CN113307770A - 一种发光辅助材料及其制备方法和应用 - Google Patents

一种发光辅助材料及其制备方法和应用 Download PDF

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CN113307770A
CN113307770A CN202110557406.XA CN202110557406A CN113307770A CN 113307770 A CN113307770 A CN 113307770A CN 202110557406 A CN202110557406 A CN 202110557406A CN 113307770 A CN113307770 A CN 113307770A
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luminescent
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汪康
马晓宇
韩瑞锋
杨天宇
金成寿
王永光
贾宇
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Jilin Optical and Electronic Materials Co Ltd
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Jilin Optical and Electronic Materials Co Ltd
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Abstract

本发明提供了一种发光辅助材料及其制备方法和应用，发光辅助材料具有式Ⅰ结构，是一种含有三芳胺类官能基的有机电致发光辅助材料，能很大程度的提高空穴传输效率，以及电子阻挡能力，空穴和电子在发光层内的电荷均衡增加，从而不再空穴输送层表面，而是在发光层内部很好的形成发光，从而判断极大化效率和寿命。本申请引入苯并五元(杂)环、六元杂环等结构，降低分子的对称性，增加分子的构象异构体，并且具有刚性平面结构，则分子间不易结晶、不易聚集，制造有机EL元件的成品率提高。因此使用本发明的有机发光化合物在有机发光器件中能够改善发光效率、驱动电压和使用寿命等特点。

Description

一种发光辅助材料及其制备方法和应用
技术领域
本发明属于有机电致发光材料技术领域，尤其涉及一种发光辅助材料及其制备方法和应用。
背景技术
有机发光二极管(OLED:Organic Light Emitting Diode)作为一种新型和有前途的显示技术逐渐进入人们的视野。OLED是一种由多层有机薄膜结构形成的电致发光器件，其中的有机薄膜是利用蒸镀、沉积或旋涂工艺在基板上形成的有机发光材料的膜。
已经进行了许多改进以使有机EL器件得到实际应用。例如，众所周知，通过进一步分配层压结构的各种作用并形成阳极，可以实现高效率和高耐久性，在基板上设置空穴注入层，空穴传输层，空穴阻挡层，发光层，电子传输层，电子注入层和阴极。
利用该有机EL器件，从两个电极注入的电荷在发光层中重新组合以获得发光。在这种情况下，如何有效地将空穴和电子的电荷转移到发光层是重要的，并且该器件需要具有优异的载流子平衡。而且，通过增强阻挡从阴极注入的电子的空穴注入特性和电子阻挡特性以增加空穴和电子的复合概率，以及通过限制在发光层内产生的激子，发光效率得以提高。
有机电致发光材料的研究已经在学术界和工业界广泛开展，但目前为止还未充分开发出稳定又高效的有机电气元件用的有机物层材料，而且该技术的产业化进程仍面临许多关键问题，所以，开发新的材料，一直是本领域技术人员亟待解决的问题。
发明内容
有鉴于此，本发明的目的在于提供一种发光辅助材料及其制备方法和应用，该发光辅助材料制备的有机电致发光器件具有较高的发光效率。
本发明提供了一种发光辅助材料，具有式Ⅰ结构：
Figure BDA0003077683090000021
所述X选自连接键、-O-、-S-、SiR3R4、CR5R6或NR7；所述R3、R4、R5、R6和R7独立地选自氢、氘、卤素、氰基、羧基、硝基、羟基、磺酸基、磷酸基、硼烷基、取代或非取代的C1～C30烷基、取代或非取代的C3～C50环烷基、取代或非取代的3元～30元杂环烷基；取代或非取代的C2～C30烯基、取代或非取代的C2～C30炔基、取代或非取代的C6～C60芳基、取代或非取代的3元～60元杂芳基；或可与一个或多个相邻取代基连接以形成单环或多环(3元～30元)脂环族环或芳香族环，其(一个或多个)碳原子可被至少一个氮、氧和硫的杂原子置换；
