CN111393616B - 一种黑色电致变色聚合物及其制备和电致变色聚合物薄膜 - Google Patents

一种黑色电致变色聚合物及其制备和电致变色聚合物薄膜 Download PDF

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CN111393616B
CN111393616B CN202010132582.4A CN202010132582A CN111393616B CN 111393616 B CN111393616 B CN 111393616B CN 202010132582 A CN202010132582 A CN 202010132582A CN 111393616 B CN111393616 B CN 111393616B
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张�诚
付海长
闫拴马
李维军
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Zhejiang University of Technology ZJUT
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Abstract

本发明公开了一种黑色电致变色聚合物及其制备和电致变色聚合物薄膜。所述电致变色聚合物具有以下结构，其中R、Y各自独立为C5～C50的烷烃链或C5～C50的烷氧基链；X为S或Se；所述电致变色聚合物的数均分子量Mn＝5000～200000，多分散系数D＝1.0～5.0。本发明提供了一种通过芳基化缩聚制备所述电致变色聚合物的方法。本发明还提供了一种由所述电致变色聚合物制得的电致变色聚合物薄膜，其在电场作用下可实现中性态黑色到氧化态高透射的稳定可逆的转变。

Description

一种黑色电致变色聚合物及其制备和电致变色聚合物薄膜
(一)技术领域
本发明涉及一种黑色电致变色聚合物及其制备方法和由该电致变色聚合物制得的薄膜。
(二)背景技术
聚合物电致变色材料因其结构易修饰，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。在现有的聚合物电致变色材料中，红色和蓝色的居多，绿色较少，黑色最少。因为黑色电致变色材料需要吸收可见光区的所有光波，这就对聚合物材料的结构设计和其合成提出了更高要求。
在过去几十年，黑色电致变色材料(Conjugated Polymer Blends for HighContrast Black-to-Transmissive Electrochromism.Adv.OpticalMater.2018,6,1800594)很少被报道。在现有的可溶液加工的黑色聚合物材料中，其大都合成工艺较复杂、步骤多且其材料对比度低、氧化态透过率不高。
因此，如何设计和合成可溶液加工的黑色电致变色聚合物材料使其实现中性态黑色到氧化态高透射是本领域的研究重点。
(三)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黑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一种电致变色聚合物的合成方法。
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，本发明提供一种电致变色聚合物，所述聚合物具有以下结构：
Figure BDA0002396201280000021
式中：R、Y各自独立为C5～C50的烷烃链或C5～C50的烷氧基链；X为S或Se；
所述电致变色聚合物的数均分子量Mn＝5000～200000，多分散系数D＝1.0～5.0。
作为优选，R为C5～C30的烷氧基链，Y为C5～C30的烷烃链。
作为优选，X为S。
作为优选，所述电致变色聚合物的数均分子量Mn＝10000～50000。
本发明所述的聚合物可以采用芳基化缩聚、Stille偶联、Suzuki偶联、三氯化铁氧化聚合等方法合成。
第二方面，本发明提供了一种黑色电致变色聚合物的制备方法，所述制备方法包括：
(1)将式3所示化合物和式4所示化合物加入到含有钯类催化剂的有机溶剂中进行反应，反应结束后经后处理得到式1所示的单体；
Figure BDA0002396201280000022
(2)将式1所示的单体与式2所示的单体加入到含有有机酸和无机弱碱以及钯类催化剂的有机溶剂中进行反应，反应结束后经后处理得到黑色电致变色聚合物；
Figure BDA0002396201280000023
式3或式4或式1或式2中，R、X、Y的定义与电致变色聚合物结构式中的定义相同。
作为优选，步骤(1)中，所述的式3所示化合物与式4所示化合物的投料摩尔比为1：2～4。
作为优选，步骤(1)中，所述的钯类催化剂为四(三苯基膦)钯和二氯二(三苯基膦)钯中的一种或两种。
作为优选，步骤(1)中，所述的式3所示化合物与钯类催化剂的投料摩尔比为1：3～10％。
作为优选，步骤(1)中，所述的有机溶剂为四氢呋喃和甲苯中的一种或者至少两种组合。
作为优选，步骤(1)中，反应温度为65～110℃，反应时间为12～36h。
作为优选，步骤(1)所述的后处理为：反应结束后用水和二氯甲烷萃取，合并有机层，干燥，经过柱层析分离得到单体1。
作为优选，步骤(2)中，所述的式1所示的单体与式2所示的单体的投料摩尔比为1:1。
作为优选，步骤(2)中，所述的有机酸为新戊酸和1-金刚烷甲酸中的一种或两种。
作为优选，步骤(2)中，所述的无机弱碱为碳酸钾、碳酸钠、碳酸氢钾以及碳酸氢钠中的一种或者至少两种的组合。
作为优选，步骤(2)中，所述的钯类催化剂为醋酸钯和二氯二(三苯基膦)钯中的一种或两种。
作为优选，步骤(2)中，所述的有机溶剂为N-甲基吡咯烷酮、二甲基甲酰胺或二甲基乙酰胺中的一种或者至少两种的组合。
作为优选，步骤(2)中，式1所示的单体与有机酸、无机弱碱、催化剂的投料摩尔比为 1：0.3～0.5：2～3：3～10％。
作为优选，步骤(2)中，所述聚合反应的反应温度为100～160℃，最优选为120～140℃。
作为优选，步骤(2)中，所述聚合反应的反应时间为6～72h，最优选为12～36h。
作为优选，步骤(2)中，所述的后处理为：将反应混合物倒入甲醇中，过滤，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，得到黑色电致变色聚合物。
本发明使用的化合物2、化合物3、化合物4可根据现有公开的文献进行合成，如[Adv. Funct.Mater.2018,28,1804512、Chem.Mater.2010,22,4034–4044]。
第三方面，本发明提供了一种电致变色聚合物薄膜，其由所述的电致变色聚合物制得。
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。
作为进一步的优选，所述的溶液加工成膜具体为：将电致变色聚合物溶于溶剂中得到溶液，然后将溶液涂覆于导电基底上，干燥得到电致变色聚合物薄膜。更进一步优选所述的溶剂为二氯甲烷、三氯甲烷、四氢呋喃、甲苯、二甲基甲酰胺。
本发明中，所述的涂覆方式可以是喷涂、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、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、防护眼镜等领域具有潜在的应用价值。
与现有的技术相比，本发明具有以下优点和有益效果：
(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在低电压下(1.0V左右)可实现中性态黑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。
(四)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、图3、图4：实施例1中所制备的聚合物薄膜在具体波长下从0～1.0V多电位阶跃下透射率随时间变化的曲线；
(五)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：
Figure BDA0002396201280000051
该聚合物的合成过程如下：
将P(3.65g，1eq.)加入到含有Br-PC-Br(1.75g，0.5eq)的30ml四氢呋喃溶液中，加入Pd(PPh3)2Cl2(105mg，0.03eq.)，回流下反应12小时，反应结束后用水和二氯甲烷萃取，干燥，经过柱层析分离得到PPCP。
PPCP的核磁氢谱表征数据如下：
PPCP:1HNMR(400MHz,CDCl3),δ(ppm):8.70、8.16、7.83(苯环C-H),6.63(噻吩环C-H), 4.56(N-CH2-),4.17、3.51、3.30(-CH2-O),0.8-1.5(烷基侧链氢)。
将PPCP(1.42g，1eq.)与Br-PBTP-Br(1.17g，1eq.)加入到含有新戊酸(30mg，0.3eq.) 和碳酸钾(0.34g，2.5eq.)的30mlDMAc溶液中，最后加入Pd(OAc)2(7mg，0.03eq.)催化剂，120℃反应24小时。反应结束后，将溶液倒入甲醇中，过滤，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＝28.1KDa，D＝4.43)。
聚合物薄膜的制备：
将所述聚合物溶于三氯甲烷在ITO基底上进行旋涂制膜，溶液浓度为18mg/ml，转速为 1000r/min，时间为1min。
所得聚合物薄膜的电致变色性能测试：在0V中性态以及1.0V氧化态下对聚合物薄膜进行色度测试，结果为中性态L*＝74.12，a*＝4.70，b*＝0.33，氧化态L*＝93.28，a*＝5.92，b*＝4.19。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高氯酸锂/碳酸丙烯酯溶液中，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，以及在阶跃电压下薄膜稳定性测试，数据处理结果如图1-4所示。从图1以及色度测试可以看出该聚合物薄膜在0V中性态下呈黑色，在电压1.0V下聚合物薄膜氧化后呈高透射状态。图2图3分别为聚合物薄膜在596nm和489nm下从0～1.0V多电位阶跃透射率随时间变化的曲线，可以看出薄膜在596nm和489nm处的对比度分别为31％和32％。从图4薄膜稳定性测试(5s阶跃时间)，可以看出在1000个循环后，对比度保留了94％。

