Synthesis and Characterization of Poly(terephthalic acid-2,5-furandicarboxylic acid-1,8-octanediol) Copolyester

Abstract

Terephthalic acid, 2,5-furandicarboxylic acid and 1,8-octanediol were adopted as monomers and antimony trioxide as catalyst, and poly(terephthalic acid-2,5-furandicarboxylic acid-1,8-octanediol) copolyesters identified as PEOT-x, where x is the mole fraction of furandicarboxylic acid in the samples, were synthesized by direct esterification. The molecular structure of the copolyesters was characterized by FTIR and ¹H NMR spectroscopy. Gel permeation chromatography (GPC), differential scanning calorimetry (DSC), and thermogravimetric analysis (TGA) were used to characterize the molecular weight, molar mass dispersity, glass transition temperature, and thermal stability of the copolyesters, respectively. The mechanical properties of the samples were also investigated. The number-average molecular weight (M _n) of the samples varies from 9 700–18 800 g/mol, and molar mass dispersity (Đ = M _w/M _n) from 2.15–3.34. The initial decomposition temperature of the copolyesters is in the 332–356 °C range, with maximum decomposition rates at 390–410 °C, while the glass transition temperature (T _g) varies from 0–33 °C. Mechanical test shows that PEOT-10 has the highest tensile strength, while PEOT-90 has the largest tensile modulus and elongation at break. The experimental results show that these copolyesters can be synthesized with relatively high molecular weights, good thermal stability, and fair mechanical properties, which makes them excellent replacements for commercial polyesters, such as PET, and these properties can be tuned through the relative amounts of biomass monomer 2,5-furandicarboxylic acid used in the reactions.

Keywords

2,5-furandicarboxylic acid / terephthalic acid / melt polymerization / copolyesters

References

[1] Abdo D, Gleadalla A, Vadim VS. Failure Behaviour of Short-fibre-reinforced PBT Composites: Effect of Strain Rate[J]. Engineering Failure Analysis, 2019, 105: 466-476.

[2] Wang L, Zhou B, Huang J, et al. Silicone Chain Extender for Recycled Polyethylene-terephthalate with Higher Flexibility[J]. Journal of Wuhan University of Technology-Materials Science Edition, 2019, 34(5): 1 228-1 232.

[3] Geeti DK, Niranjan K. Environmentally Benign Bio-based Waterborne Polyesters: Synthesis, Thermal- and Bio-degradation Studies[J]. Progress in Organic Coatings, 2019, 127: 419-428.

[4] Zhang SL, Cheng ZZ, Zeng S, et al. Synthesis and Characterization of Renewable Polyesters based on Vanillic Acid[J]. Journal of Applied Polymer Science, 2020, 137(39), DOI: https://doi.org/10.1002/app.49189

[5] Papageorgiou G. Thinking Green: Sustainable Polymers from Renewable Resources[J]. Polymers, 2018, 10(9): 952

[6] Khodaei M, Amini K, Valanezhad A. Fabrication and Characterization of Poly Lactic Acid Scaffolds by Fused Deposition Modeling for Bone Tissue Engineering[J]. Journal of Wuhan University of Technology-Materials Science Edition, 2020, 35(1): 248-251.

[7] Wang J, Liu X, Jia Z, et al. Highly Crystalline Polyesters Synthesized from Furandicarboxylic Acid (FDCA): Potential Bio-based Engineering Plastic[J]. European Polymer Journal, 2018, 109: 379-390.

[8] Sajid M, Zhao X, Liu D. Production of 2,5-furandicarboxylic Acid (FDCA) from 5-hydroxymethyl Furfural (HMF): A Recent Progress Focusing on the Chemical-catalytic Routes[J]. Green Chemistry, 2018, 20: 5 427-5 453.

[9] Guidotti G, Soccio M, García-Gutiérrez MC, et al. Fully Biobased Superpolymers of 2,5-furandicarboxylic Acid with Different Functional Properties: From Rigid to Flexible, High Performant Packaging Materials[J]. ACS Sustainable Chemistry & Engineering, 2020, 8(25): 9 558-9 568.

[10] Drewitt JGN, Lincoln J. Improvements in Polymers[P]. BR Patent, 621971. 1946-11-12

[11] Hachihama Y, Shono T, Hyono K. Synthesis of Polyesters Containing Furan Ring[J]. Technol. Rep Osaka University, 1960, 63: 176-178.

[12] Gandini A, Silvestre AJD, Neto CP, et al. The Furan Counterpart of Poly(ethylene terephthalate): An Alternative Material based on Renewable Resources[J]. Journal of Polymer Science Part A, Polymer Chemistry, 2010, 47(1): 295-298.

[13] Gomes M, Gandini A, Silvestre AJD, et al. Synthesis and Characterization of Poly(2,5-furan dicarboxylate)s based on a Variety of Diols[J]. Journal of Polymer Science Part A Polymer Chemistry, 2011, 49(17): 3 759-3 768.

[14] Nguyen HTH, Qi P, Rostagno M, et al. The Quest for High Glass Transition Temperature Bioplastics[J]. Journal of Materials Chemistry A, 2018, 6(20): 9 298-9 331.

[15] Soccio M, Costa M, Lotti N, et al. Novel Fully Biobased Poly (butylene 2,5-furanoate/diglycolate) Copolymers Containing Ether Linkages: Structure-property Relationships[J]. European Polymer Journal, 2016, 81: 397-412.

[16] Cai X, Yang X, Zhang H, et al. Aliphatic-aromatic Poly (carbonate-co-ester)s Containing Biobased Furan Monomer: Synthesis and Thermo-mechanical Properties[J]. Polymer, 2018, 134: 63-70.