CN112979946A - 一种苯并咪唑阴离子交换膜及其制备方法 - Google Patents
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Abstract
本发明公开了一种苯并咪唑阴离子交换膜及其制备方法,包括:(1)制备1‑溴丁基四甲基胍盐酸盐;(2)1,2,4,5‑四氨基苯、对苯二甲酸和3,3’,5,5’‑四氟联苯‑4,4'‑二羧酸在氮气环境下采用微波辅助溶液缩聚法合成含氟聚苯并咪唑;(3)含氟聚苯并咪唑与1‑溴丁基四甲基胍盐酸盐在有相转移催化剂和碱条件下反应制备侧烷基胍盐聚苯并咪唑(PBI‑g‑Gs),经流平制膜和离子交换后得到一种苯并咪唑阴离子交换膜;该膜以聚苯并咪唑为主链,以烷基胍盐为侧基,与现有技术相比,胍盐侧基的亲水性更强;含氟聚苯并咪唑有更高的疏水性,因此获得的AEMs有更优的耐碱性、更高的含水量和离子电导率。
Description
技术领域
本发明属于燃料电池材料技术领域,具体涉及一种苯并咪唑阴离子交换膜及其制备方法。
背景技术
目前以季铵盐为离子基团的AEMs研究最为广泛,多以聚醚酮、聚醚砜、聚苯并咪唑为聚合物骨架,该类聚合物主链都带有芳环,刚度较大,能够赋予AEMs的结构稳定性。聚苯并咪唑具有较稳定的主链杂环结构,近年来国内外开展了聚苯并咪唑阴离子膜的研究,文献(Polym.Chem.,2011,2,1641)中以聚苯并咪唑为主链,赋予了膜优良的机械性能和稳定性,但是主链咪唑环上氮原子改性为离子基团,或将影响离子膜的寿命,而且离子基团的数量受到主链的限制,离子交换容量较低,导电率较低。马宏玫(具有位阻结构的新型聚苯并咪唑阴离子交换膜的制备及性能研究[D].北京化工大学,2019.)利用具有大位阻单体四苯基对苯二甲酸与3,3’,4,4’-四氨基联苯酰化环化,在将咪唑N季铵化,制备得到主链型的苯并咪唑,大位阻的单体减少OH-进攻咪唑环而发生开环,提高其耐碱性。CN 110527088 B公开了一种侧链型的苯并咪唑阴离子交换膜,以非离子型的聚苯并咪唑作为主链,螺环季铵盐作为侧链,该改性途径既保留了聚苯并咪唑优良的机械性能和热稳定性,又能降低主链降解的容易程度,但螺环型季铵盐虽然耐碱性优异,但亲水性不足,使得阴离子交换膜的IEC、电导率和含水量都较低,因此聚苯并咪唑阴离子交换膜在结构设计合成方面需要优化。
发明内容
针对上述现有技术现状,本发明提供一种苯并咪唑阴离子交换膜,具有如下分子结构:
上述苯并咪唑阴离子交换膜的反应流程及制备方法如下:
(2)制备1,2,4,5-四氨基苯(TAB)
按CN108191669 A的专利方法制得,具体流程为:1,2,3-三氯苯硝化后得到4,6,-二硝基-1,2,3-三氯苯,继而进行氨解,得到到4,6-二硝基-2-氯-1,3-苯二胺,最后在加热加压反应条件下进行氢解,得到1,2,4,5-四氨基苯。
(3)制备含氟聚苯并咪唑(FPBI)
以1,2,4,5-四氨基苯、对苯二甲酸、3,3’,5,5’-四氟联苯-4,4'-二羧酸为混合单体,以多聚磷酸(PPA)为溶剂,在氮气环境下采用微波辅助溶液缩聚法合成含氟聚苯并咪唑。
所述1,2,4,5-四氨基苯(TAB)、对苯二甲酸(PTA)、3,3’,5,5’-四氟联苯-4,4'-二羧酸(TFA)的投料摩尔比为1:0.6~0.8:0.2~0.4。
(3)制备1-溴丁基四甲基胍盐酸盐(BGs)
四甲基胍缓慢滴入1,4-二溴丁烷的甲醇溶液中,在室温下搅拌反应16~24h,反应液过柱纯化、干燥后得到1-溴丁基四甲基胍;
1-溴丁基四甲基胍重新以去离子水溶解,滴入浓盐酸,加热反应6~10h后,得到BGs,具有如下分子结构式:
所述四甲基胍、1,4-二溴丁烷的投料摩尔比例为1:3~5。
(4)制备侧烷基胍盐聚苯并咪唑(PBI-g-Gs)
含氟聚苯并咪唑(FPBI)与1-溴丁基四甲基胍盐酸盐(BGs)在有相转移催化剂和碱条件下反应制备侧烷基胍盐聚苯并咪唑(PBI-g-Gs)。
所述相转移催化剂四丁基溴化铵。
所述碱为四甲基氢氧化铵。
反应液过滤后浇注在玻璃板内,置于真空干燥箱干燥,最后将所得膜浸泡于NaOH溶液进行离子交换后保存于去离子水中,制备得到苯并咪唑阴离子交换膜。
本发明具有如下优点和有益效果:
