CN107674181A - 聚二甲酸二乙酯基环丁烷丙撑二氧噻吩蓝色‑透明电致变色材料及制备方法、组件与应用 - Google Patents

聚二甲酸二乙酯基环丁烷丙撑二氧噻吩蓝色‑透明电致变色材料及制备方法、组件与应用 Download PDF

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CN107674181A
CN107674181A CN201710952887.8A CN201710952887A CN107674181A CN 107674181 A CN107674181 A CN 107674181A CN 201710952887 A CN201710952887 A CN 201710952887A CN 107674181 A CN107674181 A CN 107674181A
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dioxy thiophene
dicarboxylate
trimethylene dioxy
basic ring
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陈晓明
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Anhui Jianzhu University
Anhui University of Architecture
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Abstract

本发明为一种新型蓝色‑透明电致变色聚合物材料，具体为聚二甲酸二乙酯基环丁烷丙撑二氧噻吩蓝色‑透明电致变色材料及制备方法、组件与应用，这种聚二甲酸二乙酯基环丁烷丙撑二氧噻吩蓝色‑透明电致变色材料可以通过电化学聚合在ITO玻璃表面成膜，其特点为驱动电压低，着色效率高、光学对比度高，适合应用于智能窗、电致变色显示器等电致变色器件。本发明受到先进建筑材料安徽省重点实验室开放课题（JZCL201602ZZ）、安徽省高校自然科学研究项目（KJ2017A482，KJ2016JD16）、安徽省高校优秀青年人才支持计划项目（gxyq2017023）、大学生创新创业训练计划项目资助。

Description

聚二甲酸二乙酯基环丁烷丙撑二氧噻吩蓝色-透明电致变色 材料及制备方法、组件与应用
技术领域
本发明涉及电致变色材料的合成和成膜方法，具体为聚二甲酸二乙酯基环丁烷丙撑二氧噻吩蓝色-透明电致变色材料及制备方法、组件与应用。
背景技术
材料在交替的高低或正负外电场作用下通过注入或抽取电荷发生氧化还原反应，从而在低透过率的着色态和高透过率的消色态之间发生可逆变化的特殊现象称为电致变色，外观上表现为颜色及透明度的可逆变化，在电致变色窗、电致变色显示等领域有广阔的应用前景。
电致变色材料具有双稳态的性能，用电致变色材料做成的电致变色显示器件不仅不需要背光灯，而且显示静态图像后，只要显示内容不变化，就不会耗电，达到节能的目的。电致变色显示器与其它显示器相比具有无视盲角、对比度高、制造成本低、工作温度范围宽、驱动电压低、色彩丰富等优点，在仪表显示、户外广告、静态显示等领域具有很大的应用前景。
