1. Lard, lard oil and their selectively hydrogenated oil (IV 5758) with Ni and Cu-Cr-Manganese oxide (KW) catalysts were interesterified. Reactivities and properties of those interesterified oils were studies. 2. Melting points, trans acid contents and SFC of hydrogenated lard and lard oil with KW catalyst were lower than those of the hardened with Ni catalyst. 3. Melting points of interesterified oils of lard, lard oil, hydrogenated lard and hydrogenated lard oil were higher than those of their base oils. And also interesterified oils had wider plastic range than their base oils except lard oil. 4. In cooling tests, solidified latent heat was observed in interesterified oils of hydrogenated lard and lard oil, but such phenomena scarcely occurred in interesterified lard and lard oils. 5. Fatty acids bonded at 2-position of triglycerides were examined. Molar percentage of C16 fatty acid bonded at 2-position was 8283% in lard and 74% in lard oil. Additionally, such percentage of C18 and C18 : 1 in lard oil were higher than those in lard. Ester exchange reactions were not observed in hydrogenation of lard and lard oil with Ni and KW catalysts.
The effect of lipophilic sugar fatty acid esters (SE) and their acetylated derivatives (ASE) on the physical properties of solid fats was investigated by measuring open-tubed melting point (OMP), Mettler dropping point (MDP) and softening point (MSP), and solid fat index (SFI) of cacao butter, palm oil and hardened coconut oil with and without SE or ASE added. Differential scanning calorimetry (DSC) was also conducted for cacao butter with and without ASE added. Results obtained were as follows : 1) OMP, MDP, and MSP of all three solid fats gradually decreased with increasing amount of ASE added, but those tended to increase with increasing amount of SE added, although there was a slight decrease when the amount of SE added was small. However, these changes of MDP and MSP were much greater than the case of OMP. Then, the fats added 5% SE gave remarkably higher MDP and MSP compared to those added 5% ASE. 2) The larger the amount of ASE added, the lower was SFI of cacao butter and palm oil at 15 and 25°C, but SE did not cause such a difference with the amount added. However, even at 35°C at which SFI of cacao butter was 0, and at 45°C at which SFI of palm oil was 0, SFI of these fats added 5 % SE was 3.4 and 1.2, respectively. 3) DSC of cacao butter added ASE tended to give a smaller main peak and a wider range of melting temperature with increasing amount of ASE added. Also, treated at 25°C, the temperature at top of the main peak observed after 120 h, rose 2°C compared to after 24 h when ASE was not added, but it rose only 0.5°C when 1% ASE was added and did not rise when 2 or 5% ASE was added.
The ultimate biodegradabilities of cationic/anionic surfactant-complexes (molar ratio, 1 : 1) were examined using CO2 production method at 27°C under the aerobic condition. As cationic surfactants, alkyltrimethylammonium chloride (TM) and dialkyldimethylammonium chloride (DM), and as anionic surfactants, sodium alkyl sulfate (AS) and sodium linear alkylbenzenesulfonate (LAS) were used. Cationic surfactants (TM and DM) were not biodegraded at all, but cationic/anionic surfactant-complexes (TM+AS, TM+LAS, DM+AS and DM+LAS) were biodegraded and the results of the comparative biodegradabilities of 4 complexes were as follow; TM+LAS>TM+AS> (DM+LAS, DM+AS).
It has been shown in a previous paper that each component of a fatty acid mixture containing equal amounts of lauric, myristic, palmitic, stearic, and oleic acids is removed in the order of C12>C14>C18 : 1> C16≥C18, C12>C14>C16≥C18>C18 : 1 at 25°C and 50°C, respectively, from cotton fabrics by an alkaline solution of sodium dodecylbenzenesulfovate. In this paper, the removal of each component of the mixture has been examined at 3°C and 10°C and the behavior of oleic acid in the removal of the soil mixture has been explained on the basis of the thermal characteristic of the mixture using the differential scanning calorimeter. Each component of the mixture was removed in the order of C12>C18 : 1>C14>C16≥C18 at 3°C and 10°C. The endothermic melting curve of the mixture gave triple peaks near 5°C, 20°C, and 40°C and the mixture melted at 41.0°C. It was found that oleic acid took the phase separating within the mixture because a peak near 5°C shows the melting of oleic acid. Therefore, it is considered that the phase transition of the mixture accompanied by the increase in temperature changes the order of oleic acid in each fatty acid removal.
