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CN102863636B - 一种原位聚合法制备含氟聚芳醚复合阴离子交换膜的方法 - Google Patents

一种原位聚合法制备含氟聚芳醚复合阴离子交换膜的方法 Download PDF

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CN102863636B
CN102863636B CN201210351021.9A CN201210351021A CN102863636B CN 102863636 B CN102863636 B CN 102863636B CN 201210351021 A CN201210351021 A CN 201210351021A CN 102863636 B CN102863636 B CN 102863636B
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polyarylether
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CN102863636A (zh
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尚玉明
王要武
谢晓峰
徐敏
王金海
王树博
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Abstract

本发明公开了属于高分子材料制备技术领域的一种原位聚合法制备含氟聚芳醚复合阴离子交换膜的方法，此方法将氟取代聚芳醚阴离子聚合物溶于适当溶剂，加入适量无机纳米粉体、活性复合组分及催化剂，得到制膜液，经热处理脱除溶剂，并在制膜过程中活性复合组分发生原位聚合并与氟取代聚芳醚发生交联反应，得到含氟聚芳醚复合阴离子交换膜材料，该方法可有效解决膜材料的溶胀问题，所制备的阴离子聚合物电解质膜具有良好的尺寸稳定性、机械强度、离子传导能力及低的钒离子渗透性，在全钒液流电池、聚合物电解质膜燃料电池、直接甲醇燃料电池、离子交换树脂、膜分离、传感器等领域具有重要应用价值。

