An Eco-Friendly Method to Get a Bio-Based Dicarboxylic Acid Monomer 2,5-Furandicarboxylic Acid and Its Application in the Synthesis of Poly(hexylene 2,5-furandicarboxylate) (PHF)

• Published in: Polymers Vol. 11; no. 2; p. 197
• Main Authors: Zhang, Junhua, Liang, Qidi, Xie, Wenxing, Peng, Lincai, He, Liang, He, Zhibin, Chowdhury, Susmita Paul, Christensen, Ryan, Ni, Yonghao
• Format: Journal Article
• Language: English
• Published: Switzerland MDPI AG 23.01.2019; MDPI
• Subjects: 2,5-furandicarboxylic acid; 5-hydroxymethylfurfural; Antioxidants; Benzene; Biomass; biomass-based polyester; copolyester; Dicarboxylic acids; Discoloration; Esterification; Ferric hydroxide; Fourier transforms; Mechanical properties; Molecular structure; Monomers; NMR; Nuclear magnetic resonance; Phenols; poly(hexylene 2,5-furandicarboxylate); Polyester resins; Potassium ferrate; Reagents; Synthesis; Thermodynamic properties; Thermogravimetry; Viscometers; Viscosity; Weight loss; United States > US; China; Germany; poly(hexylene 2,5-furandicarboxylate); biomass-based polyester; 2,5-furandicarboxylic acid; 5-hydroxymethylfurfural; copolyester
• ISSN: 2073-4360; 2073-4360
• DOI: 10.3390/POLYM11020197

Recently, we have developed an eco-friendly method for the preparation of a renewable dicarboxylic acid 2,5-furandicarboxylic acid (FDCA) from biomass-based 5-hydroxymethylfrufural (HMF). In the present work, we optimized our reported method, which used phosphate buffer and Fe(OH)₃ as the stabilizer to improve the stability of potassium ferrate, then got a purified FDCA (up to 99%) in high yield (91.7 wt %) under mild conditions (25 °C, 15 min, air atmosphere). Subsequently, the obtained FDCA, along with 1,6-hexanediol (HDO), which was also made from HMF, were used as monomers for the synthesis of poly(hexylene 2,5-furandicarboxylate) (PHF) via direct esterification, and triphenyl phosphite was used as the antioxidant to alleviate the discoloration problem during the esterification. The intrinsic viscosity, mechanical properties, molecular structure, thermal properties, and degradability of the PHFs were measured or characterized by Koehler viscometer, universal tensile tester, Nuclear Magnetic Resonance (NMR), Fourier-transform Infrared (FTIR), X-ray diffraction (XRD), Differential Scanning Calorimeter (DSC), Derivative Thermogravimetry (DTG), Scanning Electron Microscope (SEM), and weight loss method. The experimental evidence clearly showed that the furan-aromatic polyesters prepared from biomass-based HMF are viable alternatives to the petrochemical benzene-aromatic polyesters, they can serve as low-melting heat bondable fiber, high gas-barrier packaging material, as well as specialty material for engineering applications.