CN115521442B - 一种可溶液处理的红色至透明电致变色聚合物及其制备方法和应用 - Google Patents
一种可溶液处理的红色至透明电致变色聚合物及其制备方法和应用 Download PDFInfo
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Abstract
本发明涉及一种可溶液处理且性能优异的红色至透明电致变色聚合物,聚合物的结构式如下:其中,n表示聚合度,n取8‑100的自然数。所述电致变色聚合物形成的薄膜在外加电场作用下可实现由红色至透明的高对比度颜色变换,响应时间在2秒以内,稳定变色数百次后几乎没有对比度的衰减,聚合物还可在有机溶剂甲苯、二氯甲烷等中溶解,有利于进一步的工艺处理和应用。
Description
技术领域
本发明涉及电致变色聚合物技术领域,具体涉及一种可溶液处理的红色至透明电致变色聚合物及其制备方法和应用。
背景技术
电致变色材料的原理是在外电场作用下能够发生可逆的氧化还原反应,并表现出外观颜色以及红外特性的变化,在智能窗、军事伪装等领域具有广阔的应用前景。导电聚合物作为电致变色材料的一种,相比于无机电致变色材料、紫精小分子电致变色材料等,具有颜色变换丰富、响应速率快、稳定性高等优点,因此成为电致变色领域研究与应用的热点。但一直以来,导电聚合物基电致变色薄膜主要采用电沉积方法的制备,导致其在大面积稳定制备方面存在较大问题,并且沉积的薄膜几乎不能溶解,无法进一步的处理,大大限制了其应用。
为实现导电聚合物的可溶解性,最常见的方法是引入长链的烷基和羧酸盐基团,前者可实现聚合物在油性溶剂如甲苯、氯仿等溶剂体系的溶解,后者则使聚合物溶于水性溶剂体系。由于水性体系的聚合物性能相对较差,且易与电解质体系发生反应,因此目前研究的可溶性聚合物仍以油性为主,且主要集中于聚丙撑二氧噻吩体系(ProDOT),其他体系相对研究及应用较少。另外,为实现三基色之一的红色至透明变换,导电聚合物通常需要较高的带隙,而目前常见的二氧噻吩单元均具有较低的能带范围,使其在红色电致变色材料的实现上具有一定的难度,部分已实现的红色至透明变换电致变色材料也存在稳定性不足等问题。因此,开发新型可溶液处理且性能优异和稳定的红色至透明电致变色聚合物仍是电致变色领域需要解决的难题。
发明内容
(一)要解决的技术问题
鉴于现有技术存在的问题,本发明提供一种新的可溶液处理且性能优异的红色至透明电致变色聚合物及其制备方法,所述电致变色聚合物在外加电场作用下可实现由红色至透明的高对比度颜色变换,响应时间在2秒以内,稳定变色数百次后几乎没有对比度的衰减,聚合物还可在有机溶剂甲苯、二氯甲烷等中溶解,有利于进一步的工艺处理和应用。
(二)技术方案
为了达到上述目的,本发明采用的主要技术方案包括:
第一方面,本发明提供一种可溶液处理且性能优异的红色至透明电致变色聚合物,其结构式如下:
其中,n表示聚合度,n取8-100的自然数。
第二方面,本发明提供一种式I所示红色至透明电致变色聚合物的制备方法,所述方法为:采用2,5-二溴-3,4-乙撑二氧基噻吩、2,5-二氯-3,4-乙撑二氧基噻吩及2,5-二碘-3,4-乙撑二氧基噻吩中的一种与式Ⅱ所示化合物为合成单体,将合成单体加到有机溶剂中,并向有机溶剂中加入有机酸、弱碱和钯类催化剂,在惰性气体保护条件下,加热进行芳基化偶联聚合反应,制得式I所示红色至透明电致变色聚合物;
反应过程如下:其中R为溴、氯或碘;
