一类含多磺酸结构侧链型聚芳醚酮质子交换膜材料的合成及性能研究

引用本文: 汪称意, 周远鹏, 徐常, 赵晓燕, 李坚, 任强. 一类含多磺酸结构侧链型聚芳醚酮质子交换膜材料的合成及性能研究[J]. 高分子学报, 2018, 0(9): 1194-1201. doi: 10.11777/j.issn1000-3304.2018.18010 shu

Citation: Chen-yi Wang, Yuan-peng Zhou, Chang Xu, Xiao-yan Zhao, Jian Li, Qiang Ren. Synthesis and Properties of Side-chain Type Poly(arylene ether ketone)s with Multiple Sulfonic Groups for Proton Exchange Membranes[J]. Acta Polymerica Sinica, 2018, 0(9): 1194-1201. doi: 10.11777/j.issn1000-3304.2018.18010 shu

一类含多磺酸结构侧链型聚芳醚酮质子交换膜材料的合成及性能研究

汪称意 ^{1,2,
,} ,
周远鹏 ^1, ,
徐常 ^1, ,
赵晓燕 ^1,2, ,
李坚 ^1, ,
任强 ^1,

1.
常州大学材料科学与工程学院江苏省环境友好高分子材料重点实验室　常州 213164
2.
复旦大学聚合物分子工程国家重点实验室　上海 200433

通讯作者: E-mail: wangcy@cczu.edu.cn

摘要: 为进一步改善芳香型磺化聚合物质子交换膜材料的离子传导率、尺寸稳定性和耐化学氧化稳定性，从聚合物结构设计出发，首先利用9,9-双(3-苯基-4-羟基)苯基芴与4,4′-(六氟异亚丙基)二苯酚、1,4-二(4-氟苯甲酰基)苯经芳香亲核缩聚合成了一系列含芴和苯侧基结构新型聚芳醚酮聚合物(4-PAEK-xx)，进一步通过温和的后磺化反应，制备了一系列含多磺酸结构侧链型聚芳醚酮质子交换膜(4-SPAEK-xx). 对所制备的侧链型聚芳醚酮质子交换膜的结构和性能分别进行了表征分析. 结果表明，该类质子交换膜具有适中的吸水率和较低的溶胀率，80 °C时的吸水率和溶胀率分别在21% ~ 51.2%和7.4% ~ 17.2%. 该类聚芳醚酮质子交换膜展现出了良好的离子传导性，80 °C时的离子传导率在115 ~ 171 mS/cm，其中4-PAEK-45膜(离子交换容量为2.12 mequiv/g)的离子传导率已经超过了商品化的Nafion膜. 此外，所制备的侧链型聚芳醚酮质子交换膜还表现出了良好的热稳定性、力学性能和耐化学氧化性. 磺化膜优良的综合性能主要归因于侧链多磺酸结构和长尺寸含氟疏水结构单元的同时引入，其中侧链多磺酸结构的引入降低了主链磺化结构单元的比例，同时使亲水性的磺酸基团与分子主链分隔开来；而长尺寸含氟疏水性结构单元的引入进一步提高了膜材料的尺寸稳定性和耐氧化稳定性.

关键词:

English

Synthesis and Properties of Side-chain Type Poly(arylene ether ketone)s with Multiple Sulfonic Groups for Proton Exchange Membranes

1.
Jiangsu Key Laboratory of Environmentally Friendly Polymeric Materials, School of Materials Science and Engineering, Changzhou University, Changzhou 213164
2.
State Key Laboratory of Molecular Engineering of Polymers, Fudan University, Shanghai 200433

Corresponding author: Chen-yi Wang, E-mail: wangcy@cczu.edu.cn

Received Date: 09 January 2018
Revised Date: 12 February 2018
Available Online: 01 September 2018

