侧链型含氟磺化聚醚砜/磺化聚酰亚胺共混质子交换膜的制备及性能

doi:10.7503/cjcu2010560

高等学校化学学报 ›› 2016, Vol. 37 ›› Issue (4): 793.doi: 10.7503/cjcu2010560

• 高分子化学 • 上一篇

侧链型含氟磺化聚醚砜/磺化聚酰亚胺共混质子交换膜的制备及性能

陶应勇, 张虚略, 胡朝霞(), 张晶晶, 耿慧, 高颖, 袁祖凤, 毕慧平, 陈守文(), 王连军

南京理工大学环境与生物工程学院, 南京 210094

收稿日期:2015-07-17 出版日期:2016-04-10 发布日期:2016-03-16
基金资助:
国家自然科学基金(批准号: 21276128, 21006052)、江苏省自然科学基金(批准号: BK20141398)、教育部博士点基金(批准号: 20123219120009)和中央高校基本科研业务费专项资金(批准号: 30920130121014)资助

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

TAO Yingyong, ZHANG Xulue, HU Zhaoxia^*(), ZHANG Jingjing, GENG Hui, GAO Ying, YUAN Zufeng, BI Huiping, CHEN Shouwen^*, WANG Lianjun

School of Environmental and Biological Engineering, Nanjing University of Science and Technology, Nanjing 210094, China

Received:2015-07-17 Online:2016-04-10 Published:2016-03-16
Contact: HU Zhaoxia,CHEN Shouwen E-mail:huzhaoxia@njust.edu.cn;chensw@njust.edu.cn
Supported by:
† Supported by the National Natural Science Foundation of China(Nos.21276128, 21006052), the Basic Research Program of Jiangsu Province of China(No.BK20141398), the Ph.D.Programs Foundation of Ministry of Education of China(No.20123219120009) and the Fundamental Research Funds for the Central Universities, China(No.30920130121014)

摘要/Abstract

摘要：

制备了一类侧链型含氟磺化聚醚砜(sSPFES)与磺化聚酰亚胺(SPI)共混质子交换膜(sSPFES/SPI), 研究了其吸水率、尺寸变化、质子电导率及稳定性等性能. 结果表明, 2种磺化聚合物以三乙胺盐型溶液共混及铸膜时相容性良好, 制备的sSPFES/SPI共混质子交换膜结构均一, 透明结实, 离子交换容量为1.76~1.88 mmol/g. sSPFES/SPI共混质子交换膜表现出横向低于纵向的各向异性尺寸变化特性, 在60 ℃水中横向尺寸变化率低于10%, 经140 ℃加压水处理24 h后仍能保持较好的机械强度, 质量损失低于6.1%. 当温度高于50 ℃时, 完全水合状态下的sSPFES/SPI共混质子交换膜的质子电导率均达到0.1 S/cm.

关键词: 质子交换膜, 磺化聚醚砜, 磺化聚酰亚胺, 共混, 尺寸变化率

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

中图分类号:

O631

TrendMD:

陶应勇, 张虚略, 胡朝霞, 张晶晶, 耿慧, 高颖, 袁祖凤, 毕慧平, 陈守文, 王连军. 侧链型含氟磺化聚醚砜/磺化聚酰亚胺共混质子交换膜的制备及性能. 高等学校化学学报, 2016, 37(4): 793.

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^†. Chem. J. Chinese Universities, 2016, 37(4): 793.

图/表 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.

参考文献 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

侧链型含氟磺化聚醚砜/磺化聚酰亚胺共混质子交换膜的制备及性能

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

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侧链型含氟磺化聚醚砜/磺化聚酰亚胺共混质子交换膜的制备及性能

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

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