A series of symmetric poly[(oligo(ethylene glycol) methyl ether methacrylate-co-oligo(ethylene glycol) propyl sodium sulfonate methacrylate)]-block-polystyrene (PsOEGMA-PS) diblock copolymers were synthesized as a model system to probe the effect of charge fraction on the phase behavior of charged-neutral single-ion conducting diblock copolymers. Small-angle X-ray scattering (SAXS) experiments showed that increasing the charge fraction does not alter the ordered phase morphology (lamellar) but increases the order–disorder transition temperature (T_ODT) significantly. Additionally, the effective Flory–Huggins interaction parameter (χ_eff) was found to increase linearly with the charge fraction, similar to the case of conventional salt-doped diblock copolymers. This indicates that the effect of counterion solvation, attributed to the significant mismatch between the dielectric constant of each block, provides the dominant effect in tuning the phase behavior of this charged diblock copolymer. We therefore infer that electrostatic cohesion (local charge ordering induced by Coulombic interactions), which is predicted to suppress microphase separation and lead to asymmetric phase diagrams, only plays a minor role in this model system.

中文翻译：

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电荷分数对对称单离子导电二嵌段共聚物相行为的影响

合成了一系列对称的聚[(低聚(乙二醇)甲基醚甲基丙烯酸酯-共-低聚(乙二醇)丙基磺酸钠甲基丙烯酸酯)]-嵌段-聚苯乙烯(P s OEGMA-PS)二嵌段共聚物作为模型系统来探测电荷分数对带电中性单离子导电二嵌段共聚物相行为的影响。小角 X 射线散射 (SAXS) 实验表明，增加电荷分数不会改变有序相形态（层状），但会显着提高有序-无序转变温度 ( T _ODT )。此外，有效的 Flory-Huggins 相互作用参数 (χ _eff) 被发现随着电荷分数线性增加，类似于传统的盐掺杂二嵌段共聚物的情况。这表明，由于每个嵌段的介电常数之间的显着不匹配，反离子溶剂化的影响在调节这种带电二嵌段共聚物的相行为方面提供了主要影响。因此，我们推断静电凝聚力（由库仑相互作用引起的局部电荷排序），预计会抑制微相分离并导致不对称相图，在该模型系统中仅起次要作用。