CN111333820A - 一种平面刚性单体电聚合制备自支撑薄膜的方法 - Google Patents

一种平面刚性单体电聚合制备自支撑薄膜的方法 Download PDF

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CN111333820A
CN111333820A CN202010179513.9A CN202010179513A CN111333820A CN 111333820 A CN111333820 A CN 111333820A CN 202010179513 A CN202010179513 A CN 202010179513A CN 111333820 A CN111333820 A CN 111333820A
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supporting film
monomer
dithiophene
benzo
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蒋丰兴
徐景坤
李萌
刘佩佩
姚文倩
陈晓
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Jiangxi Science and Technology Normal University
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Abstract

本发明公开了一种平面刚性单体电聚合制备自支撑薄膜的方法，属于自支撑薄膜制备技术领域，采用电化学方法，在BFEE电解液中，以苯并[1，2‑B∶4，5‑B’]二噻吩为单体制备自支撑薄膜，解决了苯并[1，2‑B∶4，5‑B’]二噻吩(BDT)刚性结构很难在常规的有机体系中聚合成自支撑的薄膜的问题，使得BDT单体可以聚合成自支撑薄膜，本发明电化学方法简单、操作方便。

Description

一种平面刚性单体电聚合制备自支撑薄膜的方法
技术领域
本发明涉及自支撑薄膜制备技术领域，具体涉及一种平面刚性单体电聚合制备自支撑薄膜的方法。
背景技术
电化学聚合简称电聚合，相比于化学聚合而言，采用电极电位作为聚合反应的引发和反应驱动力，以电流作为反应条件，将具有电化学活性的单体通过氧化还原反应在电极表面聚合形成聚合物。电化学条件比如溶剂、电解质、聚合电压、聚合时间等都会对聚合薄膜的形貌、厚度、交联度及掺杂度等性质产生影响。
石高全等人利用Lewis酸三氟化硼乙醚(BFEE)络合物作溶剂，采用电化学聚合的方法在不锈钢电极上获得了高质量的自支撑聚噻吩膜。BFEE是中等强酸，同时还是吸湿性物质，能够与空气中的水发生反应生成H+[BF3OH]-，从而形成了一个良好的电解质体系而不需要加入支持电解质。BFEE还能够和芳香性单体上的共轭π键相互作用从而降低芳香性单体的起始氧化电位，这样使得部分单体可以在较低电位下进行电化学聚合。因此，BFEE在导电高分子电化学聚合领域中具有重要的作用。
苯并[1，2-B：4，5-B’]二噻吩(BDT)结构中包含了一个苯环和两个噻吩平面刚性共轭单体(附图1)。其刚性的结构很难在常规的有机体系中聚合成自支撑的薄膜，因此为解决该单体无法聚合成自支撑薄膜的问题，本发明在BFEE电解液中运用电化学方法制备聚苯并[1，2-B：4，5-B’]二噻吩自支撑薄膜。
发明内容
针对上述技术问题，本发明提供一种平面刚性单体电聚合制备自支撑薄膜的方法，在BFEE电解液中，以苯并[1，2-B：4，5-B’]二噻吩为单体，采用电化学聚合的方法制备自支撑薄膜。
为实现上述目的，本发明采用以下技术方案：
一种平面刚性单体电聚合制备自支撑薄膜的方法，包括以下步骤：
(1)配制苯并[1，2-B：4，5-B’]二噻吩体系：称取苯并[1，2-B：4，5-B’]二噻吩单体，将单体溶解于BFEE中，配制成一定浓度的苯并[1，2-B：4，5-B’]二噻吩溶液；
(2)运用电化学工作站，采用三电极工作体系，将上述苯并[1，2-B：4，5-B’]二噻吩溶液施加恒电位，聚合成自支撑薄膜；
(3)将上述自支撑薄膜用乙醇冲洗以去除聚合物表面残留的电解质、单体等物质。
优选的，所述步骤(1)中苯并[1，2-B：4，5-B’]二噻吩溶液的浓度为0.01-0.02M，BFEE用量为6mL。
优选的，所述步骤(2)中聚合6-8h，恒电位为0.85V。
