CN111560113A - 一种基于噻唑的有机电致发光材料及其制备方法 - Google Patents

一种基于噻唑的有机电致发光材料及其制备方法 Download PDF

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CN111560113A
CN111560113A CN202010544340.6A CN202010544340A CN111560113A CN 111560113 A CN111560113 A CN 111560113A CN 202010544340 A CN202010544340 A CN 202010544340A CN 111560113 A CN111560113 A CN 111560113A
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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有机电致发光材料的制备方法，将式(II)所示化合物，3,10‑二溴‑14‑(3‑(5‑苯基‑1,3,4‑恶二唑‑2‑基)苯基)‑14H‑‑双(S,S‑二氧‑二苯并噻吩)并吡咯和2‑(3‑(3,10‑双(4,4,5,5‑四甲基‑1,3,2‑二氧杂硼烷‑2‑基)‑14H‑双(S,S‑二氧‑二苯并噻吩)并吡咯‑5‑苯基‑1,3,4‑恶二唑通过Suzuki偶联反应制得式(I)所示聚合物。本发明解决了现有的有机电致发光材料难以兼顾空穴和电子传输效率，且电致发光效率较差的技术问题。

Description

一种基于噻唑的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有机电致发光材料及其制备方法。
背景技术
21世纪被称作全新的“电子信息时代”，网络的发展使人们对信息的需求量越来越大，智能手机、手表、(平板)电脑已成为人们生活中必不可少的一部分。信息时代的到来大大推动了显示技术的发展，人们对更加轻薄及节能的大尺寸、柔性显示器的追求使有机电致发光成为市场主流。有机电致发光二极管具有低电压驱动、像素点自发光、快速响应、视角宽、厚度薄等优点，是可选用柔性基板加工的、覆盖整个可见光谱的固态全彩显示。加工工艺方面，可选用喷墨打印或旋涂工艺制造大面积面板，大大降低生产成本，成为显示技术研宄领域的一大热点。
其中，有机电致发光材料中的空穴传输材料和电子传输材料通常采用单极性小分子，尽管空穴/电子传输型小分子主体材料结构中含有供电子或吸电子基团，使得空穴和电子传输性较好，但器件中通常需要加入空穴或电子阻挡层，且驱动电压较高，电致发光效率较差。
因此，现有的有机电致发光材料难以兼顾空穴和电子传输效率，且电致发光效率较差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有机电致发光材料及其制备方法，解决了现有的有机电致发光材料难以兼顾空穴和电子传输效率，且电致发光效率较差的技术问题。
本发明提供了一种基于噻唑的有机电致发光材料，其结构如式(I)所示：
Figure BDA0002540011490000021
其中，n＝200-500。
本发明还提供了一种基于噻唑的有机电致发光材料的制备方法，将式(II)所示化合物，3,10-二溴-14-(3-(5-苯基-1,3,4-恶二唑-2-基)苯基)-14H--双(S,S-二氧-二苯并噻吩)并吡咯和2-(3-(3,10-双(4,4,5,5-四甲基-1,3,2-二氧杂硼烷-2-基)-14H-双(S,S-二氧-二苯并噻吩)并吡咯-5-苯基-1,3,4-恶二唑通过Suzuki偶联反应制得式(I)所示聚合物
Figure BDA0002540011490000022
优选的，所述Suzuki偶联反应的时间为24h-48h。
优选的，所述Suzuki偶联反应的温度为85℃。
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 BDA0002540011490000031
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 BDA0002540011490000032
