CN109119662B - 一种长支链双梳状聚芳基吲哚阴离子交换膜及其制备方法 - Google Patents
一种长支链双梳状聚芳基吲哚阴离子交换膜及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种长支链双梳状聚芳基吲哚阴离子交换膜及其制备方法,属于碱性阴离子交换膜技术领域。本发明合成了具有良好稳定性和机械性能的含芳酰胺基的聚芳基吲哚聚合物,再将聚合物接枝长支链离子液体并制膜。所制备的膜具有较好的碱性稳定性和较高的离子电导率,可应用于碱性燃料电池中。
Description
技术领域
本发明属于碱性阴离子交换膜技术领域,涉及到一种长支链双梳状聚芳基吲哚阴离子交换膜及其制备方法。
背景技术
随着环境问题和能源问题的日益突出,燃料电池作为一种清洁且功率转换效率高的设备,被认为是最有希望和最有前景的固态和移动应用。在各种燃料电池中,碱性燃料电池(AFCs)因其改善了氧还原动力学和更好燃料氧化动力学,以至于产生更高的效率和能够使用低成本的非贵金属催化剂优点而被认为是具有吸引力的选择。在过去的几十年里,人们对AFC的兴趣越来越大,特别是使用阴离子交换膜(AEMs)的AFC。在AEMFC中,AEM充当固态电解质输送氢氧根离子并防止阳极和阴极之间的燃料交叉。AEMs具有高燃料电池性能要求高的氢氧化物电导率,低溶胀度和优异的化学稳定性。
然而,氢氧根的低迁移率是成功应用阴离子交换膜燃料电池的的主要障碍。为提高AEM的阴离子电导率,许多新技术研究了含有导电基团的材料,例如聚亚芳基醚,聚醚酰亚胺,聚苯乙烯,聚苯并咪唑,聚烯烃和聚苯醚等。但最近的研究发现,这些含有醚氧键的聚合物主链均存在热碱环境中容易被攻击导致分子链降解的缺点,因此,寻找一种稳定的聚合物导电材料至关重要。此外,不同的策略表明,功能基团的不同,对膜的性能存在很大的影响。因此,如今研究中许多努力都集中在开发高性能AEM上,重在提高膜的碱性稳定性和离子电导率。
发明内容
本发明旨在提高碱性阴离子交换膜的碱性稳定性和离子电导率,提供了一种长支链双梳状聚芳基吲哚阴离子交换膜的制备方法:合成了具有良好稳定性和机械性能的含芳酰胺基的聚芳基吲哚聚合物,再将聚合物接枝长支链离子液体并制膜。所制备的膜具有较好的碱性稳定性和较高的离子电导率,可应用于碱性燃料电池中。
本发明的技术方案:
一种长支链双梳状聚芳基吲哚阴离子交换膜,其结构如下:
其中,x=0.01~1;n1=1~12的正整数;n2=1~6,8,10,12,14~19的正整数;R为引入的功能基团,为三甲胺,1-甲基咪唑、2-甲基咪唑、1,2-二甲基咪唑、N-甲基吗啡啉、N-甲基哌啶或N-甲基吡咯烷。
一种长支链双梳状聚芳基吲哚阴离子交换膜的制备方法,步骤如下:
(1)聚芳基吲哚聚合物的合成
在惰性气体保护下,将2,3-吲哚二酮与联苯溶于溶剂A和溶剂D的混合溶剂中,在冰浴环境下慢速加入催化剂C,然后逐渐升温至室温,升温时间0.5~2h;当反应变为高度黏稠液体时倾倒入析出剂D,过滤,干燥,得到粗产品;再将粗产品溶于溶剂E中,完全溶解后倾倒入析出剂D,过滤,干燥,得到纯化的聚芳基吲哚聚合物;
所述的溶剂A为二氯甲烷,所述的溶剂B为三氟乙酸,溶剂A与溶剂B的体积比为0.01~0.33;