Description

一种原位聚合法制备含氟聚芳醚复合阴离子交换膜的方法
技术领域
本发明属于功能高分子材料制备技术领域，具体涉及一种原位聚合法制备含氟聚芳醚复合阴离子交换膜的方法 。
背景技术
随着新能源电池如聚合物电解质膜燃料电池（PEMFC）、全钒氧化还原液流电池（VRB）等的研究与开发，其重要组成部分-电解质膜也受到研究者的广泛关注。目前在电池领域商业化应用的主要是美国杜邦公司生产的Nafion 系列膜。它具有离子传导率较高、化学稳定性较好、强度较大等优点；然而，全氟膜成本偏高，且阳离子交换膜属于酸性电解质，应用于PEMFC时，存在Pt电极易被腐蚀、电极反应动力学缓慢、燃料渗透率较高等不足；而在全钒氧化还原液流电池（VRB）中，全氟磺酸膜的固定基团为磺酸根阴离子，有利于电解液中的质子通过，但在质子通过的同时，同为阳离子的钒离子也可以通过膜，即发生钒渗透，造成了膜两侧电解液的交叉污染，使电池发生自放电，电池性能降低。
为改善上述缺点，人们提出用阴离子交换膜代替阳离子交换膜的构想。阴离子交换膜是一种碱性介质，在PEMFC中，由阴极产生的OH-离子作为载流子，通过离子交换膜，从阴极移动到阳极，能够有效降低电拖曳引起的燃料渗透损失，此外，该过程可以使用较便宜的镍、银等非贵金属类型的催化剂，降低电池成本。并且碱性介质腐蚀性小，对电池材料要求降低，使得电极板、集流板及密封材料的选择范围变宽。在在全钒氧化还原液流电池中，若将所用电解质膜改为阴离子交换膜，因其固定基团为阳离子，由于Donan效应，钒离子的渗透将受到制约,即阴离子膜具有更优良的阻钒性能，有利于提高电池效率，因此更适于应用在全钒液流电池中。综上所述，开发具有良好离子传导率、成本低廉、综合性能优良阴离子交换膜是下一代燃料电池、全钒液流电池的关键技术。
发明内容
针对现有膜材料的不足，本发明的目的在于提供一种原位聚合法制备含氟聚芳醚复合阴离子交换膜的方法。
一种原位聚合法制备含氟聚芳醚复合阴离子交换膜的方法，该方法包括以下步骤：
（1）在惰性气氛中，将无机纳米粉体加入有机溶剂中，于0-30℃温度下超声并搅拌处理0.5-2小时，使其分散均匀；
（2）将氟取代聚芳醚阴离子聚合物加入上述混合液中充分搅拌至聚合物完全溶解；其中无机纳米粉体与氟取代聚芳醚阴离子聚合物的质量比为1-25%，氟取代聚芳醚阴离子聚合物与有机溶剂的质量比为5-20%；
（3）搅拌下在上述混合液中加入活性复合组分至其溶解，得到混合溶液备用；所加活性复合组分与氟取代聚芳醚阴离子聚合物的质量比为1-40%；
（4）于0-30℃温度下，将交联催化剂加入上述混合液，搅拌混合均匀，得到制膜液；交联催化剂加入量为步骤（3）中加入活性复合组分的0.1-10wt%；
（5）将上述制膜液涂覆于基板上，在60-80℃保持10-24小时后再在100-200℃保持6-24小时，脱膜后用去离子水洗涤除去杂离子，得到含氟聚芳醚复合阴离子交换膜含氟聚芳醚复合阴离子交换膜。
步骤（1）中所述惰性气氛为氮气或氩气。
步骤（1）中所述无机纳米粉体为纳米二氧化硅、纳米二氧化钛、纳米氧化锆中的一种或一种以上。
步骤（1）中所述有机溶剂为二甲基甲酰胺、二甲基乙酰胺、1，2-二氯乙烷、乙腈、二甲基亚砜、二苯砜、环丁砜、N－甲基吡咯烷酮中的一种或一种以上。
步骤（2）中所述氟取代聚芳醚阴离子聚合物其结构式为式（Ⅰ），其数均分子量（Mn）为5000-200000，功能化程度为15~95%；
式（Ⅰ），
式（Ⅰ）中Ar为
（单体TMPA）或（单体TMBA）；
Ar中R为H或Rf；
Rf为下列功能基团的一种：
，，，，；
其中X为F-、Cl-、 Br-、I- 或OH-；
氟取代聚芳醚阴离子聚合物功能化程度由R中Rf与H的摩尔比来计算，功能化程度（DF）= Rf的摩尔数量：（H的摩尔数量+ Rf的摩尔数量），其DF为15~95%。
氟取代聚芳醚阴离子聚合物的表述可由上述几种结构因素(单体-功能基- -反离子-功能化程度)来表述，如（PFO-TMPA-- Br- 50）表示聚合物由单体PFO-TMPA构成，并含有功能化基团，反离子为Br-离子，功能化程度为50%。
步骤（3）中所述活性复合组分为1-乙烯基咪唑或1-烯丙基咪唑。
步骤（4）中所述交联催化剂为过氧化二苯甲酰、过氧化环己酮、偶氮二异丁腈或偶氮二异庚腈。
本发明的有益效果为：本发明方法原料易得、各组分分散均匀、操作简单，所制备的含氟聚芳醚复合阴离子交换膜具有良好的尺寸稳定性、机械强度、离子传导能力及低的钒离子渗透性，在全钒液流电池、聚合物电解质膜燃料电池、直接甲醇燃料电池、离子交换树脂、膜分离、传感器等领域具有重要应用价值。
附图说明
图1为含氟聚芳醚复合阴离子交换膜分子结构示意图。
具体实施方式
下面将结合附图和具体实施例对本发明做进一步说明。
图1为按本发明方法制备的含氟聚芳醚复合阴离子交换膜之一的分子结构示意图。
实施例1
在氮气氛中，将1g纳米二氧化硅粉加入2000mL二甲基甲酰胺中，于0℃温度下超声并搅拌处理0.5小时，然后将100g氟代聚芳醚阴离子聚合物（PFO-TMPA--Cl- 15， Mn=5000）加入上述混合液，充分搅拌至聚合物完全溶解。在搅拌下缓慢加入1g 1-乙烯基咪唑至其溶解，得到混合溶液备用. 之后，于0℃温度下，将适量交联催化剂过氧化二苯甲酰0.1g, 搅拌混合均匀，得到制膜液。将所述制膜液涂覆于基板上，在60℃保持24小时后再在150℃保持6小时，脱膜后用去离子水洗涤除去杂离子，得到含氟聚芳醚复合阴离子交换膜，其性能见表1。
实施例2
在氩气气氛中，将50g纳米氧化锆加入1000mL二甲基乙酰胺中，于0℃温度下超声并搅拌处理2小时，然后将200g氟代聚芳醚阴离子聚合物（PFO-TMBA-- Br- 95，Mn=200000）加入上述混合液，充分搅拌至聚合物完全溶解。在搅拌下缓慢加入80g 1-丙烯基咪唑至其溶解，得到混合溶液备用. 之后，于30℃温度下，将交联催化剂过氧化环己酮0.08g, 搅拌混合均匀，得到制膜液。将所述制膜液涂覆于基板上，在80℃保持10小时后再在150℃保持24小时，脱膜后用去离子水洗涤除去杂离子，得到含氟聚芳醚复合阴离子交换膜，其性能见表1。
实施例3
在氩气气氛中，将10g纳米二氧化钛加入1000mL二甲基亚砜中，于10℃温度下超声并搅拌处理1.5小时，然后将100g氟代聚芳醚阴离子聚合物（PFO-TMBA-- OH- 50，Mn=100000）加入上述混合液，充分搅拌至聚合物完全溶解。在搅拌下缓慢加入20g 1-乙烯基咪唑至其溶解，得到混合溶液备用. 之后，于10℃温度下，将交联催化剂偶氮二异庚腈0.2g, 搅拌混合均匀，得到制膜液。将所述制膜液涂覆于基板上，在70℃保持15小时后再在120℃保持20小时，脱膜后用去离子水洗涤除去杂离子，得到含氟聚芳醚复合阴离子交换膜，其性能见表1。
实施例4
在氮气气氛中，将30g纳米二氧化硅加入2000mLN－甲基吡咯烷酮中，于15℃温度下超声并搅拌处理1小时，然后将150g氟代聚芳醚阴离子聚合物（PFO-TMPA-- I- 80，Mn=150000）加入上述混合液，充分搅拌至聚合物完全溶解。在搅拌下缓慢加入45g 1-丙烯基咪唑至其溶解，得到混合溶液备用. 之后，于25℃温度下，将交联催化剂偶氮二异丁腈0.9g, 搅拌混合均匀，得到制膜液。将所述制膜液涂覆于基板上，在80℃保持16小时后再在200℃保持18小时，脱膜后用去离子水洗涤除去杂离子，得到含氟聚芳醚复合阴离子交换膜，其性能见表1。
实施例5
在氮气气氛中，将50g纳米氧化锆加入4000mL的1，2-二氯乙烷中，于0℃温度下超声并搅拌处理1小时，然后将300g氟代聚芳醚阴离子聚合物（PFO-TMBA-- F- 88，Mn=50000）加入上述混合液，充分搅拌至聚合物完全溶解。在搅拌下缓慢加入1-乙烯基咪唑80g，待其溶解，得到混合溶液备用. 之后，于30℃温度下，将交联催化剂过氧化二苯甲酰2.0g, 搅拌混合均匀，得到制膜液。将所述制膜液涂覆于基板上，在60℃保持18小时后再在180℃保持16小时，脱膜后用去离子水洗涤除去杂离子，得到含氟聚芳醚复合阴离子交换膜，其性能见表1。
实施例6
在氮气气氛中，将80g纳米氧化硅加入3000mL的1，2-二氯乙烷中，于0℃温度下超声并搅拌处理2小时，然后将400g氟代聚芳醚阴离子聚合物（PFO-TMPA-– Br- 45，Mn=150000）加入上述混合液，充分搅拌至聚合物完全溶解。在搅拌下缓慢加入1-丙烯基咪唑40g，待其溶解，得到混合溶液备用. 之后，于30℃温度下，将交联催化剂偶氮二异庚腈0.08g, 搅拌混合均匀，得到制膜液。将所述制膜液涂覆于基板上，在60℃保持20小时后再在180℃保持20小时，脱膜后用去离子水洗涤除去杂离子，得到含氟聚芳醚复合阴离子交换膜，其性能见表1。
表1.含氟聚芳醚复合阴离子交换膜的相关性能
注：膜性能测试参见文献【Feng SG et al., Journal of Membrane Science, 2009, 335 (1-2): 13-20及Tian B et al.,. Journal of Applied Electrochemistry, 2004, 34 (12):1205-1210】, 测试温度为30℃。

