CN109053609A - 一种三苯胺-三嗪衍生物及其制备方法与应用 - Google Patents
一种三苯胺-三嗪衍生物及其制备方法与应用 Download PDFInfo
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Abstract
本发明公开了一种如式1所示的三苯胺‑三嗪衍生物TTPATA及其电化学聚合制备成微孔导电聚合物薄膜的方法，以及作为电极材料在超级电容器方面的应用。将TTPATA单体电化学聚合成膜具有很好的微孔结构，同时pTTPATA薄膜在40A g‑1电流密度下表现出高的比电容430A g‑1。
Description
(一)技术领域
本发明涉及一种三苯胺-三嗪衍生物及其制备方法与应用。
(二)背景技术
随着全球能源的急剧消耗和环境的不断恶化，超级电容器作为搭建电池和传统电容器之间的桥梁，正日益引起人们的关注。目前研究较多的超级电容器材料为碳及无机材料，但能量密度不高及成本较高限制了其应用，相比于碳及无机纳米超级电容器材料，导电聚合物超级电容器具有轻便、柔性、结构易修饰及快速充放电等优点。导电聚合物超级电容器作为一种赝电容材料，主要涉及快速的氧化还原反应，目前主要为聚苯胺、聚吡咯、聚噻吩等衍生物。近期，通过合理的分子结构设计，经电聚合或化学聚合制备成微孔导电聚合物应用于超级电容器受到了研究者的广泛关注，研究结果发现这类材料具有很好的孔隙结构以及优异的超级电容器性能，因此微孔导电聚合物目前被认为是改善此类材料超级电容器性质的、非常有效的材料体系。
相比于聚吡咯、聚噻吩等衍生物，聚苯胺作为超级电容器材料表现出更高的比电容，但聚苯胺的氧化还原过程是在酸性电解质溶液中进行的，限制了其与无机金属氧化物等组成非对称超级电容器器件的应用。
(三)发明内容
本发明的目的之一在于提供一种三苯胺-三嗪衍生物及其制备方法。
本发明的技术方案如下：
一种如式1所示的三苯胺-三嗪衍生物TTPATA：
本发明所述式1所示的三苯胺-三嗪衍生物TTPATA的制备方法具体按照如下步骤进行：
(1)将二苯胺、氢化钠、对氟苯甲腈溶解于N,N-二甲基甲酰胺(DMF)中，于110℃下反应12-24h，反应完全后，得到的反应液A经后处理得到式(I)所示的中间产物；所述二苯胺、氢化钠、对氟苯甲腈的投料物质的量之比为1:2-3:1.2-1.5；
(2)氮气保护下，将式(I)所示的中间产物溶于无水氯仿中，在0℃下逐滴加入三氟甲磺酸，加完之后在常温下反应96-144h，得到的反应液B经后处理得到目标产物三苯胺-三嗪衍生物TTPATA；所述式(I)所示的中间产物、三氟甲磺酸的投料物质的量之比为1：1.5-2.5；
进一步，步骤(1)中，所述的N,N-二甲基甲酰胺的体积用量以二苯胺的质量计为20-30mL/g。
进一步，步骤(1)中，所述反应液A的后处理的方法为：反应结束后，待反应液A冷却至20～30℃，加入水和二氯甲烷进行萃取，收集有机相，再加入水至有机相反复萃取5-6次，除去N,N-二甲基甲酰胺，有机相经无水硫酸镁干燥，减压浓缩，再进行柱层析纯化，以300～400目硅胶为固定相，二氯甲烷/石油醚体积比1：2～3混合液为流动相进行洗脱，收集含目标化合物的洗脱液，减压蒸除溶剂并干燥，得到式(I)所示的中间产物。
进一步，步骤(2)中，所述无水氯仿的体积用量以式(I)所示的中间产物的质量计为15-20mL/g。
进一步，步骤(2)中，所述反应液B的后处理的方法为：反应结束后，将反应液B加入水中，再加入二氯甲烷进行萃取，收集有机相，经无水硫酸镁干燥，减压浓缩，再进行柱层析纯化，以300～400目硅胶为固定相，石油醚/二氯甲烷体积比1：1～2混合液为流动相进行洗脱，收集含目标化合物的洗脱液，减压蒸除溶剂并干燥，得到目标产物三苯胺-三嗪衍生物TTPATA。
本发明的目的之二在于所述的三苯胺-三嗪衍生物在制备超级电容器电极材料中的应用。
进一步，所述的应用为：将TTPATA作为单体，溶解于色谱级的二氯甲烷中，加入四丁基六氟磷酸铵为电解质，采用-1.2V至1.8V循环伏安聚合，扫描速度为100mV/s,，电聚合得到超级电容器电极材料即聚合物薄膜PTTPATA。
再进一步，所述二氯甲烷的体积用量以所述单体的质量计为1-1.5mL/mg。
