CN115490836A - 一种黄色到高透射可逆转变的电致变色聚合物及其应用 - Google Patents
一种黄色到高透射可逆转变的电致变色聚合物及其应用 Download PDFInfo
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Abstract
本发明公开了一种能实现黄色到高透射可逆转变的可溶性电致变色聚合物及其电致变色聚合物薄膜。本发明采用芳基化缩聚制备所述的电致变色聚合物。本发明还提供了由所述电致变色聚合物制备得到的电致变色聚合物薄膜，其可实现中性态黄色到氧化态高透射的稳定可逆的转变，在显示器、智能窗、手机壳等领域具有潜在的应用价值。
Description
技术领域
本发明涉及一种黄色到高透射可逆转变的电致变色聚合物及其制备方法和其在制备电致变色聚合物薄膜中的应用。
背景技术
“电致变色”(Electrochromism,EC)是指材料的光学属性，如透射率、反射率、吸收率等在外加电场作用下发生稳定、可逆变化的现象，宏观上表现为颜色和透明度的可逆变化。
电致变色材料主要分为无机电致变色材料、有机小分子电致变色材料和聚合物电致变色材料。其中，聚合物电致变色材料(PEC)因其结构易修饰，能带可控、加工性能好、电致变色综合性能优异等特点，在智能窗、平面显示、信息标签等领域具有巨大的应用价值，被广泛地研究。根据聚合方式的不同，PEC材料一般可分为电化学聚合的PEC材料和化学聚合的PEC材料。化学聚合的PEC材料通常具有良好的溶液加工性能，可通过喷涂、旋涂、油墨打印、丝网印刷等技术制备薄膜，从而可实现PEC器件的大面积、低成本制备，因此，备受关注。
在过去十年，溶液加工型PEC材料得到了快速的发展，各种各样的溶液加工型PEC材料被设计合成。其中，有色到高透射转变的可溶性PEC材料被广泛研究，而CMY(青、品红和黄)三基色到高透射的材料是重点研究对象，这主要是由于三基色到高透射材料是实现全色调控的关键。然而，目前三基色到高透射材料十分少且电致变色性能不佳。进一步，要实现黄色到高透射材料的设计合成十分困难，而且具有良好应用前景的黄色到高透射材料的技术专利都集中在欧美等发达国家，国内在这一领域具有自主知识产权的技术专利相对缺乏。因此，开发高性能的、具备产业化应用前景的新型黄色到高透射可溶液加工的PEC材料十分必要。
发明内容
本发明的第一个目的是提供一种电致变色聚合物，该材料在电场作用下可实现中性态黄色到氧化态高透射的稳定可逆的转变，且在有机溶剂中具有良好的溶解性。
本发明的第二个目的是提供电致变色聚合物的制备方法。
本发明的第三个目的是提供一种电致变色聚合物薄膜。
本发明的目的通过以下技术方案实现：
第一方面，本发明提供了一种式(I)所示电致变色聚合物，
式中：R为C4～C30的烷基；
所述电致变色聚合物的数均分子量Mn＝2000～200000，分子量的大小受聚合反应时间控制，多分散系数D＝1.0～5.0。
作为优选，所述电致变色聚合物的数均分子量Mn＝5000～50000。
作为优选，R为C6-C20的烷基。更加优选为C8烷基，尤其是2-乙基己基。
第二方面，本发明提供了一种式(I)所示的电致变色聚合物的制备方法，其是由单体1 与单体2经芳基化缩聚制得；
式1中，R的定义同式(I)。
式(I)所示的聚合物的制备方法具体为：将单体1、单体2、有机酸、无机弱碱、钯类催化剂加入有机溶剂中80～160℃聚合反应6～72h，所得反应液经后处理，得到式(I)所示的电致变色聚合物；单体1、单体2、有机酸、无机弱碱与钯类催化剂的物质的量之比为 1:1:0.3～0.5:2～3:0.03～0.1(优选1:1:0.3:2.5:0.03)。
