Modification of Poly(ethylene 2,5-furandicarboxylate) with Biobased 1,5-Pentanediol: Significantly Toughened Copolyesters Retaining High Tensile Strength and O2 Barrier Property

Abstract

Poly(ethylene 2,5-furandicarboxylate) (PEF) is a biobased polyester characterized by high gas barrier properties as well as high tensile modulus and strength, but poor toughness. Toughening PEF without sacrificing its modulus, strength and gas barrier performance is a great challenge for PEF modification. In this study, high molecular weight random poly(ethylene- co-1,5-pentylene 2,5-furandicarboxylate)s (PEPeFs) were synthesized via melt copolycondensation of 2,5-furandicarboxylic acid (FDCA), ethylene glycol (EG) and 1,5-pentanediol (PeDO), a cheap, biobased and commercially available odd-carbon comonomer. The synthesized PEPeFs were characterized and assessed with intrinsic viscosity, ATR-FTIR, ¹H NMR, DSC, TGA and tensile, impact and O₂ permeation test. Mayo-Lewis equation with "reactivity ratio" of 3.78 for PeDO and 0.75 for EG could be used as an empirical equation to correlate the copolyester composition (ϕ_PeF) with monomer composition. PEPeFs proved nearly amorphous copolyesters having excellent thermal stability. Brittle-ductile transition was achieved at ϕ_PeF as low as 9 mol %. Increasing ϕ_PeF led to increase in elongation at break and notch impact strength and decrease in T_g, O₂ barrier performance and tensile modulus and strength. However, in comparison with PEF, PEF-rich PEPeFs (ϕ_PeF 9-47%) not only showed greatly improved elongation at break (29-265% vs 4%) and enhanced impact strength (2.2-3.9 kJ/m²) but also retained very high Young's modulus (2.8-3.3 vs 3.3 GPa) and yielding strength (72-83 vs 82 MPa). Particularly, when compared with bottle-grade PET, PE₈₂Pe₁₈F possesses equal T_g (ca. 75 °C) and comparable elongation at break (ca. 115%), but greatly improved yielding strength (83 MPa) and O₂ gas barrier property (4.8 times). As modified PEF materials possessing superior thermo-mechanical and O₂ gas barrier properties, these integrally biobased copolyesters may find practical applications in eco-packaging and other fields.