Synthesis and Properties Investigation of Thiophene-aromatic Polyesters: Potential Alternatives for the 2,5-Furandicarboxylic Acid-based Ones

Abstract

In order to explore new substitutes for 2,5-furandicarboxylic acid (FDCA) or poly(ethylene 2,5-furandicarboxylate) (PEF) and try to develop more ideal bio-based polyesters, several thiophene-aromatic polyesters (PETH, PPTH, PBTH, and PHTH) were synthesized from dimethyl thiophene-2,5-dicarboxylate (DMTD) and different diols, including ethylene glycol, 1,3-propanediol, 1,4-butanediol, and 1,6-hexanediol. The chemical structures of obtained polyesters were confirmed by nuclear magnetic resonance spectroscopy (1H-NMR and 13C-NMR). Determined by GPC measurement, their average molecular weight (Mw) varied from 5.22 × 104 g/mol to 7.94 × 104 g/mol with the molar-mass dispersity of 1.50–2.00. Based on the DSC and TGA results, the synthesized polyesters PETH, PPTH, and PBTH displayed comparable or even better thermal properties when compared with their FDCA-based analogues. From PETH to PHTH, their Tg varied from 64.6 °C to −1 ×C while T5% ranged from 409 °C to 380 °C in nitrogen atmosphere. PETH showed elongation at break as high as 378%, tensile strength of 67 MPa, and tensile modulus of 1800 MPa. Meanwhile, the CO2 and O2 barrier of PETH was 12.0 and 6.6 folds higher than those of PET, respectively, and similar to those of PEF. Considering the overall properties, the synthesized thiophene-aromatic polyesters, especially PETH, showed great potential to be used as an excellent bio-based packaging material in the future.

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Acknowledgments

This work was financially supported by the National Natural Science Foundation of China (No. 21975270), Zhejiang Provincial Natural Science Foundation of China (No. LR20E030001), Ningbo 2025 Key Scientific Research Programs (No. 2018B10015), National Key Research and Development Program of China (No. 2018YFD0400700), and Research Project of Ningbo Natural Science Foundation (No. 2019A610141).

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Correspondence to Xiao-Qing Liu.

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Synthesis and Properties Investigation of Thiophene-aromatic Polyesters: Potential Alternatives for the 2,5-Furandicarboxylic Acid-based Ones

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Wang, JG., Zhang, XQ., Shen, A. et al. Synthesis and Properties Investigation of Thiophene-aromatic Polyesters: Potential Alternatives for the 2,5-Furandicarboxylic Acid-based Ones. Chin J Polym Sci 38, 1082–1091 (2020). https://doi.org/10.1007/s10118-020-2438-2

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Keywords

  • 2,5-Thiophenedicarboxylic acid (TDCA)
  • 2,5-Furandicarboxylic acid (FDCA)
  • Bio-based polyesters
  • Barrier properties