所述L1、L2和L3选自单键；取代或未取代的C6～C60的亚芳基；取代或未取代的5元～30元的亚杂芳基；取代或未取代的C3～C30的环烷基；或取代或未取代的3元～30元的杂环烷基；
所述R1和R2选自氢、氘、卤素、氰基、羧基、硝基、羟基、磺酸基、磷酸基、硼烷基、取代或未取代的(C1～C30)烷基、取代或未取代的(C3～C50)环烷基、取代或未取代的3元～30元杂环烷基、取代或未取代的(C2～C30)烯基、取代或未取代的C2～C30炔基、取代或未取代的C6～C60芳基、取代或未取代的3元～60元杂芳基；或可与一个或多个相邻取代基连接以形成单环或多环(3元～30元)脂环族环或芳香族环，脂环族环或芳香族环的一个或多个碳原子可被至少一个氮、氧和硫的杂原子置换；
所述a和b的取值为0～4的整数；
所述Ar1和Ar2分别独立地表示为经取代或未经取代的C3～C30环烷基、取代或未经取代的3元～30元杂环烷基；取代或未经取代的C6～C30芳基、取代或未经取代的3元～20元杂芳基；取代或未取代的C10～C30稠环基。
在本发明中，所述L1、L2和L3选自单键；经取代或未经取代的C6～C25亚芳基；或取代或未取代的5元～25元亚杂芳基，其中杂原子选自N、O、S、Si、P和Se中的一种或多种。
在本发明中，所述R1和R2选自氢；氘；卤素；氰基；硝基；取代或未取代的C1～C10烷基；取代或未取代的C3～C15环烷基；取代或未取代的3元～15元杂环烷基，其中杂原子为N、O、S、Si、P和Se中的一种或多种；取代或未取代的C6～C25芳基、取代或非取代的3元～25元杂芳基，其中杂原子至少选自N、O、S、Si、P和Se中至少一种；或可与一个或多个相邻取代基连接以形成单环或多环(3元～20元)脂环族环或芳香族环，其一个或多个碳原子可被至少一个氮、氧和硫的杂原子置换。
在本发明中，所述Ar1和Ar2独立地选自取代或未取代的C3～C15环烷基；取代或未取代的3元～20元杂环烷基，其中杂原子选自N、O、S、Si、P和Se中至少一种；取代或未取代的C6～C20芳基；取代或未取代的3元～18元杂芳基，其中杂原子选自N、O、S、Si、P和Se中至少一种；或取代或未取代的C10～C25稠环基。
在本发明中，所述发光辅助材料优选选自化合物1～80中任一种：
Figure BDA0003077683090000031
Figure BDA0003077683090000041
Figure BDA0003077683090000051
Figure BDA0003077683090000061
Figure BDA0003077683090000071
在本发明具体实施例中，所述发光辅助材料优选选自化合物4、化合物7、化合物12、化合物19、化合物24、化合物29、化合物34、化合物39、化合物42、化合物49、化合物53、化合物56、化合物60、化合物65、化合物68、化合物72、化合物77或化合物79。
本发明提供了一种上述技术方案所述发光辅助材料的制备方法，包括以下步骤：
在氮气保护下，将中间体3和Ar2-B(OH)2溶于甲苯、乙醇和水的混合溶液中，加入四三苯基膦钯和碳酸钾，搅拌均匀，升温并回流，得到具有式Ⅰ结构的发光辅助材料；
Figure BDA0003077683090000081
中间体3；其中，-Hal4代表卤素。
在本发明中，所述中间体3按照以下方法制得：
在氮气保护下，将中间体1和Hal3-L2-NH-L3-Hal4溶于甲苯溶液中，加入钯催化剂、膦配体及叔丁醇钠，搅拌均匀，升温并回流，得到中间体2；
将所述中间体2和Ar1-B(OH)2溶于甲苯乙醇和水的混合溶液中，加入四三苯基膦钯和碳酸钾，搅拌均匀，升温并回流，得到中间体3；
Figure BDA0003077683090000082
Hal1～Hal4代表卤素，如F、Cl、Br或I。
在本发明中，所述中间体1由原料A和原料B制得，具体过程如下：
在氮气保护下，将原料A和原料B溶于甲苯溶液中，加入钯催化剂、膦配体及叔丁醇钠，搅拌均匀，升温并回流，得到中间体1；
Figure BDA0003077683090000091
在本发明中，所述原料A和原料B的制备过程优选包括以下步骤：