无机电致变色材料主要以WO3、MoO3、NiO等过渡金属氧化物为代表，其光吸收变化是因为离子和电子的双注入和双抽取而引起的。有机电致变色材料则以有机小分子紫精和π-共轭聚合物如聚苯胺、聚吡咯、聚噻吩等为代表，其光吸收变化来自氧化还原反应，这类材料色彩丰富，容易进行分子设计，因而更加受到研究者的青睐。特别是3,4-二氧基噻吩(如3,4-乙撑二氧噻吩PEDOT)，由于电子给体的二氧基在高p-掺杂水平下能够稳定封闭壳双极化子结构，因而为聚(3，4-亚烷基二氧基噻吩)提供了高导电性和透明氧化态，电致变色材料无论是应用于智能窗还是显示，都需要材料具有透明态(可接近完全褪色)，因而这一发现促进了3，4-二氧基噻吩聚合物的广泛应用。
聚合物主链刚性及分子链间π-π堆积作用使得π-共轭聚合物具有不熔不溶的特性，因此在利用π-共轭聚合物制备电致变色器件时研究者们通常采用电化学聚合的方法使得到的聚合物直接沉积于电极表面形成聚合物薄膜。电聚合是利用外加电压使单体在阳极发生电化学氧化反应，通过自由基间逐步偶合形成共轭聚合物。
相对于以三氯化铁为氧化剂的化学氧化聚合以及以钯络合物为催化剂的偶联聚合反应，电聚合方法合成共轭聚合物具有以下优点：
(1)电聚合可以在适宜电压下通过阳极氧化反应直接得到聚合物，而不需要另外添加氧化剂或催化剂，减少共轭聚合物的合成成本；
(2)电聚合过程中掺杂入共轭聚合物的电解质可以方便地通过施加负电压去掺杂(还原)反应去除，使得到的聚合物更加纯净；
(3)电聚合得到的共轭聚合物可以直接沉积在导电基底上，而不需要对聚合物做进一步成膜加工，降低了共轭聚合物薄膜在应用于有机光电子学器件时的加工费用和难度。
聚二氧基噻吩由于其具有低驱动电压、快速响应、高透过率差的优点而受到电致变色材料开发研究的广泛青睐。通过聚合物主链或者侧基的化学改性来提升聚合物电致变色性能是最为经常使用的手段。二氧基噻吩及其衍生物的电聚合成为有机光电子学材料领域的研究者获得新颖的电致变色材料最常采用的合成方法。
发明内容
本发明旨在提供一种新型蓝色-透明电致变色聚合物材料，可以通过电化学聚合在ITO玻璃表面成膜，为了达到上述目的，本发明采用的技术方案如下：
聚二甲酸二乙酯基环丁烷丙撑二氧噻吩蓝色-透明电致变色材料，其特征在于，其结构式如下：
其中n表示聚合度，为自然数。
所述的聚二甲酸二乙酯基环丁烷丙撑二氧噻吩蓝色-透明电致变色材料的合成路线如下：
具体步骤如下：
步骤1、将3,4-二甲氧基噻吩、二溴新戊二醇、对甲基苯磺酸和甲苯加入上方连接内含分子筛的索氏提取器的烧瓶中，将混合物加热回流过夜，然后冷却至室温，水洗若干次，无水硫酸钠干燥，旋转蒸发除去溶剂，粗产物经柱层析得到黄白色固体，得二溴甲基丙撑二氧噻吩；
步骤2、将二溴甲基丙撑二氧噻吩、丙二酸二乙酯、乙醇钠加入上方连接有回流冷凝管的烧瓶中，将混合物加热回流5-10h，然后冷却至室温，加入适量水，乙醚萃取若干次，合并有机相后用无水硫酸镁干燥，过滤后蒸除溶剂，剩余物经柱层析得白色固体，得二甲酸二乙酯基环丁烷丙撑二氧噻吩；
步骤3、将二甲酸二乙酯基环丁烷丙撑二氧噻吩、LiClO4溶解于乙腈，置于三电极电解池中，采用循环伏安法进行电化学聚合，得到聚二甲酸二乙酯基环丁烷丙撑二氧噻吩。
