One-Pot FDCA Diester Synthesis from Mucic Acid and Their Solvent-Free Regioselective Polytransesterification for Production of Glycerol-Based Furanic Polyesters

Abstract

A one pot-two step procedure for the synthesis of diethyl furan-2,5-dicarboxylate (DEFDC) starting from mucic acid without isolation of the intermediate furan dicarboxylic acid (FDCA) was studied. Then, the production of three different kinds of furan-based polyesters— polyethylene-2,5-furan dicarboxylate (PEF), polyhydropropyl-2,5-furan dicarboxylate(PHPF) and polydiglycerol-2,5-furandicarboxylate (PDGF)—was realized through a Co(Ac)2·4H2O catalyzed polytransesterification performed at 160 °C between DEFDC and a defined diol furan-based prepolymer or pure diglycerol. In parallel to polymerization process, an unattended regioselective 1-OH acylation of glycerol by direct microwave-heated FDCA diester transesterification led to the formation of a symmetric prepolymer ready for further polymerization and clearly identified by 2D NMR sequences. Furthermore, the synthesis of a more soluble and hydrophilic diglycerol-based furanic polyester was also achieved. The resulting biobased polymers were characterized by NMR, FT-IR spectroscopy, DSC, TGA and XRD. The morphologies of the resulted polymers were observed by FE-SEM and the purity of the material by EDX.

Innovative Protocols in the Catalytic Oxidation of 5‐Hydroxymethylfurfural

“…Alternatively, MW-assisted heating method has proven to be highly efficient and selective for the biomass conversion. [23][24][25][26][27] However, despite the advantages of MW heating, HMF oxidation reaction have been rarely reported with MW due to other severe parameters such as high-pressure requirement, appropriate pH environment, and stable oxygen source; usage of MW in HMF oxidation or biomass valorization remained an interesting and challenging proposition for the research community.…”

“…[20] MW-assisted chemistry has been reported as an efficient alternative activation method to conventional heating that features homogeneous, rapid heating and energy savings; MW can penetrate the materials and deposit energy via dipolar polarization and ionic conduction, [21,22] and MW-based processes have been widely employed in the valorization of biomass-based compounds. [23][24][25][26][27] Continuous-flow regimes have realized the transformation from batch to industrial production scale where the short residence time in flow chemistry avoids the long contact between reactant and products thus increasing product selectivity. Besides, the heat transfer is fast owning to the high surface/ volume ratio in flow regime.…”

Influence of Rigid Segment Type on Copoly(ether-ester) Properties

“…Furandicarboxylic acid (FDCA) is one of the most important renewable materials, and it is recognized as one of the most important building-block chemicals by the US Department of energy [ 4 , 5 ]. Thanks to its chemical structure, FDCA is considered an alternative to terephthalic acid (TPA) [ 4 , 5 , 6 , 7 , 8 ]. Therefore, FDCA or its derivatives like dimethyl 2,5-furanodicarboxylate (DMFDC) find use in the synthesis of polyesters [ 9 ].…”

Application of sugar-containing biomass: one-step synthesis of 2-furylglyoxylic acid and its derivatives from a vitamin C precursor

“…Nevertheless, poor economic performance, resulting from the high cost of raw materials, and low yields represent the major limitations associated with two previously reported sugar acid dehydration methods, despite the minimal addition of oxygen. 30,31…”