在氮气保护下，将原料A(1.0eq)和原料B(1.0eq)溶于甲苯溶液中，加入三(二亚苄基丙酮)二钯(0.01eq)，三叔丁基膦(0.05eq)及叔丁醇钠(2.0eq)，搅拌均匀，升温至90℃，并回流5小时，待溶液冷却至室温后，保留有机相，然后用乙酸乙酯萃取水相；合并有机相后，使用无水硫酸镁进行干燥，并且使用旋转式蒸发器去除溶剂，得到固体有机物。使用少量的二氯甲烷将固体有机物完全溶解，然后缓慢滴加到石油醚溶液中，搅拌均匀，有沉淀析出，抽滤得固体，依次用无水乙醇、石油醚淋洗，烘干，制备得到中间体1。
在本发明中，所述中间体2的制备过程优选包括以下步骤：
在氮气保护下，将中间体1(1.0eq)和原料C(1.0eq)溶于甲苯溶液中，加入三(二亚苄基丙酮)二钯(0.01eq)，三叔丁基膦(0.05eq)及叔丁醇钠(2.0eq)，搅拌均匀，升温至90℃，并回流5小时，待溶液冷却至室温后，保留有机相，然后用乙酸乙酯萃取水相；合并有机相后，使用无水硫酸镁进行干燥，并且使用旋转式蒸发器去除溶剂，得到固体有机物。然后将干燥得到的固体溶于甲醇溶液中，并升温搅拌5小时，随后趁热将溶液抽滤，得到固体，然后用石油醚淋洗，烘干，制备得到中间体2。
在本发明中，所述中间体3的制备过程优选包括以下步骤：
在氮气保护下，将中间体2(1.0eq)和原料D(1.0eq)溶于甲苯乙醇和水(Vol:Vol:Vol＝3:1:1)的混合溶液中，加入四三苯基膦钯(0.01eq)和碳酸钾(2.0eq)，搅拌均匀，升温至90℃，并回流5小时，反应结束后，稍降温度，使用硅藻土进行过滤，除去盐以及催化剂，滤液冷却至室温后，水洗三遍，保留有机相，接着用乙酸乙酯萃取水相；合并有机相后，使用无水硫酸镁进行干燥，并且使用旋转式蒸发器去除溶剂；使用少量的二氯甲烷将固体有机物完全溶解，然后缓慢滴加到石油醚溶液中，搅拌均匀，有沉淀析出，抽滤得固体，依次用无水乙醇、石油醚淋洗，烘干，制备得到中间体3。
在本发明中，中间体3和Ar2-B(OH)2制备式Ⅰ结构的发光辅助材料优选按照以下步骤进行：
在氮气保护下，将中间体3(1.0eq)和Ar2-B(OH)2(1.0eq)溶于甲苯乙醇和水(Vol:V:V＝3:1:1)的混合溶液中，加入三(二亚苄基丙酮)二钯(0.01eq)，三叔丁基膦(0.05eq)及叔丁醇钠(2.0eq)，搅拌均匀，升温至90℃，并回流反应5h；反应结束后，稍降温度，使用硅藻土进行过滤，除去盐以及催化剂，滤液冷却至室温后，水洗三遍，保留有机相，接着用乙酸乙酯萃取水相；合并有机相后，使用无水硫酸镁进行干燥，并且使用旋转式蒸发器去除溶剂；利用二氯甲烷和石油醚(V:V＝10:4)的混合溶液，通过柱色谱法纯化剩余物质，得到具有式Ⅰ结构的发光辅助材料。
本发明提供了一种有机发光器件，包括依次设置的第一电极、第二电极和置于两电极之间的有机化合物层；
所述有机化合物层包括发光辅助层，所述发光辅助层中包括上述技术方案所述发光辅助材料或上述技术方案所述制备方法制备的发光辅助材料。
在本发明中，有机化合物层优选包括依次设置的空穴注入层、空穴传输层、空穴注入和传输层、电子阻挡层、发光辅助层、发光层、空穴阻挡层、电子传输层、电子注入层、电子注入和传输层中的一层或多层；
在本发明具体实施例中，所述有机化合物层包括依次设置的空穴注入层、空穴传输层、发光辅助层、发光层、电子传输层和电子注入层。
本发明提供了一种含有三芳胺类官能基的有机电致发光辅助材料，具有式Ⅰ结构，其能很大程度的提高空穴传输效率，以及电子阻挡能力，空穴和电子在发光层内的电荷均衡增加，从而不再空穴输送层表面，而是在发光层内部很好的形成发光，从而判断极大化效率和寿命。本申请引入苯并五元(杂)环、六元杂环等结构，降低分子的对称性，增加分子的构象异构体，并且具有刚性平面结构，则分子间不易结晶、不易聚集，制造有机EL元件的成品率提高。因此，使用本发明的有机发光化合物在有机发光器件中能够改善发光效率、驱动电压和使用寿命等特点。
具体实施方式
为了进一步说明本发明，下面结合实施例对本发明提供的一种发光辅助材料及其制备方法和应用进行详细地描述，但不能将它们理解为对本发明保护范围的限定。
实施例1
Figure BDA0003077683090000111
(1)中间体1的合成：在氮气保护下，将原料A-4(30.00mmol)和原料B-4(30.00mmol)溶于200.00ml的甲苯溶液中，加入三(二亚苄基丙酮)二钯(0.30mmol)，三叔丁基膦(1.50mmol)及叔丁醇钠(60.00mmol)，搅拌均匀，升温至90℃，并回流5小时，待溶液冷却至室温后，保留有机相，然后用乙酸乙酯萃取水相；合并有机相后，使用无水硫酸镁进行干燥，并且使用旋转式蒸发器去除溶剂，得到固体有机物。使用少量的二氯甲烷将固体有机物完全溶解，然后缓慢滴加到石油醚溶液中，搅拌均匀，有沉淀析出，抽滤得固体，依次用无水乙醇、石油醚淋洗，烘干，制备得到中间体1(13.99g，产率：86.67％)；
