Preparation of Glycerol Carbonate Esters by using Hybrid Nafion-Silica Catalyst

Glycerol carbonate esters (GCEs), which are valuable biomass-deriv. compds., have been prepd. through the direct esterification of glycerol carbonate and long org. acids with different chain lengths, in the absence of solvent, and with heterogeneous catalysts, including acidic-org. resins, zeolites, and hybrid org.-inorg. acids. The best results, in terms of activity and selectivity towards GCEs, were obtained using a Nafion-silica composite. A full reaction scheme has been established, and it has been demonstrated that an undesired competing reaction results in the generation of glycerol and esters derived from a secondary hydrolysis of the endocyclic ester group, which is attributed to water formed during the esterification reaction. The influence of temp., substrate ratio, catalyst-to-substrate ratio, and the use of solvent has been studied and, under optimized reaction conditions and with the adequate catalyst, it was possible to achieve 95 % selectivity for the desired product at 98 % conversion. It was demonstrated that the reaction rate decreased as the no. of carbon atoms in the linear alkyl chain of the carboxylic acid increased for both p-toluenesulfonic acid and Nafion-silica nanocomposite (Nafion SAC-13) catalysts. After fitting the exptl. data to a mechanistically based kinetic model, the reaction kinetic parameters for Nafion SAC-13 catalysis were detd. and compared for reactions involving different carboxylic acids. A kinetic study showed that the reduced reactivity of carboxylic acids with increasing chain lengths could be explained by inductive as well as steric effects.The authors wish to acknowledge the Spanish Science and Innovation Ministry (Consolider Ingenio 2010, CTQ-2011-27550 and MULTICAT CSD2009-00050 projects) and the Generalitat Valenciana (Prometeo program) for their financial support. S.M. thanks the Ministerio de Educacion for a FPI fellowship.Climent Olmedo, MJ.; Corma Canós, A.; Iborra Chornet, S.; Martínez Silvestre, S.; Velty ., A. (2013). Preparation of Glycerol Carbonate Esters by using Hybrid Nafion-Silica Catalyst. ChemSusChem. 6(7):1224-1234. doi:10.1002/cssc.201300146S1224123467BUDRONI, G., & CORMA, A. (2008). Gold and gold–platinum as active and selective catalyst for biomass conversion: Synthesis of γ-butyrolactone and one-pot synthesis of pyrrolidone. Journal of Catalysis, 257(2), 403-408. doi:10.1016/j.jcat.2008.05.031Climent, M. J., Corma, A., & Iborra, S. (2011). 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