所述的2,3-吲哚二酮与联苯的摩尔比为1~1.1:1,2,3-吲哚二酮和联苯的总质量在溶剂A和溶剂B混合溶剂中的w/v为40~80%;
所述的催化剂C为三氟甲磺酸;
所述的2,3-吲哚二酮和联苯的总质量与催化剂C的体积w/v为30~50%;
所述的析出剂D为甲醇和/或乙醇;
所述的溶剂E为二甲基亚砜(DMSO)或N-甲基吡咯烷酮(NMP);
所述的粗产品在溶剂E中的w/v为5~20%。
(2)离子液体的制备
将含有脂肪链的二溴单体F及试剂G溶解于溶剂H中,在20~60℃反应48h,将析出的固体产物用溶剂H反复清洗3~5次,真空干燥得到离子液体;
所述的含有脂肪链的二溴单体结构如下:
所述的含有脂肪链的二溴单体F与试剂G的摩尔比2~10:1;
所述的含有脂肪链的二溴单体F及试剂G的总质量在溶剂H中的w/v为10~30%;
所述的试剂G为1-甲基咪唑、2-甲基咪唑、1,2-二甲基咪唑、N-甲基吗啡啉、N-甲基哌啶、N-甲基吡咯烷中的一种;
所述的溶剂H为乙酸乙酯或乙腈;
(3)长支链双梳状聚芳基吲哚阴离子交换膜的制备
将聚芳基吲哚聚合物溶于溶剂I中,分别加入试剂J、试剂K和试剂L,80℃下反应12h,再加入离子液体,继续80℃反应24h,将反应溶液冷却至室温后倾倒至析出剂M析出产物,过滤、用去离子水洗涤三次以上、干燥得到产品;再将产物溶于溶剂N中制备铸膜液后浇铸成膜;将膜浸泡于1mol L-1氢氧化钠溶液中24~48h,用去离子水浸泡并洗涤至中性,即制得长支链双梳状聚芳基吲哚阴离子交换膜。
所述的溶剂I为二甲基亚砜(DMSO);
所述的聚芳基吲哚聚合物溶于溶剂I中的w/v为2.5~5%;
所述的试剂J为碳酸钾;
所述的试剂K为碘化钾;
所述的聚芳基吲哚聚合物:试剂J:试剂K的摩尔比为1:1~2:0.1~0.2;
所述的试剂L为1-溴脂肪链,结构如下:
所述的析出剂M为丙酮;
所述的溶剂I为二甲基亚砜(DMSO);
所述的铸膜液w/v为2%~10%;
所述的浇铸法成膜的烘干温度为50~80℃,时间为12~72h;
步骤(1)中的干燥条件:温度为40~100℃,真空干燥,时间为12h以上;
步骤(2)中的干燥条件:温度为40~80℃,真空干燥,时间为12h以上;
步骤(3)中的干燥条件:温度为20~40℃,真空干燥,时间为12h以上。
本发明的有益效果:
通过改变离子液体的反应量改变膜的功能化程度,可以控制制备出不同离子交换容量及其他相关性能的阴离子交换膜。
1.聚芳基吲哚聚合物主链的应用提高了膜的碱稳定性和热稳定性。接枝长侧链离子液体,增加了离子基团的移动性,提高了膜的离子电导率和碱稳定性。
2.侧基疏水链的引入,改善了膜的微观相分离效果,提高了膜的离子电导率和碱性稳定性。
附图说明
图1是接枝六碳哌啶离子液体和六碳烷基链的聚芳基吲哚阴离子交换膜核磁共振氢谱(1H NMR)。
具体实施方式
以下结合实施案例对本发明做进一步详细的描述,但是本发明的实施方式并不仅限于此。
实施例1
聚芳基吲哚聚合物的合成:在惰性气体保护下,将5.25g 2,3-吲哚二酮和5.42g联苯溶于6mL二氯甲烷和11mL三氟乙酸中,完全溶解后,将反应置于冰浴环境下,慢速加入25mL的三氟甲磺酸,然后逐渐升温至室温,升温时间约0.5~2h。当反应变为高度黏稠液体时反应结束,将其倾倒入甲醇中,得到块状白色固体,浸泡约12h,过滤干燥后得到粗产品。再将粗产品溶于约120mL NMP中,完全溶解后倾倒入甲醇中析出得到白色纤维状固体,浸泡24h后,过滤,甲醇洗涤三次以上,真空环境下60℃干燥24h,得到纯化后的聚芳基吲哚聚合物。
