Citation: BI Weihui, ZHENG Jifu, ZHANG Suobo. Preparation and Characterization of Sulfonated Poly(p-phenylene-co-aryl ether ketone) for Proton Exchange Membranes[J]. Chinese Journal of Applied Chemistry, ;2017, 34(10): 1117-1126. doi: 10.11944/j.issn.1000-0518.2017.10.170026 shu

Preparation and Characterization of Sulfonated Poly(p-phenylene-co-aryl ether ketone) for Proton Exchange Membranes

BI Weihui ^a,b ,
ZHENG Jifu ^a ,
ZHANG Suobo ^a,c,,

a.
Key Laboratory of Polymer Ecomaterials, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, China
b.
University of Chinese Academy of Sciences, Beijing, 100049, China
c.
Jiangsu National Synergetic Innovation Center for Advanced Materials(SICAM), Nanjing, 211816, China

Corresponding author: ZHANG Suobo, sbzhang@ciac.ac.cn
Received Date: 23 January 2017
Revised Date: 16 February 2017
Accepted Date: 19 April 2017

Fund Project: the National Basic Research Program of China 2015CB655302the National Natural Science Foundation of China 51473163the Development of Scientific and Technological Project of the Jilin Province 20160101316JCSupported by the National Basic Research Program of China(No.2015CB655302), the National Natural Science Foundation of China(No.51473163), the Development of Scientific and Technological Project of the Jilin Province(No.20160101316JC)

Figures(5)

