CN107739430B - 一种全色段电制变色聚合物及其制备方法 - Google Patents
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Abstract
本发明公开了一种全色段电制变色聚合物,所述聚合物为聚2,5‑二(2,2‑二甲基‑丙二烯)基‑3,4‑乙烯二氧噻吩,具有分子结构如式1所示的有机共轭结构。本发明依据典型的stille偶联方法,首次合成ProDOT(Me)2‑EDOT‑ProDOT(Me)2结构单元,并通过核磁氢谱手段对其结构进行了证明。通过电化学聚合单体的方法,测试其聚合物膜的电化学稳定性,1000圈之后,膜的电活性保留了96.17%;3000圈后,膜的电活性保留了90,55%;5000圈后,膜的电活性保留了85.73%。从而证明具有良好的电化学稳定性。聚合物薄膜同时是第一种基于一种结构单元能实现全彩变化的电制变色材料。并能实现由紫色、红色、黄色、绿色、青绿色、到蓝色的循环可逆变化。
Description
技术领域
本发明属于导电高分子材料领域,特别涉及一种新型导电高分子聚合物的合成,及导电高分子电致变色材料领域。
背景技术
电制变色是指电活性材料的光学特性,包括材料的透射率,反射率以及颜色等在交变电场下发生的可逆变化。电制变色即材料可以通过化学或者电化学控制来实现在不同颜色状态之间的切换,通过注入或者抽取电荷发生氧化还原反应,根据物质所处状态的不同,在外观上显示不同的颜色以及透过率大小的可逆变化。在过去电制变色材料主要应用在光学展示,电子纸,反光镜,伪装材料等方面,现在在电制变色材料作为一种新型材料已经成功应用到波音787飞机,以及奔驰高级汽车等先进,前沿的领域上,展示出了巨大的经济价值,以及广阔的应用前景。
电制变色材料主要包括两种:无机电致变色材料和有机电致变色材料。无机电致变色材料的典型代表是过渡金属氧化物,普鲁士蓝,杂多酸等,其中,以WO3为功能材料的电致变色器件已经产业化;有机电致变色材料主要有导电聚合物,紫罗精,金属酞菁类化合物等。相对于无机电制变色材料,有机变色材料在颜色选择,对比度和响应速度等方面,有机电制变色材料很容易通过分子结构设计获得具有丰富颜色,高对比度,快响应速度的电制变色材料,因而更加受到研究者的青睐。
导电聚合物又称共轭聚合物,聚合物的分子具有独特的由单双键间隔排列的共轭结构,其能带结构基于共轭结构有关,由于参杂程度有关。通过改变是加载导电聚合物两端的电压可以改变其参杂程度,即改变了其能带结构,从而改变其光学性能。常见的共轭聚合物只要有聚苯胺、聚噻吩、聚吡咯、聚吲哚、聚呋喃聚咔唑等物质。其中聚3,4-乙烯基二氧噻吩是一种已经商业化的电制变色材料。
1994年,聚(3,4-乙烯二氧噻吩)(PEDOT)是最稳定的导电聚合物之一,第一次作为电制变色材料被报道。这种聚合物与传统的聚噻吩材料相比具有更快的响应时间,更低的出事氧化电位,更优异的环境稳定性除此之外,这种物质在电压作用下可以由深蓝黑色向浅蓝色变化,并且这种变化是可逆的。同时,根据这种材料构建的电制变色器件在氧化还原状态之间具有很高的透过率(>80%),因此引起了人们的广泛关注,随后被广泛应用在可再充电电池,电致变色显示装置,有机发光二极管,超级电容器,抗静电涂料,腐蚀抑制剂,印刷电路智能窗,微波吸收材料,化学/生物传感器等领域。随后出现的PProDOT及其衍生物与PEDOT相比,因其具有中央对称的丙烯碳桥,其透过率进一步提高。作为电制变色材料,这些物质实现了高透过率,高稳定性,但这类材料大多是阳极着色材料,也就是说在氧化态时是深色,还原态是是浅色,这类物质在材料颜色变化多样性上仍有很大的进步空间。
发明内容
本发明目的是针对现有技术存在的上述问题,提供一种以EDOT和ProDOT新型化合物为单一分子结构单元的全色段电制变色聚合物,并提供上述聚合物的制备方法。本发明聚合物除保留PEDOT和PProEDOT以及他们衍生物在电致变色方面的高电化学稳定性,高重复稳定性和快响应时间的同时,还具有明显的全色段颜色变化以及良好的光学记忆性能。
