Barrier Properties of Biodegradable Aliphatic‐Aromatic Copolyesters (PBXT) Series

Abstract In this study, a series of biodegradable poly(butylene alkylene carboxylate‐ co ‐terephthalate) copolymers with varying methylene numbers in the alkylene units (0, 2, 4, and 8) are synthesized. These copolymers, namely, poly(butylene oxalate‐ co ‐terephthalate) (PBOT), poly(butylene succinate‐ co ‐terephthalate) (PBST), poly(butylene adipate‐ co ‐terephthalate) (PBAT), and poly(butylene sebacate‐ co ‐terephthalate) (PBSeT), are prepared with nearly identical structural and molar compositions. The objective of this study is to comprehensively examine the impact of alkylene unit length on the barrier properties of the materials, delving into aspects such as crystallinity, free volume, molecular chain mobility, as well as adsorption and diffusion of gases within the materials. The findings indicate a decrease in crystallinity from 17.2% for PBOT to 10.2% for PBSeT as the alkylene chain length increases, while maintaining the same chemical composition. Concurrently, the fractional free volume increases from 0.9% to 2.6%, and the melt flow activation energy decreases from 106.6 to 52.1 kJ mol −1 . Importantly, theoretical calculations are performed, demonstrating that the predominant site for gas adsorption and diffusion is within the material's free volume. These combined observations indicate a gradual decrease in barrier properties as the number of methylene groups increases.