CN111171292A - 两亲性电致变色聚合物及其制备方法 - Google Patents

两亲性电致变色聚合物及其制备方法 Download PDF

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CN111171292A
CN111171292A CN202010093539.1A CN202010093539A CN111171292A CN 111171292 A CN111171292 A CN 111171292A CN 202010093539 A CN202010093539 A CN 202010093539A CN 111171292 A CN111171292 A CN 111171292A
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石鹏杰
王家兵
韩雨桐
周颂阳
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Nanjing Yikairui New Material Co ltd
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Abstract

本发明提供一种两亲性电致变色聚合物及其制备方法,其中,制备方法包括如下步骤:将3,3‑双((2‑(2‑甲氧基乙氧基)乙氧基)甲基)‑3,4‑二氢‑2H‑噻吩并[3,4‑b][1,4]二氧杂环庚、6,8‑二溴‑3,3‑双((2‑(2‑甲氧基乙氧基)乙氧基)甲基)‑3,4‑二氢‑2H‑噻吩并[3,4‑b][1,4]二氧杂环庚、4,7‑二溴‑2,1,3‑苯并噻二唑混合,并在反应条件下进行反应。本发明由于在聚合物侧链中以两亲性基团,即单封端的聚环氧乙烷低聚体(‑(CH2CH2O)nOCH3),取代了常见的直链或者支链烷基,使得电致变色聚合物的极性增加,与离子传导层材料的结合更加紧密,更加易于实现离子的传导,从而提高材料的响应速度。制备方法简单高效,所得到的两亲性电致变色聚合物具有良好的溶解性,具有广阔的应用前景。

Description

两亲性电致变色聚合物及其制备方法
技术领域
本发明涉及电致变色聚合物技术领域,尤其涉及一种两亲性电致变色聚合物及其制备方法。
背景技术
电致变色高分子,是在电场作用下可以发生稳定可逆氧化还原的,在外观上表现为自身颜色可逆变化的聚合物,是导电高分子的一种。聚噻吩、聚吡咯、聚乙炔等导电聚合物分子均可作为电致变色材料。
由3,4-丙烯二氧噻吩(ProDOT)及其衍生物聚合得到的聚3,4-丙烯二氧噻吩(PProDOT)及其衍生物和共聚物,因其良好的溶剂溶解性、较低的电化学氧化电位,易调节的化学结构,快速的氧化还原转化速率和较高的着色态-褪色态对比度,使其成为极佳的电致变色特性材料。
然而,现有的电致变色高分子材料仍然主要使用2-乙基己基为侧链来增加材料的溶解度,使得材料的整体极性偏低,不利于制备成膜后离子的传输以及与高极性离子传导层材料的结合,从而限制了材料的响应速度。因此,针对上述问题,有必要提出进一步地解决方案。
发明内容
本发明的目的在于提供一种两亲性电致变色聚合物及其制备方法,以克服现有技术中存在的不足。
为实现上述发明目的,本发明提供一种两亲性电致变色聚合物,其结构式为:
Figure BDA0002384509760000021
其中,1.4≤m+o≤1.7,0.3≤q≤0.6,R为-(CH2CH2O)nOCH3,n为1-5的自然整数。
为实现上述发明目的,本发明提供一种如上所述的两亲性电致变色聚合物的制备方法,其包括如下步骤:
