CN111662439A - 一种蓝光有机电致发光材料及其制备方法 - Google Patents

一种蓝光有机电致发光材料及其制备方法 Download PDF

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CN111662439A
CN111662439A CN202010544885.7A CN202010544885A CN111662439A CN 111662439 A CN111662439 A CN 111662439A CN 202010544885 A CN202010544885 A CN 202010544885A CN 111662439 A CN111662439 A CN 111662439A
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朱成杰
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Abstract

本发明属光电显示器件技术领域，具体涉及一种蓝光有机电致发光材料及其制备方法。本发明提供了一种蓝光有机电致发光材料，其结构如式(I)所示：其中，R为氢原子、碳原子数1‑20的直链或者支链烷基，x的取值为0‑1，聚合度n的取值为100‑1000。本发明还提供了一种蓝光有机电致发光材料的制备方法，包括：将3,10‑二溴‑14‑(3‑(5‑苯基‑1,3,4‑恶二唑‑2‑基)苯基)‑14H‑‑双(二苯并噻吩)并吡咯、2‑(3‑(3,10‑双(4,4,5,5‑四甲基‑1,3,2‑二氧杂硼烷‑2‑基)‑14H‑双(二苯并噻吩)并吡咯‑5‑苯基‑1,3,4‑恶二唑以及二溴‑‑双(4‑辛基苯基)苯并噻二唑‑4,7‑二胺通过Suzuki偶联反应制得式(I)所示聚合物。本发明解决了现有的蓝光聚合物易产生分子聚集，使其发光纯度较差的技术问题。

Description

一种蓝光有机电致发光材料及其制备方法
技术领域
本发明属光电显示器件技术领域，具体涉及一种蓝光有机电致发光材料及其制备方法。
背景技术
21世纪是新闻、报纸、广播电视、视频和视频设备、互联网的普及、信息爆炸的时代，在显示器领域，有机发光二极管(OLED)是阴极射线显示器(Cathode Ray Tube，CRT)和液晶显示器(Liquid Crystal)OLED显示器具备主动照明、超轻、超薄、宽视角、高色彩饱和、对比度(清晰度)、快速响应速度、低能耗等优点，还可以卷曲、透明显示，引领未来的显示趋势。
在全色显示器中，红、绿、蓝三原色光的光谱纯度决定显示器的显示质量，因此从标准光源发射的聚合物材料是聚合物发光的研究重点。蓝绿色聚合物是红、蓝、三色发光聚合物发展最慢的一类，必须同时提高效率和稳定性。传统蓝光聚合物通常是聚芴，由于聚芴有强大的共轭作用，因此容易引起分子聚集，即使分子聚集增加聚合物的溶解度，聚合物的刚性也会减弱，热稳定性降低，分子聚集产生ICT效果，因此在蓝光聚合物的光谱中很容易出现红移。因此，传统蓝光聚合物易发生分子聚集，导致发光纯度下降，这一领域的技术人员需要解决的技术问题。
发明内容
本发明提供了一种蓝光有机电致发光材料及其制备方法，解决了现有的蓝光聚合物易产生分子聚集，使其发光纯度较差的技术问题。
本发明提供了一种蓝光有机电致发光材料，其结构如式(I)所示：
Figure BDA0002540343200000021
其中，R为氢原子、碳原子数1-20的直链或者支链烷基，x的取值为0-1，聚合度n的取值为100-1000。
优选的，x的取值为0.1-0.8。
本发明还提供了一种蓝光有机电致发光材料的制备方法，包括：将3,10-二溴-14-(3-(5-苯基-1,3,4-恶二唑-2-基)苯基)-14H--双(二苯并噻吩)并吡咯、2-(3-(3,10-双(4,4,5,5-四甲基-1,3,2-二氧杂硼烷-2-基)-14H-双(二苯并噻吩)并吡咯-5-苯基-1,3,4-恶二唑以及二溴--双(4-辛基苯基)苯并噻二唑-4,7-二胺通过Suzuki偶联反应制得式(I)所示聚合物。
