In order to obtain higher alkyldiethylamines, which are used as the raw material of various cationic surfactants, reaction between oleylalcohol and triethylamine was carried out using Cu-Cr-O (modified by MnO2) catalyst under moderate pressure. The reaction conditions which gave the best yield of 76% were following : Mole ratio of oleylalcohol : triethylamine= 1 : 5 Weight % of the catalyst to alcohol : 15% Initial hydrogen pressure : 20 kg/cm2 Max. reaction pressure : ca. 45 kg/cm2 Reaction temperature : 250 Reaction time : 3 hr Catalyst and triethylamine reoveries were also inveatigated and obtained good results.
The reaction of ethylene oxide with water covering wide ethylene oxide concentration (1.75 to 16.1 mol/l) was investigated. The reaction is shown as a consecutive competitive reaction including the following reactions; H2O+C2H4O_??_HOC2H4OH HOC2H4OH+C2H4O_??_HOC2H4OC2H4OH HOC2H4OC2H4OH+C2H4O_??_HOC2H4OC2H4OC2H4OH where the reactions are first order to each reactant, and the second order rate constant k1 is k1_??_ 1/2k2_??_1/2k3=2.88×105a0 exp (-21, 100/RT).
In the preceeding paper the authors reported a pronounced selectivity owing to the steric hindrance of the alkyl chain in the sulfonation of higher mono-alkylbenzenes with 20% oleum at 18. The present paper deals determination of the correlation between concentration of sulfonatiog agent and the structure of dodecylbenzenes in the selectivity of the sulfonation. The effect of dilution of sulfonating agent is increased as the position of aromatic nucleus locates toward the center of the alkylchain. When the nucleus moves from the second position to the center in the chain, the relative sulf onation rate by 95.5% sulfuric acid decreases from 10% to 25% in comparison with those by sulfur trioxide. Distribution of ortho and para isomers was also determined by infrared spectrography. The distribution in n-alkylbenzenesulf onic acid, sulfonated with 3.2 moles of 20% oleum at low temperature, was about 25% ortho and 75%, para. And in the sulfonation at 50°C it was about 21% ortho and 79%, para.
Author studied the states of dissolution in the ternary system consisting of polyoxyethylene nonylphenyl ether different in the degree of ethylene oxide polymerization, essential oil different in polarity, and water. When such ternary system is heated starting from turbid heterogeneous phase, it turns into transparent homogeneous phase then reaches again claud point on further heating. Author obtained diagrams of dissolution states of the system by the measurement of transparent point and claud point and the plotted curves deviled the diagram into three regions; the first heterogeneous phase system above the claud point curve; the second homogeneous (solubilized) phase system; and the third heterogeneous phase system below the transparent point curve. From the diagram, minimum concentration of each surfactant required (required concentration) for the solubilization of each essential oil at any temperature was obtained, and it showed a smallest value in the system of the intermediate n (degree of polymerization of ethyleneoxide) which is the optimum solubilizer. n, HLB and the required concentration of the optimum solubilizer between 0 and 40 can be easily found from the diagram. Optimum value of HLB obtained increased with increase of the polarity of essential oil. Effect of ethanol addition to the ternary system was also discussed.