序列式含芴季铵化聚芳醚砜阴离子交换膜的制备及交联改性

宁丹; 胡朝霞; 陈荣; 陈罕雯; 杨慧; 陈守文

doi:10.11777/j.issn1000-3304.2017.16232

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序列式含芴季铵化聚芳醚砜阴离子交换膜的制备及交联改性

研究论文 | 更新时间：2021-03-19

- 序列式含芴季铵化聚芳醚砜阴离子交换膜的制备及交联改性
- Sequenced Quaternized Poly (aryl ether sulfone)-based Anion Exchange Membranes and Their Crosslinking Modification
- 高分子学报 2017年第5期页码：842-850
- 作者机构：
  
  南京理工大学环境与生物工程学院南京 210094
- 作者简介：
  
  胡朝霞, E-mail:anfanyhu@hotmail.comZhao-xia Hu, E-mail:anfanyhu@hotmail.com
  陈守文, E-mail:chensw@mail.njust.edu.cnHan-wen Chen, E-mail:chensw@mail.njust.edu.cn
- 基金信息：
  
  国家自然科学基金(21276128);江苏省自然科学基金(BK20141398);中央高校基本科研业务费专项(30920130121014);教育部博士点基金(20123219120009)
- DOI：10.11777/j.issn1000-3304.2017.16232
  中图分类号：
- 纸质出版日期：2017-5，
  
  收稿日期：2016-7-20，
  
  修回日期：2016-9-1，
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宁丹, 胡朝霞, 陈荣, 陈罕雯, 杨慧, 陈守文. 序列式含芴季铵化聚芳醚砜阴离子交换膜的制备及交联改性[J]. 高分子学报, 2017,(5):842-850.

Dan Ning, Zhao-xia Hu, Rong Chen, Han-wen Chen, Hui Yang, Shou-wen Chen. Sequenced Quaternized Poly (aryl ether sulfone)-based Anion Exchange Membranes and Their Crosslinking Modification[J]. Acta Polymerica Sinica, 2017,(5):842-850.
宁丹, 胡朝霞, 陈荣, 陈罕雯, 杨慧, 陈守文. 序列式含芴季铵化聚芳醚砜阴离子交换膜的制备及交联改性[J]. 高分子学报, 2017,(5):842-850. DOI： 10.11777/j.issn1000-3304.2017.16232.

Dan Ning, Zhao-xia Hu, Rong Chen, Han-wen Chen, Hui Yang, Shou-wen Chen. Sequenced Quaternized Poly (aryl ether sulfone)-based Anion Exchange Membranes and Their Crosslinking Modification[J]. Acta Polymerica Sinica, 2017,(5):842-850. DOI： 10.11777/j.issn1000-3304.2017.16232.

摘要

为得到具有高电导率和稳定性的阴离子交换膜，采用两步聚合法合成了含芴的序列式聚芳醚砜，经付克氯甲基化、季铵化及碱化制备了季铵化聚芳醚砜，并以脂肪族二胺（

，

'，

'-四甲基丙二胺（TMPDA）及

，

'，

'-四甲基己二胺（TMHDA））为交联剂，通过直接交联及后交联法分别制备了2类序列交联型阴离子交换膜.制得的膜材料离子交换容量为1.59~2.12 mmol/g，柔韧结实.与具有相似离子交换容量的非交联膜相比，交联膜的抗溶剂性能、尺寸稳定性、离子电导率等性能均得到了提高.交联膜在高温水中的水解稳定性、强碱性条件下的化学稳定性显著增强.探讨了直接浇铸交联处理及成膜后交联处理2种交联方式对膜性能的影响，结果表明，后交联处理可以有效避免浇膜过程凝胶的形成，而且膜的稳定性相对于未交联膜有大幅度提高.尤其以TMHDA为交联剂的后交联膜的各项性能均优于相应非交联膜，IEC为2.17 mmol/g的PCL-M（H）膜，在30℃时吸水率为99%，膜径向尺寸变化率为15%，电导率为23.8 mS/cm，90℃时电导率达到82 mS/cm，经过4 mol/L的NaOH溶液室温处理240 h后，离子电导率损失为7.6%，100℃水处理24 h后重量损失为5.1%，表现出较好的稳定性.

Abstract

In order to improve the ion conductivity and alkaline stability of the anion exchange membranes (AEMs)

fluorenyl-containing sequenced poly (aryl ether sulfone) copolymers were synthesized by two-step polymerization

and converted subsequently into quaternized PAES through Freidel-Crafts chloromethylation

amination and alkalization

followed finally by a crosslinking reaction with aliphatic diamines of

'-tetramethyl-1

3-propanediamine (TMPDA) or

'-tetramethyl-1

6-hexanediamine (TMHDA). The prepared membranes owned ion exchange capacity around 1.59-2.12 mmol/g and were mechanical ductile. Compared with the non-crosslinked membranes with similar ion exchange capacity

the fundamental properties of the crosslinked membranes

such as solvent resistance

dimension stability

ionic conductivity and other properties

were enhanced. For the crosslinked membranes

the hydrolytic stability under high temperature and the alkaline stability under strong basic conditions were significantly improved. The membranes were crosslinked through two different crosslinking methods

namely

the direct-crosslinking by adding the crosslinking agent to the casting solution and the post-crosslinking by dipping the membranes in the crosslinking agent solution. The effects of the two crosslinking methods on the properties of the membranes were investigated. The results showed that

with the post-crosslinking

the gelation was avoided during the solution casting

while the membranes showed enhanced stability compared to the non-crosslinking ones. Especially

for the membranes post-crosslinked with TMHDA

all the properties were superior to those of the non-crosslinking ones. The membrane of PCL-M (H) (IEC=1.45 mmol/g) showed 99% of water uptake

lower than 15% of size change in-plane direction at 30℃

while with the high ionic conductivity of 23.8 and 82 mS/cm at 30℃ and 90℃ in water

respectively. The PCL-M (H) membrane showed excellent stability

only 7.6% loss in ionic conductivity after treatment in 4 mol/L NaOH solution for 240 h and 5.1% loss in weight after treatment in 100℃ water for 24 h

while 18% and 6.7% losses were found for the non-crosslinking membrane (QPES)

respectively. The PCL-M (H) membranes are good candidates for the applications in the fuel cell system.

关键词

燃料电池阴离子交换膜季铵化聚醚砜序列式聚合物交联

Keywords

Fuel cellAnion exchange membraneQuaternized poly (aryl ether sulfone)Sequenced polymerCrosslinking

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