{"title":"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","authors":"Mitsutoshi Hoshide, Hiromu Kawasaki, Shota Abe, Sayaka Iwabuchi, Shinnosuke Kogure, Yuji Sasanuma","doi":"10.1021/acs.macromol.4c00838","DOIUrl":null,"url":null,"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(CH<sub>2</sub>)<sub><i>y</i></sub>O (<i>y</i> = 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 <sup>±</sup> t, tg <sup>±</sup> g <sup>±</sup> t, and tg <sup>±</sup> tg<sup>∓</sup>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 <i>a</i>, <i>b</i>, and <i>c</i> 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).","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":null,"pages":null},"PeriodicalIF":5.1000,"publicationDate":"2024-06-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Insights into Conformation, Crystal Structure, and Material Properties of Plant-Derived Poly(alkylene 2,5-furandicarboxylate)s as Sustainable Alternatives to Petroleum-Derived Analogues\",\"authors\":\"Mitsutoshi Hoshide, Hiromu Kawasaki, Shota Abe, Sayaka Iwabuchi, Shinnosuke Kogure, Yuji Sasanuma\",\"doi\":\"10.1021/acs.macromol.4c00838\",\"DOIUrl\":null,\"url\":null,\"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(CH<sub>2</sub>)<sub><i>y</i></sub>O (<i>y</i> = 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 <sup>±</sup> t, tg <sup>±</sup> g <sup>±</sup> t, and tg <sup>±</sup> tg<sup>∓</sup>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 <i>a</i>, <i>b</i>, and <i>c</i> 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).\",\"PeriodicalId\":51,\"journal\":{\"name\":\"Macromolecules\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":5.1000,\"publicationDate\":\"2024-06-27\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Macromolecules\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://doi.org/10.1021/acs.macromol.4c00838\",\"RegionNum\":1,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"POLYMER SCIENCE\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Macromolecules","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1021/acs.macromol.4c00838","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"POLYMER SCIENCE","Score":null,"Total":0}
Insights into Conformation, Crystal Structure, and Material Properties of Plant-Derived Poly(alkylene 2,5-furandicarboxylate)s as Sustainable Alternatives to Petroleum-Derived Analogues
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).
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.