Study on Impact of Monomers Towards High Molecular Weight Bio-Based Poly(ethylene Furanoate) via Solid State Polymerization Technique

Polymers (Basel). 2024 Nov 26;16(23):3305. doi: 10.3390/polym16233305.

Abstract

In recent years, bio-based poly(ethylene furanoate) has gained the attention of packaging industries owing to its remarkable properties as a promising alternative to fossil-based polymers. It is necessary to synthesize high-molecular-weight polymers using effective and straightforward techniques for their commercialization. In this present work, poly(ethylene 2,5-furan dicarboxylate) (PEF) was produced with a high molecular weight of 0.43 dL/g using 2,5-furan dicarboxylic acid (FDCA) or its derivative Dimethyl-2,5-Furan dicarboxylate (DMFD), followed by solid-state polymerization (SSP) conducted at different temperatures and reaction times. The intrinsic viscosity ([η]), carboxyl end-group concentration (-COOH), and thermal properties of the produced polyesters were evaluated using differential scanning calorimetry (DSC). The results indicated that the SSP process improved the melting temperature and crystallinity of both the PEF samples as the reaction times and temperatures increased, as corroborated by DSC and X-ray diffraction (XRD) analyses. Additionally, both intrinsic viscosity and number-average molecular weight saw an increase with longer SSP durations and higher temperatures, while the concentration of carboxyl end groups decreased, aligning with expectations. The overall results indicate that PEF (DMFD) samples exhibited a significant increase in crystallization and molecular weight, attributed to their lower degree of crystallinity and their monomer's high purity.

Keywords: 2,5-furan dicarboxylic acid; Dimethyl 2,5-furan dicarboxylate; bio-based polymers; poly(ethylene 2,5-furan dicarboxylate); poly(ethylene furanoate); solid state polymerization; thermal properties.

Grants and funding

This research is funded by EU Horizon 2020 research and innovation program under the project ‘Advanced Research and Training Network in Food quality, safety, and security’—FoodTraNet—H2020-MSCA-ITN-2020′ (grant agreement no. 956265).