CN103746133B - 咪唑类离子液体掺杂改性磺化聚苯硫醚质子交换膜材料及其制备方法 - Google Patents
咪唑类离子液体掺杂改性磺化聚苯硫醚质子交换膜材料及其制备方法 Download PDFInfo
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Abstract
本发明涉及一种咪唑类离子液体掺杂改性磺化聚苯硫醚质子交换膜材料及其制备方法。该质子交换膜的组成及质量百分比为:磺化度为57%~80%的SPPS:70%~90%;咪唑类离子液体:0.1%~5%;制膜溶剂:5%~25%。本发明方法是以SPPS为基体,咪唑类离子液体为填充相,制备出均匀混合制膜液,采用流延成膜的方法经干燥制备出复合膜。本发明制备成本低,工艺简单,所制得的质子交换膜电导率高,阻醇性能好,在30 °C~110 °C下的电导率为3.10×10‑3 S/cm~3.50×10‑2 S/cm,阻醇系数达到1.00×10‑7 cm2/s~9.00×10‑7 cm2/s,吸水率为20%~200%。
Description
技术领域
本发明涉及一种咪唑类离子液体掺杂改性磺化聚苯硫醚质子交换膜材料及其制备方法。
背景技术
离子液体是在室温或近于室温下呈液态的由阴阳离子组成的室温熔融盐,具有导电性、难挥发、不燃烧、电化学稳定等优点。因此,将离子液体应用与电化学研究可以减轻放电负荷,作为电解质的使用温度也远远低于熔融盐。
磺化聚苯硫醚(SPPS)材料因具有高机械强度、优异的热稳定性及化学稳定性成为直接甲醇燃料电池用质子交换膜的重点研究材料。用浓硫酸对聚苯硫醚磺化,将磺酸基团引入到聚苯硫醚的主链上,由于磺酸基亲水相与聚合物骨架上苯环、碳硫键等疏水相的存在,可使得聚苯硫醚材料具有一定的质子传导率,并且聚苯硫醚制备成本较低、耐热稳定性优异能满足燃料电池对质子交换膜材料的要求。但是,这种材料的磺化度(DS,SPPS每100个重复单元所含的磺酸基团数目)会直接影响质子交换膜的性能,因此要选择合适的磺化度来进行掺杂制膜。在磺化聚苯硫醚质子交换膜的方案设计上,通常需要对磺化聚苯硫醚磺化度及改性的方法进行综合考虑,得到最佳的质子交换膜。
发明内容
本发明的目的之一在于提供一种咪唑类离子液体掺杂改性磺化聚苯硫醚质子交换膜材料。
本发明的目的之二在于提供该质子交换膜材料的制备方法。
一种咪唑类离子液体掺杂改性磺化聚苯硫醚质子交换膜材料,其特征在于该材料的组成及其质量百分含量为:
磺化聚苯硫醚 70%~90%;
咪唑类离子液体 0.1%~5%;
制模溶剂 5%~25%;
所述的磺化聚苯硫醚的结构为:
所述的咪唑类离子液体的结构为:,式中f=2~7;R’为氢或含1~4个碳原子的烷基;R为含1~4个碳原子的烷基;X为:Cl、Br、I、BF4或PF6。
上述的磺化聚苯硫醚的磺化度为57%~80%。
一种制备上述的咪唑类离子液体掺杂改性磺化聚苯硫醚质子交换膜材料的方法,其特征在于该方法的具体步骤为:
a. 将不同磺化度的磺化聚苯硫醚溶解在制膜溶剂中,配制成质量百分比浓度为5.0%~35.0%的制膜液;
b. 在步骤a所得的制膜液中加入咪唑类离子液体,70 °C~100 °C下,惰性气氛保护下搅拌10 h~24 h,冷却至室温,抽滤除去不溶物,干燥,即得到咪唑类离子液体掺杂改性磺化聚苯硫醚质子交换膜材料。
上述的咪唑类离子液体掺杂改性磺化聚苯硫醚质子交换膜材料的制备方法,其特征在于所用的制膜溶剂为:N,N-二甲基甲酰胺DMF、N,N-二甲基乙酰胺DMAC或二甲基亚砜DMSO。该咪唑类离子液体名称为:咪唑-1-甲(乙或丙或丁)烷基-3-烷基硅氧基氯(或溴或碘或四氟硼酸或六氟硼酸)盐离子液体。