Figure BDA0003077683090000112
(2)中间体2的合成：在氮气保护下，将中间体1(18.58mmol)和原料C-4(18.58mmol)溶于160.00ml甲苯溶液中，加入三(二亚苄基丙酮)二钯(0.19mmol)，三叔丁基膦(0.93mmol)及叔丁醇钠(37.16mmol)，搅拌均匀，升温至90℃，并回流5小时，待溶液冷却至室温后，保留有机相，然后用乙酸乙酯萃取水相；合并有机相后，使用无水硫酸镁进行干燥，并且使用旋转式蒸发器去除溶剂，得到固体有机物。然后将干燥得到的固体溶于甲醇溶液中，并升温搅拌5小时，随后趁热将溶液抽滤，得到固体，然后用石油醚淋洗，烘干，制备得到中间体2(13.17g，产率：86.66％)；
Figure BDA0003077683090000121
(3)中间体3的合成：在氮气保护下，将中间体2(15.89mmol)和原料D-4(15.89mmol)溶于120.00ml甲苯、乙醇和水(V甲苯:V乙醇:V水＝3:1:1)的混合溶液中，加入四三苯基膦钯(0.16mmol)和碳酸钾(31.78mmol)，搅拌均匀，升温至90℃，并回流5小时，反应结束后，稍降温度，使用硅藻土进行过滤，除去盐以及催化剂，滤液冷却至室温后，水洗三遍，保留有机相，接着用乙酸乙酯萃取水相；合并有机相后，使用无水硫酸镁进行干燥，并且使用旋转式蒸发器去除溶剂；使用少量的二氯甲烷将固体有机物完全溶解，然后缓慢滴加到石油醚溶液中，搅拌均匀，有沉淀析出，抽滤得固体，依次用无水乙醇、石油醚淋洗，烘干，制备得到中间体3(10.93g，产率：84.37％)；
Figure BDA0003077683090000122
(4)化合物4的合成：在氮气保护下，将中间体3(12.26mmol)和原料E-4(12.26mmol)溶于120.00ml甲苯、乙醇和水(V甲苯:V乙醇:V水＝3:1:1)的混合溶液中，加入四三苯基膦钯(0.12mmol)和碳酸钾(24.52mmol)，搅拌均匀，升温至90℃，并回流反应5h；反应结束后，稍降温度，使用硅藻土进行过滤，除去盐以及催化剂，滤液冷却至室温后，水洗三遍，保留有机相，接着用乙酸乙酯萃取水相；合并有机相后，使用无水硫酸镁进行干燥，并且使用旋转式蒸发器去除溶剂；利用二氯甲烷和石油醚(V:V＝10:4)的混合溶液，通过柱色谱法纯化剩余物质获得化合物-4(9.39g，产率：84.41％，Mw：907.15)。
本发明对所得化合物4进行检测分析，结果如下：
HPLC纯度：＞99％。
质谱测试：理论值为907.17；测试值为907.15。
元素分析：
计算值为：C,91.36；H,5.56；N,3.09。
测试值为：C,91.37；H,5.57；N,3.07。
实施例2
Figure BDA0003077683090000131
(1)中间体1的合成：在氮气保护下，将原料A-34(30.00mmol)和原料B-34(30.00mmol)溶于210.00ml的甲苯溶液中，加入三(二亚苄基丙酮)二钯(0.30mmol)，三叔丁基膦(1.50mmol)及叔丁醇钠(60.00mmol)，搅拌均匀，升温至90℃，并回流5小时，待溶液冷却至室温后，保留有机相，然后用乙酸乙酯萃取水相；合并有机相后，使用无水硫酸镁进行干燥，并且使用旋转式蒸发器去除溶剂，得到固体有机物。使用少量的二氯甲烷将固体有机物完全溶解，然后缓慢滴加到石油醚溶液中，搅拌均匀，有沉淀析出，抽滤得固体，依次用无水乙醇、石油醚淋洗，烘干，制备得到中间体1(16.07g，产率：86.63％)；
Figure BDA0003077683090000132
(2)中间体2的合成：在氮气保护下，将中间体1(16.17
mmol)和原料C-34(16.17mmol)溶于150.00ml甲苯溶液中，加入三(二亚苄基丙酮)二钯(0.16mmol)，三叔丁基膦(0.81mmol)及叔丁醇钠(32.34mmol)，搅拌均匀，升温至90℃，并回流5小时，待溶液冷却至室温后，保留有机相，然后用乙酸乙酯萃取水相；合并有机相后，使用无水硫酸镁进行干燥，并且使用旋转式蒸发器去除溶剂，得到固体有机物。然后将干燥得到的固体溶于甲醇溶液中，并升温搅拌5小时，随后趁热将溶液抽滤，得到固体，然后用石油醚淋洗，烘干，制备得到中间体2(11.89g，产率：86.64％)；
