WO2015085727A1 - 葸类化合物、其制备方法及其应用、有机电致发光器件 - Google Patents

葸类化合物、其制备方法及其应用、有机电致发光器件 Download PDF

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WO2015085727A1
WO2015085727A1 PCT/CN2014/078780 CN2014078780W WO2015085727A1 WO 2015085727 A1 WO2015085727 A1 WO 2015085727A1 CN 2014078780 W CN2014078780 W CN 2014078780W WO 2015085727 A1 WO2015085727 A1 WO 2015085727A1
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acid
group
compound
reaction
organic electroluminescent
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PCT/CN2014/078780
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French (fr)
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李彦松
马晓宇
王辉
李娜
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京东方科技集团股份有限公司
吉林奥来德光电材料股份有限公司
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Priority to US14/416,794 priority Critical patent/US20150376085A1/en
Publication of WO2015085727A1 publication Critical patent/WO2015085727A1/zh

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Definitions

  • the organic material layer may comprise a different multilayer structure to increase the efficiency and stability of the formed organic electroluminescent device.
  • the organic material layer may include a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and the like.
  • the luminescent material emits several kinds of light such as blue, green, red and yellow.
  • other luminescent materials having a higher quantum yield may be added to the luminescent layer.
  • an exciton has a material that transfers its energy to a material having a smaller band gap in a material that is closer to the recombination site.
  • the dopant is selected from materials having a higher quantum yield and a smaller band gap (larger wavelength) than the host material; otherwise, the energy of the excitons will be transferred to the host material with a lower quantum yield, and Therefore, a weak emission or no emission is generated.
  • a stable and efficient material can be used as the organic material layer in the organic electroluminescent device, that is, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron. Inject layers, etc.
  • a hole injection layer a hole transport layer
  • a light emitting layer a hole transport layer
  • an electron transport layer a light emitting layer
  • an electron transport layer a light emitting layer
  • an electron transport layer an electron transport layer
  • the present invention introduces an aromatic having high efficiency and good thermal stability on the crucible, thereby improving the luminous efficiency and stability of the material. It is an object of the present invention to provide an anthraquinone compound, a preparation method and use thereof, and to provide a novel, highly efficient organic electroluminescent material.
  • the technical scheme of the present invention is as follows: An anthraquinone compound is represented by the following molecular formula:
  • the R group is selected from an aromatic group consisting of 6 to 19 carbon atoms, a fused ring aryl group, a heterocyclic aryl group or a substituted heterocyclic aryl group.
  • the R group is selected from a phenyl group, a biphenyl group, a naphthyl group, a quinolyl group, a phenanthryl group, a pyridyl group, a phenalkenyl group, a 9,9-dimethylhydrazine group composed of 6 to 50 atoms, Terphenyl, fluorenyl, aromatic amino, carbazolyl, benzothiazolyl, thienyl, aromatic amino, heterocyclic aryl, substituted Heterocyclic aryl or aniline.
  • the hydrazine compound is represented by any of the following structural formulas:
  • Step S2 Then adding a catalyst, raising the reaction temperature to 701: and refluxing, and fully reacting;
  • Step S3 purifying by extraction, washing, drying, column chromatography to obtain the quinone compound, wherein the R group is selected from 6 ⁇ An aromatic group consisting of 19 carbon atoms, a fused ring aryl group, a heterocyclic aryl group or a substituted heterocyclic aryl group.
  • the step S1 Prepared by 9,10- ⁇
  • step S1 2-bromo 6-benzoquinone and 9,10-indole are used as raw materials, and after alcoholization, dehydration, and bromination: less
  • Step N1 deaeration of the reaction vessel, adding 2-bromo-6-benzoquinone, tetrahydrogen step ⁇ 2 to the reaction vessel: cooling the reaction system, adding n-BuLi;
  • Step N3 adding the 9,10- ⁇
  • Step N 4 Raise the reaction temperature to room temperature, and fully react with NH 4 C1 to terminate;
  • Step N5 After extraction, washing, drying Step N6: adding potassium iodide, dihydrogen phosphate, glacial acetic acid for dehydration reaction
  • the specific step R is obtained, and the R-based boric acid is selected from the group consisting of phenylboronic acid, 4-biphenylboronic acid, 2- Naphthylboronic acid, 8-quinoline boric acid, 9 phenanthronic acid, 4 1 -pyridylboronic acid, phenalenylboronic acid, 4-(4-pyridyl)phenylboronic acid. 9, 9-dimethylmercaptoboric acid, 3, 5-diphenylphenylboronic acid or 9-indoleboronic acid or 2-benzothiazolylboronic acid.
