CN106008862B - 一种碱性阴离子交换膜的制备方法 - Google Patents
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Abstract
本发明涉及一种碱性阴离子交换膜的制备方法,它包括以下步骤:(1)将聚合物单体、聚合型离子液体改性氧化石墨烯、交联剂、引发剂以重量比为60~95:0.1~20:0.1~15:1~5混合,进行原位聚合得高分子膜;(2)将所述高分子膜浸泡在碱液中进行阴离子交换即可。聚合型离子液体改性氧化石墨烯通过化学键将氧化石墨烯接到聚合物基体上提高了杂化阴离子交换膜的物理和化学稳定性;将聚合型离子液体制备成阴离子交换膜,离子液体的热稳定性好,化学性质稳定,制备的基于离子液体的阴离子交换膜有更好的热稳定性和耐碱性;引入交联剂调节阴离子交换膜的吸水率和溶胀度,交联网络的形成大大提高了阴离子交换膜的机械性能。
Description
技术领域
本发明属于高分子材料领域,涉及一种阴离子交换膜的制备方法,具体涉及一种碱性阴离子交换膜的制备方法。
背景技术
碱性阴离子交换膜是碱性阴离子交换膜燃料电池的核心组件,它起到传导离子和阻隔燃料的双重作用,其性能的好坏直接决定着燃料电池的性能和寿命。传统的季铵盐类聚合物碱性阴离子交换膜具有尺寸稳定性差,吸水率高,溶胀度大,机械性能差等缺点;并且制备季铵盐类聚合物需要大量的有机溶剂,剧毒物质氯甲醚也是必不可少的原料,后期有机溶剂的处理不仅增加了生产成本,对环境的危害也很大;更大的问题是季铵盐类聚合物在高温强碱环境下稳定性差,严重影响碱性阴离子交换膜的寿命和性能。因此,人们一直在探索一种制备方法绿色、简单、电导率高、成本低、机械性能优异和耐碱性能良好的碱性阴离子膜。
中国专利201010555682.4公开了一种基于咪唑类离子液体的阴离子交换膜:将单体、咪唑类离子液体、交联剂和引发剂通过原位聚合制备阴离子交换膜;该方法避免了有机溶剂的使用,膜的厚度易于调控,通过调控交联剂二乙烯基苯的含量来调节阴离子交换膜的吸水率和溶胀度;交联剂二乙烯基苯的加入能提高膜的机械性能但却大大降低了阴离子交换膜的电导率。中国专利201210212673.4公开了一种基于离子液体交联剂的阴离子交换膜:离子液体交联剂在阴离子交换膜中起到传导离子和提高阴离子交换膜机械性能的双重作用;然而,该体系中所用烯丙基类离子液体交联剂具有自阻聚作用,交联能力较弱,阴离子交换膜的机械性能仍然需要进一步提高。
发明内容
本发明目的是为了克服现有技术的不足而提供一种碱性阴离子交换膜的制备方法。
为达到上述目的,本发明采用的技术方案是:一种碱性阴离子交换膜的制备方法,它包括以下步骤:
(1)将聚合物单体、聚合型离子液体改性氧化石墨烯、交联剂、引发剂以重量比为60~95:0.1~20:0.1~15:1~5混合,进行原位聚合得高分子膜;
(2)将所述高分子膜浸泡在碱液中进行阴离子交换即可。
优化地,所述聚合型离子液体改性氧化石墨烯的化学结构式为:
式中,R为-H、-CH3、-CH2CH3、-CH(CH3)2和-C6H5的一种,X为Cl或Br。
进一步地,所述聚合型离子液体改性氧化石墨烯的制备方法为:
(a)将含有乙烯基的咪唑类单体、硅烷偶联剂和阻聚剂加入到乙腈中,在50~80℃回流反应20~75小时,反应结束后用无水乙醇清洗多次,旋转蒸发后干燥,得到聚合型离子液体;
(b)将聚合型离子液体、氧化石墨烯添加到乙醇中,调节混合液pH=2~5,在室温下反应24~130小时后过滤,用无水乙醇清洗多次,旋转蒸发后干燥,即得到聚合型离子液体改性氧化石墨烯。
进一步地,所述含有乙烯基的咪唑类单体和硅烷偶联剂的摩尔比为1:0.8~1.5,所述阻聚剂的质量为所述含有乙烯基的咪唑类单体质量的0.5~2%,所述聚合型离子液体和氧化石墨烯的质量比为3~10:1。
进一步地,所述含有乙烯基的咪唑类单体为