Figure BDA0003077683090000141
(3)中间体3的合成：在氮气保护下，将中间体2(11.79mmol)和原料D-34(11.79mmol)溶于120.00ml甲苯、乙醇和水(V甲苯:V乙醇:V水＝3:1:1)的混合溶液中，加入四三苯基膦钯(0.12mmol)和碳酸钾(23.58mmol)，搅拌均匀，升温至90℃，并回流5小时，反应结束后，稍降温度，使用硅藻土进行过滤，除去盐以及催化剂，滤液冷却至室温后，水洗三遍，保留有机相，接着用乙酸乙酯萃取水相；合并有机相后，使用无水硫酸镁进行干燥，并且使用旋转式蒸发器去除溶剂；使用少量的二氯甲烷将固体有机物完全溶解，然后缓慢滴加到石油醚溶液中，搅拌均匀，有沉淀析出，抽滤得固体，依次用无水乙醇、石油醚淋洗，烘干，制备得到中间体3(8.43g，产率：84.55％)；
Figure BDA0003077683090000142
(4)化合物34的合成：在氮气保护下，将中间体3(9.46mmol)和原料E-34(9.46mmol)溶于100.00ml甲苯、乙醇和水(V甲苯:V乙醇:V水＝3:1:1)的混合溶液中，加入四三苯基膦钯(0.10mmol)和碳酸钾(18.92mmol)，搅拌均匀，升温至90℃，并回流反应5h；反应结束后，稍降温度，使用硅藻土进行过滤，除去盐以及催化剂，滤液冷却至室温后，水洗三遍，保留有机相，接着用乙酸乙酯萃取水相；合并有机相后，使用无水硫酸镁进行干燥，并且使用旋转式蒸发器去除溶剂；利用二氯甲烷和石油醚(V:V＝10:4)的混合溶液，通过柱色谱法纯化剩余物质获得化合物-34(7.08g，产率：84.42％，Mw：887.16)。
本发明对所得化合物34进行检测分析，结果如下：
HPLC纯度：＞99％。
质谱测试：理论值为887.18；测试值为887.16。
元素分析：
计算值为：C,90.71；H,6.13；N,3.16。
测试值为：C,90.70；H,6.14；N,3.15。
实施例3
Figure BDA0003077683090000151
(1)中间体1的合成：在氮气保护下，将原料A-68(30.00mmol)和原料B-68(30.00mmol)溶于150.00ml的甲苯溶液中，加入三(二亚苄基丙酮)二钯(0.30mmol)，三叔丁基膦(1.50mmol)及叔丁醇钠(60.00mmol)，搅拌均匀，升温至90℃，并回流5小时,待溶液冷却至室温后，保留有机相，然后用乙酸乙酯萃取水相；合并有机相后，使用无水硫酸镁进行干燥，并且使用旋转式蒸发器去除溶剂，得到固体有机物。使用少量的二氯甲烷将固体有机物完全溶解，然后缓慢滴加到石油醚溶液中，搅拌均匀，有沉淀析出，抽滤得固体，依次用无水乙醇、石油醚淋洗，烘干，制备得到中间体1(11.82g，产率：86.60％)；
Figure BDA0003077683090000152
(2)中间体2的合成：在氮气保护下，将中间体1(21.98mmol)和原料C-68(21.98mmol)溶于160.00ml甲苯溶液中，加入三(二亚苄基丙酮)二钯(0.22mmol)，三叔丁基膦(1.10mmol)及叔丁醇钠(43.96mmol)，搅拌均匀，升温至90℃，并回流5小时，待溶液冷却至室温后，保留有机相，然后用乙酸乙酯萃取水相；合并有机相后，使用无水硫酸镁进行干燥，并且使用旋转式蒸发器去除溶剂，得到固体有机物。然后将干燥得到的固体溶于甲醇溶液中，并升温搅拌5小时，随后趁热将溶液抽滤，得到固体，然后用石油醚淋洗，烘干，制备得到中间体2(13.34g，产率：86.59％)；
Figure BDA0003077683090000161
(3)中间体3的合成：在氮气保护下，将中间体2(14.26mmol)和原料D-68(14.26mmol)溶于140.00ml甲苯、乙醇和水(V甲苯:V乙醇:V水＝3:1:1)的混合溶液中，加入四三苯基膦钯(0.14mmol)和碳酸钾(28.52mmol)，搅拌均匀，升温至90℃，并回流5小时，反应结束后，稍降温度，使用硅藻土进行过滤，除去盐以及催化剂，滤液冷却至室温后，水洗三遍，保留有机相，接着用乙酸乙酯萃取水相；合并有机相后，使用无水硫酸镁进行干燥，并且使用旋转式蒸发器去除溶剂；使用少量的二氯甲烷将固体有机物完全溶解，然后缓慢滴加到石油醚溶液中，搅拌均匀，有沉淀析出，抽滤得固体，依次用无水乙醇、石油醚淋洗，烘干，制备得到中间体3(9.68g，产率：84.41％)；
Figure BDA0003077683090000162
