RSC Advances
Paper
ratios of proton conductivity per water uptake (vol%) values
were considered, the PTFQSH-XX displays higher values in
comparison to PTAQSH-XX membranes, which shows better
management of water in the enhancement of the proton
conductivity.
References
1 M. A. Hickner, H. Ghassemi, Y. S. Kim, B. R. Einsla and
J. E. McGrath, Chem. Rev., 2004, 104, 4587.
2 H. Zhang and P. K. Shen, Chem. Soc. Rev., 2012, 41, 2382.
3 Y. Chikashige, Y. Chikyu, K. Miyatake and M. Watanabe,
Macromolecules, 2005, 38, 7121.
The Arrhenius plots of the PTFQSH-XX membranes were used
to investigate the temperature dependence of the proton
conductivity (Fig. 11), and the activation energy (E
a
) for the
4 J. K. Lee, W. Li and A. Manthiram, J. Membr. Sci., 2009, 330,
73.
5 C. Wang, N. Li, D. W. Shin, S. Y. Lee, N. R. Kang, Y. M. Lee
and M. D. Guiver, Macromolecules, 2011, 44, 7296.
6 G. Li, C. Zhao, X. Li, D. Qi, C. Liu, F. Bu and H. Na, Polym.
Chem., 2015, 6, 5911.
proton conductivity of the polytriazole membranes was calcu-
30
lated according the procedure reported in literature. The acti-
vation energies of the PTFQSH-XX membranes were found to be
ꢀ
1
in the range of 22.83–16.23 kJ mol , which was close to the
21
reported value of Naon® 117 and other sulfonated polymers.
7
P. Xing, G. P. Robertson, M. D. Guiver, S. D. Mikhailenko and
S. Kaliaguine, Macromolecules, 2004, 37, 7960.
8
P. Xing, G. P. Robertson, M. D. Guiver, S. D. Mikhailenko and
S. Kaliaguine, Polymer, 2005, 46, 3257.
4
. Conclusion
A new series of highly uorinated sulfonated polytriazoles
PTFQSH-XX) with a controlled degree of sulfonation were
9 K. Shao, J. Zhu, C. Zhao, X. Li, Z. Cui, Y. Zhang and W. Xing,
J. Polym. Sci., Part A: Polym. Chem., 2009, 47, 5772.
(
synthesized by azide-alkyne click polymerization. The PTFQSH- 10 M. D. T. Nguyen, H. S. Dang and D. Kim, J. Membr. Sci., 2015,
XX copolymers were converted into exible membranes by
496, 13.
using solution casting method. The structures of the poly- 11 K. Miyatake, H. Zhou, T. Matsuo, H. Uchida and
1
13
triazole copolymers were conrmed by FTIR and H, C, and
M. Watanabe, Macromolecules, 2004, 37, 4961.
1
9
F NMR spectroscopic studies. The ion exchange capacities of 12 K. Yamazaki and H. Kawakami, Macromolecules, 2010, 43,
the copolymers were determined from titrimetry and H NMR
1
7185.
analysis and matched nicely with the monomer feed ratio. The 13 Z. Zhang and T. Xu, J. Mater. Chem. A, 2014, 2, 11583.
use of rigid hexauoroisopropylidene and quadribiphenyl 14 H. Yao, P. Feng, P. Liu, B. Liu, Y. Zhang, S. Guan and Z. Jiang,
moieties in the main chain played major role in realizing good
thermal stability and high mechanical strength. The copoly- 15 S. Kang, C. Zhang, G. Xiao, D. Yan and G. Sun, J. Membr. Sci.,
Polym. Chem., 2015, 6, 2626.
mers showed 10% decomposition temperature in the range of
2009, 334, 91.
ꢁ
267–380 C. The tensile strength of the PTFQSH-XX membranes 16 J. A. Mader and B. C. Benicewicz, Macromolecules, 2010, 43,
were found to be in the range of 42–60 MPa, which was much
6706.
higher than that of Naons®117 (22 MPa) and many other 17 L. Sheng, H. Xu, X. Guo, J. Fang, L. Fang and J. Yin, J. Power
sulfonated copolymers. The membranes from PTFQSH-XX
Sources, 2011, 196, 3039.
copolymers showed lower water uptake, lower swelling and 18 I. I. Ponomarev, M. Y. Zharinova, P. V. Petrovskii and
relatively higher oxidative stability in comparison to the anal-
Z. S. Klemenkova, Dokl. Chem., 2009, 429, 305.
ogous PTAQSH-XX based membranes, which is due to the 19 Y. J. Huang, Y. S. Ye, Y. C. Yen, L. D. Tsai, B. J. Hwang and
higher uorine content in the PTFQSH-XX based copolymers.
F. C. Chang, Int. J. Hydrogen Energy, 2011, 36, 15333.
The presence of highly hydrophobic –CF and pC(CF moie- 20 Y. J. Huang, Y. S. Ye, Y. J. Syu, B. J. Hwang and F. C. Chang, J.
ties in the high DS polymers creates a polarity difference in
Power Sources, 2012, 208, 144.
hydrophilic and hydrophobic segments in the polymer due to 21 A. Singh, R. Mukherjee, S. Banerjee, H. Komber and B. Voit,
which PTFQSH-XX copolymers showed better phase separated
J. Membr. Sci., 2014, 469, 225.
3
3 2
)
ꢀ1
morphology and high proton conductivity (27–136 mS cm at 22 H. C. Kolb, M. G. Finn and K. B. Sharpless, Angew. Chem.,
ꢁ
8
0 C). The PTFQSH-90 is the best in the series considering its
2001, 40, 2004.
overall membrane properties like, oxidative stability (18 h), 23 J. E. Moses and A. D. Moorhouse, Chem. Soc. Rev., 2007, 36,
ꢁ
thermal (10% weight degradation temperature ¼ 280 C) and
1249.
mechanical stability (tensile strength ¼ 49 MPa and young 24 V. V. Rostovtsev, L. G. Green, V. V. Fokin and K. B. Sharpless,
ꢀ1
ꢁ
modulus ¼ 1.93 GPa), proton conductivity (86 mS cm at 80 C)
Angew. Chem., 2002, 114, 2708.
25 R. X. Yao, L. Kong, Z. S. Yin and F. L. Qing, J. Fluorine Chem.,
and dimensional stability.
2008, 129, 1003.
2
6 K. A. Smith, Y. H. Lin, D. B. Dement, J. Strzalka, S. B. Darling,
D. L. Pickel and R. Verduzco, Macromolecules, 2013, 46, 2636.
7 I. Dimitrov, S. Takamuku, K. Jankova, P. Jannasch and
S. Hvilsted, J. Membr. Sci., 2014, 450, 362.
Acknowledgements
2
A. Singh thank to the Council of Scientic and Industrial
Research, New Delhi, India for providing the fellowship to carry 28 W. Wu, Z. Wang, R. Xiao, Z. Xu and Z. Li, Polym. Chem., 2015,
out this work. The authors thank Ms Ch. Harnisch and Dr A.
Lederer (IPF Dresden) for GPC analysis of the polymers.
6, 4396.
13488 | RSC Adv., 2016, 6, 13478–13489
This journal is © The Royal Society of Chemistry 2016