优选的，所述Suzuki偶联反应的温度为85℃。
优选的，所述Suzuki偶联反应的时间为40h。
优选的，所述二溴--双(4-辛基苯基)苯并噻二唑-4,7-二胺的制备方法包括以下步骤：
步骤1：将4,7-二溴-2，1，3-苯并噻二唑通过取代反应生成4,7-双(N-(4-(正丁基)苯基)-氨基)-2,1,3-苯并噻二唑；
步骤2：将所述4,7-双(N-(4-(正丁基)苯基)-氨基)-2,1,3-苯并噻二唑通过取代反应生成二溴--双(4-辛基苯基)苯并噻二唑-4,7-二胺。
与现有技术相比，本发明具有如下优点和有益效果：
本发明制备的蓝光聚合物在450nm处有主发射峰，表明本发明实施例制得的蓝光聚合物实现了较好的蓝光发射，表明本发明制备的本发明制备的蓝光聚合物获得了最好的器件效果，最大流明效率为2.78cd/A，最大亮度也达到了3947cd/m2。从色坐标上看，当噻唑含量较高时，其色坐标为(0.16,0.09)发出深蓝光，而其他聚合物也都发出蓝光，表明本发明实施例制备得到了纯度较高的蓝光聚合物。
附图说明
图1为本发明实施例9-14制备的蓝光聚合物在薄膜状态下的PL光谱；
图2为本发明实施例9-14制备的蓝光聚合物的EL光谱。
具体实施方式
下面结合具体实施例对本发明做进一步详细说明，但实施例并不对本发明做任何形式的限定。除非特别说明，本发明采用的试剂、方法和设备为本技术领域常规试剂、方法和设备。
实施例1
向500mL烧瓶中加入4,7-二溴-2，1，3-苯并噻二唑(2.95g，10mmol)，4-辛基苯胺(6.16g，30mmol)和新鲜蒸馏的甲苯(100mL)。然后在氩气下分4批加入叔丁醇钠(3.01g，31mmol)。将混合物在室温下搅拌10分钟，随后添加双(2-二苯基膦基苯基)醚(0.8g，1.5mmol)和乙酸钯(II)(0.268g，1.2mmol)。将反应加热至90℃并搅拌24小时。反应完毕将混合物倒入500ml去离子水中，并用二氯甲烷(3×200mL)萃取，有机相用饱和盐水洗涤，并用无水硫酸镁干燥，将获得的粗产物以石油/乙酸乙酯＝50/1为洗脱剂进行硅胶色谱纯化。然后将产物在二氯甲烷/乙醇(1:5)中重结晶，得到产物4,7-双(N-(4-(正丁基)苯基)-氨基)-2,1,3-苯并噻二唑(3.96g，产率74％。)
Figure BDA0002540343200000041
实施例2
向250mL烧瓶中加入新鲜蒸馏的100ml四氢呋喃和4,7-双(N-(4-(正丁基)苯基)-氨基)-2,1,3-苯并噻二唑(0.81g，1.5mmol)。然后将温度降低至0℃，在10分钟内滴加NBS(0.53g，3mmol)的THF(20mL)溶液。将混合物在0℃下搅拌2小时，然后减压除去挥发物，残余物以石油/乙酸乙酯＝100/1为洗脱剂进行硅胶色谱纯化，得到二溴--双(4-辛基苯基)苯并噻二唑-4,7-二胺(0.84g，80％)，其反应方程式如下所示：
Figure BDA0002540343200000042
实施例3
将2,7-二溴咔唑(6.5g,20mmol)溶于50mlN,N-二甲基甲酰胺(DMF)中，加入氢氧化钾(2.7g,48mmol)，室温下搅拌30min，再加入2-(3-溴苯基)-5-苯基-1,3,4-恶二唑(12.94g,43mmol)，滴加完毕后，85℃下继续搅拌10h。反应完毕将反应液倒入水中，有浅黄色固体析出。固体通过减压抽滤，并多次用蒸馏水淋洗，减压抽干后得2-(3-(2,7-二溴9H-咔唑-9-基)苯基)-5-苯基-1,3,4-恶二唑(9.8g，产率90％)，该反应的化学方程式为：
Figure BDA0002540343200000051
实施例4
