Preparation and properties of sulfonated poly(vinyl alcohol)/sulfonated poly(aryl ether ketone) copolymer with pendant crosslinked structure composite membranes
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摘要: 磺化芳香类聚合物质子交换膜(PEM)为了达到较好的质子传导性能就必需具有较高的磺化度，然而较高的磺化度就会增加PEM的溶胀率、降低PEM的尺寸稳定性及增加PEM的甲醇渗透率等一系列问题。为此，通过直接缩聚的方法合成了含有羧基的聚芳醚酮共聚物(PAEK-x)，利用刚果红作为交联剂并引入磺酸基团，与磺化聚乙烯醇(SPVA)复合制备磺化聚乙烯醇/磺化聚芳醚酮交联复合膜(Cr-SPAEK-x)，通过红外光谱对交联复合膜进行了表征。对膜的性能测试发现，该系列交联复合膜表现出了良好的热性能、力学性能、氧化稳定性和适度的吸水性。交联结构形成于PAEK-x的羧基与刚果红的氨基及SPVA的羟基之间，不消耗膜中的传导基团磺酸基，因此该系列交联复合膜表现出了较高的质子传导率，酚酞啉(PPL)摩尔含量为100mol%的磺化聚乙烯醇/磺化聚芳醚酮交联复合膜Cr-SPAEK-100在25℃和80℃分别达到了0.053 S·cm−1和0.109 S·cm−1。交联网络结构的形成，抑制了膜的水溶胀性，提高了膜的尺寸稳定性，即使是吸水率最高的Cr-SPAEK-100膜的溶胀率室温下也只有5.26%，同时由于致密的交联网络结构的形成及具有高阻醇性能的SPVA的引入，有效地降低了该系列交联复合膜的甲醇渗透系数，最高也只有3.92×10−7 cm2·s−1，可见该系列交联复合膜有望在直接甲醇燃料电池中得到应用。
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关键词:
- 侧链交联型磺化聚芳醚酮 /
- 磺化聚乙烯醇 /
- 交联复合质子交换膜 /
- 尺寸稳定性 /
- 阻醇性能
Abstract: A high degree of sulfonation is necessary for sulfonated aromatic polymer proton exchange membranes to achieve high proton conductivity. Nevertheless, an elevated sulfonation level will give rise to a range of complications, including heightened swelling ratio, reduced dimensional stability, and greater methanol permeability. To address this challenge, the poly(aryl ether ketone) containing carboxyl group (PAEK-x) was synthesized using the direct condensation method. Subsequently, the sulfonated poly(vinyl alcohol) (SPVA)/crosslinked sulfonated poly(aryl ether ketone) proton exchange membranes (Cr-SPAEK-x) were prepared with Congo red as the crosslinking agent. The crosslinked composite membranes were characterized by infrared spectroscopy. It is found that these series of crosslinked composite membranes show excellent thermal properties, mechanical properties, oxidation stability and appropriate water absorption. The crosslinked structure formed between the carboxyl group of PAEK-x and the amidogen of Congo red, along with the hydroxyl of SPVA. Notably, the crosslinking reaction does not consume the sulfonic acid groups in the crosslinked composite membrane. Therefore, these series of crosslinked composite membranes show a high proton conductivity. The sulfonated poly(vinyl alcohol)/sulfonated poly(aryl ether ketone) crosslinked composite membrane with a phenolphthalin content of 100mol% (Cr-SPAEK-100) demonstrated a proton conductivity of 0.053 S·cm−1 at 25℃ and 0.109 S·cm−1 at 80℃. The crosslinked network structure effectively inhibits the water swelling of the membrane and improves the dimensional stability of the crosslinked composite membrane. At 20℃, the Cr-SPAEK-100 membrane with the highest water uptake exhibits a minimal swelling ratio of only 5.26%. Moreover, the dense crosslinked network structure and the inclusion of SPVA with excellent methanol barrier properties significantly reduce the methanol diffusion coefficients in the crosslinked membranes, with the highest methanol diffusion coefficients being only 3.92×10−7 cm2·s−1. These series crosslinked composite membranes hold promise for applications in direct methanol fuel cells. -
