Micro-block versus random quaternized poly(arylene ether sulfones) with highly dense quaternization units for anion exchange membranes,Polymer Chemistry

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Micro-block versus random quaternized poly(arylene ether sulfones) with highly dense quaternization units for anion exchange membranes
Polymer Chemistry ( IF 4.1 ) Pub Date : 2020/02/25 , DOI: 10.1039/c9py01951k
Su Li _{1,

2,

3,

4,

5} , Haibo Zhang _{1,

2,

3,

4,

5} , Kaiqi Wang _{1,

2,

3,

4,

5} , Fan Yang _{1,

2,

3,

4,

5} , Yuntao Han _{1,

2,

3,

4,

5} , Yirong Sun _{1,

2,

3,

4,

5} , Jinhui Pang _{1,

2,

3,

4,

5} , Zhenhua Jiang _{1,

2,

3,

4,

5}

Affiliation

To investigate the effect of the segment architecture on membrane performance, a series of micro-block-type poly(ether sulfone)s with long hydrophilic segments were synthesized. Meanwhile, two other classes of polymers with random and intermediate construction were also synthesized. After optimized chloromethylation and quaternization reactions, respectively, the resulting AEMs were obtained with comparable IEC values. TTP-n-QAPES with the longest hydrophilic segment and the most intensive ion clustering produced the most distinct hydrophilic–hydrophobic phase morphology, which was confirmed by small-angle X-ray scattering (SAXS) and atomic force microscopy (AFM) observation. TTP-18.2-QAPES with an IEC of 2.17 meq g⁻¹ showed a hydroxide conductivity of 64.5 mS cm⁻¹ at 80 °C, which was almost 1.34 times higher than that of a random copolymer based AEM with the same IEC value, while preserving the promoted water management capacity and dimensional stability (about 20% lower than that of random type AEMs) due to the well-defined ion nanochannels. Moreover, TTP-n-QAPES was more stable than the corresponding random type AEMs under harsh basic conditions. A systematic study of long-term alkaline stability was performed, and S_N2 nucleophilic substitution could be determined as the main degradation method by ¹H NMR spectroscopy. Furthermore, the TTP-18.2-QAPES based MEA achieved a considerable power density of 148 mW cm⁻² at 60 °C. These results suggest that the construction of long hydrophilic segments is a promising approach to promote the comprehensive performance of AEMs.

中文翻译：

具有高密度季铵化单元的阴离子交换膜的微嵌段与无规季铵化聚亚芳基醚砜

为了研究链段结构对膜性能的影响，合成了一系列具有长亲水链段的微嵌段型聚醚砜。同时，还合成了另外两种具有无规和中间结构的聚合物。分别经过优化的氯甲基化和季铵化反应后，得到的AEM具有可比较的IEC值。具有最长亲水链段和最强离子簇的TTP- n -QAPES产生了最独特的亲水-疏水相形态，这一点已通过小角X射线散射（SAXS）和原子力显微镜（AFM）观察得到了证实。IEC为2.17 meq g ^-1的TTP-18.2-QAPES显示氢氧化物电导率为64.5 mS cm ^-1在80°C时，比具有相同IEC值的无规共聚物基AEM几乎高1.34倍，同时由于以下原因可保持提高的水管理能力和尺寸稳定性（比无规型AEM降低约20％）。定义明确的离子纳米通道。而且，在苛刻的基本条件下，TTP- n -QAPES比相应的随机型AEM更稳定。进行了长期碱性稳定性的系统研究，并通过¹ H NMR光谱确定了S _N 2亲核取代是主要的降解方法。此外，基于TTP-18.2-QAPES的MEA的功率密度高达148 mW cm ^-2在60°C下。这些结果表明，长亲水链段的构建是提高AEM的综合性能的有前途的方法。

更新日期：2020-03-31

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