交联型季铵聚芳醚砜阴离子交换膜的制备

doi:10.7503/cjcu20150983

摘要/Abstract

摘要：

采用简便环保的方法制备了具有低溶胀、高离子交换容量(IEC)的交联型季铵聚芳醚砜阴离子交换膜. 随着交联度的提高, 膜的吸水率和溶胀率降低, 说明交联可以抑制膜的溶胀. 20 ℃时所有交联膜的离子传导率均达0.045 S/cm以上, 拉伸强度在50.1 MPa以上, 表明在高IEC值下, 交联膜仍具有良好的力学性能和较高的离子传导能力. 同时, 交联度提高会加强膜的甲醇阻隔性能.

关键词: 阴离子交换膜, 燃料电池, 聚芳醚砜, 交联

Abstract:

Cross-linked anion exchange membranes(AEMs) for poly(aryl ether sulfone) bearing pendant quaternary ammonium groups were prepared by a simplified and environmental-friendly approach, which possess low swelling radio and high ion exchange capacity(IEC). The membrane test showed that the water uptake and swelling ratio reduce with increase of cross-linking degree. At 20 ℃, the cross-linking membranes show the ion conductivity above 0.045 S/cm and the tensile strength above 50.1 MPa, which indicates that the cross-linked film still keep good mechanical properties and higher ionic transmission ability under high IEC. Meanwhile, when the cross-linking degree increasing, the methanol barrier property of the membranes will enhance.

Key words: Anion exchange membrane, Fuel cell, Poly(aryl ether sulfone), Cross-linking

中图分类号:

TrendMD:

汪丽梅, 窦立岩, 辛鹏. 交联型季铵聚芳醚砜阴离子交换膜的制备. 高等学校化学学报, 2016, 37(7): 1408.

WANG Limei, DOU Liyan, XIN Peng. Preparation of Cross-linked Poly(aryl ether sulfone) Containing Pendant Quaternary Ammonium Groups for Anion Exchange Membrane^†. Chem. J. Chinese Universities, 2016, 37(7): 1408.

图/表 10

Scheme 1 Synthetic routes of L-PAES-x(x=70, 80, 100)

Scheme 2 Synthetic routes of C-PAES-m/n(m/n=90/10, 80/20, 70/30, 60/40)

Fig.1 1H NMR spectra of TA-PAES-70(a), TA-PAES-80(b) and TA-PAES-100(c) in CDCl3(A) (B) Magnification of the circle in (A).

Fig.2 1H NMR spectrum of QA-PAES-100 in DMSO-d6

Fig.3 1H NMR spectrum of the QA-PAES-90/10 in DMSO-d6

Table 1 Properties of the C-PAES and L-PAES membranes

Sample	IEC/(mmol·g^-1)		Water uptake(%)		Swelling ratio(%)
Sample	Theoretical	Experimental	20 ℃	60 ℃	20 ℃	60 ℃
C-PAES-60/40	3.26	3.20	42	48	17	19
C-PAES-70/30	3.29	3.27	54	63	28	32
C-PAES-80/20	3.31	3.28	78	94	39	45
C-PAES-90/10	3.34	3.31	94	115	53	63
L-PAES-70	2.61	2.60	110	276	62	132
L-PAES-80	2.88	2.82	198		176

Fig.4 Hydroxide conductivity of C-PAES-m/n membranes at 20 ℃

Fig.5 Impact of temperature on conductivity of C-PAES-90/10(a), C-PAES-80/20(b), C-PAES-70/30(c) and C-PAES-60/40(d)

Table 2 Mechanical properties of the C-PAES-m/n and L-PAES-x

Sample	Tensile strength/MPa	Young’s modulus/MPa	Elongation at break(%)	Sample	Tensile strength/MPa	Young’s modulus/MPa	Elongation at break(%)
C-PAES-60/40	64.0	1720	15.9	C-PAES-90/10	50.1	1430	22.3
C-PAES-70/30	60.5	1650	18.7	L-PAES-70	48.5	530	90.9
C-PAES-80/20	56.0	1540	19.8	L-PAES-80	30.3	320	120.2

