CIESC Journal ›› 2016, Vol. 67 ›› Issue (S1): 390-395.doi: 10.11949/j.issn.0438-1157.20160710

Previous Articles     Next Articles

Synthesis, characterization, simulation of 4-styrenesulfonyl chloride and its application in preparation of proton exchange membrane through radiation induced grafting

LI Xue1, ZHAO Yang1, GAO Jinjin2, LI Weiwei1, WANG Shubo1, XIE Xiaofeng1   

  1. 1 Institute of Nuclear and New Energy Technology, Tsinghua University, Beijing 100084, China;
    2 College of Materials Science and Engineering, Yanshan University, Qinhuangdao 066004, Hebei, China
  • Received:2016-05-24 Revised:2016-06-02 Online:2016-08-31 Published:2016-08-31
  • Supported by:

    supported by the National High Technology Research and Development Program of China (2012AA051201).


4-Styrenesulfonyl chloride was synthesized successfully and characterized by FTIR,1H NMR and 13C NMR spectra. Quantum chemistry calculation based on density functional theory was carried out for this synthesized monomer, and the Mulliken population analysis showed that 4-styrenesulfonyl chloride possess comparative charge distribution to styrene, which is commonly used as graft monomer in the preparation of proton exchange membrane, indicating that 4-styrenesulfonyl chloride is possible to be used as graft monomer. Fukui function of 4-styrenesulfonyl chloride declared that the alpha carbon of the vinyl is susceptible to electrophilic attack while the beta carbon showed higher reactivity with respect to nucleophilic and radical attack. Radiation induced graft polymerization of 4-styrenesulfonyl chloride on to FEP film was taken under 60Co gamma rays. After hydrolysis with KOH, H2SO4 solution and rinsing by deionized water to neutral, the membrane turned into proton conductive. The conductivities of these membrane are in accordance with the graft yield and increase with temperature. Conductivity of the membrane with does rate of 20 Gy·min-1 reached 84.56 m S·cm-1 at 348 K.

Key words: 4-styrenesulfonyl chloride, quantum chemistry, fukui function, proton exchange membrane, graft yield

CLC Number: 

