Effect of Side Chain Structure on Properties of Side Chain-style Sulfonated Poly(arylene ether)†

doi:10.7503/cjcu20131222

Abstract

Abstract:

Three kinds of sulfonated poly(arylene ether)(SPAE) with the same backbone and different side chains were prepared from the new difluoride monomer and other commercial monomers by nucleophilic substitution reaction. The relationship between structures and properties of these polymers were investigated. As a result, sulfonated polymers with flexibility aliphatic side chains exhibited high proton conductivity and low swelling ratio than that with aromatic ones at the same IEC level. Because the sulfonic acid groups located at the end of aliphatic side chain have better motility than located aromatic ones, which helps for aggregation of sulfonic acid and forming ionic clusters in the membranes. The microphase-separation morphology of the three polymers were analized by SAXS, The results indicate that polymers with more flexible side chains(SPAE-Ⅲ) have large phase separation size. Combined proton conductivity and water swelling data, SPAE-Ⅲ membranes are the most suitable one for proton exchange membrane application.

Key words: Sulfonated poly(arylene ether), Proton exchange membrane, Fuel cell

CLC Number:

O631

TrendMD:

ZHANG Zhenpeng, WANG Yan, ZHANG Jingjing, ZHANG Xiaofei, PANG Jinhui, JIANG Zhenhua. Effect of Side Chain Structure on Properties of Side Chain-style Sulfonated Poly(arylene ether)^†[J]. Chem. J. Chinese Universities, 2014, 35(6): 1343.

Figures/Tables 6

Scheme 1 Syntheses of difluoride monomers Ⅰ, Ⅱ and Ⅲ

Scheme 2 Syntheses of sulfonated poly(arylene ether sulfone) copolymer SPAE-Ⅰx, SPAE-Ⅱx, SPAE-Ⅲx

Table 1 IEC and proton conductivity(σ, at 80 ℃) of the fum of polymer

Polymer	IEC/(mmol·g^-1)					σ/(mS·cm^-1)
Polymer	x=50	x=60	x=70	x=80	x=90	x=50	x=60	x=70	x=80	x=90
SPAE-Ⅰx	0.96	1.22	1.36	1.50	1.61	0.9	3.7	13.1	35.2	54.8
SPAE-Ⅱx	1.09	1.28	1.47	1.65		6.0	36.0	66.0	91.0
SPAE-Ⅲx	1.07	1.26	1.43	1.60		7.4	31.2	68.9	99.4

Fig.1 Relationship between water swelling ratio and IEC of SPAE-Ⅰ(a), SPAE-Ⅱ(b) and SPAE-Ⅲ(c) at 20 ℃(A), 80 ℃(B) and 100 ℃(C)

Fig.2 Relationship between proton conductivity and IEC of SPAE-Ⅰ(a), SPAE-Ⅱ(b) and SPAE-Ⅲ(c) at 20 ℃(A), 80 ℃(B) and 100 ℃(C)

Fig.3 SAXS profiles of polymer

References 12

[1]	Hickner M. A., Ghassemi H., Kim Y. S., Einsla B. R., McGrath J. E., Chem. Rev., 2004, 104(10), 4587—4612
[2]	Xu J. M., Cheng H. L., Ma L., Bai H. W., Ren C. L., Zhang H. X., Wang Z., Chem. J. Chinese Universities, 2013, 34(7), 1776—1781
	(徐晶美, 程海龙, 马丽, 白洪伟, 任春丽, 张会轩, 王哲.高等学校化学学报, 2013,34(7), 1776—1781)
[3]	Li X. F., Guo M. M., Liu B. J., Jiang Z. H., Chem. J. Chinese Universities, 2011, 32(5), 1022—1024
	(李雪峰, 郭梅梅, 刘佰军, 姜振华.高等学校化学学报, 2011,32(5), 1022—1024)
[4]	Bae B., Hoshi T., Miyatake K., Watanabe M., Macromolecules, 2011, 44(10), 3884—3892
[5]	Tang W. F., Ling Y., Chen S. S., Hu Z. X., Chen S. W., Chem. J. Chinese Universities, 2013, 34(11), 2661—2666
	(唐卫芬, 凌瑛, 陈珊珊, 胡朝霞, 陈守文.高等学校化学学报, 2013,34(11), 2661—2666)
[6]	Kobayashi T., Rikukawa M., Sanui K., Solid State Ionics, 1998, 106(314), 219—225
[7]	Miyatake K., Chikashige Y., Higuchi E., Watanabe M., J. Am. Chem. Soc., 2007, 129(13), 3879—3887
[8]	Zhang H. W., Shen P. K., Chem. Rev., 2012, 112(5), 2708—2832
[9]	Pang J. H., Zhang H. B., Li X. F., Liu B. J., Jiang Z. H., J. Power Sources, 2008, 184(1), 1—8
[10]	Pang J. H., Zhang H. B., Li X. F., Wang L. F., Liu B. J., Jiang Z. H., J. Memb. Sci., 2008, 318(1/2), 271—279
[11]	Pang J.H., Synthesis and Properties of Sulfonated Poly(arylene ether)s with Sulfonic Acid Groups on Pendant, Jilin University, Changchun, 2009
	(庞金辉. 侧链型磺化聚芳醚质子交换膜材料的制备及其性能研究, 长春: 吉林大学, 2009)
[12]	Pang J. H., Zhang H. B., Li X. F., Jiang Z. H., Macromolecules, 2007, 40(26), 9435—9442

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