Acid-catalyzed etherification of glycerol with tert-butanol: reaction monitoring through a complete identification of the produced alkyl ethers

Abstract

Higher tert-Butyl glycerol ethers (tBGEs) are interesting glycerol derivatives that can be produced from tert-butyl alcohol (TBA) and glycerol using an acid catalyst. Glycerol tert-butylation is a complex reaction that leads to the formation of five tBGEs (two monoethers, two diethers, and one triether). In order to gain insight into the reaction progress, the present work reports on the monitoring of glycerol etherification with TBA and p-toluensulfonic acid (PTSA) as homogeneous catalysts. Two analytical techniques were used: gas chromatography (GC), which constitutes the benchmark method, and( 1)H nuclear magnetic resonance (H-1 NMR), whose use for this purpose has not been reported to date. A method for the quantitative analysis of tBGEs and glycerol based on H-1 NMR is presented that greatly reduced the analysis time and relative error compared with GC-based methods. The combined use of both techniques allowed for a complete quantitative and qualitative description of the glycerol tert-butylation progress. The set of experimental results collected showed the influence of the catalyst concentration and TBA/glycerol ratio on the etherification reaction and evidenced the intrinsic difficulties of this process to achieve high selectivities and yields to the triether.