Oxo spirobifluorene substituted arylamine compound and application thereof

Abstract

The invention relates to the technical field of organic light-emitting display, in particular to an oxospirobifluorene substituted arylamine compound and application thereof. The present invention provides a compound of formula (I) which can be used in hole transport materials. The compound has a parent structure of oxospirobifluorene substituted arylamine, has high bond energy between atoms and good thermal stability, is beneficial to solid-state accumulation between molecules, has strong hole transition ability, and can effectively reduce the voltage of a device and prolong the service life of the material when being used as a hole transport material and a light-emitting auxiliary layer material. The invention also provides an organic electroluminescent device and a display device containing the compound shown in the formula (I).

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of organic light-emitting display, in particular to a compound of oxaspirofluorene substituted arylamine and application thereof. BACKGROUND

[0002] Electroluminescence (EL) refers to the phenomenon that a luminescent material emits light under the action of an electric field, which is a luminescent process of directly converting electric energy into light energy. An organic electroluminescent display (hereinafter referred to as OLED) has a series of advantages such as self-luminescence, low-voltage direct-current driving, full solidification, wide viewing angle, light weight, simple composition and process, etc. Compared with liquid crystal displays, the organic electroluminescent display does not need a backlight source, has a wide viewing angle, low power consumption, and the response speed can reach 1000 times of that of a liquid crystal display, and the manufacturing cost is lower than that of a liquid crystal display with the same resolution. Therefore, the organic electroluminescent device has a very broad application prospect.

[0003] With the continuous advancement of OLED technology in the fields of lighting and display, people pay more attention to the research on high-efficiency organic materials affecting the performance of OLED devices. An organic electroluminescent device with high efficiency and long service life is usually the result of the optimization of the device structure and the optimization of various organic materials, which provides great opportunities and challenges for the design and development of functional materials with various structures for those skilled in the art.

[0004] Compared with inorganic luminescent materials, organic electroluminescent materials have many advantages, such as: good processing performance, can be formed into a film on any substrate by evaporation or spin coating method, can realize flexible display and large-area display; the optical properties, electrical properties and stability of the material can be adjusted by changing the structure of the molecule, and the selection of the material has a large space. In the most common OLED device structure, the following kinds of organic materials are usually included: hole injection material, hole transport material, electron transport material, and various luminescent materials (dye or doped guest material) and corresponding host material, etc. Among them, the hole transport material as an important functional material has a direct influence on the hole mobility, and ultimately affects the light-emitting efficiency of the OLED. However, the hole transport material currently applied in the OLED has a low hole mobility, a poor energy level matching with the adjacent layer, and cannot balance the efficiency and the service life, which seriously restricts the display function and development of the OLED display device. SUMMARY

[0005] In view of the deficiencies of the prior art, the purpose of the present application is to provide a compound of oxaspirofluorene substituted arylamine and application thereof, which can be used as a hole transport material, and can realize the improvement of the working efficiency and the prolongation of the service life of the organic electroluminescent device.

[0006] To achieve the above object, the technical scheme adopted is as follows:

[0007] The first aspect of the present application aims to provide an oxaspirobifluorene-substituted arylamine compound having a structure as shown in formula (I):

[0008]

[0009] R 1 -R 8 are independently selected from hydrogen, deuterium, O, S, N, C1-C4 alkyl, C3-C6 cycloalkane, substituted and unsubstituted C6-C 30 aromatic group, which can be connected into a ring between adjacent substituents;

[0010] L1, L2 are independently selected from a chemical bond, substituted and unsubstituted C6-C 30 aromatic group, substituted and unsubstituted C5-C 30 heteroaromatic group;

[0011] R 9 , R 10 are independently selected from hydrogen, deuterium, substituted and unsubstituted C6-C 30 aromatic group, substituted and unsubstituted C5-C 30 heteroaromatic group;

[0012] Ar1 is selected from substituted and unsubstituted C6-C 30 aromatic group, substituted and unsubstituted C5-C 30 heteroaromatic group;

[0013] the heteroatoms on the heteroaromatic group are each independently selected from O, S, N;

[0014] the hydrogen atoms on the aromatic group and heteroaromatic group can each independently be substituted with Ra, Ra is independently selected from deuterium, halogen, nitro, cyano, C1-C4 alkyl, C5-C 20 cycloalkyl, phenyl, biphenyl, terphenyl, naphthyl.

