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Molecular Mobility in Amorphous Biobased Poly(ethylene 2,5-furandicarboxylate) and Poly(ethylene 2,4-furandicarboxylate)
Macromolecules ( IF 5.1 ) Pub Date : 2018-02-23 00:00:00 , DOI: 10.1021/acs.macromol.8b00108 Aurélie Bourdet 1 , Antonella Esposito 1 , Shanmugam Thiyagarajan 2 , Laurent Delbreilh 1 , Frédéric Affouard 3 , Rutger J. I. Knoop 2 , Eric Dargent 1
Macromolecules ( IF 5.1 ) Pub Date : 2018-02-23 00:00:00 , DOI: 10.1021/acs.macromol.8b00108 Aurélie Bourdet 1 , Antonella Esposito 1 , Shanmugam Thiyagarajan 2 , Laurent Delbreilh 1 , Frédéric Affouard 3 , Rutger J. I. Knoop 2 , Eric Dargent 1
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Among all the emergent biobased polymers, poly(ethylene 2,5-furandicarboxylate) (2,5-PEF) seems to be particularly interesting for packaging applications. This work is focused on the investigation of the relaxation dynamics and the macromolecular mobility in totally amorphous 2,5-PEF as well as in the less studied poly(ethylene 2,4-furandicarboxylate) (2,4-PEF). Both biopolymers were investigated by differential scanning calorimetry and dielectric relaxation spectroscopy in a large range of temperatures and frequencies. The main parameters describing the relaxation dynamics and the molecular mobility in 2,5-PEF and 2,4-PEF, such as the glass transition temperature, the temperature dependence of the α and β relaxation times, the fragility index, and the apparent activation energy of the secondary relaxation, were determined and discussed. 2,5-PEF showed a higher value of the dielectric strength as compared to 2,4-PEF and other well-known polyesters, such as poly(ethylene terephthalate), which was confirmed by molecular dynamics simulations. According to the Angell’s classification of glass-forming liquids, amorphous PEFs behave as stronger glass-formers in comparison with other polyesters, which may be correlated to the packing efficiency of the macromolecular chains and therefore to the free volume and the barrier properties.
中文翻译：
非晶态生物基聚2,5-呋喃二甲酸乙二醇酯和聚2,4-呋喃二甲酸乙烯酯的分子迁移率
在所有新兴的基于生物的聚合物中，聚（2,5-呋喃二甲酸乙烯酯）（2,5-PEF）似乎对于包装应用特别有趣。这项工作的重点是在完全无定形的2,5-PEF以及研究较少的聚（2,4-呋喃二甲酸乙烯酯）（2,4-PEF）中研究松弛动力学和大分子迁移率。两种生物聚合物均通过差示扫描量热法和介电弛豫光谱法在很大的温度和频率范围内进行了研究。描述2,5-PEF和2,4-PEF中弛豫动力学和分子迁移率的主要参数，例如玻璃化转变温度，α和β弛豫时间的温度依赖性，脆性指数和表观活化确定并讨论了二次弛豫的能量。2，与2,4-PEF和其他众所周知的聚酯（例如，聚对苯二甲酸乙二酯）相比，5-PEF显示出更高的介电强度值，这已通过分子动力学模拟得到了证实。根据Angell对玻璃形成液体的分类，与其他聚酯相比，无定形PEF表现出更强的玻璃形成能力，这可能与大分子链的填充效率相关，因此与自由体积和阻隔性能相关。
更新日期：2018-02-23
中文翻译：
非晶态生物基聚2,5-呋喃二甲酸乙二醇酯和聚2,4-呋喃二甲酸乙烯酯的分子迁移率
在所有新兴的基于生物的聚合物中，聚（2,5-呋喃二甲酸乙烯酯）（2,5-PEF）似乎对于包装应用特别有趣。这项工作的重点是在完全无定形的2,5-PEF以及研究较少的聚（2,4-呋喃二甲酸乙烯酯）（2,4-PEF）中研究松弛动力学和大分子迁移率。两种生物聚合物均通过差示扫描量热法和介电弛豫光谱法在很大的温度和频率范围内进行了研究。描述2,5-PEF和2,4-PEF中弛豫动力学和分子迁移率的主要参数，例如玻璃化转变温度，α和β弛豫时间的温度依赖性，脆性指数和表观活化确定并讨论了二次弛豫的能量。2，与2,4-PEF和其他众所周知的聚酯（例如，聚对苯二甲酸乙二酯）相比，5-PEF显示出更高的介电强度值，这已通过分子动力学模拟得到了证实。根据Angell对玻璃形成液体的分类，与其他聚酯相比，无定形PEF表现出更强的玻璃形成能力，这可能与大分子链的填充效率相关，因此与自由体积和阻隔性能相关。
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