新型高分子量全生物基2,5-噻吩二甲酸基聚酯的合成及构效关系,Biomacromolecules

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新型高分子量全生物基2,5-噻吩二甲酸基聚酯的合成及构效关系
Biomacromolecules ( IF 5.5 ) Pub Date : 2023-06-05 , DOI: 10.1021/acs.biomac.3c00001
Sunan Tian ₁ , Kaihuan Shi ₁ , Jun Xu ₁ , Baohua Guo _{1,

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Affiliation

高分子量全生物基聚（丁二酸丙二醇酯）通过熔融缩聚合成了基于新兴生物基芳香族二酸 2,5-噻吩二甲酸 (TFDCA) 的全组成范围的 -2,5-噻吩二甲酸 (PPSTF) 无规共聚酯。系统地研究了它们的结晶行为、热机械、气体阻隔和生物降解特性。XRD证明了一定程度的共聚单体共结晶，并且由于TFDCA单元具有更高的刚度，PTF单元与PS单元相比具有更强的结晶竞争能力。这些共聚酯表现出优异的热稳定性，并且可以通过调节柔性与刚性链段的变化比例来轻松控制机械性能。从理论计算和实验两个角度研究气体阻隔性能，即使PS单元含量为50 mol%，共聚酯仍表现出优异的耐气体渗透性。所选择的脂肪酶来自米曲霉可以降解含有高达 60 mol% PTF 单元的共聚酯。发现不可生物降解-可生物降解转变发生在芳香族 PTF 单元的数均序列长度低至约 3 时。有趣的是，与基于对苯二甲酸（TA 基）和 2,5-呋喃二甲酸基的 PTF 单元相比，具有相同芳香单元含量的（FDCA基）类似物，PPSTF60的表观降解速率常数（k）和半周期（t _1/2）实际上介于它们之间。这些发现为含奇数碳二醇单体的聚酯在绿色包装等领域的应用提供了广阔的前景。

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Synthesis and Structure–Property Relationships of Novel High Molecular Weight Fully Biobased 2,5-Thiophenedicarboxylic Acid-Based Polyesters

High molecular weight fully biobased poly(propylene succinate-co-2,5-thiophenedicarboxylate) (PPSTF) random copolyesters based on the emerging biobased aromatic diacid, 2,5-thiophenedicarboxylic acid (TFDCA), in full composition range were synthesized via melt polycondensation. Their crystallization behavior, thermal-mechanical, gas barrier, and biodegradable properties were systematically investigated. A certain level of comonomer cocrystallization was evidenced by XRD, and PTF units had stronger crystallization competitive capability compared to PS units due to the higher stiffness of TFDCA units. These copolyesters exhibited excellent thermal stability, and mechanical properties can be easily controlled by tuning the varied ratio of flexible to rigid segments. Gas barrier properties were studied from both theoretically calculated and experimental perspectives, and the copolyesters even with 50 mol % PS units still showed superior gas permeation resistance. The selected lipase from Aspergillus oryzae can degrade the copolyesters with up to 60 mol % PTF units. The nonbiodegradable-biodegradable transition was found to occur at the number-average sequence length of aromatic PTF units as low as about 3. Interestingly, when compared with their terephthalic acid-based (TA-based) and 2,5-furandicarboxylic acid-based (FDCA-based) analogues with the same content of aromatic units, the apparent degradation rate constant (k) and half period (t_1/2) of PPSTF60 were actually between them. These findings offer much promise for the application of polyesters containing odd-carbon diol monomers in green packaging and other fields.

更新日期：2023-06-05

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