CN107445884A - 一种三芳胺类衍生物及其制备方法和应用 - Google Patents
一种三芳胺类衍生物及其制备方法和应用 Download PDFInfo
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- QARVLSVVCXYDNA-UHFFFAOYSA-N Brc1ccccc1 Chemical compound Brc1ccccc1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 1
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- SISSGQKYNZJXAS-UHFFFAOYSA-N CC1(C)c(ccc(C(F)(F)F)c2)c2-c2ccccc12 Chemical compound CC1(C)c(ccc(C(F)(F)F)c2)c2-c2ccccc12 SISSGQKYNZJXAS-UHFFFAOYSA-N 0.000 description 1
- HBSPMLJUXWBHPO-UHFFFAOYSA-N Cc1cccc(-c2cccc(-[n]3c(C=CC4C=CC(C)=CC44)c4c4c(cccc5)c5ccc34)c2)c1 Chemical compound Cc1cccc(-c2cccc(-[n]3c(C=CC4C=CC(C)=CC44)c4c4c(cccc5)c5ccc34)c2)c1 HBSPMLJUXWBHPO-UHFFFAOYSA-N 0.000 description 1
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- DMBHHRLKUKUOEG-UHFFFAOYSA-N c(cc1)ccc1Nc1ccccc1 Chemical compound c(cc1)ccc1Nc1ccccc1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明提供一种三芳胺类衍生物及其制备方法和应用,涉及有机光电材料技术领域。主体结构的不对称性,加上引入稠环类刚性、不对称、密集结构,使本发明所得到的三芳胺类衍生物热稳定性能高、成膜性好,可用于制备有机发光器件,尤其是作为有机发光器件中的空穴传输材料,表现出高效率、长寿命和不易结晶的优点,优于现有常用OLED器件。本发明还提供一种芳香族胺类衍生物的制备方法,该制备方法简单、原料易得。
Description
技术领域
本发明涉及有机光电材料技术领域,具体涉及一种三芳胺类衍生物及其制备方法和应用。
背景技术
近年来有机发光二极管(Organic Light-Emitting Diodes,电致发光)已经成为国内外非常热门的新兴的平板显示产业,主要是因为电致发光显示器具有自发光、视角宽(达170°以上)、响应速度快(~1μs)、色彩逼真、清晰度高、高发光效率、操作电压低(3~10V)、面板厚度薄(小于2mm)、可制作大尺寸和可弯曲性面板以及制作流程简单等突出优势,具有低成本的潜力,因此,被认为是下一代的平板显示技术。
作为OLED中的空穴传输层,其基本作用是提高空穴在器件中的传输效率,并将电子有效地阻挡在发光层内,实现载流子的最大复合;同时降低空穴在注入过程中的能量壁垒,提高空穴的注入效率,从而提高器件的亮度、效率和寿命。因此对于有机电致发光空穴传输材料,要满足以下几点:(1)能够形成无针孔的均一无定形薄膜;(2)所形成的无定形薄膜具有很好的热稳定性;(3)具有合适的HOMO轨道能级,以保证空穴在电极/有机层以及有机层/有机层界面之间的有效注入与传输:(4)具有很高的空穴迁移率。
目前,有机电致发光器件已经向着实用化、商品化发展,但在器件的亮度、效率和寿命上仍需要进一步的提高,这对有机空穴传输材料也提出了更高的要求。如何设计新的性能更好的材料进行调节,一直是本领域技术人员亟待解决的问题。
发明内容
本发明的目的是提供一种三芳胺类衍生物及其制备方法和应用,本发明提供的有机化合物热稳定性能高、成膜性好,制备方法简单,由该化合物制成的有机发光器件,表现出高效率、长寿命和不易结晶的优点,是性能优良的有机发光材料。
