Methods in the synthesis and conversion of 2,5-Bis-(hydroxylmethyl)furan from bio-derived 5-hydroxymethylfurfural and its great potential in polymerization

Abstract

To meet increasing demands for alternatives to fossil-based chemicals, environment-friendly and renewable energy materials are of great importance. Biomass-derived 2,5-bis-(hydroxylmethyl)furan (BHMF) has the potential to partly substitute petroleum-based aromatic diols during polymerization. This paper summarizes recent research on the synthesis of BHMF by the reaction of hydrogen from biomass-based 5-hydroxymethylfurfural through different reduction routes, including the Cannizzaro reaction, catalytic hydrogenation, and catalytic transfer hydrogenation. Applications of BHMF as a direct material and intermediate in fabricating polyurethane, self-healing materials, resins, and more, which utilize ring-opening, double-bond addition, and oxidation reactions, are discussed briefly. Additionally, the challenges and opportunities in the formation and application of BHMF in the future are discussed.

Catalytic Transfer Hydrogenation and Acid Reactions of Furfural and 5-(Hydroxymethyl)furfural over Hf-TUD-1 Type Catalysts

“…−100 ppm and −91 ppm, in relation to siliceous TUD-1 (Figure 3a), suggesting that these signals may be related to Si sites influenced by proximal Hf atoms; e.g., ca. −91.9 ppm for siliceous TUD-1 compared with −91.2 ppm for Hf-TUD-1(50) and Hf-TUD-1(75), and 90.8 ppm for Hf-TUD-1 (25).…”

“…The degree of the decomposition of 2BuOH increased with decreasing x. Specifically, 2-sec-(butoxy)butane was formed in 0.02%, 0.12%, and 0.25% yield for Hf-TUD-1(75), Hf-TUD-1 (50), and Hf-TUD-1 (25), respectively. At the highest 2BMF yield reached for each catalyst, the ratio of moles of 2-sec-(butoxy)butane/initial moles of Fur was 0.01, 0.03, and 0.04 for x = 75, 50, and 25, respectively.…”

“…The median mesopore size distributions were in the range of ca. 6-10 nm for Hf-TUD-1 (25) and Hf-TUD-1(50), and of ca. 11-18 nm for Hf-TUD-1(75) (inset of Figure 2).…”

Homogeneous Catalyzed Valorization of Furanics: A Sustainable Bridge to Fuels and Chemicals

“…In fact, the selective hydrogenation of HMF into DHMF is very similar to the reduction of α,β-unsaturated aldehydes or ketones to the corresponding unsaturated alcohols [97]. This reductive process has been achieved by different hydrogenation methodologies, including electrocatalytic hydrogenation [98] or in the presence of heterogeneous catalysts at high temperatures and pressures [99].…”

“…Moreover, DHMF is an important starting molecule for the polymerization or etherification processes (biodiesel, polyester, and polyurethane foams) [98]. Other bulk chemicals are derived from FAL, such as FA, methyl-tetrahydrofuran (MTHF), THF, and maleic acid (MA) [26].…”