In this work, novel polyester amides (PEAs) based on renewable poly(propylene furanoate) (PPF) were prepared via traditional melt polycondensation utilizing a preformed symmetric amido diol (AD) containing two internal amide bonds. Owing to this innovative synthetic strategy, enhanced crystallization, both in terms of quantity and rate, was observed compared to neat PPF, which is characterized by slow crystallization kinetics. Moreover, the intramolecular hydrogen bonding usually observed in furan dicarboxylic acid (FDCA)-based polyamides, that results in the formation of low-molecular weight materials, was circumvented and copolymers of random structure and higher molecular weight were obtained. Due to the AD unit and the ensuing suppression of intramolecular hydrogen bonds, chain mobility (diffusion) is improved, leading in turn to enhanced crystallization. The crystallinity and crystal structure of PEAs were assessed via the combination of differential scanning calorimetry (DSC), X-ray diffraction (XRD) and polarized optical microscopy (POM). Furthermore, thermal degradation of the furan-based PEAs was thoroughly investigated for the first time, employing thermogravimetric analysis (TGA) kinetic modeling and Pyrolysis-Gas Chromatography–Mass Spectroscopy (Py-GC/MS). Finally, the complex molecular dynamics of PEAs was studied employing broadband dielectric spectroscopy (BDS). This study shows that PEAs have the potential to further enlarge the properties and applications of polyesters derived from FDCA.

中文翻译：

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释放呋喃基聚（酯酰胺）的潜力：基于可再生聚（呋喃丙二醇）的新型聚（酯酰胺）的结晶、分子动力学和降解动力学研究

在这项工作中，基于可再生聚（呋喃丙二醇）（PPF）的新型聚酯酰胺（PEA）是通过以下方法制备的：传统的熔融缩聚反应利用预先形成的含有两个内部酰胺键的对称酰胺二醇 (AD)。由于这种创新的合成策略，与纯 PPF 相比，在数量和速率方面都观察到了增强的结晶，其特点是结晶动力学缓慢。此外，通常在呋喃二甲酸 (FDCA) 基聚酰胺中观察到的分子内氢键导致低分子量材料的形成，被规避并获得了无规结构和更高分子量的共聚物。由于 AD 单元和随后对分子内氢键的抑制，链移动性（扩散）得到改善，进而导致结晶增强。通过评估 PEA 的结晶度和晶体结构差示扫描量热法 (DSC)、X 射线衍射 (XRD) 和偏光显微镜 (POM) 的组合。此外，首次利用热重分析 (TGA) 动力学模型和热解-气相色谱-质谱 (Py-GC/MS) 彻底研究了呋喃基 PEA 的热降解。最后，使用宽带介电光谱 (BDS) 研究了 PEA 的复杂分子动力学。该研究表明，PEA 具有进一步扩大 FDCA 衍生聚酯的性能和应用的潜力。