Fig.6 Methanol diffusion coefficients of cross-linked membranes

参考文献 21

[1]	Varcoe J. R., Slade R. C. T., Fuel Cells,2005, 5, 187—200
[2]	Yu H. M., Yi B. L., Scientia Sinica Chimica,2012, 42, 480—494(俞红梅, 衣宝廉. 中国科学: 化学, 2012,42, 480—494)
[3]	Han K. F., Yand Q. T., Yu S. P., Yu J. H., Zhu H., Wang Z. M., Chem. J. Chinese Universities,2013, 34(10), 2437—2444(韩克飞, 杨起涛, 于书平, 于景华, 朱红, 汪中明. 高等学校化学学报, 2013, 34(10), 2437—2444)
[4]	Du R.K., Gao B. J., Li Y. B., Wang L., Acta Polymerica Sinica, 2010, (7), 924—931(杜瑞奎, 高保娇, 李延斌, 王玲. 高分子学报, 2010, (7), 924—931)
[5]	Wang Q.X., Preparation and Property of Crosslinked Alkaline Anion Exchange Membrane, Dalian University of Technology, Dalian, 2013(王秋熹. 交联型碱性阴离子交换膜的制备及性能. 大连: 大连理工大学, 2013)
[6]	Zhang H. W., Shen P. K., Scientia Sinica Chimica,2012, 7, 954—982(张宏伟, 沈培康. 中国科学: 化学, 2012,7, 954—982)
[7]	Hickner M. A., Ghassemi H., Kim Y. S., Einsla B. R., McGrath J. E., Chem. Rev., 2004, 104, 4587—4593
[8]	Pan J., Chen C., Zhuang L., Lu J. T., Accounts of Chemical Research,2012, 45(3), 473—481
[9]	Wang X., Li M. Q., Golding B. T., Sadeghi M., Cao Y. C., Yu E. H., Scott K., Int. J. Hydrogen Energy,2011, 36(16), 10022—10026
[10]	Antolini E., Journal of Power Sources, 2010, 195, 3431—3450
[11]	Kickelbick G., Prog. Polym. Sci., 2003, 28(1), 83—114
[12]	Lin B., Qiu L., Lu J., Yan F., Chem. Mater., 2010, 22(24), 6718—6725
[13]	Gu S., Cai R., Yan Y. S., Chem. Commun., 2011, 47, 2856—2858
[14]	Wu X. M., He G. H., Gu S., Dong C. X., Yao P. J., Polymer Materials Science and Engineering,2006, 22(4), 28—31(吴雪梅, 贺高红, 顾爽, 董春旭, 姚平经. 高分子材料科学与工程, 2006, 22(4), 28—31)
[15]	Lin X. C., Liu Y. B., Poynton S. D., Ong A. L., Varcoe J. R., Wu L., Li Y. L., Liang X. H., Li Q. H., Xu T. W., J. Power Sources,2013, 233, 259—268
[16]	Zhao C.X., He D., Yue J., Li H., Li Y. T., Acta Polymerica Sinica, 2015, (1), 80—87(赵春霞, 何达, 岳杰, 李辉, 李云涛. 高分子学报, 2015, (1), 80—87)
[17]	Wang L. Z., Hickner M. A., Polymer Chemistry,2014, 5(8), 2928—2935
[18]	Wang J., Wang J. H., Zhang S. B., J. Membr. Sci., 2012, 415, 205—212
[19]	Wang J. H., Zhao Z., Gong F. X., Li S. H., Zhang S. B., Macromolecules,2009, 42, 8711—8717
[20]	Xu T. W., J. Membr. Sci., 2002, 199, 203—210
[21]	Wang L. M., Zhang Q. F., Zhang S. B., Chinese Journal of Polymer Science,2015, 33(9), 1225—1233