CN113072688B - 一类新型紫精聚合物及其制备方法与应用 - Google Patents

一类新型紫精聚合物及其制备方法与应用 Download PDF

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CN113072688B
CN113072688B CN202110406882.1A CN202110406882A CN113072688B CN 113072688 B CN113072688 B CN 113072688B CN 202110406882 A CN202110406882 A CN 202110406882A CN 113072688 B CN113072688 B CN 113072688B
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刘淑娟
车雪婷
赵强
庄艳玲
黄维
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Nanjing University of Posts and Telecommunications
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Abstract

本发明公开了一类新型紫精聚合物及其制备和应用，所述新型紫精聚合物由紫精受体单元与咔唑衍生物或芴衍生物给体单元结合形成，是一种同时包含供体‑受体的聚合物且在聚合物化学结构中的每个聚合重复单元中既存在电子供体部分，又存在受体部分，在外加电场作用下聚合物可以在两种导电状态之间切换，可应用于电阻开关存储器；同时所述新型紫精聚合物本身具有良好的氧化还原性，在得失电子的过程中伴随着颜色变化，可应用于电致变色器件。

Description

一类新型紫精聚合物及其制备方法与应用
技术领域
本发明属于有机光电功能材料领域，更具体地说，涉及一类新型紫精聚合物及其制备方法与应用。
背景技术
传统半导体存储器的信息存储主要通过半导体的充电和放电实现，而有机存储器的信息存储则利用有机活性层在外电场刺激下通过低导态与高导态之间的电学转变实现的。有机存储材料具有多样化的分子结构，通过分子结构的设计，可以实现对有机存储器存储性能的调控。以咔唑为骨架结构的电致变色聚合物作为广泛的电致变色聚合物中的一类，表现出良好的电致变色性能。在电阻型存储器中，材料固有的特性在电场作用下会发生变化，如构象转变、电荷转移、氧化还原、相位变化等，从而产生高阻态和低阻态，实现存储性。有机存储材料在电阻式存储领域得到了科学家的广泛关注，被认为是很有潜力的一种新型存储材料。导电聚合物因其独特的光电性能而成为非常具有发展前景的材料。其中咔唑类导电聚合物以其容易形成稳定的极子，拥有高电荷迁移率，电致变色特性和光化学稳定性等各种有利的特性不断吸引着人们的研究热情。
专利CN110105336A-紫精衍生物电致变色材料及其制备方法，提供了一种可以得到双极性电致变色器件，采用的是一种具有较高对比度的电致变色的紫精衍生物，该紫精衍生物同时引入了吡咯和咔
Figure BDA0003022639110000011
改善了紫精化合物核心基团上的缺电子状态。此方案中制备的紫精衍生物应用于电致变色器件具有一定的优越性，但作为有机存储材料其电荷转移能力和稳定性均仍有待提高。
发明内容
针对上述存在的问题，本发明旨在提供一类新型紫精聚合物的制备与应用。
为了实现上述目的，本发明采用以下技术方案：本发明的一类新型紫精聚合物是将芴衍生物给体单元或咔唑衍生物给体单元引入紫精受体上，利用一个重复单元中既存在电子供体部分，又存在受体部分，在外加电场作用下聚合物可以在两种导电状态之间切换，该性能在电阻开关存储器应用中得到了广泛研究。与此同时，重复单元中的紫精受体部分在外加电场的刺激下，其光学属性，包括透射率、吸收率和反射率也会发生可逆变化，进而可制成颜色变化明显的电致变色功能器件。
本发明公开的一类新型紫精聚合物包括Vio-W，Vio-K两种，结构式分别为：
Figure BDA0003022639110000021
其中，X-为下列中的任意一个：X-＝Cl-,Br-,I-,PF6 -,BF4 -,TFSI-；
其中，R1和R2为具有正整数个碳原子的支链、直链、环状烷基链或环状烷醚链；
其中，n1为2～6正整数个碳原子的烷基直链；n为大于1的整数。
所述的新型紫精聚合物的合成路线如下：
Figure BDA0003022639110000031
所述的新型紫精电致变色聚合物具体合成步骤为：
(1)化合物2的制备：4,4'-联吡啶和碘甲烷在乙腈或二氯甲烷中回流反应12h以内，反应结束后，将溶液旋干，层析柱提纯，旋干得到化合物2；
(2)化合物4的制备：将化合物3即3,5-二溴苯酚和二溴乙烷溶解在丙酮中，再向溶液中加入适量的相转移催化剂四丁基溴化铵和氢氧化钾，回流反应16～36h；冷却到室温，旋蒸除去大量溶剂，之后用二氯甲烷与水萃取，取有机相旋干，层析柱提纯得到化合物4；
