When linseed oil and α- or β-eleostearic acid obtained from tung oil were heated, it is known that cyclic monomers are produced. But there are many unclear points about the cyclic structure. In this study, in order to identify the cyclic monomeric structure which was prepared from heated C18 trienoic acid, a methyl 10- (o-ethylphenyl) decanoate and its hydrogenate; methyl 10- (2'-ethyl cyclohexyl) decanoate; were synthesized. Bromination of ethylbenzene according to the method of Lamneck gave ortho-bromo-ethylbenzene, and which was reacted with magnesium in dry ether to give Grignard reagent. The organocadmium reagent was prepared by the addition of anhydrous cadmium chloride powder directly to the Grignard Reagent. Methyl (9-chloroformyl) -nonanoate prepared from sebacic acid was reacted with the organo-cadmium reagent and gave methyl 9- (2'-ethyl-benzoyl) nonanoate. After the reduction of the carbonyl group in the methyl 9- (2'-ethyl-benzoyl) nonanoate, methyl 10- (o-ethylphenyl) decanoate was obtained by methylation of the reduction product. Methyl 10- (2'-ethylcyclohexyl) decanoate was derived from methyl 10- (o-ethylphenyl) decanoate following the hydrogenation in ethyl acetate using palladium-black catalyst under high pressure and temperature of 200°C. When methyl 10- (o-ethylphenyl) decanoate were compared by G.L.C. with the cyclic monomer produced by heated methyl α- or β-eleostearate at 250°C for 10 hours, it was identified that synthesized compound was the one component of the cyclic monomers.
Oligomerisation of isoprene catalysed by nickel naphthenate and isoprene magnesium was studied under various conditions. The use of various phosphites as donors gives cyclic dimers containing dimethylcyclooctadiene (about 80%); in particular 1, 1, 1-trishydroxymethyipropane phosphite gives trimethylcyclododecatriene selectively. At 500°C and under atmospheric pressure, 1, 5-dimethyl-1-cyclooctene thermally isomerized to 2, 6-dimethyl-1, 7-octadiene. Trimethylcyclododecanone having weak musk-like odour was prepared from trimethyl-1, 5, 9-cyclododecatriene.
Molecular interactions between oil soluble and water soluble components were studied by measurement of interfacial tension of oil/water interface. The water soluble component, such as sodium dodecyl sulfate interacted with oil soluble components in the following order : cholesterol>lauryl and octadecyl alcohols>oleyol alcohol. The cholesterol-sodium dodecyl sulfate system led spontaneous emulsification into the oil phase, while the lauryl alcohol-sodium dodecyl sulfate system led into the water phase. With the water soluble surfactants having different polar group, the oil soluble cholesterol component interacted in the following order : sodium dodecyl sulfate>sodium laurate>sodium dodecylbenzene sulfonate. In these systems spontaneous emulsification was observed at interfacial tension about 2 dynes/cm except sodium dodecylbenzene sulfonate. In addition, from the rate of penetration of surfactants into the interface, the reactivities to cholesterol were similar to above results and it was found that sodium dodecylbenzene sulfonate takes an appreciable period of time to penetrate into the interface.
Experimental results reported by the auther in previous papers on flow birefringence and viscosity of highly concentrated aqueous solutions of nonionic surface active agents, with polyoxyethylene chains as the hydrophilic group, are summarized and some considerations are given on the structures of the solutions. The data cover the concentration range from 5 to 95% and the temperature range from 10 to 80°C. The concentration dependence of flow birefringence can be classified into four types with regard to the temperature, and the temperature dependence into three with regard to the concentration. These experimental results together with the data of cloud point and gelation temperature are possible to be arranged in diagrams illustrating the optical properties of their aqueous solutions. The solution structure, which shows positive or negative birefringence, is discussed in terms of hydrotropic liquid crytalline phase formed in the highly concentrated solutions of these nonionic surface active agents with the aid of the diagrams obtained.
A rapid method for the determination of ethylene oxide contents in POE type nonionic surfactants by near-infrared (NIR) spectroscopy was established. POE type nonionic surfactants have strong absorption at 1.42μ and 1.74μ in near-infrared region. The band at 1.42μ is the O-H stretching vibration, and the band at 1.74μ is the first overtone of the C-H stretching vibration. The linear relationship is obtained between the absorbance ratio a1.74/a1.42 and EO contents of POE type nonionics. The absorbance ratio is not affected by concentration (0.21.2g/50ml) and by temperature (8°38°C) of the sample solution. Based on these facts, in this method, a 0.7 to 1.0g of nonionics sample was dissolved into 50ml of carbon tetrachloride solution. The solution was mesured by NIR from 1.2 to 2.0μ in 10cm silica cell. The absorbances were obtained from peak-height of the band at 1.42 and 1.74μ. The EO contents was calculated from the absorbance ratio and the calibration curve. This method allows determination of the EO contents in POE type nonionics within relative accuracy of 3.5% until about 30 moles.
Determination method for the mixture of alcohol sulfate (AS) and alcohol ethoxysulfate (AES) was investigated by means of NMR spectroscopy using shift reagents. In the NMR spectrum of mixture of AS and AES in deutelized acetic acid, each methylene protons adjacent to sulfate radical indicated the signals at somewhat different position but slightly overlap. In the NMR spectrum of alcohol and alcohol ethoxylate yielded from hydrolysis of AS and AES, there were no signals for determination because of their overlap. But, the addition of Eu (DPM) 3 to alcohol and alcohol ethoxylate caused low magnetic field shift in different manner. And, methylene proton under β-position of alcohol indicated as an isolated signal by the addition of suitable amount of Eu (DPM) 3. Therefore, alcohol and alcohol ethoxylate were determined from NMR spectrum using the ratio of signal areas among methylene of alcohol and duplicated methyl of alcohol and alcohol ethoxylate.
Removal of chlorinated pesticide residues in four crude animal and eight crude vegetable oils and fats were studied in manufacturing process. Results obtained were as follows : 1) Crude vegetable oils were generally less contaminated by chlorinated pesticide residues than crude animal oils. 2) It was recognized that chlorinated pesticides were not reduced in deacidifying and decolorizing process, but remarkable reduction was observed in hydrogenating and deodorizing process, especially in the deodorized oil after hydrogenation, chlorinated pesticides were eliminated almost all. 3) Total DDT was reduced more effectively than total BHC in hydrogenating and deodorizing process. 4) Chlorinated pesticides in animal oils were removed by deodorizing process more effectively than those in vegetable oils were. But no difference in the removal was observed in the case of hydrogenating process.