CN109369557B - 一种萘并七元氮氧杂环为核心结构的有机化合物制备及其在oled上的应用 - Google Patents
一种萘并七元氮氧杂环为核心结构的有机化合物制备及其在oled上的应用 Download PDFInfo
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Abstract
本发明主要保护以萘并七元氮氧杂环为核心结构的有机化合物制备及其在OLED上的应用。下述式中所示的化合物作为OLED发光材料中间体具有较高的玻璃化转变温度及分子热稳定性,易形成非晶态薄膜,具有良好的光电性能,有效的提升OLED器件的发光效率和使用寿命,具有良好的市场应用前景。
Description
技术领域
本发明涉及有机光电材料技术领域,尤其是涉及一种以萘并七元氮氧杂环为中心结构的有机化合物材料及其在OLED发光显示器或照明器件的应用。
技术背景
有机发光二极管(Organic Light Emitting Diode)简称OLED显示器,对比液晶显示器, OLED显示器具有亮度高、体积薄、响应迅速,还具有功耗低、性能稳定,对比度高、宽视角、全彩色、工作温度范围宽等特点,在显示和照明领域凸显出十分优越的应用前景。
OLED器件大多采用“三明治”结构。该结构由多个作用不同的功能层组成,分别是透明金属氧化物的阳极层(通常为氧化铟锡ITO)、空穴传输层(HTL)、发光层(EML)、电子传输层(ETL)和金属阴极层(通常为低功函数金属Li,Ca,Al,Mg,Ag等)构成。阴阳两极之间夹杂着有机层,辐射光由侧面的透明导电基板射出。
目前,对于OLED发光器件,主要对器件的驱动电压,发光效率,使用寿命等性能进行优化研究。提高OLED器件的性能,除了器件结构和制作工艺要创新外,OLED有机发光材料也要不断创新,研究出发光效率高、发光层成膜性好、使用寿命长等更高性能的OLED发光材料来适应。目前OLED有机发光材料在发光效率、使用寿命等方面无法满足器件制造商的要求,研究开发一种高性能的OLED发光材料尤为重要。
发明内容
针对上述问题,申请人提供了一种萘并七元氮氧杂环为核心结构的有机化合物的制备及其在OLED发光器件上的应用,本发明有机化合物含有萘并七元氮氧杂环结构,具有较好的分子稳定性。制备出的OLED器件具备优越的光电性能,具有较高的热稳定性、较低的驱动电压和较高的效率,延长器件使用寿命,可以很好的满足器件制造商的要求。
一种萘并七元氮氧杂环为核心结构的有机化合物,所述化合物的结构如通式(1)所示:
所述R1和R2选自:
本申请人还提供了所述的萘并七元氮氧杂环类有机化合物用于制备有机电致发光器件的应用。所述有机电致发光器件包括至少一层功能层含有所述的萘并七元氮氧杂环类有机化合物。
本申请人还提供了一种电致发光器件,包括电子传输层,所述电子传输层为所述的萘并七元氮氧杂环类有机化合物。
本申请人还提供了一种电致发光器件,包括发光层,所述发光层含有所述的萘并七元氮氧杂环类有机化合物。
本发明优于其它技术效果在于:
本发明中涉及到的有机化合物所应用的OLED器件可应用于AM驱动OLED显示,PM驱动OLED显示,或者OLED照明领域。
本发明中涉及到的有机化合物应用于OLED发光器件制作,作为主体发光材料或电子传输材料时,器件的外量子效率,功率效率,电流效率都得到较大的提升,从而对器件的使用寿命也有明显的延长。具有良好的市场前景。
附图及说明
图1为本发明OLED器件结构示意图
其中,1为透明基板层,2为透明电极层,3为空穴注入层(HIM),4为空穴传输层(HTL), 5为发光层(EML),6为电子传输层(ETL),7为电子注入层,8为阴极反射电极层。
具体实施方式
下面结合图示及实施例,对本发明进行具体说明。
实施例1:中间体Ⅰ的合成
