Four guanidinuium-functionalized model compounds containing different substituent groups were prepared, and the substituent effects on the overall alkaline stability of the guanidinium cations were investigated. Based on the good alkaline stability of the model compounds, novel guanidinium-based anion exchange membranes (AEMs), GPP-co-PAEK x, with controlled microblock structures were subsequently designed and synthesized in good yield via a three step reaction that included a fluorophenyl-amine reaction, methylation and nickel (0)-catalyzed coupling. Notably, the use of a hydrophilic, guanidinium cation-containing component as a raw material in the direct synthesis of AEMs via nickel(0)-catalyzed coupling avoided using hygroscopic Vilsmeier salts and is obviously different from the conventional method that involves bromomethylation or post-quaternization. The GPP-co-PAEK x membranes exhibited lower water uptake values (≤23.4% at 60°C) and hydroxide conductivities comparable to those of others reported randomly functionalized guanidinium-based AEMs with similar ion exchange capacity (IEC) values. This finding indicates that the GPP-co-PAEK x membranes with controlled microblock structures possess well-developed hydrophilic/hydrophobic nanophase separation, which was confirmed by transmission electron microscopy (TEM). Moreover, long-term alkaline stability tests demonstrated that the alkaline stability of both the hydrophilic guanidiniums groups and the copolymer backbone contributed to the good alkaline stabilities of the GPP-co-PAEK x membranes.

中文翻译：

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具有可控微嵌段结构的新型胍基阴离子交换膜的合成

制备了四种具有不同取代基的胍官能化模型化合物，研究了取代基对胍阳离子整体碱稳定性的影响。基于模型化合物的良好碱性稳定性，随后设计了具有受控微嵌段结构的新型胍基阴离子交换膜（AEM）GPP-co-PAEK x，并通过包含氟苯基的三步反应以高收率合成-胺反应，甲基化和镍（0）催化的偶联。值得注意的是，使用亲水性 在使用吸水的Vilsmeier盐避免通过镍（0）催化的偶联直接合成AEM的过程中，将含有胍盐阳离子的成分作为原料，这与涉及溴甲基化或后季铵化的常规方法明显不同。GPP-co-PAEK x膜的吸水率更低（在60°C时≤23.4％）和氢氧化物电导率可与其他报道的具有相似离子交换容量（IEC）值的随机官能化的基于胍的AEM相比。这一发现表明，具有受控微嵌段结构的GPP-co-PAEK x膜具有发达的亲水/疏水纳米相分离，这已通过透射电子显微镜（TEM）得以证实。而且，