CN111662438A - 一种基于噻唑的蓝光有机电致发光材料及其制备方法 - Google Patents

一种基于噻唑的蓝光有机电致发光材料及其制备方法 Download PDF

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CN111662438A
CN111662438A CN202010544282.7A CN202010544282A CN111662438A CN 111662438 A CN111662438 A CN 111662438A CN 202010544282 A CN202010544282 A CN 202010544282A CN 111662438 A CN111662438 A CN 111662438A
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胡金超
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Abstract

本发明属光电显示器件技术领域，具体涉及一种基于噻唑的蓝光有机电致发光材料及其制备方法。本发明提供了一种基于噻唑的蓝光有机电致发光材料，其结构如式(I)所示。本发明还提供了一种基于噻唑的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‑恶二唑以及式(II)所示化合物通过Suzuki偶联反应制得式(I)所示聚合物。本发明解决了现有的基于噻唑的有机电致发光材料驱动电压偏高，电致发光效率较低的技术问题。

Description

一种基于噻唑的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，具体涉及一种基于噻唑的蓝光有机电致发光材料及其制备方法。
背景技术
新材料技术、信息技术及新能源开发是影响现代技术发展的三大主流因素，新材料技术是最根本的。据悉，在21世纪，随着信息高速发展，我们的生活环境每天都在发生巨大变化，光电功能材料从最接近生活的标显示到高级激光加工，其出现和发展也成为信息持续进步的基础。因此，世界许多国家的科学家都喜欢光电功能材料。
有机光电材料(Organic optoelectronic materials)是具有光电活性的有机材料，包括有机发光二极管(Organic electrooluminescence display，OLED)、场效应晶体管有机物质通过分子设计，可以获得多种结构组成和卓越的性能，通过自我组装等装置的组装，可以制造纳米大小的装置。其中，噻唑广泛用作有机物，并在有机电致发光领域广泛使用，但目前以噻唑为基础的有机电致发光材料普遍存在驱动电压高、亮度高、效率衰减过快等严重问题，其根本原因主要是界面载体(尤其是电子)注入效率低、发光层载体传输不平衡、激子猝灭严重。
因此，现有的基于噻唑的有机电致发光材料驱动电压偏高，电致发光效率较低成为了本领域技术人员亟待解决的技术问题。
发明内容
本发明提供了一种基于噻唑的蓝光有机电致发光材料及其制备方法，解决了现有的基于噻唑的有机电致发光材料驱动电压偏高，电致发光效率较低的技术问题。
本发明提供了一种基于噻唑的蓝光有机电致发光材料，其结构如式(I)所示：
Figure BDA0002539998620000021
其中，x＝0-1，n＝200-1000。
优选的，x的取值范围为0.1-0.9。
本发明还提供了一种基于噻唑的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-恶二唑以及式(II)所示化合物通过Suzuki偶联反应制得式(I)所示聚合物，
Figure BDA0002539998620000031
优选的，所述Suzuki偶联反应的温度80℃。
优选的，所述Suzuki偶联反应的时间为24h。
优选的，所述式(II)所示化合物由以下步骤制得：
步骤1：将2-氨基苯甲醛和50mL丙酮在冰浴下搅拌30min后，向体系中滴加6％氢氧化钠溶液(120mL)，待滴加完毕，撤去冰浴，常温搅拌12h得到式(III)所示化合物
Figure BDA0002539998620000032
步骤2：将4,7-二溴-2，1，3-苯并噻二唑和式(III)所示化合物通过取代反应制得式(IV)所示化合物
Figure BDA0002539998620000033
步骤3：将式(IV)所示化合物通过溴化反应制得式(II)所示化合物。
本发明的有益效果如下：
本发明制得的聚合物随着噻唑单元含量的增加，相应的HOMO能级呈增高趋势；表明噻唑单元中甲基和氮原子起到了给电子的作用，对HOMO能级影响较大，有利于聚合物的空穴注入。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2.15cd/A，最大亮度也达到了9874cd/m2，其色坐标均位于(0.17,0.08)附近，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10-14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10-14制备的蓝光聚合物的能级示意图。
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
将2-氨基苯甲醛(4.8g，40mmol)和50mL丙酮加入250mL圆底烧瓶内，冰浴下搅拌30min后，向体系中滴加6％氢氧化钠溶液(120mL)，待滴加完毕，撤去冰浴，常温搅拌12h；后将体系转移至1000mL烧杯内，加入适量冰水，8％稀盐酸溶液调节体系pH至5.5，析出大量黄色固体，抽滤，用乙醇/水＝2:1重结晶，得式(III)所示化合物(5.15，产率80％)，其化学反应方程式为：
Figure BDA0002539998620000041
实施例2
向500mL烧瓶中加入4,7-二溴-2，1，3-苯并噻二唑(2.95g，10mmol)，碳酸钾(4g，30mmol)和80mL乙腈。在氩气下搅拌溶解后加入式(III)所示化合物(4.8g.30mmol)，于85℃下搅拌回流，TLC检测反应进程；反应结束后，滤掉碳酸钾，减压除去溶剂，将获得的粗产物以石油/乙酸乙酯＝10/1为洗脱剂进行硅胶色谱纯化。然后将产物在乙醇中重结晶，得到式(IV)所示化合物(6.54g，产率72％。)，其化学反应方程式为：
Figure BDA0002539998620000051
实施例3
向250ml的单口反应瓶内加入式(IV)所示化合物(4.54g，10mmol)，再加入三氯甲烷溶剂直至原料完全溶解(100ml)，将NBS粉末(7.12g，40mmol)溶解在30ml的三氯甲烷溶液中，逐滴滴加到反应瓶内，避光反应24小时。用DCM萃取三次，水洗一次，收集有机相，旋干DCM，再用THF重结晶纯化，得到式(II)所示化合物(11.3g，产率为92％)，其化学反应方程式为：
Figure BDA0002539998620000061
实施例4
将2,7-二溴咔唑(6.5g,20mmol)溶于50ml N,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 BDA0002539998620000062
实施例5
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 BDA0002539998620000071
实施例6
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 BDA0002539998620000081
实施例7
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 BDA0002539998620000082
实施例8
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 BDA0002539998620000091
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(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 BDA0002539998620000101
实施例10
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)以及式(II)所示化合物(0.06g，0.1mmol)用15毫升的精制甲苯搅拌溶解。再向反应瓶内一次性加入醋酸钯(Pd(OAc)2)(3.7mg，0.01mmol)和三环己基膦(Cy3P)(8.4mg，0.03mmol)的混合物。再用锡箔纸避光处理，将反应瓶用封口膜密封，缓慢升温。待温度稳定在80℃时，在用注射器一次性加入有机碱(Et4NOH，15wt/v％，5mL)。通气10分钟后，关闭气体，维持该温度反应24小时。然后将10mg苯硼酸溶解在5ml精制甲苯并加入到反应体系中，继续反应10小时。最后用注射器一次性注入0.5ml溴苯封端，再反应8小时。待反应体系降至室温后，将反应液缓慢滴加到400ml甲醇溶液中沉析，过滤。将粗品依次用甲醇，丙酮，正己烷用索氏提取器抽提至溶液呈无色。以200-300目的硅胶为固定相，石油醚：二氯甲烷＝3:1为淋洗剂进行硅胶柱层析，旋掉大部分溶液以浓缩，最后在150ml甲醇溶液中沉析，过滤，真空干燥，即可得到聚合物P1(5.6g，产率70％)，其反应方程式为：
Figure BDA0002539998620000111
实施例11
本实施例与实施例10的区别为：式(II)所示化合物的含量为(0.18g，0.3mmol)，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)最终制得聚合物P2(6.7g，产率72％)。
Figure BDA0002539998620000112
实施例12
本实施例与实施例10的区别：式(II)所示化合物的含量为(0.3g，0.5mmol)，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)，最终制得聚合物P3(9.6g，产率75％)
Figure BDA0002539998620000121
实施例13
本实施例与实施例10的区别为：式(II)所示化合物的含量为(0.42g，0.7mmol)，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)，最终制得聚合物P4(10.2g，产率73％)
Figure BDA0002539998620000122
实施例14
本实施例与实施例10的区别为：式(II)所示化合物的含量为(0.54g，0.9mmol)，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(0.08g，0.1mmol)，最终制得聚合物P5(13.3g，产率71％)
综上，图1为本发明实施例10-14制备的蓝光聚合物在薄膜状态下的PL光谱，由图1可知，其荧光发射峰均在450nm左右，为蓝光发射，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，具有大位阻的结构挤压使得共轭长度变短，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10-14制备的蓝光聚合物的能级示意图：EHOMO＝-e(Eox+4.2)(eV)和ELUMO＝-e(Ered+4.2)(eV)。由图2可知，随着噻唑单元含量的增加，聚合物P1-P5的氧化电位是呈减小趋势，从1.38V减小到1.04V。其中，本发明实施例制备的P1-P5具体的电致发光性能和电化学数据如表1所示：
表1聚合物P1-P5器件电致发光性能和电化学数据
Figure BDA0002539998620000131
表1可知，本发明制得的聚合物P1-P5随着噻唑单元含量的增加，相应的HOMO能级呈增高趋势；表明噻唑单元中甲基和氮原子起到了给电子的作用，对HOMO能级影响较大，有利于聚合物的空穴注入。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2.15cd/A，最大亮度也达到了9874cd/m2。从色坐标上看，当噻唑含量较高时，其色坐标为(0.17,0.08)发出标准蓝光，而其他不同比例的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)