单体1参考文献(Adv.Mater.2010,22,4949–4953)合成，利用不同长度的醇与烷基溴通过缩合反应合成得到不同碳链长度的单体1。
作为优选，所述的有机酸为新戊酸和1-金刚烷甲酸中的一种或两种的混合物(优选新戊酸)。
作为优选，所述的无机弱碱为碳酸钾、碳酸钠、碳酸铯、碳酸氢钾以及碳酸氢钠中的一种或者两种以上的混合物(优选碳酸钾)。
作为优选，所述的钯类催化剂为醋酸钯、二氯二(三苯基膦)钯、三(二亚苄基丙酮)二钯(0)-氯仿加合物中的一种或两种以上的混合物(优选醋酸钯)。
作为优选，所述的有机溶剂为四氢呋喃、N-甲基吡咯烷酮、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺中的一种或者两种以上的混合物(优选N,N-二甲基乙酰胺)。
作为优选，所述聚合反应的反应温度为120～140℃。
作为优选，所述聚合反应的反应时间为12～36h。
进一步，所述的有机溶剂的体积以所述式(I)所示单体1和单体2的总物质的量计为 1～20L/mol(优选5L/mol)。
进一步，所述的后处理为：将所述反应液倒入甲醇中，过滤，取滤饼烘干，依次用甲醇、丙酮、己烷、三氯甲烷索氏提取，收集三氯甲烷中溶解的聚合物，旋干，得到所述的式(I)所示的电致变色聚合物。
第三方面，本发明提供了一种上述电致变色聚合物在制备电致变色聚合物薄膜中的应用。
作为优选，所述的电致变色聚合物薄膜是由所述的电致变色聚合物通过溶液加工成膜的方式获得。
具体地，所述应用为：将所述电致变色聚合物溶于溶剂中，得到聚合物溶液，然后将所述聚合物溶液涂覆于导电基底上，得到所述电致变色聚合物薄膜；所述的溶剂为二氯甲烷、三氯甲烷、四氢呋喃、甲苯、N,N-二甲基甲酰胺中的一种或两种以上的混合物；所述聚合物溶液中电致变色聚合物的浓度为5～30mg/mL(优选15mg/mL)。
本发明中，所述的涂覆可以是喷涂、旋涂、丝网印刷等。所述的导电基底可以是ITO玻璃、FTO玻璃、ITO-PET基底或FTO-PET基底等。
本发明获得的电致变色聚合物薄膜在智能窗、显示器、电子纸等领域具有潜在的应用价值。
与现有的技术相比，本发明具有以下有益效果：
(1)本发明涉及的聚合物在常见的有机溶剂中具有良好的溶解性，可通过溶液加工的方法实现其薄膜材料的大面积制备。
(2)本发明制备的聚合物薄膜可实现中性态黄色到氧化态高透射的稳定可逆的转变，在显示器、智能窗、手机壳等领域具有潜在的应用价值。
附图说明
图1：实施例1中所制备的聚合物薄膜在不同电压下的光学吸收；
图2：实施例1中所制备的聚合物薄膜在具体波长下从0～1.3V多电位阶跃下透射率随时间变化的曲线。
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的说明，但本发明的保护范围不限于此。
实施例1
所使用的共轭聚合物的合成及分子结构如下所示：
该聚合物的合成过程如下：
将M1(0.44g，1eq.)与M2(0.28g，1eq.)加入到含有新戊酸(30mg，0.3eq.)和碳酸钾(345mg，2.5eq.)的10mLDMAc溶液中，最后加入Pd(OAc)2(7mg，0.03eq.)催化剂， 130℃反应24小时。反应结束后，将溶液倒入200mL甲醇中，过滤，取滤饼烘干，依次用甲醇、丙酮、己烷、三氯甲烷索提，收集三氯甲烷中溶解的聚合物，旋干。聚合物GPC测试结果(Mn＝18.0KDa，D＝2.76)。
聚合物薄膜的制备：