长支链双梳状聚芳基吲哚阴离子交换膜的制备:将0.3g聚芳基吲哚聚合物溶于9mL二甲基亚砜中,完全溶解后,加入0.22g碳酸钾和0.03g碘化钾,然后加入0.55g六碳哌啶功能化离子液体,80℃下反应36h后,将反应溶液冷却至室温后倾倒至丙酮中析出产物,过滤、用去离子水洗涤三次以上,室温真空干燥24h得到产物。再将0.12g产物溶于3mL二甲基亚砜中,完全溶解制备成铸膜液,将铸膜液离心后浇铸在玻璃模具中,60℃下干燥36h,得到聚合物膜。将膜浸泡于1mol L-1氢氧化钠溶液中24~48h,用去离子水浸泡并洗涤至中性,即可制得长支链梳状聚芳基吲哚阴离子交换膜。
本实例所得到的阴离子交换膜的结构如下:
经测试表明,本实施例中所制备的长支链双梳状聚芳基吲哚阴离子交换膜在20℃时离子传导率为60mS cm-1,吸水率为69%,溶胀度为26%,80℃浸泡于1mol L-1的KOH溶液中4周,离子交换容量和离子电导率几乎未发生变化,膜表现出良好的碱稳定性能。
实施例2
聚芳基吲哚聚合物的合成:在惰性气体保护下,将5.25g 2,3-吲哚二酮和5.42g联苯溶于6mL二氯甲烷和11mL三氟乙酸中,完全溶解后,将反应置于冰浴环境下,慢速加入25mL的三氟甲磺酸,然后逐渐升温至室温,升温时间约0.5~2h。当反应变为高度黏稠液体时反应结束,将其倾倒入甲醇中,得到块状白色固体,浸泡约12h,过滤干燥后得到粗产品。再将粗产品溶于约120mL NMP中,完全溶解后倾倒入甲醇中析出得到白色纤维状固体,浸泡24h后,过滤,甲醇洗涤三次以上,真空环境下60℃干燥24h,得到纯化后的聚芳基吲哚聚合物。
长支链双梳状聚芳基吲哚阴离子交换膜的制备:将0.3g聚芳基吲哚聚合物溶于9mL二甲基亚砜中,完全溶解后,加入0.22g碳酸钾和0.03g碘化钾,然后加入0.035g 1-溴代正己烷,80℃反应12h,然后加入0.44g六碳吗晽功能化离子液体,80℃下反应24h后,将反应溶液冷却至室温后倾倒至丙酮中析出产物,过滤、用去离子水洗涤三次以上,室温真空干燥24h得到产物。再将0.12g产物溶于3mL二甲基亚砜中,完全溶解制备成铸膜液,将铸膜液离心后浇铸在玻璃模具中,60℃下干燥36h,得到聚合物膜。将膜浸泡于1mol L-1氢氧化钠溶液中24~48h,用去离子水浸泡并洗涤至中性,即可制得长支链梳状聚芳基吲哚阴离子交换膜。
本实例所得到的阴离子交换膜的结构如下:
经测试表明,本实施例中所制备的长支链双梳状聚芳基吲哚阴离子交换膜在20℃时离子传导率为34mS cm-1,吸水率为40%,溶胀度为16%,80℃浸泡于1mol L-1的KOH溶液中4周,离子交换容量和离子电导率几乎未发生变化,膜表现出良好的碱稳定性能。
实施例3
聚芳基吲哚聚合物的合成:在惰性气体保护下,将5.25g 2,3-吲哚二酮和5.42g联苯溶于6mL二氯甲烷和11mL三氟乙酸中,完全溶解后,将反应置于冰浴环境下,慢速加入25mL的三氟甲磺酸,然后逐渐升温至室温,升温时间约0.5~2h。当反应变为高度黏稠液体时反应结束,将其倾倒入甲醇中,得到块状白色固体,浸泡约12h,过滤干燥后得到粗产品。再将粗产品溶于约120mL NMP中,完全溶解后倾倒入甲醇中析出得到白色纤维状固体,浸泡24h后,过滤,甲醇洗涤三次以上,真空环境下60℃干燥24h,得到纯化后的聚芳基吲哚聚合物。