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的HOMO能级在-5.67～-5.76eV范围内，LUMO能级在-2.12～-2.33eV范围内。当聚合度增加时，聚合物的氧化电位明显减小，HOMO能级增加；还原电位明显增加，LUMO能级减小，电学带隙变窄，有效的提高了聚合物的电致发光效率。本发明制得的聚合物的发射主峰在450nm左右，随着聚合度的增加，光谱会稍微的宽化。CIE(x+y)的值在0.3～0.4内。
此外，本发明制得的聚合物随着聚合度的增加，启亮电压有所降低，电流密度和亮度呈增加趋势，表明在发光层中有更多的载流子复合，是因为噻唑单元和SO单元的引入使得载流子的注入和传输相对平衡。
附图说明
图1为本发明实施例6-10制备的聚合物的电化学曲线；
图2为本发明实施例6-10制得的聚合物电致发光光谱(EL)图；
图3为本发明实施例6-10制得的聚合物的电流密度-亮度-电压曲线；
图4为本发明实施例6-10制得的聚合物的电流密度-电流效率曲线。
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
在氮气保护下，向50ml两口烧瓶中加入9，9-双(4-四唑基苯基)芴(1.5g，3.3mmol)和15mL吡啶，并在混合溶液中滴加4-叔丁基苯甲酰氯(2mL，10mmol)。将反应混合物在130℃下加热4小时。反应完毕后，将反应液倒入水和MeOH(150mL，1：3)的混合物中，干燥，过滤，通过旋转蒸发仪除去溶剂。粗产物经硅胶柱层层析，(淋洗剂为石油醚：乙酸乙酯＝4：1)，并在甲苯/CHCl3(5：1)中重结晶，制得5,5'-(((9H-芴-9,9-二基)双(4,1-亚苯基))双(2-(4-(叔丁基)苯基)-1,3,4-恶二唑)(2.3g，产率90.3％)，其反应方程式如下所示：
Figure BDA0002540011490000051
实施例2
在氮气气氛下，向100ml的长颈两口瓶中加入5,5'-(((9H-芴-9,9-二基)双(4,1-亚苯基))双(2-(4-(叔丁基)苯基)-1,3,4-恶二唑)(0.5g，0.70mmol)和CHCl3(50mL)，搅拌均匀后向混合溶液中加入三氟乙酸(0.5g，1.16mmol)和溴(0.24gg，1.50mmol)。将反应混合物在50℃下搅拌48h，随后用100mlNaHCO3水溶液进行洗涤，直到溴的红色消失。有机层经Na2SO4干燥，并真空除去溶剂。残余物通过CH2Cl2/乙酸乙酯(20∶1)的洗脱剂进行硅胶柱层层析，得到5,5'-(((2,7-二溴9H-芴-9,9-二基)双(4,1-亚苯基))双(2-(4-(叔丁基)苯基)-1,3,4-恶二唑)(0.4g，产率65.0％)，其反应方程式如下所示：
Figure BDA0002540011490000052
实施例3
将5,5'-(((2,7-二溴9H-芴-9,9-二基)双(4,1-亚苯基))双(2-(4-(叔丁基)苯基)-1,3,4-恶二唑)(11.36g，15mmol)，2-异丙基-4,4’,5,5’-四甲基-1，3,2-二氧杂硼烷(16.3mL,80mmol)放入250ml三颈烧瓶中，使其溶于80mL甲苯，氩气气氛中室温搅拌溶解，然后升温至80℃反应18h。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-(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(10.1g，产率70％)，其化学反应方程式为：
Figure BDA0002540011490000061
实施例3
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 BDA0002540011490000062
实施例4
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 BDA0002540011490000071
实施例5
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 BDA0002540011490000072
实施例6
向100ml两口瓶中加入式(II)所示化合物(0.52g，0.5mmol)，3,10-二溴-14-(3-(5-苯基-1,3,4-恶二唑-2-基)苯基)-14H--双(S,S-二氧-二苯并噻吩)并吡咯(0.41g，0.5mmol)和2-(3-(3,10-双(4,4,5,5-四甲基-1,3,2-二氧杂硼烷-2-基)-14H-双(S,S-二氧-二苯并噻吩)并吡咯-5-苯基-1,3,4-恶二唑(0.91g，1mmol)，在10ml精制甲苯中溶解，再加入10mgPd(PPh3)4。在氩气的保护下，85℃下反应24h，冷却后将反应液倒入200ml甲醇中，将收集到的沉淀在索氏提取器中分别用甲醇、丙酮、正己烷各抽提12小时，残余的固体用100ml氯仿溶解，过滤，以200-300目的硅胶为固定相，石油醚：二氯甲烷＝8:1为淋洗剂进行硅胶柱层析，过滤，真空干燥，得到聚合物P1(0.54g，产率80％)，其反应化学方程式为：
