Setting the lab scale-up of homogeneously catalysed hydrogenation of 5-hydroxymethylfurfural to 2,5-bishydroxymethylfuran: production of an innovative building block for new polymer synthesis

This work reports on the study of the Shvo’s ruthenium-based catalyst activity in the homogeneous hydrogenation of the bio-based chemical 5-hydroxymethylfurfural (HMF) to 2,5-bishydroxymethylfuran (BHMF). The work aimed to scale-up the homogeneous system in a 300 mL autoclave using molecular hydrogen as the reducing agent, modifying the reaction conditions to reach high yields and high purity of the product, and recycling the Shvo’s complex as many times as possible to achieve a highly productive and competitive catalytic system. Additionally, the scaled-up system performance was optimized using both toluene and anisole as the solvent. This latter solvent is indeed greener and safer compared to toluene, and it would represent a more viable and less impactful alternative from the perspective of industrial scale-up. Thereafter, the BHMF produced through the ruthenium-mediated hydrogenation process was employed as a monomer for bio-based polymer synthesis and preparation of bio-based polymer precursors. Indeed, as a diol, BHMF could serve as a building block for the production of more sustainable plastics and resins, replacing hazardous petrochemical-derived starting materials like bisphenol A. BHMF was therefore reacted with di-methyl carbonate (DMC) and catechol carbonate (CC) to synthesize furanic polycarbonates. Moreover, the reactivity of BHMF with di-allyl carbonate (DAC) and allyl bromide (AllBr) was investigated to produce bis-allylated furanic compounds that may function as intermediates for the synthesis of BOF, a bio-based furanic precursor for epoxy resin production.