For the first time, dielectric and calorimetric investigations of a homologous series of Janus polynorbornenes with rigid main backbones and flexible −Si(OR)₃ side groups of differing length alkyl chains (R = propyl, butyl, hexyl, octyl, and decyl) is reported. Generally, this class of polymers has some potential for applications in the field of gas separation membranes. Two dielectrically active processes are observed at low temperatures, denoted as β- and α-relaxation. The former can be assigned to localized fluctuations, while the latter is related to the glassy dynamics of the flexible −Si(OR)₃ side groups, creating a nanophase separation in both the alkyl chain-rich and backbone-rich domains. This is confirmed through temperature-modulated differential scanning calorimetry (TMDSC) measurements and X-ray scattering experiments. The glass transition temperatures of the backbone rich domains, which are beyond or near to their degradation temperatures in terms of conventional DSC, are determined for the first time using fast scanning calorimetry employing both fast heating and cooling rates. This is complemented with scattering experiments that show how the size of the alkyl chain-rich domains increases with the side chain length. Alongside these results, a significant conductivity contribution was observed for all poly(tricyclononenes) with −Si(OR)₃ side groups, which is interpreted in terms of a percolation model.

中文翻译：

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Janus聚降冰片烯的分子动力学：玻璃化转变和纳米相分离

首次对具有一系列刚性主链和不同长度烷基链（R =丙基，丁基，己基，辛基和癸基）的柔性-Si（OR）₃侧基的Janus聚降冰片烯同源系列进行介电和量热研究报告。通常，这类聚合物在气体分离膜领域具有一定的应用潜力。在低温下观察到两个介电活性过程，称为β-松弛和α-松弛。前者可以分配给局部波动，而后者则与柔性-Si（OR）₃的玻璃态动力学有关。侧基，在富含烷基链的域和富含主链的域中均产生纳米相分离。通过温度调制差示扫描量热法（TMDSC）测量和X射线散射实验可以证实这一点。首次使用快速扫描量热法（同时采用快速加热和冷却速率）来确定富含骨架的区域的玻璃化转变温度（相对于常规DSC而言，其超过或接近其降解温度）。这与散射实验相辅相成，后者显示了富含烷基链的结构域的大小如何随侧链长度的增加而增加。除这些结果外，还观察到所有带有-Si（OR）_3的聚（三环壬烯）的电导率贡献 侧基，这是根据渗流模型来解释的。