将2-(3-(2,7-二溴9H-咔唑-9-基)苯基)-5-苯基-1,3,4-恶二唑(10.9g,20mmol)溶于150mL绝干四氢呋喃，氩气气氛中室温搅拌溶解，之后将反应瓶放入-80℃低温反应器中，取正丁基锂(33ml,80mmol)缓慢滴加到反应瓶中，反应液低温下反应2h之后快速加入2-异丙基-4,4’,5,5’-四甲基-1，3,2-二氧杂硼烷(16.3mL,80mmol)，之后室温下过夜反应。停止反应将反应液倒入水中淬灭，将反应液浓缩并用二氯甲烷萃取，用柱层析法纯化处理，以200～300目硅胶为固定相，洗脱剂为石油醚/二氯甲烷(2:1)，得到2-(3-(2,7-双(4,4,5,5-四甲基-1,3,2-二氧杂硼烷-2-基)-9H-咔唑-9-基)苯基)-5-苯基-1,3,4-恶二唑(8.31g，产率65％)，其化学反应方程式为：
Figure BDA0002540343200000061
实施例5
将2-(3-(2,7-双(4,4,5,5-四甲基-1,3,2-二氧杂硼烷-2-基)-9H-咔唑-9-基)苯基)-5-苯基-1,3,4-恶二唑(19.18g,30mmol)，1-溴-2-甲亚磺酰苯(14.5g,66mmol)，四丁基溴化铵(0.84g,2.6mmol)和浓度为2M的碳酸钾(34.5g,250mmol)水溶液加入到500ml的三口圆底烧瓶中，并加入250ml甲苯充分溶解，氩气气氛中加热回流搅拌，温度稳定在85℃时加入四(三苯基膦)钯(1.5g,1.3mmol)，过夜反应。停止反应并且冷却到室温，用水洗反应液2～3次，将反应液浓缩过层析柱纯化，硅胶200～300目，洗脱剂为石油醚/乙酸乙酯(3:1)，得到产物2-(3-(2,7-双(2-(甲基亚磺酰基)苯基)-9H-咔唑-9-基)苯基)-5-苯基-1,3,4-恶二唑(15.9g，产率80％)。其化学反应方程式为：
Figure BDA0002540343200000062
实施例6
将2-(3-(2,7-双(2-(甲基亚磺酰基)苯基)-9H-咔唑-9-基)苯基)-5-苯基-1,3,4-恶二唑(6.63g,10mmol)加入到50mL的单口圆底烧瓶中，加入五氧化二磷(151.7mg,1mmol)和9mL的三氟甲烷磺酸并在冰浴条件下反应10h。停止反应，将反应液滴加到冰水中搅拌，混合液抽滤得到黄色粉末状固体并晾干。将滤渣加入到250mL三口圆底烧瓶中并加入100mL吡啶，氩气气氛中加热回流反应6h。停止反应并且冷却到室温，将反应液倒入冰水中，缓慢加入盐酸中和过量吡啶，用二氯甲烷萃取，之后浓缩有机相过层析柱纯化，硅胶200～300目，洗脱剂为石油醚/二氯甲烷(6:1)，过完柱用乙醇重结晶得到2-(3-(14H-双(二苯并噻吩)并吡咯-14-基)苯基)-5-苯基-1,3,4-恶二唑(3.47g，产率58％)。
Figure BDA0002540343200000071
实施例7
将2-(3-(14H-双(二苯并噻吩)并吡咯-14-基)苯基)-5-苯基-1,3,4-恶二唑(2.95g，5mmol)溶解在50mL四氢呋喃中，冰浴条件下搅拌直至反应物完全溶解，再将N-溴代丁二酰亚胺(17.8g,20mmol)用30mL四氢呋喃溶解，避光条件下缓慢滴加到反应液中，反应避光进行4h。将反应液倒入水中并用二氯甲烷萃取，用柱层析法进行纯化处理，以200-300目硅胶为固定相，石油醚/二氯甲烷(10:1)为洗脱剂，过完柱之后用乙醇重结晶得到3,10-二溴-14-(3-(5-苯基-1,3,4-恶二唑-2-基)苯基)-14H--双(二苯并噻吩)并吡咯(3.06g，产率81％)。
Figure BDA0002540343200000081
实施例8
