No abstract

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.

Benzoic acid adds to oleic acid in methanesulfonic acid as catalyst‐solvent to form an addition product in 30% yield. Saponification studies on the product reveal that the addition is made via the carboxyl group and no rearrangement of the initial product takes place. A number of substituted benzoic acids were also tried but the yield of addition product was nil. Data are included for the experiments with a number of phenols not previously reported. These include: o‐chlorophenol,2,6‐di‐tert.‐butylphenol, 2,4,6‐trichlorophenol, resorcinol, 5‐n‐pentadecylresorcinol, hydroquinone, methyl salicylate, and 3‐n‐pentadecylphenol. Good yields of addition products of cyclohexene are obtained using methanesulfonic acid as catalyst‐solvent and the same nucleophiles employed previously.

In efforts to prepare wax esters chemically similar to those comprising sperm oil, selected fats or blends thereof were reduced to alcohols which then were reacted with the initial triglycerides to get such wax esters. For instance, lard oil was reduced to lard oil alcohol in the presence of sodium and methyl isobutyl carbinol in xylene. Most of the resulting sodium alcohotates (95-98%) were decomposed with urea, and subsequent addition of lard oil (triglycerides) resulted in rapid formation of the desired wax esters in ca. 80-90% yields. In preliminary studies, the same wax esters were prepared by a more circuitous route. The alcoholates were decomposed completely with urea, the fatty alcohols were liberated, and they then were esterified with free lard oil acids. Similarly treated were a blend of lard, coconut and crambe oils, fractionated tallow, and a commercial grade oleic acid.

Infrared study of the products of the addition of m‐cresol to oleic acid in methanesulfonic acid, revealed the presence of both the m‐creasoxy and hydroxytolyl substituted stearic acids. By employing a modified extractive procedure to recover the products of the reaction, followed by chromatography on a Florisil column, a separation of the two types of addition products was effected.The methanesulfonic acid catalyzed addition reaction was extended to include aryl thiols. Among the sulfur analogues of the previously used phenols that were added are: benzenethiol, p‐t‐butyl‐benzenthiol, 2‐naphthalenethiol, o‐, m‐, and p‐toluenethiol. The yields of addition products (which were unobtainable in sulfuric acid media) ranged from 37舑70%. In contrast with the results obtained when phenolic nuleophiles were employed no evidence for the formation of rearranged addition products has been found. Thioethers were the only products identified.