根据本发明的较佳实施例,其中,所述有机酸为特戊酸或叔癸酸;所述无机弱碱为碳酸钾、碳酸铯或醋酸钾;所述钯类催化剂为乙酸钯。
根据本发明的较佳实施例,其中,所述有机溶剂为N,N-二甲基乙酰胺或N,N-二甲基丙酰胺。
根据本发明的较佳实施例,其中,2,5-二溴-3,4-乙撑二氧基噻吩、2,5-二氯-3,4-乙撑二氧基噻吩及2,5-二碘-3,4-乙撑二氧基噻吩中的一种与式Ⅱ所示化合物的摩尔比控制为1:1。
根据本发明的较佳实施例,其中,所述无机弱碱与式Ⅱ所示化合物的摩尔比为2-4:1;有机酸与式Ⅱ所示化合物的摩尔比为0.08-0.2:1;所述钯类催化剂与式Ⅱ所示化合物的摩尔比为0.03-0.05:1。
根据本发明的较佳实施例,其中,加热至120-140℃反应36-72h。
根据本发明的较佳实施例,其中,反应结束后,冷却至室温,将反应液滴入至冷甲醇中进行沉淀,干燥过滤沉淀物;再分别以甲醇、正已烷和氯仿进行索氏提取,将氯仿提取液浓缩,再滴入至冷甲醇中沉淀,过滤干燥,即得到式I所示红色至透明电致变色聚合物。
第三方面,本发明还涉及式I所示红色至透明电致变色聚合物在制备电致变色薄膜和电致变色器件中的应用。
根据本发明的较佳实施例,所述电致变色薄膜为将式I所示红色至透明电致变色聚合物溶解在有机溶剂中形成溶液或浆料,然后将所述溶液或浆料涂布在导电基材表面或光洁板体表面并干燥制得。其中,有机溶剂可使用甲苯或二氯甲烷。
根据本发明的较佳实施例,所述电致变色器件包括依次层叠的上电极层、电解质层、电致变色薄膜和下电极层,所述电致变色薄膜为由式I所示红色至透明电致变色聚合物形成的薄膜。
(三)有益效果
本发明的有益效果是:
本发明以2,5-二溴-3,4-乙撑二氧基噻吩(或者是2,5-二氯-3,4-乙撑二氧基噻吩或2,5-二碘-3,4-乙撑二氧基噻吩)和式Ⅱ所示结构的分子为合成单体,将二氧基噻吩作为嵌入单元引入至聚合物主链结构中,制备的聚合物利用式Ⅱ所示结构造成的空间位阻以及其内部苯环所具有的吸电子效应,结合二氧噻吩内较强的供电子侧链基团,使聚合物的分子吸收位于蓝光区而显示红色;由于式Ⅱ所示分子结构中引入了长链烷基基团,减弱了分子间的相互作用,使聚合物可溶解在有机溶剂如甲苯、二氯甲烷等之中,有利于聚合物的可溶液化处理,有利于制作大面积电致变色薄膜等应用工艺,例如采用喷涂或者刮涂方式成膜。
经实验证明,本发明制备的式I所示红色至透明电致变色聚合物溶解在有机溶剂中制成溶液或浆料后,经喷涂或刮涂成膜,可实现高对比度的红色至透明态间转换,且具有驱动电压低、响应速率快、稳定性高等特点,适用于制作电致变色器件。经测试,聚合物薄膜应用的阶跃电位为0V和1.0V,电压的驻留时间分别为5s和20s,透过率对比度为38%,着色和褪色时间分别为0.6s和2.6s左右,测试共聚物的电化学稳定性,方波电位扫描500次依然保持良好的稳定性。
附图说明
图1为式I所示红色至透明电致变色聚合物的分子结构式。
图2为式I所示红色至透明电致变色聚合物的核磁氢谱。
图3为通过凝胶渗透色谱法测定的式I所示聚合物的分子量及分布图,参比样品为聚苯乙烯,溶剂为四氢呋喃,图中纵坐标为检出强度,横坐标为滞留时间。
图4为式I所示红色至透明电致变色聚合物溶于氯仿的光谱吸收曲线。
图5为式I所示红色至透明电致变色聚合物薄膜变色前后的光谱透过率曲线与颜色变换照片。
图6为式I所示红色至透明电致变色聚合物薄膜的循环伏安曲线。
图7为式I所示红色至透明电致变色聚合物薄膜的方波电位循环曲线。
图8为式I所示红色至透明电致变色聚合物薄膜与水的接触角照片。
具体实施方式
