The classical HLB (Hydrophile-Lipophile Balance) value of nonionic surfactants based on an original molecular structure does not take into account several factors affecting the performance of surfactants such as presence of additives, structural modifications of surfactant molecule, temperature, decomposition, etc. as is deduced from our own experiences and that of other authors. If these factors are taken into account, the HLB value becomes a variable depending upon the physical and chemical conditions at the time of the measurement. These effects may be described by assigning a more practical value, socalled effective HLB value which is defined as equivalent HLB of the reference surfactant which yields the same physical results as the one under investigation. The detailed knowledge of the relationship between the correctly estimated or calculated HLB and the physico-chemical properties appears to facilitate the choice of the best surfactant for a particular purpose.
Polymorphism of monoglyceride was examined in the three kinds of binary systems of 1-monostearin-sucrose heptaacetate monofatty acid ester (SHAF) using differential scanning calorimetry and infrared spectrophotometry. Three kinds of SHAF are sucrose heptaacetate monostearate (SHAS), sucrose heptaacetate monopalmitate (SHAP), and sucrose heptaacetate monomyristate (SHAM). 1) Monostearin in the binary systems showed α-type by chilling and it transformed to β-type by heat treatment. This phenomenon occured in all binary systems. 2) Phase diagrams were very analogous in three binary systems. Transition temperatures of Sub-α1, Sub-α1, α-and β-type of monostearin in these phase diagrams were same as it alone, respectivelly. 3) Transition time from α to β-type of monostearin was different with kinds and proportions of binary system. Transition of monosteain from α to β-type was more rapidly in SHAM system than in SHAS system and rapidly with increasing amount of SHAF. 4) Transition time of monostearin in binary systems was dependent on the temperature of heat treatment. This influence of the temperature of heat treatment was pronounced when SHAF was less than 25% of binary systems, but was not when it was 50%.
In order to study the deposition of polystyrene (PS) and poly (methyl methacrylate) (PMMA) latices on Nylon 6 fabric in aqueous solutions of sodium dodecyl sulfate (SDS), the rate of deposition of latex particle on fabric and the interaction energy between fabric and latex particles were determined and the state of deposition of latex particles on fabric surface was observed by scanning electron microscope. At pH 3, in aqueous SDS solution (1×10-3M) below the critical micelle concentration (cmc), both the rate constant of deposition and the state of deposition observed were scarcely changed in comparison with those in the absence of SDS in spite of large maximum value of total interaction energy-VTmax. In aqueous SDS solution (1×10-2M) above the cmc, further increase in VTmax and the decrease in rate constant were recognized and the latex particle deposited on fabric surface observed by scanning electron microscope decreased considerably. At pH 5.7 for PS latex, as well as at pH 3, in aqueous SDS solution (1×10-2M) above the cmc, both the rate constant of deposition and the latex particle deposited decreased remarkably. This results may indicate the effect of prevention to the deposition of latex on fabric by steric protective action of the ion or the micelle of SDS in SDS concentration above the cmc. Also regardless of the presence of SDS, PS latex was easier to deposit on the fabric than PMMA latex.
The behavior of kaolin which was coated with palmitic acid in a detergent solution was discussed in terms of the ζ-potential and the potential energy of interaction. The detergent was composed of 20% sodium dodecyl sulfate (SDS), 20% zeolite, 5% sodium silicate, 3% sodium carbonate, 1% sodium carboxymethyl cellulose, and 51% sodium sulfate. The ζ-potentials of kaolin coated with palmitic acid ineach aqueous solution of SDS, various builders, and the detergent were measured by an electrophoretic mass-transfer method. The potential energies of interactions between the coated kaolin and fabrics (nylon and cellulose), between the coated kaolin and zeolite, and between the coated kaolin and the other particulate soils (carbon black, coated carbon black, and kaolin) were calculated by the use of the theory of heterocoagulation and that between coated kaolin particles by the use of the DLVO theory. It is suggested from the total potential energy curves thus obtained that in SDS solution the coated kaolin may deposit onto fabrics or may coagulate with the other particulate soils more easily than kaolin, but in the detergent solution the deposition of the coated kaolin onto fabrics may take place with difficulty and the behavior of coated kaolin may be similar to kaolin.
The experiments on the autoxidation of methyl oleate (OM) and the decomposition of by droperoxide of methyl oleate (OMH) in OM were carried out in the presence of acetyl acetonates (VO, MoO2, Co and Cr) at 80°C. The effects of the catalysts were investigated by observing the changes in peroxide value, iodine value, saponification value, refractive index, molecular weight and content of trans isomer. The identification of autoxidation products of OM and decomposition products of OMH were carried out by gas chromatography of trimethylsilyl ether derivatives. VO (acac) 2 inhibited the autoxidation of OM, but had a remarkable effect for the decomposition of OMH. The main decomposition product was the methyl hydroxyepoxyoctadecanoate (HE), which was produced by the intramolecular reaction of OMH. MoO2 (acac) 2 had remarkable effects for the autoxidation of OM and the decomposition of OMH. The both products were the cis methyl epoxyoctadecanoate (CE), methyl hydroxyoctadecenoate (HO) and HE. The CE and HO seemed to be produced by the intermolecular reaction of OMH and OM and by the intramolecular reaction of OMH in the case of HE. Co (acac) 3 and Cr (acac) 3 had remarkable effects which were different from the acetylacetonates of VO and MoO2 for oxidation of OM and decomposition of OMH. The epoxide produced by autoxidation of OM was a trans-form.
Compositional and quantitative changes of fatty acids, tocopherols, and sterols in lipids of sunflower seeds harvested at 5 to 80d after flowering were investigated. The fatty acid and tocopherol compositions of lipids were determined by GLC and HPLC. Sterol compositions in unsaponif iable matter separated by using preparative thin layer chromatography were determined by GLC with cholesterol as an internal standard. The weights of the sunflower seeds increased rapidly during 35d after flowering, and the lipids accumulated at a steady rate up to 16d after flowering. The highest concentration of unsaponifiable matter and 4-desmethylsterol in lipids were found at an early stage after flowering, but the contents then decreased steadily. The percentages of campesterol, stigmasterol and β-sitosterol were 10.3, 23.9, and 65.7, respectively, in immature seed lipids (8d after flowering). But the percentages of campesterol and stigmasterol decreased markedly, whereas β-sitosterol increased up to maturity. The main tocopherol in seed lipids were α-and γ-tocopherol showed marked increase up to maturity, whereas γ-tocopherol contents in lipids were almost constant during maturation of seed. Generally, the percentage of linoleic acid in total lipids increased up to maturity, but the percentages of palmitic and linolenic acids decreased. The percentage of oleic acid in lipids reached a maximum at 16d after flowering, and decreased ever since. In the developing seeds of sunflower cultivars, the total tocopherol contents rapidly increased with increasing amounts of unsaturated fatty acids and their esters.
The reaction of esters of Rf perfluorocarboxylic acids (C4, C8) with ethylenediamine (ED) in the absence of catalyst was studied, using ethanol as a solvent. The main product was N, N'-bis (perfluoroacyl) ethylenediamine (NB) when the molar ratio of ED to the esters was nearly equal to 0.5, the rate being very slow. At higher ratio of ED to the esters, N- (perfluoroacyl) ethylenediamine (NF) was the main product. NB was crystallized out of reaction mixture, while NF was separated by distilling the mother liquor under a reduced pressure. The properties of NF are presented.