Dimethyl 2,5-furandicarboxylate synthesis from 2,5-furanodicarboxylic acid and dimethyl carbonate in presence of MgO-Al2O3 and tetrabutylammonium bromide

2,5-furandicarboxylic acid (FDCA) and dimethyl 2,5-furandicarboxylate (DMFDCA) are attracting increasing attention as important biomass-based chemical feedstocks. Considering the physicochemical properties of FDCA with high polarity, poor solubility and easy decarboxylation, the synthesis of DMFDCA from FDCA is especially necessary. However, how to synthesize DMFDCA in case of avoiding a series of side reactions such as furan ring opening and double bond addition is a huge challenge. Herein, we used FDCA and dimethyl carbonate (DMC) to synthesize DMFDCA in presence of MgO-Al2O3 and tetrabutylammonium bromide (TBAB), and the optimized yield and selectivity of DMFDCA came up to 76.38% and 80.19%, respectively. In addition, the used catalysts were characterized by SEM, XRD, BET, XPS and CO2-TPD analysis, and the structure, composition, morphology and basic site distribution of catalyst were well studied, and the relationship between catalyst structure and catalytic performance in the esterification of FDCA into DMFDCA thorough organic acid exchange reaction method was also analyzed. This work provides a promising solution for the preparation of furan-based polyester monomers.

Automated summary

FDCA and DMFDCA are important biomass-based chemical feedstocks, with the synthesis of DMFDCA from FDCA presenting a significant challenge in avoiding side reactions. Through the use of specific catalysts, DMFDCA was successfully synthesized with an optimized yield of 76.38% and selectivity of 80.19%, providing a promising solution for the preparation of furan-based polyester monomers.