为了实现上述目的,本发明采用以下技术方案:一种全色段电制变色聚合物,所述聚合物为聚2,5-二(2,2-二甲基-丙二烯)基-3,4-乙烯二氧噻吩,具有分子结构如式1所示的有机共轭结构:
进一步的,聚合物的分子量为103~105。
一种电致变色聚合物的制备方法,采用以下的制备路线:
进一步的,制备具体包括以下步骤:
(1)以2,2-二甲基-1,3-丙二醇和3,4-甲氧噻吩为原料在甲苯中合成2,2-ProDOT(Me)2;
(2)2,2-ProDOT(Me)2经低温反应在α位上发生锡化反应,得到中间体三丁基锡化合物;
(3)EDOT在氯仿中经过溴化反应在2位和5位取代溴,得到中间体2,5-二溴-3,4-乙烯二氧噻吩;
(4)将步骤(2)和步骤(3)所得的两种产物经过Stille偶联的方法得到聚合单体2,5-二(22-二甲基-丙二烯)基-3,4-乙烯二氧噻吩;
(5)单体通过电化学氧化方法聚合得到聚2,5-二(22-二甲基-丙二烯)基-3,4-乙烯二氧噻吩。
进一步的,步骤1的合成反应条件如下:保护氛围为氮气,催化剂为Ptsa,反应溶剂甲苯,反应温度80℃,反应时间为12h。
进一步的,步骤2的反应条件如下:保护氛围为氮气,在反应溶剂为无水THF,溶解温度为-78℃,催化剂为n-BuLi,反应温度为25~30℃,反应时间为12h。
进一步的,步骤3的反应条件如下:保护氛围为氮气,溴化剂为NBS,反应温度为25~30℃,反应时间为2h,产物通过分层、层析柱分离获得。
进一步的,步骤4的反应条件如下:保护氛围为氮气,催化剂为Pd(PPh3)4,溶剂为无水THF,25~30℃搅拌0.5h后加热回流24小时。
进一步的,步骤5的反应条件如下:保护氛围为氮气,电解液为ACN,电解质为六氟化磷四丁基铵,工作电极为ITO导电玻璃,对电极为铂片,参比电极为Ag/AgCl。
本发明有益的技术效果在于:
1、本发明依据典型的stille偶联方法,首次合成ProDOT(Me)2-EDOT-ProDOT(Me)2结构单元,并通过核磁氢谱手段对其结构进行了证明。通过电化学聚合单体的方法,测试其聚合物膜的电化学稳定性,1000圈之后,膜的电活性保留了96.17%;3000圈后,膜的电活性保留了90,55%;5000圈后,膜的电活性保留了85.73%。从而证明具有良好的电化学稳定性。
2、本发明聚合物为以ProDOT(Me)2-EDOT-ProDOT(Me)2结构单元聚合物薄膜,是第一种基于一种结构单元能实现全彩变化的电制变色材料。并能实现由紫色、红色、黄色、绿色、青绿色、到蓝色的循环可逆变化。
3、本发明聚合物的薄膜还具有良好的光谱稳定性,记忆性能。
附图说明
图1是实施例化合物2,2-ProDOT(Me)2的核磁氢谱图。
图2是实施例化合物2-三丁基甲锡烷基-EDOT的核磁氢谱图。
图3是实施例化合物2,5-二溴-EDOT的核磁氢谱图。
图4是实施例化合物ProDOT(Me)2-EDOT-ProDOT(Me)2的核磁氢谱图。
图5是实施例聚合物PProDOT(Me)2-EDOT-ProDOT(Me)2膜的电化学光谱稳定性动力学研究图。
图6是实施例聚合物PProDOT(Me)2-EDOT-ProDOT(Me)2膜的光谱电化学图。
图7是实施例聚合物PProDOT(Me)2-EDOT-ProDOT(Me)2膜的电化学光谱稳定性动力学研究图。
图8是实施例P(DBF-EDOT)的光学记忆效应研究图。
具体实施方式
下面结合附图和实施例,对本发明进行具体描述。
1、ProDOT(Me)2-EDOT-ProDOT(Me)2的合成及其聚合物的制备
具体合成路线如下:
(1)2,2-二甲基-3,4-丙烯二氧噻吩(2,2-ProDOT(Me)2)的制备:将3,4-二甲氧噻吩(4.5g,31.2mmol),21.6g(208mmol)2,2-甲基-1,3-丙二醇,0.4g(3.1mmol)对甲苯磺酸溶解在30mL甲苯中,溶液加热到80℃,均匀不断搅拌,反应12小时。随后过滤,并用去离子水洗涤,通过真空抽滤将甲苯除去,将处理好的液体旋蒸得到一种绿色粘稠状物质。用体积比为2:3的二氯甲烷/庚烷作为淋洗液,用硅胶柱提纯,得到2.1g白色产物,产率为46%;产物的核磁氢谱图见图1,数据为:1H NMR(400MHz,CDCl3):Δ1.02(s,6H),3.73(s,4H),6.47(s,2H)。
