Oxidized rapeseed oil methyl ester as a bitumen flux: Structural changes in the ester during catalytic oxidation

Abstract

Structural changes occurring in the rapeseed oil methyl ester upon catalytic oxidation at 200 °C were examined. Oxidative decomposition of fatty acid chains to lower molecular weight compounds and the formation of oligomers were the major oxidation pathways at 200 °C. FT-IR and 1H NMR examinations, as well as the fall in iodine number, revealed the disappearance of double bonds. Quantitative analysis of the rapeseed oil methyl ester and the liquid products of its oxidation showed that oxidation of fatty acid methyl esters possessing three and two double bonds was practically complete whereas for structures possessing one double bond the loss of unsaturation amounted to 25% only. The decrease in iodine number from about 110 to about 65 and the 1.5-fold increase in molecular weight of the liquid products in the course of 25-h oxidation suggest that only a part of the unsaturated bonds in the fatty acid methyl ester was engaged in the formation of liquid oligomers and volatile oxidation products. The addition of dicumyl peroxide promoted the formation of organic peroxides during the initial stage of oxidation, which resulted in a higher molecular weight of the liquid products. The volatile oxidation products were found to contain lower molecular weight aldehydes, ketones, free fatty acids and their methyl esters, alkylfurans, lactones, n- and isoalkanes. The reaction schemes for their formation were presented. The results of the study are of importance to the optimization of the conditions for oxidation of the ester in order to obtain a quality ecological bitumen flux.