再进一步，所述四丁基六氟磷酸铵的用量以二氯甲烷的体积计为0.1mol/L。
本发明采用电化学工作站660E，紫外-可见吸收光谱表征了所得膜的电化学及光学性能，所测试的溶液为含有0.1M四丁基六氟磷酸铵的乙腈溶液中进行，将两片完全相同的薄膜分别作为工作电极和对电极、银/氯化银作为辅助电极组成三电极体系，在含有0.1M四丁基六氟磷酸铵的乙腈溶液中测试超级电容器性质，测试结果表明该类薄膜在40A g-1表现出高的比电容430F g-1。
与现有技术相比，本发明的有益效果在于：
采用电化学聚合得到的三苯胺-三嗪衍生物微孔薄膜，具有较大的比表面积，表现出很好的电化学可逆性，同时显现出高的比电容(430F g-1)，是目前有机导电聚合物超级电容器材料的最高值，甚至可媲美无机超级电容器材料，是一类非常潜在的储能材料。
(四)附图说明
图1：本发明实施例3中薄膜pTTPATA的CV聚合曲线图；
图2：本发明实施例4中薄膜pTTPATA组成对称超级电容器不同电流密度下的超级电容器性质。
(五)具体实施方式
下面以具体实施例对本发明的技术方案作进一步说明，但本发明的保护范围不限于此。
实施例1
(1)氢化钠(53.75mmol，1.29g)加入到含有100mL N,N-二甲基甲酰胺的圆底烧瓶中，搅拌至无气泡产生，加入二苯胺(26.09mmol，4.41g)，常温搅拌至反应液变成奶茶绿，将反应升温至110℃，在此温度下，缓慢加入4-氟苯甲腈(31.54mmol，3.82g)，反应溶液变成酒红色，然后逐渐变为棕色，110℃下反应12h。反应结束后，冷却至室温，加入水和二氯甲烷进行萃取，收集有机相，后又向反应液中加入水反复萃取5次，除去N,N-二甲基甲酰胺，然后收集有机相，加入无水硫酸镁干燥，减压浓缩，再用柱层析分离提纯，固定相为300-400目硅胶，流动相为二氯甲烷/石油醚(体积比1：2)，最后得到白色固态的中间产物4-(二苯胺)苯甲腈4.09g，产率为58％。
(2)氮气保护下，将制备的中间产物4-(二苯胺)苯甲腈(I)(7.40mmol，2g)加入30mL无水氯仿溶液中，搅拌至完全溶解，0℃下逐滴加入三氟甲磺酸(11.80mmol，1.78g)，加完后将反应装置移置常温下搅拌反应4d，反应液由透明变为粉红色，最后变成紫黑色。反应结束后，将反应液加入水中，再加入二氯甲烷萃取，收集有机相，加入无水硫酸镁干燥，减压浓缩，再用柱层析分离提纯，固定相为300-400目硅胶，流动相为二氯甲烷/石油醚(体积比1：1)，最后得到浅黄色固态的最终产物0.81g TTPATA，产率为40.6％。1H NMR(500MHz,CDCl3,25℃,TMS,δ):8.56(d,J＝8.8Hz,6H),7.33(t,J＝7.8Hz,12H),7.20(d,J＝7.6Hz,12H),7.14(dd,J＝15.1,8.0Hz,12H).MALDI-TOF MS(mass m/z):808.1[M++H].
实施例2
(1)将实施例1中步骤(1)中原料的投入量改为投入二苯胺(26.09mmol,4.41g),氟化钠(78.27mmol，1.88g)和4-氟苯甲腈(39.13mmol,4.74g)，三种物质的摩尔比为1：3：1.5，反应24h，采用相同的后处理条件，最后得到白色固态的中间产物4-(二苯胺)苯甲腈4.52g，产率为64％。
(2)氮气保护下，将制备的中间产物4-(二苯胺)苯甲腈(I)(7.40mmol，2g)加入30mL无水氯仿溶液中，搅拌至完全溶解，0℃下逐滴加入三氟甲磺酸(18.5mmol，2.79g)，三氟甲磺酸的量为4-(二苯胺)苯甲腈(I)的2.5倍，加完后将反应装置移置常温下搅拌反应延长至6d，反应液由透明变为粉红色，最后变成紫黑色。其余条件不变，后处理相同，最后得到浅黄色固态的产物0.85g TTPATA，产率42.6％。1H NMR(500MHz,CDCl3,25℃,TMS,δ):8.56(d,J＝8.8Hz,6H),7.33(t,J＝7.8Hz,12H),7.20(d,J＝7.6Hz,12H),7.14(dd,J＝15.1,8.0Hz,12H).MALDI-TOF MS(mass m/z):808.1[M++H].