本发明所得咪唑类离子液体掺杂改性磺化聚苯硫醚质子交换膜材料经流延或压制成膜,然后在40 °C~90 °C下挥发溶剂,得到湿膜;再将所得湿膜在50 °C ~100 °C下恒温干燥2 h~24 h;或者先在50 °C~70 °C下干燥10 h~12 h,再升温至70 °C~120 °C干燥4h~10 h,得到咪唑类离子液体掺杂改性磺化聚苯硫醚质子交换膜。
说明:
1.磺化聚苯硫醚磺化度(DS):SPPS每100个重复单元所含的磺酸基团数。根据反应时间的不同,可制备出不同DS的磺化聚苯硫醚。本实施例中,采用DS为57%~80%的SPPS进行咪唑类离子液体掺杂改性,磺化度可通过核磁共振或化学反滴定法测得。
2.使用的咪唑类离子液体的结构通式为
其中,R'为氢或含1~4个碳原子的烷基;R为含1~4个碳原子的烷基;X-为无机或有机离子单元,包括:Cl-、Br-、I-、BF4 -、PF6 -,f=2~7。
本发明的离子液体掺杂改性磺化聚苯硫醚质子交换膜及制备方法的优点在于:1.操作简单,采用中等磺化度的SPPS作为基体材料,以克服过高磺化度SPPS存在的吸水率过高,复合膜稳定性较差的缺点,并保证复合膜具有一定的机械强度;2.离子液体本身具有导电性、难挥发性、电化学稳定窗口比其它电解质水溶液大等特点,采用咪唑类离子液体掺杂的方式,使SPPS基体与离子液体之间发生协同效应,不仅降低离子液体在SPPS基体中的流失率,同时也能提高质子交换膜的电导率,以提高复合膜的综合性能。
本发明方法制备成本低,所制得的质子交换膜电导率高,阻醇性能好,在30 °C~110 °C下的电导率为3.10×10-3 S/cm~3.50×10-2 S/cm,阻醇系数达到1.00×10-7 cm2/s~9.00×10-7 cm2/s,吸水率为20%~200%。
附图说明
图1 咪唑氯盐离子液体掺杂改性磺化聚苯硫醚红外谱图。
具体实施方式
实施例一:
(1)取1.28115 g SPPS(DS为61.4%)于100 ml单口瓶中,加入30 ml DMF,组装油浴加热装置、球形冷凝管,打开磁力搅拌,升温至60 °C,配成制膜液;
(2)取20ml N-甲基咪唑和20ml γ-氯丙基三乙氧基硅烷加入到150ml平底烧瓶中,在40 °C下磁力搅拌反应4 h制备得到咪唑氯盐离子液体,其结构式:
(3)在步骤(1)所得的制膜液中加入0.12863 g咪唑氯盐离子液体,氮气保护70 °C下机械搅拌反应10 h;冷却至室温,抽滤除去不溶物,即得到咪唑类离子液体掺杂改性磺化聚苯硫醚质子交换膜材料;
取7 ml咪唑类离子液体掺杂改性磺化聚苯硫醚质子交换膜材料流延成膜,得到湿膜,首先在50 °C下干燥10 h,然后在80 °C下干燥4 h,从烘箱中取出,待其自然冷却至室温后,揭膜。
对上述实施例所制得的咪唑氯盐离子液体掺杂改性SPPS质子交换膜应用实验,其过程和结果如下所述:
(1)咪唑氯盐离子液体掺杂SPPS质子交换膜电导率测试:
在交流两电极法的基础上进行改进,自行设计并建立了一套简易可靠的膜电阻测试装置。检测温度为30 °C~110 °C。咪唑氯盐离子液体掺杂的磺化聚苯硫醚质子交换膜30°C时的电导率为3.10×10-3 S/cm,90 °C时达到最大值1.10×10-2 S/cm。
(2)咪唑氯盐离子液体掺杂SPPS质子交换膜阻醇性能测试:
采用隔膜扩散池评价膜的阻醇性能。测试前将膜试样在去离子水中浸泡24 h,并在测试温度下稳定1 h以上后进行测试。将膜夹于两半室中间,在一侧注入60 ml的4 mol/L甲醇溶液,另一侧注入相当体积的去离子水使得其液面与甲醇的液面相平。采用气相色谱测量去离子水中甲醇浓度随时间的变化情况。由Fick扩散第二定律可得甲醇透过系数:
P······膜试样的甲醇渗透系数(cm2/s)
S······去离子水侧甲醇浓度随时间变化率(mol L-1s-1)
V2······去离子水侧体积(ml)
l······膜试样的厚度(cm)
A······膜试样的有效面积(cm2)
c10······甲醇溶液侧的初始甲醇浓度(mol/L)
通过试验,在如上所述反应条件下,咪唑氯盐离子液体掺杂SPPS的质子交换膜的阻醇系数为1.25×10-7 cm2/s。
(3)咪唑氯盐离子液体掺杂SPPS质子交换膜吸水率测试:
将咪唑氯盐离子液体掺杂SPPS膜试样置于烘箱中,在120 °C下干燥24 h,称得干膜质量(Mdry),然后将膜浸入去离子水中,室温浸泡24 h使其充分溶胀,取出湿膜,吸去表面水份,称得湿膜质量(Mwet)。膜的吸水率Sw为:
通过试验,在如上所述反应条件下,咪唑氯盐离子液体掺杂改性SPPS质子交换膜的吸水率为24.9%。
实施例二:
(1)取1.13115 g SPPS(DS为69.7%)于100 ml单口瓶中,加入30 ml DMAC,组装油浴加热装置、球形冷凝管,打开磁力搅拌,升温至60 °C,配成制膜液;
(2)取20ml N-甲基咪唑和20ml γ-氯丙基三乙氧基硅烷加入到150ml平底烧瓶中,在40 °C下磁力搅拌反应4 h制备得到咪唑氯盐离子液体,向溶液中继续加入10 ml四氟硼酸铵反应2 h后过滤得到咪唑四氟硼酸盐离子液体。其结构式:
(3)在步骤(1)所得的制膜液中加入0.13873 g咪唑四氟硼酸盐离子液体,氮气保护70 °C下机械搅拌反应10 h;冷却至室温,抽滤除去不溶物,即得到咪唑类离子液体掺杂改性磺化聚苯硫醚质子交换膜材料。
取7 ml咪唑类离子液体掺杂改性磺化聚苯硫醚质子交换膜材料流延成膜,得到湿膜,首先在50 °C下干燥10 h,然后在80 °C下干燥4 h,从烘箱中取出,待其自然冷却至室温后,揭膜。
对上述实施例所制得的咪唑四氟硼酸盐离子液体掺杂SPPS质子交换膜应用实验,其过程和结果如下所述:
(1)咪唑四氟硼酸盐离子液体掺杂SPPS质子交换膜电导率测试:
测试方法如实例1所述。咪唑四氟硼酸盐离子液体掺杂SPPS质子交换膜30 °C时的电导率为3.32×10-3 S/cm,90 °C时达到最大值1.42×10-2 S/cm。
(2)咪唑四氟硼酸盐离子液体掺杂SPPS质子交换膜阻醇性能测试:
测试方法如实例1所述。咪唑四氟硼酸盐离子液体掺杂SPPS质子交换膜的阻醇系数为3.52×10-7 cm2/s。
(3)咪唑四氟硼酸盐离子液体掺杂SPPS质子交换膜吸水率测试:
测试方法如实例1所述。咪唑四氟硼酸盐离子液体掺杂SPPS质子交换膜的吸水率为49.8%。
实施例三:
(1)取1.03100 g SPPS(DS为75.4%)于100 ml单口瓶中,加入30 ml DMSO,组装油浴加热装置、球形冷凝管,打开磁力搅拌,升温至60 °C,配成制膜液;
(2)取20ml N-甲基咪唑和20ml γ-氯丙基三乙氧基硅烷加入到150ml平底烧瓶中,在40 °C下磁力搅拌反应4 h制备得到咪唑氯盐离子液体,向溶液中继续加入10 ml六氟硼酸铵反应2 h后过滤得到咪唑六氟硼酸盐离子液体。其结构式:
(3)在步骤(1)所得的制膜液中加入0.11872 g咪唑六氟硼酸盐离子液体,氮气保护70 °C下机械搅拌反应10 h;冷却至室温,抽滤除去不溶物,即得到咪唑类离子液体掺杂改性磺化聚苯硫醚质子交换膜材料。
取7 ml咪唑类离子液体掺杂改性磺化聚苯硫醚质子交换膜材料流延成膜,得到湿膜,首先在50 °C下干燥10 h,然后在80 °C下干燥4 h,从烘箱中取出,待其自然冷却至室温后,揭膜。
