Preparation and Properties of Blend Proton Exchange Membranes Based on Side-chain Type Fluorine-containing Sulfonated Poly(ether sulfone) and Sulfonated Polyimide†

doi:10.7503/cjcu2010560

Abstract

Abstract:

A series of blend membranes from a side-chain type fluorine-containing sulfonated poly(ether sulfone)s(sSPFES) and sulfonated polyimide(SPI) was prepared and characterized. The two sulfonated copolymers showed good compatibility in their trimethylamine salt form, producing uniform, transparent and ductile blend membranes during solution blending and casting processes. The resulting sSPFES/SPI blend membranes with ion exchange capacities in the range of 1.76—1.88 mmol/g showed some property differences in the water uptakes, size changes, proton conductivity and hydrolytic stability with the un-modified ones. Especially, their swelling behavior was considerable effected by the composition with obvious larger size changes in the membrane out-of-plane direction than the in-plane direction, exhibiting size changes no more than 10% in in-plane direction at 60 ℃ in water. The blend membranes could maintain rather good mechanical toughness after aging in water at 140 ℃ for 24 h with mass loss less than 6.1%. For the fully hydrated blend membranes, their proton conductivity all reached 0.1 S/cm at temperature above 50 ℃.

Key words: Proton exchange membrane, Sulfonated poly(ether sulfone), Sulfonated polyimide, Blend, Size change

CLC Number:

O631

TrendMD:

TAO Yingyong, ZHANG Xulue, HU Zhaoxia, ZHANG Jingjing, GENG Hui, GAO Ying, YUAN Zufeng, BI Huiping, CHEN Shouwen, WANG Lianjun. Preparation and Properties of Blend Proton Exchange Membranes Based on Side-chain Type Fluorine-containing Sulfonated Poly(ether sulfone) and Sulfonated Polyimide^†[J]. Chem. J. Chinese Universities, 2016, 37(4): 793.

Figures/Tables 8

Scheme 1 Synthesis routes of sSPFES and structure of SPI copolymers

Fig.1 13C NMR spectra of PFES in CDCl3(a) and sSPFES in DMSO-d6(b)

Fig.2 FTIR spectra of SPI(a), sSPFES70(b) and sSPFES70/SPI(5∶5)(c)

Fig.3 Photograph(A) and SEM images(B, C) of sSPFES60/SPI(5∶5) blend membrane (B) Surface; (C) cross-section

Table 1 Properties of sSPFES/SPI blend membranes

Code	IEC/(mmol·g^-1)		WU^c(%)	λ^d	Δt^e	Δl^f	σ^g/ (mS·cm^-1)	Y_M/GPa	S_M/MPa	E_b(%)	WL^h(%)
Code	Cal.^a		WU^c(%)	λ^d	Δt^e	Δl^f	σ^g/ (mS·cm^-1)	Y_M/GPa	S_M/MPa	E_b(%)	Titr.^b
sSPFES60/SPI(6∶4)	1.63	1.45	44	16.6	8.0	5.1	138	1.26	42	127	0
sSPFES60/SPI(5∶5)	1.67	1.49	45	16.8	8.7	5.7	130	1.22	39	169	0
sSPFES60/SPI(4∶6)	1.71	1.52	48	17.5	9.2	6.4	112	1.35	44	175	0
sSPFES70/SPI(6∶4)	1.73	1.58	57	19.8	10.6	8.1	167	1.23	37	124	6.1
sSPFES70/SPI(5∶5)	1.76	1.56	58	20.6	10.9	7.4	158	1.09	36	175	5.5
sSPFES70/SPI(4∶6)	1.79	1.59	63	20.9	11.3	6.9	143	1.17	49	185	3.8
sSPFES60	1.45	1.31	37	15.4	8.0	10.6	124	1.28	42	10.2	6.7
sSPFES70	1.63	1.54	48	17.4	9.9	12.8	172	1.23	42	9.8	$i$
SPI	1.89	1.78	68	21.8	14.5	5.1	127	1.56	70	216	3.1

Table 1 Properties of sSPFES/SPI blend membranes

Code	IEC/(mmol·g^-1)		WU^c(%)	λ^d	Δt^e	Δl^f	σ^g/ (mS·cm^-1)	Y_M/GPa	S_M/MPa	E_b(%)	WL^h(%)
Code	Cal.^a		WU^c(%)	λ^d	Δt^e	Δl^f	σ^g/ (mS·cm^-1)	Y_M/GPa	S_M/MPa	E_b(%)	Titr.^b
sSPFES60/SPI(6∶4)	1.63	1.45	44	16.6	8.0	5.1	138	1.26	42	127	0
sSPFES60/SPI(5∶5)	1.67	1.49	45	16.8	8.7	5.7	130	1.22	39	169	0
sSPFES60/SPI(4∶6)	1.71	1.52	48	17.5	9.2	6.4	112	1.35	44	175	0
sSPFES70/SPI(6∶4)	1.73	1.58	57	19.8	10.6	8.1	167	1.23	37	124	6.1
sSPFES70/SPI(5∶5)	1.76	1.56	58	20.6	10.9	7.4	158	1.09	36	175	5.5
sSPFES70/SPI(4∶6)	1.79	1.59	63	20.9	11.3	6.9	143	1.17	49	185	3.8
sSPFES60	1.45	1.31	37	15.4	8.0	10.6	124	1.28	42	10.2	6.7
sSPFES70	1.63	1.54	48	17.4	9.9	12.8	172	1.23	42	9.8	$i$
SPI	1.89	1.78	68	21.8	14.5	5.1	127	1.56	70	216	3.1

Fig.4 Water uptake as a function of temperature^a. sSPFES60/SPI(4∶6); b. sSPFES60/SPI(5∶5); c. sSPFES60/SPI(6∶4); d. sSPFES70/SPI(4∶6); e. sSPFES70/SPI(5∶5); f. sSPFES70/SPI(6∶4); g. sSPFES60; h. sSPFES70; i. SPI.

