The cometathesis reaction of methyl oleate (MO) with unsaturated dicarboxylic acid esters has been studied using either a homogeneous catalyst system (WCl6‐Me4Sn) or a heterogeneous catalyst system (Re2O3‐Al2O3‐Me4Sn). In the presence of the homogeneous catalyst, dimethyl‐3‐hexenedioate (DMHD) reacted with MO to give cometathesis products in 47% yield with a distribution of products that agreed with the theoretical equilibrium composition. When dipropyl‐4‐octenedioate (DPOD) was used, however, the yield of cometathesis products was less than 1%. The lower reactivity of DPOD might be due to the formation of a stable complex of DPOD with the catalyst. The cometathesis reaction of MO and DMHD was also catalyzed by the heterogeneous catalyst. However, the reaction rate decreased significantly and the distribution of products did not attain the theoretical. Similar results were obtained in the cometathesis reaction of MO and DPOD catalyzed by the heterogeneous catalyst. These results suggest that MO and DMHD are preferentially adsorbed onto the surface of this catalyst according to their polarity, and that the molar ratio of MO and DMHD at the catalytic site was different from that in the reaction medium.

The addition of aromatic compounds to the double bond of oleic acid was studied using solid acid catalysts. For example, in the presence of an acid clay catalyst (bentonite), phenol reacted with oleic acid to yield 96% of an alkylphenol addition product. When toluene was used as the aromatic reactant, however, the yield of alkylbenzene addition product was less than 2%. In this instance, the major reactions observed were elaidinization and migration of the double bond of oleic acid. The addition of phenol to oleic acid in greater than 95% yield also was accomplished with the use of a sulfonic acid ion-exchange resin catalyst. This same catalyst also catalyzed the addition of toluene and benzene to oleic acid to yield 82% and 22%, respectively, of alkylbenzene-type addition products. In the latter instances, the major side product formed was 3,-stearolactone. Capillary gas chromatographic (GC) analyses of the alkylbenzene addition products obtained showed them to be mixtures of positional isomers. The isomer distributions were subsequently determined by GC-mass spectrometry (MS).

The effects of added co‐catalysts on the clay catalyzed polymerization of oleic acid have been investigated. Heating oleic acid at 230 C for 3 hr with a clay catalyst gave a polymer fraction (dimer and trimer acids, 35% yield) and a monomer fraction (branched chain isomers of oleic acid, 27% yield) as the major products. The variation in yield between the polymer and monomer products was found to be dependent upon the co‐catalyst used with the clay catalyst. For example, with both acidic and basic clays, polymer formation is favored (55% yield) in the presence of water and/or metal ions. In contrast, when Bronsted acids such as methanesulfonic or phosphoric acid are used as co‐catalysts, the yield of branched monomer increased significantly (50%). Studies on the adsorption of oleic and Bronsted acids onto the clay surface showed that isomer formation is favored when both the oleic acid and the Bronsted acids are adsorbed onto the clay surface at selected molar ratios.