CN106519282A - 一种聚偏氟乙烯接枝聚（α‑甲基苯乙烯）共聚物磺酸质子交换膜的制备方法 - Google Patents
一种聚偏氟乙烯接枝聚（α‑甲基苯乙烯）共聚物磺酸质子交换膜的制备方法 Download PDFInfo
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Abstract
本发明公开了一种聚偏氟乙烯接枝聚(α‑甲基苯乙烯)共聚物磺酸质子交换膜的制备方法，包含以下步骤：1、碱处理；2、酸洗工艺；3、室温溶胀2～3小时；4、将溶胀后的聚偏氟乙烯膜放入均相溶剂中，加入α‑甲基苯乙烯、共聚单体和催化剂，在引发剂的引发下于50～60℃聚合60小时，得到接枝改性的聚偏氟乙烯膜；5、室温溶胀2～3小时；6、接枝膜在浓硫酸中于70℃反应5小时。本发明还公开了上述方法制得的聚偏氟乙烯接枝聚(α‑甲基苯乙烯)共聚物磺酸质子交换膜，具有良好的电导性和耐甲醇透过性。
Description
技术领域
本发明涉及氢氧燃料电池质子交换膜，具体地指一种聚偏氟乙烯接枝聚(α-甲基苯乙烯)共聚物磺酸质子交换膜的制备方法。
背景技术
质子交换膜燃料电池(PEMFC)是以聚合物质子交换膜为电解质的燃料电池，由若干单电池串联而成，单电池由表面涂有催化剂的多孔阳极、多孔阴极和置于二者之间的固体聚合物电解质构成。在燃料电池内部，质子交换膜为质子的迁移和输送提供通道，使得质子经过膜从阳极到达阴极，与外电路的电子转移构成回路，向外界提供电流，因此质子交换膜的性能对燃料电池的性能起着非常重要的作用，它的好坏直接影响电池的使用寿命。聚合物质子交换膜要具有良好的离子导电性、电子绝缘性、机械强度、机械气密性和电化学稳定性能。现在广为使用的商品化离子交换膜是Dupont公司的Nafion系列膜，具有质子电导率高和化学稳定性好等优点，但仍存在制作成本高、对温度和含水量要求高、甲醇渗透率较高等缺点，限制了nafion质子交换膜的进一步应用。为此，开发成本低、性能与nafion相近的高分子电解质膜就成为科研人员的研究热点。
聚偏氟乙烯是指偏氟乙烯均聚物或者偏氟乙烯与其它少量含氟乙烯基单体的共聚物，具有良好的耐化学腐蚀性、耐高温性和耐氧化性。要使聚偏氟乙烯具有导电性，必须在其主链上接枝具有离子交换功能的官能团。聚偏氟乙烯的接枝聚合方法主要有辐射接枝法、强碱溶液接枝法等。可用于聚偏氟乙烯接枝聚合的单体主要是可以引入离子交换基团的苯乙烯类单体。苯乙烯可通过磺化反应在苯环上引入磺酸基官能团而使其具有离子交换功能，且离子交换容量可控，但缺点是在有氧或催化条件下易发生聚合物降解。含取代基苯乙烯的化学稳定性要好于苯乙烯，其中α-甲基苯乙烯(AMS)的稳定性最好。但纯α-甲基苯乙烯进行自由基聚合时反应速度很慢，得到的均聚物的分子量较低(通常在1～2万)，很难实际应用。在自由基聚合体系中引入新的共聚单体，如苯乙烯、丙烯腈或甲基丙烯腈等，可提高α-甲基苯乙烯的聚合速率。