  • the quinone compound of the present invention can be used as a fluorescent host material in an organic electroluminescent device. Specifically, the quinone compound is used as a fluorescent green host in an organic electroluminescent device.
  • the quinone compound provided by the present invention has high luminous efficiency.
  • the high luminous efficiency indicates that the compound can be used as a luminescent material or a luminescent host material, and particularly as a fluorescent host material.
  • the quinone compound also has a high glass transition temperature and has the advantage of being difficult to crystallize, and exhibits high efficiency, high brightness, long life, and better charge transport capability in an organic electroluminescent device.
  • the quinone compound can extend the life of the organic electroluminescent device and reduce the manufacturing cost of the organic electroluminescent device by fabricating the organic electroluminescent device.
  • R group is selected from an aromatic group consisting of 6 to 19 carbon atoms, a fused ring aryl group, a heterocyclic aryl group or a substituted heterocyclic aryl group.
  • the R group is selected from the group consisting of a phenyl group of 6 to 50 atoms, a biphenyl group, a naphthyl group, a quinolyl group, a phenanthryl group, a pyridyl group, a phenalkenyl group, a 9, 9-dimethyl fluorenyl group, Terphenyl, fluorenyl, Aromatic amino, carbazolyl, benzothiazolyl, porphinyl, aromatic amino, heterocyclic aryl, substituted heteroaryl or aniline.
  • anthraquinone compound is represented by one of the structural formulas 1 in Table 1.
  • the preparation method of the quinone compound provided by the invention comprises the following steps: Step S1 : degassing the reaction vessel to the reaction Step S2 : then adding a catalyst, raising the reaction temperature to 70 Torr and refluxing, and fully reacting; Step S3: purifying by extraction, washing, drying, column chromatography to obtain the quinone compound, wherein the R group is selected from 6 to 19 An aromatic group consisting of a carbon atom, a fused ring aryl group, a heterocyclic aryl group or a substituted heterocyclic aryl group.
  • the 2-bromo 6-benzoquinone, 9, 0-oxime in the step S] is obtained as a raw material, and is obtained by a multi-step reaction such as alcoholization, dehydration, bromination, etc., which comprises the following steps: Step N1: Pair reaction The vessel is degassed, and 2 bromo-6-benzoquinone or tetrahydrofuran is added to the reaction vessel;
  • Step N2 cooling the reaction system, adding 11-BuLi;
  • Step N3 adding the 9,10- ⁇
  • Step N4 Raise the reaction temperature to room temperature, and fully react with NH 4 C1 to terminate;
  • Step N5 Purification by extraction, washing, drying and column chromatography
  • Step N6 Add potassium iodide
  • Step N7 Force [Bromo bromine after bromination to obtain the step SI
  • the R-based boric acid is selected from the group consisting of phenylboronic acid, 4-biphenylboronic acid, 2-naphthylboronic acid, 8-quinolinylboronic acid, 9-phenanthronic acid, 44!pyridylboronic acid, phenalenylboronic acid, 4-(4-pyridyl)phenylboronic acid, 9,9-dimethylmercaptoboronic acid, 3,5-diphenylphenylboronic acid or 9-indoleboronic acid or 2benzothiazolylboronic acid.
  • the reduced pressure and pressure are filtered through the filter to obtain the crude product of the target compound, and the) 3 ⁇ 43 ⁇ 4 distilled distilled water is washed and washed three times three times, and then used with C.
  • Acetone ketone, methyl ketone benzene, TTHHFF heavy recrystallized crystals are obtained by solid phase solidification and then raised to Huahua fine refining treatment, and ⁇ benzene benzene is heavily recrystallized, and a pale yellowish color is obtained.
  • the solid-solid target is a standardized compound [[88]] 5500..5522gg, and the yield is 7788%%. .
  • the preparation process of the terpenoids represented by Structural Formulas 1 to 12 in Table 1 is substantially the same, and will not be further described herein, and only the specific results thereof are shown in Table 2. Further, in the process of preparing the terpenoid compound of the present invention, the amount of each substance added can be determined according to the ratio of each substance in the above embodiment, and the present invention focuses on the description of the process, and the amount of each substance added will not be described.
