Ionomers from Step-Growth Polymerization: Highly Ordered Ionic Aggregates and Ion Conduction
Ionomers from Step-Growth Polymerization: Highly Ordered Ionic Aggregates and Ion Conduction
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逐步增长聚合的离聚物：高度有序的离子聚集体和离子传导
DOI：
10.1021/acs.macromol.9b02220
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发表时间：
2020
期刊：
影响因子：
5.5
通讯作者：
Winey, Karen I.
中科院分区：
文献类型：
--
作者：
Yan, Lu;Hoang, Lauren;Winey, Karen I.
在离聚体中，精确地控制离子基团沿中性聚合物骨架的位置已经导致了新颖的纳米级形貌和良好的性能，尽管合成路线可能相当苛刻。在这里，我们报道了一系列含锂离聚体的合成，这些离聚体是由市售的二元醇单体(x=6或12)和二酸酐单体逐步聚合，然后与不同量的锂盐中和而直接合成的。结果是近乎精确的线性聚合物，其中非极性链段精确地具有6或12个亚甲基，如二醇所确定的。功能段有两个羧酸侧基和6-8个主干原子，这取决于二酸酐的加成。从X射线散射来看，与传统的无规离聚体相比，这些嵌段离聚体显示出定义良好的纳米结构。这些链段离聚体的近乎精确的性质不会影响形态有序。在单离子导体中，随着Li+的中和水平，随温度变化的离子电导率呈现出系统的增加。值得注意的是，在高中和水平(≥65%)下，这些无定形离聚体的离子电导率甚至在ATT&>Tg也表现出阿累尼乌斯行为，这表明离子迁移率与聚合物链段运动是解耦的，并且主要是在聚集体内；这一发现可能是一种有前途的固体聚合物电解质的设计策略。这里报道的合成方案提供了一套易于获得的几乎精确的离聚体，通过这些离聚体可以在聚合物微结构、纳米级离子聚集体形态和离子导电性之间建立目前所缺乏的基本关联。
Precisely controlling the position of ionic groups along neutral polymer backbones in ionomers has led to novel nanoscale morphologies and promising properties, although the synthetic routes can be quite demanding. Here, we report a series of Li+-containing ionomers directly synthesized from step-growth polymerization of commercially available diol monomers (x= 6 or 12) and dianhydride monomers followed by neutralization with various amounts of lithium salts. The results are nearly precise linear polymers wherein nonpolar segments have precisely 6 or 12 methylene groups, as determined by the diol. The functional segment has two carboxylic acid pendant groups and 6–8 backbone atoms depending on the dianhydride addition. From X-ray scattering, these segmented ionomers exhibit well-defined nanostructures in contrast to the conventional random ionomers. The nearly precise nature of these segmented ionomers does not compromise the morphological ordering. The temperature-dependent ionic conductivities exhibit a systematic increase with Li+neutralization level, as expected in a single-ion conductor. Notably, the ionic conductivities in these amorphous ionomers at high neutralization levels (≥65%) exhibit Arrhenius behavior even atT>Tg, suggesting that ion mobility is decoupled from polymer segmental motion and largely within the aggregates; this finding could be a promising design strategy for solid polymer electrolytes. The synthetic scheme reported here provides a readily accessible suite of nearly precise ionomers by which to build fundamental correlations between polymer microstructures, nanoscale ionic aggregate morphologies, and ionic conductivities that are currently lacking.
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精密酸共聚物中的氢键聚集体。
DOI：
10.1063/1.4863326
发表时间：
2014
期刊：
The Journal of chemical physics
影响因子：
--
作者：
C. Lueth;D. Bolintineanu;M. Stevens;A. Frischknecht
通讯作者：
A. Frischknecht
影响因子：
4.6
作者：
Deschanel, S.;Greviskes, B. P.;Boyce, M. C.
通讯作者：
Boyce, M. C.
含有离子液体功能的精确乙烯离聚物的动力学
影响因子：
5.5
作者：
U. Choi;L. R. Middleton;M. Soccio;C. F. Buitrago;Brian S. Aitken;Hanqing Masser;K. Wagener;K. Winey;J. Runt
通讯作者：
J. Runt
影响因子：
4.4
作者：
Christina L. Ting;Karen E Sorensen;M. Stevens;A. Frischknecht
通讯作者：
A. Frischknecht
影响因子：
15
作者：
Hall, Lisa M.;Seitz, Michelle E.;Frischknecht, Amalie L.
通讯作者：
Frischknecht, Amalie L.