A novel monomer was designed and synthesized, in which the cyano groups were distributed on three benzene rings linked by meta ether linkages. Then using this monomer and 2, 5-dichloro-3'-sulfobenzophenone as raw materials, a series of novel micro-block copolymer proton exchange membranes(middle length-sulfonated polyphenylene-co-poly aryl ether ketone 3CN(m-SPP-co-PAEK 3CN x), x represents the ion exchange capacity of the polymer) was prepared by nickel(0) catalyzed coupling copolymerization. The experimental results show that these membranes exhibit low water uptake and swelling ratio as well as methanol permeability under similar ion exchange capacity. As the ion exchange capacity is equal to 2.16 and the temperature is 80℃, the water uptake and swelling ratio of m-SPP-co-PAEK 3CN 2.16 are 29.7% and 28.2%, respectively, while the water uptake and swelling ratio of SPP-co-PAEK MO 2.33 are 80.2% and 37.2%, respectively. At 25℃, the methanol permeability of the two membranes is 2.38 and 7.20, respectively. The good dimensional stability of the as-synthesized membrane can be attributed to the introduction of the polar-CN groups into the skeleton. With these properties, the prepared membranes are promising proton exchange membrane materials in fuel cell applications.
- sulfonated poly(p-phenylene-co-aryl ether ketone)s,
- proton exchange membranes,
- microblock,
- swelling ratio,
- methanol permeability
1. [1]
  Kreuer K D. On the Development of Proton Conducting Polymer Membranes for Hydrogen and Methanol Fuel Cells[J]. J Membr Sci, 2001,185:29-39. doi: 10.1016/S0376-7388(00)00632-3
2. [2]
  Zhang H W, Shen P K. Recent Development of Polymer Electrolyte Membranes for Fuel Cells[J]. Chem Rev, 2012,112:2780-2832. doi: 10.1021/cr200035s
3. [3]
  Kakati N, Maiti J, Lee S H. Anode Catalysts for Direct Methanol Fuel Cells in Acidic Wedia:Do We Have Any Alternative for Pt or Pt-Ru?[J]. Chem Rev, 2014,114:12397-12429. doi: 10.1021/cr400389f
4. [4]
  Zheng J F, Zhang S B. Polyphenylenes and Their Derivatives for Direct Methanol Fuel Cells Applications[J]. Adv Mater Sci Res, 2017,27(5):127-158.
5. [5]
  Park C H, Lee C H, Guiver M D. Sulfonated Hydrocarbon Membranes for Medium-Temperature and Low-Humidity Proton Exchange Membrane Fuel Cells(PEMFCs)[J]. Prog Polym Sci, 2011,36:1443-1498. doi: 10.1016/j.progpolymsci.2011.06.001
6. [6]
  Pang J H, Zhang H B, Li X F. Synthesis and Characterization of Sulfonated Poly(arylene Ether) with Sulfoalkyl Pendant Groups for Proton Exchange Membranes[J]. J Membr Sci, 2008,318:271-279. doi: 10.1016/j.memsci.2008.02.051
7. [7]
  Argun A A, Ashcraft J N, Hammond P T. Highly Conductive, Methanol Resistant PolyelectrolyteMultilayers[J]. Adv Mater, 2008,20:1539-1543. doi: 10.1002/(ISSN)1521-4095
8. [8]
  Xiang Y, Lu S F, Jiang S P. Layer-by-Layer Self-Assembly in the Development of Electrochemical Energy Conversion and Storage Devices from Fuel Cells to Supercapacitors[J]. Chem Soc Rev, 2012,41:7291-7321. doi: 10.1039/c2cs35048c
9. [9]
  Yuan T, Pu L J, Huang Q H. An Effective Methanol-Blocking Membrane Modified with Graphene Oxide Nanosheets for Passive Direct Methanol Fuel Cells[J]. Electrochim Acta, 2014,117:393-397. doi: 10.1016/j.electacta.2013.11.063
10. [10]
  Lee K S, Jeong M H, Lee J P. End-Group Cross-Linked Poly(arylene ether) for Proton Exchange Membranes[J]. Macromolecules, 2009,42:584-590. doi: 10.1021/ma802233j
11. [11]
  Zheng J F, He Q Y, Liu C L. Nafion-Microporous Organic Polymer Networks Composite Membranes[J]. J Membr Sci, 2015,476:571-579. doi: 10.1016/j.memsci.2014.10.057
12. [12]
  Chen Z W, Holmberg B, Li W Z. Nafion/Zeolite Nanocomposite Membrane by In Situ Crystallization for a Direct Methanol Fuel Cell[J]. Chem Mater, 2006,18:5669-5675. doi: 10.1021/cm060841q
13. [13]
  Pandey R P, Thakur A K, Shahi V K. Sulfonated Polyimide/Acid-Functionalized Graphene Oxide Composite Polymer Electrolyte Membranes with Improved Proton Conductivity and Water-Retention Properties[J]. ACS Appl Mater Interfaces, 2014,6:16993-17002. doi: 10.1021/am504597a