  • test value is C: 94,92%; H: 5.08%;
  • i is calculated as C: 94,85%; H: 5.15%;
  • test value is C: 94,84%; H: 5.16%;
  • Test value is 95.09%; H: 4.91%;
  • i is calculated as C: 90, 73%; H: 4, 57%; N: 4.70%;
  • i ⁇ 95.21%; H-4.79%;
  • i is calculated as C: 90, 85%; H: 4.82%; N: 4.33%;
  • test value is C: 94, 31%; H: 5, 69%;
  • i is calculated as C: 81.03%; H: 3.81%; N: 4.61%; S: 10, 55%;
  • the following compound a is used as a fluorescent green host material, c as a fluorescent green doping material, 2-TNATA as a hole injecting layer material, a-NPD (N,N'-dinaphthyl-anthracene, anthracene-diphenylene linkage) Aniline:)
  • a-NPD N,N'-dinaphthyl-anthracene, anthracene-diphenylene linkage
  • Aniline As a material for the hole transport layer, an organic electroluminescent device of the following structure was fabricated.
  • iTO/2-TNATA 80 nm) / a-NPD (30 nrn) / compound a + compound c (30 nm) / A] [q 3 (30 nm) / LiF (0.5 nm) / A! (60 nm).
  • the anode was a 15 ⁇ / ⁇ 2 (1000 ⁇ ) ⁇ glass substrate, cut to a size of 50 mm x 50 mm x 0.7 mm, then ultrasonically cleaned in acetone, isopropanol and purified water for 15 minutes, and washed with UV ozone for 30 minutes.
  • a hole injection layer having a thickness of 80 nm was formed by vacuum coating 2-TANATA on the substrate.
  • a hole transport layer was formed by vacuum-coating a-NPD at a thickness of 30 nm on the hole injection layer.
  • Compound a and Compound c (3% coating) were vacuum-coated on the hole transport layer to form a light-emitting layer having a thickness of 30 nm.
  • Comparative Example 1 and the organic electroluminescent devices obtained in Examples 1 to 12 were measured. Light source luminance, luminous efficiency, and luminescent color were evaluated using a source measuring unit Keithl ey SMU235. Comparative Example 1 and the organic electroluminescent devices obtained in Examples 1 to 12 were subjected to the same test, and the results are shown in Table 3. / ⁇ - Fork wavelength number host compound doping compound