对上述实施例所制得的咪唑六氟硼酸盐离子液体掺杂SPPS质子交换膜应用实验,其过程和结果如下所述:
(1)咪唑六氟硼酸盐离子液体掺杂SPPS质子交换膜电导率测试:
测试方法如实例1所述。咪唑六氟硼酸盐离子液体掺杂SPPS质子交换膜30 °C时的电导率为5.92×10-3 S/cm,90 °C时达到最大值2.98×10-2 S/cm。
(2)咪唑六氟硼酸盐离子液体掺杂SPPS质子交换膜阻醇性能测试:
测试方法如实例1所述。咪唑六氟硼酸盐离子液体掺杂SPPS质子交换膜的阻醇系数为5.76×10-7 cm2/s。
(3)咪唑六氟硼酸盐离子液体掺杂SPPS质子交换膜吸水率测试:
测试方法如实例1所述。咪唑六氟硼酸盐离子液体掺杂SPPS质子交换膜的吸水率为98.02%。
实施例四:
(1)取0.94562 g SPPS(DS为79.2%)于100 ml单口瓶中,加入30 ml DMF,组装油浴加热装置、球形冷凝管,打开磁力搅拌,升温至60 °C,配成制膜液;
(2) )取20ml N-甲基咪唑和20ml γ-氯丙基三乙氧基硅烷加入到150ml平底烧瓶中,在40 °C下磁力搅拌反应4 h制备得到咪唑氯盐离子液体,向溶液中继续加入10 ml溴化铵反应2 h后过滤得到咪唑溴盐离子液体。其结构式:
(3)在步骤(1)所得的制膜液中加入0.12873 g咪唑溴盐离子液体,氮气保护70 °C下机械搅拌反应10 h;冷却至室温,抽滤除去不溶物,即得到咪唑类离子液体掺杂改性磺化聚苯硫醚质子交换膜材料。
取7 ml咪唑类离子液体掺杂改性磺化聚苯硫醚质子交换膜材料流延成膜,得到湿膜,首先在50 °C下干燥10 h,然后在80 °C下干燥4 h,从烘箱中取出,待其自然冷却至室温后,揭膜。
对上述实施例所制得的咪唑溴盐离子液体掺杂SPPS质子交换膜应用实验,其过程和结果如下所述:
(1)咪唑溴盐离子液体掺杂SPPS质子交换膜电导率测试:
测试方法如实例1所述。咪唑溴盐离子液体掺杂SPPS质子交换膜30 °C时的电导率为3.93×10-3 S/cm,90 °C时达到最大值1.89×10-2 S/cm。
(2)咪唑溴盐离子液体掺杂SPPS质子交换膜阻醇性能测试:
测试方法如实例1所述。咪唑溴盐离子液体掺杂SPPS质子交换膜的阻醇系数为2.71×10-7 cm2/s。
(3)咪唑溴盐离子液体掺杂SPPS质子交换膜吸水率测试:
测试方法如实例1所述。咪唑溴盐离子液体掺杂SPPS质子交换膜的吸水率为123.46%。
Claims (2)
1.一种咪唑类离子液体掺杂改性磺化聚苯硫醚质子交换膜材料的制备方法,该材料的组成及其质量百分含量为:
磺化聚苯硫醚 70%~90%;
咪唑类离子液体 0.1%~5%;
制模溶剂 5%~25%;
所述的磺化聚苯硫醚的结构为:
所述的咪唑类离子液体的结构为:,式中f=2~7;R’为氢或含1~4个碳原子的烷基;R为含1~4个碳原子的烷基;X为:Cl、Br、I、BF4或PF6;其特征在于该方法的具体步骤为:
a.将不同磺化度的磺化聚苯硫醚溶解在制膜溶剂中,配制成质量百分比浓度为5.0%~35.0%的制膜液;
b.在步骤a所得的制膜液中加入咪唑类离子液体,70 °C~100 °C下,惰性气氛保护下搅拌10 h~24 h,冷却至室温,抽滤除去不溶物,干燥,即得到咪唑类离子液体掺杂改性磺化聚苯硫醚质子交换膜材料。
2.根据权利要求1所述的咪唑类离子液体掺杂改性磺化聚苯硫醚质子交换膜材料的制备方法,其特征在于所用的制膜溶剂为:N,N-二甲基甲酰胺DMF、N,N-二甲基乙酰胺DMAC或二甲基亚砜DMSO。
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