CN105916960A - 用于合成pedot-(共聚)-聚合物电解质的方法 - Google Patents

用于合成pedot-(共聚)-聚合物电解质的方法 Download PDF

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CN105916960A
CN105916960A CN201480059689.3A CN201480059689A CN105916960A CN 105916960 A CN105916960 A CN 105916960A CN 201480059689 A CN201480059689 A CN 201480059689A CN 105916960 A CN105916960 A CN 105916960A
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C.纳瓦罗
U.伊斯梅洛夫
M.蒙塔斯
E.克劳泰特
C.布罗乔恩
G.哈齐约安努
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Bordeaux, University of
Institute Of Technology Of Bordeaux
Centre National de la Recherche Scientifique CNRS
Arkema France SA
Universite de Bordeaux
Institut Polytechnique de Bordeaux
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Arkema France SA
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Abstract

本发明涉及用于以单步合成复合物聚(3,4‑亚乙基二氧噻吩)‑(共聚)‑聚合物电解质的方法。

Description

用于合成PEDOT-(共聚)-聚合物电解质的方法
技术领域
本发明涉及用于以单步合成聚(3,4-亚乙基二氧噻吩)-电解质(共)聚合物复合物的方法。
背景技术
以缩写PEDOT已知的聚(3,4-亚乙基二氧噻吩)是20世纪80年代末在与AGFA集团合作的德国的Bayer AG的实验室中发现的聚合物。
考虑到聚(3,4-亚乙基二氧噻吩)的良好的导电性和特别地考虑到其对氧化的稳定性及其透明度，其特别地用于有机电子应用中，尤其地用于光伏电池中，但是更通常地用于光电子应用中。
其与电解质(共)聚合物一起使用，所述电解质(共)聚合物在合成之后添加，使得所得到的复合物形成供体-受体体系，并且为水溶性的。PEDOT的合成通常在表面活性剂存在下进行，所述表面活性剂有时难以除去。
申请人已发现，可伴随地(同时地)(即，以单步)制备PEDOT-电解质(共)聚合物的复合物乳胶。除了方法的简化之外，还在没有另外的添加剂例如表面活性剂(充当稳定剂的电解质(共)聚合物)的情况下，直接获得PEDOT-电解质(共)聚合物。在以该方式制备时获得的乳胶还更加稳定(当与添加电解质(共)聚合物至预制备的PEDOT相比时)。
发明内容
本发明涉及用于PEDOT和电解质(共)聚合物的伴随合成的方法，其包括下列相继的步骤：
-在反应器中在15-25℃的温度在搅拌下制备水和离子单体的溶液，
-引入预溶解在溶剂中的EDOT的溶液，
-搅拌直到溶解，
-引入溶剂-非离子单体分散体，
-搅拌直到所得到的分散体已经变成白色，
-加热至35-55℃的温度，
-引入剩余EDOT和引发剂的溶液，
-在连续或半连续地引入引发剂和剩余EDOT的溶液的同时，持续搅拌和加热。
清楚地理解，该方法可包括其它预备或中间步骤或在以上那些之后的步骤。
具体实施方式
术语“聚(3,4-亚乙基二氧噻吩)和电解质(共)聚合物的复合物乳胶的伴随聚合”意为这样的聚合，其中使用相同的引发剂将单体3,4-亚乙基二氧噻吩(EDOT)和电解质(共)聚合物的前体单体同时聚合。
术语“电解质(共)聚合物”意为包括至少一种离子单体的任何聚合物。
其可为离子和非离子单体的任何组合。
所述离子单体可为苯乙烯磺酸盐、丙烯酸盐、具有膦酰亚胺官能团或磺酰亚胺官能团的化合物。优选地，其为苯乙烯磺酸钠或苯乙烯磺酸钾和更优选地其为苯乙烯磺酸钠。
非离子单体可为苯乙烯、取代的苯乙烯或(甲基)丙烯酸烷基酯。该单体优选地为苯乙烯。
使用水溶性引发剂以乳液进行EDOT和电解质(共)聚合物的前体单体的伴随聚合。其优选地为过硫酸盐和更特别地过硫酸铵，但是可使用任何其它水溶性引发剂。过硫酸铵使得可经由自由基途径将EDOT氧化性地聚合成PEDOT和将电解质(共)聚合物的前体单体氧化性地聚合成电解质(共)聚合物。聚合可以分批、连续或半连续模式进行，具有或不具有接种(seeding)的预备合成步骤。优选地，聚合半连续地进行。合成温度为35-55℃、优选地40-50℃和更优选地44-46℃。
(3,4-亚乙基二氧噻吩)-聚电解质(共)聚合物复合物乳胶可用于分散纳米填料例如碳纳米管(CNT)(无论其为单壁的或多壁的)、石墨烯、富勒烯或这些纳米填料的组合。
(3,4-亚乙基二氧噻吩)-聚电解质(共)聚合物复合物乳胶可用于在存在或不存在纳米填料的情况下制造导电透明膜。导电透明膜可用于光伏有机电池或任何其它光电子应用中。
实施例1：
PEDOT-聚苯乙烯-共聚-聚苯乙烯磺酸盐乳胶的合成：
聚合反应器装配有：用于循环加热/冷却系统的热交换流体的夹套、用于引入探针以测量介质温度的颈部、用于引入氮气以冲走易于抑制聚合反应的氧气的颈部、用于以可变速度旋转的连接至发动机的搅拌器、用于添加添加剂的两个颈部和连接至冷凝/回流系统的颈部。
将溶解于10ml脱矿质水中的390mg苯乙烯磺酸盐(1mol/当量)(浓度0.04g/ml)放置在反应器中。搅拌设置在450转/分钟(rpm)。经由氮气管线，将反应器原料脱气至少15分钟直到溶液是均匀的。然后，所述反应器保持在恒定的氮气流下。
在第二阶段中，在合适的容器中制备下列三种混合物：
a)由0.2ml(即266mg＝1mol/当量)的EDOT和6.6ml的异丙醇制得的溶液；
b)借助超声浴的0.15ml(即137.2mg＝0.6mol/当量)的苯乙烯(St)在3.4ml的异丙醇中的分散体；
c)1.057g(即相对于EDOT为2.3mol/当量和相对于St+SS为0.1mol/当量)的过硫酸铵在26.4ml的脱矿质水中的溶液(浓度0.04g/ml)。
然后以600rpm搅拌反应器并且引入第一EDOT溶液(a)。将反应温度保持在25℃±2℃。当混合反应器组分时，将苯乙烯单体的分散体(b)引入所述反应器中。在反应介质已经变成白色(形成乳胶种)后，提高标称热(额定加热)以在反应器中达到45℃的温度。当达到该温度时，引入引发剂溶液(c)的第一个四分之一并且反应介质的颜色逐渐地变为绿色/蓝绿色，这表示EDOT的聚合的开始。在反应3小时之后，使用泵或注射器压机(syringe presses)以每3小时四分之一(三次)连续地开始进行剩余引发剂(c)的配量(计量)，同时将反应器温度保持在45℃±2℃。
在添加结束时，将温度再保持在45℃±2℃2小时，然后冷却并卸出产物。通过超滤进行最终产物的纯化。所用的过滤器为100千道尔顿(kilodalton)过滤器。该反应的产率稳定在80％。
通过下列多种技术表征最终产物。
DLS(动态光散射)技术显示约0.16的颗粒的多分散性(PDI)和80nm的体积直径(图1)。所述颗粒带负电并且Z-电势(ζ电势)值等于-75.8mV(图2)。
通过透射显微镜法(图3)和AFM(图4)观察到球形颗粒。
实施例2：
将实施例1中制备的PEDOT-聚苯乙烯-共聚-聚苯乙烯磺酸盐乳胶与商业乳胶(来自Clevios公司的PH1000)比较。
将这些产物分散在去离子水中(1质量％)并且使用IKA T18 Ultra-Turrax机器以多种速度(15 500、20 000、24 000rpm)经受剪切，对于各速度经受剪切5分钟。
然后通过DLS测量颗粒的尺寸。颗粒的尺寸在任何测试中都不改变，证明根据本发明制备的产物或商业产品的令人满意的稳定性。