将3,10-二溴-14-(3-(5-苯基-1,3,4-恶二唑-2-基)苯基)-14H--双(二苯并噻吩)并吡咯(11.36g,15mmol)溶于100mL绝干四氢呋喃，氩气气氛中室温搅拌溶解，之后将反应瓶放入-78℃低温反应器中，取正丁基锂(33mL,80mmol)缓慢滴加到反应瓶中，反应液低温下反应4h之后快速加入2-异丙基-4,4’,5,5’-四甲基-1，3,2-二氧杂硼烷(16.3mL,80mmol)，之后室温下过夜反应。停止反应将反应液倒入水中淬灭，将反应液浓缩并用二氯甲烷萃取，用柱层析法纯化处理，以300-400目硅胶为固定相，洗脱剂为石油醚/二氯甲烷(4:1)，得到2-(3-(3,10-双(4,4,5,5-四甲基-1,3,2-二氧杂硼烷-2-基)-14H-双(二苯并噻吩)并吡咯-5-苯基-1,3,4-恶二唑(8.9g，产率70％)，其化学反应方程式为：
Figure BDA0002540343200000082
实施例9
将3,10-二溴-14-(3-(5-苯基-1,3,4-恶二唑-2-基)苯基)-14H--双(二苯并噻吩)并吡咯(0.68g，0.9mmol)、2-(3-(3,10-双(4,4,5,5-四甲基-1,3,2-二氧杂硼烷-2-基)-14H-双(二苯并噻吩)并吡咯-5-苯基-1,3,4-恶二唑(0.85g，1mmol)以及二溴--双(4-辛基苯基)苯并噻二唑-4,7-二胺(0.07g，0.1mmol)加入到20ml精制甲苯和10mL四氢呋喃的混合溶液中，氩气气氛中加热搅拌，10min后加入10mg三环己基膦，温度稳定在85℃时加入1mL浓度为20％的四乙基羟氨水溶液，30min后停止通气，氩气气氛中反应40h。之后加入苯硼酸(50mg,0.4mmol)和0.3ml溴苯封端并反应12h。将反应停止并冷却到室温，沉析到300mL甲醇中，过滤干燥后索氏提取(先后用甲醇，丙酮和正己烷各抽提12h)。之后将聚合物干燥，用甲苯溶解，以200-300目硅胶为固定相，(石油醚:二氯甲烷＝4:1)为洗脱剂进行柱层析，将溶液浓缩后再次沉析到甲醇中，固体过滤后放入真空干燥箱干燥，得到聚合物P1(3.1g，产率85％),其反应方程式为：
Figure BDA0002540343200000091
实施例10
本实施例与实施例9的区别为：3,10-二溴-14-(3-(5-苯基-1,3,4-恶二唑-2-基)苯基)-14H--双(二苯并噻吩)并吡咯的含量为(0.6g，0.8mmol)，二溴--双(4-辛基苯基)苯并噻二唑-4,7-二胺的含量为(0.14g，0.2mmol)最终制得聚合物P2,其化学式为：
Figure BDA0002540343200000101
实施例11
本实施例与实施例9的区别：3,10-二溴-14-(3-(5-苯基-1,3,4-恶二唑-2-基)苯基)-14H--双(二苯并噻吩)并吡咯的含量为(0.53g，0.7mmol)，二溴--双(4-辛基苯基)苯并噻二唑-4,7-二胺的含量为(0.21g，0.3mmol)，最终制得聚合物P3，其化学式为：
Figure BDA0002540343200000102
实施例12
本实施例与实施例9的区别为：3,10-二溴-14-(3-(5-苯基-1,3,4-恶二唑-2-基)苯基)-14H--双(二苯并噻吩)并吡咯的含量为(0.38g，0.5mmol)，二溴--双(4-辛基苯基)苯并噻二唑-4,7-二胺的含量为(0.35g，0.5mmol)，最终制得聚合物P4，其化学式为：
Figure BDA0002540343200000111
实施例13
本实施例与实施例9的区别为：3,10-二溴-14-(3-(5-苯基-1,3,4-恶二唑-2-基)苯基)-14H--双(二苯并噻吩)并吡咯的含量为(0.23g，0.3mmol)，二溴--双(4-辛基苯基)苯并噻二唑-4,7-二胺的含量为(0.49g，0.7mmol)，最终制得聚合物P5，其化学式为：
Figure BDA0002540343200000112
实施例14
本实施例与实施例9的区别为：3,10-二溴-14-(3-(5-苯基-1,3,4-恶二唑-2-基)苯基)-14H--双(二苯并噻吩)并吡咯的含量为(0.15g，0.2mmol)，二溴--双(4-辛基苯基)苯并噻二唑-4,7-二胺的含量为(0.56g，0.8mmol)，最终制得聚合物P5，其化学式为：
