The distribution of fatty acid sand oryzanol absorbed in a bed of strongly basic anion exchange resin of OH type was determined by passing through the rice bran oil and its methyl ester, independently dissolved in the mixture of benzene and methanol. The amount of oryzanol absorbed in the bed decreased remarkably when ratio of the resin to the oil exceeds a certain limit. From the quantitative relation between oryzanol and fatty acids in the effluents, it is assumed that oryzanol once absorbed on the resin would be replaced by the fatty acids existing in excess.
In the extraction of oryzanol with anion exchange resin, the influence of the free fatty acids of rice bran oil on the adsorbency of the oryzanol was investigated. All the same procedures as reported in the previous papery were used to determine the behaviour. A tendency was found that the less the freshness of rice bran oil, the adsorbency of oryzanol to the resin decreases.
Rice bran oils having ranged acid values were molecular-distilled to analyze their properties, difficulties on distillation and applicabilities on processing. Mono- or diester contents and their differences, estimated from the hydroxyl values of each fraction, were small for each samples of various acid values. Bottom residue from the sample oil of high acid value contained more quantity of unsaponifiable matter of high melting point than that from the samples of middle or low acid value. Appearance of the bottom oil was not good, being unsuitable as the raw material of edible oil. The unsaponifiable matter content in the bottom was less than original sample of low and middle acid value, but in case of high acid value the u.s.m. content was more than that of original. There is a limit in acid value of crude rice bran oil to be refined by distillation or solvent extraction, where by high acid value oil is not suitable.
It was found that highly active alkaline co-precipitated copper binary or ternary catalysts were obtained only when acidic metal containing solutions were poured into excessive alkaline solutions. Through the above procedure, catalysts of different Cu : Cr mole ratio were prepared and their activities were compared, which made it possible to decrease Cr against Cu. Co-precipitation of Cr in minor amount (i.e. Cu : Cr=9 : 1 or less), as compared with the Adkins catalyst, quite improved the catalytic activity as well as heat treatment stability, and proved almost the same hydrogenation results obtainable as with the KW type catalyst. Also, a marked increase in catalytic activity was caused by adding such metals as Zn, Al, Co, whereas Cu alone proved to be almost inactive. These observations disagreed with the result reported heretofore (C. A., 352 b ; 353 a, 1950), and support the theory of sintering prevention effect by the additives. Investigations were made to decrease Ni in the Ni-Cu binary catalyst so as to make Cu predominant over Ni to avoid the inherent catalytic effect of the latter. Though the definite ratio was not determined, less than 1 mole of Ni against 9 mole of Cu was presumed to realize the contemplation. Solid fat index of hydrogenated soyabean oil and cotton seed oil indicated that the Ni-Cu catalyst produced hydrogenated products having less solid fat index than the KW type at a same iodine number down to about 70. It was found that pH of co-precipitating atomosphere would cause serious effects on catalytic activities, and for Cu : Ni/9 : 1 combination pH of over 9, for Cu : Cr/9 : 1 combination, pH of over 8 were proved to be suitable to obtain active catalysts. Five kinds hydrogenated finback whale oil having almost same Iodine Number (68-69) were prepared with Adkins, Cu-Cr (9 : 1), Cu-Al (3 : 2), Cu-Ni (9 : 1) and the KW type catalysts. The analytical data showed no significant difference of the three catalysts excepting the Cu-Ni and Adkins, wherein the former made slightly harder products, the latter produced considerable amount of solid and iso-oleic acids.
A refined finback whale oil was hydrogenated under atomospheric hydrogen pressure using three different type catalysts, namely, KW type (J. Pat. 200, 077), U-Ni-A (J. Pat. 204, 353), and reduced Ni-Cu catalysts. A micropenetration test was observed to compare the products, hydrogenated to almost the same level of 70 in Iodine Number, and the soft products in order were using KW, U-Ni-A and reduced Ni-Cu. The KW type catalyst presumed to be sensitive against free fatty acid content in material oil and the lowering in Acid Number to less than 0.4 was indispensable to re-use the catalyst. A simple method was proposed to regain and accelerate activity of the KW type catalyst by treating spent catalyst with alkaline solution under aerating oxidation. By applying the above treatment, the KW type catalyst could be re-used four times satisfactorily in whale oil hydrogenation and a possibility of further re-using was predicted. A refined sperm whale oil was hydrogenated under atomospheric hydrogen pressure with 2% KW type catalyst and a highly decolored and almost odorless stabilized product was obtained without any conspicuous change in its inherent characteristics. A carefully prepared 2% Adkins catalyst proved to hydrogenate refined finback whale oil almost as active as the KW type and could also be re-activated and re-used by the above treatment.