  • TM911.4
[1] APPLEBY A J, YEAGER E S. A Special Issue on ‘Assessment of Research Needs for Advanced Fuel Cells’ (edited by S. S. Penner)[M]. New York:Pergamon Press, 1986:137.
[2] MAURITZ K A, MOORE, R B. State of understanding of Nafion[J]. Chemical Reviews, 2004, 104:4535-4586.
[3] WANG Y, CHEN K S, MISHLER J, et al. A review of polymer electrolyte membrane fuel cells:technology, applications, and needs on fundamental research[J]. Applied Energy, 2011, 88:981-1007.
[4] CHEN J, ASANO M, YAMAKI T, et al. Preparation and characterization of chemically stable polymer electrolyte membranes by radiation-induced graft copolymerization of four monomers into ETFE films[J]. Journal of Membrane Science, 2006, 269:194-204.
[5] FEI G, SHIN J, KANG S A, et al. Preparation and characterization of a poly(vinylbenzyl sulfonic acid)-grafted FEP membrane[J]. Journal of Polymer Science Part A:Polymer Chemistry, 2010, 48:563-569.
[6] HASEGAWA S, SUZUKI Y, MAEKAWA Y. Preparation of poly(ether ether ketone)-based polymer electrolytes for fuel cell membranes using grafting technique[J]. Radiation Physics and Chemistry, 2008, 77:617-621.
[7] PARK J, TAKAYAMA T, ASANO M, et al. Graft-type polymer electrolyte membranes for fuel cells prepared through radiation-induced graft polymerization into alicyclic polybenzimidazoles[J]. Polymer, 2013, 54:4570-4577.
[8] BHATTACHARYA A, MISRA B. Grafting:a versatile means to modify polymers:techniques, factors and applications[J]. Progress in Polymer Science, 2004, 29:767-814.
[9] KABANOV V Y. Preparation of polymer membranes for fuel cells by radiation graft polymerization[J]. High Energy Chemistry, 2004, 38:57-65.
[10] KAMOGAWA H, KANZAWA A, KADOYA M, et al. Conversion of carbonyl compounds via their sulfonylhy-drazones into alkenes, alkanes and nitriles[J]. Bulletin of the Chemical Society of Japan, 1983, 56(3):762-765.
[11] 赵永彬, 石艳, 魏杰, 等. 对乙烯基苯磺酰氯与苯乙烯的原子转移自由基共聚制备支化聚苯乙烯[J]. 北京化工大学学报, 2003, 30(4):60-64. ZHAO Y B, SHI Y, WEI J, et al. Synthesis of highly branched polystyrene via atom transfer radical polymerization with p-styrenesulfonyl chloride as an initiator[J]. Journal of Beijing University of Chemical Technology, 2003, 30(4):60-64.
[12] 赵永彬.自缩合原子转移自由基共聚合制备支化聚苯乙烯[D]. 北京:北京化工大学, 2003. ZHAO Y B. Synthesis of branched polystyrene by self-condensing atom transfer radial copolymerization[D]. Beijing:Beijing University of Chemical Technology, 2003.
[13] 冯锋, 刘育坚, 汤令, 等. 中间体对乙烯基苯磺酰氯的合成研究[J]. 化学世界, 2015, (9):551-553. FENG F, LIU Y J, TANG L, et al. Synthesis of p-vinylbenzenesulfonyl chloride intermediate[J]. World of Chemistry, 2015, (9):551-553.
[14] DELLEY B. An all-electron numerical method for solving the local density functional for polyatomic molecules[J]. Journal of Chemical Physics, 1990, 92(92):508-517.
[15] DELLEY B. From molecules to solids with the Dmol3 approach[J]. Journal of Chemical Physics, 2000, 113(18):7756-7764.
[16] PARR R G, YANG W. Density-Functional Theory of Atoms and Molecules[M]. New York:Oxford University Press, 1989.
[1] Jiawang YONG, Qianqian ZHAO, Nenglian FENG. Fault diagnosis of proton exchange membrane fuel cell based on nonlinear dynamic model [J]. CIESC Journal, 2022, 73(9): 3983-3993.
[2] LI Hui, YANG Zhengjin, XU Tongwen. Research progress of high temperature proton exchange membranes [J]. CIESC Journal, 2021, 72(1): 132-142.
[3] LIU Lin, REN Zhengbo, SU Hongyu, ZHANG Qian, QIAN Jianhua. Inhibition behavior of self-assembled films of Schiff bases for copper [J]. CIESC Journal, 2018, 69(10): 4324-4334.
[4] FENG Zhiming, LI Weiwei, LI Xue, ZHAO Yang, XIE Xiaofeng, CHAI Chunpeng, LUO Yunjun. Molecular dynamics simulation on effect of different carboxylic acid group contents on norbornene derivatives proton exchange membranes bearing bifunctional groups [J]. CIESC Journal, 2016, 67(S1): 253-259.
[5] GAO Jinjin, LI Xue, ZHAO Yubin, LI Weiwei, ZHAO Yang, WANG Shubo, XIE Xiaofeng, ZHANG Zhenlin. Preparation of proton exchange membrane by radiation-induced grafting of PVDF film [J]. CIESC Journal, 2016, 67(S1): 384-389.
[6] FENG Zhiming, ZHAO Yang, LI Xue, XIE Xiaofeng, CHAI Chunpeng, LUO Yunjun. Synthesis and characterization of a novel norbornene based copolymer [J]. CIESC Journal, 2015, 66(S2): 439-444.
[7] FEI Zhejun, JUNG Minsuk, ZHANG Xuefei, WANG Shubo, XIE Xiaofeng, YUN Sukhwan, HUANG Haiyan. Properties of fluorinated poly fluorene ether oxadiazole proton exchange membrane [J]. CIESC Journal, 2015, 66(S2): 445-449.
[8] WANG Lisha, LAI Aonan, ZHUO Yizhi, ZHANG Qiugen, ZHU Aimei, LIU Qinglin. Properties of hybrid SPEK-C/GO composite proton exchange membranes [J]. CIESC Journal, 2015, 66(9): 3605-3610.
[9] PENG Yuejin, PENG Yun, LI Lun, LIU Zhixiang, CHEN Weirong. Shutdown process and shutdown strategy of PEMFC power system [J]. CIESC Journal, 2015, 66(3): 1178-1184.
[10] SHEN Jun, ZHOU Bing, QIU Zizhao, TU Zhengkai, LIU Zhichun, LIU Wei. Mass transfer enhancement of proton exchange membrane fuel cell [J]. CIESC Journal, 2014, 65(S1): 421-425.
[11] LI Ying, ZHOU Qinwen, ZHANG Xiangping. Numerical analysis of steady state self-humidification performance of PEMFC [J]. CIESC Journal, 2014, 65(5): 1893-1899.
[12] QU Shuguo1,LIU Xin2,GAI Hengjun1,LI Jianlong1. Research progress of electro-osmotic drag coefficient of proton exchange membranes for fuel cells [J]. Chemical Industry and Engineering Progree, 2014, 33(04): 861-865.
[13] CAI Guangxu1,2,GUO Jianwei2,WANG Jia1. Application of electrochemical impedance spectroscopy to study of proton exchange membrane fuel cell [J]. Chemical Industry and Engineering Progree, 2014, 33(01): 56-63.
[14] GAO Zhengyang, ZHOU Liming, YU Hang, YIN Libao, CHEN Chuanmin. Reactivity between mercury and bromine compounds by quantum chemistry calculation [J]. CIESC Journal, 2013, 64(9): 3235-3240.
[15] WU Gang, HAO Ningmei, CHEN Yinjuan, MI Siqi, JIA Xiaolin, HU Songqing. Synthesis of new oleic imidazoline corrosion inhibitors and evaluation of their performance [J]. CIESC Journal, 2013, 64(4): 1485-1492.
Full text



No Suggested Reading articles found!