(3)化合物6的制备：先将化合物4溶于无水乙腈中，再向溶液中加入化合物2，并在氮气气氛下回流反应60～84h；反应结束后将溶液冷却至室温，旋蒸除去溶剂，加入少量的甲醇将固体完全溶解，再加入大量的乙醚沉降得化合物5；将化合物5分别和溴化钾、碘化钾、六氟磷酸铵、四氟硼酸钠、双三氟甲基磺酰亚胺锂在有机溶剂或去离子水中室温搅拌12～24h；反应结束后，用有机溶剂和水萃取，无水硫酸钠干燥，旋蒸除去有机溶剂，或者过滤，并用去离子水洗涤三次，真空干燥得化合物6；
(4)化合物Vio-W的制备：首先配置2M的碳酸钠水溶液，然后将化合物6与化合物7溶解在无水甲苯与碳酸钠水溶液的混合溶液中，并加入相转移催化剂四丁基溴化铵和催化剂四三苯基膦钯，在氮气气氛中避光反应24～36h；反应结束后，冷却至室温，用有机溶剂和水萃取，无水硫酸钠干燥，旋蒸除去有机溶剂；用少量四氢呋喃将固体完全溶解，用甲醇透析提纯3～4天，得到澄清溶液旋干，真空干燥得到化合物Vio-W。
(5)化合物Vio-K的制备：首先配置2M的碳酸钠水溶液，然后将化合物6与化合物8溶解在无水甲苯与碳酸钠水溶液的混合溶液中，并加入相转移催化剂四丁基溴化铵和催化剂四三苯基膦钯，在氮气气氛中避光反应24～36h；反应结束后，冷却至室温，用有机溶剂和水萃取，无水硫酸钠干燥，旋蒸除去有机溶剂；用少量四氢呋喃将固体完全溶解，用甲醇透析提纯3～4天，得到澄清溶液旋干，真空干燥得到化合物Vio-K。
本发明所述的一类新型紫精聚合物可用作电致变色功能材料，重复单元中的紫精受体部分在外加电场的刺激下，其光学属性包括透射率、吸收率和反射率也会发生可逆变化，通过掺杂不同电解质制成颜色变化明显的电致变色功能器件。
本发明所述的一类新型紫精聚合物在信息储存中的应用，作为电阻式开关存储器中的电存储材料；或应用于信息的记录-擦除，加密-解密与防伪；或通过掺杂电解质制成电池、电存储器和超级电容器。
本发明所述的一类新型紫精聚合物可用作忆阻材料，通过器件结构优化制成忆阻器和神经突触电子仿生器件。
本发明的有益效果是：
本发明提供的紫精聚合物是一种新的紫精材料，合成方法简单，且本发明制备的聚合物还具有良好的成膜性，可直接滴涂成膜，不需要特定的设备配置如旋涂机等繁琐的旋涂操作，用于制备电致变色材料或存储器的成本和效率均有所提高；
本发明提供的紫精聚合物在电刺激下可实现紫色-黄色的颜色变化；得到的电致变色聚合物分子量大，应用于电致变色器件，性能更加稳定。
本发明提供的紫精聚合物是将芴衍生物给体单元或咔唑衍生物给体单元引入紫精受体上，利用一个重复单元中既存在电子供体部分，又存在受体部分，在外加电场作用下聚合物可以在两种导电状态之间进行切换；相对于现有技术中已公开的小分子紫精化合物而言，具有强大的供体-受体电荷转移能力，每个重复单元都存在电子转移能力，用于电阻开关存储器，在读取记忆方面具有显著的优势；从而优化现有的电阻开关存储器的性能。
附图说明
图1为实施例3中Vio-W和Vio-K的紫外-可见吸收光谱；
图2为实施例3中Vio-W和Vio-K的发射光谱；
图3为实施例4中Vio-W的循环伏安图；
图4为实施例4中Vio-K的循环伏安图；
图5为实施例5中用Vio-W制成的器件在不同电压下的紫外-可见吸收光谱图。
具体实施方式
下面对本发明的实施例作详细说明，本实施例在以本发明技术方案为前提下进行实施，给出了详细的实施方式和具体的操作过程，但本发明的保护范围不限于下述的实例。
实施例1：Vio-W和Vio-K的制备
Figure BDA0003022639110000061
Figure BDA0003022639110000071
(1)化合物2的制备:4,4'-联吡啶(1252mg,8mmol)和碘甲烷(0.5mL,8mmol)在乙腈或二氯甲烷溶剂中50℃回流反应6h，反应结束后，冷却至室温，将溶液旋干，过层析柱提纯(二氯甲烷比甲醇等于4比1)，将溶液旋干，真空干燥得到化合物2。1H NMR(400MHz,D2O)δ(ppm):9.15(d,J＝6.8Hz,2H),8.87(d,J＝6Hz,2H),8.62(d,J＝6.8Hz,2H),8.04(d,J＝6.4Hz,2H),4.40(s,3H)。
(2)化合物4的制备：将化合物3即3,5-二溴苯酚(1000mg,4mmol)和二溴乙烷(6.5mL,57mmol)溶解在丙酮中，再向溶液中加入适量的相转移催化加四丁基溴化铵和氢氧化钾(1100mg,19mmol)，90℃回流反应24h；冷却到室温，旋蒸除去大量溶剂，之后用二氯甲烷与水萃取，取有机相旋干，层析柱(纯石油醚)提纯得到化合物4。1H NMR(400MHz,DMSO)δ(ppm):7.39(s,1H),7.23(d,J＝1.6Hz,2H),4.38(m,2H),3.78(m,2H)。