将所述聚合物溶于三氯甲烷中，得到聚合物溶液，在ITO基底上旋涂制膜，溶液浓度为 15mg/mL，转速为800r/min，时间为1min。旋涂一次取溶液体积为0.5mL。
所得聚合物薄膜的电致变色性能测试：在0V中性态以及1.3V氧化态下对聚合物薄膜进行色度测试，结果为中性态L*＝91.98，a*＝0.13，b*＝82.8，氧化态L*＝78.10，a*＝-3.84，b*＝-10.32。使用电化学工作站与紫外-可见分光光度仪联用装置，在0.1M四丁基六氟磷酸铵/乙腈溶液中，分别测试所制备的薄膜在不同电压下的紫外-可见光吸收，在特定波长下的透射率和时间的关系，数据处理结果如图1和2所示。从图1以及色度测试可以看出该聚合物薄膜在0V中性态下呈黄色，在电压1.3V下聚合物薄膜氧化后呈高透射状态。从图2可以看出薄膜在446nm 的对比度为57.3％。同时，聚合物薄膜的着色时间和褪色时间分别1.9s和0.4s。通过电化学、紫外-可见分光光度仪以及色度仪等一系列测试表明制备得到的可溶性电致变色共轭聚合物能实现黄色到高透射的可逆转变，同时还具有优异的电致变色综合性能。
Claims (10)
1.一种式(I)所示电致变色聚合物，
式中：R为C4～C30的烷基；
所述电致变色聚合物的数均分子量Mn＝2000～200000。
2.如权利要求1所述的式(I)所示的电致变色聚合物的制备方法，其特征在于所述方法为：
将单体1、单体2、有机酸、无机弱碱、钯类催化剂加入有机溶剂中80～160℃聚合反应6～72h，所得反应液经后处理，得到式(I)所示的电致变色聚合物；单体1、单体2、有机酸、无机弱碱与钯类催化剂的物质的量之比为1:1:0.3～0.5:2～3:0.03～0.1；
式1、(I)中，R为C4～C30的烷基。
3.如权利要求2所述的式(I)所示的电致变色聚合物的制备方法，其特征在于：所述的有机酸为新戊酸和1-金刚烷甲酸中的一种或两种的混合物。
4.如权利要求2所述的式(I)所示的电致变色聚合物的制备方法，其特征在于：所述的无机弱碱为碳酸钾、碳酸钠、碳酸铯、碳酸氢钾以及碳酸氢钠中的一种或者两种以上的混合物。
5.如权利要求2所述的式(I)所示的电致变色聚合物的制备方法，其特征在于：所述的钯类催化剂为醋酸钯、二氯二(三苯基膦)钯、三(二亚苄基丙酮)二钯(0)-氯仿加合物中的一种或两种以上的混合物。
6.如权利要求2所述的式(I)所示的电致变色聚合物的制备方法，其特征在于：所述的有机溶剂为四氢呋喃、N-甲基吡咯烷酮、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺中的一种或者两种以上的混合物。
7.如权利要求2所述的式(I)所示的电致变色聚合物的制备方法，其特征在于：所述的有机溶剂的体积以所述式(I)所示单体1和单体2的总物质的量计为1～20L/mol。
8.如权利要求2所述的式(I)所示的电致变色聚合物的制备方法，其特征在于所述的后处理为：将所述反应液倒入甲醇中，过滤，取滤饼烘干，依次用甲醇、丙酮、己烷、三氯甲烷索氏提取，收集三氯甲烷中溶解的聚合物，旋干，得到所述的式(I)所示的电致变色聚合物。
9.如权利要求1所述的电致变色聚合物在制备电致变色聚合物薄膜中的应用。
10.如权利要求9所述的应用，其特征在于所述应用为：将所述电致变色聚合物溶于溶剂中，得到聚合物溶液，然后将所述聚合物溶液涂覆于导电基底上，得到所述电致变色聚合物薄膜；所述的溶剂为二氯甲烷、三氯甲烷、四氢呋喃、甲苯、N,N-二甲基甲酰胺中的一种或两种以上的混合物；所述聚合物溶液中电致变色聚合物的浓度为5～30mg/mL。
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