[0015] Preferably, L1, L2 are independently selected from a chemical bond, unsubstituted and substituted with Ra the following groups: phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, triphenylene, fluorenyl, dibenzofuranyl, dibenzothiophenyl, 9,9-dimethylfluorenyl, spirofluorenyl.

[0016] Preferably, R 1 -R 8independently of one another selected from the group consisting of hydrogen, deuterium, hydroxyl, thiol, methyl, ethyl, isopropyl, tert-butyl, cyclopentyl, cyclohexyl, the following radicals which are unsubstituted and substituted with Ra: phenyl, biphenyl, naphthyl, phenanthryl, fluorenyl, dibenzofuranyl, dibenzothiophenyl, carbazolyl, anilino.

[0017] Preferably, R 9 , R 10 independently of one another selected from the group consisting of hydrogen, deuterium, the following radicals which are unsubstituted and substituted with Ra: phenyl, biphenyl, triphenyl, naphthyl, phenanthryl, triphenylenyl, fluorenyl, dibenzofuranyl, dibenzothiophenyl, 9,9-dimethylfluorenyl, spirofluorenyl.

[0018] Preferably, Ar1is selected from the group consisting of the following radicals which are unsubstituted and substituted with Ra: phenyl, biphenyl, triphenyl, naphthyl, phenanthryl, triphenylenyl, fluorenyl, benzofuranyl, dibenzofuranyl, benzothiophenyl, dibenzothiophenyl, 9,9-dimethylfluorenyl, spirofluorenyl, arylanilino, carbazolyl.

[0019] More preferably, the oxygen-spiro-bifluorene-substituted arylanilino compound is selected from the group consisting of compounds A1 to A20:

[0020]

[0021] The second object of the present application is to provide a hole transport material comprising at least one of the oxygen-spiro-bifluorene-substituted arylanilino compounds described above.

[0022] The third object of the present application is to provide an organic electroluminescent device comprising at least one of the hole transport materials described above.

[0023] The fourth object of the present application is to provide a display device comprising the organic electroluminescent device described above.

[0024] Compared with the prior art, the present application has the following advantages:

[0025] The compounds disclosed in the present application have the parent structure of oxygen-spiro-bifluorene-substituted arylanilino, high bond energy between atoms, good thermal stability, and favorable solid-state packing between molecules, strong hole transition ability, and can effectively reduce the device voltage and improve the service life of the material when used as a hole transport layer material;

[0026] The compounds described in the present application, when applied in a hole transport layer, have suitable energy level between adjacent layers, which is conducive to the injection and migration of holes, can effectively reduce the driving voltage, and at the same time, the high hole migration rate can achieve good luminous efficiency in the device. The compounds of the present application have a large conjugated plane, which is conducive to molecular packing and exhibits good thermodynamic stability, and exhibits long service life in the device.

[0027] Meanwhile, the preparation process of the compound is simple and easy to operate, raw materials are easy to obtain, and is suitable for industrial production. BRIEF DESCRIPTION OF DRAWINGS

[0028] In order to more clearly illustrate the technical solutions in the embodiments of the present application or the prior art, the following will briefly introduce the drawings needed to be used in the embodiments or prior art description. Obviously, the drawings in the following description are only one embodiment of the present application, and other embodiments can also be obtained by those skilled in the art based on these drawings.

[0029] Figure 1 It is a schematic diagram of the structure of a typical organic electroluminescent device.

[0030] The figure mark explanation: 1, substrate; 2, reflective anode electrode; 3, hole injection layer; 4, hole transport layer; 5, light emitting layer; 6, electron transport layer; 7, electron injection layer; 8, cathode electrode. DETAILED DESCRIPTION

[0031] The technical solutions in the present application will be described clearly and completely below in combination with the drawings. Obviously, the described embodiments are only part of the embodiments of the present application, rather than all the embodiments. All other embodiments obtained by those skilled in the art based on the embodiments in the present application belong to the scope of protection of the present application.

[0032] In the present application, the type and structure of the organic electroluminescent device are not particularly limited, as long as the hole transport material provided by the present application can be used.

[0033] The organic electroluminescent device of the present application can be a light emitting device with a top light emitting structure, for example, sequentially containing an anode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and a transparent or semi-transparent cathode on a substrate.

