Macromolecular Chemistry & New Polymeric Materials, Zernike Institute for Advanced Materials, University of Groningen, Nijenborgh 4, Groningen 9747 AG, The Netherlands.
CICECO─Aveiro Institute of Materials, Department of Chemistry, University of Aveiro, Aveiro 3810-193, Portugal.
Biomacromolecules. 2024 May 13;25(5):2792-2802. doi: 10.1021/acs.biomac.3c01433. Epub 2024 Apr 11.
Polyesters from furandicarboxylic acid derivatives, i.e., dimethyl 2,5-furandicarboxylate (2,5-DMFDCA) and 2,4-DMFDCA, show interesting properties among bio-based polymers. Another potential heteroaromatic monomer, 3,4-bis(hydroxymethyl)furan (3,4-BHMF), is often overlooked but holds promise for biopolymer synthesis. Cleaning and greening synthetic procedures, i.e., enzymatic polymerization, offer sustainable pathways. This study explores the lipase B (CALB)-catalyzed copolymerization of 3,4-BHMF with furan dicarboxylate isomers and aliphatic diols. The furanic copolyesters (co-FPEs) with higher polymerization degrees are obtained using 2,4-isomer, indicating CALB's preference. Material analysis revealed semicrystalline properties in all synthesized 2,5-FDCA-based co-FPEs, with multiple melting temperatures () from 53 to 124 °C and a glass-transition temperature () of 9-10 °C. 2,4-FDCA-based co-FPEs showed multiple from 43 to 61 °C and of -14 to 12 °C; one of them was amorphous. In addition, all co-FPEs showed a two-step decomposition profile, indicating aliphatic and semiaromatic segments in the polymer chains.
聚呋喃二酸衍生物聚酯，如 2,5-二甲基呋喃二甲酸二甲酯 (2,5-DMFDCA) 和 2,4-DMFDCA，在生物基聚合物中表现出有趣的性质。另一种潜在的杂芳族单体，3,4-双羟甲基呋喃 (3,4-BHMF)，通常被忽视，但在生物聚合物合成中具有很大的潜力。清洁和绿色的合成工艺，如酶聚合，提供了可持续的途径。本研究探索了脂肪族二醇与 3,4-BHMF 与呋喃二羧酸异构体的脂肪酶 B (CALB) 催化共聚反应。使用 2,4-异构体获得了具有较高聚合度的呋喃共聚酯（co-FPE），表明 CALB 的偏好。材料分析表明，所有合成的基于 2,5-FDCA 的 co-FPE 均具有半结晶性质，多个熔融温度（）从 53 到 124°C，玻璃化转变温度（）为 9-10°C。基于 2,4-FDCA 的 co-FPE 显示出多个从 43 到 61°C 和-14 到 12°C 的；其中一种是无定形的。此外，所有 co-FPE 都显示出两步分解曲线，表明聚合物链中存在脂肪族和半芳族段。