(4)化合物68的合成：在氮气保护下，将中间体3(11.19mmol)和原料E-68(11.19mmol)溶于110.00ml甲苯、乙醇和水(V甲苯:V乙醇:V水＝3:1:1)的混合溶液中，加入四三苯基膦钯(0.11mmol)和碳酸钾(22.38mmol)，搅拌均匀，升温至90℃，并回流反应5h；反应结束后，稍降温度，使用硅藻土进行过滤，除去盐以及催化剂，滤液冷却至室温后，水洗三遍，保留有机相，接着用乙酸乙酯萃取水相；合并有机相后，使用无水硫酸镁进行干燥，并且使用旋转式蒸发器去除溶剂；利用二氯甲烷和石油醚(V:V＝10:4)的混合溶液，通过柱色谱法纯化剩余物质获得化合物-68(8.71g，产率：84.43％，Mw：922.17)。
本发明对所得化合物-68进行检测分析，结果如下：
HPLC纯度：＞99％。
质谱测试：理论值为922.16；测试值为922.17。
元素分析：
计算值为：C,88.57；H,4.70；N,1.52；O,1.73；S,3.48。
测试值为：C,88.56；H,4.71；N,1.53；O,1.72；S,3.48。
实施例4
Figure BDA0003077683090000171
(1)中间体1的合成：在氮气保护下，将原料A-79(30.00mmol)和原料B-79(30.00mmol)溶于180.00ml的甲苯溶液中，加入三(二亚苄基丙酮)二钯(0.30mmol)，三叔丁基膦(1.50mmol)及叔丁醇钠(60.00mmol)，搅拌均匀，升温至90℃，并回流5小时，待溶液冷却至室温后，保留有机相，然后用乙酸乙酯萃取水相；合并有机相后，使用无水硫酸镁进行干燥，并且使用旋转式蒸发器去除溶剂，得到固体有机物。使用少量的二氯甲烷将固体有机物完全溶解，然后缓慢滴加到石油醚溶液中，搅拌均匀，有沉淀析出，抽滤得固体，依次用无水乙醇、石油醚淋洗，烘干，制备得到中间体1(12.27g，产率：86.65％)；
Figure BDA0003077683090000172
(2)中间体2的合成：在氮气保护下，将中间体1(21.19mmol)和原料C-79(21.19mmol)溶于180.00ml甲苯溶液中，加入三(二亚苄基丙酮)二钯(0.21mmol)，三叔丁基膦(1.06mmol)及叔丁醇钠(42.38mmol)，搅拌均匀，升温至90℃，并回流5小时，待溶液冷却至室温后，保留有机相，然后用乙酸乙酯萃取水相；合并有机相后，使用无水硫酸镁进行干燥，并且使用旋转式蒸发器去除溶剂，得到固体有机物。然后将干燥得到的固体溶于甲醇溶液中，并升温搅拌5小时，随后趁热将溶液抽滤，得到固体，然后用石油醚淋洗，烘干，制备得到中间体2(14.50g，产率：86.63％)；
Figure BDA0003077683090000181
(3)化合物79的合成：在氮气保护下，将中间体2(12.66mmol)和原料D-79(12.66mmol)溶于120.00ml甲苯、乙醇和水(V甲苯:V乙醇:V水＝3:1:1)的混合溶液中，加入四三苯基膦钯(0.13mmol)和碳酸钾(25.32mmol)，搅拌均匀，升温至90℃，并回流反应5h；反应结束后，稍降温度，使用硅藻土进行过滤，除去盐以及催化剂，滤液冷却至室温后，水洗三遍，保留有机相，接着用乙酸乙酯萃取水相；合并有机相后，使用无水硫酸镁进行干燥，并且使用旋转式蒸发器去除溶剂；利用二氯甲烷和石油醚(V:V＝10:4)的混合溶液，通过柱色谱法纯化剩余物质获得化合物-81(9.38g，产率：84.47％，Mw：877.07)。
本发明对所得化合物79进行检测分析，结果如下：
HPLC纯度：＞99％。
质谱测试：理论值为877.09；测试值为877.07。
元素分析：
计算值为：C,83.53；H,4.14；N,3.19；O,1.82；S,7.31。
测试值为：C,83.54；H,4.15；N,3.18；O,1.80；S,7.32。
因结构通式为发明内容中的式I，其他化合物的合成路线和原理均与上述所列举的实施例相同，所以在此不再穷举。
采用TMA4000对上述实施例合成的化合物测试其玻璃化转变温度(tg)，如表1所示：
表1：实施例制备的化合物的玻璃化转变温度
Figure BDA0003077683090000182
Figure BDA0003077683090000191
从表1中可以看出，本申请提供的发光辅助材料具有较好的热稳定性。
采用上述实施例提供的发光辅助材料制备得到的有机电致发光器件，当有机物层包括发光辅助层时，所述发光辅助层包括上述实施例提供的发光辅助材料。
器件实施例1
