Rates of hydrolysis of soybean oil were examined in relation to the water introducing conditions in the water-spraying and heating apparatus described in the previous paper, and it was found that when dry steam was introduced instead of sprayed water, the rate of fat hydrolysis was lower than the case of water-spraying (Fig.-1, 2, 3, Table-1). On the other hand, when the water content of treated oils was compared after rapid cooling for the water-spraying and the dry steam blowing, it was observed that the water content of the water-sprayed samples was about two times greater than that of the steam blowed samples (Table-3). This fact may indicate that there is some difference in the degree of water saturation into the oils according to the water introducing conditions, that is, the contact of liquid water with high temperature oil results the high degree of water saturation, and the contact of dry steam results the low degree of water saturation, and this difference of water saturation may affect to the rate of fat hydrolysis. Accordingly, in connection with the fat hydrolysis during deep fat frying, it is considered that the condition of water which contacts with oil is one of the important factor, and in the practical frying, the structure of frying materials influences to the water discharging condition from inside of the materials and thus to the rate of fat hydrolysis.
Previously there was report on the isolation of, β-sitosteryl ferulate, cycloartanyl ferulate and 24-methylenecycloartanyl ferulate from rice bran oil by several other authors. Recently the authors confirmed the existence of seven ferulates, in which above-cited compounds were contained, in rice bran oil. Owing to the success of separation of free steroids and ferulates from the so-called “pitch”, followed by isolation and identification of the steroids and triterpenoids from their unsaponifiable matterr by means of techniques of various chromatographies and other procedures, it was found that the steroids and triterpenoids consisted of 7 compounds......that is, campesterol, stigmasterol, β-sitosterol, cycloartanol, cycloartenol, 24-methylenecycloartanol and a new terpenoid whose literature is not yet known and which may be reported later on. In this paper, physico-chemical properties and chromatographic data of these compounds which are complex alcohols and their ferulates are given in detail. This report is the introductory part of our “Studies on the ferulates in rice bran oil”, which will be followed by several reports.
Preparation of oligomers of β-propiolactone (β-PL) and ε-caprolactone (ε-CL) having reactive functional groups such as hydroxyl, carboxyl and acid chloride groups have been studied. In order to clarify the pattern of bond fission of the lactones, reactions of β-PLwith ethanol, acetic acid and acetyl chloride were carried out with or without catalysts. The investigation of the reaction products revealed that β-PL cleaved exclusively at alkyl oxygen bond in the absence of catalyst and in general at acyl-oxygen bond in the presence of acid or base catalysts. In the reaction of β-PL and ethanol with sodium ethoxide as catlayst, ethyl acrylate was produced as byproduct, and when this reaction was carried out at higher temperature (50°C), polymerization of β-PL was induced even in the presence of a large excess of ethanol. The reaction of β-PL and acetic acid with sulfuric acid as catalyst afforded a small amount of acrylic acid besides the main product, β-acetoxypropionic acid. Reaction of ε-CL and ethanol in the presence of acid or base catalysts gave, as a sole product, ε-hydroxy ethyl hexanoate, indicating the exclusive acyl-oxygen bond fission of ε-CL. This reaction, however, did not take place at all without catalyst. Based on these results, several oligomers of β-PL and ε-CL having reactive functional groups such as hydroxyl, carboxyl and acid chloride groups were prepared by the reaction of β-PL or ε-CL with various difunctional compounds (ethylene glycol, ethanolamine, ethylenediamine, succinic acid, succinyl chloride, terephthalic acid and terephthalyl chloride). These oligomers were characterized by end group analysis, infrared spectrum and molecular weight determination. Molecular weight of these oligomers ranged from 135 to 1800. In the reaction of β-PL and ethanolamine, the first molecule of β-PL was added to the amino group of ethanolamine, and further addition of β-PL took place not at the hydroxyl group of ethanolamine unit but at the hydroxyl group of β-PL unit formed by the addition of β-PL to the amino group of ethanolamine. Polycondensation of some oligomers having hydroxyl end groups with terephthalyl chloride was attempted in tetrachloroethane or anisole in the presence of magnesium powder at 140 to 160°C. The polymers obtained were white or light yellow and powdery or gummy materials which showed reduced viscosity of about 0.2. These polymers were confirmed by infrared spectra to have aromatic ester bond together with aliphatic ester or amide bonds in the polymer chain.
The authors synthesized chelate surfactants having hydrophobic alkyl group and hydrophilic metal ion which was bonded to the former in chelate configuration, and investigated their properties. N-lauroyl ethylenediamine (LEDA) was introduced as hydrophobic chelating agent and salts of some transitional metals (e.g. iron, cobalt, nickel, copper, chromium) were adopted. The reaction of LEDA with ferric sulfate in 1 : 1 equivalent reaction ratio afforded [Fe (LEDA) (H2O) 4] 3/2 SO4. In other reactions pure chelates were not obtained, but the products showed good surface activities.
In order to improve the lean solubility of zinc dialkyl dithiophosphates having lower alkyl radical (isopropyl, n-butyl etc.) in liquid paraffin, binary or ternary mixture containing longer chain dialkyl dithiophosphates was studied. When the content of longer chain compound (e.g., 4-methyl-2-pentyl, cyclohexyl, 2-ethylhexyl) in the mixture containing 2 or 3 kinds of dialkyl dithiophosphates exceeds above 60%, the mixture of dialkyl dithiophosphates becomes soluble in liquid paraffin. Their antioxidant actions in the paraffin auto-xidation are similar to those obtained in the use of single component of the mixed system. The combination of dialkyl dithiophosphates and phenothi-azine or phenyl-α-naphthylamine exhibits high synergism. In order to improve lean mutual solubities of phenothiazine to the dialkyl dithiophosphate in liquid paraffin the addition of dilauryl phthalate or methyl naphthalene is effective for the improvement of solubilities as well as antioxidant action.
The adhering states of soils of the natural soiled cloth (a part of collar of soiled white shirt) and artificial soiled cloth (Yukagaku Association's method) have been observed by scanning electron microscope. The natural soils were observed to be gathered between fibers by mechanical forces in a sticky adhesion on the fiber surface. On the other hand the artificial soils looked like an aggregated adhesion on the fiber surface.