所述步骤1中3,4-二甲氧基噻吩、二溴新戊二醇、对甲基苯磺酸和甲苯的用量比为(20-40)mmol：(40-80)mmol：(2-4)mmol：(100-400)mL。
所述步骤2中二溴甲基丙撑二氧噻吩、丙二酸二乙酯、乙醇钠三者的摩尔比为(10-20)mmol：(20-40)mmol：(40-80)mmol。
所述步骤3的溶液体系中二甲酸二乙酯基环丁烷丙撑二氧噻吩的浓度为0.005-0.1mol/L，LiClO4的浓度为0.05-0.5mol/L。
所述步骤3中的电化学聚合是以ITO导电玻璃为工作电极，Pt丝为对电极，Ag丝为参比电极，使用CHI600E电化学分析仪通过在氮气保护下0-1.7V连续循环伏安扫描4-15次。
本发明还保护所述的聚二甲酸二乙酯基环丁烷丙撑二氧噻吩蓝色-透明电致变色材料在制造电致变色器件中的应用。
本发明还保护所述的聚二甲酸二乙酯基环丁烷丙撑二氧噻吩蓝色-透明电致变色材料的组件。
所述的组件为电致变色薄膜。
所述的电致变色薄膜的成膜方法为将聚二甲酸二乙酯基环丁烷丙撑二氧噻吩电聚合薄膜直接电镀在ITO玻璃表面。
本发明为一种新型蓝色-透明电致变色聚合物材料，可以通过电化学聚合在ITO玻璃表面成膜，其特点为驱动电压低，着色效率高、光学对比度高，形成的组件适合应用于智能窗、电致变色显示器等电致变色器件。
附图说明
图1为二甲酸二乙酯基环丁烷丙撑二氧噻吩的核磁氢谱。
图2为电聚合实验连续循环伏安曲线。
图3为聚合物薄膜氧化过程中色坐标变化。
图4为聚合物-聚二甲酸二乙酯基环丁烷丙撑二氧噻吩薄膜循环伏安曲线。
图5为聚合物薄膜在不同外加电压下的光谱电化学谱图。
图6为聚合物薄膜电压阶跃计时吸光度图。
图7为聚合物薄膜电压阶跃计时电量/计时吸光度图。
图8为聚合物薄膜长期循环伏安稳定性实验曲线，包括第2圈和第200圈循环伏安曲线。
具体实施方式
实施例1聚二甲酸二乙酯基环丁烷丙撑二氧噻吩蓝色-透明电致变色薄膜
一种聚二甲酸二乙酯基环丁烷丙撑二氧噻吩蓝色-透明电致变色薄膜的制备步骤如下：
步骤1、将35mmol 3,4-二甲氧基噻吩、70mmol二溴新戊二醇、3.5mmol对甲基苯磺酸和300mL甲苯加入上方连接索氏提取器(内含分子筛)的烧瓶中，将混合物加热回流过夜，然后冷却至室温，水洗若干次，无水硫酸钠干燥，旋转蒸发除去溶剂，粗产物经柱层析得到黄白色固体，得二溴甲基丙撑二氧噻吩；
步骤2、将16mmol二溴甲基丙撑二氧噻吩、32mmol丙二酸二乙酯、64mmol乙醇钠加入上方连接有回流冷凝管的烧瓶中,将混合物加热回流6h，然后冷却至室温，加入适量水，乙醚萃取若干次，合并有机相后用无水硫酸镁干燥，过滤后蒸除溶剂，剩余物经柱层析得白色固体，得二甲酸二乙酯基环丁烷丙撑二氧噻吩；
步骤3、将二甲酸二乙酯基环丁烷丙撑二氧噻吩、LiClO4溶解于10mL乙腈，体系中二甲酸二乙酯基环丁烷丙撑二氧噻吩浓度为0.01mol/L，LiClO4浓度为0.1mol/L；置于三电极电解池中，以ITO导电玻璃为工作电极，Pt丝为对电极，Ag丝为参比电极，使用CHI600E电化学分析仪通过在氮气保护下0-1.7V连续循环伏安扫描8次，使电聚合薄膜直接电镀于ITO玻璃表面，得到聚二甲酸二乙酯基环丁烷丙撑二氧噻吩薄膜。