将3,3-双((2-(2-甲氧基乙氧基)乙氧基)甲基)-3,4-二氢-2H-噻吩并[3,4-b][1,4]二氧杂环庚、6,8-二溴-3,3-双((2-(2-甲氧基乙氧基)乙氧基)甲基)-3,4-二氢-2H-噻吩并[3,4-b][1,4]二氧杂环庚、4,7-二溴-2,1,3-苯并噻二唑混合,并在反应条件下进行反应。
作为本发明的两亲性电致变色聚合物的制备方法的改进,所述反应条件包括:
向3,3-双((2-(2-甲氧基乙氧基)乙氧基)甲基)-3,4-二氢-2H-噻吩并[3,4-b][1,4]二氧杂环庚、6,8-二溴-3,3-双((2-(2-甲氧基乙氧基)乙氧基)甲基)-3,4-二氢-2H-噻吩并[3,4-b][1,4]二氧杂环庚、4,7-二溴-2,1,3-苯并噻二唑的混合物中加入乙酸钯、碳酸钾、特戊酸和1-甲基-2-吡咯烷酮,在反应温度的油浴中,在有持续的氩气气流通过的状态下反应。
作为本发明的两亲性电致变色聚合物的制备方法的改进,在120℃的油浴中,在有持续的氩气气流通过的状态下反应24h。
作为本发明的两亲性电致变色聚合物的制备方法的改进,所述制备方法还包括:
在油浴中反应之前还包括:反应环境抽真空,然后通入氩气置换,重复抽真空-氩气置换多次。
作为本发明的两亲性电致变色聚合物的制备方法的改进,所述制备方法还包括:反应之后降至室温,将反应混合物倒入体积比为1比1的甲醇/1M稀盐酸水溶液中沉淀,过滤分离析出的黑色固体。
与现有技术相比,本发明的有益效果是:本发明由于在聚合物侧链中以两亲性基团,即单封端的聚环氧乙烷低聚体(-(CH2CH2O)nOCH3),取代了常见的直链或者支链烷基,使得电致变色聚合物的极性增加,与离子传导层材料的结合更加紧密,更加易于实现离子的传导,从而提高材料的响应速度。制备方法简单高效,所得到的两亲性电致变色聚合物具有良好的溶解性,可被应用于智能电致变色窗,电子纸张和显示设备,伪装等多种技术领域,具有广阔的应用前景。
附图说明
为了更清楚地说明本发明实施例或现有技术中的技术方案,下面将对实施例或现有技术描述中所需要使用的附图作简单地介绍,显而易见地,下面描述中的附图仅仅是本发明中记载的一些实施例,对于本领域普通技术人员来讲,在不付出创造性劳动的前提下,还可以根据这些附图获得其他的附图。
图1为本发明对比例中涉及的反应方程式;
图2为针对对比例得到的电致变色聚合物,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3为本发明实施例1中涉及的反应方程式;
图4为针对实施例1得到的两亲性电致变色聚合物,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5为本发明实施例2中涉及的反应方程式;
图6为针对实施例2得到的两亲性电致变色聚合物,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7为对比例和实施例1-2的聚合物在ITO玻璃上的薄膜的紫外-可见光吸收光谱,图中纵坐标代表归一化吸收,横坐标代表波长;
图8为对比例聚合物薄膜的响应时间测定,图中纵坐标代表透过率,横坐标代表时间;
图9为实施例1聚合物薄膜的响应时间测定,图中纵坐标代表透过率,横坐标代表时间。
具体实施方式
下面结合各实施方式对本发明进行详细说明,但应当说明的是,这些实施方式并非对本发明的限制,本领域普通技术人员根据这些实施方式所作的功能、方法、或者结构上的等效变换或替代,均属于本发明的保护范围之内。
本发明面临现有技术中不利于制备成膜后离子的传输以及与高极性离子传导层材料的结合,从而限制了材料的响应速度的技术问题,考虑如何增加电致变色层与离子传输层之间的相互作用,降低电致变色层和离子传导层因为材料极性相差过大而产生的离子在层与层之间的传导障碍,提升材料的响应速度。
本发明的一个方面提供一种两亲性电致变色聚合物,该两亲性电致变色聚合物的结构式为:
Figure BDA0002384509760000041
其中,1.4≤m+o≤1.7,0.3≤q≤0.6,R为-(CH2CH2O)nOCH3,n为1-5的自然整数。
具有如上所示结构的电致变色聚合物结构由于在未改变主链共轭环境的条件下,以两亲性基团,即单封端的聚环氧乙烷低聚体(-(CH2CH2O)nOCH3),取代了现有的直链或者支链烷基,并且所述各单体结构在聚合过程中满足所述比例关系,得到了极性更高,且可以被溶解的两亲性电致变色聚。一个实施方式中,当n为2时,R为-CH2CH2OCH2CH2OCH3
针对上述两亲性电致变色聚合物,本发明的另一个方面还提供该两亲性电致变色聚合物的制备方法。该制备方法包括如下步骤:
如图3所示,将3,3-双((2-(2-甲氧基乙氧基)乙氧基)甲基)-3,4-二氢-2H-噻吩并[3,4-b][1,4]二氧杂环庚、6,8-二溴-3,3-双((2-(2-甲氧基乙氧基)乙氧基)甲基)-3,4-二氢-2H-噻吩并[3,4-b][1,4]二氧杂环庚、4,7-二溴-2,1,3-苯并噻二唑混合,并在反应条件下进行反应。
其中,反应条件包括:向3,3-双((2-(2-甲氧基乙氧基)乙氧基)甲基)-3,4-二氢-2H-噻吩并[3,4-b][1,4]二氧杂环庚、6,8-二溴-3,3-双((2-(2-甲氧基乙氧基)乙氧基)甲基)-3,4-二氢-2H-噻吩并[3,4-b][1,4]二氧杂环庚、4,7-二溴-2,1,3-苯并噻二唑的混合物中加入乙酸钯、碳酸钾、特戊酸和1-甲基-2-吡咯烷酮,在反应温度的油浴中,在有持续的氩气气流通过的状态下反应。
上述3,3-双((2-(2-甲氧基乙氧基)乙氧基)甲基)-3,4-二氢-2H-噻吩并[3,4-b][1,4]二氧杂环庚、6,8-二溴-3,3-双((2-(2-甲氧基乙氧基)乙氧基)甲基)-3,4-二氢-2H-噻吩并[3,4-b][1,4]二氧杂环庚均具有形成上述单封端的聚环氧乙烷低聚体的R基。
下面结合对比例以及实施例对本发明的两亲性电致变色聚合物的制备方法进行举例说明。
对比例【油溶性电致变色聚合物,即以烷基为侧链的聚合物的合成】
反应方程式如图1所示,在三口圆底烧瓶中装入3,3-双[[(2-乙基己基)氧基]甲基]-3,4-二氢-2H-噻吩并[3,4-b][1,4]二氧杂环庚(15g,34.038mmol,1eq),6,8-二溴-3,3-双[[(2-乙基己基)氧基]甲基]-3,4-二氢-2H-噻吩并[3,4-b][1,4]二氧杂环庚(15.278g,25.529mmol,0.75eq)、4,7-二溴-2,1,3-苯并噻二唑(2.502g,8.510mmol,0.25eq),乙酸钯(0.153g,0.681mmol,0.02eq),碳酸钾(12.232g,88.500mmol,2.6eq),特戊酸(1.043g,10.211mmol,0.3eq)和1-甲基-2-吡咯烷酮(280mL)。将反应瓶抽真空10分钟,然后通入氩气置换。此抽真空-通氩气过程重复3次。然后将反应瓶置入120℃的油浴中,在有持续的氩气气流通过的状态下反应24h。降至室温后,将反应混合物倒入体积比为1比1的甲醇/1M稀盐酸水溶液中沉淀,会发现有大量黑色固体析出。用布氏漏斗将混合物过滤分离即得到黑色至透明电致变色聚合物19.3g,产率为73.5%。
为了表征对比例得到的两亲性电致变色聚合物。如图2所示,为其GPC测量结果。其中,以色谱级的四氢呋喃为流动相,以聚苯乙烯为标样,使用凝胶色谱法测量聚合物的分子量Mn为20233道尔顿,Mw为37030道尔顿,PDI为1.8。
实施例1【两亲性黑色至无色电致变色聚合物,即侧链为聚环氧乙烷低聚体的聚合物的合成】
