Multicatalysis from renewable resources: a direct route to furan-based polyesters Lucie Guillaume, Adam Marshall, Nicolas Niessen, Pingping Ni, Régis M. Gauvin,
Christophe M. Thomas Université PSL, France
Due to environmental and availability concerns associated with the use of fossil feedstocks, the production of new types of materials using renewable resources is currently receiving a lot of attention. Furanic materials are one of the most promising classes of bio-based polymers, because their corresponding monomers are widely available in the market. As such, 2,5-bis(hydroxy- methyl)furan (BHMF) which is obtained by hydrogenation of 5- (hydroxymethyl)furfural (HMF), is becoming an interesting building block for the synthesis of high glass transition temperature polymers with good mechanical properties. [1],[2] However, HMF is generally contaminated by coloured oligomeric impurities called humins, and their purification from HMF remains challenging. To circumvent this contamination issue, we investigated the synthesis of BHMF and the corresponding (co)polymers from bio-based 2,5-furanedicarboxylic acid (FDCA), which is a stable monomer produced on industrial scale, and free of humins. [3] By a combination of two commercial catalysts, our multicatalytic one-pot procedure allowed the synthesis of two key furanic intermediates, not contaminated by humins. These systems allow the dimethyl 2,5-furanedicarboxylate (MeFDCA) formation starting from FDCA, and then its hydrogenation to BHMF, as well as the polycondensation of the newly quantitatively formed monomer with aliphatic diols, providing direct access to furan based-polyesters without needing to isolate or purify any intermediates. [4] References 1. Shuo C.,Wojcieszak R.,Dumeignil F., Marceau E., Roy S., How Catalysts and Experimental Conditions Determine the Selective Hydroconversion of Furfural and 5-Hydroxymethylfurfural, Chem. Rev ., 2018 , 118 , 11023–11117. 2. Jiang Y., Woortman A. J. J., Alberda van Ekenstein G. O. R., Petrović D. M, Loos K., Enzymatic synthesis of biobased polyesters using 2,5-bis(hydroxymethyl)furan as the building block, Biomacromolecules , 2014 , 15 , 2482–2493. 3. Metkar P. S., Ozer R., Rajagopalan B., Processes for pre- paring 2,5-furandicarboxylic acid and esters thereof, WO- 2017019441, 2017 . 4. Guillaume L., Marshall A., Niessen N., Ni P., Gauvin R. M., Thomas C. M., Multicatalysis from renewable resources: a direct route to uran-based polyesters, Green. Chem ., 2021 , 23 , 6231-6235.
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© The Author(s), 2022
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