Polyol Structure Influences Enzymatic Hydrolysis of Bio‐Based 2,5‐Furandicarboxylic Acid (FDCA) Polyesters

Abstract

Polyesters of 2,5-furandicarboxylic acid (FDCA) have gained attention as they can be regarded as the bio-based alternatives to the petroleum-based polyesters of terephthalic acid. However, only little is known about the biodegradation and enzymatic hydrolysis of FDCA-based polyesters. This work aims to investigate the influence of different polyols on enzymatic hydrolysis of FDCA-based polyesters. A series of polyesters containing various polyols are synthesized and analyzed regarding susceptibility to enzymatic hydrolysis by cutinase 1 from Thermobifida cellulosilytica (Thc_Cut1). FDCA-based polyesters' number average molecular weight (M ) ranged from 9360-35 800 g mol according to gel permeation chromatography (GPC) analysis. Differential scanning calorimetry (DSC) analyses show decreasing glass transition temperature (T ) with increasing diol chain length. Crystallinity of all polyesters is below 1% except for polyesters containing 1,6-hexanediol, 1,8-octanediol, and 1,12-dodecanediol for which calculated crystallinities are 27, 37, and 30%, respectively. Thc_Cut1 hydrolyzes all tested polyesters with preference for polyesters containing 1,5-pentanediol and 1,9-nonanediol (57.7 ± 7.5 and 52.8 ± 4.0% released FDCA). Enzyme activity increases when the linear diol 1,3-propanediol is replaced by the branched analog 1,2-propanediol or ethoxy units are introduced into the polyester chain. The results will contribute to expand the knowledge of microbial biodegradation of FDCA-based polyesters.

Co-Polymers based on Poly(1,4-butylene 2,5-furandicarboxylate) and Poly(propylene oxide) with Tuneable Thermal Properties: Synthesis and Characterization

“…Some examples of polyesters synthesized from FDCA are poly(ethylene 2,5-furandicarboxylate) (PEF) [3] and poly(1,4-butylene 2,5-furandicarboxylate) (PBF), among others, with similar properties to those of their TPA counterparts [4,5,6,7,8,9,10,11] or even enhanced properties such as for example barrier properties or degradability under enzymatic conditions [12,13]. Furthermore, several other diols besides linear ones have been explored to prepare FDCA-based homopolymers, namely branched diols such as 1,2-propanediol, 2,3-butanediol, 2-methyl-1,3-propanediol and 2,2-dimethyl-1,3-propanediol [14,15,16,17,18,19,20]. The ensuing materials presented even higher T g s than those of their corresponding homopolyesters synthesized with linear diols with the same number of carbon atoms.…”

Copolyesters developed from bio‐based 2,5‐furandicarboxylic acid: Synthesis, sequence distribution, mechanical, and barrier properties of poly(propylene‐co‐1,4‐cyclohexanedimethylene 2,5‐furandicarboxylate)s

“…In Figure , the thermal properties of TPA‐based (PET, PPT, and PBT) and FDCA‐based (PEF, PPF, PBF, PCF, PHF, POF, PDeF, and PDoF) polyesters are illustrated. It is easy to notice that when the same aliphatic diols were employed for polycondensation, the TPA‐based polyesters showed much higher T g and T m , when compared with their FDCA‐based counterparts.…”

“…Most of the studies have been focused on the FDCA‐based polyesters. Taking different diols, a large quantity of polyesters, such as poly(octylene 2,5‐furandicarboxylate) (POF), poly (ethylene 2,5‐furandicarboxylate) (PEF), poly(propylene 2,5‐furandicarboxylate) (PPF), poly(butylene 2,5‐furandicarboxylate) (PBF), poly(decylene‐2,5‐furanote) (PDeF), and poly(hexamethylene 2,5‐furandicarboxylate) (PHF) have been synthesized. Among them, PEF, PPF, and PBF demonstrate excellent barrier properties, good thermal stability, and mechanical properties .…”

Effects of Methyl Branching on the Properties and Performance of Furandioate-Adipate Copolyesters of Bio-Based Secondary Diols

“… 1 , 14 Literature data for 1,4-PBAFs and PHF are from higher M w materials than those reported in this study; as a result, they have higher T g s ( Table S8 ). 24 , 29 …”