合成的二甲酸二乙酯基环丁烷丙撑二氧噻吩核磁氢谱见图1，图中δ＝6.5(s,2H)峰对应噻吩环2-、5-位氢原子，δ＝4.25(q,4H)、δ＝3.97(s,4H)、δ＝2.52(s,4H)、δ＝1.27(t,6H)峰对应二甲酸二乙酯基环丁烷丙撑二氧基氢原子，说明单体化学结构的正确性。
电聚合实验连续循环伏安曲线见图2，说明电聚合得到的聚合物薄膜不断沉积于ITO工作电极表面使氧化电流和还原电流随扫描段数增加而增加。
制备的聚合物薄膜氧化过程中色坐标变化见图3，图中横坐标为a*(红绿平衡值)，纵坐标为b*(黄蓝平衡值)，说明聚合物中性态色坐标为a*＝14.72，b*＝－37.13，为蓝色态；聚合物完全氧化态色坐标为a*＝2.34，b*＝－16.66，为透明态，聚合物为蓝色-透明电致变色材料。
实施例2聚二甲酸二乙酯基环丁烷丙撑二氧噻吩蓝色-透明电致变色薄膜循环伏安试验
循环伏安实验条件：采用三电极电解池，Pt丝为对电极，Ag丝为参比电极，镀有实施例1的聚合物薄膜(2cm×0.7cm)ITO导电玻璃为工作电极，扫描电压范围-0.1V－0.7V，扫描速率分别为50mV/s，100mV/s，150mV/s，200mV/s；支持电解液配置：0.1mol/L高氯酸锂(LiClO4)溶于10mL碳酸丙烯酯(PC)。测试结果见图4，说明扫描速率为50mV/s时聚合物氧化峰电位为0.35V，还原峰电位为0.15V，在扫描电压范围-0.1V－0.7V内聚合物可完成氧化还原过程。
实施例3聚二甲酸二乙酯基环丁烷丙撑二氧噻吩蓝色-透明电致变色薄膜在不同外加电压下的光谱电化学性能
采用三电极电解池，Pt丝为对电极，Ag丝为参比电极，镀有实施例1制备的聚合物薄膜(2cm×0.7cm)ITO导电玻璃为工作电极，支持电解液配置：0.1mol/L高氯酸锂(LiClO4)溶于10mL碳酸丙烯酯(PC)。测试结果见图5，说明中性态聚合物薄膜(-0.1V)为蓝色，最大吸收波长为571nm，聚合物完全氧化态(0.7V)为透明态，在可见光区基本无吸收。
实施例4聚二甲酸二乙酯基环丁烷丙撑二氧噻吩蓝色-透明电致变色薄膜电压阶跃计时吸光度测试
采用三电极电解池，Pt丝为对电极，Ag丝为参比电极，镀有实施例1制备的聚合物薄膜(2cm×0.7cm)ITO导电玻璃为工作电极，阶跃电压为-0.1V和0.7V，电压驻留时间分别为30s，20s，15s，10s；支持电解液配置：0.1mol/L高氯酸锂(LiClO4)溶于10mL碳酸丙烯酯(PC)。测试结果见图6，图中纵坐标代表聚合物薄膜在571nm处的透过率，横坐标代表时间，说明聚合物的氧化还原过程可逆，在571nm处的透过率差ΔTmax＝44.6％，其氧化过程达到95％透过率差响应时间t95＝3.5s。
实施例5聚二甲酸二乙酯基环丁烷丙撑二氧噻吩蓝色-透明电致变色薄膜电压阶跃计时电量/计时吸光度测试
采用三电极电解池，Pt丝为对电极，Ag丝为参比电极，镀有实施例1制备的聚合物薄膜(2cm×0.7cm)ITO导电玻璃为工作电极。阶跃电压为-0.1V和0.7V，电压驻留时间分别为20s，支持电解液配置：0.1mol/L高氯酸锂(LiClO4)溶于10mL碳酸丙烯酯(PC)。测试结果见图7，图中纵坐标代表电荷密度或透过率，横坐标代表时间，说明聚合物薄膜氧化过程在571nm处达到95％透过率差时的着色效率为103.9cm2/C(计算公式为CE＝ΔOD/(Q/A)＝lg(Tb/Tc)/(Q/A))。
