The order of the hydrogenation reaction of unsaturated fatty oils by nickel catalysts has been measured by a number of investigators. As might be expected, their conclusion varied widely, depending upon the operation condition employed. We have been investigated the hydrogenation reaction order of cotton seed oil by the copper-chromium-manganese oxide catalyst by the standard operation condition, and found that the reaction is the first order until the most of linoleic acid has hydrogenated to oleic acid.
In order to study the effects of the polar groups of rust inhibitors upon the results of different corrosion tests, we took up in this installment petroleum sulfonates and carboxylic acids as the inhibitors, and carried out several corrosion tests employing six sorts of petroleum sulfonates and as many sorts of carboxylic acids respectively. As a result it was found that the anti-corrosion properties of petroleum sulfonates were most finely indicated in the salt water immersion test, the non-ferrous metal immersion test and the heat stability test ; and in the reaction test by potassium ferricyanide and the sulfuric acid immersion test also, they were shown with reasonably good effect; while in the humidity cabinet test and the shed storage test they did not yield good results. It was found further that the rust inhibitors prepared with carboxylic acids added to lubricating oils showed good anti-corrosion results in the shed storage conditions at a relatively low temperature; whereas in the salt water immersion and the sulfuric acid immersion tests they indicated very little anti-corrosion property. In addition some corrosion was found on the surface of the test panels in the heat stability test and non-ferrous metal immersion test by use of these rust inhibitors except Ca-naphthenate. On the other hand it was also found that in measuring the amount of displacement energy in the interfaces between steel and oil and water, both inhibitors, petroleum sulfonates and organic carboxylic acids, showed minus value and that the absolute values of petroleum sulfonates against salt water were larger than those against distilled one.
Among factors relating to alkyl ketene dimer which have an effect on paper sizing, qualities of fatty acid chloride which is an ingredient of alkyl ketene dimer, synthesis process, emulsifying agents and alkyl radicals were investigated. In sizing effect, distilled fatty acid chloride with less free fatty acid, was superior to undistilled fatty acid chloride with more free fatty acid. The products by filtration method and water washing method to separate amine salt made no difference in sizing effect. Alkyl radical shows a larger reaction velocity with OH radicals of fibre ; therefore adoption of alkyl ketene dimer having relatively short chain length, is recommended for increasing sizing effect at low temperature, but if curred sufficiently, the longer chain length it has, the better it is in sizing effect, however, the difference is not so much. In consideration sizing effect of hexadecenyl ketene dimer, blockade of OH radical of fibre is primary, but at the same time sizing effect is considered to be affected by hydrophilic and lipophilic balance of alkyl radical sizing effect was not affected by any kinds of nonionic surfactants blended, but the less the quantity is, the better the result is.
The best reaction condition for disproportionation of tall rosin with active carbon was investigated. For 250°C of reaction temperature, 20% of catalyst and 5 hr of reaction were found optimum, and the quantity of catalyst could be reduced with increase of reaction temperature. Range of 250260°C was found suitable. At 300°C, some side reaction occurred. More side reaction was caused by using dry active carbon than wet active carbon. Dry active carbon produces slightly more unsaponifiable matter, and also the saponifiable matter produced by dry active carbon includes side reaction product with maximum absorption at 224 mμ and 260 mμ. It was difficult to halt production of unsaponifiable matter remarkably with water contained in the catalyst or by adding water to reaction system. Active carbon produced 1417% range of unsaponifiable matter. Active carbon, once used, lowers remarkably in catalytic activity and it tends to decrease in its activity by subsequent uses.
The experimental conditions selected in the previous report have been expanded to enlarge the application range of the conclusion. As the ionic substances, a kind of inorganic salt was added to the sort of agents used. Both the application ratio (between ionic substance and nonionic surfactant) and the solution concentration have been varied. The electric resistances of treated Terrylene fabric have been measured at lower and normal atmospheric humidity. The relation curves of concentration (mol or owf) against electric resistance have been investigated. Conclusions : 1. With the antistatic capacity, inorganic salt was seriously inferior to ionic surfactant in case of individual application, but was much improved by means of simultaneous application with nonionic surfactant. 2. Anionic surfactant, in case of simultaneous application with nonionic one, showed convex curve, and the concentration effect to resistivity with same application ratio between them was not so great. The application ratio (1 : 1) used in the previous report is within the range near the top of the curve ; thus it was found to be the most disadvantageous selection. 3. Cationic surfactant, in case of simultaneous application with nonionic surfactant, showed descending curve and the concentration effect to resistivity with same application ratio between them was decisive. The application ratio (1 : 1) used in the previous report is within the range near the point of intersection of this curve with that of individual application of nonionic surfactant. 4. Thus, in case of simultaneous application of ionic substances and nonionic surfactant, there can be seen a more efficient portion on their curves than those of individual application of nonionic surfactant. The relation curves between electric resistivity and mol concentration obtained from agents containing ionic substances shows similar and steeper inclination. It follows that the quantities of discharge are proportional to the numbers of released ions.
