Structure and dynamics are examined for unentangled randomly-sulfonated polystyrene ionomer samples with cesium as counterion, using the X-ray scattering, DSC, and linear viscoelasticity (LVE) measurements. The large size of cesium cation leads to low association energy, enabling the dynamics to be examined for the high-ion-content samples, i.e., samples having a fraction of ionized monomers p up to 19%. X-ray scattering data shows an ionic peak, indicating the formation of ion aggregates. DSC reveals the glass transition process that shifts to higher T and broadens significantly when the ion content p is higher than 10%. In accordance with this broadening, the glassy and rubbery regimes seen in the LVE merge into one broad process with a wide relaxation distribution. We propose that the transition occurs when the number of ionic groups per chain becomes comparable to that of Kuhn segments per chain so that the polymer strands between ionic groups become non-flexible.

使用X射线散射，DSC和线性粘弹性（LVE）测量，对以铯为抗衡离子的无缠结的随机磺化聚苯乙烯离聚物样品的结构和动力学进行了研究。铯阳离子的大尺寸导致低的缔合能，使得能够检查高离子含量样品（即，离子化单体p的分数高达19％的样品）的动力学。X射线散射数据显示离子峰，表明离子聚集体的形成。DSC揭示了当离子含量为p时玻璃化转变过程会转变为更高的T并显着展宽高于10％。根据这种扩展，在LVE中看到的玻璃态和橡胶态合并为具有宽松弛分布的一个广泛过程。我们提出，当每条链上的离子基团的数量变得与每条链上的库恩链段的数量相当时，就会发生过渡，从而使各离子基团之间的聚合物链变得不灵活。