Study on the Preparation of FDCA and Its Esterification via Homogeneous Oxidation of MMF with Co/Mn/Br Catalysts
Ma Yu’ang1,2, Tu Zhu3, Ma Huixia3, Zhou Feng3, Qiao Kai3, Zhang Zhenyu1,2, Fu Jie1,2
1. Key Laboratory of Biomass Chemical Engineering of Ministry of Education, College of Chemical and Biological Engineering, Zhejiang University, Hangzhou 310058, China;
2. Zhejiang Key Laboratory of Green Biomanufacturing of Functional Sugar Alcohols, Institute of Zhejiang University-Quzhou, Quzhou 324000, China;
3. SINOPEC (Dalian) Research Institute of Petroleum and Petrochemicals Company Limited, Dalian 116041, China
Abstract： In this work, 2,5-furan dicarboxylic acid (FDCA) was prepared from 5-methoxymethylfurfural (MMF) using a Co/Mn/Br homogeneous oxidation system, followed by esterification to produce dimethyl 2,5-furandicarboxylate (DMFD). In the oxidation stage, the effects of catalyst composition, concentration, reaction temperature, oxygen pressure, reaction time and water content on the oxidation reaction were systematically investigated. Based on the evolution of intermediates and target products with reaction time, MMF was proposed to be gradually oxidized to FDCA through two possible parallel pathways. Under optimal conditions (140 ℃, 1 MPa O2, Co/Mn/Br molar ratio of 2∶1∶1.5, Co concentration of 6 200 mg/L), the combined yield of FDCA and 5-(methoxycarbonyl)furan-2-carboxylic acid (MFCA) exceeded 85%. In the esterification stage, FDCA standard was used as a model compound, and esterification was catalyzed by Amberlyst-15 (A-15) with anhydrous silica gel was introduced for in-situ water removal, resulting in a DMFD yield of 83.1%. Subsequent polymerization yielded polyethylene 2,5-furandicarboxylate (PEF). The number-average molecular weight of the resulting PEF was 60.4 kg/mol, with a glass transition temperature of 80.1 ℃ and a tensile strength of 98.87 MPa. These results indicate that the Co/Mn/Br homogeneous oxidation system can efficiently convert MMF into FDCA, and the subsequent esterification and polymerization processes further demonstrate the feasibility of producing PEF from MMF via an oxidation-esterification-polymerization route, providing an experimental basis for the development of bio-based FDCA monomers and PEF materials.
Ma Yu’ang,Tu Zhu,Ma Huixia et al. Study on the Preparation of FDCA and Its Esterification via Homogeneous Oxidation of MMF with Co/Mn/Br Catalysts[J]. Chemical Reaction Engineering and Technology, 2026, 42(4): 341-350.
