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

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

Chen-yi Wang ^1,2,, ,
Yuan-peng Zhou ¹ ,
Chang Xu ¹ ,
Xiao-yan Zhao ^1,2 ,
Jian Li ¹ ,
Qiang Ren ¹

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, wangcy@cczu.edu.cn
Received Date: 9 January 2018
Revised Date: 12 February 2018
Available Online: 13 April 2018

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.
- Sulfonated poly(arylene ether ketone)s,
- Proton exchange membrane,
- Proton conductivity,
- Swelling ratio,
- Chemical oxidative stability
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