One-pot green synthesis and characterization of novel furan-based oligoesters

Abstract

The synthesis of bio-based poly(5-hydroxymethyl-2-furancarboxylate-co-ricinoleate) was investigated either from ricinoleic acid and 5-hydroxymethyl-2-furancarboxylic acid or directly from castor oil by green biocatalytic pathways. The reactions were carried out using commercially available native and immobilized hydrolases. The reactions were performed either in the absence of solvent or in different organic solvents or ionic liquids at various molar ratios and temperatures up to 80 °C. The lipase from Pseudomonas stutzeri showed the highest catalytic efficiency at 50 °C in t-butanol. To increase the sustainability of the process, in the next step, an original “one-pot” system consisting of two consecutive reactions catalyzed by the same enzyme was developed. Ricinoleic acid, obtained by in-situ hydrolysis of castor oil, was used together with 5-hydroxymethyl-2-furancarboxylic acid as raw material for the oligoester synthesis at 100 mbar pressure in a solventless reaction system, yielding a product with average molecular weight of about 5800 gmol-1, in optimized conditions. The insertion of 5-hydroxymethyl-2-furancarboxylic acid units into the ricinoleic acid estolide backbone was demonstrated by MALDI-TOF MS and 2D NMR analysis. The thermal properties of the resulting products were evaluated by TG and DSC.