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

Fitrilia Silvianti; Dina Maniar; Beatriz Agostinho; Tijn C de Leeuw; Albert Jan Jacob Woortman; Jur van Dijken; Shanmugam Thiyagarajan; Andreia F Sousa; Katja Loos

doi:10.1021/acs.biomac.3c01433

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

Biomacromolecules. 2024 Apr 11. doi: 10.1021/acs.biomac.3c01433. Online ahead of print.

Authors

Fitrilia Silvianti¹, Dina Maniar¹, Beatriz Agostinho², Tijn C de Leeuw³, Albert Jan Jacob Woortman¹, Jur van Dijken¹, Shanmugam Thiyagarajan⁴, Andreia F Sousa^{2

5}, Katja Loos¹

Affiliations

¹ Macromolecular Chemistry & New Polymeric Materials, Zernike Institute for Advanced Materials, University of Groningen, Nijenborgh 4, Groningen 9747 AG, The Netherlands.
² CICECO─Aveiro Institute of Materials, Department of Chemistry, University of Aveiro, Aveiro 3810-193, Portugal.
³ CarbExplore Research B.V., Groningen 9747 AA, The Netherlands.
⁴ Wageningen Food & Biobased Research, Wageningen University and Research, P.O. Box 17, Wageningen 6700 AA, The Netherlands.
⁵ Centre for Mechanical Engineering, Materials and Processes, Department of Chemical Engineering, University of Coimbra Rua Sílvio Lima─Polo II, Coimbra 3030-790, Portugal.

PMID: 38602263
DOI: 10.1021/acs.biomac.3c01433

Abstract

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.