实施例6聚二甲酸二乙酯基环丁烷丙撑二氧噻吩蓝色-透明电致变色薄膜长期循环伏安稳定性实验
循环伏安实验条件：采用三电极电解池，Pt丝为对电极，Ag丝为参比电极，镀有实施例1制备的聚合物薄膜(2cm×0.7cm)ITO导电玻璃为工作电极，扫描电压范围-0.1V－0.7V，扫描速率分别为100mV/s，支持电解液配置：0.1mol/L高氯酸锂(LiClO4)溶于10mL碳酸丙烯酯(PC)。测试结果见图8，图中纵坐标为电流密度，横坐标为电压，说明经过200次氧化还原循环，电流密度没有明显衰减，聚合物具有良好的长期氧化还原循环稳定性。

Claims (10)

1.聚二甲酸二乙酯基环丁烷丙撑二氧噻吩蓝色-透明电致变色材料，其特征在于，其结构式如下：
其中n表示聚合度，为自然数。
2.如权利要求1所述的聚二甲酸二乙酯基环丁烷丙撑二氧噻吩蓝色-透明电致变色材料的制备方法，其特征在于，包括以下步骤：
步骤1、将3,4-二甲氧基噻吩、二溴新戊二醇、对甲基苯磺酸和甲苯加入上方连接内含分子筛的索氏提取器的烧瓶中。将混合物加热回流过夜，然后冷却至室温，水洗若干次，无水硫酸钠干燥，旋转蒸发除去溶剂，粗产物经柱层析得到黄白色固体，得二溴甲基丙撑二氧噻吩；
步骤2、将二溴甲基丙撑二氧噻吩、丙二酸二乙酯、乙醇钠加入上方连接有回流冷凝管的烧瓶中，将混合物加热回流5-10h，然后冷却至室温，加入适量水，乙醚萃取若干次，合并有机相后用无水硫酸镁干燥，过滤后蒸除溶剂，剩余物经柱层析得白色固体，得二甲酸二乙酯基环丁烷丙撑二氧噻吩；
步骤3、将二甲酸二乙酯基环丁烷丙撑二氧噻吩、LiClO4溶解于乙腈，置于三电极电解池中，采用循环伏安法进行电化学聚合，得到聚二甲酸二乙酯基环丁烷丙撑二氧噻吩。
3.如权利要求2所述的制备方法，其特征在于，所述步骤1中3,4-二甲氧基噻吩、二溴新戊二醇、对甲基苯磺酸和甲苯的用量比为(20-40)mmol：(40-80)mmol：(2-4)mmol：(100-400)mL。
4.如权利要求2所述的制备方法，其特征在于，所述步骤2中二溴甲基丙撑二氧噻吩、丙二酸二乙酯、乙醇钠三者的摩尔比为(10-20)mmol：(20-40)mmol：(40-80)mmol。
5.如权利要求2所述的制备方法，其特征在于，所述步骤3的溶液体系中二甲酸二乙酯基环丁烷丙撑二氧噻吩的浓度为0.005-0.1mol/L，LiClO4的浓度为0.05-0.5mol/L。
6.如权利要求2所述的制备方法，其特征在于，所述步骤3中的电化学聚合是以ITO导电玻璃为工作电极，Pt丝为对电极，Ag丝为参比电极，使用CHI600E电化学分析仪通过在氮气保护下0-1.7V连续循环伏安扫描4-15次。
7.如权利要求1所述的聚二甲酸二乙酯基环丁烷丙撑二氧噻吩蓝色-透明电致变色材料在制造电致变色器件中的应用。
8.含有如权利要求1所述的聚二甲酸二乙酯基环丁烷丙撑二氧噻吩蓝色-透明电致变色材料的组件。
9.如权利要求8所述的组件，其特征在于，所述的组件为电致变色薄膜。
10.如权利要求9所述的组件，其特征在于，所述的电致变色薄膜的成膜方法为将聚二甲酸二乙酯基环丁烷丙撑二氧噻吩电聚合薄膜直接电镀在ITO玻璃表面。
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