Synthesis by Melt-Polymerization of a Novel Series of Bio-Based and Biodegradable Thiophene-Containing Copolyesters with Promising Gas Barrier and High Thermomechanical Properties

Lesly Dasilva Wandji Djouonkep; Christian Tatchum Tamo; Belle Elda Simo; Nasiru Issah; Marc Nivic Tchouagtie; Naomie Beolle Songwe Selabi; Ingo Doench; Arnaud Kamdem Tamo; Binqiang Xie; Anayancy Osorio-Madrazo

doi:10.3390/molecules28041825

Synthesis by Melt-Polymerization of a Novel Series of Bio-Based and Biodegradable Thiophene-Containing Copolyesters with Promising Gas Barrier and High Thermomechanical Properties

Molecules. 2023 Feb 15;28(4):1825. doi: 10.3390/molecules28041825.

Authors

Lesly Dasilva Wandji Djouonkep^{1

2

3}, Christian Tatchum Tamo⁴, Belle Elda Simo⁵, Nasiru Issah⁶, Marc Nivic Tchouagtie⁷, Naomie Beolle Songwe Selabi⁸, Ingo Doench^{9

10

11}, Arnaud Kamdem Tamo^{9

10

11}, Binqiang Xie^{1

2

3}, Anayancy Osorio-Madrazo^{9

10

11}

Affiliations

¹ Department of Petroleum Engineering, Applied Chemistry in Oil and Gas Fields, Yangtze University, Wuhan 430100, China.
² Lost Circulation Control Laboratory, National Engineering Laboratory for Petroleum Drilling Engineering, Yangtze University, Wuhan 430100, China.
³ Key Laboratory of Drilling and Production Engineering for Oil and Gas, Wuhan 430100, China.
⁴ National Advanced School of Engineering, University of Maroua, Maroua P.O. Box 46, Cameroon.
⁵ Department of Earth Sciences, University of Dschang, Dschang P.O. Box 96, Cameroon.
⁶ Department of Biochemistry, Kwame Nkrumah University, Kabwe P.O. Box 80404, Ghana.
⁷ Department of Geography, University of Douala, Douala P.O. Box 2701, Cameroon.
⁸ Institute of Advanced Materials and Nanotechnology, Wuhan University of Science and Technology, Wuhan 430081, China.
⁹ Laboratory for Bioinspired Materials, Institute of Microsystems Engineering-IMTEK, University of Freiburg, 79110 Freiburg, Germany.
¹⁰ Freiburg Center for Interactive Materials and Bioinspired Technologies-FIT, University of Freiburg, 79110 Freiburg, Germany.
¹¹ Freiburg Materials Research Center-FMF, University of Freiburg, 79104 Freiburg, Germany.

Abstract

Volatile global oil prices, owing to the scarcity of fossil resources, have impacted the cost of producing petrochemicals. Therefore, there is a need to seek novel, renewable chemicals from biomass feedstocks that have comparable properties to petrochemicals. In this study, synthesis, thermal and mechanical properties, and degradability studies of a novel series of sustainable thiophene-based copolyesters like poly(hexylene 2,5-thiophenedicarboxylate-co-bis(2-hydroxyethoxybenzene) (PTB_xH_y) were conducted via a controlled melt polymerization method. Fourier-transform infrared (FTIR) and nuclear magnetic resonance (¹H NMR) spectroscopy techniques elucidated the degree of randomness and structural properties of copolyesters. Meanwhile, gel permeation chromatography (GPC) analysis showed a high average molecular weight in the range of 67.4-78.7 × 10³ g/mol. The glass transition temperature (T_g) was between 69.4 and 105.5 °C, and the melting point between 173.7 and 194.2 °C. The synthesized polymers outperformed poly(ethylene 2,5-thiophenedicarboxylate) (PETF) and behaved similarly to polyethylene terephthalate. The copolyesters exhibited a high tensile strength of 46.4-70.5 MPa and a toughness of more than 600%, superior to their corresponding homopolyesters. The copolyesters, which ranged from 1,4-bis(2-hydroxyethyl)benzene thiophenedicarboxylate (TBB)-enriched to hexylene thiophenedicarboxylate (THH)-enriched, offered significant control over crystallinity, thermal and mechanical properties. Enzymatic hydrolysis of synthetized polymers using porcine pancreatic lipase (PP-L) over a short period resulted in significant weight losses of 9.6, 11.4, 30.2, and 35 wt%, as observed by scanning electron microscopy (SEM), with perforations visible on all surfaces of the films. Thus, thiophene-based polyesters with cyclic aromatic structures similar to terephthalic acid (TPA) show great promise as PET mimics. At the same time, PP-L appears to be a promising biocatalyst for the degradation of bioplastic waste and its recycling via re-synthesis processes.

Keywords: 2,5-thiophenedicarboxylate; aliphatic diols; biodegradation; bis(hydroxyalkyl)benzene; mechanical properties; thiophene-based polyesters.

MeSH terms

Animals
Hydrolysis
Lipase* / metabolism
Polyesters / chemistry
Polymerization
Polymers*
Swine

Substances

Polymers
Lipase
Polyesters

Grants and funding

OS 497/6-1/Deutsche Forschungsgemeinschaft