Unraveling The Impact of Isomerism on Enzymatic Polymerization of Furanic Polyesters

abstract

As awareness of the environmental impact of fossil-based polymers grows, the demand for biobased alternatives rises. In this context, combining eco-friendly synthesis techniques with renewable resources is important to produce polymers efficiently and sustainably. Furandicarboxylic acid (FDCA) is one of the key building blocks for producing biobased polymers. However, most studies predominantly focus on 2,5-FDCA, while FDCA encompasses other noteworthy isomers, namely, 2,4- and 3,4-FDCA. The polymers derived from these two isomers have recently gained attention due to their promising properties. In this study, an environmentally friendly approach for producing biobased polyesters from 2,5-, 2,4-, and 3,4-FDCA dimethyl ester isomers is proposed. The synthesis is conducted under greener conditions, utilizing Candida antarctica lipase B (CALB) enzyme as a biocatalyst. The performance of the enzyme is assessed, revealing CALB preference for polymerizing 2,5-FDCA over 2,4- and 3,4-FDCA dimethyl ester, which is elucidated by docking analysis. Moreover, CALB shows varying rates of cyclic oligomer formation for each isomer, favoring 2,5-FDCA cyclization. The structure-property relationship, encompassing the variation in isomeric structure, is evaluated through structural characterization, thermal analysis, and surface properties. This study primarily emphasized enzymatic polymerization and highlighted its versatility in accommodating different monomer isomeric substitutions. As the demand for eco-friendly polymers grows, this study proposes a green synthesis approach using Candida antarctica lipase B enzyme. Evaluating isomeric variations in FDCA, the research unveils CALB's preference for certain isomers and assesses cyclization rates during polymerization. Structural, thermal, and surface analyses demonstrate the versatility of enzymatic polymerization, emphasizing its potential for accommodating diverse monomer isomers. image

keywords

UNSATURATED ALIPHATIC POLYESTERS; LIPASE-CATALYZED SYNTHESIS; BIOBASED POLYESTERS; MOLECULAR-DYNAMICS; THERMAL-PROPERTIES; PI-STACKING; POLYMERS; CONFORMATION; POLYAMIDES; DIOLS

subject category

Science & Technology - Other Topics; Materials Science

authors

Silvianti, F; Maniar, D; Agostinho, B; de Leeuw, TC; Pelras, T; Dijkstra, L; Woortman, AJJ; van Dijken, J; Thiyagarajan, S; Sousa, AF; Loos, K

Groups

G4 - Renewable Materials and Circular Economy

Projects

European network of FURan based chemicals and materials FOR a Sustainable development (FUR4Sustain)

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/50 011/2020 & UIDP/50 011/2020) & LA/P/0006/2020, financed by national funds through the FCT-Fundacao para a Ciencia e a Tecnologia/MEC (PIDDAC). This research was also sponsored by FEDER funds through the program COMPETE-Programa Operacional Factores de Competitividade and by national funds through the FCT under the project UID/EMS/00285/2020. The FCT was also acknowledged for the research contract under Scientific Employment Stimulus to A.F.S. (CEECIND/02322/2020) 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).