Ethylenediaminetetraacetic acid (EDTA) was treated with diamine (p-phenylenediamine) and two triamines [2, 4, 6-triaminopyrimidine (A) and 1, 2, 4-triaminobenzene (B)] to prepare the polyamides which had chelate-forming ligands and could selectively adsorb (or desorb) heavy metal ions. The A-resin obtained by the reaction of EDTA-diamine-triamine (A) (10 : 9 : 2/3 in molar ratio) was found to have the minimal bulk specific gravity (0.36) and the maximal water absorbing capacity (225%). The bulk specific gravity increased and the water absorbing capacity decreased with an increase in molar ratio of the triamine. The B-resins obtained by the reaction of EDTA-diamine-triamine (B) had larger bulk specific gravity (0.630.69) and smaller water absorbing capacity (82104%) than those of A-resins. By comparing IR spectra of the two types of both A and B-resins, one type adsorbed copper ion and the other type adsorbed sodium ion, the carboxylate ion of the former type resin was seen to coordinate to the copper ion. From the above discussion on IR spectra and from results of pH-titration of both A and B-resins on the aqueous suspension in the presence of copper ion, it was concluded that copper ion was adsorbed by way of chelate-bonding by the resins. The experiments of the adsorption of 8 metal ions on a B-resin revealed that adsorption capacity was greatly dependent both on the ion species and pH.
The adsorption equilibrium of water soluble alkyl sulfates on the surface-modified and surface-unmodified activated carbons in aqueous solutions was examined. An activated carbon, Pittsburg Activated Carbon (Calgon Co.), was used as an adsorbent, and it was treated with nitric acid, hydrochloric acid, hydrofluoric acid, and hydrogen. Alkyl sulfates used in this experiment were sodium salts of octyl sulfate, decyl sulfate, dodecyl sulfate, tetradecyl sulfate, hexadecyl sulfate, and octadecyl sulfate. The adsorption characteristics were found to conform with the Freundlich type isotherm, and also to obey the Traube's law. The adsorption capacity of sodium dodecyl sulfate on the modified activated carbons decreased in the following order. H2·HCl·HF>H2 treated>HCl·HF> unmodified>13.2N-HNO3 The adsorption capacity is expected to change in relation to the nature of surface oxides on the activated carbons.
Alkylation of carboxylic acids at the 2-position with conjugated olefins such as isoprene, butadiene, myrcene, and styrene were carried out. For example, 2, 2, 5-trimethyl-4-hexenoic acid (3) was obtained in 66% yield from the reaction of isobutyric acid (1) and isoprene (2) using sodium naphthalenide in the presence of N, N, N', N'-tetramethylethylenediamine. Similarly, from isobutyric acid (1) and styrene (5), 2, 2-dimethyl-4-phenylbutyric acid (6) was obtained in 57% yield. Furthermore, conversion of these carboxylic acids to alcohols, aldehydes, and lactones were examined.
Surface tension of fatty acids (C4C13) and fatty alcohols (C4C18) was estimated by contact angle measurements. Geometric mean approximation method (extended Fowkes' Equation) was applied to estimate the dispersion force component (γd) and the polar force component (γp) to the total surface tension (γ) from contact angle data. Surface tension of liquid oils, i.e., fatty acids (C4C8) and fatty alcohols (C4C11), increases with increasing carbon number between 24.428.9 dyn/cm. The contribution of dispersion force component to surface tension of these oils, γ1d/γ1, is 90% or more and the rest part is the polar force component. Surface tension of solid fatts, i.e., fatty acids (C12C18) and fatty alcohols (C14C18), decreases with the carbon number increase between 62.424.1 dyn/cm. The contribution of polar force component to surface tension of fatty alcohol is rather high, especially in C14 and C16, however, that of fatty acids is lower and nearly constant ratio (about 10%). Surface tension of decanoic acid (C10), 1-dodecanol (C12), and 1-tetradecanol (C14) at 10°C (solid state) and 40°C (liquid state) was compared in these two states of materials. It was proved that solid fatty substrates have higher surface tension than liquid ones. The work of adhesion (Wa) between these model oily soils and the polymer substrates in liquid media may offer the clue to clarify the mechanism of oily soil removal.