长支链双梳状聚芳基吲哚阴离子交换膜的制备:将0.3g聚芳基吲哚聚合物溶于9mL二甲基亚砜中,完全溶解后,加入0.22g碳酸钾和0.03g碘化钾,然后加入0.024g癸基溴,80℃反应12h,然后加入0.39g四碳三甲胺功能化离子液体,80℃下反应24h后,将反应溶液冷却至室温后倾倒至丙酮中析出产物,过滤、用去离子水洗涤三次以上,室温真空干燥24h得到产物。再将0.12g产物溶于3mL二甲基亚砜中,完全溶解制备成铸膜液,将铸膜液离心后浇铸在玻璃模具中,60℃下干燥36h,得到聚合物膜。将膜浸泡于1mol L-1氢氧化钠溶液中24~48h,用去离子水浸泡并洗涤至中性,即可制得长支链梳状聚芳基吲哚阴离子交换膜。
本实例所得到的阴离子交换膜的结构如下:
经测试表明,本实施例中所制备的长支链双梳状聚芳基吲哚阴离子交换膜在20℃时离子传导率为41mS cm-1,吸水率为46%,溶胀度为19%,80℃浸泡于1mol L-1的KOH溶液中4周,离子交换容量保留率为95%和离子电导率保留率为93%,膜表现出良好的碱稳定性能。
实施例4
聚芳基吲哚聚合物的合成:在惰性气体保护下,将5.25g 2,3-吲哚二酮和5.42g联苯溶于6mL二氯甲烷和11mL三氟乙酸中,完全溶解后,将反应置于冰浴环境下,慢速加入25mL的三氟甲磺酸,然后逐渐升温至室温,升温时间约0.5~2h。当反应变为高度黏稠液体时反应结束,将其倾倒入甲醇中,得到块状白色固体,浸泡约12h,过滤干燥后得到粗产品。再将粗产品溶于约120mL NMP中,完全溶解后倾倒入甲醇中析出得到白色纤维状固体,浸泡24h后,过滤,甲醇洗涤三次以上,真空环境下60℃干燥24h,得到纯化后的聚芳基吲哚聚合物。
长支链双梳状聚芳基吲哚阴离子交换膜的制备:将0.3g聚芳基吲哚聚合物溶于9mL二甲基亚砜中,完全溶解后,加入0.22g碳酸钾和0.03g碘化钾,然后加入0.052g 1-溴辛烷,80℃反应12h,然后加入0.42g八碳吡咯烷功能化离子液体,80℃下反应24h后,将反应溶液冷却至室温后倾倒至丙酮中析出产物,过滤、用去离子水洗涤三次以上,室温真空干燥24h得到产物。再将0.12g产物溶于3mL二甲基亚砜中,完全溶解制备成铸膜液,将铸膜液离心后浇铸在玻璃模具中,60℃下干燥36h,得到聚合物膜。将膜浸泡于1mol L-1氢氧化钠溶液中24~48h,用去离子水浸泡并洗涤至中性,即可制得长支链梳状聚芳基吲哚阴离子交换膜。
本实例所得到的阴离子交换膜的结构如下:
经测试表明,本实施例中所制备的长支链双梳状聚芳基吲哚阴离子交换膜在20℃时离子传导率为28mS cm-1,吸水率为31%,溶胀度为15%,80℃浸泡于1mol L-1的KOH溶液中4周,离子交换容量保留率为96%和离子电导率保留率为94%,膜表现出良好的碱稳定性能。
Claims (5)
1.一种长支链双梳状聚芳基吲哚阴离子交换膜的制备方法,其特征在于,所述的长支链双梳状聚芳基吲哚阴离子交换膜的结构如下:
其中,x=0.01~1;n1=1~12的正整数;n2=1~6,8,10,12,14~19的正整数;R为引入的功能基团,为三甲胺,1-甲基咪唑、2-甲基咪唑、1,2-二甲基咪唑、N-甲基吗啡啉、N-甲基哌啶或N-甲基吡咯烷;