[0034] The organic electroluminescent device of the present application can also be a light emitting device with a bottom light emitting structure, for example, sequentially containing a transparent or semi-transparent anode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and a cathode structure on a substrate.

[0035] The organic electroluminescent device of the present application can also be a light emitting device with a double-sided light emitting structure, for example, sequentially containing a transparent or semi-transparent anode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and a transparent or semi-transparent cathode structure on a substrate.

[0036] In the organic electroluminescent device of the present application, in addition to the hole transport layer containing the hole transport material provided by the present application, any material used in the layer in the prior art can be used for other layers.

[0037] Figure 1 A schematic diagram of a typical organic electroluminescent device is shown, in which, from bottom to top, a substrate 1, a reflective anode electrode 2, a hole injection layer 3, a hole transport layer 4, a light emitting layer 5, an electron transport layer 6, an electron injection layer 7, and a cathode electrode 8 are sequentially provided.

[0038] It can be understood that Figure 1 A structure of a typical organic electroluminescent device is only schematically shown, and the present application is not limited to this structure, and the hole transport material of the present application can be used in any type of organic electroluminescent device. For example, the organic electroluminescent device can further include an electron blocking layer, a hole blocking layer, a light extraction layer, etc., and in actual applications, these layers can be added or omitted according to specific circumstances.

[0039] For convenience, the following refers to Figure 1 The organic electroluminescent device of the present application is described, but this does not mean any limitation on the scope of protection of the present application. It can be understood that all organic electroluminescent devices capable of using the hole transport material of the present application are within the scope of protection of the present application.

[0040] In the present application, the substrate 1 is not particularly limited, and conventional substrates used in organic electroluminescent devices in the prior art can be used, for example, glass, polymeric materials, and glass and polymeric materials with TFT components, etc.

[0041] In the present application, the material of the reflective anode electrode 2 is not particularly limited, and can be selected from transparent conductive materials known in the prior art, such as indium tin oxide (ITO), indium zinc oxide (IZO), tin dioxide (SnO2), zinc oxide (ZnO), low-temperature polysilicon (LTPS), etc., can also be metal materials such as silver and its alloys, aluminum and its alloys, etc., can also be organic conductive materials such as PEDOT (poly 3,4-ethylenedioxythiophene), or a multilayer structure of the above materials, etc.

[0042] In the present application, the material of the hole injection layer 3 is not particularly limited, and can be selected from hole injection materials known in the art or hole transport materials provided by the present application as hole injection materials.

[0043] For example, the material of the hole injection layer 3 can be selected from at least one of the following HT-1 to HT-31 compounds:

[0044]

[0045]

[0046]

[0047] In the present application, the hole injection layer 3 can further include a p-type dopant, which is not particularly limited in kind, and various p-type dopants known in the art can be used. For example, the p-type dopant can be selected from at least one of the following compounds:

[0048]

[0049] In the present application, the amount of the p-type dopant is not particularly limited, and can be an amount known to those skilled in the art.

[0050] In the present application, the hole transport layer 4 includes at least one of the hole transport materials of the present application. The hole transport layer 4 can also include at least one of the hole transport materials of the present application in combination with any known hole transport material. The known hole transport material can be selected from at least one of the above-mentioned HT-1 to HT-31 compounds, but is not limited to the above-mentioned compounds.

[0051] In the present application, the light emitting material of the light emitting layer 5 is not particularly limited, and any light emitting material known to those skilled in the art can be used. For example, the light emitting material can include a host material and a guest material. For example, the known light emitting layer host material can be selected from at least one of the following BH-1 to BH-10 compounds:

[0052]

[0053] In the present application, the light emitting layer guest material is not particularly limited, and at least one of the light emitting layer guest materials known in the art can be used. For example, the light emitting layer guest material can be selected from, but is not limited to, at least one of the following BD-1 to BD-9 compounds:

[0054]

[0055]

[0056] In the present application, the material of the electron transport layer 6 is not particularly limited, and can be made of an electron transport material known in the art. For example, the material of the electron transport layer 6 can be selected from at least one of the following ET-1 to ET-57 compounds:

[0057]

[0058]

[0059]

[0060]

[0061] In the present application, the electron transport layer 6 can also include an n-type dopant, which is not particularly limited in kind and can be various n-type dopants known in the art. For example, the n-type dopant can be a compound represented by the following formula:

[0062]

[0063] In the present application, the amount of the n-type dopant is not particularly limited and can be an amount known to those skilled in the art.

