Enzymatic Synthesis of Copolyesters with the Heteroaromatic Diol 3,4-Bis(hydroxymethyl)furan and Isomeric Dimethyl Furandicarboxylate Substitutions

• Published in: Biomacromolecules 2024-05, Vol.25 (5), p.2792-2802
• Main Authors: Silvianti, Fitrilia, Maniar, Dina, Agostinho, Beatriz, de Leeuw, Tijn C., Woortman, Albert Jan Jacob, van Dijken, Jur, Thiyagarajan, Shanmugam, Sousa, Andreia F., Loos, Katja
• Format: Article
• Language: English
• Subjects: Basidiomycota; Dicarboxylic Acids - chemistry; Fungal Proteins - chemistry; Furans - chemistry; Isomerism; Lipase - chemistry; Lipase - metabolism; Polyesters - chemical synthesis; Polyesters - chemistry; Polymerization
• ISSN: 1525-7797; 1526-4602; 1526-4602
• DOI: 10.1021/acs.biomac.3c01433

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 Candida antarctica 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 (T m) from 53 to 124 °C and a glass-transition temperature (T g) of 9–10 °C. 2,4-FDCA-based co-FPEs showed multiple T m from 43 to 61 °C and T g 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.