反应方程式如图3所示,在三口圆底烧瓶中装入3,3-双((2-(2-甲氧基乙氧基)乙氧基)甲基)-3,4-二氢-2H-噻吩并[3,4-b][1,4]二氧杂环庚(15g,35.670mmol,1eq),6,8-二溴-3,3-双((2-(2-甲氧基乙氧基)乙氧基)甲基)-3,4-二氢-2H-噻吩并[3,4-b][1,4]二氧杂环庚(15.471g,26.753mmol,0.75eq),4,7-二溴-2,1,3-苯并噻二唑(2.621g,8.918mmol,0.25eq),乙酸钯(0.160g,0.713mmol,0.02eq),碳酸钾(12.818g,92.742mmol,2.6eq),特戊酸(1.093g,10.701mmol,0.3eq)和1-甲基-2-吡咯烷酮(280mL)。将反应瓶抽真空10min,然后通入氩气置换。此抽真空-通氩气过程重复3次。然后将反应瓶置入120℃的油浴中,在有持续的氩气气流通过的状态下反应24h。降至室温后,将反应混合物倒入体积比为1比1的甲醇/1M稀盐酸水溶液中沉淀,会发现有大量黑色固体析出。用布氏漏斗将混合物过滤分离即得到两亲性电致变色聚合物22.7g,产率为82.5%。
为了表征实施例1得到的两亲性电致变色聚合物。如图4所示,为其GPC测量结果,以色谱级的四氢呋喃为流动相,以聚苯乙烯为标样,使用凝胶色谱法测量聚合物的分子量Mn为26716道尔顿,Mw为56722道尔顿,PDI为2.1。
实施例2【两亲性黑色至无色电致变色聚合物,即侧链为聚环氧乙烷低聚体的聚合物的合成】
反应方程式如图5所示,在三口圆底烧瓶中装入3,3-双((2-(2-甲氧基乙氧基)乙氧基)甲基)-3,4-二氢-2H-噻吩并[3,4-b][1,4]二氧杂环庚(15g,35.670mmol,1eq),6,8-二溴-3,3-双((2-(2-甲氧基乙氧基)乙氧基)甲基)-3,4-二氢-2H-噻吩并[3,4-b][1,4]二氧杂环庚(14.440g,24.969mmol,0.70eq)、4,7-二溴-2,1,3-苯并噻二唑(3.146g,10.701mmol,0.30eq),乙酸钯(0.160g,0.713mmol,0.02eq),碳酸钾(12.818g,92.742mmol,2.6eq),特戊酸(1.093g,10.701mmol,0.3eq)和1-甲基-2-吡咯烷酮(280mL)。将反应瓶抽真空10分钟,然后通入氩气置换。此抽真空-通氩气过程重复3次。然后将反应瓶置入120摄氏度的油浴中,在有持续的氩气气流通过的状态下反应24小时。降至室温后,将反应混合物倒入体积比为1比1的甲醇/1M稀盐酸水溶液中沉淀,会发现有大量黑色固体析出。用布氏漏斗将混合物过滤分离即得到两亲性电致变色聚合物20.6克,产率为75.3%。
为了表征实施例2得到的两亲性电致变色聚合物。如图6所示,为其GPC测量结果,以色谱级的四氢呋喃为流动相,以聚苯乙烯为标样,使用凝胶色谱法测量聚合物的分子量Mn为19875道尔顿,Mw为29304道尔顿,PDI为1.5。
为了验证对比例和实施例1和2得到的电致变色聚合物的性能。将对比例和实施例1-2制备得到的聚合物按4mg/mL的浓度配置成甲苯溶液,经喷枪喷涂至带有ITO导电层的玻璃上,测定聚合物薄膜紫外-可见光吸收光谱,其结果如图7所示,由结果可以看出,在不改变共轭主链单体的结构和配比的情况下,仅仅改变侧链基团时,聚合物在紫外-可见光范围内的吸收性质并未有较大改变。
同时,当实施例2中4,7-二溴-2,1,3-苯并噻二唑的比例由0.25升至0.3,即6,8-二溴-3,3-双((2-(2-甲氧基乙氧基)乙氧基)甲基)-3,4-二氢-2H-噻吩并[3,4-b][1,4]二氧杂环庚单体比例由0.75降至0.7时,聚合物在波长500nm左右的吸收强度明显下降,同时,造成了聚合物颜色的改变。