Abstract

本发明公开了一种葸类化合物、其制备方法及其应用和包含该葸类化合物的有机电致发光器件。该葸类化合物由分子结构通式（I）表示。其中，R基团选自由6～19个碳原子构成的芳香基、稠环芳基、杂环芳基或取代的杂环芳基。该葸类化合物具有良好的热稳定性，是一种高效率、长寿命的材料。

Description

其应 ffi。
Figure imgf000002_0001
的分子发光，
利用单线态激子的荧光; 另一组， 由利用三线态激子的 光物质组
Figure imgf000002_0002
Figure imgf000002_0003
。 就这一点而言， 有机材料层可包含由不同 ；的多层结 构以提高所形成的有机电致发光器件的效率和稳定性。 例如， 有机材料层可 包含空穴注入层、 空穴传输层、 发光层、 电子传输层、 电子注入层等。
发光材料可发出蓝色、 绿色、 红色和黄色等几种光。 为提高发光层的发 光效率， 可在发光层中加入其他具有更高量子产量的发光材料。 已知激发子 具有将其能量转移给重新组合部位 ^近的材料中具有更小带隙的材料的倾 向。 因此， 掺杂剂选自比主材料具有更高的量子产量和更小的带隙 （更大的 波长） 的材料； 否则， 激发子的能量将转移至具有更低量子产量的主材料， 并因此产生弱的发射或者不发射。 为了有效发挥有机电致发光器件的优秀特征， 可以采用稳定有效率的材 料作为有机电致发光器件内的有机材料层， 即空穴注入层、 空穴传输层、 发 光层， 电子传输层、 电子注入层等。 但是至今没有理想的、 稳定高效率的有 机发光 料用于有机材料层， 新材料的研究势在必行。
发明内容
鉴于上述现有技术的不足， 本发明在蒽上引入高效率及热稳定性好的芳 香族， 提高了材料的发光效率及稳定性。 本发明的目的在于提供一种蒽类化 合物、 制备方法及其应用， 旨在提供一种新的、 高效的有机电致发光材料。 本发明的技术方案如下； 一种蒽类化合物， 由如下分子通式表示：
Figure imgf000003_0001
其中， R基团选自由 6~19个碳原子构成的芳香基、 稠环芳基、 杂环芳基 或取代杂环芳基。 具体地， R基团选自由 6〜50个原子构成的苯基、 联苯基、 萘基、 喹 啉基、 菲基、 吡啶基、 非那烯基、 9,9-二甲基芴基、 三联苯基、 蒽基、 芳香氨基、 咔唑基、 苯并噻唑基、 噻吩基、 芳香氨基、 杂环芳基、 取代 的杂环芳基或苯胺。 具悻的， 所述的蒽类化合物由如下任一结构式表示:
Figure imgf000004_0001
Figure imgf000004_0002
Figure imgf000005_0001
Figure imgf000005_0002
Figure imgf000005_0003
步骤 S2: 然后加入催化剂， 升高反应温度至 701：并回流， 充分反应； 步骤 S3 : 经萃取、 洗涤、 干燥、 柱层析纯化得到所述蒽类化合物， 其中， R基团选自由 6~19个碳原子构成的芳香基、 稠环芳基、 杂环芳基 或取代的杂环芳基。 具侔地， 所述步骤 S1中的
Figure imgf000006_0001
由 9,10-蒽醌制备
具体的，歩骤 S1中的 是以 2-溴 6-苯蒽、 9,10- 蒽醌为原料， 经过醇化、 脱水、 溴化 ：少
Figure imgf000006_0002
骤 N1: 对反应容器进行脱气， 向反应容器中加入 2-溴- 6-苯蒽、 四氢 步骤 Ν2: 对反应体系降温， 加入 n- BuLi;
步骤 N3: 加入所述 9,10-蒽醌；
步骤 N4: 升高反应温度至室温， 充分反应后加 NH4C1终止;
步 骤 N5 ： 经 萃 取 、 洗涤 、 千燥
Figure imgf000006_0003
步骤 N6: 加入碘化钾、 磷酸二氢铺、 冰醋酸进行脱水反应得到
Figure imgf000006_0004
(〜人人人 Jr、 、 人 j .人'、 少 3骤 N7: 加入溴水溴化后得到步骤 SI中的 具体的， R 基硼酸选自苯硼酸、 4-联苯基硼酸、 2-萘基硼酸、 8-喹啉塞 硼酸、 9菲基硼酸、 4 1比啶基硼酸、 非那烯基硼酸、 4-(4-吡啶基)苯基硼酸. 9， 9二甲基芴基硼酸、 3， 5-二苯基苯基硼酸或 9-蒽硼酸或 2-苯并噻唑基硼 酸。