(2)2-三丁基甲锡烷基-2,2-二甲基-3,4-丙烯二氧噻吩(2-三丁基甲锡烷基-EDOT)的制备:氩气保护下,将溶解有2,2-ProDOT(Me)2(4.0g,21.7mmol)的溶解于100mL无水THF溶液冷却至-78℃,在30分钟内缓慢地将12.8mL的n-BuLi(2.5mol·L-1的己烷溶液)逐滴加入到上述溶液中;在-78℃下搅拌该混合物1.5小时,然后温度调至-40℃,三丁基氯化锡缓慢加入到该溶液中,将温度升温至25℃,并且将混合物在室温下搅拌12小时。反应结束后,将残余物过滤,然后将溶剂通过旋转蒸发减压除去,2-三丁基甲锡烷基-2,2-二甲基-3,4-丙烯二氧噻吩(9.92g,产率:89%)在下一步的Stille偶联反应中无需进一步纯化可直接使用;产物的核磁氢谱图见图2,数据为:1H NMR(400MHz,CDCl3):δ6.72(s,1H),3.70(s,2H),3.63(s,2H),1.01(s,6H),1.56(t,6H),1.32(t,6H),1.08(t,6H),0.89(t,9H)。
(3)2,5-二溴-3,4-乙烯二氧噻吩(2,5-二溴-EDOT)的制备:将EDOT(2.0g,14.07mmol)和N-溴代丁二酰亚胺(5.5g,30.9mmol)溶解在50mLDMF溶液中。25℃下搅拌2.5个小时,随后加入到200mL去离子水中。有机层用碳酸氢钠中和,分离过滤。随后转移到旋蒸仪中,纯化。粗产物用硅胶层析柱提纯(氯仿作为淋洗液),得到白色晶体(3.63g,产率:85%);产物的核磁氢谱图见图3,数据为:1H NMR(400MHz,CDCl3):δ4.27(s,4H)。
(4)2,5-二(2,2-二甲基-丙二烯)基-3,4-乙烯二氧噻吩(ProDOT(Me)2-EDOT-ProDOT(Me)2)的制备:在氩气氛围下,1.8g 2,5-二溴-3,4-乙烯二氧噻吩和6.1g 2-三丁基甲锡烷基-2,2-二甲基-3,4-丙烯二氧噻吩加入到干燥的THF溶液中,随后加入Pd(PPh3)4作为催化剂。随后将混合溶液在25℃下剧烈搅拌30分钟。然后,将混合溶液加热回流24小时。反应完毕后在真空下浓缩,随后通过硅胶层析柱分离,氯仿用作淋洗液,分离后得到一种黄绿色粉末(0.6g,产率:20%);产物的核磁氢谱图见图4,数据为:1H NMR(400MHz,CDCl3):δ6.43(s,2H),4.35(s,4H),3.84(s,4H),3.73(s,4H),1.08(s,12H)。
(5)聚2,5-二(2,2-二甲基-丙二烯)基-3,4-乙烯二氧噻吩(PProDOT(Me)2-EDOT-ProDOT(Me)2)的制备:以精制的ACN 10mL为电解液,浓度为0.02mol/L的2,5-二(2,2-二甲基-丙二烯)基-3,4-乙烯二氧噻吩为聚合单体,0.1mol/L的六氟化磷四丁基铵为电解质,搅拌均匀,持续通入氮气保护20分钟排空溶液里面的空气:氮气氛围下,以ITO导电玻璃为工作电极,铂片为对电极,Ag/AgCl为参比电极,在相应的的电压下恒电位聚合,得到沉积在ITO导电玻璃上的紫黑色聚合物。
性能测试:聚合物在乙腈中的电化学及电致变色性能
(1)电化学稳定性
导电聚合物的稳定对于有机电子器件的应用至关重要电活性聚合物的长期稳定性能是评估电制变色材料性能的一个重要参数。为了研究聚合物PProDOT(Me)2-EDOT-ProDOT(Me)2膜的稳定性,我们以100mV s-1扫速在无单体的ACN-Bu4NPF6(0.1mol/L)空白电解质溶液中用循环伏安方法研究了其在不同状态之间的长期循环稳定性,如图5所示。在0V到0.6V的范围内,1000圈之后,膜的电活性保留了96.17%;3000圈后,膜的电活性保留了90,55%;5000圈后,膜的电活性保留了85.73%。从而证明具聚合物PProDOT(Me)2-EDOT-ProDOT(Me)2膜具有良好的电化学稳定性。
(2)光谱电化学
