CN114853987B - 一种含二氧噻吩和9,9`-螺二芴结构的电致变色共聚物及其制备方法和聚合物薄膜 - Google Patents
一种含二氧噻吩和9,9`-螺二芴结构的电致变色共聚物及其制备方法和聚合物薄膜 Download PDFInfo
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- SNFCXVRWFNAHQX-UHFFFAOYSA-N 9,9'-spirobi[fluorene] Chemical group C12=CC=CC=C2C2=CC=CC=C2C21C1=CC=CC=C1C1=CC=CC=C21 SNFCXVRWFNAHQX-UHFFFAOYSA-N 0.000 title claims abstract description 19
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Abstract
提供了一种含二氧噻吩和9,9'‑螺二芴结构的电致变色共聚物，其分子式中包括如下结构：其中，A表示硫或者氧，m和n均表示聚合度且为8‑100之间的整数。制备方法如下：1)将二氧丙撑噻吩、2,2’,7,7’‑四溴‑9,9'‑螺二芴、3,4‑二溴乙撑二氧噻吩或者3,4‑二溴乙撑二硫噻吩、N,N‑二甲基乙酰胺、碳酸钾、乙酸钯、特戊酸加入至单口烧瓶中，用氮气或氩气对单口烧瓶进行抽换气并保持换气气氛，将混合物依次加热反应、冷却至室温、滴入甲醇中，过滤收集橙红色沉淀物；2)将橙红色沉淀物置于脂肪提取器中，依次用甲醇、正已烷、氯仿中溶解洗涤、浓缩氯仿洗涤液，最后滴入甲醇中，过滤收集沉淀物，即为目标产物。
Description
本发明总体地涉及电致变色技术领域，具体地涉及一种含二氧噻吩和9,9′-螺二芴结构的电致变色共聚物及其制备方法和聚合物薄膜。
背景技术
电致变色材料是指在外加电场作用下，因发生可逆氧化还原反应而产生光学特性变化的材料，在智能窗、防眩后视镜以及军事智能伪装等领域具有广阔的应用前景。一般，电致变色材料包括过渡金属氧化物、紫精小分子、导电聚合物等，其中导电聚合物因具有结构可设计、颜色变换丰富、对比度高、响应速率快、着色效率高及稳定性好等优点，而成为当前电致变色领域的研究和应用热点。一直以来，开发新型电致变色性能优异特别是显示黄、橙、红色的导电聚合物对聚合物电致变色的研究具有重要的意义。
为实现黄、橙、红颜色的显示，需要聚合物具有较高的带隙，而为提高聚合物的稳定性，其带隙提高因尽量由空间位阻效应引起，而非电子诱导效应造成。因此，聚合物结构内应包括富电子基团以及破坏平面共轭特性的基团。通常富电子基团主要是噻吩类结构，而破坏平面共轭的基团有苯环、萘环等，其对应的聚合物通常具有较高的变色电位，而导致变色稳定性较差。
螺二芴衍生物作为一种有机共轭单元，由其组成的导电聚合物在有机电致发光领域表现出优异的发光性能，且螺二芴衍生物结构共轭平面性不强，嵌入共轭聚合物主链中可打断其共轭平面的连续性，同时由于其自身具有较大的芳香环结构，使其形成的导电聚合物电化学氧化电位并不高，因此，可以作为理想的嵌段单元，用于黄色、橙色、红色等高带隙电致变色聚合物的设计与制备。而目前，也尚未见相关聚合物的报道。
发明内容
本发明的目的是设计和制备含二氧噻吩和9,9′-螺二芴结构的电致变色共聚物及聚合物薄膜，主要通过芳基化偶联的方法，制备了9,9′-螺二芴、3，4-乙撑二氧(硫)噻吩作为嵌入单元与3，4-二氧丙撑噻吩的电致变色共聚物。
本发明的技术方案如下：首先，本发明提供了一种含二氧噻吩和9,9′-螺二芴结构的电致变色共聚物，其分子式中包括如下式(1)所示的结构：
式(1)中，A表示硫或者氧，m和n均表示聚合度，为自然数，优选8-100之间的整数。
本发明还提供了上述含二氧噻吩和9,9′-螺二芴结构的电致变色共聚物的制备方法，合成路线如下式(2)所示：
具体步骤如下：