(3)化合物6的制备：先将化合物4(1000mg,2.8mmol)溶于无水乙腈溶剂中，再向溶液中加入和化合物2(1194mg,7mmol)，并在氮气气氛下85℃回流反应72h；反应结束后将溶液冷却至室温，旋蒸除去溶剂，加入少量的甲醇将固体完全溶解，再加入大量的乙醚沉降得化合物5，将化合物5分别和溴化钾、碘化钾、六氟磷酸铵、四氟硼酸钠、双三氟甲基磺酰亚胺锂在有机溶剂或去离子水中室温搅拌12h；反应结束后，用有机溶剂和水萃取，无水硫酸钠干燥，旋蒸除去有机溶剂，或者过滤，并用去离子水洗涤三次，真空干燥得化合物6。1H NMR(400MHz,DMSO)δ(ppm):9.38(d,J＝7.2Hz,2H),9.27(d,J＝6.8Hz,2H),8.76(m,4H),7.44(s,1H),7.25(m,2H),5.12(m,2H),4.64(m,2H),1.24(s,3H)。
(4)化合物Vio-W的制备：首先配置2M的碳酸钠水溶液，然后将化合物6(50mg,0.068mmol)与化合物7(43.4mg,0.068mmol)溶解在无水甲苯比碳酸钠水溶液等于2比1的混合溶液中，并加入相转移催化剂四丁基溴化铵和催化剂四三苯基膦钯(4mg)，在氮气气氛中90℃避光反应24h；反应结束后，冷却至室温，用有机溶剂和水萃取，无水硫酸钠干燥，旋蒸除去有机溶剂；用少量四氢呋喃将固体完全溶解，用甲醇透析提纯3～4天，得到澄清溶液旋干，真空干燥得到化合物Vio-W。GPC(Mn:171492,Mw:179521,Mz:187741,Mw/Mn:1.04682,Mz/Mw:1.04579.)。
(5)化合物Vio-K的制备：首先配置2M的碳酸钠水溶液，然后将化合物6(50mg,0.068mmol)与化合物8(44.4mg,0.068mmol)溶解在无水甲苯比碳酸钠水溶液等于2比1的混合溶液中，并加入相转移催化剂四丁基溴化铵和催化剂四三苯基膦钯(4mg)，在氮气气氛中90℃避光反应24h；反应结束后，冷却至室温，用有机溶剂和水萃取，无水硫酸钠干燥，旋蒸除去有机溶剂；用少量四氢呋喃将固体完全溶解，用甲醇透析提纯3～4天，得到澄清溶液旋干，真空干燥得到化合物Vio-K。GPC(Mn:183379,Mw:187992,Mz:192758,Mw/Mn:1.02515,Mz/Mw:1.02535.)。
实施例2：电致变色器件的制备
(1)将Vio-K或Vio-W溶于低沸点的有机溶剂中，之后将其滴涂到ITO玻璃上，放置在烘箱中干燥处理6h；
(2)将质量比为10:1:15的聚甲基丙烯酸甲酯(PMMA)、高氯酸锂(LiClO4)、碳酸亚丙酯(PC)溶于低沸点的有机溶剂中，并滴涂到另一片ITO玻璃上，使两片ITO玻璃粘合到一起。
实施例3：Vio-W和Vio-K的吸收和发射光谱测试
本发明采用的光谱测试浓度为10μM，测试溶剂为乙腈。测发射光谱时，Vio-W和Vio-K的激发波长均为365nm。
Vio-W和Vio-K的吸收和发射光谱如图1和图2所示。两种聚合物在300nm到350nm左右具有宽的吸收峰；Vio-W的发射峰在400nm左右和420nm左右，发蓝光，而Vio-K的发射峰在410nm左右，发蓝光。这是由两种分子内电荷转移能力的强弱不同所导致的。
实施例4：Vio-W和Vio-K的循环伏安测试
Vio-W和Vio-K的循环伏安测试采用三电极体系，Ag/AgNO3作为参比电极、铂丝电极作为对电极、钯碳电极作为工作电极。电解质为0.1M的四丁基六氟磷酸铵的乙腈溶液。扫描速度是100mV·s-1。
具体操作步骤：在小烧杯中加入1mg的Vio-W聚合物或Vio-K聚合物和3mL无水乙腈，三电极在无水乙腈中互不接触且不触碰到烧杯底部；除氧5min后，进行测试。
Vio-W的循环伏安图如图3所示。由图可知，加负压时，紫精受体单元上的两个氮原子分别得一个电子和两个电子的还原产生了两对可逆的氧化还原峰；芴衍生物给体单元与紫精受体单元之间通过电子转移产生一对可逆的氧化还原峰；加正压时，芴衍生物给体单元氧化产生一对可逆的氧化还原峰。说明聚合物Vio-K在外加电压下具有可逆性，经历两次电子得失，能更好的传递电子，实现电阻式存储的效果。
Vio-K的循环伏安图如图4所示。由图可知，一共产生了三对可逆的氧化还原峰。加负压时，紫精受体单元还原产生了一对可逆的氧化还原峰；咔唑衍生物给体单元与紫精受体单元之间通过电子转移产生一对可逆的氧化还原峰；加正压时，咔唑衍生物给体单元氧化产生一对可逆的氧化还原峰。
实施例5：Vio-K制成的器件在施加负电压情况下的吸收强度测试。
将紫外可见分光光度计与电化学工作站连用，其中电化学工作站的作用是对器件施加电压，紫外可见分光光度计的作用是测不同电压下器件吸收强度的变化。
图5为含有聚合物Vio-K的器件在不同电压下的吸射光谱。由图可知，聚、合物Vio-K在未施加电压时，在320nm左右和520nm左右具有两个吸收峰，随着电压的不断加大，520nm左右的吸收峰逐渐降低至消失，320nm左右的吸收强度略有降低；电压增大至-2.6V时，在400nm左右出现新的吸收峰。
Vio-K在电压驱动下，吸收光谱和透射光谱都会发生明显变化，可用作电致变色材料制备成电致变色器件。电子转移到不同的状态会发生可逆的颜色变化，有利于信息的存储加密。