1000ml三口瓶,在通氮气的情况下,加入50.0g原料A(211mmol)、50.7g叔丁醇钠(527mmol),0.97g Pd2(dba)3(1.05mmol)、0.87g S-phos(2.04mmol)和150ml二甲苯,升温至130℃~140℃,控温130℃~140℃缓慢滴加43.0g原料B(211mmol)和400ml二甲苯混合溶液,滴加毕,保温15h,TLC检测原料反应完毕;降温至室温,过滤,滤饼用二甲苯淋洗,过柱液减压旋蒸至无馏分,粗品黄色固体,用甲苯精制,烘干得到53.2g中间体A,收率:70%,
500ml三口瓶,在通氮气的情况下,加入53.2g化合物中间体A(148mmol),加入300ml 二氯乙烷,降温至0℃~5℃,控温0℃~15℃缓慢滴加40.7g三溴化硼(162mmol),滴加毕控温0℃~15℃保温。TLC检测原料反应完毕,水解,用水洗至中性,有机相减压旋蒸,用石油醚精制得45.0g中间体B,收率88%。
500ml三口瓶,在通氮气的情况下,加入45.0g中间体B(130mmol),加入53.9g K2CO3(390mmol),300mlDMF,升温至130℃~140℃保温,保温5h,TLC检测原料反应完毕;降温至室温,过滤,滤饼用DMF淋洗,脱干溶剂,用乙醇精制得38.2g中间体C,收率90%。
1000ml三口瓶,在通氮气的情况下,加入38.2g中间体C(117mmol)和400ml四氢呋喃,降温至-80℃~-90℃,控温-80℃~-90℃缓慢滴加46.8ml丁基锂正己烷溶液(2.5mol/L),滴加毕保温1h,控温-80℃~-90℃缓慢滴加33.0g硼酸三异丙酯(176mmol),滴加毕保温3h,盐酸酸化,用水洗至中性,有机相减压旋蒸,用乙酸乙酯、石油醚精制得26.6g中间体Ⅰ,收率78%。
LC-MS:中间体Ⅰ理论分子量为291.1,实际检测结果分子量为292.2。
实施例1化合物1的合成
化合物1的具体合成路线
在氮气保护下,向1000ml三口瓶中加入26.6g中间体Ⅰ(91.4mmol)、14.4g原料C(91.4mmol)、25.3g碳酸钾(182.8mmol),59.0g水、500g甲苯、1.06g Pd(PPh3)4(0.9mmol),开启搅拌,使用油浴锅加热,控温70~80℃保温6~8h,TLC检测反应完全后,分层,水洗,脱溶剂得粗品后,用甲苯精制,烘干得到22.3g中间体1,收率75.5%。
在氮气保护下,向1000ml三口瓶中加入22.3g中间体1(69.0mmol)、62.8g原料C(69.0mmol)、13.3g叔丁醇钠(137.9mmol)、0.6gPd2(dba)3(0.7mmol)、0.3g三叔丁基膦(1.4mmol),用甲苯搅拌混合,加热至100~110℃,回流反应12~24小时,取样点板,显示无中间体1剩余,反应完全;自然冷却至室温,过滤,滤液过硅胶柱,过柱液减压旋蒸至无馏分,粗品棕黄色固体,用甲苯精制,烘干得到19.3g化合物1,收率:70%。
HPLC-MS:化合物1理论分子量为399.5,实际检测结果分子量为399.1。
实施例2化合物8的合成
化合物8的具体合成路线
在氮气保护下,向1000ml三口瓶中加入26.6g中间体Ⅰ(91.4mmol)、25.7g原料C(91.4mmol)、25.3g碳酸钾(182.8mmol),59.0g水、500g甲苯、1.06g Pd(PPh3)4(0.9mmol),开启搅拌,使用油浴锅加热,控温70~80℃保温6~8h,TLC检测反应完全后,分层,水洗,脱溶剂得粗品后,用甲苯精制,烘干得到31.2g中间体2,收率76.2%。
在氮气保护下,向1000ml三口瓶中加入31.2g中间体2(69.7mmol)、11.0g原料C(69.7mmol)、13.4g叔丁醇钠(139.4mmol)、0.6gPd2(dba)3(0.7mmol)、0.3g三叔丁基膦(1.4mmol),用甲苯搅拌混合,加热至100~110℃,回流反应12~24小时,取样点板,显示无中间体2剩余,反应完全;自然冷却至室温,过滤,滤液过硅胶柱,过柱液减压旋蒸至无馏分,粗品棕黄色固体,用甲苯精制,烘干得到29.8g化合物8,收率:81.5%。
