution on carbon black were determined at 30°C, The adsorption isotherms were fitted to a Langmuir type equation. The amount of saturated adsorption and equilibrium constant which characterize the adsorption were determined by Langmuir plot. The saturated amount depended upon the builder added, but did not upon alkyl chain length. On the other hand, equilibrium constant were markedly affected by alkyl chain length and the builder added. Authers also investigated the correlation between the adsorption of surface active agent on carbon black and the deposition phenomena of carbon black on textile fibers in surface active agent solution, but could not obtain a clear conclusion.
Authors have recently reported a series of surfactants containing silicon. In this report the syntheses of nonionic and cationic surfactants with three-chained hydorophobic groups containing tin or silicon, which are represented by the following formulae (1) and (2), are described. R3M (CH2) 3O (CH2CH2O) nH (1) (M=Sn, Si; R=CH3, CH3CH2CH2CH2) (CH3CH2CH2CH2) 3M (CH2) 3N+ (CH3) 3·Cl- (2) (M=Sn, Si) Then, some of their properties were compared with each other. Also, authors synthesized new nonionic and cationic surfactants containing siloxane bonds, which are represented by the following formulae (3) and (4), and compared some of their properties with those of above-mentioned surfactants. [(CH3) 3SiO] 3Si (CH2) 3O (CH2CH2O) nH (3) [(CH3) 3SiO] 3Si (CH2) 3N+ (CH3) 3·Cl- (4) In the case of nonionic surfactants, surface tension of their solutions and interfacial tension between the solutions and kerosene oil, and in the case of cationic surfactants, surface tension of their solutions, were determined. As a result, the surfactants containing tin were found to have as strong surface activities as those of the surfactants of same type containing silicon. Among the surfactants with three-chained hydrophobic groups, the nonionic and cationic surfactants containing siloxane bonds were characterized by their ability to depress the surface tension of water down to as low as 2223 dynes per cm.
Seed oils from Pterocarya stenocarpa (Juglandaceae), Morus bombycis (Moraceae), Ficus pumila (Moraceae), Humulus japonicus (Moraceae) and Distylium racemosum (Hamamelidaceae), were analyzed for their characteristics (Table-1). The bromination test on the fatty acids indicated the presence of linoleic acid in each oil and linolenic acid in each oil except M. bombycis oil. The fatty acid methyl ester prepared from each oil by the routine method was analyzed by GLC. The triglyceride fraction of each oil was separated by column chromatography using silica gel, and then partially hydrolyzed with a pancreatic lipase. The 2-monoglyceride fraction of the hydrolysed product was separated by TLC, and converted into the methyl esters. The methyl esters were then analyzed by GLC. Thus, all fatty acid compositions in the sample oils and the 2-position of triglyceried were contrasted (Table-2).
Seed oils from two species of Rosaceae (Karin and Boke) were examined on their general properties, on the fatty acid compositions determined by GLC and on the characteristics of unsaponifiable matters. The oils were obtained by extracting the dried seeds with ether. The general properties were as follows; Karin (d114 0, 9264; n22D 1.4710, IV 98.1, AV 1.4, S.V 189.7), Boke (d204 0.9166, n20D 1.4699, I.V, 80.6, A.V, 4.3, S.V 197.6). The fatty acid compositions were C10:0, 1.7, C14:0, 0.9; C14:1(?), 0.3, C16:0, 13.5, C18:0, 1.3, C18:1, 22.5, C18:2 50.5, C18:3(?) 1.1, C20:0 2.6, C20:1(?) 3.1, C22:0 2.5 in the case of Karin, and C10:0 4.3, C14:0 0.8 C14:1(?) 0.5 C16:0 7.3, C16:1(?) 0.6, C18:0 1.2, C18:1, 50.7, C18:2, 26.7; C18:3(?), 1.0, C20:0, 3.4, C20:1(?), 3.5 in the cace of Boke. The unsaponifiable matters were both yellowish orange soft-solid. The sterol-percentages in unsaponifiable matters were 22.6% (Karin), and 28.4% (Boke). The main sterols of Karin and Boke were both considered to be β-sitosterol from the data of their melting points, IR absorption spectra and GLC of the sterols and their acetates.
It has been well known that acetylenic compounds react with cobaltcarbonyl and give benze derivatives via cyclic intermediate (II). The authors found that a new complex compound (IV) wa formed in the reaction of propargyl undecynoate with cobalt carbonyl. The structure of (IV) was identified by molecular weight measurement, elementary analysis and on the basis of the following information : (a) (IV) (1 mole) was formed by the reaction of propargyl undecynoate (1 mole) and cobaltcarbonyl (2 moles) at room temperature in n-hexane with evolution of 4 moles of carbon monoxide. (b) (IV) (1 mole) was decomposed by iodine with the evolution of 12 moles of carbon monoxide. (c) (IV) was decomposed by iodine or CrO3, and propargyl undecynoate was given. (d) (IV) was decomposed by the hydrogenation at 80°C for 24 hrs over Pd-alumina (5%) to give propyl undecanoate. (e) The i.r. spectrum of (IV) showed the absorptions at ca 2000cm-1 due to terminal carbonyl groups and no absorption at ca 1860cm-1 of bridged carbonyl group. (f) The n.m.r. spectrum of (IV) exhibited a proton signal at 6.5τ attributable to methine proton.