Claims (10)

1.一种电致变色聚合物，所述聚合物具有以下结构：
Figure DEST_PATH_IMAGE002
式中：R、Y各自独立为C5~C50的烷烃链或C5~C50的烷氧基链；X为S或Se；
所述电致变色聚合物的数均分子量Mn=5000~200000，多分散系数D=1.0~5.0。
2.如权利要求1所述的电致变色聚合物，其特征在于：R为C5~C30的烷氧基链，Y为C5~C30的烷烃链。
3.如权利要求1所述的电致变色聚合物，其特征在于：X为S。
4.如权利要求1所述的电致变色聚合物，其特征在于：所述电致变色聚合物的数均分子量Mn=10000~50000。
5.一种权利要求1所述的电致变色聚合物的制备方法，所述制备方法包括：
（1）将式3所示化合物和式4所示化合物加入到含有钯类催化剂的有机溶剂中进行反应，反应结束后经后处理得到式1所示的单体；
Figure DEST_PATH_IMAGE004
（2）将式1所示的单体与式2所示的单体加入到含有有机酸和无机弱碱以及钯类催化剂的有机溶剂中进行反应，反应结束后经后处理得到黑色电致变色聚合物；
Figure DEST_PATH_IMAGE006
式3或式4或式1或式2中，R、X、Y的定义与电致变色聚合物结构式中的定义相同。
6.如权利要求5所述的制备方法，其特征在于：步骤（2）中，所述的有机酸为新戊酸和1-金刚烷甲酸中的一种或两种；所述的无机弱碱为碳酸钾、碳酸钠、碳酸氢钾以及碳酸氢钠中的一种或者至少两种的组合；所述的钯类催化剂为醋酸钯和二氯二（三苯基膦）钯中的一种或两种；所述的有机溶剂为N-甲基吡咯烷酮、二甲基甲酰胺或二甲基乙酰胺中的一种或者至少两种的组合。
7.如权利要求5所述的制备方法，其特征在于：步骤（2）中，所述反应的反应温度为100~160℃，反应时间为6~72h。
8.如权利要求5所述的制备方法，其特征在于：步骤（2）中，所述反应的反应温度为120~140℃，反应时间为12~36h。
9.一种电致变色聚合物薄膜，其由权利要求1所述的电致变色聚合物制得。
10.如权利要求9所述的电致变色聚合物薄膜，其特征在于：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。
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