本发明首先提供一种三芳胺类衍生物,结构式为:
其中,Ar1、Ar2独立的选自C6~C50的取代或未取代的芳基、C6~C50的取代或未取代的杂芳基、C10~C30的取代或未取代的稠环、C8~C30的取代或未取代的稠杂环中的一种。
优选的,其结构式I如下面结构式Ⅱ、结构式Ⅲ所示的任意一种结构表示:
优选的,所述Ar1、Ar2独立的选自C6~C18的取代或未取代的芳基、C6~C18的取代或未取代的杂芳基、C10~C22的取代或未取代的稠环、C8~C20的取代或未取代的稠杂环。
优选的,所述Ar1、Ar2独立的选自取代或未取代的苯基、萘基、蒽基、芘基、联苯基、三联苯基、茚基、吲哚基、吡啶基、呋喃基、噻吩基、二苯并噻吩基、二苯并呋喃基、喹啉基、异喹啉基、咔唑基、芴基或螺二芴基。
优选的,所述一种三芳胺类衍生物选自如下所示结构中的任意一种:
本发明还提供一种三芳胺类衍生物的制备方法,制备路线如下:
其中,Ar1、Ar2独立的选自C6~C50的取代或未取代的芳基、C6~C50的取代或未取代的杂芳基、C10~C30的取代或未取代的稠环、C8~C30的取代或未取代的稠杂环中的一种。
本发明还提供上述三芳胺类衍生物在有机发光器件中的应用。
优选的,所述有机发光器件包括阴极、阳极和置于所述两电极之间的一个或多个有机化合物层,所述的有机化合物层含有所述的一种三芳胺类衍生物。
优选的,所述的一种有机发光器件,其特征在于,所述有机化合物层包括空穴注入层、空穴传输层,电子阻挡层、发光层、空穴阻挡层、电子传输层、电子注入层中的至少一层;所述有机化合物层中至少一层含有所述的一种三芳胺类衍生物。
优选的,所述的一种有机发光器件,其特征在于,空穴传输层中含有所述的一种三芳胺类衍生物。
本发明的有益效果:
本发明首先提供一种三芳胺类衍生物,该三芳胺类衍生物具有式I所示结构,主体结构的不对称性,加上引入稠环类刚性、不对称、密集结构,使本发明所得到的三芳胺类衍生物热稳定性能高、成膜性好,可用于制备有机发光器件,尤其是作为有机发光器件中的空穴传输材料,表现出高效率、长寿命和不易结晶的优点,优于现有常用OLED器件。本发明还提供一种三芳胺类衍生物的制备方法,该制备方法简单、原料易得,能够满足工业化发展的需要。本发明芳香族胺类衍生物在OLED发光器件中具有良好的应用效果,具有良好的产业化前景。
具体实施方式
为了进一步理解本发明,下面结合实施例对本发明优选实施方案进行描述,但是应当理解,这些描述只是为进一步说明本发明的特征和优点,而不是对本发明权利要求的限制。
本发明首先提供一种三芳胺类衍生物,结构式为:
其中,Ar1、Ar2独立的选自C6~C50的取代或未取代的芳基、C6~C50的取代或未取代的杂芳基、C10~C30的取代或未取代的稠环、C8~C30的取代或未取代的稠杂环中的一种。
优选为其结构式I如下面结构式Ⅱ、结构式Ⅲ所示的任意一种结构表示:
优选为Ar1、Ar2独立的选自C6~C18的取代或未取代的芳基、C6~C18的取代或未取代的杂芳基、C10~C22的取代或未取代的稠环、C8~C20的取代或未取代的稠杂环。
按照本发明,所述的取代的芳基、取代的五元杂环、取代的六元杂环、取代的稠杂环中,取代基独立的选自烷基、烷氧基、氨基、卤素、氰基、硝基、羟基或巯基。
最优选Ar1、Ar2独立的选自取代或未取代的苯基、萘基、蒽基、芘基、联苯基、三联苯基、茚基、吲哚基、吡啶基、呋喃基、噻吩基、二苯并噻吩基、二苯并呋喃基、喹啉基、异喹啉基、咔唑基、芴基或螺二芴基。
具体的,所述三芳胺类衍生物优选选自如下所示结构中的任意一种:
本发明还提供一种三芳胺类衍生物的制备方法,制备路线如下:
其中,Ar1、Ar2独立的选自C6~C50的取代或未取代的芳基、C6~C50的取代或未取代的杂芳基、C10~C30的取代或未取代的稠环、C8~C30的取代或未取代的稠杂环中的一种。
按照本发明,中间体A所示的化合物按照如下所示方法制备得到:
在氮气保护下,醋酸钯与三叔丁基膦为催化剂,叔丁醇钠为碱的情况下,将伯胺化合物与所示卤代物反应,得到仲胺中间体A。
按照本发明,中间体B所示的化合物按照如下所示方法制备得到:
在氮气保护下,醋酸钯与三叔丁基膦为催化剂,叔丁醇钠为碱的情况下,将中间体A与卤代联苯反应,得到中间体B。
