Transesterification of Isosorbide with Dimethyl Carbonate Catalyzed by Task-Specific Ionic Liquids.

Abstract

Green synthesis of high-molecular-weight isosorbide-based polycarbonate (PIC) with excellent properties is a tremendous challenge and is profoundly influenced by the precursor. Herein, an ecofriendly catalyst was employed to obtain the more reactive PIC precursor dicarboxymethyl isosorbide (DC) with 99.0 % selectivity through the transesterification reaction of isosorbide with dimethyl carbonate. This is the indispensable stage of a one-pot green synthesis of PIC, playing a critical role in giving an insight into the polymerization mechanism of polymer synthesis through the melt transesterification reaction. To this end, a series of 4-substituted phenolate ionic liquids (ILs) were developed as a new type of high-efficiency catalyst for this reaction. These homogeneous ILs exhibited outstanding catalytic performances. The DC selectivity increased gradually with decreasing IL basicity; among the ILs studied, trihexyl(tetradecyl)phosphonium 4-iodophenolate ([P66614 ][4-I-Phen]) showed the highest catalytic activity. Additionally, according to the experimental results and DFT calculations, a plausible nucleophilic activation mechanism was proposed, which confirmed that the reaction is activated through the formation of H-bonds and electrostatic interactions with the IL catalyst. This strategy of tunable basicity and structure of anions in ILs affords an opportunity to develop other ILs for the transesterification reaction, thereby conveniently providing a variety of polymers through a green synthetic pathway.