HPLC-MS:化合物1理论分子量为523.6,实际检测结果分子量为523.5。
实施例3化合物13的合成
化合物13的合成路线
在氮气保护下,向1000ml三口瓶中加入26.6g中间体Ⅰ(91.4mmol)、22.6g原料E(91.4mmol)、25.3g碳酸钾(182.8mmol),59.0g水、500g甲苯、1.06g Pd(PPh3)4(0.9mmol),开启搅拌,使用油浴锅加热,控温70~80℃保温6~8h,TLC检测反应完全后,分层,水洗,脱溶剂得粗品后,用甲苯精制,烘干得到30.0g中间体3,收率79.4%。
在氮气保护下,向1000ml三口瓶中加入30.0g中间体3(72.6mmol)、11.4g原料C(72.6mmol)、14.0g叔丁醇钠(145.1mmol)、0.6gPd2(dba)3(0.7mmol)、0.3g三叔丁基膦(1.4mmol),用甲苯搅拌混合,加热至100~110℃,回流反应12~24小时,取样点板,显示无中间体3剩余,反应完全;自然冷却至室温,过滤,滤液过硅胶柱,过柱液减压旋蒸至无馏分,粗品棕黄色固体,用甲苯精制,烘干得到25.6g化合物13,收率:72.0%。
HPLC-MS:化合物1理论分子量为489.5,实际检测结果分子量为499.1。
实施例4化合物32的合成
化合物32的合成路线
在氮气保护下,向1000ml三口瓶中加入26.6g中间体Ⅰ(91.4mmol)、25.7g原料C(91.4mmol)、25.3g碳酸钾(182.8mmol),59.0g水、500g甲苯、1.06g Pd(PPh3)4(0.9mmol),开启搅拌,使用油浴锅加热,控温70~80℃保温6~8h,TLC检测反应完全后,分层,水洗,脱溶剂得粗品后,用甲苯精制,烘干得到31.2g中间体2,收率76.2%。
在氮气保护下,向1000ml三口瓶中加入31.2g中间体2(69.7mmol)、16.3g原料F(69.7mmol)、13.4g叔丁醇钠(139.4mmol)、0.6gPd2(dba)3(0.7mmol)、0.3g三叔丁基膦(1.4mmol),用甲苯搅拌混合,加热至100~110℃,回流反应12~24小时,取样点板,显示无中间体2剩余,反应完全;自然冷却至室温,过滤,滤液过硅胶柱,过柱液减压旋蒸至无馏分,粗品棕黄色固体,用甲苯精制,烘干得到30.6g化合物32,收率:73.3%。
HPLC-MS:化合物1理论分子量为599.7,实际检测结果分子量为599.2。
实施例5化合物47的合成
化合物47的合成路线
在氮气保护下,向1000ml三口瓶中加入26.6g中间体Ⅰ(91.4mmol)、29.4g原料G(91.4mmol)、25.3g碳酸钾(182.8mmol),59.0g水、500g甲苯、1.06g Pd(PPh3)4(0.9mmol),开启搅拌,使用油浴锅加热,控温70~80℃保温6~8h,TLC检测反应完全后,分层,水洗,脱溶剂得粗品后,用甲苯精制,烘干得到34.9g中间体4,收率78.2%。
在氮气保护下,向1000ml三口瓶中加入31.2g中间体4(71.4mmol)、16.7g原料F(71.4mmol)、13.7g叔丁醇钠(139.4mmol)、0.6gPd2(dba)3(0.7mmol)、0.3g三叔丁基膦(1.4mmol),用甲苯搅拌混合,加热至100~110℃,回流反应12~24小时,取样点板,显示无中间体4剩余,反应完全;自然冷却至室温,过滤,滤液过硅胶柱,过柱液减压旋蒸至无馏分,粗品棕黄色固体,用甲苯精制,烘干得到35.4g化合物32,收率:77.3%。