14. [14]
  Li N W, Guiver M D. Ion Transport by Nanochannels in Ion-containing Aromatic Copolymers[J]. Macromolecules, 2014,47:2175-2198. doi: 10.1021/ma402254h
15. [15]
  Zhang X, Higashihara T, Ueda M. Polyphenylenes and the Related Copolymer Membranes for Electrochemical Device Applications[J]. Polym Chem, 2014,5:6121-6141. doi: 10.1039/C4PY00898G
16. [16]
  Ghassemi H, McGrath J E. Synthesis and Properties of New Sulfonated Poly(p-phenylene) Derivatives for Proton Exchange Membranes I[J]. Polymer, 2004,45:5847-5854. doi: 10.1016/j.polymer.2004.06.021
17. [17]
  Wu S Q, Qiu Z M, Zhang S B. The Direct Synthesis of Wholly Aromatic Poly(p-phenylene)s Bearing Sulfobenzoyl Side Groups as Proton Exchange Membranes[J]. Polymer, 2006,47:6993-7000. doi: 10.1016/j.polymer.2006.08.017
18. [18]
  Seesukphronrarak S, Ohira K, Kidena K. Synthesis and Properties of Sulfonated Copoly(p-Phenylene)s Containing Aliphatic Alkyl Pendant for Fuel Cell Applications[J]. Polymer, 2010,51:623-631. doi: 10.1016/j.polymer.2009.12.023
19. [19]
  Chen S W, Chen K C, Zhang X. Poly(Sulfonated Phenylene)-Block-Poly(arylene ether sulfone) Copolymer for Polymer Electrolyte Fuel Cell Application[J]. Polymer, 2013,54:236-245. doi: 10.1016/j.polymer.2012.10.058
20. [20]
  He Q Y, Zheng J F, Zhang S B. Preparation and Characterization of High Performance Sulfonated Poly(p-phenylene-co-aryl ether ketone) Membranes for Direct Methanol Fuel Cells[J]. J Power Sources, 2014,260:317-325. doi: 10.1016/j.jpowsour.2014.03.028
21. [21]
  He Q Y, Xu T, Qian H D. Enhanced Proton Conductivity of Sulfonated Poly(p-phenylene-co-aryl ether ketone) Proton Exchange Membranes with Controlled Microblock Structure[J]. J Power Sources, 2015,278:590-598. doi: 10.1016/j.jpowsour.2014.12.135
22. [22]
  Zheng J F, Bi W H, Dong X. High Performance Tetra-sulfonated Poly(p-phenylene-co-aryl ether ketone) Membranes with Microblock Moieties for Passive Direct Methanol Fuel Cells[J]. J Membr Sci, 2016,517:47-56. doi: 10.1016/j.memsci.2016.06.029
23. [23]
  Song Y, Jin Y H, Liang Q J. Novel Sulfonated Polyimides Containing Multiple Cyano Groups for Polymer Electrolyte Membranes[J]. J Power Sources, 2013,238:236-244. doi: 10.1016/j.jpowsour.2013.03.088
24. [24]
  Gao Y, Robertson G P, Guiver M D. Synthesis of Copoly(aryl ether ether nitrile)s Containing Sulfonic Acid Groups for PEM Application[J]. Macromolecules, 2005,38:3237-3245. doi: 10.1021/ma047572e
25. [25]
  Kim D S, Kim Y S, Guiver M D. High Performance Nitrile Copolymers for Polymer Electrolyte Membrane Fuel Cells[J]. J Membr Sci, 2008,321:199-208. doi: 10.1016/j.memsci.2008.04.059
1. [1]
  Xinghai Li , Zhisen Wu , Lijing Zhang , Shengyang Tao . Machine Learning Enables the Prediction of Amide Bond Synthesis Based on Small Datasets. Acta Physico-Chimica Sinica, 2025, 41(2): 100010-. doi: 10.3866/PKU.WHXB202309041
2. [2]
  Hong Wu , Yuxi Wang , Hongyan Feng , Xiaokui Wang , Bangkun Jin , Xuan Lei , Qianghua Wu , Hongchun Li . Application of Computational Chemistry in the Determination of Magnetic Susceptibility of Metal Complexes. University Chemistry, 2025, 40(3): 116-123. doi: 10.12461/PKU.DXHX202405141
3. [3]
  Yiping HUANG , Liqin TANG , Yufan JI , Cheng CHEN , Shuangtao LI , Jingjing HUANG , Xuechao GAO , Xuehong GU . Hollow fiber NaA zeolite membrane for deep dehydration of ethanol solvent by vapor permeation. Chinese Journal of Inorganic Chemistry, 2025, 41(2): 225-234. doi: 10.11862/CJIC.20240224
4. [4]
  Kun Li , Na Gao , Shuangyan Huan , Yuzhi Wang . Design of Ideological and Political Education for the Experiment of Detecting Cadmium with Anodic Stripping Voltammetry. University Chemistry, 2024, 39(2): 155-161. doi: 10.3866/PKU.DXHX202307068
5. [5]
  Yukai Jiang , Yihan Wang , Yunkai Zhang , Yunping Wei , Ying Ma , Na Du . Characterization and Phase Diagram of Surfactant Lyotropic Liquid Crystal. University Chemistry, 2024, 39(4): 114-118. doi: 10.3866/PKU.DXHX202309033
6. [6]
