苯乙烯磺酰氯的理论模拟及用于辐照接枝法制备质子交换膜

doi:10.11949/j.issn.0438-1157.20160710

化工学报 ›› 2016, Vol. 67 ›› Issue (S1): 390-395.DOI: 10.11949/j.issn.0438-1157.20160710

• 材料化学工程与纳米技术 • 上一篇下一篇

苯乙烯磺酰氯的理论模拟及用于辐照接枝法制备质子交换膜

李雪¹, 赵阳¹, 高金津², 李微微¹, 王树博¹, 谢晓峰¹

1 清华大学核能与新能源技术研究院, 北京 100084;
2 燕山大学材料科学与工程学院, 河北秦皇岛 066004

收稿日期:2016-05-24 修回日期:2016-06-02 出版日期:2016-08-31 发布日期:2016-08-31
通讯作者: 谢晓峰,xiexf@tsinghua.edu.cn
基金资助:
国家高技术研究发展计划项目（2012AA051201）。

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 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).

摘要/Abstract

摘要：

合成了用于辐照接枝制备质子交换膜的对苯乙烯磺酰氯单体，并采用红外光谱（FTIR）、核磁共振氢谱（¹H NMR）和核磁共振碳谱（¹³C NMR）对其结构进行了表征分析，分析结果表明：成功得到了目标产物对苯乙烯磺酰氯。基于密度泛函的量子化学方法对合成的单体进行了理论模拟，结果表明该单体具有与苯乙烯一致的电荷分布，乙烯基α碳位易发生亲电反应，β碳位易发生亲核反应和自由基反应。采用辐射接枝聚合的方法，将对苯乙烯磺酰氯单体接枝到聚全氟乙丙烯薄膜基材上并通过后处理制备用于燃料电池的质子交换膜，结果表明膜的质子传导率与接枝率正相关，在20 Gy·min^-1和40 Gy·min^-1条件下膜的室温质子传导率分别为45.74 mS·cm^-1和47.46 mS·cm^-1，20 Gy·min^-1条件下制备的质子交换膜其传导率在75℃时可达84.56 mS·cm^-1。

关键词: 对苯乙烯磺酰氯, 量子化学, fukui函数, 质子交换膜, 接枝率

Abstract:

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

中图分类号:

TM911.4

李雪, 赵阳, 高金津, 李微微, 王树博, 谢晓峰. 苯乙烯磺酰氯的理论模拟及用于辐照接枝法制备质子交换膜[J]. 化工学报, 2016, 67(S1): 390-395.

LI Xue, ZHAO Yang, GAO Jinjin, LI Weiwei, WANG Shubo, XIE Xiaofeng. Synthesis, characterization, simulation of 4-styrenesulfonyl chloride and its application in preparation of proton exchange membrane through radiation induced grafting[J]. CIESC Journal, 2016, 67(S1): 390-395.

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苯乙烯磺酰氯的理论模拟及用于辐照接枝法制备质子交换膜

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

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