本发明制备的苯并咪唑阴离子交换膜,以聚苯并咪唑为主链,以烷基胍盐为侧基,与现有技术相比,胍盐侧基的亲水性更强;含氟聚苯并咪唑有更高的疏水性,因此获得的AEMs有更优的耐碱性、更高的含水量和离子电导率。
附图说明
图1为实施例4制备的PBI-g-Gs-2的1H-NMR。
图2为实施例4制备的AEMs在60℃2mol/L KOH溶液中电导率随时间的变化关系。
图3为苯并咪唑阴离子交换膜的分子结构式。
具体实施方式
下面结合具体实施例对本发明做进一步详细说明,但实施例并不对本发明做任何形式的限定。除非特别说明,本发明采用的试剂、方法和设备为本技术领域常规试剂、方法和设备。
实施例1
制备1,2,4,5-四氨基苯
称取1,2,3-三氯苯(20.14g 0.11mol)放入三口烧瓶中,加入80mL98%浓硫酸,加热至50℃,开始滴加浓硝酸(65wt%~68wt%)20mL,滴毕后升温至70℃,继续反应5h,停止反应,得到黄色固体粗品4,6-二硝基-1,2,3-三氯苯,收率为82.4%;
称取4,6-二硝基-1,2,3-三氯苯(22.25g,0.08mol)放入高压反应釜中,并加入50mL乙二醇,加热至150℃,通入氨气,氨压1.0MPa,反应8h后停止反应,冷却至室温后将反应物过滤,得到粗品,经无水乙醇重结晶得到4,6-二硝基-2-氯-1,3-苯二胺,收率为86.5%。
称取4,6-二硝基-2-氯-1,3-苯二胺(28.56g,0.12mol)、1.42g Pd/C(3%)溶于80mL N,N-二甲基甲酰胺(DMF)中,并加入至高压反应釜中,加热至80℃,通入氢气,氢压1MPa,反应8h后停止反应,冷却至室温后过滤,得到粗品,经丙酮重结晶后得到1,2,4,5-四氨基苯,收率为74.8%。
实施例2
制备含氟聚苯并咪唑(FPBI)。
提前将微波合成仪的程序按要求设定好,首先在N2的存在下微波辐射多聚磷酸(PPA)脱氧0.5h,混合1,2,4,5-四氨基苯(TAB)、对苯二甲酸(PTA)、3,3’,5,5’-四氟联苯-4,4'-二羧酸(TFA)和PPA后将混合料在N2下剧烈搅拌,采用程序升温法:90℃0.5h,120℃0.5h,140℃5h,180℃0.5h,200℃10h。反应结束后,将反应液倒入等体积去离子水中沉淀,过滤后用去离子水和乙醇交替洗涤,重复多次至水相呈中性为止,将所得深色固体在100℃真空干燥箱中干燥48h,得到含氟聚苯并咪唑(FPBI)。
各FPBI样品的投料质量、编号和分子量列于表1。
表1
a.数均分子量Mn采用WATERS 515型凝胶渗透色谱仪测定:以N,N-二甲基甲酰胺为溶剂,窄分布线型聚苯乙烯为标样。
b.以TAB的投入量计算产率。
实施例3
制备1-溴丁基四甲基胍盐酸盐(BGs)。
在装有恒压滴液漏斗的反应瓶中加入1,4-二溴丁烷(29.02g,0.13mol),加入80mL乙醇搅拌溶解,然后开始滴加四甲基胍(5.16g,0.04mol),滴完后在室温下搅拌反应20h;反应结束后,过滤反应溶液,然后60℃下旋蒸挥发低沸点化合物,得到粗产物。以二氯甲烷为洗脱剂,过硅胶色谱柱,所得滤份干燥后得到白色固体粉末,为1-溴丁基四甲基胍,产率为75.6%。
重新用20mL去离子水溶解1-溴丁基四甲基胍放入装有恒压滴液漏斗的单口烧瓶中,升温至60℃,开始滴加20g 30%的盐酸溶液,滴完后保温反应6h,反应结束后旋蒸除去溶剂,得到1-溴丁基四甲基胍盐酸盐(BGs),产率94.8%
实施例4
制备侧烷基胍盐聚苯并咪唑(PBI-g-Gs)。
称取实施例2制备的含氟聚苯并咪唑(FPBI)和四丁基溴化铵(TBA)、四甲基氢氧化铵(TMAH)放入装有冷凝管和恒压滴液漏斗的三口烧瓶中,并加入甲苯,升温至80℃搅拌使固体完全溶解后,开始滴加1-溴丁基四甲基胍盐酸盐(BGs)的甲苯溶液,滴完后继续保温反应3h。反应结束后,反应溶液用孔径为0.45μm的PTFE滤头过滤后浇注在玻璃板上,置于150℃真空干燥箱干燥1h,后降温至100℃继续干燥24h,最后将所得膜浸泡于1mol/L的NaOH溶液中进行离子交换24h后,保存于去离子水中,得到苯并咪唑阴离子交换膜。
各PBI-g-Gs样品的投料质量及性能测试结果列于表2。
表2
实施例5
对实施例4制备的苯并咪唑阴离子交换膜进行如下性能测试:
