Brominated or chlorinated nonionic surfactants for sol. extreme pressure cutting oils are significantly more efficient than cycloparaffins. The performance of the surfactants is a function of the emulsion stability and its availability to the surface in contact with the metal. Surfactants with sufficient Cl or Br contents have excellent wear and friction properties. [on SciFinder(R)]

The polymorphic behavior of 1,3-distearoyl-2-oleoyl glycerol (SOS) was investigated in the presence of a selected food emulsifier, sorbitan monostearate. Five polymorphs, named $\alpha$, $\gamma$, pseudo-$\beta$', $\beta$2, and $\beta$1, were crystd. and identified by x-ray anal. and DSC. Each polymorph was treated with 2 selected protocols - the screen cycle and the aging cycle. Sorbitan monostearate, when present in the molten fat, retarded the $\alpha$ to $\gamma$ transition during both the screen cycle and the aging cycle. A retardation effect was not detected for the $\gamma$ to pseudo-$\beta$' transition (during the screen or the aging cycle). The emulsifier inserted into the fat behaved as a conventional impurity, causing significant redn. in the melting temps. of each polymorph. As a result, the fat tended to melt prior to its transition. The behavior of SOS in the presence of the sorbitan monostearate is therefore different from that of SSS (tristearin), and may explain, in part, the absence of the strong blooming transition to high melting polymorph that occurs when the fat is rich in SOS. This behavior can also shed some light on the behavior of cocoa butter in the presence of sorbitan esters. [on SciFinder(R)]

Oligomeric polyglycerol was esterified with C12-16 fatty acids and then maleated. The maleates were sulfonated with Na2SO3 to give anionic sulfosuccinate surfactants. Higher crit. micelle concn. (CMC) and better foaming performance but lower wetting power were obtained by increasing the hydrophilic chain length to d.p 6; above this length the opposite trend was noted. A linear relation between hydrophobic chain length and log(CMC) was obsd. Optimization of surface properties could be obtained by regulating the maleation conditions. [on SciFinder(R)]

The appearance of the $\beta$' form in the $\alpha$-$\beta$ transformation in tristearin was hardly detectable. On the other hand, in mixts. of tristearin and tripalmitin at different ratios, $\beta$' formation was favored. This observation confirmed the statement in the literature that in mixts. of different chain lengths orthorhombic packing was stabilized. When an emulsifier (sorbitan monostearate) was added to the mixts., both the $\beta$' and $\beta$ formation were inhibited. The effect caused by the addn. of the emulsifier as an impurity to tristearin was compared to that caused by the addn. of tripalmitin: their effects, although both kinetic, were very different. [on SciFinder(R)]

A review with 3 refs. on the crystn. and polymorphic transformations of fats and fatty acids. [on SciFinder(R)]

Different oxidizing agents for performing the cleavage oxidn. of the double bond of the unsatd. fatty acids are presented, and their economic performance is analyzed. Ozone and sodium hypochlorite are the most com. efficient oxidants. Lab. work for the oxidn. of oleic acid to azelaic and pelargonic acids using hypochlorite as oxidant is described. The advantages of working in an emulsion system and using RuCl3 as a catalyst are discussed, and a possible mechanism of the reaction is presented. A flow sheet for an industrial process based on this concept is proposed. A simulation of a plant using this technol. is made by a computerized model, and the economic parameters obtained suggest that sodium hypochlorite can be an interesting reagent for industrial oxidns. of double bonds in fatty acids. [on SciFinder(R)]

Trilaurin, trimyristin, tripalmitin, and tristearin heats of fusion of $\alpha$ and $\beta$ polymorphs and the heat of transition were detd. alone and in the presence of sorbitan and ethoxylated sorbitan fatty acid esters, glycerol 1-stearate, triglycerol 1-stearate, triglycerol 1-monooleate, and monoglyceride citric acid ester. The emulsifiers could affect melting of the $\alpha$ form and/or recrystn. of the $\beta$ form, depending on triglyceride chain length and emulsifier structure. All the solid emulsifiers suppressed crystn. of the higher triglycerides. The sorbitan satd. esters promoted melting of the $\alpha$ polymorph rather than transformation to the $\beta$ form, and the other surfactants had the opposite effect. Slower heating minimized the inhibition of $\beta$ crystn. of tristearin by solid emulsifiers. Emulsifiers apparently modify the kinetic character of triglyceride polymorphic transitions. [on SciFinder(R)]

