The characteristics of soaps prepared from waste edible oil (oils before desgarding used frying oils at home or school refectory) or soybean and rapeseed oils with different degrees of thermal oxidation were investigated. Thermal oxidation oils were prepared by heating in a fryer (National NF-F 100) at 180°C for 20 and 40 h. Waste edible oil collected from home and school was combined. Preparation method of soap, method I. Soaps from fresh and thermal oxidation oils were prepared by heating at 90°C for 3 h with mixtures of 100 g fresh or thermal oxidation oils, 25 g potassium hydroxide and 300 g water. Method II. Soaps from waste edible oil were prepared at room temperature for. 30 d with mixtures of 2500 g waste edible oil, 450 g sodium hydroxide, 2000 g water (added hot water of 500 g every third day) and one cup of left-over rice. They were stored in beakers at room temperature. Anisidine, carbonyl and peroxide values and content of oxidized fatty acids (fatty substances insoluble in petroleum ether) in soap were determined with fatty acids isolated by acidifying the mixture with hydrochloric acid. Anisidine and carbonyl values of soaps prepared from thermal oxidation oil were markedly lower than those of thermal oxidation oil. Anisidine and carbonyl values were much higher in waste edible oil soap than in waste edible oil. Oxidized fatty acid content in each soap was similar to that of thermally oxidized waste edible oils. Increase in anisidine, carbonyl and peroxide values was observed during storage.
The thermal oxidation reactions of thin film (thickness 16170 μm) of trilinoleoylglycerol (TLEG) were investigated by thermogravimetric analysis. By thermal oxidation reactions the weight of TLEG increased in the temperature range of 25°C to 170°C in air and in oxygen [heating rate : 2°C/min]. Elemental analysis of these sampleswas carried out and their compositions were determined. At 90°C, 1 mol of the hydroperoxide of TLEG (TLEGHPO) was formed for 5.6 mol of TLEG, and agreement between calculated and found values was whthin the usual limits of variation of elemental analysis ; degradation reactions did not occur. At 104°C, 1 mol of TLEGHPO was formed for 3.3 mol of TLEG. The dehydrogenation of TLEGHPO started at this temperature. At 130°C, 1 mol of TLEGHPO was formed for 1.1 mol of TLEG. The degradation of TLEGHPO occurred slightly at C-C and C-H bonds of TLEGHPO. At 155°C, the degradation of C-C and C-H bonds of TLEGHPO occurred. The relationship between maximum increase in weight Y (% μg/cm2) and film thickness of TLEG X (μm) is given by the following equations. Film thickness Equation Atmospheres < 30 μm Y=6.6 X in air 30μm130μm Y=2.2 X+150 in air 130μm300 μm Y=0.4 X+380 in air < 30μm Y=9.6 X in oxygen 30μ m168μm Y=5.4 X+75 in oxygen In the temperature range of thermal degradation (180°C600°C), the relation between the layer thickness of thermal oxidative degradation Y (μm) and film thickness of TLEG X (μm) is given by the following equations. Film thickness Equation Atmospheres < 70μm Y=0.66 X in air 70μm168 μm Y=0.28 X+42 in air < 42μm Y=0.80 X in oxygen 42μm95μm Y=0.35 X+19 in oxygen
β-Sultones obtained by sulfonation of internal olefins with sulfur trioxide (SO3) were desulfonated to the original olefins under certain conditions. This study was carried out to clarify the path way of this desulfonation using the β-sultone obtained by the sulfonation of trans-2-octene. The olefin produced by the desulfonation of the β-sultone gave trans-2-octene, indicating that geometrical isomerism was preserved. Reactions of olefins with SO3 to form β-sultones would thus appear to be reversible. For comfirmation of this, cis-2-octene was added to a sample consisting mainly of β-sultone from trans-2-octene and NMR observation was made to detect β-sultone originating from cis-2-octene. The formation reaction ofβ-sultone from internal olefins was found to be reversible, in thatthe production of β-sultone from cis-2-olefin was confirmed.
Fluoroalkylated oligomers with carbon-carbon bond formation were obtained by reactions of acrylic acid, methyl methacrylate, and ethylene oxide units-containing methacrylates, acrylates with fluoroalkanoyl peroxides in excellent to moderate yields under very mild conditions. A mechanistic study of these reactions was carried out by the MNDO-PM 3 semiempirical MO method. A strong interaction between HOMO of the monomer and SOMO of fluoroalkyl radical produced by the thermal decomposition of the peroxide appeared to cause the addition of the fluoroalkyl radical, to the monomer to afford the corresponding fluoroalkylated oligomer. Fluoroalkylated acrylic acid oligomers were found capable of reducing the surface tension of water to 10 mN/m. Fluoroalkylated-methacrylates, and-acrylates oligomers containing ethylene oxide units became typical fluorinated amphipathic compounds.