Evaluation of Esterification of Oleic Acid and Glycerol in the Presence of Organotin(IV) Compounds

• Published in: European journal of lipid science and technology Vol. 121; no. 6
• Main Authors: da Silva, Mônica A., dos Santos, Anderson S. S., Neto, Antonio J. S., Giertyas, Cristian J., Bortoluzzi, Janaína H., Meneghetti, Mario R., Plentz Meneghetti, Simoni M.
• Format: Journal Article
• Language: English
• Published: Weinheim Wiley Subscription Services, Inc 01.06.2019
• Subjects: Butyltin; Catalysis; Catalysts; Chlorides; Conversion; Dibutyltin; Dichlorides; Esterification; Exchanging; Glycerol; Ligands; mechanisms; Oleic acid; Organotin; tin catalysts
• ISSN: 1438-7697; 1438-9312
• DOI: 10.1002/ejlt.201900103

Esterification of oleic acid (OA) and glycerol (GLY) is studied in the absence and in the presence of the organotin(IV) catalysts (CAT) dibutyltin dichloride (Bu2SnCl2), butyltin trichloride (BuSnCl3), dibutyltin dilaurate (Bu2SnLau2), butyl stannoic acid (BuSnO(OH)), and di‐n‐butyl‐oxo‐stannane (Bu2SnO). The reactivity order observed at 180 °C using a OA/GLY/CAT molar ratio of 1/1/0.01 was BuSnCl3 > Bu2SnLau2 > Bu2SnCl2 > Bu2SnO > BuSnO(OH), and a kap of −0.6237 h−1 is obtained for BuSnCl3. The estimated activation energy for the conversion reaction of OA at the above molar ratio using BuSnCl3 is 60.9 kJ mol−1, whereas it is 71.3 kJ mol−1 for the reaction performed without the catalyst. Moreover, the most active catalytic systems are those that act as typical and pure Lewis acids, and the least active systems are those that follow the ligand exchange mechanism, suggesting that GLY and AO are involved in the ligand exchange process and may form less reactive catalytic species. Practical Applications: In order to expand the glycerol utilization, the aim of the present work is to systematically investigate the behavior of organotin(IV) compounds bearing different substituents on the metal center (oxo, carboxyl, chloro, and hydroxy groups) in the esterification of OA and GLY without a solvent for obtaining MAGs, DAGs and TAGs. Best results of esterification of AO + GLY are attained at 180 °C using BuSnCl3 as a catalyst, and the kap = −0.6237 h−1 for OA conversion is obtained. Best results of esterification of AO + GLY are attained at 180 °C using BuSnCl3 as a catalyst, and the kap = −0.6237 h−1 for OA conversion is obtained.