[0064] In the present application, the material of the electron injection layer 7 is not particularly limited and can be an electron injection material known in the art, for example, can include but is not limited to at least one of LiQ, LiF, NaCl, CsF, Li2O, Cs2CO3, BaO, Na, Li, Ca, etc. materials in the prior art.

[0065] In the present application, the material of the cathode electrode 8 is not particularly limited, for example, can be selected from but not limited to magnesium silver mixture, LiF / Al, ITO, Al, etc. metals, metal mixtures, oxides, etc.

[0066] The display device provided by the present application comprises the organic electroluminescent device provided by the present application. The display device includes but is not limited to display, television, tablet computer, mobile communication terminal, etc.

[0067] The method for preparing the organic electroluminescent device of the present application is not particularly limited and can be any method known in the art, for example, the present application can be prepared by the following preparation method:

[0068] (1) cleaning the reflective anode electrode 2 on the top-emitting OLED device substrate 1, respectively through the steps of pickling, washing, brushing, high-pressure washing, air knife, etc. in a cleaning machine, and then heating treatment;

[0069] (2) vacuum evaporation of a hole injection material as a hole injection layer 3 on the reflective anode electrode 2;

[0070] (3) vacuum evaporation of a hole transport material as a hole transport layer 4 on the hole injection layer 3;

[0071] (4) vacuum evaporation of a light-emitting layer 5 containing a host material and a guest material on the hole transport layer 4;

[0072] (5) vacuum evaporation of an electron transport material as an electron transport layer 6 on the light-emitting layer 5;

[0073] (6) vacuum-evaporating an electron injection material selected from one or a combination of LiQ, LiF, NaCl, CsF, Li2O, Cs2CO3, BaO, Na, Li, Ca, and the like, as an electron injection layer 7 on the electron transport layer 6;

[0074] (7) vacuum-evaporating a cathode material as a cathode electrode 8 on the electron injection layer 7.

[0075] The above describes only one typical structure of an organic electroluminescent device and a method of fabricating the same, and it should be understood that the present application is not limited to this structure. The hole transport material of the present application can be used in an organic electroluminescent device of any structure, and the organic electroluminescent device can be fabricated using any method known in the art.

[0076] The method of synthesizing the compound of the present application is not particularly limited, and any method known to those skilled in the art can be used for the synthesis. The following illustrates the synthesis of the compound of the present application.

[0077] Synthesis Example 1: Synthesis of Compound A1

[0078]

[0079] In a reaction flask, 100 mmol of p-bromofluorobenzene, 100 mmol of carbazole, 41.4 g of potassium carbonate (300 mmol), and 800 mL of N,N-dimethylformamide (DMF) were added. The reaction was performed at 100°C for 12 h. After the completion of the reaction, the reaction was stopped, and the reaction was cooled to room temperature, water was added, and the organic phase was concentrated to obtain a white solid, which was filtered, washed with water, and purified by recrystallization with toluene to obtain a white powder M1.

[0080] In a reaction flask, 100 mmol of 4-aminobiphenyl, 100 mmol of M1, 28.83 g of sodium tert-butoxide (300 mmol), 800 mL of xylene, and 1 mmol of bis(dibenzylideneacetone)palladium (Pd(dba)) were added. The reaction was performed at 120°C for 12 h. After the completion of the reaction, the reaction was stopped, and the reaction was cooled to room temperature, water was added, and the reaction was filtered, washed with water, and purified by recrystallization with toluene to obtain a white powder M2.

[0081] In a reaction flask, 100 mmol of 4-bromofluorenone, 300 mmol of phenol, and 800 mL of polyphosphoric acid were added. The reaction was performed at 120°C for 12 h. After the completion of the reaction, the reaction was stopped, and the reaction was cooled to room temperature, water was added, and the organic phase was concentrated to obtain a white solid, which was filtered, washed with water, and purified by recrystallization with toluene to obtain a white powder M3.