Fig.5 Size change of out-of-plane direction(Δt, A) and in-plane direction(Δl, B) as a function of

Fig.6 Proton conductivity as a function of temperature in water^a. sSPFES60/SPI(4∶6); b. sSPFES60/SPI(5∶5); c. sSPFES60/SPI(6∶4); d. sSPFES70/SPI(4∶6); e. sSPFES70/SPI(5∶5); f. sSPFES70/SPI(6∶4); g. sSPFES60; h. sSPFES70; i. SPI.

References 22

[1]	Hickner M. A., Ghassemi H., Kim Y. S., Einsla B. R., McGrath J. E., Chemical Reviews, 2004, 104(10), 4587—4611
[2]	Casciola M., Alberti G., Sganappa M., Narducci R., Journal of Power Sources, 2006, 162(1), 141—145
[3]	Miyatake K., Chikashige Y., Higuchi E., Watanabe M., Journal of the American Chemical Society, 2007, 129(13), 3879—3887
[4]	Wang F., Hickner M., Kim Y. S., Zawodzinski T. A., McGrath J. E., Journal of Membrane Science, 2002, 197(1/2), 231—242
[5]	Zhang Z. P., Wang Y., Zhang J. J., Zhang X. F., Pang J. H., Jiang Z. H., Chem. J. Chinese Universities, 2014, 35(6), 1343—1347
	(张振鹏, 王岩, 张静静, 张晓菲, 庞金辉, 姜振华. 高等学校化学学报, 2014, 35(6), 1343—1347)
[6]	Yin Y., Yamada O., Tanaka K., Okamoto K., Polymer Journal, 2006, 38(3), 197—219
[7]	Park C. H., Lee C. H., Guiver M. D., Lee Y. M., Progress in Polymer Science, 2011, 36(11), 1443—1498
[8]	Bi H. P., Wang J. L., Chen S. W., Hu Z. X., Gao Z. L., Wang L. J., Okamoto K., Journal of Membrane Science, 2010, 350(1/2), 109—116
[9]	Bi H.P., Wang J. L., Chen S. W., Hu Z. X., Gao Z. L., Zhang X., Wang L. J., Okamoto K.,Acta Polymerica Sinica, 2010, (8), 966—972
	(毕慧平, 王佳力, 陈守文, 胡朝霞, 高智琳, 张轩, 王连军, 冈本健一. 高分子学报, 2010, (8), 966—972)
[10]	Chen Y., Guo R., Lee C. H., Lee M., McGrath J. E., International Journal of Hydrogen Energy, 2012, 37(7), 6132—6139
[11]	Feng S., Shang Y., Wang S., Xie X., Wang Y., Wang Y., Xu J., Journal of Membrane Science, 2010, 346(1), 105—112
[12]	Tripathi B. P., Shahi V. K., Progress in Polymer Science, 2011, 36(7), 945—979
[13]	Tao Y. Y., Gao Z. L., Bi H. P., Hu Z. X., Chen S. W., Wang L. J., Journal of Nanjing University of Science and Technology, 2011, 35(6), 869—873
	(陶应勇, 高智琳, 毕慧平, 胡朝霞, 陈守文, 王连军. 南京理工大学学报, 2011, 35(6), 869—873)
[14]	Kim D. J., Lee H. J., Nam S. Y., International Journal of Hydrogen Energy, 2014, 39(30), 17524—17532
[15]	Li N., Hwang D. S., Lee S. Y., Liu Y. L., Lee Y. M., Guiver M. D., Macromolecules, 2011, 44(12), 4901—4910
[16]	Li X. F., Paoloni F. P. V., Weiber E. A., Jiang Z. H., Jannasch P., Macromolecules, 2012, 45(3), 1447—1459
[17]	Zhang Q., Liu B., Hu W., Xu W., Jiang A., Xing W., Guiver M. D., Journal of Membrane Science, 2013, 428, 629—638
[18]	Chen K. C., Bai W. X., Zhao Z. P., Liu W. F., Yang Z., Chem. J. Chinese Universities, 2015, 36(4), 781—787
	(陈康成, 白文馨, 赵之平, 刘文芳, 杨智. 高等学校化学学报, 2015, 36(4), 781—787)
[19]	Lafitte B., Puchner M., Jannasch P., Macromolecular Rapid Communications, 2005, 26, 1464—1468
[20]	Watari T., Fang J. H., Tanaka K., Kita H., Okamoto K., Hirano T., Journal of Membrane Science, 2004, 230(1/2), 111—120
[21]	Liu J., He J.S., Chen S. J.,Acta Polymerica Sinica, 1998, (3), 276—281
	(刘杰, 何嘉松, 陈士娟. 高分子学报, 1998, (3), 276—281)
[22]	Sutou Y., Yin Y., Hu Z., Chen S., Kita H., Okamoto K., Journal of Membrane Science, 2011, 375(1/2), 204—211