为了更好的解释本发明,以便于理解,下面结合附图,通过具体实施方式,对本发明作详细描述。
实施例1
本实施例为式I所示结构的聚合物的合成方法:
将0.1mmol的2,5-二溴-3,4-乙撑二氧基噻吩、0.1mmol的式Ⅱ所示分子、0.004mmol醋酸钯、0.25mmol的碳酸钾、0.01mmol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140℃反应48h,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红色固体,过滤干燥即得到式I所示结构的目标聚合物。如图1所示为目标聚合物的结构图。
其中,式Ⅱ所示分子的合成方法如下:
将2-溴并噻吩、镁粉和碘加到四氢呋喃中,加入氯化锌,在0℃下反应4h制得2-氯化锌并噻吩中间产物,将该中间产物与二溴对苯二甲酸乙酯混合,以四(三苯基膦)钯为催化剂在四氢呋喃中,10-20℃下反应12h,制得二并噻吩对苯二甲酸乙酯;将二并噻吩对苯二甲酸乙酯与1-溴化镁-4甲基苯混合,在乙酸中通入HCl反应制得式Ⅱ所示分子。
反应过程中可参见Chan,S.-H.;Chen,C.-P.;Chao,T.-C.;Ting,C.;Ko,B.-T.Macromolecules 2008,41,5519。将该文献记载的反应过程中反应原料2-溴噻吩换成2-溴并噻吩,则该文献记载的产物TPT即可变为本发明所需的式Ⅱ所示化合物,并将其用作合成本发明式I结构聚合物的单体。
如图2所示为式I所示结构的目标聚合物的核磁共振氢谱。如图3所示为式I所示结构的目标聚合物通过凝胶渗透色谱法测定的分子量及分布图,参比样品为PS,溶剂为四氢呋喃,图中纵坐标为检出强度,横坐标为滞留时间。测量式I所示聚合物的分子量Mn为22065道尔顿,Mw为道尔顿51738,PDI为2.3448。
将本实施例制备的式I所示结构的聚合物进行溶液光谱测试:将式I所示结构的聚合物溶于氯仿,配制成浓度为1*10-4mg/mL的溶液,溶液吸收曲线如图4所示,聚合物吸收峰分别位于541nm处,聚合物溶液呈现为紫红色。
实施例2
本实施例为使用式I所示分子形成聚合物薄膜:
将实施例1制备的式I所示结构的聚合物溶于甲苯中,配制4mg/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1.0左右,喷涂后置于真空干燥箱中40℃真空烘干待用。
聚合物薄膜性能测试
采用聚合物薄膜为工作电极、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0.1mol/L的高氯酸锂丙烯碳酸酯溶液,进行如下各项测试:
(1)测试不同电压下的聚合物薄膜的光谱电化学性能
聚合物薄膜变色前后的透过率谱图和照片如图5所示。由图示内容可以看出,式I所示分子形成的聚合物薄膜具有明显的电致变色性能,施加电场前薄膜显示红色(中性态),施加电场后薄膜呈透明(氧化态),且该薄膜能呈现高对比度的红色至透明变化范围,特别是在褪色态几乎完全透明,且透过率对比度高于50%以上。
(2)采用循环伏安法测试电致变色聚合物的初始氧化还原电压
如图6所示,式I所示分子形成的聚合物薄膜的起始氧化电位为0.35V。
(3)采用阶跃法测试共聚物薄膜的光谱响应与稳定性能
如图7所示,聚合物薄膜应用的阶跃电位为0V和1.0V,电压的驻留时间分别为5s和20s,透过率对比度为38%,着色和褪色时间分别为0.6s和2.6s左右,测试共聚物的电化学稳定性,方波电位扫描500次依然保持良好的稳定性。
