揭示了3,4- pef不寻常的结晶特征，热分析和DFT研究

IF 4.1 2区化学 Q2 POLYMER SCIENCE

Polymer Pub Date : 2025-01-20 DOI:10.1016/j.polymer.2025.128065

Simão V. Pandeirada, Catarina F. Araújo, Mariela M. Nolasco, Pedro D. Vaz, Svemir Rudić, Armando J.D. Silvestre, Nathanael Guigo, Paulo Ribeiro-Claro, Andreia F. Sousa

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引用次数: 0

摘要

基于呋喃二甲酸（FDCA）的聚合物和材料的发展是学术界和工业界快速发展的研究领域，这是由更可持续的替代品取代化石基聚合物的需求所驱动的。尽管聚（乙烯2,5-呋喃二羧酸酯）（2,5- pef）具有明确的潜力，但许多其他的呋喃聚酯，如聚（乙烯3,4-呋喃二羧酸酯）（3,4- pef），由3,4- fdca异构体合成，仍未得到充分开发。这项研究首次利用振动光谱和密度泛函理论计算来探索3,4- pef聚酯的构象偏好。此外，3,4- pef的综合热表征解决了文献中的电流空白。结果表明，在晶体结构域中，3,4- pef链为ss-t构象，其中3,4- fdca片段为syn-syn基序，乙二醇（EG）片段为反式构象（ss-t）。然而，在非晶态区域，多种构象共存，同步-同步-间扭式（ss-g）和反同步-间扭式（as-g）片段占了大部分的人口分布。正如之前在2,5- pef中观察到的那样，在结晶域中形成C-H···O相互作用是3,4- pef结晶偏好的主要驱动因素。链间C-H··O键形成带来的能量增益补偿了从ss-g/as-g到ss-t构象转变带来的能量损失。差示扫描量热法（DSC）分析表明，3,4- pef的玻璃化转变温度（Tg）为39℃，熔融温度（Tm）为155℃。动力学研究表明，3,4- pef的最快结晶速率发生在110℃，半结晶时间为12 min。有趣的是，在最佳结晶温度（170℃）下，3,4- pef的结晶速度比2,5- pef快，但仍比聚对苯二甲酸乙酯慢。这些发现表明3,4- pef有望成为一种具有快速结晶行为的可再生聚合物。

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Unveiling the uncommon crystallization features of 3,4-PEF, a thermal and DFT study

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Unveiling the uncommon crystallization features of 3,4-PEF, a thermal and DFT study

The development of furandicarboxylic acid (FDCA) based polymers and materials is a rapidly growing research field in both academia and industry, driven by the need to replace fossil-based polymers with more sustainable alternatives. Despite the unequivocal potential of poly(ethylene 2,5-furandicarboxylate) (2,5-PEF), many other furanic polyesters, such as poly(ethylene 3,4-furandicarboxylate) (3,4-PEF), synthetized from the 3,4-FDCA isomer, remain underexplored. This study is the first to explore the conformational preferences of 3,4-PEF polyester using vibrational spectroscopy and density functional theory calculations. Additionally, a comprehensive thermal characterization of 3,4-PEF addresses current gaps in the literature.The results suggest that, in crystalline domains, 3,4-PEF chains adopt the ss-t conformation, where the 3,4-FDCA segment exhibits a syn-syn motif and the ethylene glycol (EG) segment is in the trans conformation (ss-t). In amorphous regions, however, multiple conformations coexist, with syn-syn-gauche (ss-g) and anti-syn-gauche (as-g) segments accounting for the bulk of the population distribution. As previously observed for 2,5-PEF, the formation of C-H···O interactions in the crystalline domain is the main driver for the crystallization preferences of 3,4-PEF. The energetic gain from interchain C-H···O bond formation compensates for the energy penalty associated with the ss-g/as-g to ss-t conformational transition.Differential scanning calorimetry (DSC) analysis revealed that 3,4-PEF has a glass transition temperature (T_g) of 39 °C and a melting temperature (T_m) of 155 °C. Kinetic studies showed that the fastest crystallization rate for 3,4-PEF occurs at 110 °C, with a half crystallization time of 12 min. Interestingly, 3,4-PEF crystallizes faster than 2,5-PEF at its optimal crystallization temperature (170 °C), though still more slowly than poly(ethylene terephthalate). These findings suggest that 3,4-PEF holds promise as a renewable polymer with fast crystallization behaviour.

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来源期刊

Polymer 化学-高分子科学

CiteScore

7.90

自引率

8.70%

发文量

959

审稿时长

32 days

期刊介绍： Polymer is an interdisciplinary journal dedicated to publishing innovative and significant advances in Polymer Physics, Chemistry and Technology. We welcome submissions on polymer hybrids, nanocomposites, characterisation and self-assembly. Polymer also publishes work on the technological application of polymers in energy and optoelectronics. The main scope is covered but not limited to the following core areas: Polymer Materials Nanocomposites and hybrid nanomaterials Polymer blends, films, fibres, networks and porous materials Physical Characterization Characterisation, modelling and simulation* of molecular and materials properties in bulk, solution, and thin films Polymer Engineering Advanced multiscale processing methods Polymer Synthesis, Modification and Self-assembly Including designer polymer architectures, mechanisms and kinetics, and supramolecular polymerization Technological Applications Polymers for energy generation and storage Polymer membranes for separation technology Polymers for opto- and microelectronics.