本发明所述蒽类化合物可在有机电致发光器件中用作荧光主体材 具体地， 所述的蒽类化合物在有机电致发光器件中用作荧光绿色主
致发
Figure imgf000007_0001
电极之间的一个或多个有机化合物层， 至少一个所述有机化合物层包含 所述蒽类化合物。
本发明提供的蒽类化合物具有高的发光效率。 高的发光效率表明该化 合物可作为发光材料或发光主体材料， 尤其是可以作为荧光主体材料。 该蒽类化合物还具有高的玻璃化温度并— §不易结晶的优点， 用于有机电 致发光器件中表现出高效率、高亮度、长寿命以及更好的电荷传输能力。 该蒽类化合物 于制造有机电致发光器件可以延长有机电致发光器件的 寿命， 降低有机电致发光器件的制造成本。 了一种: :类化合物、玲 i 及其应) ¾， 为使本发明的目的、 技术方案及效果更加清楚、 明确， 以下对本发明进一歩详细说明。 应当理解， 描述的具体实施例仅仅用以解释本发明， 并不) ¾于限定本发明。
：发明提供了 - 种蒽类化合物由如下分子通式表示：
Figure imgf000007_0002
其中， R基团选自由 6~19个碳原子构成的芳香基、 稠环芳基、 杂环芳基 或取代的杂环芳基。
具体地， R基团选自 6~50个原子构成的苯基、 联苯基、 萘基、 喹 啉基、 菲基、 吡啶基、 非那烯基、 9， 9-二甲基芴基、 三联苯基、 蒽基、 芳香氨基、 咔唑基、 苯并噻唑基、 嚷吩基、 芳香氨基、 杂环芳基、 取代 的杂环芳基或苯胺。
更具体地， 该蒽类化合物由表 1中结构式 1 2中的一种表示。
Figure imgf000008_0001
Figure imgf000009_0001
Figure imgf000010_0001
本发明提供的蒽类化合物的制备方法， 包括如下步骤： 步骤 S1 : 对反应容器进行脱气 ， 向 反应
Figure imgf000011_0001
步骤 S2: 然后加入催化剂， 升高反应温度至 70Ό并回流， 充分反应； 步骤 S3 : 经萃取、 洗涤、 干燥、 柱层析纯化得到所述蒽类化合物， 其中， R基团选自由 6~19个碳原子构成的芳香基、 稠环芳基、 杂环芳基 或取代的杂环芳基。
Figure imgf000011_0002
具体的，步骤 S】中的 2-溴 6苯蒽、 9,】0- 蒽醌为原料， 经过醇化、 脱水、 溴化等多步反应得到的， 其包括如下歩 骤： 步骤 N1 : 对反应容器进行脱气， 向反应容器中加入 2溴- 6-苯蒽、 四氢 呋嚙；
步骤 N2; 对反应体系降温， 加入 11- BuLi;
步骤 N3 : 加入所述 9,10-蒽醌；
步骤 N4; 升高反应温度至室温， 充分反应后加 NH4C1终止；
步骤 N5 ： 经 萃 取 、 洗涤 、 干燥 、 柱 层 析 纯化 得 到
Figure imgf000011_0003
步骤 N6 : 加入碘化钾
Figure imgf000012_0001
步骤 N7: 力[ 溴水溴化后得到步骤 SI中的
Figure imgf000012_0002
具体的， R基硼酸选自苯硼酸、 4-联苯基硼酸、 2-萘基硼酸、 8-喹琳基 硼酸、 9-菲基硼酸、 44!比啶基硼酸、 非那烯基硼酸、 4- (4-吡啶基)苯基硼酸、 9， 9二甲基芴基硼酸、 3 , 5-二苯基苯基硼酸或 9-蒽硼酸或 2苯并噻唑基硼 酸。
为了更详尽的说明本发明中的制备方法， 以下以表 1中标号为 1
%、 1 1的蒽
Figure imgf000012_0003
为例进行描述。 其具钵的反应方程式如下式所示:
Figure imgf000013_0001
勿 [i- η的合成方法：
在氮气保护下， 向反应容器中加入 2-溴- 6苯蒽 （83.31g， 0,25mol) 、 THF (；四氢呋喃）250mL, 常温搅拌 10分钟。
2、 原料完全溶解后降温至- 72 Ό， 慢慢滴加 11- BuLi i 00mL。
3、低温反应 3h后，加入 9， 10-蒽醌（2L02g, 0.1mol)的 THF溶液 150mL。
4、 然后慢慢升温至常温， 搅摔 24b。 加入蒸馏水 500mL， NH4C1过饱和 溶液 500mL和二氯甲垸 500mL搅摔 2h。
5、 萃取有机层， 减压千燥。 此固体加 1L丙酮搅拌 lh后， 过滤， 减压浓 缩有机溶剂， 得出淡褐色固体 [1- 3]化合物 48,89g， 产率 68%。