Claims (3)

1.一类紫精聚合物的制备方法，其特征在于，所述紫精聚合物化学结构式如下所示：
Figure FDA0003806101160000011
其中，X-为Cl-,Br-,I-,PF6 -,BF4 -,TFSI-中的任意一个；其中，R1和R2为具有正整数个碳原子的支链、直链、环状烷基链或环状烷醚链中的任意一个，n为大于1的整数；
所述紫精聚合物的具体合成路线为：
Figure FDA0003806101160000012
2.权利要求1所述的一类紫精聚合物的制备方法，其特征在于，所述制备方法包括步骤：4,4'-联吡啶和碘甲烷反应得到化合物2；化合物3即3,5-二溴苯酚和二溴乙烷反应得到化合物4即1,3-二溴-5-(2-溴乙氧基)苯；然后化合物4与化合物2反应，得到化合物5，化合物5进行离子交换得到化合物6即吡啶季铵盐；最后所述化合物6与化合物7芴衍生物反应得到紫精聚合物Vio-W；化合物6与化合物8咔唑衍生物反应得到紫精聚合物Vio-K。
3.权利要求2所述的一类紫精聚合物的制备方法，其特征在于，所述吡啶季铵盐与芴衍生物或咔唑衍生物反应得到紫精聚合物的步骤包括：首先配制2M的碳酸钠水溶液，然后将吡啶季铵盐与芴衍生物或咔唑衍生物溶解在无水甲苯与碳酸钠水溶液的混合溶液中，并加入相转移催化剂四丁基溴化铵和催化剂四三苯基膦钯，在氮气气氛中避光反应24～36h；反应结束后，冷却至室温，用有机溶剂和水萃取，无水硫酸钠干燥，旋蒸除去有机溶剂；用少量四氢呋喃将固体完全溶解，用甲醇透析提纯3～4天，得到澄清溶液旋干，真空干燥得到化合物Vio-W或Vio-K。
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