将制备的沉积在ITO导电玻璃上的聚合物薄膜,放在三电极电解池中,电解池中有溶有六氟化磷四丁基胺的乙腈溶液;其中工作电极为附有聚合物薄膜的ITO导电玻璃,对电极为铂片,参比电极为Ag/AgCl电极。利用恒电位方法,通过电化学工作站调节施加在工作电极上的电压,同时用紫外可见光谱仪记录聚合物在不同电压下吸收光谱的变化趋势,即得到了聚合物的光谱电化学图谱。如图6所示。图中430nm到500nm间的峰是聚合物本身的特征峰,随着电压的升高,在800nm处出现新的峰,这主要是由于产生极化子和双极化子所造成的。同时,聚合物PProDOT(Me)2-EDOT-ProDOT(Me)2膜的颜色随施加电压的不同而实时变化。在施加电压由-1V到+1V变化的过程中,聚合物薄膜的颜色一次为紫色,红色,橙色,黄色,黄绿色,绿色,青色和蓝色。实现了全色彩的变化。
(3)聚合物膜的动力学研究
利用紫外可见分光光度计来测定方波电位下,聚合物膜在特定波长下,氧化态和还原态的透过率,从而计算出光学对比度,影响时间等。图7为聚合物PProDOT(Me)2-EDOT-ProDOT(Me)2膜的光谱透过率随时间的变化,对应电位分别为-0.6V,0.2V,方波电位间隔为10s。图7表示经过3000s后聚合物PProDOT(Me)2-EDOT-ProDOT(Me)2膜的透过率基本保持不变,响应时间为两状态之间完全切换所耗费时间的95%,计算后得到,响应时间分别为0.6s,0.8s。
(4)光学记忆效应研究
图8所示为膜在空白ACN-Bu4NPF6(0.1mol/L)体系中的记忆曲线。聚合物膜最初氧化或还原2s,然后断开电路,100s,同时记录透过率的变化。由图8可以看出,在长时间的交替变化中,聚合物膜保持有良好的记忆效应,尤其是在0.2V时,记忆效应经过4000s后仍能保持在99%。进一步说明聚合物PProDOT(Me)2-EDOT-ProDOT(Me)2膜具有良好的记忆效应。
虽然本发明已以较佳实施例公开如上,但实施例和附图并不是用来限定本发明,任何熟悉此技艺者,在不脱离本发明之精神和范围内,自当可作各种变化或润饰,但同样在本发明的保护范围之内。因此本发明的保护范围应当以本申请的权利要求保护范围所界定的为准。
Claims (8)
3.根据权利要求2所述的制备方法,其特征在于:所述制备具体包括以下步骤:
(1)以2,2-二甲基-1,3-丙二醇和3,4-甲氧噻吩为原料在甲苯中合成2,2-ProDOT(Me)2;
(2)2,2-ProDOT(Me)2经低温反应在α位上发生锡化反应,得到中间体三丁基锡化合物;
(3)EDOT在氯仿中经过溴化反应在2位和5位取代溴,得到中间体2,5-二溴-3,4-乙烯二氧噻吩;
(4)将步骤(2)和步骤(3)所得的两种产物经过Stille偶联的方法得到聚合单体2,5-二(3,4-(2,2-二甲基丙烯)二氧噻吩-2,5-二基)-3,4-乙烯二氧噻吩;
(5)单体通过电化学氧化方法聚合得到聚2,5-二(3,4-(2,2-二甲基丙烯)二氧噻吩-2,5-二基)-3,4-乙烯二氧噻吩。
4.根据权利要求3所述的制备方法,其特征在于:所述步骤1的合成反应条件如下:保护氛围为氮气,催化剂为Ptsa,反应溶剂甲苯,反应温度80℃,反应时间为12h。
5.根据权利要求3所述的制备方法,其特征在于:所述步骤2的反应条件如下:保护氛围为氮气,在反应溶剂为无水THF,溶解温度为-78℃,催化剂为n-BuLi,反应温度为25~30℃,反应时间为12h。
6.根据权利要求3所述的制备方法,其特征在于:所述步骤3的反应条件如下:保护氛围为氮气,溴化剂为NBS,反应温度为25~30℃,反应时间为2h,产物通过分层、层析柱分离获得。
7.根据权利要求3所述的制备方法,其特征在于:所述步骤4的反应条件如下:保护氛围为氮气,催化剂为Pd(PPh3)4,溶剂为无水THF,25~30℃搅拌0.5h后加热回流24小时。
8.根据权利要求3所述的制备方法,其特征在于:所述步骤5的反应条件如下:保护氛围为氮气,电解液为ACN,电解质为六氟化磷四丁基铵,工作电极为ITO导电玻璃,对电级为铂片,参比电极为Ag/AgCl。
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