IDENTIFICATION AND QUANTITATIVE DETERMINATION OF ESTERS OF CITRIC ACID

Abstract

The necessity and possibility of creating a domestic technology for the production of citric acid esters - trialkyl citrates - effective and environmentally friendly plasticizing compositions based on renewable raw materials are substantiated. Trialkylcitrates a purity of 98-99% are obtained by azeotropic esterification of citric acid with aliphatic alcohols C4-C5 under conditions of homogeneous acid catalysis. Using the synthesis of triamyl citrate as an example, the esterification of a polybasic hydroxy acid has been considered. It was established that during the synthesis a complex mixture is formed consisting of unreacted citric acid, incomplete mono-, diesters and triamyl citrate. The influence of synthesis conditions (temperature, reagent ratio, catalyst amount and reaction time) on the composition of the reaction mass is shown. A method of gas chromatographic analysis of citric acid esters has been developed. Taking into account the structural features of citric acid and its partial esters containing polar carboxyl groups, the reaction mass was pre-methylated with synthesized diazomethane. The resulting mixture consists of six esters of citric acid: trimethylcitrate; 2-hydroxy-1,3-dicarboxymethyl-2-carboxyamylpropane; 2-hydroxy-1,2-dicarboxymethyl-3-carboxyamil propane; 2-hydroxy-1-carboxymethyl-2,3-dicarboxysamyl propane; 2-hydroxy-2-carboxymethyl-1,3-dicarboxyamyl propane; triamylcitrate. The analysis was performed on a chromatographic complex "Crystal-2000M" on a capillary column with a grafted non-polar phase OV-101, length 100 m. The analysis time ranged from 22 to 49.5 min. Empirical equations were obtained using the internal standard method (the standard is dicyclohexyl adipate) to determine the calibration coefficients of the starting (trimethyl citrate т citric acid) and final (triamyl citrate) products in a wide concentration range. The results of identification of structures of six esters of citric acid for which there is no information in existing databases are presented. The study was carried out by method of chromato-mass spectrometry on the instrument SHIMADZU GCMS – QP2010 with ionization by electron impact at ionization energy of 130 eV. The analysis of the obtained spectra made it possible to determine the most probable ways of fragmentation of organic molecules and the intensity of the peaks of the ions formed.