中国专利200910195300.9、文献Journal ofMembrane Science 407-408(2012)184-192、文献Journal of Membrane Science 339(2009)68-77均报道了利用辐射接枝法来制备磺酸型聚偏氟乙烯接枝改性质子交换膜的研究。但是辐射接枝需要使用放射源产生射线，对实验操作人员及发备要求较高。文献Journal of Membrane Science 339(2009)68-77研究了α-甲基苯乙烯和丙烯腈作为共聚单体接枝聚(四氟乙烯-全氟丙烯共聚物)的辐射接枝聚合工艺，文献Journal of Membrane Science 363(2010)80-86进一步研究了α-甲基苯乙烯、苯乙烯和丙烯腈的聚合工艺及其共聚物对PVC基膜共混改性的影响。文献“高分子材料科学与工程26(2010)93-96”研究了原硅酸钠改性的聚偏氟乙烯接枝聚苯乙烯磺化膜的接枝聚合工艺，聚苯乙烯的接枝率为14～17％。文献“石油化工应用28(2)(2009)14-17”对碱处理聚偏氟乙烯膜接枝聚苯乙烯的接枝工艺进行了研究，聚苯乙烯的接枝率为10～35％。中国专利201510835863.5公开了一种采用碱溶液法制备磺酸型聚偏氟乙烯膜接枝(α-甲基苯乙烯)共聚物质子交换膜的制备方法，其接枝率从3％提高到49％。
发明内容
本发明的目的是提供一种聚偏氟乙烯接枝聚(α-甲基苯乙烯)共聚物磺酸质子交换膜的制备方法，以解决现有的碱溶液法制备的聚偏氟乙烯接枝改性聚(α-甲基苯乙烯)共聚物接枝率较低及其磺酸质子交换膜电导率较低的问题。
为达到上述目的，本发明所提供的聚偏氟乙烯接枝聚(α-甲基苯乙烯)共聚物磺酸质子交换膜的制备方法，包含以下步骤：
①将聚偏氟乙烯用碱处理；
②将碱处理后的聚偏氟乙烯膜依次放入质量分数25％的过氧化氢水溶液、0.5mol/L的硫酸水溶液中各煮沸30分钟，用去离子水洗至中性、烘干；
③将烘干后的聚偏氟乙烯膜放入溶剂中室温溶胀；
④将溶胀后的聚偏氟乙烯膜放入溶剂中，加入α-甲基苯乙烯及其共聚单体，加入催化剂，在引发剂的引发下于50～60℃接枝聚合60～70小时，清洗、干燥，得到接枝改性的聚偏氟乙烯膜；
⑤将接枝后的聚偏氟乙烯膜放入溶剂中室温溶胀；
⑥将溶胀后的接枝聚偏氟乙烯膜在浓硫酸中于60～70℃反应5～7小时，清洗、干燥，得到聚偏氟乙烯接枝聚(α-甲基苯乙烯)共聚物磺酸质子交换膜。
本发明在步骤①中，所用的碱为氢氧化钠或氢氧化钾的一种，对聚偏氟乙烯膜的处理工艺为：将聚偏氟乙烯膜浸入含3mg/ml四丁基溴化胺的1.5mol/l氢氧化物/乙醇溶液中于60℃反应30分钟。氢氧化钠与聚偏氟乙烯的摩尔比为10～1，优选10～5。
本发明在步骤①中，所用的碱为原硅酸钠或原硅酸钾的一种，对聚偏氟乙烯膜的处理工艺为：将原硅酸盐溶于含水质量分数3％的N-甲基吡咯烷酮中，再加入聚偏氟乙烯粉末，于60℃搅拌2h，成膜，烘干。原硅酸盐的用量为聚偏氟乙烯质量的5～40％，优选15～25％。
本发明在步骤③中，所用的溶剂为二氯甲烷、三氯甲烷中的一种，优选三氯甲烷；其目的是使碱处理后的聚偏氟乙烯膜充分溶胀，以利于后续接枝聚合反应的进行。
本发明在步骤③中，所用的溶胀时间为0.5～5小时，优选2～3小时。
本发明在步骤④中，所使用的溶剂为四氢呋喃、丙酮或乙醇中的一种，优选四氢呋喃。
本发明在步骤④中，所使用的四氢呋喃用量为溶液总体积的10～35％，优选18～30％。
本发明在步骤④中，所使用的催化剂为三氯化铝、氯化铁或氯化锌中的一种，优选三氯化铝。
