Insights into Conformation, Crystal Structure, and Material Properties of Plant-Derived Poly(alkylene 2,5-furandicarboxylate)s as Sustainable Alternatives to Petroleum-Derived Analogues

IF 5.1 1区化学 Q1 POLYMER SCIENCE Macromolecules Pub Date : 2024-06-27 DOI:10.1021/acs.macromol.4c00838

Mitsutoshi Hoshide, Hiromu Kawasaki, Shota Abe, Sayaka Iwabuchi, Shinnosuke Kogure, Yuji Sasanuma

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Abstract

Conformational characteristics and conformation-dependent properties of poly(ethylene 2,5-furandicarboxylate) (PEF), poly(trimethylene 2,5-furandicarboxylate) (PTF), and poly(butylene 2,5-furandicarboxylate) (PBF) have been revealed via NMR experiments and molecular orbital calculations on their model compounds, along with refined rotational isomeric state calculations for the polymers. The O(CH₂)_yO (y = 2, 3, and 4) segments of the polyesters exhibit conformational preferences similar to those found in the corresponding poly(alkylene terephthalate)s. The most stable conformations identified for PEF, PTF, and PBF are tg ^± t, tg ^± g ^± t, and tg ^± tg^∓t, respectively. Their spatial configurations and conformational flexibilities significantly depend on conformations around the (furan)C–C(═O) bonds. Additionally, periodic density functional theory calculations were employed to optimize the α′ crystal structure of PEF, resulting in the equilibrium α form with a monoclinic lattice containing two all-trans chains. Young’s moduli along the a, b, and c axes of the optimized α crystal were calculated to be 26.8, 12.5, and 141 GPa, respectively. These values are comparable to those of poly(ethylene terephthalate).

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植物提取的聚(2,5-呋喃二甲酸烯丙酯)作为石油提取的类似物的可持续替代品的构象、晶体结构和材料特性的见解

通过对模型化合物的核磁共振实验和分子轨道计算，以及对聚合物的精制旋转异构态计算，揭示了聚(2,5-呋喃二甲酸乙烯酯)(PEF)、聚(2,5-呋喃二甲酸三亚甲基酯)(PTF)和聚(2,5-呋喃二甲酸丁烯酯)(PBF)的构象特征和构象依赖特性。聚酯的 O(CH2)yO（y = 2、3 和 4）段表现出与相应的聚（对苯二甲酸烯丙酯）类似的构象偏好。PEF、PTF 和 PBF 最稳定的构象分别是 tg ± t、tg ± g ± t 和 tg ± tg∓t。它们的空间构型和构象灵活性在很大程度上取决于围绕（呋喃）C-C（═O）键的构象。此外，还利用周期密度泛函理论计算优化了 PEF 的 α′ 晶体结构，从而得到了含有两条全反式链的单斜晶格的平衡 α 形。经计算，优化 α 晶体沿 a、b 和 c 轴的杨氏模量分别为 26.8、12.5 和 141 GPa。这些数值与聚对苯二甲酸乙二醇酯的数值相当。

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来源期刊

Macromolecules 工程技术-高分子科学

CiteScore

9.30

自引率

16.40%

发文量

942

审稿时长

2 months

期刊介绍： Macromolecules publishes original, fundamental, and impactful research on all aspects of polymer science. Topics of interest include synthesis (e.g., controlled polymerizations, polymerization catalysis, post polymerization modification, new monomer structures and polymer architectures, and polymerization mechanisms/kinetics analysis); phase behavior, thermodynamics, dynamic, and ordering/disordering phenomena (e.g., self-assembly, gelation, crystallization, solution/melt/solid-state characteristics); structure and properties (e.g., mechanical and rheological properties, surface/interfacial characteristics, electronic and transport properties); new state of the art characterization (e.g., spectroscopy, scattering, microscopy, rheology), simulation (e.g., Monte Carlo, molecular dynamics, multi-scale/coarse-grained modeling), and theoretical methods. Renewable/sustainable polymers, polymer networks, responsive polymers, electro-, magneto- and opto-active macromolecules, inorganic polymers, charge-transporting polymers (ion-containing, semiconducting, and conducting), nanostructured polymers, and polymer composites are also of interest. Typical papers published in Macromolecules showcase important and innovative concepts, experimental methods/observations, and theoretical/computational approaches that demonstrate a fundamental advance in the understanding of polymers.