The polymerzation of linoleic acid, and of its ester, in the presence of carbonyl catalyst was studied under the following conditions ; catalyst concentration : 515%, temperature : 220300°C and time : 120 hr. The polymers were obtained in high yields and the maximum polymer content of the crude reaction products was about 65%. The polymer content of the product obtained from linoleic acid was smaller than that of the product from methyl linoleate under the same reaction conditions. The time required for the polymer content to reach 60% decreased with increase in the reaction temperature or in the amount of catalyst. The polymeric fractions separated from the products usually had darker color, higher acid number, and lower saponification number, than the original ester. The polymeric fractions contained mainly the dimer and a small proportions of polymers of higher molecular weight. From the results of analysis of the polymers, it is believed that the polymerization involves DielsAlder reaction and some other type of reaction.
Authors investigated the catalytic behavior of iron pentacarbonyl in the hydrogenation of C-C double bond. Each 30 g of cotton seed oil was reacted with 1.2 or 2.4 g of iron-pentacarbonyl in the following reaction conditions ; initial hydrogen pressure : 25 or 50 kg/cm2, temperature : 180 or 200°C and time : 2 or 4 hr. From the statistical consideration of the relations between reaction conditions and the composition of reaction products authors recognized the selectivity of hydrogenation between linoleic acid and oleic acid, namely, higher temperature and smaller quantity of catalyst were favourable to the selective formation of oleic acid, on the other hand higher temperature, higher hydrogen pressure and increase in amount of catalyst accelerated the stearic acid formation. As the side reactions the formation of high boiling substance and an iron-carbonyl complex compound were also detected. The former is considered as dimer of linoleic acid, and was preponderately produced in the case of lower temperature and more catalyst. The latter was revealed to be conjugated linoleic acid iron-tricarbonyl. Experimental results suggest the following reaction mechanism : -A certain labile complex compound such as monoene-iron-tetracarbonyl is formed at first from linoleic acid. If iron-pentacarbonyl is present in a larger amount, such intermediate is also formed from oleic acid. In the next step of hydrogencracking, oleic acid or stearic acid is formed from each of their respective intermediates. The intermediate, formed from linoleic acid, is simultaneously converted into comparatively stable type of diene iron-tricarbonyl, which can be also produced directly through the conjugation reaction of linoleic acid followed by complex formation reaction. In the excess thermal treatment this compound is decomposed and converted into dimer, on this occasion the iron-carbonyl residue of transition state may also act as the catalyst for dimerization.
Authors studied on the synthesis of bis- (β-cyanoethyl) -alkyl amine in cyanoethylation of methyl amine. As well in the previous report, the reactivity of cyanoethylation in polar or non-polar solvent was investigated. As a result, consequently, authors obtained the following conclusion. As compared with fatty amines of C6, C9 and C16 the methyl amine was easier to form bis- (β-cyanoethyl) -alkyl amine. Under the condittion, using methyl amine saturated in methanol or water solvent and three moles of acrylonitrile per mole of amine at reaction temperature of, 70°C for 6 hr reaction timeor at 20°C for 24 hrs, bis- (β-cyanoethyl) -methyl amine was obtained in almost stoichiometric quantity. As compared with I.N. Nazarov's method achieving the maximum yield in many literatures hitherto reported, the authors' method above mentioned is much easier in the operation and the yield of biscyanoethylate is higher than that.
In this report authors investigated the detergency of nonionic surfactant (polyoxyethylene nonyl phenyl ether, EO 10 mol) blended with anionic surfactant (sodium dodecyl benzene sulfonate). As a result, the detergency becomes lower by blending and steeply falls down to minimum by blending a small definit amount of anionics to nonionics, also minimizing in dispersing power and maximizing in surface tension. It is considered that some change in micelle structure of nonionics might have occurred by blending to affect detergency.
As previously reported, properties of polymeric surfactants derived from nonylphenol-formaldehyde condensates in aqueous solution differed in many respects from those of monomeric ones. To ascertain these differences which might come from the colloidal states of solutions, the determination of CMC was carried out by the method which S. Ross and co-workers developed for nonionic surfactants. While the aqueous solution of ethoxylated nonylphenol showed a break in the concentration-absorbance curve and the CMC determined fairly agreed with values shown in the literature which were measured by other procedures, polymeric surfactants did not show any such point. From these results, it was suggested that polymeric surfactants would not take regular configurations like ordinary monomeric ones in aqueous solution and that each molecule of the former corresponds to the micelle of the latter in dilute solution. And even the product of which mean molecular weight was roughly equal to the dimer showed such features. On this basis, the said characteristic properties of polymeric surfactants could be interpreted.