Dehydration of ricinoleic acid, a main constituent of castor oil, has long been investigated in order to increase double bond for use as drying oil. The dehydrated products were reported to be a mixture of various isomers, of which only the properties of final products have been majorly investigated. Authors studied the change of double bond structure during dehydration with catalysts by using the ultraviolet and infrared absorption spectrophotometry. The results can be summerized as follows ; 1) The same isomers were found in each sample, but their relative amounts were different by the type of catalyst. 2) Dehydration occurred both at C11-12 and C12-13 position, and it was confirmed that the cis-trans conjugated isomer resulted from the dehydration at C11-12 position, were isomerized at the dehydration temperature to trans-trans conjugated and trans isolated one. 3) The dimer was also formed, as the dehydration proceeded, and was separated by vacuum distillation (0.2mmHg at 141143°C). The diene content of the monomer thus obtained was found to be 2134%. 4) The thermal isomerization of the monomer was carried out and it's behaviour was investigated. It was found that the amount of trans-trans conjugated iosmer reached to equilibrium at about 12% of trans isolated isomer in the recovered monomer after the thermal isomerization. The same result had been obtained about pure methyl linoleate in our previous papers.
Highly unsaturated fatty acids, carrying more than 4 nonconjugated double bonds, that were prepared from cuttle fish oils, changed their structure from non-conjugated polyene to conjugated polyene, that is, to cis-cis-trans conjugated triene structure, when heated at about 200°C under interruption of air and also to conjugated diene form, when heated at 250°C. The produced triene gave the absorption maxima at 266, 277 and 287.5mμ and changed easily their structure to conjugated diene form, when heated at more than 230°C, where by absorption maximum was recognized at 236mμ. The compounds that carry conjugated triene structure were monomeric and distillable at 155167°C/0.01mmHg and were easily isomerized to conjugated polyene by 21% KOH-glycol, whereas the conjugated diene bearing compounds were polymeric and were hardly isomerized by alkali. But when highly unsaturated fatty acids were heated under the condition of diluted solutions (mixed with microcrystallinewax), the produced conjugated diene and triene were both monomeric and distillable at 158165°C/0.01mmHg.
The lipid of a fresh water plankton, Neomysis intermedia Czerniaysky, was examined. Neomysis intermedia (a fresh water plankton) and Neomysis nakazawai Ii (a marine plankton) belong to the same genus, and it is interesting to compare the properties of the lipids each other. The ether extract was obtained from the sun-dried material of the plankton caught at Lake Kasumiga-ura, Ibaragi Prefecture. The content of the lipid was 3.9% of dry matter. Properties of the lipid were as follows : n20D 1.4821, S.V. 150.0, I.V. 109.8, A.V. 76.7, and unsaponifiable matter 17.89%. The fatty acids of the lipid were composed of 42% of saturated acids (C14 4.5%, C16 24.5%, C18 11.5%, C20 1.5%) and 58% of unsaturated acids (C14 1%, C16 11%, C18 18%, C20 and C22 28%). The lipid contained larger amount of saturated C16 and C18 acids, and smaller quantity of unsaturated C20 and C22 acids than that of Neomysis nakazawai Ii, a marine plankton. In comparison with the lipid of some of the fresh water species, the lipid of Neomysis intermedia was poor in the amount of unsaturated C16 and C18 acids, and rich in saturated C16 and C18 acids.
Extraction of the crushed seed kernels of Momordica charantia L. with ethyl ether gives a high yield (44.64%) of oil. The ultraviolet absorption spectrum of the oil suggests that about 57.8% of it is a conjugated trienoic acid. When refluxed with alcoholic potassium hydroxide, the oil gives an acid fraction which readily yields a crystalline acid, C18H30O2, mp 48.049.0°C, identified as α-elaeostearic acid.