按照本发明,结构式I所示的化合物按照如下所示方法制备得到:
在氮气保护下,醋酸钯与三叔丁基膦为催化剂,叔丁醇钠为碱的情况下,将中间体B与二苯并咔唑反应,得到目标产物I。
本发明对所述偶联反应没有特殊的限制,采用本领域技术人员所熟知的偶联反应即可,该制备方法简单,原料易得。
本发明还提供上述三芳胺类衍生物在有机发光器件中的应用,本发明的三芳胺类衍生物可以作为空穴传输材料在有机发光器件方面得到应用,所述有机电致发光器件包括阳极、阴极和有机物层,有机物层包含空穴注入层、空穴传输层、电子阻挡层、发光层、空穴阻挡层、电子传输层、电子注入层中的至少一层;所述有机物层中的至少一层含有上述所述的三芳胺类衍生物。所述三芳胺类衍生物具体可以作为制备有机电致发光器件的空穴传输层。采用的器件结构优选具体为:EML用作发光层物质,2-TNATA用作空穴注入层物质,所述的三芳胺类衍生物用作空穴传输层物质,用以制造有以下相同构造的有机发光器件:ITO/2-TNATA(80nm)/所述的三芳胺衍生物(30nm)/EML(30nm)/Alq3(30nm)/LiF(0.5nm)/Al(60nm)。本发明的有机发光器件是平面面板显示、平面发光体、照明用面发光OLED发光体、柔性发光体、复印机、打印机、LCD背光灯或计量机类的光源、显示板、标识等适合使用。
本发明对以下实施例中所采用的原料没有特别的限制,可以为市售产品或采用本领域技术人员所熟知的制备方法制备得到。
实施例1:
中间体A1的制备
将三叔丁基膦(4.4mL的1.0M的甲苯溶液,1.48g,0.05mmol)、醋酸钯(0.4g,1.83mmol)和叔丁醇钠(22.8g,238mmol)添加至苯胺(17.0g,183mmol)和溴苯(28.5g,183mmol)在脱气甲苯(500mL)中的溶液,并且将该混合物在回流下加热2小时。将该反应混合物冷却至室温,用甲苯稀释并且经由硅藻土过滤。将该滤液用水稀释,并用甲苯提取,并且合并有机相,将其在真空下进行蒸发。将该残余物经由硅胶进行过滤,并重结晶。得到中间体A1(24.7g,理论值80%)。质谱m/z:169.12(计算值:169.09)。理论元素含量(%)C12H11N:C,85.17;H,6.55;N,8.28实测元素含量(%):C,85.16;H,6.56;N,8.28。上述结果证实获得产物为目标产品。
中间体B1的制备
将三叔丁基膦(4.4mL的1.0M的甲苯溶液,1.48g,0.05mmol)、醋酸钯(0.4g,1.83mmol)和叔丁醇钠(22.8g,238mmol)添加至中间体A1(30.9g,183mmol)和3-溴-4’-碘-1,1’-联苯(65.5g,183mmol)在脱气甲苯(500mL)中的溶液,并且将该混合物在回流下加热2小时。将该反应混合物冷却至室温,用甲苯稀释并且经由硅藻土过滤。将该滤液用水稀释,并用甲苯提取,并且合并有机相,将其在真空下进行蒸发。将该残余物经由硅胶进行过滤,并重结晶。得到中间体B1(39.3g,理论值75%)。质谱m/z:399.02(计算值:399.06)。理论元素含量(%)C24H18BrN:C,72.01;H,4.53;Br,19.96;N,3.50实测元素含量(%):C,72.01;H,4.53;Br,19.95;N,3.51。上述结果证实获得产物为目标产品。
化合物TM1的制备
将三叔丁基膦(4.4mL的1.0M的甲苯溶液,1.48g,0.05mmol)、醋酸钯(0.4g,1.83mmol)和叔丁醇钠(22.8g,238mmol)添加至中间体B1(73.0g,183mmol)和7H-二苯并[c,g]咔唑(48.8g,183mmol)在脱气甲苯(500mL)中的溶液,并且将该混合物在回流下加热2小时。将该反应混合物冷却至室温,用甲苯稀释并且经由硅藻土过滤。将该滤液用水稀释,并用甲苯提取,并且合并有机相,将其在真空下进行蒸发。将该残余物经由硅胶进行过滤,并重结晶。得到目标产物化合物TM1(24.7g,理论值70%)。质谱m/z:586.27(计算值:586.24)。理论元素含量(%)C44H30N2:C,90.07;H,5.15;N,4.77实测元素含量(%):C,90.08;H,5.16;N,4.76。上述结果证实获得产物为目标产品。