Figure BDA0002540343200000121
综上，图1为本发明实施例9-14制备的蓝光聚合物在薄膜状态下的PL光谱，由图1可知，均表现出两个主要的荧光峰，分别在435nm和450nm处，其中出现在450nm左右的PL带主要归因于固态薄膜状态下的振动和激子结合效应。且通过在噻唑单元上引入共轭结构，使聚合物产生空间扭曲构型，减弱了分子间的ICT效应，抑制了光谱的红移。随着噻唑单元含量的增加，光谱出现明显蓝移，表明本发明实施例制得的蓝光聚合物实现了较好的蓝光发射。
图2为本发明实施例9-14制备的蓝光聚合物的EL光谱(器件结构为：ITO/PEDOT:PSS(40nm)/Polymer(80nm)/CsF(1nm)/Al(100nm)，电流密度为10mA/m2)，由图2可知，随着主链噻唑单元的增加，使有效共轭长度变短导致光谱的蓝移和窄化，且扰乱了噻吩并吲哚主链的共轭结构，扭曲的空间结构可以抑制分子聚集，使聚合物刚性增强，热稳定性更好。
其中，表1为本发明实施例9-14制备的蓝光聚合物的电致发光性能数据
表1聚合物P1-P6器件电致发光性能数据
Figure BDA0002540343200000122
Figure BDA0002540343200000131
由表1可知，本发明制备的蓝光材料获得了最好的器件效果，最大流明效率为2.78cd/A，最大亮度也达到了3947cd/m2。从色坐标上看，当噻唑含量较高时，其色坐标为(0.16,0.09)发出深蓝光，而其他聚合物也都发出蓝光，表明本发明实施例制备得到了纯度较高的蓝光聚合物。
上述实施例为本发明较佳的实施方式，但本发明的实施方式并不受上述实施例的限制，其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化，均应为等效的置换方式，都包含在本发明的保护范围之内。

Claims (6)

1.一种蓝光有机电致发光材料，其特征在于，其结构如式(I)所示：
Figure FDA0002540343190000011
其中，R为氢原子、碳原子数1-20的直链或者支链烷基，x的取值为0-1，聚合度n的取值为100-1000。
2.根据权利要求1所述的一种蓝光有机电致发光材料，其特征在于，x的取值为0.1-0.8。
3.一种蓝光有机电致发光材料的制备方法，其特征在于，包括：将3,10-二溴-14-(3-(5-苯基-1,3,4-恶二唑-2-基)苯基)-14H--双(二苯并噻吩)并吡咯、2-(3-(3,10-双(4,4,5,5-四甲基-1,3,2-二氧杂硼烷-2-基)-14H-双(二苯并噻吩)并吡咯-5-苯基-1,3,4-恶二唑以及二溴--双(4-辛基苯基)苯并噻二唑-4,7-二胺通过Suzuki偶联反应制得式(I)所示聚合物。
4.根据权利要求2所述的蓝光有机电致发光材料的制备方法，其特征在于，所述Suzuki偶联反应的温度为85℃。
5.根据权利要求2所述的蓝光有机电致发光材料的制备方法，其特征在于，所述Suzuki偶联反应的时间为40h。
6.根据权利要求2所述的蓝光有机电致发光材料的制备方法，其特征在于，所述二溴--双(4-辛基苯基)苯并噻二唑-4,7-二胺的制备方法包括以下步骤：
步骤1：将4,7-二溴-2，1，3-苯并噻二唑通过取代反应生成4,7-双(N-(4-(正丁基)苯基)-氨基)-2,1,3-苯并噻二唑；
步骤2：将所述4,7-双(N-(4-(正丁基)苯基)-氨基)-2,1,3-苯并噻二唑通过取代反应生成二溴--双(4-辛基苯基)苯并噻二唑-4,7-二胺。
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Application publication date: 20200915