Abstract: Aromatic sulfonated polymers are one class of very important functional polymers and can be used as proton exchange membranes (PEMs) for fuel cells. As one of the key components in fuel cells, they can provide ionic pathway for proton transport and act as a separator for the reactants. In order to improve their ionic conductivity and dimensional and chemical oxidation stabilities, this study reports a series of sulfonated poly(aryl ether ketone)s proton exchange membrane materials from their design of macromolecular structures. A series of novel poly(arylene ether ketone)s containing fluorene and pendant phenyl groups (4-PAEK-xx) were first synthesized through nucleophilic polycondensation reaction using 9,9-bis(3-phenyl-4-hydroxy) phenyl fluorene, 4,4′-(hexafluoroisopropylidene)diphenol and 1,4-bis(4-fluorobenzoyl)benzene as starting materials. They were then used to prepare a series of side-chain type poly(arylene ether ketone)s proton exchange membranes with multiple sulfonic groups (4-SPAEK-xx) by mild post-sulfonation reaction and solution casting. The structures and properties of these membranes were investigated. The results indicated that 4-SPAEK-xx membranes displayed moderate water absorption and low swelling ratio with the values in the range of 21% − 51.2% and 7.4% − 17.2% at 80 °C, respectively. These proton exchange membranes also exhibited good ionic conductivity with the values in the range of 115 − 171 mS/cm at 80 °C. The ionic conductivity of 4-PAEK-45 membrane (the ion exchange capacity of 2.12 mequiv/g) was even higher than that of the commercialized Nafion membrane. Moreover, these membranes had good thermal and mechanical property and chemical oxidative stability. Excellent comprehensive properties of 4-SPAEK- xx membranes were mainly ascribed to the incorporation of multiple pendant sulfonic groups and long fluorinated hydrophobic structures. The incorporation of multiple pendant sulfonic groups can not only effectively reduce the content of sulfonated units in the polymers, but also separate the ionic groups from the polymer backbones. Meanwhile, the incorporation of long fluorinated hydrophobic structures could further improve the dimensional and chemical oxidation stability of the obtained membranes. It is believed that this research would provide a valuable insight for the design and preparation of proton exchange polymer membranes of high-performance with aromatic sulfonated groups.

Key words:

1. [1]
  Brlan C H, Steele A H. Nature, 2001, 414: 345 − 352 doi: 10.1038/35104620
2. [2]
  Hickner M A, Ghassemi H, Kim Y S, Einsla B R, McGrath J E. Chem Rev, 2004, 104: 4587 − 4611 doi: 10.1021/cr020711a
3. [3]
  Park C H, Lee S Y, Hwang D S, Shin D W, Cho D H, Lee K H, Kim T W, Kim T W, Lee M, Kim D S, Doherty C M, Thornton A W, Hill A J, Guiver M D, Lee Y M. Nature, 2016, 532: 480 − 483 doi: 10.1038/nature17634
4. [4]
  Asano N, Aoki M, Suzuki S, Miyatake K, Uchida H, Watanabe M. J Am Chem Soc, 2006, 128: 1762 − 1769 doi: 10.1021/ja0571491
5. [5]
  Bose S, Kuila T, Nguyen T X H, Kim N H, Laua K T, Lee J H. Prog Polym Sci, 2011, 36: 813 − 843 doi: 10.1016/j.progpolymsci.2011.01.003
6. [6]
  Zhang H, Shen P. Chem Rev, 2012, 112: 2780 − 2832 doi: 10.1021/cr200035s
7. [7]
  Xing P, Robertson G P, Guiver M D, Mikhailenko S D, Kaliaguine S. Macromolecules, 2004, 37: 7960 − 7967 doi: 10.1021/ma0494941
8. [8]
  Roy A, Hichner M A, Einsla B R, Harrison W L, McGrath J E. J Polym Sci, Part A: Polym Chem, 2009, 47: 384 − 391 doi: 10.1002/pola.v47:2
9. [9]
  Tan N, Xiao G, Yan D. Chem Mater, 2010, 22: 1022 − 1031 doi: 10.1021/cm9019217
10. [10]
  Weiber E A, Takamuku S, Jannasch P. Macromolecules, 2013, 46: 3476 − 3485 doi: 10.1021/ma4002929
11. [11]
  Zhang Z, Wu L, Xu T. J Membr Sci, 2011, 373: 160 − 166 doi: 10.1016/j.memsci.2011.03.002
12. [12]
  Li M, Zhang G, Xu S, Zhao C, Han M, Zhang L, Jiang H, Liu Z, Na H. J Power Sources, 2014, 255: 101 − 107 doi: 10.1016/j.jpowsour.2013.12.116
13. [13]
  Wang C, Shen B, Zhou Y, Xu C, Chen W, Zhao X, Li J. Int J Hydrogen Energy, 2015, 40: 6422 − 6429 doi: 10.1016/j.ijhydene.2015.03.078
14. [14]
  Yan Xiaobo(严小波), Zhang Xulue(张虚略), Yuan Zufeng(袁祖凤), Geng Hui(耿慧), Bi Huiping(毕慧平), Hu Zhaoxia(胡朝霞), Chen Shouwen(陈守文). Acta Polymerica Sinica(高分子学报), 2016, (5): 577-583
15. [15]
  Hu Meishao(胡美韶), Ni Jiangpeng(倪江鹏), Liu Danqing(刘丹青), Wang Lei(王雷). Acta Polymerica Sinica(高分子学报), 2017, (3): 534-541
16. [16]
  Kreuer K D. J Membr Sci, 2001, 185: 29 − 39 doi: 10.1016/S0376-7388(00)00632-3
17. [17]
  Peckham T J, Holdcroft S. Adv Mater, 2010, 22: 4667 − 4690 doi: 10.1002/adma.v22:42
18. [18]
  Li N, Guiver M D. Macromolecules, 2014, 47: 2175 − 2198 doi: 10.1021/ma402254h
19. [19]
  Liu B, Robertson G P, Kim D S, Sun X, Jiang Z, Guiver M D. Polymer, 2010, 51: 403 − 413 doi: 10.1016/j.polymer.2009.12.014
20. [20]
  Wang C, Li N, Shin D W, Lee S Y, Kang N R, Lee Y M, Guiver M D. Macromolecules, 2011, 44: 7296 − 7306 doi: 10.1021/ma2015968
21. [21]
  Wang C, Shin D W, Lee S Y, Kang N R, Robertson G P, Lee Y M, Guiver M D. J Mater Chem, 2012, 22: 25093 − 25101 doi: 10.1039/c2jm34414a
22. [22]
  Shen Bin(沈斌), Wang Chenyi(汪称意), Xu Chang(徐常), Chen Wentao(陈文涛), Li Jian(李坚), Ren Qiang(任强). Acta Polymerica Sinica(高分子学报), 2016, (10): 1409-1417
23. [23]
  Gong F X, Zhang S B. J Power Sources, 2011, 196: 9876 − 9883 doi: 10.1016/j.jpowsour.2011.08.028

扫一扫看文章

计量

PDF下载量: 0
文章访问数: 179
HTML全文浏览量: 49

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142

一类含多磺酸结构侧链型聚芳醚酮质子交换膜材料的合成及性能研究

通讯作者: E-mail: wangcy@cczu.edu.cn

English

Synthesis and Properties of Side-chain Type Poly(arylene ether ketone)s with Multiple Sulfonic Groups for Proton Exchange Membranes

Corresponding author: Chen-yi Wang, E-mail: wangcy@cczu.edu.cn

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南：你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

计量

通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

一类含多磺酸结构侧链型聚芳醚酮质子交换膜材料的合成及性能研究

通讯作者: E-mail: wangcy@cczu.edu.cn

English

Synthesis and Properties of Side-chain Type Poly(arylene ether ketone)s with Multiple Sulfonic Groups for Proton Exchange Membranes

Corresponding author: Chen-yi Wang, E-mail: wangcy@cczu.edu.cn

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南： 你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

计量

文章相关

通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

CCS Chemistry：颜徐州、鲍哲南：你的皮肤可能是一片SPMs