6、 将 [1-3]化合物、 碘化钾 (l l ,62g, 0.07mol)， 、 辚酸二氢钠 (16.80 g, 0.14mol), 冰醋酸 200 mL 加入到反应容器中， 回流搅拌反应 20b。 反应结 束后冷却至室温， 加入 500mL 蒸馏水搅拌后减压抽滤。 固体加入 500mL NaHC03过饱和溶液中， 搅拌 30miii后减压抽滤， 用过饱和的 500mL NaCl 和 iL蒸馏水洗涤， 减压抽滤。得到深黄色固体， 室温下真空干燥后得出 [1-2] 化合物 40.63g, 产率 85%。
7、 氮气保护下向 2L烧瓶中加入化合物 [1 - 2](40„63g, 0.06mol) , 加 入 1L四氯化碳作溶剂， 加溴室温反应半小时。 用 TLC (薄膜色谱） 方法确 认反应结束后， 减压过滤， ^ 500mL丙酮搅拌。 减压过滤后得到淡绿色固体 目的化合物 [1- l] 49,72g, 产率 83%。
具体的， 结构式 1的化合物的合成方法：
Figure imgf000014_0001
11、、 在在氮氮气气保保护护下下，， 向向 22LL 反反应应釜釜中中加加入入化化合合物物 [[11-- ll]]((4499..7722gg ,, 00..0055mmooll))、、 苯苯硼硼酸酸（（2277..4433gg ,, 00..222255mmooll)) ,, KK22CC0033((3344..5555gg ,, 00,,2255mmooll))、、 甲甲 苯苯 550000mmLL搅搅拌拌。。
22、、 温温度度升升高高到到 7700°°CC时时，， 加加入入催催化化剂剂 PPdd((PPPPhh33))44 ((ll .. ii 66gg,, OO..OOOOllmmooll)) ,, 加加入入蒸蒸馏馏水水 7755mmLL搅搅摔摔 ll llhh。。 充充分分反反应应后后，， 加加 iiOOOOmmLL水水结结東東反反应应。。
33、、 减减压压过过滤滤得得到到目目标标化化合合物物粗粗产产品品，， 蒸蒸馏馏水水洗洗涤涤三三次次，， 然然后后用用 丙丙酮酮，， 甲甲苯苯，， TTHHFF重重结结晶晶得得到到固固体体再再升升华华精精制制处处理理，， 苯苯重重结结晶晶，， 得得到到 淡淡黄黄色色固固体体目目标标化化合合物物 [[ll]]3366..5533gg,, 产产率率 7744%%。。
Figure imgf000014_0002
Figure imgf000015_0001
Figure imgf000015_0002
1、 在氮气保护下， 向 2L 反应釜中加入化合物 [1- l](49.72g，
O.OSmol)
Figure imgf000015_0003
, 0,225mol), K2C03(34.55g,
00..2255mmooll)) ,, 甲甲苯苯 550000mmLL搅搅拌拌。。
22、、 温温度度升升高高到到 7700ΌΌ时时，， 加加入入催催化化剂剂 PPdd((PPPPllii33))44((ii..ll66gg,, OO..OOOOllmmooll)),, 加加入入蒸蒸馏馏水水 7755mmLL搅搅拌拌 iillhh。。 充充分分反反应应后后，， 加加 llOOOOmmLL水水结结束束反反应应。。
33、、 减减压压过过滤滤得得到到目目标标化化合合物物粗粗产产品品，， ））¾¾蒸蒸馏馏水水洗洗涤涤三三次次，， 然然后后用用 丙丙酮酮，， 甲甲苯苯，， TTHHFF重重结结晶晶得得到到固固体体再再升升华华精精制制处处理理，， ¥¥苯苯重重结结晶晶，， 得得到到 淡淡黄黄色色固固体体目目标标化化合合物物 [[88]]5500..5522gg，， 产产率率 7788%%。。
Figure imgf000015_0004
Figure imgf000016_0001
[11]
1、 在氮气保护下， 向 2L 反应釜中加入化合物 [1 l](49.72g， O.OSmol), 9蒽硼酸（49,96g， 0,225mol)， K2C03(34.55g, 0.25mo1), 甲 苯 500mL搅拌。
2、 温度升高到 70°C时， 加入催化剂 Pd(PPh3)4(l.i6g, O.OOlmol), 加入蒸馏水 75mL搅摔 llh。 充分反应后， 加 iOOmL水结東反应。
3、 减压过滤得到目标化合物粗产品， 蒸馏水洗涤三次， 然后用 丙酮， 甲苯， THF重结晶得到固体再升华精制处理， 苯重结晶， 得到 淡黄色固体目标化合物 [ll]52.71g, 产率 76%。