HPLC-MS:化合物1理论分子量为640.7,实际检测结果分子量为639.9。
下面通过应用实施例1~5详细说明本发明合成的化合物在OLED器件上的应用效果。
对比实施例1,对具有透明基板层1的透明电极层2(透明电极层2的膜厚210nm)进行光刻和蚀刻,使其形成所需的规则的透明电极层2的图形,然后对玻璃透明基板层1进行清洗,即依次进行碱洗、高纯水洗涤,干燥后再进行紫外线-臭氧洗涤来清除透明电极层2表面的有机残留物。清理完毕后,进行有机层蒸镀,具体利用真空蒸镀装置(钼坩锅、蒸镀速度1A/s、真空度约5.0*10-7Torr)在透明基板层1的阳极上,蒸镀一层有机化合物A1(结构式如下式)作为空穴类材料,制作膜厚为60nm,该层为空穴注入层3
在空穴注入层3上,通过真空蒸镀装置(钼坩埚、蒸镀速度1A/s,真空度约5.0*10- 7Torr),蒸镀如下式结构式的有机化合物B1,作为空穴传输层4使用,其膜厚为80nm
将下式结构的化合物C1蒸镀在空穴传输层4之上(钼坩埚、蒸镀速度1A/s,真空度约 5.0*10-7Torr),镀膜厚度为30nm,这层有机材料作为器件的发光层5使用;
在上述发光层之上,通过蒸镀装置(钼坩埚、蒸镀速度1A/s,真空度约5.0*10- 7Torr),将下式结构的化合物D1作为电子传输材料蒸镀到发光层上面,制作出膜厚度为40nm的电子传输层6;
通过真空蒸镀装置(钼坩埚、蒸镀速度1A/s,真空度约5.0*10-7Torr)蒸镀在电子传输层 6之上,制作出膜厚为1nm的氟化锂(LiF)层,该层为电子注入层7;在电子注入层7之上,通过真空蒸镀装置(BN坩埚、蒸镀速度1A/s,真空度约5.0*10-7Torr),制作膜厚为130nm的铝(Al)层,此层为反射电极层8使用。
器件制作完成后,用公知的驱动电路将阳极和阴极连接起来,测量器件的发光效率,发光光谱以及器件的电流-电压特性,上述器件发光特性的测量是利用辉度测定仪(株式会社 TOPCON制,商品名BM7)进行的。
本发明所述应用例1~5所述器件的制作工艺完全相同,并且使用相同的基板材料和电极材料,并且电极材料的膜厚度相同,不同处仅将发光层或电子传输材料分别换成了本发明材料,对比例1和应用例1~5所制作的器件各主要结构层所用化合物如表1
表1
对比例1和应用例1~11所制作的OLED发光器件的结果如表2所示。
表2
实施例 | 发光效率(cd/A) | 色彩 | CIE坐标(x,y) |
对比例1 | 9 | 蓝光 | 0.14,0.08 |
应用例1 | 9.4 | 蓝光 | 0.15,0.28 |
应用例2 | 9.9 | 蓝光 | 0.16,0.29 |
应用例3 | 9.7 | 蓝光 | 0.14,0.25 |
应用例4 | 10.5 | 蓝光 | 0.14,0.20 |
应用例5 | 10.4 | 蓝光 | 0.15,0.24 |
由表2分析得出,选用本发明的化合物作为OLED器件发光材料,对比现有材料应用的OLED 发光器件,器件的发光效率,器件的色纯度等性能均有良好的表现;在OLED器件的应用上具有很大的应用价值和商业价值,具备良好的产业化前景。
Claims (6)
3.一种权利要求1~2中的任意一项所述的萘并七元氮氧杂环为核心结构的有机化合物用于制备有机电致发光器件。
4.一种有机电致发光器件,其特征在于:所述有机电致发光器件包括至少一层功能层含有权利要求1~2任一项所述的萘并七元氮氧杂环为核心结构的有机化合物。
5.一种有机电致发光器件,包括电子传输层,其特征在于,所述电子传输层材料为权利要求1~2任一项所述的萘并七元氮氧杂环为核心结构的有机化合物。
6.一种有机电致发光器件,包括发光层,其特征在于,所述发光层含有权利要求1~2任一项所述的萘并七元氮氧杂环为核心结构的有机化合物。
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