进一步地,所述硅烷偶联剂为γ-氯丙基三甲氧基硅烷、γ-溴丙基三甲氧基硅烷、γ-溴丙基甲基二甲氧基硅烷和γ-氯丙基甲基二甲氧基硅烷的一种或多种组成的混合物。
优化地,所述聚合物单体选自丙烯腈、苯乙烯、α-甲基苯乙烯和α-甲基丙烯腈中的一种或多种组成的混合物。
优化地,所述交联剂为二乙烯基苯,所述引发剂为安息香乙醚、
优化地,步骤(b)中,所述碱液为氢氧化钾或氢氧化钠的水溶液,浸泡温度为50~80℃。
由于上述技术方案运用,本发明与现有技术相比具有下列优点:本发明碱性阴离子交换膜的制备方法,与现有技术相比具有下列优点:设计了一种新型的基于离子液体的用于碱性燃料电池的聚合物阴离子交换膜;聚合型离子液体改性氧化石墨烯通过化学键将氧化石墨烯接到聚合物基体上避免了传统物理掺杂方法,提高了杂化阴离子交换膜的物理和化学稳定性;将聚合型离子液体制备成阴离子交换膜,离子液体的热稳定性好,化学性质稳定,与传统的季铵盐类阴离子交换膜相比,本发明制备的基于离子液体的阴离子交换膜有更好的热稳定性和耐碱性;引入交联剂调节阴离子交换膜的吸水率和溶胀度,交联网络的形成大大提高了阴离子交换膜的机械性能;通过在较高温度下进行阴离子交换,以及聚合物基体的选择使得离子交换更完全,本发明制备的阴离子交换膜具有接近理论值的离子交换容量,从而具有较高的离子电导率。
具体实施方式
下面将结合实施例对本发明进行进一步说明。
实施例1
本实施例提供一种聚合型离子液体改性氧化石墨烯,其制备方法包括以下步骤:
(1)将9.41g(0.10mol),19.87gγ-氯丙基三甲氧基硅烷(0.10mol)和0.09g苯醌加入到100ml无水乙腈中,在50℃回流反应30小时;反应结束后用无水乙醇清洗3~5次,旋转蒸发后干燥,得到聚合型离子液体
(2)将2.0g步骤(1)中得到的聚合型离子液体和2.0g氧化石墨烯添加到100ml乙醇中,添加少量氨水调节混合液pH=2,在室温下反应40小时后过滤,用无水乙醇清洗3次,旋转蒸发后干燥,即得到聚合型离子液体改性氧化石墨烯,其的化学结构通式为
其它结构的聚合型离子液体改性氧化石墨烯合成方法参照实施例1。
实施例2
本实施例提供一种碱性阴离子交换膜的制备方法,它包括以下步骤:
(1)取0.006g、苯乙烯0.45g、丙烯腈0.14g、安息香乙醚0.006g、交联剂0.012g混合,将其在超声波震荡下3分钟至混合均匀,涂到模具上,用波长为250nm的紫外光照射30min,原位聚合得高分子膜;
(2)然后将该阴离子交换膜浸泡在60℃、1M KOH溶液中24小时,将阴离子转换成OH-,本实施例获得的OH-型阴离子交换膜室温下离子传导率为1.10×10-2S cm-1,90℃下离子传导率为3.05×10-2S cm-1,抗张强度为13.33Mpa,杨氏模量为393.57Mpa,断裂伸长率为4.35%。
实施例3
本实施例提供一种碱性阴离子交换膜的制备方法,其制备步骤与实施例2中的基本一致,不同的是原料配比不一样,具体为:苯乙烯0.44g、丙烯腈0.15g、聚合型离子液体改性氧化石墨烯0.012g、安息香乙醚0.01g、交联剂0.02g,本实施例获得的OH-型阴离子交换膜室温下离子传导率为1.50×10-2S cm-1,90℃下离子传导率为3.55×10-2S cm-1,抗张强度为16.67Mpa,杨氏模量为445.08Mpa,断裂伸长率为4.54%。
实施例4
本实施例提供一种碱性阴离子交换膜的制备方法,其制备步骤与实施例2中的基本一致,不同的是原料配比不一样,具体为:苯乙烯0.43g、丙烯腈0.14g、聚合型离子液体改性氧化石墨烯0.12g、安息香乙醚0.006g、交联剂0.08g,本实施例获得的OH-型阴离子交换膜室温下离子传导率为2.10×10-2S cm-1,90℃下离子传导率为4.05×10-2S cm-1,抗张强度为18.05Mpa,杨氏模量为484.50Mpa,断裂伸长率为4.99%。
实施例5