1.一种基于噻唑的蓝光有机电致发光材料，其特征在于，其结构如式(I)所示：
Figure FDA0002539998610000011
其中，x＝0-1，n＝200-1000。
2.根据权利要求1所述的基于噻唑的蓝光有机电致发光材料，其特征在于，x的取值范围为0.1-0.9。
3.一种基于噻唑的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-恶二唑以及式(II)所示化合物通过Suzuki偶联反应制得式(I)所示聚合物，
Figure FDA0002539998610000012
4.根据权利要求3所述的噻唑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80℃。
5.根据权利要求3所述的噻唑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24h。
6.根据权利要求3所述的噻唑的蓝光有机电致发光材料的制备方法，其特征在于，所述式(II)所示化合物由以下步骤制得：
步骤1：将2-氨基苯甲醛和50mL丙酮在冰浴下搅拌30min后，向体系中滴加6％氢氧化钠溶液(120mL)，待滴加完毕，撤去冰浴，常温搅拌12h得到式(III)所示化合物
Figure FDA0002539998610000021
步骤2：将4,7-二溴-2，1，3-苯并噻二唑和式(III)所示化合物通过取代反应制得式(IV)所示化合物
Figure FDA0002539998610000022
步骤3：将式(IV)所示化合物通过溴化反应制得式(II)所示化合物。
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