  Yanan Jiang , Yuchen Ma . Brief Discussion on the Electronic Exchange Interaction in Quantum Chemistry Computations. University Chemistry, 2025, 40(3): 10-15. doi: 10.12461/PKU.DXHX202402058
7. [7]
  Lihui Jiang , Wanrong Dong , Hua Yang , Yongqing Xia , Hongjian Peng , Jun Yuan , Xiaoqian Hu , Zihan Zeng , Yingping Zou , Yiming Luo . Study on Extraction of p-Hydroxyacetophenone. University Chemistry, 2024, 39(11): 259-268. doi: 10.12461/PKU.DXHX202402056
8. [8]
  Xinlong WANG , Zhenguo CHENG , Guo WANG , Xiaokuen ZHANG , Yong XIANG , Xinquan WANG . Enhancement of the fragile interface of high voltage LiCoO₂ by surface gradient permeation of trace amounts of Mg/F. Chinese Journal of Inorganic Chemistry, 2024, 40(3): 571-580. doi: 10.11862/CJIC.20230259
9. [9]
  Guangming YIN , Huaiyao WANG , Jianhua ZHENG , Xinyue DONG , Jian LI , Yi'nan SUN , Yiming GAO , Bingbing WANG . Preparation and photocatalytic degradation performance of Ag/protonated g-C₃N₄ nanorod materials. Chinese Journal of Inorganic Chemistry, 2024, 40(8): 1491-1500. doi: 10.11862/CJIC.20240086
10. [10]
  Gaofeng Zeng , Shuyu Liu , Manle Jiang , Yu Wang , Ping Xu , Lei Wang . Micro/Nanorobots for Pollution Detection and Toxic Removal. University Chemistry, 2024, 39(9): 229-234. doi: 10.12461/PKU.DXHX202311055
11. [11]
  Xiao Liu , Guangzhong Cao , Mingli Gao , Hong Wu , Hongyan Feng , Chenxiao Jiang , Tongwen Xu . Seawater Salinity Gradient Energy’s Job Application in the Field of Membranes. University Chemistry, 2024, 39(9): 279-282. doi: 10.3866/PKU.DXHX202306043
12. [12]
  Shuyu Liu , Xiaomin Sun , Bohan Song , Gaofeng Zeng , Bingbing Du , Chongshen Guo , Cong Wang , Lei Wang . Design and Fabrication of Phospholipid-Vesicle-based Artificial Cells towards Biomedical Applications. University Chemistry, 2024, 39(11): 182-188. doi: 10.12461/PKU.DXHX202404113
13. [13]
  Yue Zhao , Yanfei Li , Tao Xiong . Copper Hydride-Catalyzed Nucleophilic Additions of Unsaturated Hydrocarbons to Aldehydes and Ketones. University Chemistry, 2024, 39(4): 280-285. doi: 10.3866/PKU.DXHX202309001
14. [14]
  Liangzhen Hu , Li Ni , Ziyi Liu , Xiaohui Zhang , Bo Qin , Yan Xiong . A Green Chemistry Experiment on Electrochemical Synthesis of Benzophenone. University Chemistry, 2024, 39(6): 350-356. doi: 10.3866/PKU.DXHX202312001
15. [15]
  Guojie Xu , Fang Yu , Yunxia Wang , Meng Sun . Introduction to Metal-Catalyzed β-Carbon Elimination Reaction of Cyclopropenones. University Chemistry, 2024, 39(8): 169-173. doi: 10.3866/PKU.DXHX202401060
16. [16]
  Yinwu Su , Xuanwen Zheng , Jianghui Du , Boda Li , Tao Wang , Zhiyan Huang . Green Synthesis of 1,3-Dibromoacetone Using Halogen Exchange Method: Recommending a Basic Organic Synthesis Teaching Experiment. University Chemistry, 2024, 39(5): 307-314. doi: 10.3866/PKU.DXHX202311092
17. [17]
  Yinuo Wu , Jiantao Ye , Xie Zhou , Yu Qian , Lei Guo . Teaching Design of Basic Chemistry Based on PBL Methodology for Medical Undergraduates: A Case Study on “Osmotic Pressure of Solution”. University Chemistry, 2024, 39(3): 149-157. doi: 10.3866/PKU.DXHX202309077
18. [18]
  Kai CHEN , Fengshun WU , Shun XIAO , Jinbao ZHANG , Lihua ZHU . PtRu/nitrogen-doped carbon for electrocatalytic methanol oxidation and hydrogen evolution by water electrolysis. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1357-1367. doi: 10.11862/CJIC.20230350
19. [19]
  Yongmei Liu , Lisen Sun , Zhen Huang , Tao Tu . Curriculum-Based Ideological and Political Design for the Experiment of Methanol Oxidation to Formaldehyde Catalyzed by Electrolytic Silver. University Chemistry, 2024, 39(2): 67-71. doi: 10.3866/PKU.DXHX202308020
20. [20]
  Ling Liu , Haibin Wang , Genrong Qiang . Curriculum Ideological and Political Design for the Comprehensive Preparation Experiment of Ethyl Benzoate Synthesized from Benzyl Alcohol. University Chemistry, 2024, 39(2): 94-98. doi: 10.3866/PKU.DXHX202304080

Get Citation

PDF

XML

Metrics

PDF Downloads(0)
Abstract views(262)
HTML views(40)

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