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

摘要

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, H-1 NMR, DSC, TGA and tensile, impact and O-2 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 (phi(PeF)) with monomer composition. PEPeFs proved nearly amorphous copolyesters having excellent thermal stability. Brittle-ductile transition was achieved at phi(PeF) as low as 9 mol %. Increasing phi(PeF) led to increase in elongation at break and notch impact strength and decrease in T-g, O-2 barrier performance and tensile modulus and strength. However, in comparison with PEF, PEF-rich PEPeFs (phi(PeF) 9-47%) not only showed greatly improved elongation at break (29-265% vs 4%) and enhanced impact strength (2.2-3.9 kJ/m(2)) 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, PE(82)Pe(18)F possesses equal T-g (ca. 75 degrees C) and comparable elongation at break (ca. 115%), but greatly improved yielding strength (83 MPa) and O-2 gas barrier property (4.8 times). As modified PEF materials possessing superior thermo-mechanical and O-2 gas barrier properties, these integrally biobased copolyesters may find practical applications in eco-packaging and other fields.