(1)含水量(WU)、溶胀率(SR):裁取1cm×4cm的膜浸入80℃的去离子水中24h,测量湿膜的质量mw和长度lw.将膜置于60℃下真空干燥至恒重,测量干膜质量md和长度ld根据下式计算WU或SR的值:
(2)离子交换容量(IEC)测试:利用莫尔滴定法测定,完全干燥的样品膜,称重记为Wdry,在室温下浸入1mol/L NaCl溶液中24h进行离子交换,取出膜用去离子水洗涤,以除去游离的Cl-,然后将膜浸入0.5mol/L Na2SO4水溶液中24h进行离子交换,以完全释放Cl-。然后以K2CrO4为指示剂,用0.01mol/L AgNO3水溶液滴定溶液。IEC值根据下式计算:
(4)水合数(λ),即每个功能基团能吸收的水分子的个数,根据下式计算λ值:
(4)离子电导率测试:使用Princeton VersaSTAT 4电化学综合测试系统测量阴离子交换膜的阻抗,频率范围在1MHz~1Hz。根据下式计算膜的在80℃下的离子电导率(σ,mS/cm)
式中,L指两铜电极之间的距离,cm;A指在两电极间的膜横截面积,cm2;R为膜的阻抗值,KΩ。
(5)耐碱性测试:将膜浸于60℃、2mol/L的KOH溶液,间隔一段时间取样,测定膜的离子电导率。
(6)机械性能测试:采用Instron3343型万能试验机测试样品膜的拉伸强度和断裂伸长率。测试条件为:室温,拉伸速率为0.2mm/s,测试前将膜在去离子水中浸泡24h。
各样品性能测试结果如表3所示。
表3
耐碱性测试结果参阅附图2。
从表3和附图2数据可知,本发明提供的苯并咪唑阴离子交换膜具有良好的机械性能和耐碱性,与现有技术相比,本发明的阴离子交换膜的含水量更高,是由于胍盐阳离子相比于杂环中的铵离子有更强的碱性,吸水性更强。由于聚苯并咪唑主链上引入氟原子,在相同IEC水平下,阴离子交换膜的离子电导率更高,是由于氟原子增加了主链的疏水性,使其与侧基自由端的胍阳离子微相分离,构建出更有效的离子通道。综上所述,本发明提供的苯并咪唑阴离子交换膜性能上具有更显著的的进步。
上述实施例为本发明较佳的实施方式,但本发明的实施方式并不受上述实施例的限制,其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化,均应为等效的置换方式,都包含在本发明的保护范围之内。
Claims (6)
2.一种苯并咪唑阴离子交换膜的制备方法,其特征在于,包括以下步骤:
(1)制备含氟聚苯并咪唑(FPBI)
以1,2,4,5-四氨基苯、对苯二甲酸、3,3’,5,5’-四氟联苯-4,4'-二羧酸为混合单体,以多聚磷酸(PPA)为溶剂,在氮气环境下采用微波辅助溶液缩聚法合成含氟聚苯并咪唑;
(2)制备1-溴丁基四甲基胍盐酸盐(BGs)
四甲基胍缓慢滴入1,4-二溴丁烷的甲醇溶液中,在室温下搅拌反应16~24h,反应液过柱纯化、干燥后得到1-溴丁基四甲基胍;
1-溴丁基四甲基胍重新以去离子水溶解,滴入浓盐酸,加热反应6~10h后,得到BGs,具有如下式(II)分子结构:
(3)制备侧烷基胍盐聚苯并咪唑(PBI-g-Gs)
含氟聚苯并咪唑(FPBI)与1-溴丁基四甲基胍盐酸盐(BGs)在有相转移催化剂和碱条件下反应制备侧烷基胍盐聚苯并咪唑(PBI-g-Gs);
反应液过滤后浇注在玻璃板内,置于真空干燥箱干燥,最后将所得膜浸泡于NaOH溶液进行离子交换后保存于去离子水中,制备得到苯并咪唑阴离子交换膜。
3.根据权利要求2所述的一种苯并咪唑阴离子交换膜的制备方法,其特征在于,步骤(1)所述1,2,4,5-四氨基苯(TAB)、对苯二甲酸(PTA)、3,3’,5,5’-四氟联苯-4,4'-二羧酸(TFA)的投料摩尔比为1:0.6~0.8:0.2~0.4。
4.根据权利要求2所述的一种苯并咪唑阴离子交换膜的制备方法,其特征在于,步骤(2)所述四甲基胍、1,4-二溴丁烷的投料摩尔比例为1:3~5。
5.根据权利要求2所述的一种苯并咪唑阴离子交换膜的制备方法,其特征在于,步骤(3)所述相转移催化剂四丁基溴化铵。
6.根据权利要求2所述的一种苯并咪唑阴离子交换膜的制备方法,其特征在于,步骤(3)所述碱选用四甲基氢氧化铵。
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