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 degrees C and a glass-transition temperature (T-g) of 9-10 degrees C. 2,4-FDCA-based co-FPEs showed multiple T-m from 43 to 61 degrees C and T-g of -14 to 12 degrees 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.
keywords
6-MEMBERED CYCLIC CARBONATES; LIPASE-MEDIATED SYNTHESIS; ALIPHATIC POLYESTERS; BISPHENOL-A; END-GROUPS; ACID; POLYMERIZATION; TRIMETHYLOLPROPANE; POLYCONDENSATION; POLYMERS
subject category
Biochemistry & Molecular Biology; Chemistry; Polymer Science
authors
Silvianti, F; Maniar, D; Agostinho, B; de Leeuw, TC; Woortman, AJJ; van Dijken, J; Thiyagarajan, S; Sousa, AF; Loos, K
our authors
Andreia Fernandes de Sousa
Principal Researcher
Beatriz Agostinho
PhD StudentProjects
European network of FURan based chemicals and materials FOR a Sustainable development (FUR4Sustain)
CICECO - Aveiro Institute of Materials (UIDB/50011/2020)
CICECO - Aveiro Institute of Materials (UIDP/50011/2020)
Associated Laboratory CICECO-Aveiro Institute of Materials (LA/P/0006/2020)
acknowledgements
This publication was supported by COST Action FUR4Sustain-European network of FURan-based chemicals and materials FOR a Sustainable development, CA18220, supported by COST (European Cooperation in Science and Technology). This work was developed within the scope of the CICECO-Aveiro Institute of Materials UIDB/50011/2020 (DOI 10.54499/UIDB/50011/2020), UIDP/50011/2020 (DOI 10.54499/UIDP/50011/2020) & LA/P/0006/2020 (DOI 10.54499/LA/P/0006/2020), financed by national funds through the FCT/MCTES (PIDDAC). The FCT is also acknowledged for the research contract under Scientific Employment Stimulus to A.F.S. (CEECIND/02322/2020, DOI 10.54499/2020.02322.CEECIND/CP1589/CT0008) and for a doctorate grant to B.A. (2020.04495.BD). F.S. gratefully acknowledges the financial support from the Industrial Human Resource Development Agency of the Ministry of Industry of the Republic of Indonesia (BPSDMI, Kemenperin).