Chem. J. Chinese Universities ›› 2014, Vol. 35 ›› Issue (2): 433.doi: 10.7503/cjcu20130605
• Polymer Chemistry • Previous Articles Next Articles
GONG Feixiang*(), QI Yonghong, XUE Qunxiang
Received:
2013-07-01
Online:
2014-02-10
Published:
2013-09-02
Contact:
GONG Feixiang
E-mail:gong_fx@163.com
CLC Number:
TrendMD:
GONG Feixiang, QI Yonghong, XUE Qunxiang. Synthesis and Properties of Fluorinated Poly(arylene ether sulfone)s with Sulfonated Pentiptycene Pendants as Proton Exchange Membranes†[J]. Chem. J. Chinese Universities, 2014, 35(2): 433.
Polymer | n(PPD)/ mmol | n(6F-BPA)/ mmol | n(TFDPS) or n(DFBP)/ mmol | 10-4 Mn | PDI | (dL·g-1) | (dL·g-1) |
---|---|---|---|---|---|---|---|
PES-30-PPD(4F) | 1.5 | 3.5 | 5 | 6.5 | 2.1 | 0.42 | 0.59 |
PES-35-PPD(4F) | 1.75 | 3.25 | 5 | 6.8 | 2.2 | 0.45 | 0.65 |
PES-32-PPD(10F) | 1.6 | 3.4 | 5 | 7.3 | 2.5 | 0.51 | 0.73 |
PES-36-PPD(10F) | 1.8 | 3.2 | 5 | 7.5 | 2.3 | 0.52 | 0.75 |
Table 1 Physical properties of PES-x-PPD copolymers
Polymer | n(PPD)/ mmol | n(6F-BPA)/ mmol | n(TFDPS) or n(DFBP)/ mmol | 10-4 Mn | PDI | (dL·g-1) | (dL·g-1) |
---|---|---|---|---|---|---|---|
PES-30-PPD(4F) | 1.5 | 3.5 | 5 | 6.5 | 2.1 | 0.42 | 0.59 |
PES-35-PPD(4F) | 1.75 | 3.25 | 5 | 6.8 | 2.2 | 0.45 | 0.65 |
PES-32-PPD(10F) | 1.6 | 3.4 | 5 | 7.3 | 2.5 | 0.51 | 0.73 |
PES-36-PPD(10F) | 1.8 | 3.2 | 5 | 7.5 | 2.3 | 0.52 | 0.75 |
Polymer | IEC/(mmol·g-1) | σmax/MPa(r.t., 60%RH) | ε(%) | E/GPa | ||
---|---|---|---|---|---|---|
Calcd. | 1H NMR | Titration | ||||
SPES-30-PPD(4F) | 1.66 | 1.65 | 1.66 | 46.2 | 7.8 | 1.145 |
SPES-35-PPD(4F) | 1.88 | 1.85 | 1.87 | 42.5 | 14 | 0.916 |
SPES-32-PPD(10F) | 1.65 | 1.65 | 1.65 | 44.7 | 13 | 0.989 |
SPES-36-PPD(10F) | 1.82 | 1.79 | 1.81 | 37.7 | 28 | 0.710 |
Table 2 IEC and mechanical properties of SPES-x-PPD(10F) and SPES-x-PPD(4F) membranes
Polymer | IEC/(mmol·g-1) | σmax/MPa(r.t., 60%RH) | ε(%) | E/GPa | ||
---|---|---|---|---|---|---|
Calcd. | 1H NMR | Titration | ||||
SPES-30-PPD(4F) | 1.66 | 1.65 | 1.66 | 46.2 | 7.8 | 1.145 |
SPES-35-PPD(4F) | 1.88 | 1.85 | 1.87 | 42.5 | 14 | 0.916 |
SPES-32-PPD(10F) | 1.65 | 1.65 | 1.65 | 44.7 | 13 | 0.989 |
SPES-36-PPD(10F) | 1.82 | 1.79 | 1.81 | 37.7 | 28 | 0.710 |
Polymer | IEC/(mmol·g-1) | WU(%)(80 ℃) | Swelling ratio(%) | ||
---|---|---|---|---|---|
34%RH | 94%RH | Δl(20 ℃) | Δt(80 ℃) | ||
SPES-30-PPD(4F) | 1.66 | 7.9 | 17.6 | 3.5 | 7.3 |
SPES-35-PPD(4F) | 1.88 | 9.8 | 29.9 | 6.3 | 11.6 |
SPES-32-PPD(10F) | 1.65 | 6.7 | 13.9 | 3.1 | 6.5 |
SPES-36-PPD(10F) | 1.82 | 8.5 | 25.2 | 5.6 | 10.4 |
SPES-25-PPD[ | 1.67 | 9.3 | 31.8 | 11.8 | 15.6 |
