Direct Catalytic Route to Biomass-Derived 2,5-Furandicarboxylic Acid and Its Use as Monomer in a Multicomponent Polymerization

Oliver R Schade; Patrick-Kurt Dannecker; Kai F Kalz; David Steinbach; Michael A R Meier; Jan-Dierk Grunwaldt

doi:10.1021/acsomega.9b02373

Direct Catalytic Route to Biomass-Derived 2,5-Furandicarboxylic Acid and Its Use as Monomer in a Multicomponent Polymerization

ACS Omega. 2019 Oct 1;4(16):16972-16979. doi: 10.1021/acsomega.9b02373. eCollection 2019 Oct 15.

Authors

Oliver R Schade^{1

2}, Patrick-Kurt Dannecker³, Kai F Kalz^{1

2}, David Steinbach^{2

4}, Michael A R Meier³, Jan-Dierk Grunwaldt^{1

2}

Affiliations

¹ Institute for Chemical Technology and Polymer Chemistry (ITCP), Karlsruhe Institute of Technology (KIT), Engesserstr. 20, 76131 Karlsruhe, Germany.
² Institute of Catalysis Research and Technology (IKFT), KIT, Hermann-von-Helmholtz-Platz 1, 76344 Eggenstein-Leopoldshafen, Germany.
³ Institute for Organic Chemistry (IOC), KIT, Straße am Forum 7, 76131 Karlsruhe, Germany.
⁴ Institute of Agricultural Engineering, Conversion Technologies of Biobased Resources, University of Hohenheim, Garbenstraße 9, 70599 Stuttgart, Germany.

Abstract

Efficient synthesis of valuable platform chemicals from renewable feedstock is a challenging, yet essential strategy for developing technologies that are both economical and sustainable. In the present study, we investigated the synthesis of 2,5-furandicarboxylic acid (FDCA) in a two-step catalytic process starting from sucrose as largely available biomass feedstock. In the first step, 5-(hydroxymethyl)furfural (HMF) was synthesized by hydrolysis and dehydration of sucrose using sulfuric acid in a continuous reactor in 34% yield. In a second step, the resulting reaction solution was directly oxidized to FDCA without further purification over a Au/ZrO₂ catalyst with 84% yield (87% selectivity, batch process), corresponding to 29% overall yield with respect to sucrose. This two-step process could afford the production of pure FDCA after the respective extraction/crystallization despite the impure intermediate HMF solution. To demonstrate the direct application of the biomass-derived FDCA as monomer, the isolated product was used for Ugi-multicomponent polymerizations, establishing a new application possibility for FDCA. In the future, this efficient two-step process strategy toward FDCA should be extended to further renewable feedstock.