将涂层厚度为150nm的ITO玻璃基板放在蒸馏水中清洗2次，超声波洗涤30分钟，用蒸馏水反复清洗2次，超声波洗涤10分钟，蒸馏水清洗结束后，异丙醇、丙酮、甲醇等溶剂按顺序超声波洗涤以后干燥，转移到等离子体清洗机里，将上述基板洗涤5分钟，送到蒸镀机里；
在ITO阳极层上，通过真空蒸镀方式蒸镀空穴注入层材料HAT-CN，厚度为10nm；在空穴注入层上面真空蒸镀15nm的N,N'-二苯基-N,N'-(1-萘基)-1,1′-联苯-4,4'-二胺(NPB)作为空穴传输层；在空穴传输层上面真空蒸镀95nm的上述实施例1提供的化合物4作为发光辅助层；然后在上述发光辅助层上真空蒸镀厚度为40nm的主体材料CBP和掺杂材料(btp)2Ir(acac)作为发光层，其中主体材料和掺杂材料的重量比为97:3；接着在上述发光层上真空蒸镀厚度为35nm的TPBi和Liq作为电子传输层，其中TPBi和Liq的重量比为60:40；在上述电子传输层上真空蒸镀厚度为1nm的Yb作为电子注入层；最后在电子注入层上真空蒸镀镁和银作为阴极，镁和银的重量比为1:9，蒸镀厚度为18nm；在阴极上真空蒸镀厚度为70nm的IDX001作为光取出层，
参照上述器件实施例1提供的方法，分别选用化合物7、化合物12、化合物19、化合物24、化合物29、化合物34、化合物39、化合物42、化合物49、化合物53、化合物56、化合物60、化合物65、化合物68、化合物72、化合物77、化合物79替代化合物4，进行发光辅助层的蒸镀，并制备得到相应的有机电致发光器件，分别记为器件实施例2～18。
器件对比例1：
该对比例提供了一种有机电致发光器件，该有机电致发光器件的制备方法与器件实施例1的唯一区别在于，该有机电致发光器件是采用现有的对比化合物a替代上述器件实施例1中的发光辅助材料(化合物4)进行蒸镀。其中，对比化合物a的化学结构式为：
Figure BDA0003077683090000201
在6000(nits)亮度下对上述器件实施例1～18以及器件对比例1得到的有机电致发光器件的驱动电压、发光效率以及寿命进行表征，测试结果如下表2：
表2：器件实施例制备的电致发光器件的性能测试结果
Figure BDA0003077683090000202
表2可以看出，使用本发明提供的发光辅助材料制备的有机电致发光器件与对比例1提供的现有的有机电致发光器件相比较而言，其驱动电压明显降低，发光效率和寿命得到显著提高。
由以上实施例可知，本发明提供了一种发光辅助材料，具有式Ⅰ结构，是一种含有三芳胺类官能基的有机电致发光辅助材料，能很大程度的提高空穴传输效率，以及电子阻挡能力，空穴和电子在发光层内的电荷均衡增加，从而不再空穴输送层表面，而是在发光层内部很好的形成发光，从而判断极大化效率和寿命。本申请引入苯并五元(杂)环、六元杂环等结构，降低分子的对称性，增加分子的构象异构体，并且具有刚性平面结构，则分子间不易结晶、不易聚集，制造有机EL元件的成品率提高。因此使用本发明的有机发光化合物在有机发光器件中能够改善发光效率、驱动电压和使用寿命等特点。
以上所述仅是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。

Claims (8)

1.一种发光辅助材料，具有式Ⅰ结构：
Figure FDA0003077683080000011
所述X选自连接键、-O-、-S-、SiR3R4、CR5R6或NR7；所述R3、R4、R5、R6和R7独立地选自氢、氘、卤素、氰基、羧基、硝基、羟基、磺酸基、磷酸基、硼烷基、取代或非取代的C1～C30烷基、取代或非取代的C3～C50环烷基、取代或非取代的3元～30元杂环烷基；取代或非取代的C2～C30烯基、取代或非取代的C2～C30炔基、取代或非取代的C6～C60芳基、取代或非取代的3元～60元杂芳基；或可与一个或多个相邻取代基连接以形成单环或多环(3元～30元)脂环族环或芳香族环，其(一个或多个)碳原子可被至少一个氮、氧和硫的杂原子置换；
所述L1、L2和L3选自单键；取代或未取代的C6～C60的亚芳基；取代或未取代的5元～30元的亚杂芳基；取代或未取代的C3～C30的环烷基；或取代或未取代的3元～30元的杂环烷基；
所述R1和R2选自氢、氘、卤素、氰基、羧基、硝基、羟基、磺酸基、磷酸基、硼烷基、取代或未取代的(C1～C30)烷基、取代或未取代的(C3～C50)环烷基、取代或未取代的3元～30元杂环烷基、取代或未取代的(C2～C30)烯基、取代或未取代的C2～C30炔基、取代或未取代的C6～C60芳基、取代或未取代的3元～60元杂芳基；或可与一个或多个相邻取代基连接以形成单环或多环(3元～30元)脂环族环或芳香族环，其一个或多个碳原子可被至少一个氮、氧和硫的杂原子置换；