如图8,对由对比例制备得到的油溶性聚合物薄膜进行光谱电化学性能进行测定,当检测的吸收波长设定为540nm时,聚合物由着色态转化至透明态过程中,实现95%对比度变化的转化时间为1.6秒;聚合物由透明态转化至着色态过程中,实现95%对比度变化的转化时间为0.8秒。
如图9,对由实施例1制备得到的两亲性聚合物薄膜进行光谱电化学性能进行测定,当检测的吸收波长设定为540nm时,聚合物由着色态转化至透明态过程中,实现95%对比度变化的转化时间为1.3秒;聚合物由透明态转化至着色态过程中,实现95%对比度变化的转化时间为0.6秒。很明显,在相同条件下,两亲性聚合物薄膜的变色速度有所提升。
综上所述,本发明由于在聚合物侧链中以两亲性基团,即单封端的聚环氧乙烷低聚体(-(CH2CH2O)nOCH3),取代了常见的直链或者支链烷基,使得电致变色聚合物的极性增加,与离子传导层材料的结合更加紧密,更加易于实现离子的传导,从而提高材料的响应速度。制备方法简单高效,所得到的两亲性电致变色聚合物具有良好的溶解性,可被应用于智能电致变色窗,电子纸张和显示设备,伪装等多种技术领域,具有广阔的应用前景。
对于本领域技术人员而言,显然本发明不限于上述示范性实施例的细节,而且在不背离本发明的精神或基本特征的情况下,能够以其他的具体形式实现本发明。因此,无论从哪一点来看,均应将实施例看作是示范性的,而且是非限制性的,本发明的范围由所附权利要求而不是上述说明限定,因此旨在将落在权利要求的等同要件的含义和范围内的所有变化囊括在本发明内。
此外,应当理解,虽然本说明书按照实施方式加以描述,但并非每个实施方式仅包含一个独立的技术方案,说明书的这种叙述方式仅仅是为清楚起见,本领域技术人员应当将说明书作为一个整体,各实施例中的技术方案也可以经适当组合,形成本领域技术人员可以理解的其他实施方式。

Claims (6)

1.一种两亲性电致变色聚合物,其特征在于,所述两亲性电致变色聚合物的结构式为:
Figure FDA0002384509750000011
其中,1.4≤m+o≤1.7,0.3≤q≤0.6,R为-(CH2CH2O)nOCH3,n为1-5的自然整数。
2.一种如权利要求1所述的两亲性电致变色聚合物的制备方法,其特征在于,该制备方法包括如下步骤:
将3,3-双((2-(2-甲氧基乙氧基)乙氧基)甲基)-3,4-二氢-2H-噻吩并[3,4-b][1,4]二氧杂环庚、6,8-二溴-3,3-双((2-(2-甲氧基乙氧基)乙氧基)甲基)-3,4-二氢-2H-噻吩并[3,4-b][1,4]二氧杂环庚、4,7-二溴-2,1,3-苯并噻二唑混合,并在反应条件下进行反应。
3.根据权利要求2所述的两亲性电致变色聚合物的制备方法,其特征在于,所述反应条件包括:
向3,3-双((2-(2-甲氧基乙氧基)乙氧基)甲基)-3,4-二氢-2H-噻吩并[3,4-b][1,4]二氧杂环庚、6,8-二溴-3,3-双((2-(2-甲氧基乙氧基)乙氧基)甲基)-3,4-二氢-2H-噻吩并[3,4-b][1,4]二氧杂环庚、4,7-二溴-2,1,3-苯并噻二唑的混合物中加入乙酸钯、碳酸钾、特戊酸和1-甲基-2-吡咯烷酮,在反应温度的油浴中,在有持续的氩气气流通过的状态下反应。
4.根据权利要求3所述的两亲性电致变色聚合物的制备方法,其特征在于,在120℃的油浴中,在有持续的氩气气流通过的状态下反应24h。
5.根据权利要求3所述的两亲性电致变色聚合物的制备方法,其特征在于,所述制备方法还包括:
在油浴中反应之前还包括:反应环境抽真空,然后通入氩气置换,重复抽真空-氩气置换多次。
6.根据权利要求2至5任一项所述的两亲性电致变色聚合物的制备方法,其特征在于,所述制备方法还包括:反应之后降至室温,将反应混合物倒入体积比为1比1的甲醇/1M稀盐酸水溶液中沉淀,过滤分离析出的黑色固体。
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