本实施例提供一种碱性阴离子交换膜的制备方法,其制备步骤与实施例6中的基本一致,不同的是原料配比不一样,具体为:苯乙烯0.45g、丙烯腈0.14g、聚合型离子液体改性氧化石墨烯0.08g、安息香乙醚0.009g、交联剂0.011g;本实施例获得的OH-型阴离子交换膜室温下离子传导率为1.20×10-2S cm-1,90℃下离子传导率为3.07×10-2S cm-1。抗张强度为12.68Mpa,杨氏模量为375.12Mpa,断裂伸长率为3.62%。
实施例6
本实施例提供一种碱性阴离子交换膜的制备方法,其制备步骤与实施例6中的基本一致,不同的是原料配比不一样,具体为:苯乙烯0.43g、丙烯腈0.14g、实施例2中的聚合型离子液体改性氧化石墨烯0.13g、安息香乙醚0.006g、交联剂0.018g;本实施例获得的OH-型阴离子交换膜室温下离子传导率为2.20×10-2S cm-1,90℃下离子传导率为4.07×10-2S cm-1,抗张强度为17.99Mpa,杨氏模量为559.30Mpa,断裂伸长率为4.39%。
实施例7
本实施例提供一种碱性阴离子交换膜的制备方法,其制备步骤与实施例2中的基本一致,不同的是原料配比不一样,具体为:苯乙烯0.43g、丙烯腈0.14g、聚合型离子液体改性氧化石墨烯0.13g、安息香乙醚0.007g、交联剂0.013g;本实施例获得的OH-型阴离子交换膜室温下离子传导率为3.30×10-2S cm-1,90℃下离子传导率为4.95×10-2S cm-1,抗张强度为13.23Mpa,杨氏模量为383.57Mpa,断裂伸长率为3.25%。
上述实施例只为说明本发明的技术构思及特点,其目的在于让熟悉此项技术的人士能够了解本发明的内容并据以实施,并不能以此限制本发明的保护范围,凡根据本发明精神实质所作的等效变化或修饰,都应涵盖在本发明的保护范围之内。
Claims (7)
1.一种碱性阴离子交换膜的制备方法,其特征在于,它包括以下步骤:
(1)将聚合物单体、聚合型离子液体改性氧化石墨烯、交联剂、引发剂以重量比为60~95:0.1~20:0.1~15:1~5混合,进行原位聚合得高分子膜;所述聚合型离子液体改性氧化石墨烯的化学结构式为:
式中,R为-H、-CH3、-CH2CH3、-CH(CH3)2和-C6H5的一种,X为Cl或Br;
(2)将所述高分子膜浸泡在碱液中进行阴离子交换即可;
所述聚合型离子液体改性氧化石墨烯的制备方法为:
(a)将含有乙烯基的咪唑类单体、硅烷偶联剂和阻聚剂加入到乙腈中,在50~80℃回流反应20~75小时,反应结束后用无水乙醇清洗多次,旋转蒸发后干燥,得到聚合型离子液体;
(b)将聚合型离子液体、氧化石墨烯添加到乙醇中,调节混合液pH=2~5,在室温下反应24~130小时后过滤,用无水乙醇清洗多次,旋转蒸发后干燥,即得到聚合型离子液体改性氧化石墨烯。
2.根据权利要求1所述碱性阴离子交换膜的制备方法,其特征在于:所述含有乙烯基的咪唑类单体和硅烷偶联剂的摩尔比为1:0.8~1.5,所述阻聚剂的质量为所述含有乙烯基的咪唑类单体质量的0.5~2%,所述聚合型离子液体和氧化石墨烯的质量比为3~10:1。
3.根据权利要求1所述碱性阴离子交换膜的制备方法,其特征在于:所述含有乙烯基的咪唑类单体为
4.根据权利要求1所述碱性阴离子交换膜的制备方法,其特征在于:所述硅烷偶联剂为γ-氯丙基三甲氧基硅烷、γ-溴丙基三甲氧基硅烷、γ-溴丙基甲基二甲氧基硅烷和γ-氯丙基甲基二甲氧基硅烷的一种或多种组成的混合物。
5.根据权利要求1所述碱性阴离子交换膜的制备方法,其特征在于:所述聚合物单体选自丙烯腈、苯乙烯、α-甲基苯乙烯和α-甲基丙烯腈中的一种或多种组成的混合物。
6.根据权利要求1所述碱性阴离子交换膜的制备方法,其特征在于:所述交联剂为二乙烯基苯,所述引发剂为安息香乙醚、
7.根据权利要求1所述碱性阴离子交换膜的制备方法,其特征在于:步骤(b)中,所述碱液为氢氧化钾或氢氧化钠的水溶液,浸泡温度为50~80℃。
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