Influences on emulsion polymerization of stylene and butadiene with K-soaps of disproportionated rosins under hydrogen stream which is considered effective because of low contents of phenolic matter were investigated. The yield of polymer was not affected with disproportionated rosins, having value less than 2.3 in extinction coefficient at 241 mμ (α241) in ultraviolet absorption spectra, but disproportionated rosins, having value more than 2.8 in α241, indicated the tendency to decrease the yield of polymer. The yield of polymer was not affected with amounts of unsaponifiable matter contained in K-soaps. The yield of polymer was scarcely affected with amounts of free resin acid contained in K-soap and large amounts (15 as acid value) of free acid indicated the tendency that the yield of polymer would be a little up. The tests on stability of latex polymerized with K-soaps having various α241 value, amounts of unsaponifiable matter and acid value, were carried out by estimating the coagulation value. The stabilities of various latex were equal, but there was some difference in comparison with that polymerized with Dresinate 214, especially, when sodium sulfate was used as coagulating agent, the difference became larger. Dresinate 214 was inferior than others in stability.
In the previous report, the antistatic effect of the surfactants on propylene fibres relating to their stability for temperature, humidity and for heat-setting has been studied. In this paper, differences in degree of antistatic effect of them on the above mentioned fibres by prolonged storage were investigated. Alkyl-phosphates, quarternary ammonium type cationics and betain type amphoterics gave good results even after 90 day storage, and in the case of other surfactants, the diminutions of the antistatic effect by prolonged storage were comparatively low.
An experiment has been carried out to determine the effect of dye-dispersing power of surface active agents on the dyeability of two refined disperse dyes, C. I. Disperse Red 1 and C. I. Disperse Red 15, on polyester fibers at 80 and 95°C. In general, the additional dispersing agent decreased the dyeing rate in each case. Using at the same concentration, higher dispersing power of the agents lowers the exhaustion of dyes. Sodium naphthalene sulfonate formalin condensate has an excellent dye-dispersing power, but shows a marked tendency to inhibit the absorption of dyes. At low concentration, however, being equal or superior than other dispersing agents on the exhaustion of dyes, it is most suitable for dyeing of polyester fibers because of its high dispersing power.
An investigation has been made on the emulsifying power of surface active agents for hydrophobic carriers, o-dichlorobenzene and 1, 2, 4-trichlorobenzene, and the influence of emulsifiers on the dyeability of two disperse dyes, C. I. Disperse Red 1 and C. I. Disperse Red 15, on polyester fibers at 80 and 95°C. 1, 2, 4-Trichlorobenzene was more difficult to emulsify, but a little more effective as dyeing accelerent than o-dichlorobenzene. POE nonyl phenyl ether (P=25) had an excellent emulsifying power but inhibited the absorption of dyes. Triethanolamine salts of dodecylbenzene sulfonate and lauryl sulfate were better emulsifiers than diethanolamine, monoethanolamine and sodium salts. Of the triethanolamine salts of sulfonated products, the emulsifying power ranked in the order of dodecylxylene, dodecyltoluene, dodecylbenzene. Among the emulsifiers examined for the dyeing of polyester fibers with o-dichlorobenzene or 1, 2, 4-trichlorobenzene, triethanolamine salt of dodecylxylene sulfonate was most suitable without affecting the dyeability of disperse dyes.
In ordinary manufacturing of anionic surface active agents, sulfation or sulfonation is a major part. Nonaqueous titration method, dodecyl trimethyl ammonium hydroxide as a titrant, isopropyl alcohol as as a solvent, was available for analysis of the acid-intermediates. In this method, a correction of the first inflections based upon impurites in the titrant was necessary, but the experimental results with various acid mixtures and sulfonated matters were quite satisfactory.