1)通过芳基化偶联制备聚合物：将二氧丙撑噻吩(M1)、2,2’,7,7’-四溴-9,9′-螺二芴(M2)、3,4-二溴乙撑二氧噻吩或者3,4-二溴乙撑二硫噻吩(M3)、N,N-二甲基乙酰胺、碳酸钾、乙酸钯、特戊酸加入至单口烧瓶中，所述单口烧瓶上方有气源连接装置和冷凝管，对单口烧瓶进行抽换气，保持单口烧瓶内换气后气氛保护，将混合物加热反应一定时间，然后冷却至室温，再将反应后混合物溶液滴入甲醇中进行沉淀，过滤收集橙红色沉淀物；
2)通过索氏提取纯化聚合物：将步骤1)所得橙红色沉淀物用滤纸包裹，置于脂肪提取器中，先采用甲醇进行洗涤，洗涤出的沉淀物用正已烷再次洗涤，然后将沉淀物在氯仿中进行反向溶解洗涤，分离去除其中的沉淀物，将氯仿洗涤液进行浓缩，最后滴入甲醇中进行再沉淀，过滤收集沉淀物，即为纯化后的含二氧噻吩和9,9′-螺二芴结构的电致变色共聚物。
本发明第2)步的甲醇和正已烷洗涤中，是将产品中的小分子杂质通过溶解的方式从沉淀物中去除；氯仿洗涤中，是将产品中的大分子杂质通过不溶解的方式从氯仿洗涤液中分离(目标共聚物溶解在氯仿中)。
进一步的，上述步骤1)中的二氧丙撑噻吩、2,2’,7,7’-四溴-9,9′-螺二芴和3,4-二溴乙撑二氧噻吩或者3,4-二溴乙撑二硫噻吩的摩尔比为4：1：2。
进一步的，上述步骤1)中的二氧丙撑噻吩与碳酸钾的摩尔比为1：(2～4)，二氧丙撑噻吩与特戊酸的摩尔比为1：(0.1～0.25)，二氧丙撑噻吩与乙酸钯的摩尔比为1：(0.002～0.02)；所述N,N-二甲基乙酰胺用作溶剂。
进一步的，上述步骤1)中的反应温度为70～100℃，反应时间为48～96小时；所述抽换气是将单口烧瓶中的空气抽取替换为氮气或氩气。
本发明同时提供了一种聚合物薄膜，所述聚合物薄膜由上述含二氧噻吩和9,9′-螺二芴结构的电致变色共聚物经溶剂稀释后通过喷涂或刮涂得到，所述聚合物薄膜的为厚度为200～800nm。
上述聚合物薄膜显示橙红色至透明色的电致变色行为：颜色对比度达到40％以上、响应速率在3秒以内、变色循环次数500次且无衰减。电致变色器件的结构为导电基底、电致变色材料、电解质、对电极和导电基底。
本发明的聚合物薄膜优选应用于电致变色器件中。
本发明的含二氧噻吩和9,9′-螺二芴结构的电致变色共聚物，可通过溶剂(溶剂为甲苯、氯仿、四氢呋喃等有机体系，不需要其他组分)稀释后溶液刮涂和喷涂在导电基底表面成膜，其颜色变换范围为高带隙聚合物显示的橙红色至透明态，且驱动电压低于1V、光学对比度达到40％以上、循环变色500次几乎几衰减的特点，适用于电致变色器件的组装应用。
本发明的先进性在于：本发明将螺二芴衍生物单元引入至二氧噻吩主链中，利用其平面扭曲特性，打断聚合物共平面性，同时所得共聚物基于自身的大芳香环结构以及二氧噻吩的强供电子性，实现了高稳定的橙红色高带隙电致变色聚合物的制备。
附图说明
从下面结合附图对本发明实施例的详细描述中，本发明的这些和/或其它方面和优点将变得更加清楚并更容易理解，其中：
图1为本发明实施例制备的含二氧噻吩和9,9′-螺二芴结构的电致变色共聚物的核磁氢谱，其中(a)为P(PRODOT-C20-4PH-EDTT)的核磁氢谱；(b)为P(PRODOT-C20-4PH-EDOT)核磁氢谱；
图2为本发明实施例制备的含二氧噻吩和9,9′-螺二芴结构的电致变色共聚物溶于二氯甲烷的光谱吸收曲线；
图3为本发明实施例制备的聚合物薄膜在不同电位下的紫外-可见吸收光谱曲线，其中(a)为P(PRODOT-C20-4PH-EDTT)在不同电位下的紫外-可见吸收光谱曲线；(b)为P(PRODOT-C20-4PH-EDOT)在不同电位下的紫外-可见吸收光谱曲线；
图4为本发明实施例制备的聚合物薄膜的循环伏安曲线；
图5为本发明实施例制备的聚合物薄膜的热稳定性曲线。
具体实施方式
为了使本领域技术人员更好地理解本发明，下面结合附图和具体实施方式对本发明作进一步详细说明。
实施例1
含二氧噻吩和9,9′-螺二芴结构的电致变色共聚物的制备方法为：
(1)3，4-乙撑二硫基噻吩的合成