(4)测试电致变色聚合物的表面亲和性:测试式I所示分子形成的聚合物薄膜表面与水的接触角,如图8所示,约为96.8度,小于100度,说明式I所示分子形成的聚合物薄膜具有亲和性,较易于在导电基底上成膜。
由上述测试可以看出,本发明制备的式I所示结构的电致变色聚合物,可实现红色至透明的变换,并且具有对比度高、驱动电位低、变色速率快、着色效率高、稳定性好等特点,可弥补目前红色型高性能电致变色材料种类不足的问题,制备的聚合物薄膜在电致变色显示、自适应伪装等领域可应用。
最后应说明的是:以上各实施例仅用以说明本发明的技术方案,而非对其限制;尽管参照前述各实施例对本发明进行了详细的说明,本领域的普通技术人员应当理解:其依然可以对前述各实施例所记载的技术方案进行修改,或者对其中部分或者全部技术特征进行等同替换;而这些修改或者替换,并不使相应技术方案的本质脱离本发明各实施例技术方案的范围。
Claims (10)
1.一种可溶液处理且性能优异的红色至透明电致变色聚合物,其特征在于,聚合物的结构式如下:
;
其中,n表示聚合度,n取8-100的自然数。
2.一种式I所示红色至透明电致变色聚合物的制备方法,其特征在于,所述方法为:采用2,5-二溴-3,4-乙撑二氧基噻吩、2,5-二氯-3,4-乙撑二氧基噻吩及2,5-二碘-3,4-乙撑二氧基噻吩中的一种与式Ⅱ所示化合物为合成单体,将合成单体加到有机溶剂中,并向有机溶剂中加入有机酸、弱碱和钯类催化剂,在惰性气体保护条件下,加热进行芳基化偶联聚合反应,制得式I所示红色至透明电致变色聚合物;
反应过程如下:其中R为溴、氯或碘;
3.根据权利要求2所述的制备方法,其特征在于,所述有机酸为特戊酸或叔癸酸;所述无机弱碱为碳酸钾、碳酸铯或醋酸钾;所述钯类催化剂为乙酸钯。
4.根据权利要求2所述的制备方法,其特征在于,所述有机溶剂为N,N-二甲基乙酰胺或N,N-二甲基丙酰胺。
5.根据权利要求2所述的制备方法,其特征在于,2,5-二溴-3,4-乙撑二氧基噻吩、2,5-二氯-3,4-乙撑二氧基噻吩及2,5-二碘-3,4-乙撑二氧基噻吩中的一种与式Ⅱ所示化合物的摩尔比控制为1:1。
6.根据权利要求2所述的制备方法,其特征在于,所述无机弱碱与式Ⅱ所示化合物的摩尔比为2-4:1;有机酸与式Ⅱ所示化合物的摩尔比为0.08-0.2:1;所述钯类催化剂与式Ⅱ所示化合物的摩尔比为0.03-0.05:1。
7.根据权利要求2所述的制备方法,其特征在于,加热至120-140℃反应36-72h。
8.根据权利要求2所述的制备方法,其特征在于,反应结束后,冷却至室温,将反应液滴入至冷甲醇中进行沉淀,干燥过滤沉淀物;再分别以甲醇、正已烷和氯仿进行索氏提取,将氯仿提取液浓缩,再滴入至冷甲醇中沉淀,过滤干燥,即得到式I所示红色至透明电致变色聚合物。
9.权利要求1中式I所示红色至透明电致变色聚合物在制备电致变色薄膜和电致变色器件中的应用。
10.根据权利要求9所述的应用,其特征在于,所述电致变色薄膜为将式I所示红色至透明电致变色聚合物溶解在有机溶剂中形成溶液或浆料,然后将所述溶液或浆料涂布在导电基材表面或光洁板体表面并干燥制得;
所述电致变色器件包括依次层叠的上电极层、电解质层、电致变色薄膜和下电极层,所述电致变色薄膜为由式I所示红色至透明电致变色聚合物形成的薄膜。
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