Aliphatic-aromatic copolyesters offer a promising solution to mitigate plastic pollution, but high content of aliphatic units (>40 %) often suffer from diminished comprehensive performances. Poly(butylene oxalate-co-furandicarboxylate) (PBOF) copolyesters were synthesized by precisely controlling the oxalic acid content from 10 % to 60 %. Compared with commercial PBAT, the barrier properties of PBOF for H2O and O2 increased by more than 6 and 26 times, respectively. The introduction of the oxalic acid units allowed the water contact angle to be reduced from 82.5° to 62.9°. Superior hydrophilicity gave PBOF an excellent degradation performance within a 35-day hydrolysis. Interestingly, PBO20F and PBO30F also displayed obvious decrease of molecular weight during hydrolysis, with elastic modulus >1 GPa and tensile strength between 35-54 MPa. PBOF achieved the highest hydrolysis rates among the reported PBF-based copolyesters. The hydrolytic mechanism was further explored based on Fukui function analysis and density functional theory (DFT) calculation. Noncovalent analysis indicated that the water molecules formed hydrogen bonding interaction with adjacent ester groups and thus improved the reactivity of carbonyl carbon. PBOF not only meet the requirements of the high-performance packaging market but can quickly degrade after the end of their usage cycles, providing a new choice for green and environmental protection.
Keywords: Fast degradation; Fully bio-based polyesters; High barrier; Hydrolytic mechanism; Oxalic acid.
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