Catalytic carboxylation of fats: Carboxy acids from polyunsaturates

Abstract

Studies with a palladium chloride-triphenylphosphine catalyst have been extended to the carboxylation of polyunsaturated fats. Linseed, soybean, and safflower oils, acids, and esters were carboxylated catalytically with water-carbon monoxide (4000 psig) at 120-160 C with or without acetone as a solvent. Main products were monocarboxy, 1,3-and 1,4dicarboxy and tricarboxy acids. Minor products were carbomethoxy esters and disubstituted 2-cyclopentenone. Optimum reaction conditions were determined for the carboxylation of linseed oil and methyl esters by statistically designed experiments. Yields of total carboxy and tricarboxy acids were maximized at low triphenylphosphine and water levels, low temperatures, and high palladium-chloride concentrations. Carboxylated soybean esters were separated by ether extraction of the palladium catalyst from sodium carbonate or hydroxide carboxylate salts. This salt extraction permits catalyst recycling.

Some esters of mono‐, di‐, and tricarboxystearic acid as plasticizers: Preparation and evaluation

“…13-16) are 5-6 C lower than the corresponding alkyl DiMe triesters (Nos. [8][9][10][11][12]. An increase in the size of the internal ester group from Bu-DiEt (No.…”

“…For permanance, plasticizers ideally should have a low tendency to migrate, but as a group alkyl-dialkyl triesters (Nos. [8][9][10][11][12][13][14][15][16] Table IV meet these requirements. Volatility wt loss of 0.6-0.8% for several samples is lower than that of the three controls.…”

“…Heat stability for samples prepared with Geon 102EP is greater than that of samples prepared with Geon 101, as shown for the two DOP controls. Consequently, the higher heat stability values for samples [8][9][10][11][12][13][14][15][16] are also attributed to Geon 102EP.…”

“…B. From hydrocarboxylation: Hydrocarboxylated soybean and linseed methyl esters were prepared as previously reported (11,12). The carboxylic acids were purified either as the sodium salts to remove saturates and keto byproducts (16) or as the esters by fractional distillation.…”