图 2 交联复合膜的制备示意图
Figure 2. Preparation of the crosslinked composite membranes
PAEK-x—Poly(aryl ether ketone) containing carboxyl group carboxyl group; TMS—Tetramethylsilane
图 4 PAEK-60膜和Cr-SPAEK-60膜红外图谱
Figure 4. FTIR of PAEK-60 membrane and Cr-SPAEK-60 membrane
图 5 交联复合膜Cr-SPAEK-x及SPVA的TGA曲线
Figure 5. TGA curves of crosslinked composite membranes Cr-SPAEK-x and SPVA
图 6 交联复合膜的AFM相图：(a) PAEK-80；(b) Cr-SPAEK-80；(c) Cr-SPAEK-100
Figure 6. AFM tapping phase images of crosslinked composite membranes: (a) PAEK-80; (b) Cr-SPAEK-80; (c) Cr-SPAEK-100
图 7 交联复合膜Cr-SPAEK-x的吸水率曲线
Figure 7. Water uptake of the crosslinked composite membrane Cr-SPAEK-x
图 8 交联复合膜Cr-SPAEK-x的溶胀率曲线
Figure 8. Water swelling rate of the crosslinked composite membrane Cr-SPAEK-x
图 9 交联复合膜Cr-SPAEK-x的质子传导率
Figure 9. Proton conductivity of crosslinked composite membrane Cr-SPAEK-x
图 10 交联复合膜Cr-SPAEK-x质子传导率Arrhenius图
T—Temperature
Figure 10. Arrhenius plot of proton conductivity of crosslinked composite membrane Cr-SPAEK- x
图 11 交联复合膜Cr-SPAEK-x的结构及传输机制
Figure 11. Schematic structure and transmission mechanism of the crosslinked composite membrane Cr-SPAEK-x
表 1 交联复合膜Cr-SPAEK-x的力学性能、凝胶分数和氧化稳定性数据
Table 1. Mechanical properties, gel fraction and oxidative stability of crosslinked composite membranes Cr-SPAEK-x
Sample PPL/DFB
mol/molYoung's
modulus/MPaTensile
strength/MPaElongation
at break/%Gel fraction/% Oxidative
stability/%Cr-SPAEK-100 100/0 1549.31 73.57 5.32 93.92 97.98 Cr-SPAEK-80 80/20 1388.43 62.65 6.94 78.15 92.11 Cr-SPAEK-60 60/40 1264.57 50.84 9.39 72.14 84.62 Cr-SPAEK-40 40/60 1085.28 45.87 11.74 57.27 80.37 Notes: PPL—Phenolphthalin; DFB—4, 4'-difluorobenzophenone. 
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表 2 交联复合膜Cr-SPAEK-x的离子交换容量(IEC)、质子传导率、甲醇渗透率、质子选择性及活化能(Ea)数据
Table 2. Ion exchange capacity (IEC), proton conductivity, methanol permeability, proton selectivity and activation energy (Ea) of crosslinked composite membranes Cr-SPAEK-x
Sample IEC/
(mmol·g−1)Proton conductivity/
(S·cm−1)Methanol diffusion
coefficient/(cm2·s−1)Proton selectivity/
(104 S·cm−3)Ea/
(kJ·mol−1)25℃ 80℃ Cr-SPAEK-100 1.58 0.053 0.109 3.92×10−7 13.52 11.37 Cr-SPAEK-80 1.36 0.040 0.086 2.53×10−7 15.81 12.08 Cr-SPAEK-60 1.19 0.029 0.064 1.14×10−7 25.44 12.50 Cr-SPAEK-40 0.81 0.017 0.045 0.39×10−7 43.59 15.85 Nafion 117a) — 0.076 0.146 23.8×10−7 3.67 9.10 Note: a)—Data adapted from the Ref.[32].
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