所述a和b的取值为0～4的整数；
所述Ar1和Ar2分别独立地表示为经取代或未经取代的C3～C30环烷基、取代或未经取代的3元～30元杂环烷基；取代或未经取代的C6～C30芳基、取代或未经取代的3元～20元杂芳基；取代或未取代的C10～C30稠环基。
2.根据权利要求1所述的发光辅助材料，其特征在于，所述L1、L2和L3选自单键；经取代或未经取代的C6～C25亚芳基；或取代或未取代的5元～25元亚杂芳基，其中杂原子选自N、O、S、Si、P和Se中的一种或多种。
3.根据权利要求1所述的发光辅助材料，其特征在于，所述R1和R2选自氢；氘；卤素；氰基；硝基；取代或未取代的C1～C10烷基；取代或未取代的C3～C15环烷基；取代或未取代的3元～15元杂环烷基，其中杂原子为N、O、S、Si、P和Se中的一种或多种；取代或未取代的C6～C25芳基、取代或非取代的3元～25元杂芳基，其中杂原子至少选自N、O、S、Si、P和Se中至少一种；或可与一个或多个相邻取代基连接以形成单环或多环(3元～20元)脂环族环或芳香族环，其一个或多个碳原子可被至少一个氮、氧和硫的杂原子置换。
4.根据权利要求1所述的发光辅助材料，其特征在于，所述Ar1和Ar2独立地选自取代或未取代的C3～C15环烷基；取代或未取代的3元～20元杂环烷基，其中杂原子选自N、O、S、Si、P和Se中至少一种；取代或未取代的C6～C20芳基；取代或未取代的3元～18元杂芳基，其中杂原子选自N、O、S、Si、P和Se中至少一种；或取代或未取代的C10～C25稠环基。
5.根据权利要求1所述的发光辅助材料，其特征在于，所述发光辅助材料选自化合物1～80中任一种：
Figure FDA0003077683080000021
Figure FDA0003077683080000031
Figure FDA0003077683080000041
Figure FDA0003077683080000051
Figure FDA0003077683080000061
Figure FDA0003077683080000071
6.一种权利要求1～5任一项所述发光辅助材料的制备方法，包括以下步骤：
在氮气保护下，将中间体3和Ar2-B(OH)2溶于甲苯、乙醇和水的混合溶液中，加入四三苯基膦钯和碳酸钾，搅拌均匀，升温并回流，得到具有式Ⅰ结构的发光辅助材料；
Figure FDA0003077683080000072
中间体3；其中，-Hal4代表卤素。
7.根据权利要求6所述的制备方法，其特征在于，所述中间体3按照以下方法制得：
在氮气保护下，将中间体1和Hal3-L2-NH-L3-Hal4溶于甲苯溶液中，加入钯催化剂、膦配体及叔丁醇钠，搅拌均匀，升温并回流，得到中间体2；
将所述中间体2和Ar1-B(OH)2溶于甲苯乙醇和水的混合溶液中，加入四三苯基膦钯和碳酸钾，搅拌均匀，升温并回流，得到中间体3；
Figure FDA0003077683080000081
Hal1～Hal4代表卤素。
8.一种有机发光器件，包括依次设置的第一电极、第二电极和置于两电极之间的有机化合物层；
所述有机化合物层包括发光辅助层，所述发光辅助层中包括权利要求1～5任一项所述发光辅助材料或权利要求6～7任一项所述制备方法制备的发光辅助材料。
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CN115304491A (zh) * 2022-09-01 2022-11-08 吉林奥来德光电材料股份有限公司 一种空穴类有机电致发光化合物及其制备方法和应用

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CN115181074A (zh) * 2022-06-10 2022-10-14 吉林奥来德光电材料股份有限公司 一种发光辅助材料及其制备方法、发光器件
CN115304491A (zh) * 2022-09-01 2022-11-08 吉林奥来德光电材料股份有限公司 一种空穴类有机电致发光化合物及其制备方法和应用
CN115304491B (zh) * 2022-09-01 2023-12-26 吉林奥来德光电材料股份有限公司 一种空穴类有机电致发光化合物及其制备方法和应用

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