其中表 1中结构式 1〜12表示的蒽类化合物的制备过程基本相同， 在此不再一一赘述， 仅将其具体结果列于表 2中。 并且在制备本发明蒽 类化合物过程中， 添加各个物质的量， 可以根据上述实施例中各个物质 的比例进行确定， 本发明重点是描述工艺过程， 对添加各个物质的量不 再作 阐述。
Figure imgf000016_0002
Figure imgf000016_0003
测试值为 C: 94,92%； H: 5.08%；
i十算值为 C: 94,85%； H: 5.15%；
2
测试值为 C: 94,84%； H: 5.16%；
计算值为 C: 95,08%； H: 4,92%;
1187.47 测试值为 95.09%； H: 4.91%；
i十算值为 C: 90,73%； H: 4,57%; N: 4.70%;
4 1191.42 测试值为 C: 90.73%； H: 4.56%； N: 4.71%；
i†算值为 95.21%； H- 4.79%；
5 1387.70 测试值为 C: 95,21%； H: 4,79%;
计算值为 Cr 89.67%； H: 4.68%； N: 5.65%；
6 991.18 测试值为 C: 89,64%； H: 4,69%; N: 5.67%;
计算值为 C: 95,03%； H: 4,97%;
7 1339,66 测试值为 95.03%； H: 4.97%；
i十算值为 C: 90,85%； H: 4.82%； N: 4.33%;
8 1295.57 测试值为 Cr 90.84%； H: 4.81%； N: 4.35%；
i†算值为 94.31%； H- 5.69%；
9 寸
测试值为 C: 94,31%； H: 5,69%;
计算值为 Cr 94.82%； H: 5.18%； r、
10 1596,00 测试值为 C: 94,81%； H: 5.19%；
计算值为 C: 94,31%； H: 5,69%;
11 1387,70 测试值为 C: 94.32%； Η· 5.68%；
i十算值为 C: 81.03%； H: 3.81%； N: 4.61%； S: 10,55%；
12 1215.53 测试值为 C: 81.01%; H: 3.82%； N: 4.63%； S: 10.54%； 以下'内容以应用为荧光绿色主体村料为例， 进 -- 提供的蒽类化合物。
对 t匕样品 1
下面化合物 a用作荧光绿色主体材料， c作为荧光绿色掺杂材料， 2-TNATA 作为空穴注入层材料， a- NPD(N,N'-二萘基 - Ν,Ν'-二苯基联苯 胺：)作为空穴传输层材料使] ¾， 制作下面结构的有机电致发光器件。 iTO/2-TNATA(80nm)/a-NPD(30nrn)/化合物 a+化合物 c(30nm)/A][q3 (30nm)/LiF(0.5nm)/ A!(60nm)。
阳极是 15Ω/ ιι2 (1000 Α ) ΙΤΟ玻璃基板，按照 50mmx50mmx0.7mm大小 切割， 然后在丙酮、异丙醇和纯净水中超声波 15分钟清洗， 30分钟 UV臭氧 洗净使用。 在基板上面真空镀膜 2-TANATA形成 80nm厚度的空穴注入层。 在空穴注入层上真空镀膜 a- NPD 30nm厚度形成空穴传输层。 在空穴传输层 上真空镀膜化合物 a及化合物 c ( 3%涂料） ， 形成 30nm厚度的发光层。 之 后， 在发光层上真空镀膜 Alq3 30nm厚度形成电子传输层。 在电子传输层上 面， 在依次真空镀膜 LiF 0.5nm (电子注入层） 和 Al 60nm (阴极） 。
Figure imgf000018_0001
a b
实施例 1〜12 :
将对比样品 1中的荧光绿色主体材料用表 1中结构式 1 ~12表示的蒽 类化合物替代原化合物 ， 其余的处理工艺以及条件均相同， 制得有机电 致发光器件 〜 12。
测量对比样品 1 以及实施例 1〜12所得有机电致发光器件的发光性 能。 采用源测量单元 Keithley SMU235， 评价发光亮度， 发光效率， 发 光颜色。 对比样品 1 以及实施例 1〜12所得有机电致发光器件进行同样 的试验， 结果列于表 3中。 /又儿 - 叉 波长 编号 主体化合物掺杂化合物