SPES-30-PPD[ | 1.92 | 10.9 | 39.3 | 13.7 | 18.8 |
Nafion 117 | 0.91 | 6.6 | 11.6 |
Table 3 Water uptake(WU) and swelling ratio of SPES-x-PPD(10F) and SPES-x-PPD(4F) copolymers
Polymer | IEC/(mmol·g-1) | WU(%)(80 ℃) | Swelling ratio(%) | ||
---|---|---|---|---|---|
34%RH | 94%RH | Δl(20 ℃) | Δt(80 ℃) | ||
SPES-30-PPD(4F) | 1.66 | 7.9 | 17.6 | 3.5 | 7.3 |
SPES-35-PPD(4F) | 1.88 | 9.8 | 29.9 | 6.3 | 11.6 |
SPES-32-PPD(10F) | 1.65 | 6.7 | 13.9 | 3.1 | 6.5 |
SPES-36-PPD(10F) | 1.82 | 8.5 | 25.2 | 5.6 | 10.4 |
SPES-25-PPD[ | 1.67 | 9.3 | 31.8 | 11.8 | 15.6 |
SPES-30-PPD[ | 1.92 | 10.9 | 39.3 | 13.7 | 18.8 |
Nafion 117 | 0.91 | 6.6 | 11.6 |
Polymer | IEC/(mmol·g-1) | WU(%)(80 ℃) | σ/(S·cm-1)(80 ℃) | ||
---|---|---|---|---|---|
34%RH | 94%RH | 34%RH | 94%RH | ||
SPES-30-PPD(4F) | 1.66 | 7.9 | 17.6 | 8.56×104 | 0.173 |
SPES-35-PPD(4F) | 1.88 | 9.8 | 29.9 | 1.46×103 | 0.191 |
SPES-32-PPD(10F) | 1.65 | 6.7 | 13.9 | 1.21×103 | 0.181 |
SPES-36-PPD(10F) | 1.82 | 8.5 | 25.2 | 2.25×103 | 0.213 |
Nafion 117 | 6.6 | 11.6 | 3.0×103 | 0.110 |
Table 4 Water uptake(WU) and conductivity of SPES-x-PPD(10F), SPES-x-PPD(4F) and Nafion 117 membranes
Polymer | IEC/(mmol·g-1) | WU(%)(80 ℃) | σ/(S·cm-1)(80 ℃) | ||
---|---|---|---|---|---|
34%RH | 94%RH | 34%RH | 94%RH | ||
SPES-30-PPD(4F) | 1.66 | 7.9 | 17.6 | 8.56×104 | 0.173 |
SPES-35-PPD(4F) | 1.88 | 9.8 | 29.9 | 1.46×103 | 0.191 |
SPES-32-PPD(10F) | 1.65 | 6.7 | 13.9 | 1.21×103 | 0.181 |
SPES-36-PPD(10F) | 1.82 | 8.5 | 25.2 | 2.25×103 | 0.213 |
Nafion 117 | 6.6 | 11.6 | 3.0×103 | 0.110 |
Fig.3 Humidity dependence of the proton conductivity of Nafion 117(a), SPES-36-PPD(10F)(b), SPES-35-PPD(4F)(c), SPES-32-PPD(10F)(d), and SPES-30-PPD(4F)(e) membranes at 80 ℃
Fig.4 TEM images of SPES-30-PPD(4F)(IEC=1.66 mmol/g)(A), SPES-32-PPD(10F)(IEC=1.65 mmol/g)(B), SPES-35-PPD(4F)(IEC=1.88 mmol/g)(C) and SPES-36-PPD(10F)(IEC=1.82 mmol/g)(D)
Polymer | IEC/(mmol·g-1) | Oxidative stabilitya | |
---|---|---|---|
Decrease in mass(%) | Decrease in ηinh(%) | ||
SPES-30-PPD(4F) | 1.66 | 0a; 7b | 2 |
SPES-35-PPD(4F) | 1.88 | 2a; 18b | 7 |
SPES-32-PPD(10F) | 1.65 | 0a; 0b | 1 |
SPES-36-PPD(10F) | 1.82 | 1a; 10c | 5 |
Nafion 117 | 0.91 | 0a; 0b |
Table 5 Oxidative stability results of SPES-x-PPD(10F) and SPES-x-PPD(4F) membranes
Polymer | IEC/(mmol·g-1) | Oxidative stabilitya | |
---|---|---|---|
Decrease in mass(%) | Decrease in ηinh(%) | ||
SPES-30-PPD(4F) | 1.66 | 0a; 7b | 2 |
SPES-35-PPD(4F) | 1.88 | 2a; 18b | 7 |
SPES-32-PPD(10F) | 1.65 | 0a; 0b | 1 |
SPES-36-PPD(10F) | 1.82 | 1a; 10c | 5 |
Nafion 117 | 0.91 | 0a; 0b |
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