The kinetics of polymorphic transformations in monoacid satd. triglycerides and the effect of the presence of certain solid surfactants were investigated. Selected emulsifiers can be incorporated at the level of 10% by wt. within the triglyceride, without changing the crystal lattice; on the other hand, their presence affects the heat capacity of the triglyceride and the NMR relaxation time T1. Following the polymorphic transformation both during aging and during heating in the DSC, both the mechanism and rate of transformation of the triglyceride strongly depend on the kinetic conditions and on its own chem. structure. In conjunction with these results, the effect of the emulsifier is strongly dependent on the transformation conditions. The kinetic effect of the additive on the solid-solid transformation was strictly assocd. with its hydrophilic moiety structure. A model of mol. incorporation describes the arrangement of the surfactant mols. parallel to the triglyceride chains and formation of vacancies. The selectivity of the additive concerning its effect of dynamic controller of polymorphic transformations was explained by its capacity to create H bonds with the neighboring triglycerides, which was called the Button Syndrome. [on SciFinder(R)]

A review and discussion with 48 refs. The crystn. of fatty acids from soln., soln.-mediated polymorphic transformation, mixed and monoacid triglyceride crystn., and the effects of food emulsifiers on the transition kinetics are discussed. [on SciFinder(R)]

Proton magnetic resonance measurements were performed on $\alpha$- and $\beta$-polymorphs of tristearin (I) crystals. The spin-lattice relaxation time (T1) was measured at 20 MHz and 37° on the pure I crystals and on I crystd. in the presence of different solid surfactants. A significant neg. correlation for T1 values and different compns. of $\alpha$- and $\beta$-polymorphs in a mech. mixt. was found. The shortening of T1 relaxation time of the $\beta$-form was different for the various types of the added surfactants while they had no effect on the relaxation time of the $\alpha$-form. A model was proposed according to which the presence of additives, such as surfactants, generated vacancies within the crystal lattice of I and enhanced the freedom of rotation of the fat mol. about the terminal carbon-carbon bond. [on SciFinder(R)]

The polymorphic transitions of hydrogenated canola oil in the presence of some selected food emulsifiers such as sorbitan monostearate, monodiglycerides, and DATAE esters were studied. During the temp. (aging) and heating cycles, the fully hydrogenated canola oil is transformed from its $\alpha$- and $\beta$'-forms to the $\beta$-form. The presence of 5 wt% surfactant will retard such transition and mostly $\beta$'- and $\alpha$-forms will be stabilized. The partially hydrogenated oil (IV = 3-69) shows the existence of different low and high m.p. forms. The low melting forms will transform into high melting forms at much lower rates of transition in the presence of those emulsifiers than in their absence. [on SciFinder(R)]

Cocoa butter was crystd. in the differential scanning calorimeter in the presence and the absence of sorbitan monostearate at different cooling rates. The solidification and fusion curves were recorded. The cooling rate affects enthalpies and temps. of phase transitions. Very slow cooling causes a significant decrease in crystn. enthalpy, suggesting that fractionation of glycerides occurs under these conditions. In the presence of 5% sorbitan monostearate, cooling and heating curves of cocoa butter are sharper, the solidification point is higher, and the fusion point is slightly lower; further, both crystn. and fusion enthalpies are lower than in pure cocoa butter. The presence of the emulsifier seems mainly to promote fractional crystn. Fusion curves after different periods of isothermal crystn. suggest that higher polymorphic forms differ in chem. compn. from lower ones, and that the presence of sorbitan monostearate affects the fractionation in the fat. [on SciFinder(R)]

A review and discussion with 74 refs. The chem. properties, compn., phase behavior and polymorphism, with and without added fats and impurities, are discussed with respect to the bloom problem and the role of tempering. [on SciFinder(R)]

The effect of solid emulsifiers, added at the level of 10%, on the lattice parameters of tristearin and trilaurin, was studied by x-ray powder diffraction. The presence of sorbitan monostearate and glycerol-l-stearate affects slightly the lattice const. a in tristearin; on the other hand, although sorbitan monostearate causes an increase in a of trilaurin, glycerol-l-stearate does not. The presence of sorbitan monolaurate and glycerol-l-stearate affect a of trilaurin similarly to the long chain emulsifiers. A correlation between the effect on a and the increase in m.p. was found. The presence of the emulsifier does not alter drastically the lattice dimensions of the fat. The slight dissimilarity in crystal structure between tristearin and trilaurin is confirmed by the diverse effects of the emulsifiers on the internal structure of the fat. [on SciFinder(R)]

Polymd. and crosslinked unsatd. glycerides were used as emulsifying agents (3-5%) for soybean oil, giving ≤50% aq. emulsions. The d.p., mol. wt. distribution, viscosity, dielec. const., and refractive index of the emulsifier were correlated with the emulsion stability, with mol. wt. ∼40,000 giving the best results. [on SciFinder(R)]