将0.1mol的3，4-二甲氧基噻吩、0.15mol的1，2-乙二硫醇以及0.001mol的对甲苯磺酸-水合物溶于200mL甲苯，置于500mL单口烧瓶中，连接带有分子筛的索氏提取器和冷凝管。回流搅拌反应24h，然后降至室温，将反应液倒入水中，分液收集有机相，水相用20mL二氯甲烷萃取两次，合并有机相，用无水硫酸镁干燥，采用湿法上样过硅胶柱，淋洗剂为二氯甲烷/正已烷(1：1)，得到白色固体，产率为76％；该步骤制备得到的化合物核磁氢谱1HNMR(400MHz,CDCl3,δ,ppm):3.24(s,4H),6.99(s,2H)。
(2)2，5-二溴-3，4-乙撑二硫基噻吩的合成
将0.1mmol的3，4-乙撑二硫基噻吩溶于20mL氯仿置于双口瓶中，用锡箔纸包覆避光降至0度，气氛保护，将0.3mmol的NBS溶于10mL的DMF中，缓慢滴入双口瓶中，完成滴入后升至室温反应8h。将反应液旋蒸，除去溶剂，将残留物用二氯甲烷溶解，采用湿法上样过硅胶柱，淋洗剂为二氯甲烷/正已烷(1：2)，得到白色固体，产率为63％；该步骤制备得到的化合物核磁氢谱1HNMR(400MHz,CDCl3,δ,ppm):3.44(s,4H)。
(3)电致变色聚合物的合成
1、将0.2mmol的步骤(2)制备的2,5-二溴3,4-乙撑二硫基噻吩、0.1mmol的2,2’,7,7’-四溴-9,9′-螺二芴、0.4mmol的二十烷氧基甲基丙撑二氧噻吩(限定了，没有做其他实验的)、0.006mmol的醋酸钯、0.3mmol的碳酸钾、0.03mmol的特戊酸置于25mL双口瓶中，抽换气注入氮气，注入15mL无水N,N-二甲基乙酰胺(DMAC)，再抽换气充满氮气，加热至120℃回流反应72h，反应结束冷却至室温，将反应液滴入至冷甲醇中进行沉淀，过滤沉淀物进行干燥；再分别以甲醇、正已烷(主要是洗涤去除沉淀物中的杂质)和氯仿(将正已烷洗涤后的沉淀物溶解于氯仿中)进行索氏提取，每一次提取时间为24h，将氯仿提取液进行浓缩至15mL，再滴入至冷甲醇中沉淀得到黑色固体，过滤干燥即得到目标聚合物P(PRODOT-C20-4PH-EDTT)，产率为60％。
2、将0.2mmol的2，5-二溴-3，4-乙撑二氧基噻吩、0.1mmol的2,2’,7,7’-四溴-9,9′-螺二芴、0.4mmol的十二烷氧基甲基丙撑二氧噻吩、0.006mmol的醋酸钯、0.3mmol的碳酸钾、0.03mmol的特戊酸置于25mL双口瓶中，抽换气注入氮气，注入15mL无水N,N-二甲基乙酰胺(DMAC)，再抽换气充满氮气，加热至120℃回流反应72h，反应结束冷却至室温，将反应液滴入至冷甲醇中进行沉淀，过滤沉淀物进行干燥；再分别以甲醇、正已烷和氯仿进行索氏提取，每一次提取时间为24h，将氯仿提取液进行浓缩至15mL，再滴入至冷甲醇中沉淀得到黑色固体，过滤干燥即得到目标聚合物P(PRODOT-C20-4PH-EDOT)，产率为66％。
所得目标聚合物的核磁共振氢谱见图1，其中(a)为P(PRODOT-C20-4PH-EDTT)；(b)为P(PRODOT-C20-4PH-EDOT)。
实施例2
实施例1制备的聚合物进行溶液光谱以及电化学性能测试。将聚合物溶于二氯甲烷，配制成浓度为2*10-4mg/mL的溶液，溶液吸收曲线如图2所示，聚合物P(PRODOT-C20-4PH-EDTT)和P(PRODOT-C20-4PH-EDOT)溶液分别呈现为橙黄和橙红色。通过紫外-可见分光光度计的测试，溶液对应的吸收峰分别在在434nm和488nm处。
聚合物薄膜制备：将聚合物溶于氯仿中，配制2mg/ml的溶液，通过滤嘴过滤出不溶物，再置于喷枪中，控制气压为2MPa，在导电玻璃上进行喷涂，薄膜吸光度为0.8左右，喷涂后置于真空干燥箱中40度真空烘干待用。采用聚合物膜为工作电极、铂丝为对电极、标定过的银丝为参比电极的三电极体系，支持电解质为：0.2mol/L的高氯酸锂丙烯碳酸酯溶液。
