Ethyl perfluorooctanoate was reacted at 30°C for 2h in ethanol with ethyl ester of amino acid (glycine, α- and β-alanine) to prepare N-perfluorooctanoylamino acid ester. The esters thus prepared were saponified to form the desired surface active agents by atidification with hydrochloric acid and successive neutralization with alkali hydroxides. The aqueous solution of these surfactants were subjected to the determination of surface tension, critical micelle concentration, Krafft point, wettability and oil repellency according to the conventional methods. Generally, the glycine derivatives were only slightly soluble in water showing higher Krafft points and poor surface activities. The α-alanine derivatives showed lower Krafft point due to the presence of methyl side chain and superior wettability to other amino acid derivatives. The β-alanine derivatives exhibited significant surface tension depression and in the case of K salt the surface tension was depressed to 15dyn/cm.
To gain an understanding of the mechanism by which silicone oil (SO) suppresses the thermal deterioration of a frying oil, the following experiments were carried out. 1) Soybean and linseed oil without and with 1ppm SO were heated in an oven or plate heater for 4, 6h, at 50, 70, 90, 110 and 130°C. The degree of deterioration of these heated oils was evaluated by POV, COV and the viscosity ratio. Oils heated on the plate heater deteriorated much more than those heated in the oven. SO had a protective effect on all oils used in this experiment, particularly on those heated on the plate heater. 2) Linseed oil without and with 1ppm SO was heated under a stream of nitrogen for 16, 32 and 48h at 220°C. The degree of deterioration was evaluated by the viscosity ratio. The ratio of viscosity of heated linseed oil with SO was just the same as those without SO. Linseed oil fatty acid methyl ester (LFM) without and with 1ppm SO was heated under a stream of nitrogen at 150°C, 180°C and 240°C. The iodine value and ratio of viscosity showed that SO had no protective effect on the methyl esters of linoleic and linolenic acid. Tung oil with and without 1ppm SO was heated under a stream of nitrogen for 10, 20, 30, 40 and 60min, at 220°C. The degree of polymerization was evaluated by the ratio of viscosity and reflactive index. SO was found to have no protective effect on tung oil. It was thus concluded that under the stream of nitrogen, SO has no protective effect on either non-conjugated or conjugated unsaturated glyceride.
The selective extraction of n-olefins from n-olefin/n-paraffin mixture using an iodine-dimethylformamide (DMF) solution was studied. Iodine dissolved in DMF absorbed n-olefin at ambient temperature, forming a DMF-I2-olefin complex (Fig.-1). This complex was decomposed on heating at temperatures above 85°C, liberating the absorved olefin (Fig.-2). However, the I2-DMF solution, after olefin liberation, was no longer able to absorb olefins repeatedly even at ambient temperature. The addition of the excess amounts of other olefins, which can be separated by distillation from the recovered olefin, to the DMF-I2-olefin complex liberated the absorbed olefin by replacement at ambient temperature (Fig.-3). A remarkable effect of light irradiation on this replacement rate was observed (Fig.-4). To study the industrial applications of this selective extraction method, a C10-C13n-olefin/n-paraffin mixture, a raw material for the production of linear detergent alkylate, was used. Normal-olefin having a purity of 94.6% was recovered from the mixture (Table-3).
The antioxidative activity of oils extracted from soybean fermented with fungi and their synergism with tocopherols (Toc) were investigated. These oils, fermented with Rhizopus oligosporus and Actinomucor elegans at 30°C for 30d possessed no antioxidative activity, but showed excellent synergism with Toc on the autoxidation of lard. These fungi are used to make Tempeh and Sufu, respectively. The tocoperol content in the extracted oil from fermented soybean with R. oligosporus decreased with the time of incubation. However, the synergisitc effect of the extracted oil became remarkably pronounced with a decrease in Toc content. The extracted oil from soybean after being maintained at 30d without inoculation showed no synergism with Toc. These results indicate that enzymes produced by fungi convert a certain constituents in the soybean to synergistic substances. The extracted oil from fermented soybean with R. oligosporus retarded the autoxidation of vegetable oils, but did not appreciably inhibit the thermal oxidation of the oils. Thus, synergistic substances in fermented soybean were concluded to be unstale at high temperature.
In the decomposition of benzenediazonium chloride (BDC) in the presence of peracetic acid, o-chlorophenol (OCP) was obtained. When the molar ratio of peracetic acid against BDC was less than unity, only OCP was obtained. The sum of the yields of parachlorinated products such as p-chlorophenol, 2, 4-dichlorophenol (2, 4-DCP) and 2, 4, 6-trichlorophenol (TCP), incresed with the molar ratio. p-Toluenediazonium chloride (TDC) also showed the same tendency. It should be noted that in no case was 2-chloro-p-cresol (OCPC) formed without peracetic acid, but p-cresol (PC), p-chlorotoluene (PCT) and p-tolyl acetate (PTA) were formed. No toluene or p, p'-bitolyl could be detected. The rate constant for the consumption reaction of peracetic acid in the titled decomposition reaction of BDC was equal to that in the reaction with phenol instead of BDC, and smaller than that of the decomposition of BDC. This should be the rate constant for the formation of chlorinating species, considered to be acetyl hypochlorite, judging from the o/p ratio of chlorophenol formed. In the reaction of TDC, the rate constant for the consumption of peracetic acid was greater than the decomposition rate constant of TDC equal to that for the formation of any product. From these findings, a probable mechanism involving an attack of acetyl hypochlorite formed by the oxidation of chloride anion with peracetic acid on phenols produced by the ionic decomposition of benzenediazonium chlorides is postulated and discussed.
Effects of cations on the micellar structure of dodecyl poly (oxyethylene) ether (C12EOn, n : the average number of ethylene oxide groups) were investigated. The results are summarized as follows. 1) C12EO7 and C12EO8 micelles were spherical, the micellar volume remaining approximately the same regardless of kind of alkali cation, but the C12EO6 micelle was not spherical and had a different shape. 2) The contribution of cations to decreasing the polarity within C12EOn micelles was effective in the order of K+>Na+>Li+. 3) The contribution of cations an increase in micellar weight and the aggregation number of C12EOn was effective in order of K+>Na+>Li+. Based on the above, it was concluded that micelles having large aggregation numbers prevented water penetration from the outside, thus decreasing polarity within the micelles.
Tocopherol content in the germ, pericarp and endosperm of rice grains, four leaf rice plants and mature rice plants were determined by HPLC. The contents in the germ of rice grains, the young leaves of four leaf plants and mature rice plants were 264μg/g, 257μg/g and 134μg/g, respectively in dry samples. α-Tocopherol was the main tocopherol in young leaves and mature plants. The tocopherol content was 76μg/g in the pericarp and a very little in the endosperm. Tocopherol content in stored commercial rice bran was reduced from 275μg/g to 227μg/g at room temperature over a period of two months. The tocopherol content in stored mature rice plants was reduced from 134μg/g to 12μg/g at room temperature in three months.