本发明在步骤④中，所使用的三氯化铝催化剂用量为：2～25mg/100ml共聚单体，优选10～20mg/100ml共聚单体。
本发明在步骤④中，所使用的α-甲基苯乙烯的共聚单体为丙烯腈、甲基丙烯腈或苯乙烯的一种或多种，优选丙烯腈、甲基丙烯腈。
本发明在步骤④中，所使用的α-甲基苯乙烯与丙烯腈摩尔比为3∶2，二者体积之和占溶液总体积的23～80％，优选70～80％。
本发明在步骤④中，所使用的引发剂为偶氮二异丁腈、过氧化苯甲酰中的一种，优选过氧化苯甲酰。
本发明在步骤⑤中，所用的溶剂为二氯甲烷、三氯甲烷中的一种，优选三氯甲烷。
本发明在步骤⑤中，所用的溶胀时间为0.5～5小时，优选2～3小时。
本发明进一步涉及上述方法制得的磺酸质子交换膜。
本发明中，上述各优选技术特征可在不违背本领域常识的前提下任意组合，即得本发明的各较佳实例。
除特殊说明外，本发明涉及的原料和试剂均市售可得。
本发明与现有的聚偏氟乙烯碱溶液接枝聚合方法相比，本发明的方法在接枝聚合过程中使用均相溶剂，并加入催化剂三氯化铝，可使接枝组分的接枝率提高到60％。这种接枝率较高的聚偏氟乙烯膜进行磺化反应，可引入较多的磺酸型离子交换基团，使聚偏氟乙烯接枝聚(α-甲基苯乙烯)共聚物磺酸质子交换膜的电导率进一步提高到0.022S/cm。
具体实施方式
以下结合实施例对本发明的有关技术问题作进一步的解释和说明，而本发明并不局限于以下实施例。
实施例1
①16％原硅酸钠对聚偏氟乙烯膜的处理：将0.32g粉末状的原硅酸钠溶于含水3％的20ml N-甲基吡咯烷酮中，搅拌均匀；再加入2g粉末状聚偏氟乙烯，在60℃搅拌2h，然后将溶液浇铸到洁净的玻璃板上，烘干，得到16％原硅酸钠改性的聚偏氟乙烯膜。
②膜的酸洗：将碱处理后的聚偏氟乙烯膜依次用25％过氧化氢水溶液、0.5mol/L硫酸水溶液各煮沸30分钟，分别用去离子水、无水乙醇清洗三次，烘干。
③接枝前膜的溶胀：将碱处理后的聚偏氟乙烯膜放入三氯甲烷中在室温下溶胀两小时。
④接枝聚合：将溶胀后的聚偏氟乙烯膜放入24ml四氢呋喃中，加入α-甲基苯乙烯71ml、丙烯腈24ml、过氧化苯甲酰0.387g，加入10mg三氯化铝，在60℃接枝聚合60小时。将接枝后的聚偏氟乙烯膜放入丙酮中清洗两次。然后放入三氯甲烷中清洗两次。再用去离子水冲洗，烘干，得到聚偏氟乙烯接枝膜。
⑤磺化前膜的溶胀：将接枝后的聚偏氟乙烯接枝膜放入三氯甲烷中溶胀两小时。
⑥磺化反应：将接枝后的聚偏氟乙烯膜在浓硫酸中于70℃反应5小时。将磺化后的膜用去离子水洗至中性。用丙酮溶液洗两次，烘干，得到磺酸质子交换膜。
实施例2
①16％原硅酸钠对聚偏氟乙烯膜的处理：同实施例1。
②膜的酸洗：同实施例1。
③接枝前膜的溶胀：同实施例1。
④接枝聚合：将溶胀后的聚偏氟乙烯膜放入38ml四氢呋喃中，加入α-甲基苯乙烯71ml、丙烯腈24ml、过氧化苯甲酰0.6128g，加入15mg三氯化铝，在50℃接枝聚合60小时。将接枝后的聚偏氟乙烯膜放入丙酮中浸泡两次，每次30分钟。然后放入三氯甲烷中浸泡两次，每次一小时。再用去离子水冲洗，烘干，得到聚偏氟乙烯接枝膜。
⑤磺化前膜的溶胀：同实施例1。
⑥磺化反应：同实施例1。
对照实施例
对比实验1：
①16％原硅酸钠对聚偏氟乙烯膜的处理：同实施例1。
②膜的酸洗：同实施例1。