[0082] In a reaction flask, 100 mmol of M2, 100 mmol of M3, 28.83 g of sodium tert-butoxide (300 mmol), 800 mL of xylene, and 1 mmol of bis(dibenzylideneacetone)palladium (Pd(dba)) were added. The reaction was performed at 120°C for 12 h. After the reaction was completed, the reaction was stopped, and the reaction was cooled to room temperature, water was added, filtered, washed with water, and the obtained solid was purified by recrystallization with toluene to obtain a white powder A1.

[0083] 1 H NMR (400 MHz, Chloroform) δ 8.55 (d, J = 7.6 Hz, 1H), 8.22-8.17 (m, 1H), 7.90 (d, J = 7.6 Hz, 1H), 7.76-7.62 (m, 6H), 7.58 (d, J = 7.6 Hz, 2H), 7.55-7.24 (m, 14H), 7.20-7, 07 (m, 9H), 7.00 (t, J = 7.6 Hz, 2H).

[0084] Synthesis Example 2: Synthesis of Compound A8

[0085]

[0086] In a reaction flask, 100 mmol of p-bromofluorobenzene, 100 mmol of 5,7-dihydro-7,7-dimethyl-indeno[2,1-B]carbazole, 41.4 g of potassium carbonate (300 mmol), 800 mL of DMF were added. The reaction was performed at 100°C for 12 h. After the reaction was completed, the reaction was stopped, and the reaction was cooled to room temperature, water was added, the organic phase was concentrated to obtain a white solid, filtered, washed with water, and the obtained solid was purified by recrystallization with toluene to obtain a white powder M1.

[0087] In a reaction flask, 100 mmol of 2-naphthylamine, 100 mmol of M1, 28.83 g of sodium tert-butoxide (300 mmol), 800 mL of xylene, and 1 mmol of bis(dibenzylideneacetone)palladium (Pd(dba)) were added. The reaction was performed at 120°C for 12 h. After the reaction was completed, the reaction was stopped, and the reaction was cooled to room temperature, water was added, filtered, washed with water, and the obtained solid was purified by recrystallization with toluene to obtain a white powder M2.

[0088] In a reaction flask, 100 mmol of 4-bromofluorenone, 300 mmol of phenol, 800 mL of polyphosphoric acid were added. The reaction was performed at 120°C for 12 h. After the reaction was completed, the reaction was stopped, and the reaction was cooled to room temperature, water was added, the organic phase was concentrated to obtain a white solid, filtered, washed with water, and the obtained solid was purified by recrystallization with toluene to obtain a white powder M3.

[0089] In a reaction flask, 100 mmol of M2, 100 mmol of M3, 28.83 g of sodium tert-butoxide (300 mmol), 800 mL of xylene, and 1 mmol of bis(dibenzylideneacetone)palladium (Pd(dba)) were added. The reaction was performed at 120°C for 12 h. After the reaction was completed, the reaction was stopped, and the reaction was cooled to room temperature, water was added, filtered, washed with water, and the obtained solid was purified by recrystallization with toluene to obtain a white powder A8.

[0090] 1 H NMR (400 MHz, Chloroform) δ 8.55 (d, J = 7.6 Hz, 1H), 8.44 (s, 2H), 8.32 (d, J = 7.6 Hz, 1H), 8.23 (d, J = 7.6 Hz, 1H), 7.92 (dd, J = 7.2 Hz, 2H), 7.76 (d, J = 7.2 Hz, 1H), 7.72 (d, J = 7.6 Hz, 2H), 7.64 (d, J = 7.2 Hz, 1H), 7.54 - 7.28 (m, 14H), 7.25 - 7.10 (m, 9H), 7.01 (t, J = 7.2 Hz, 2H), 1.69 (s, 6H).

[0091] Synthesis Example 3: Synthesis of Compound A14

[0092]

[0093] In a reaction flask, 100 mmol of 2-iodo-4-bromobenzoic acid methyl ester, 100 mmol of 2-chlorobenzenboronic acid, 41.4 g of potassium carbonate (300 mmol), 800 mL of tetrahydrofuran (THF), and 200 mL of water, and 1 mmol of tetrakis(triphenylphosphine)palladium (Pd(PPh3)4) were added. The reaction was performed at 60°C for 12 h. After the reaction was completed, the reaction was stopped, and the reaction was cooled to room temperature, water was added, the organic phase was concentrated to obtain a white solid, filtered, washed with water, and the obtained solid was purified by recrystallization with toluene to obtain a white powder M1.