实施例2:
将实施例1中溴苯换成等摩尔的1-溴化萘,其他步骤相同,得到化合物TM5。质谱m/z:636.27(计算值:636.26)。理论元素含量(%)C48H32N2:C,90.54;H,5.07;N,4.40实测元素含量(%):C,90.53;H,5.06;N,4.41。上述结果证实获得产物为目标产品。
实施例3:
将实施例1中溴苯换成等摩尔的9-溴化蒽,其他步骤相同,得到化合物TM9。质谱m/z:686.29(计算值:686.27)。理论元素含量(%)C52H34N2:C,90.93;H,4.99;N,4.08实测元素含量(%):C,90.96;H,4.97;N,4.07。上述结果证实获得产物为目标产品。
实施例4:
将实施例1中溴苯换成等摩尔的3-溴-9-苯基-9H-咔唑,其他步骤相同,得到化合物TM14。质谱m/z:751.29(计算值:751.30)。理论元素含量(%)C56H37N3:C,89.45;H,4.96;N,5.59实测元素含量(%):C,89.46;H,4.96;N,5.58。上述结果证实获得产物为目标产品。
实施例5:
将实施例1中溴苯换成等摩尔的2-溴-9,9-二甲基芴,其他步骤相同,得到化合物TM16。质谱m/z:702.29(计算值:702.30)。理论元素含量(%)C53H38N2:C,90.57;H,5.45;N,3.99实测元素含量(%):C,90.58;H,5.45;N,3.98。上述结果证实获得产物为目标产品。
实施例6:
将实施例1中3-溴-4’-碘-1,1’-联苯换成等摩尔的3-溴-3’-碘-1,1’-联苯,其他步骤相同,得到化合物TM19。质谱m/z:586.27(计算值:586.24)。理论元素含量(%)C44H30N2:C,90.07;H,5.15;N,4.77实测元素含量(%):C,90.08;H,5.16;N,4.76。上述结果证实获得产物为目标产品。
实施例7:
将实施例1中溴苯换成等摩尔的2-溴-9,9-二甲基芴,3-溴-4’-碘-1,1’-联苯换成等摩尔的3-溴-3’-碘-1,1’-联苯,其他步骤相同,得到化合物TM34。质谱m/z:702.29(计算值:702.30)。理论元素含量(%)C53H38N2:C,90.57;H,5.45;N,3.99实测元素含量(%):C,90.58;H,5.45;N,3.98。上述结果证实获得产物为目标产品。
实施例8:
将实施例1中溴苯换成等摩尔的2-溴-9,9-二苯基芴,其他步骤相同,得到化合物TM50。质谱m/z:876.39(计算值:876.35)。理论元素含量(%)C67H44N2:C,91.75;H,5.06;N,3.19实测元素含量(%):C,91.75;H,5.07;N,3.18。上述结果证实获得产物为目标产品。
实施例9:
将实施例1中溴苯换成等摩尔的2-溴-9,9-螺二芴,3-溴-4’-碘-1,1’-联苯换成等摩尔的3-溴-3’-碘-1,1’-联苯,其他步骤相同,得到化合物TM69。质谱m/z:874.39(计算值:874.33)。理论元素含量(%)C67H42N2:C,91.96;H,4.84;N,3.20实测元素含量(%):C,91.96;H,4.82;N,3.22。上述结果证实获得产物为目标产品。
实施例10:
将实施例1中溴苯换成等摩尔的3-溴-9-苯基-9H-咔唑,苯胺换成等摩尔的3-氨基-9-苯基-9H-咔唑,其他步骤相同,得到化合物TM86。质谱m/z:916.35(计算值:916.36)。理论元素含量(%)C68H44N4:C,89.06;H,4.84;N,6.11实测元素含量(%):C,89.05;H,4.82;N,6.13。上述结果证实获得产物为目标产品。
实施例11:
将实施例1中溴苯换成等摩尔的3-溴-9-苯基-9H-咔唑,苯胺换成等摩尔的3-氨基-9-苯基-9H-咔唑,其他步骤相同,得到化合物TM86。质谱m/z:916.35(计算值:916.36)。理论元素含量(%)C68H44N4:C,89.06;H,4.84;N,6.11实测元素含量(%):C,89.05;H,4.82;N,6.13。上述结果证实获得产物为目标产品。
实施例12:
