Biodegradable Copolyesters Derived from 2,5-Thiophenedicarboxylic Acid for High Gas Barrier Packaging Applications: Synthesis, Crystallization Properties, and Biodegradation Mechanisms,ACS Sustainable Chemistry & Engineering

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Biodegradable Copolyesters Derived from 2,5-Thiophenedicarboxylic Acid for High Gas Barrier Packaging Applications: Synthesis, Crystallization Properties, and Biodegradation Mechanisms
ACS Sustainable Chemistry & Engineering ( IF 7.1 ) Pub Date : 2024-08-01 , DOI: 10.1021/acssuschemeng.4c03611
Qianfeng Wang _{1,

2} , Jiayi Li ₃ , Yunxiao Dong ₁ , Han Hu ₁ , Drow Lionel OYoung ₂ , Di Hu ₂ , Yufang Zhang ₄ , Dong-Qing Wei ₃ , Jinggang Wang ₁ , Jin Zhu ₁

Affiliation

2,5-Thiophenedicarboxylic acid (TDCA) is a biobased building block for aromatic–aliphatic copolyesters. This study synthesized poly(propylene succinate-co-thiophenedicarboxylate) (PPSTh) and poly(propylene adipate-co-thiophenedicarboxylate) (PPATh) via two-step melt polycondensation. PPATh₇₀ exhibits the highest melting temperature at 144.8 °C. Crystallization kinetics indicate that diol-TDCA segments primarily form crystalline phases in PPXThs, with long aliphatic units enhancing crystallization. PPXThs containing over 50 mol % TDCA have a higher tensile modulus than poly(butylene adipate-co-terephthalate) (PBAT) and possess excellent gas barrier properties, outperforming PBAT by over 200 times. Dynamic mechanical analysis links the superior gas barrier properties to reduced free volumes. PPAThs degrade faster than PPSThs, with hydrolytic differences explained by Fukui function analysis and DFT calculations. Molecular dynamics simulations clarified the degradation mechanism catalyzed by Candida antarctica lipase B, showing that residues at the entrance interact with PPXTh₅₀ residues, hindering the carbonyl carbon from approaching the catalytic nucleophile, while the flexible PPXTh₄₀ more easily achieves an ideal Bürgi–Dunitz angle for nucleophilic attack.

中文翻译：

用于高阻气性包装应用的 2,5-噻吩二甲酸衍生的可生物降解共聚酯：合成、结晶性能和生物降解机制

2,5-噻吩二甲酸 (TDCA) 是芳香族-脂肪族共聚酯的生物基结构单元。本研究通过两步熔融缩聚合成了聚（琥珀酸丙烯酯-共-噻吩二甲酸）（PPSTh）和聚（己二酸丙烯-共-噻吩二甲酸）（PPATh）。 PPATh _{70 的}最高熔化温度为 144.8 °C。结晶动力学表明二醇-TDCA 链段主要在 PPXThs 中形成结晶相，长脂肪族单元增强结晶。含有超过 50 mol% TDCA 的 PPXThs 具有比聚己二酸对苯二甲酸丁二醇酯(PBAT) 更高的拉伸模量，并且具有优异的气体阻隔性能，是 PBAT 的 200 倍以上。动态机械分析将卓越的气体阻隔性能与减少的自由体积联系起来。 PPAThs 的降解速度比 PPSThs 更快，Fukui 函数分析和 DFT 计算解释了水解差异。分子动力学模拟阐明了南极假丝酵母脂肪酶 B 催化的降解机制，表明入口处的残基与 PPXTh ₅₀残基相互作用，阻碍羰基碳接近催化亲核试剂，而柔性的 PPXTh ₄₀更容易实现理想的 Bürgi-Dunitz 角用于亲核攻击。

更新日期：2024-08-01

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