步骤如下:
(1)聚芳基吲哚聚合物的合成
在惰性气体保护下,将2,3-吲哚二酮与联苯溶于溶剂A和溶剂D的混合溶剂中,在冰浴环境下慢速加入催化剂C,然后逐渐升温至室温,升温时间0.5~2h;当反应变为高度黏稠液体时倾倒入析出剂D,过滤,干燥,得到粗产品;再将粗产品溶于溶剂E中,完全溶解后倾倒入析出剂D,过滤,干燥,得到纯化的聚芳基吲哚聚合物;
所述的溶剂A为二氯甲烷;
所述的溶剂B为三氟乙酸;
所述的溶剂A与溶剂B的体积比为0.01~0.33;
所述的2,3-吲哚二酮与联苯的摩尔比为1~1.1:1,2,3-吲哚二酮和联苯的总质量在溶剂A和溶剂B混合溶剂中的w/v为40~80%;
所述的催化剂C为三氟甲磺酸;
所述的2,3-吲哚二酮和联苯的总质量与催化剂C的体积w/v为30~50%;
所述的析出剂D为甲醇和/或乙醇;
所述的溶剂E为二甲基亚砜或N-甲基吡咯烷酮;
所述的粗产品在溶剂E中的w/v为5~20%;
(2)离子液体的制备
将含有脂肪链的二溴单体F及试剂G溶解于溶剂H中,在20~60℃反应48h,将析出的固体产物用溶剂H反复清洗3~5次,真空干燥得到离子液体;
所述的含有脂肪链的二溴单体结构如下:
所述的含有脂肪链的二溴单体F与试剂G的摩尔比2~10:1;
所述的含有脂肪链的二溴单体F及试剂G的总质量在溶剂H中的w/v为10~30%;
所述的试剂G为1-甲基咪唑、2-甲基咪唑、1,2-二甲基咪唑、N-甲基吗啡啉、N-甲基哌啶、N-甲基吡咯烷中的一种;
所述的溶剂H为乙酸乙酯或乙腈;
(3)长支链双梳状聚芳基吲哚阴离子交换膜的制备
将聚芳基吲哚聚合物溶于溶剂I中,分别加入试剂J、试剂K和试剂L,80℃下反应12h,再加入离子液体,继续80℃反应24h,将反应溶液冷却至室温后倾倒至析出剂M析出产物,过滤、用去离子水洗涤三次以上、干燥得到产品;再将产物溶于溶剂N中制备铸膜液后浇铸成膜;将膜浸泡于1mol L-1氢氧化钠溶液中24~48h,用去离子水浸泡并洗涤至中性,即制得长支链双梳状聚芳基吲哚阴离子交换膜;
所述的溶剂I为二甲基亚砜;
所述的聚芳基吲哚聚合物溶于溶剂I中的w/v为2.5~5%;
所述的试剂J为碳酸钾;
所述的试剂K为碘化钾;
所述的聚芳基吲哚聚合物:试剂J:试剂K的摩尔比为1:1~2:0.1~0.2;
所述的试剂L为1-溴脂肪链,结构如下:
所述的析出剂M为丙酮;
所述的溶剂I为二甲基亚砜;
所述的铸膜液w/v为2%~10%;
所述的浇铸法成膜的烘干温度为50~80℃,时间为12~72h。
2.根据权利要求1所述的制备方法,其特征在于,步骤(1)中的干燥条件:温度为40~100℃,真空干燥,时间为12h以上。
3.根据权利要求1或2所述的制备方法,其特征在于,步骤(2)中的干燥条件:温度为40~80℃,真空干燥,时间为12h以上。
4.根据权利要求1或2所述的制备方法,其特征在于,步骤(3)中的干燥条件:温度为20~40℃,真空干燥,时间为12h以上。
5.根据权利要求3所述的制备方法,其特征在于,步骤(3)中的干燥条件:温度为20~40℃,真空干燥,时间为12h以上。
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