[0094] In a reaction flask, 100 mmol of M1, 800 mL of methylsulfonic acid, and 1 mmol of tetrakis(triphenylphosphine)palladium (Pd(PPh3)4) were added. The reaction was performed at 100°C for 12 h. After the reaction was completed, the reaction was stopped, and the reaction was cooled to room temperature, water was added, the organic phase was concentrated to obtain a white solid, filtered, washed with water, and the obtained solid was purified by recrystallization with toluene to obtain a white powder M2.

[0095] In a reaction flask, 100 mmol of M2, 100 mmol of phenylboronic acid, 41.4 g of potassium carbonate (300 mmol), 800 mL of tetrahydrofuran (THF), and 200 mL of water were added, and 1 mmol of tetrakis(triphenylphosphine)palladium (Pd(PPh3)4) was added. The reaction was performed at 60°C for 12 h. After the reaction was completed, the reaction was stopped, and the reaction was cooled to room temperature, water was added, the organic phase was concentrated to obtain a white solid, which was filtered, washed with water, and the obtained solid was purified by recrystallization with toluene to obtain a white powder M3.

[0096] In a reaction flask, 100 mmol of M3, 300 mmol of phenol, 800 mL of polyphosphoric acid were added. The reaction was performed at 120°C for 12 h. After the reaction was completed, the reaction was stopped, and the reaction was cooled to room temperature, water was added, the organic phase was concentrated to obtain a white solid, which was filtered, washed with water, and the obtained solid was purified by recrystallization with toluene to obtain a white powder M4.

[0097] In a reaction flask, 100 mmol of 2-bromonitrobenzene, 100 mmol of deuterated phenylboronic acid, 41.4 g of potassium carbonate (300 mmol), 800 mL of tetrahydrofuran (THF), and 200 mL of water were added, and 1 mmol of tetrakis(triphenylphosphine)palladium (Pd(PPh3)4) was added. The reaction was performed at 60°C for 12 h. After the reaction was completed, the reaction was stopped, and the reaction was cooled to room temperature, water was added, the organic phase was concentrated to obtain a white solid, which was filtered, washed with water, and the obtained solid was purified by recrystallization with toluene to obtain a white powder M5.

[0098] In a reaction flask, 100 mmol of M5, 300 mmol of triphenylphosphine, 800 mL of o-dichlorobenzene were added, and the reaction was performed at reflux for 8 h. After the reaction was completed, the reaction was stopped, and the reaction was cooled to room temperature, water was added, the organic phase was concentrated, and the obtained solid was purified by column chromatography to obtain a white solid M6.

[0099] In a reaction flask, 100 mmol of p-bromofluorobenzene, 100 mmol of M6, 41.4 g of potassium carbonate (300 mmol), 800 mL of DMF were added. The reaction was performed at 100°C for 12 h. After the reaction was completed, the reaction was stopped, and the reaction was cooled to room temperature, water was added, the organic phase was concentrated to obtain a white solid, which was filtered, washed with water, and the obtained solid was purified by recrystallization with toluene to obtain a white powder M7.

[0100] In a reaction bottle, 100 mmol of 1-naphthylamine, 100 mmol of M7, 28.83 g of sodium tert-butoxide (300 mmol), 800 mL of xylene, and 1 mmol of bisbenzylideneacetone palladium (Pd(dba)) were added. The reaction was carried out at 120°C for 12 hours. After the reaction was completed, the reaction was stopped, and the reaction was cooled to room temperature, water was added, filtered, washed with water, and the obtained solid was purified by recrystallization with toluene to obtain a white powder M8.

[0101] In a reaction bottle, 100 mmol of M4, 100 mmol of M8, 28.83 g of sodium tert-butoxide (300 mmol), 800 mL of xylene, and 1 mmol of bisbenzylideneacetone palladium (Pd(dba)) were added. The reaction was carried out at 120°C for 12 hours. After the reaction was completed, the reaction was stopped, and the reaction was cooled to room temperature, water was added, filtered, washed with water, and the obtained solid was purified by recrystallization with toluene to obtain a white powder A14.