Figure BDA0002540011490000081
实施例7
本实施例与实施例6的区别为，实施例6的反应时间为24h，本实施例的反应时间为30h，最终制得聚合物P2(0.64g，产率79％)。
实施例8
本实施例与实施例6的区别为，实施例6的反应时间为24h，本实施例的反应时间为36h，最终制得聚合物P3(0.78g，产率75％)。
实施例9
本实施例与实施例6的区别为，实施例6的反应时间为24h，本实施例的反应时间为42h，最终制得聚合物P4(0.85g，产率74％)。
实施例10
本实施例与实施例6的区别为，实施例6的反应时间为24h，本实施例的反应时间为48h，最终制得聚合物P5(0.97g，产率75％)。
综上，图1为本发明实施例6-10制备的聚合物的电化学曲线，如图所示，聚合物P1-P5的氧化电势在1.28～1.37V范围内，还原电势在-2.07～-2.28V区域内，通过公式进行计算，聚合物的HOMO能级在-5.67～-5.76eV范围内，LUMO能级在-2.12～-2.33eV范围内。当聚合度增加时，聚合物的氧化电位明显减小，HOMO能级增加；还原电位明显增加，LUMO能级减小，电学带隙变窄，有效的提高了聚合物的电致发光效率。
图2为本发明实施例6-10制得的聚合物在7mAcm-2的电流密度条件下的电致发光光谱(EL)图。其发射主峰在450nm左右，随着聚合度的增加，光谱会稍微的宽化。聚合物的色坐标中x为0.16不变，y值在0.13-0.16之间变动，当聚合度较低时，聚合物为深蓝光发射；聚合度较高时，CIE(x+y)的值在0.3～0.4内，虽不为深蓝光，但仍是纯正蓝光。
图3和图4分别是本发明实施例6-10制得的聚合物的电流密度-亮度-电压曲线(J-L-V)和电流密度-电流效率(LE-J)曲线。当聚合度较低时，聚合物P1和P2的启亮电压为4V，当聚合度增加时，启亮电压降至4V以下。这是因为相比于P1和P2，聚合度较高的P3-P5的LUMO能级降低了约0.17eV，电子注入势垒降低使得注入变得简单，导致启亮电压聚合度的增加而减小。此外，在相同的外加电压作用下电流密度和亮度呈增加趋势，表明在发光层中有更多的载流子复合，是因为噻唑单元和SO单元的引入使得载流子的注入和传输相对平衡。
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 (5)

1.一种基于噻唑的有机电致发光材料，其特征在于，其结构如式(I)所示：
Figure FDA0002540011480000011
其中，n＝200-500。
2.一种基于噻唑的有机电致发光材料的制备方法，其特征在于，将式(II)所示化合物，3,10-二溴-14-(3-(5-苯基-1,3,4-恶二唑-2-基)苯基)-14H--双(S,S-二氧-二苯并噻吩)并吡咯和2-(3-(3,10-双(4,4,5,5-四甲基-1,3,2-二氧杂硼烷-2-基)-14H-双(S,S-二氧-二苯并噻吩)并吡咯-5-苯基-1,3,4-恶二唑通过Suzuki偶联反应制得式(I)所示聚合物
Figure FDA0002540011480000012
3.根据权利要求2所述的基于噻唑的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-48h。
4.根据权利要求2所述的基于噻唑的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所述的基于噻唑的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 FDA0002540011480000021
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 FDA0002540011480000022
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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