③接枝前膜的溶胀：同实施例1。
④接枝聚合：将碱处理后的聚偏氟乙烯膜放入70ml异丙醇/水(体积比＝5∶2)的混合溶剂中，加入α-甲基苯乙烯16ml、丙烯腈5ml、过氧化苯甲酰0.3524g，于50℃恒温接枝聚合60小时。将接枝后的聚偏氟乙烯膜放入丙酮中浸泡两次，每次30分钟。然后在三氯甲烷中浸泡两次，每次一小时。再用去离子水冲洗，烘干，得到聚偏氟乙烯接枝膜。
⑤磺化前膜的溶胀：同实施例1。
⑥磺化反应：同实施例1。
应用实施例1
接枝率：将接枝前后的聚偏氟乙烯膜分别称重，计算其增重百分率，如公式(1)所示。
电导率：将磺化后得到的聚偏氟乙烯接枝聚(α-甲基苯乙烯)共聚物磺酸质子交换膜在水中浸泡48小时后，用SI 1287交流阻抗测试仪测定其离子电导率。测试条件为：温度25℃，相对湿度100％，交流信号振幅：100mV，频率：0.1～1×106Hz。
对甲醇的面积溶胀度：将聚偏氟乙烯接枝聚(α-甲基苯乙烯)共聚物磺酸质子交换膜于室温分别浸泡在1mol/L甲醇水溶液、纯甲醇溶液中48小时后按公式(2)计算膜的面积溶胀度。
本发明所述的聚偏氟乙烯接枝聚(α-甲基苯乙烯)共聚物磺酸质子交换膜的性质如表1所示。
表1 聚偏氟乙烯接枝聚(α-甲基苯乙烯)共聚物磺酸质子交换膜的性质
由表1可知，本发明实施例1、2制备的聚偏氟乙烯接枝聚(α-甲基苯乙烯)共聚物的接枝率可达50～60％，而按照中国专利201510835863.5进行制备得到的对比实验例1中的接枝率为49.2％。另外，本发明实施例2制备的磺酸质子交换膜的电导率为0.22S/cm，接近于nafion的一半，前者在纯甲醇和1mol/L甲醇水溶液中的面积溶胀度为0，远小于nafion的49.9％和10.27％。
Claims (5)
1.一种聚偏氟乙烯接枝聚(α-甲基苯乙烯)共聚物磺酸质子交换膜的制备方法，其特征在于包含以下步骤：
①将聚偏氟乙烯用碱处理；
②将碱处理后的聚偏氟乙烯膜依次放入质量分数25％的过氧化氢水溶液、0.5mol/L的硫酸水溶液中各煮沸30分钟，用去离子水洗至中性、烘干；
③将烘干后的聚偏氟乙烯膜放入溶剂中室温溶胀；
④将溶胀后的聚偏氟乙烯膜放入溶剂中，加入α-甲基苯乙烯及其共聚单体，加入催化剂，在引发剂的引发下于50～60℃接枝聚合60～70小时，清洗、干燥，得到接枝改性的聚偏氟乙烯膜；
⑤将接枝后的聚偏氟乙烯膜放入溶剂中室温溶胀；
⑥将溶胀后的接枝聚偏氟乙烯膜在浓硫酸中于60～70℃反应5～7小时，清洗、干燥，得到聚偏氟乙烯接枝聚(α-甲基苯乙烯)共聚物磺酸质子交换膜。
2.根据权利要求1所述的制备方法，其特征在于步骤④中，所使用的溶剂为四氢呋喃、丙酮、乙醇中的一种，优选四氢呋喃。
3.根据权利要求2所述的制备方法，其特征在于步骤④中，所使用的四氢呋喃用量为溶液总体积的10～35％，优选18～30％。
4.根据权利要求1所述的制备方法，其特征在于步骤④中，所使用的催化剂为三氯化铝、氯化铁、氯化锌中的一种，优选三氯化铝。
5.根据权利要求4所述的制备方法，其特征在于步骤④中，所用的三氯化铝用量为：2～25mg/100ml共聚单体，优选10～20mg/100ml共聚单体。
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