本发明的有益技术效果为：本发明采用电化学方法，在BFEE电解液中，以苯并[1，2-B：4，5-B’]二噻吩为单体制备自支撑薄膜，解决了苯并[1，2-B：4，5-B’]二噻吩(BDT)刚性结构很难在常规的有机体系中聚合成自支撑的薄膜的问题，使得BDT单体可以聚合成自支撑薄膜，本发明电化学方法简单、操作方便；将刚性单体BDT制备成自支撑薄膜PBDT为其应用于柔性电子材料打下了坚实的基础，例如本发明制备的PBDT自支撑薄膜可应用于电致变色器件，同时还可应用于有机场效应晶体管、柔性薄膜传感等方面。
附图说明
图1为单体苯并[1，2-B：4，5-B’]二噻吩(BDT)的分子结构图；
图2为实施例2单体BDT在BFEE电解液中的LSV(a)图、CV(b)图；
图3为实施例2制取的聚苯并[1，2-B：4，5-B’]二噻吩自支撑薄膜图片。
具体实施方式
下面结合具体实施例对本发明作进一步说明。
实施例1
一种平面刚性单体电聚合制备自支撑薄膜的方法，包括以下步骤：
(1)配制0.01M苯并[1，2-B：4，5-B’]二噻吩体系：称取苯并[1，2-B：4，5-B’]二噻吩单体0.0114g，将单体溶解于6mL BFEE中，配制成0.01M的苯并[1，2-B：4，5-B’]二噻吩溶液；
(2)运用电化学工作站，采用三电极工作体系，将上述苯并[1，2-B：4，5-B’]二噻吩溶液施加恒电位0.85V，聚合6h成自支撑薄膜；
(3)将上述自支撑薄膜用乙醇冲洗以去除聚合物表面残留的电解质、单体等物质。
实施例2
一种平面刚性单体电聚合制备自支撑薄膜的方法，包括以下步骤：
(1)配制0.02M苯并[1，2-B：4，5-B’]二噻吩体系：称取苯并[1，2-B：4，5-B’]二噻吩单体0.0228g，将单体溶解于6mL BFEE中，配制成0.02M的苯并[1，2-B：4，5-B’]二噻吩溶液；
(2)运用电化学工作站，采用三电极工作体系，将上述苯并[1，2-B：4，5-B’]二噻吩溶液施加恒电位0.85V，聚合8h成自支撑薄膜；
(3)将上述自支撑薄膜用乙醇冲洗以去除聚合物表面残留的电解质、单体等物质。
图1为单体苯并[1，2-B：4，5-B’]二噻吩(BDT)的分子结构图。
图2为本实施例2单体BDT在BFEE电解液中的LSV(a)图、CV(b)图；图3为本实施例2制取的聚苯并[1，2-B：4，5-B’]二噻吩自支撑薄膜图片。由附图2与附图3可知，苯并[1，2-B：4，5-B’]二噻吩单体的起始氧化电位约为0.65V左右。CV图显示出与其他导电高分子相似的电化学聚合特征，聚合电流随着连续扫描的进行逐渐增加，表明工作电极上相应聚苯并[1，2-B：4，5-B’]二噻吩聚合物的生长，同时这也意味着制备的导电聚合物具有良好的电化学活性。
实施例3
一种平面刚性单体电聚合制备自支撑薄膜的方法，包括以下步骤：
(1)配制0.015M苯并[1，2-B：4，5-B’]二噻吩体系：称取苯并[1，2-B：4，5-B’]二噻吩单体0.0171g，将单体溶解于6mL BFEE中，配制成0.015M的苯并[1，2-B：4，5-B’]二噻吩溶液；
(2)运用电化学工作站，采用三电极工作体系，将上述苯并[1，2-B：4，5-B’]二噻吩溶液施加恒电位0.85V，聚合7h成自支撑薄膜；
(3)将上述自支撑薄膜用乙醇冲洗以去除聚合物表面残留的电解质、单体等物质。
以上所述仅为本发明的较佳实施例而已，并不用以限制本发明，凡在本发明的技术方案的基础上，本领域技术人员不需要付出创造性劳动即可做出的各种修改或变形仍在本发明的保护范围内。

Claims (3)

1.一种平面刚性单体电聚合制备自支撑薄膜的方法，其特征在于，包括以下步骤：
(1)配制苯并[1，2-B：4，5-B’]二噻吩体系：称取苯并[1，2-B：4，5-B’]二噻吩单体，将单体溶解于BFEE中，配制成一定浓度的苯并[1，2-B：4，5-B’]二噻吩溶液；
(2)运用电化学工作站，采用三电极工作体系，将上述苯并[1，2-B：4，5-B’]二噻吩溶液施加恒电位，聚合成自支撑薄膜；
(3)将上述自支撑薄膜用乙醇冲洗以去除聚合物表面残留的电解质、单体等物质。
2.根据权利要求1所述的一种平面刚性单体电聚合制备自支撑薄膜的方法，其特征在于，所述步骤(1)中苯并[1，2-B：4，5-B’]二噻吩溶液的浓度为0.01-0.02M，BFEE用量为6mL。
3.根据权利要求1所述的一种平面刚性单体电聚合制备自支撑薄膜的方法，其特征在于，所述步骤(2)中聚合6-8h，恒电位为0.85V。
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