将实施例1中溴苯换成等摩尔的2-溴-9,9-二甲基芴,苯胺换成等摩尔的3-氨基吡啶,其他步骤相同,得到化合物TM126。质谱m/z:703.35(计算值:703.30。理论元素含量(%)C52H37N3:C,88.73;H,5.30;N,5.97实测元素含量(%):C,88.73;H,5.31;N,5.96。上述结果证实获得产物为目标产品。
对比应用实施例
将费希尔公司涂层厚度为的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。
将已经准备好的ITO透明电极上蒸镀空穴注入层2-TNATA/蒸镀空穴传输层a-NPD/蒸镀发光层AND和掺杂物质DPAP-DPPA(5%)/然后蒸镀空穴阻挡层及空穴传输层TPBi/阴极LiF/Al/上述过程有机物蒸镀速度是保持LiF是Al是
应用实施例:
将所述的三芳胺类衍生物代替α-NPD作为空穴传输层中的化合物,用和上述对比应用实施例中同样的方法制造了拥有如下结构的有机发光器件:ITO/2-TNATA/实施例合成的三芳胺类化合物/AND:DPAP-DPPA(5%)/TPBi//LiF/Al
评价例1:比较对比应用实施例及应用实施例发光特性评价
将如以上这样制作的有机发光器件通过直流电流驱动使其发光,测定亮度、电流密度,求出电流密度10mA/cm2时的发光效率和驱动电压。进一步求出初始亮度20000cd/m2时的器件寿命。对结果以下表1的形式展现。
表1
以上结果表明,本发明的三芳胺类衍生物应用于有机电致发光器件中,尤其是作为空穴传输材料,表现出低驱动电压、高发光效率、长寿命的优点,是性能良好的有机发光材料。
显然,以上实施例的说明只是用于帮助理解本发明的方法及其核心思想。应当指出,对于所述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,还可以对本发明进行若干改进和修饰,这些改进和修饰也落入本发明权利要求的保护范围内。
Claims (9)
1.一种三芳胺类衍生物,其特征在于,结构式如式I所示:
其中,Ar1、Ar2独立的选自C6~C50的取代或未取代的芳基、C6~C50的取代或未取代的杂芳基、C10~C30的取代或未取代的稠环、C8~C30的取代或未取代的稠杂环中的一种。
2.根据权利要求1所述的一种三芳胺类衍生物,其特征在于,其结构式I如下面结构式Ⅱ、结构式Ⅲ所示的任意一种结构表示:
3.根据权利要求1所述的一种三芳胺类衍生物,其特征在于,Ar1、Ar2独立的选自C6~C18的取代或未取代的芳基、C6~C18的取代或未取代的杂芳基、C10~C22的取代或未取代的稠环、C8~C20的取代或未取代的稠杂环。
4.根据权利要求1所述的一种三芳胺胺类衍生物,其特征在于,Ar1、Ar2独立的选自取代或未取代的苯基、萘基、蒽基、芘基、联苯基、三联苯基、茚基、吲哚基、吡啶基、呋喃基、噻吩基、二苯并噻吩基、二苯并呋喃基、喹啉基、异喹啉基、咔唑基、芴基或螺二芴基。
5.根据权利要求1所述的一种三芳胺胺类衍生物,其特征在于,所述芳香族胺类衍生物选自如下所示结构中的任意一种:
6.权利要求1-5任一项所述的一种三芳胺类衍生物的制备方法,其特征在于,通过如下路线合成得到所述一种三芳胺类衍生物:
其中,Ar1、Ar2独立的选自C6~C50的取代或未取代的芳基、C6~C50的取代或未取代的杂芳基、C10~C30的取代或未取代的稠环、C8~C30的取代或未取代的稠杂环中的一种。
7.一种有机发光器件,其特征在于,所述有机发光器件包括阴极、阳极和置于所述两电极之间的一个或多个有机化合物层,所述的有机化合物层含有权利要求1-5任一项所述的一种三芳胺类衍生物。
8.根据权利要求7中所述的一种有机发光器件,其特征在于,所述有机化合物层包括空穴注入层、空穴传输层,电子阻挡层、发光层、空穴阻挡层、电子传输层、电子注入层中的至少一层;所述有机化合物层中至少一层含有权利要求1-5任一项所述的一种三芳胺类衍生物。
9.根据权利要求8中所述的一种有机发光器件,其特征在于,空穴传输层中含有权利要求书1-5中所述的一种三芳胺类衍生物。
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