实施例3
将8.1mg 4,4’,4”-(1,3,5-三嗪-2,4,6-三苯)三(N,N-二苯胺)TTPATA、0.3874g四丁基六氟磷酸铵溶解于二氯甲烷溶液中，定容至10mL，超声3min，直至完全溶解，采用循环伏安聚合5圈(-1.2V to 1.8V)制备成膜，采用乙腈/二氯甲烷混合溶液(体积比，1/1)清洗薄膜3次，用于测试。
实施例4
将实例3制备好的薄膜置于含有0.1M四丁基六氟磷酸铵的乙腈溶液中进行性能测试，将制备好的两片薄膜分别作为工作电极、对电极，银/氯化银电极作为辅助电极，组装成三电极体系，用于超级电容器性能测试，超级电容器输入的电流信号分别为5A g-1、10A g-1、20A g-1、30A g-1、40A g-1、50A g-1，测试不同电流密度下的充放电曲线，实际结果表明40A g-1表现出高的比电容430F g-1。
Claims (10)
1.一种如式1所示的三苯胺-三嗪衍生物TTPATA：
2.一种如权利要求1所述式1所示的三苯胺-三嗪衍生物TTPATA的制备方法，其特征在于：所述的方法具体按照如下步骤进行：
(1)将二苯胺、氢化钠、对氟苯甲腈溶解于N,N-二甲基甲酰胺中，于110℃下反应12-24h，反应完全后，得到的反应液A经后处理得到式(I)所示的中间产物；所述二苯胺、氢化钠、对氟苯甲腈的投料物质的量之比为1:2-3:1.2-1.5；
(2)氮气保护下，将式(I)所示的中间产物溶于无水氯仿中，在0℃下逐滴加入三氟甲磺酸，加完之后在常温下反应96-144h，得到的反应液B经后处理得到目标产物三苯胺-三嗪衍生物TTPATA；所述式(I)所示的中间产物与三氟甲磺酸的投料物质的量之比为1：1.5-2.5；
3.如权利要求2所述的制备方法，其特征在于：步骤(1)中，所述的N,N-二甲基甲酰胺的体积用量以二苯胺的质量计为20-30mL/g。
4.如权利要求2所述的制备方法，其特征在于：步骤(1)中，所述反应液A的后处理的方法为：反应结束后，待反应液A冷却至20～30℃，加入水和二氯甲烷进行萃取，收集有机相，再加入水至有机相反复萃取5-6次，除去N,N-二甲基甲酰胺，有机相经无水硫酸镁干燥，减压浓缩，再进行柱层析纯化，以300～400目硅胶为固定相，二氯甲烷/石油醚体积比1：2～3混合液为流动相进行洗脱，收集含目标化合物的洗脱液，减压蒸除溶剂并干燥，得到式(I)所示的中间产物。
5.如权利要求2所述的制备方法，其特征在于：步骤(2)中，所述无水氯仿的体积用量以式(I)所示的中间产物的质量计为15-20mL/g。
6.如权利要求2所述的制备方法，其特征在于：步骤(2)中，所述反应液B的后处理的方法为：反应结束后，将反应液B加入水中，再加入二氯甲烷进行萃取，收集有机相，经无水硫酸镁干燥，减压浓缩，再进行柱层析纯化，以300～400目硅胶为固定相，石油醚/二氯甲烷体积比1：1～2混合液为流动相进行洗脱，收集含目标化合物的洗脱液，减压蒸除溶剂并干燥，得到目标产物三苯胺-三嗪衍生物TTPATA。
7.如权利要求1所述的三苯胺-三嗪衍生物在制备超级电容器电极材料中的应用。
8.如权利要求7所述的应用，其特征在于：所述的应用为：将TTPATA作为单体，溶解于二氯甲烷中，加入四丁基六氟磷酸铵为电解质，采用-1.2V至1.8V循环伏安聚合，扫描速度为100mV/s，电聚合得到超级电容器电极材料即聚合物薄膜PTTPATA。
9.如权利要求8所述的应用，其特征在于：所述二氯甲烷的体积用量以所述单体的质量计为1-1.5mL/mg。
10.如权利要求9所述的应用，其特征在于：所述四丁基六氟磷酸铵的用量以二氯甲烷的体积计为0.1mol/L。
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