[cd/m2] [cd/A] [nm] 对比样品 a b 2032 20.3 51 6 实施例 1 1 b 2538 25.4 516 实施例 2 ■2 b 3140 31 ,4 519 实施例 3 3 b 3029 29.3 521 实施例 4 4 b 2942 2.9,4 518 实施例 5 5 b 3001 21 ,4 523 实施例 6 6 b 3155 23.6 520 实施例 Ί 7 b 2736 27,4 512 实施例 8 8 b 2828 28.3 51 8 实施例 9 9 b 2756 26.6 521 实施例 10 10 b 2967 27,7 519 实施例 1 1 1 1 b 2934 28.3 512 实施例 12 12 b 2595 26,0 524 如表 3所示， 上述样品都在 512〜524nm波长范围内显示发光颜色为绿色。 实施例 1〜12所得有机电致发光器件与对比样品 1相比有显著提高的发光特 性。
虽然本发明用示范性实施方案进行了特别的描述和图示， 但应该理 解在不偏离下列权利要求所限定的本发明的精神与范围的情况下， 本领 域普通技术人员可对其进行各种形式和细节上的改变。
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， 还可以做出若千改进和润 饰， 这些改进和润饰也应视本发明的保护范围。

Claims

一 由如下分子结构通式表示
Figure imgf000020_0001
其中， R基团选自由 6~19个碳原子构成的芳香基、 稠环芳基、 杂环芳基 或取代的杂环芳基。
2、 根据权利要求 1所述的蒽类化合物， 其特征在于， 所述 R基团选 自 Eil 6~50个原子构成的苯基、 联苯基、 萘基、 喹 1 基、 菲基、 吡啶基、 非那烯基、 9,9-二甲基芴基、 三联苯基、 蒽基、 芳香氨基、 ^唑基、 苯 并噻唑基、 噻吩基、 芳香氨基、 杂环芳基、 取代的杂环芳基或苯胺。
3、 根据权利要求 1 所述的蒽类化合物， 其特征在于， 所述蒽类化 合物选自如下任一种：
Figure imgf000020_0002
Figure imgf000021_0001
4、 根据权利要求 i〜3任一项所述的蒽类化合物在有机电致发光器 件中的应用， 其特征在于， 所述的蔥类化合物在所述有机电致发光器件 中用作荧光主体材料、 空穴注入材料或者空穴传输材料。 5、 根据权利要求 4 的应用， 其特征在于， 所述的蒽类化合物在所 述有机电致发光器件中 ffi作荧光绿色主体材料。
6、 一种有机电致发光器件， 包括第一电极、 第二电极和置于所述 两电极之间的一个或多个有机化合物层， 其特征在于， 至少一个有机化 合物层包含如权利要求】〜'3中任一项所述蒽类化合 要求 1所述的蒽类化合物的制备方法， 包括如下步骤: 步骤 S i ： 对反应容器进行脱气 ， 向 反应容器 中 加入
Figure imgf000022_0001
R基硼酸、 碳酸钾和甲苯; 步骤 S2: 然后加入催化剂， 升高反应温度至 70Ό并回流， 充分反应； 步骤 S3 : 经萃取、 洗涤、 千燥、 柱层析纯化得到所述蔥类化合物， 其中， R基团选自由 6〜19个碳原子构成的芳香基、 稠环芳基、 杂环芳基 的杂环芳基。
8、 根据权利要求 7所述的制备方法， 其特征在于， 所述歩骤 S 1中
备而成 , 其特征在于， 所述步骤 S1 中的
Figure imgf000022_0002
是以 2溴- 6-苯蒽、 9,10-蒽醌为原料， 经过醇化 脱水、 溴化等多步反应得到的
Figure imgf000022_0003
Figure imgf000022_0004
容器进行脱气， 向反应容器中加入 2-溴- 6-苯蒽、 四氢 呋喃； 步骤 N2: 对反应体系降温， 加入 n-BuLi;
步骤 N3 : 加入所述 9,10-蒽醌；
步骤 N4: 升高反应温度至室温， 充分反应后加 ΝΗ4α终止；
步骤 Ν5 ： 经 萃 取 、 洗涤 、 干燥 、 柱层 析纯 化 得 到
Figure imgf000023_0001
步骤 Ν7: 加入溴水溴化后得到步骤 S1中的
Figure imgf000023_0002
10. 根据权利要求 7所述的制备方法， 其特征在于， 所述 R基硼酸选自 苯硼酸、 4-联苯基硼酸、 2-萘基硼酸、 8-喹啦基硼酸、 9菲基硼酸、 4咄啶 基硼酸、 非那烯基硼酸、 4 (44ί比啶基)-苯基硼酸、 9， 9-二甲基芴基硼酸、 3， 5—二苯基苯基硼酸或 9-蒽硼酸或 2-苯并噻唑基硼酸。
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