Claims (4)

1.一种原位聚合法制备含氟聚芳醚复合阴离子交换膜的方法，其特征在于，该方法包括以下步骤：
(1)在惰性气氛中，将无机纳米粉体加入有机溶剂中，于0-30℃温度下超声并搅拌处理0.5-2小时，使其分散均匀；
(2)将氟取代聚芳醚阴离子聚合物加入上述混合液中充分搅拌至聚合物完全溶解；其中无机纳米粉体与氟取代聚芳醚阴离子聚合物的质量比为1-25％，氟取代聚芳醚阴离子聚合物与有机溶剂的质量比为5-20％；
(3)搅拌下在上述混合液中加入活性复合组分至其溶解，得到混合溶液备用；所加活性复合组分与氟取代聚芳醚阴离子聚合物的质量比为1-40％；所述活性复合组分为1-乙烯基咪唑或1-烯丙基咪唑；
(4)于0-30℃温度下，将交联催化剂加入上述混合液，搅拌混合均匀，得到制膜液；交联催化剂加入量为步骤(3)中加入活性复合组分的0.1-10wt％；所述交联催化剂为过氧化二苯甲酰、过氧化环己酮、偶氮二异丁腈或偶氮二异庚腈；
(5)将上述制膜液涂覆于基板上，在60-80℃保持10-24小时后再在100-200℃保持6-24小时，脱膜后用去离子水洗涤除去杂离子，得到含氟聚芳醚复合阴离子交换膜；
步骤(2)中所述氟取代聚芳醚阴离子聚合物其结构式为式(Ⅰ)，其数均分子量为5000-200000，功能化程度为15～95％；所述功能化程度由R中Rf与H的摩尔比来计算，功能化程度＝Rf的摩尔数量：(H的摩尔数量+Rf的摩尔数量)；
式(Ⅰ)中Ar为
Ar中R为H或Rf；
Rf为下列功能基团的一种：
其中X为F-、Cl-、Br-、I-或OH-。
2.根据权利要求1所述的制备方法，其特征在于，步骤(1)中所述惰性气氛为氮气或氩气。
3.根据权利要求1所述的制备方法，其特征在于，步骤(1)中所述无机纳米粉体为纳米二氧化硅、纳米二氧化钛、纳米氧化锆中的一种或一种以上。
4.根据权利要求1所述的制备方法，其特征在于，步骤(1)中所述有机溶剂为二甲基甲酰胺、二甲基乙酰胺、1，2-二氯乙烷、乙腈、二甲基亚砜、二苯砜、环丁砜、N－甲基吡咯烷酮中的一种或一种以上。
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