聚合物薄膜进行不同电压下的光谱电化学性能测试。采用三电极体系，铂丝为对电极，标定过的银丝为参比电极，聚合物膜为工作电极，支持电解质为：0.1mol/L的高氯酸锂丙烯碳酸酯溶液。两种共聚物薄膜在不同外加电压下的光谱电化学谱图见图3，说明共聚物膜均具有明显的电致变色性能。由于π-π*键的堆积，聚合物薄膜相对于溶液的光谱具有一定的红移，所对应的吸收峰值分别为460nm和502nm。它们在较低电压下都能实现有色至透明的可逆变化。
采用循环伏安法测试共聚物的电化学稳定性(见图4)，其中P(PRODOT-C20-4PH-EDOT)的氧化电位为1.2V，循环伏安扫描多次依然保持稳定性。
测试电致变色聚合物的热稳定性(见图5)：聚合物的热分解温度大于310℃，表明其可以应用于温度较高的工作环境中。
由以上实施例可以看出，本发明制备的共聚物薄膜可实现有色至透明的变换，并且具有驱动电位低、着色效率高、稳定性好等特点，制备的共聚物薄膜在电致变色显示、自适应伪装等领域可应用。
以上已经描述了本发明的各实施例，上述说明是示例性的，并非穷尽性的，并且也不限于所披露的各实施例。在不偏离所说明的各实施例的范围和精神的情况下，对于本技术领域的普通技术人员来说许多修改和变更都是显而易见的。因此，本发明的保护范围应该以权利要求的保护范围为准。
Claims (8)
1.一种含二氧噻吩和9,9'-螺二芴结构的电致变色共聚物，其特征在于，其分子式中包括如下所示的结构：
其中，A表示硫或者氧，m和n均表示聚合度，m和n均为8-100之间的整数；
所述含二氧噻吩和9,9'-螺二芴结构的电致变色共聚物由二氧丙撑噻吩(M1)、2,2’,7,7’-四溴-9,9'-螺二芴(M2)、3,4-二溴乙撑二氧噻吩或者3,4-二溴乙撑二硫噻吩(M3)聚合得到。
2.如权利要求1所述的含二氧噻吩和9,9'-螺二芴结构的电致变色共聚物的制备方法，其特征在于，包括以下步骤：
1)通过芳基化偶联制备聚合物：将二氧丙撑噻吩(M1)、2,2’,7,7’-四溴-9,9'-螺二芴(M2)、3,4-二溴乙撑二氧噻吩或者3,4-二溴乙撑二硫噻吩(M3)、N,N-二甲基乙酰胺、碳酸钾、乙酸钯、特戊酸加入至单口烧瓶中，所述单口烧瓶上方有气源连接装置和冷凝管，对单口烧瓶进行抽换气，保持单口烧瓶内换气后气氛保护，将混合物加热反应一定时间，然后冷却至室温，再将反应后混合物溶液滴入甲醇中进行沉淀，过滤收集橙红色沉淀物；
2)通过索氏提取纯化聚合物：将步骤1)所得橙红色沉淀物用滤纸包裹，置于脂肪提取器中，先采用甲醇进行洗涤，洗涤出的沉淀物用正已烷再次洗涤，然后将沉淀物在氯仿中进行反向溶解洗涤，分离去除其中的沉淀物，将氯仿洗涤液进行浓缩，最后滴入甲醇中进行再沉淀，过滤收集沉淀物，即为纯化后的含二氧噻吩和9,9'-螺二芴结构的电致变色共聚物。
3.如权利要求2所述的制备方法，其特征在于，所述步骤1)中的二氧丙撑噻吩、2,2’,7,7’-四溴-9,9'-螺二芴和3,4-二溴乙撑二氧噻吩或者3,4-二溴乙撑二硫噻吩的摩尔比为4：1：2。
4.如权利要求2所述的制备方法，其特征在于，所述步骤1)中的二氧丙撑噻吩与碳酸钾的摩尔比为1：(2～4)，二氧丙撑噻吩与特戊酸的摩尔比为1：(0.1～0.25)，二氧丙撑噻吩与乙酸钯的摩尔比为1：(0.002～0.02)；所述N,N-二甲基乙酰胺用作溶剂。
5.如权利要求2所述的制备方法，其特征在于，所述步骤1)中的反应温度为70～100℃，反应时间为48～96小时；所述抽换气是将单口烧瓶中的空气抽取替换为氮气或氩气。
6.一种聚合物薄膜，其特征在于，所述聚合物薄膜由如权利要求1所述的含二氧噻吩和9,9'-螺二芴结构的电致变色共聚物经溶剂稀释后通过喷涂或刮涂得到，所述聚合物薄膜的厚度为200～800nm。
7.如权利要求6所述的聚合物薄膜，其特征在于，所述聚合物薄膜显示橙红色至透明色的电致变色行为：颜色对比度达到40％以上、响应速率在3秒以内、变色循环次数500次且无衰减。
8.如权利要求6所述的聚合物薄膜，其特征在于，将其应用于电致变色器件中。
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