Claims (13)

1.用于PEDOT和电解质(共)聚合物的伴随合成的方法，其包括下列相继的步骤：
-在反应器中在15-25℃的温度在搅拌下制备水和离子单体的溶液，
-引入预溶解在溶剂中的EDOT的溶液，
-搅拌直到溶解，
-引入溶剂-非离子单体分散体，
-搅拌直到所得到的分散体已经变成白色，
-加热至35-55℃的温度，
-引入剩余EDOT和引发剂的溶液，
-在连续或半连续地引入引发剂和剩余EDOT的溶液的同时，持续搅拌和加热。
2.如权利要求1所述的方法，其中所述电解质(共)聚合物由苯乙烯和苯乙烯磺酸盐组成。
3.如权利要求1所述的方法，其中所述电解质(共)聚合物由丙烯酸的盐和至少一种(甲基)丙烯酸烷基酯组成。
4.如权利要求1所述的方法，其中所述引发剂为水溶性的。
5.如权利要求1所述的方法，其中所述引发剂为过硫酸盐。
6.如权利要求1所述的方法，其中所述引发剂为过硫酸铵。
7.如权利要求1-6之一的方法所述获得的乳胶。
8.如权利要求7所述的乳胶的用途，其用于分散纳米填料。
9.如权利要求8所述的乳胶的用途，其中所述纳米填料为碳纳米管。
10.如权利要求8所述的乳胶的用途，其中所述纳米填料为单壁碳纳米管。
11.如权利要求7-10之一所述的乳胶的用途，其用于制备导电透明膜。
12.如权利要求11所述获得的导电透明膜。
13.如权利要求12所述的透明膜在光电子应用中、特别地在光伏有机电池中的用途。
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