[0102] 1 H NMR (400 MHz, Chloroform) δ 9.01 (s, 1H), 8.56 (d, J = 7.2 Hz, 1H), 8.42 (d, J = 7.6 Hz, 1H), 8.22 (d, J = 7.2 Hz, 1H), 8.00 (d, J = 7.2 Hz, 1H), 7.83 (d, J = 7.2 Hz, 1H), 7.75 - 7.36 (m, 15H), 7.34 - 7.26 (m, 4H), 7.21 - 7.13 (m, 7H), 7.02 (t, J = 7.2 Hz, 2H).

[0103] Other compounds of the present application can be synthesized according to the above synthesis examples 1-3, selecting appropriate starting materials, or any other suitable method and starting materials.

[0104] Example 1

[0105] A glass substrate 1 coated with an ITO transparent conductive layer was ultrasonically treated in a commercial cleaning agent, rinsed in deionized water, ultrasonically degreased in an acetone-ethanol mixed solvent, baked in a clean environment until water was completely removed, cleaned with ultraviolet light and ozone, and the surface was bombarded with a low-energy cation beam;

[0106] The above glass substrate 1 with a reflective anode electrode 2 was placed in a vacuum chamber, vacuumed to less than 10 -5 Hg, and Hg, and vacuum evaporated HT-11 as a hole injection layer 3 on the above reflective anode electrode 2 layer film at a deposition rate of 0.1 nm / s and a film thickness of 10 nm;

[0107] A1 material was vacuum evaporated as a hole transport layer 4 on the hole injection layer 3, the evaporation rate was 0.1 nm / s, and the film thickness was 80 nm;

[0108] A light emitting layer 5 was vacuum evaporated on the hole transport layer 4, the light emitting layer 5 included a host material BH-1 and a dye material BD-1, and the evaporation was performed by a multi-source co-evaporation method, the evaporation rate of the host material BH-1 was adjusted to 0.1 nm / s, the evaporation rate of the dye BD-1 was 3% of the evaporation rate of the host material, and the total film thickness was 30 nm;

[0109] An electron transport layer 6 was vacuum evaporated on the light emitting layer 5, and a material ET-42 was selected as the electron transport material, the evaporation rate was 0.1 nm / s, and the film thickness was 30 nm;

[0110] LiF with a thickness of 0.5 nm was vacuum evaporated on the electron transport layer (ETL) 6 as an electron injection layer 7, the evaporation rate was 0.1 nm / s;

[0111] Finally, an aluminum layer with a thickness of 150 nm was evaporated on the electron injection layer 7 as a cathode electrode 8 of the organic electroluminescent device, the evaporation rate was 0.1 nm / s.

[0112] Example 2-3

[0113] Except that A8 and A14 were used instead of A1 respectively, the rest was the same as Example 1.

[0114] Comparative Example 1

[0115] Except that HT-30 was used instead of A1, the rest was the same as Example 1.

[0116] Comparative Example 2

[0117] Except that R was used instead of A1, the rest was the same as Example 1.

[0118]

[0119] The organic electroluminescent devices prepared by the above process were subjected to the following performance tests:

[0120] The driving voltage and current efficiency of the organic electroluminescent devices prepared in the examples and comparative examples were measured at the same brightness using a digital source meter and a luminance meter, and the lifetime of the device was measured, specifically, the voltage when the brightness of the organic electroluminescent device reached 1000 cd / m 2 was measured at a rate of 0.1 V per second, the driving voltage was measured, and the current density at this time was also measured; the ratio of the brightness to the current density was the current efficiency; the LT95 lifetime test was as follows: a luminance meter was used to measure the brightness of the device at 1000 cd / m 2Under the brightness, the current is kept constant, and the brightness of the organic electroluminescent device is measured to be 950 cd / m 2 The results are shown in Table 1.

[0121] Table 1. Performance results of the organic electroluminescent device

[0122]

[0123] From the data in the above table, it can be seen that the compound prepared by the application is used for the hole transport material of the organic electroluminescent device, can effectively reduce the driving voltage, improve the current efficiency, and prolong the device life, and is a good hole transport material.

[0124] The above description is only the preferred embodiment of the application, and is not used to limit the protection scope of the application. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the application shall be included in the protection scope of the application.

Claims

1. An oxaspiro-difluorene substituted arylamine compound, characterized by, having the structure of Formula (I): R 1 -R 8 are independently selected from hydrogen, deuterium, O, S, N, C1-C4 alkyl, C3-C6 cycloalkane, substituted and unsubstituted C6-C 30 The aromatic group, adjacent substituents can be connected to form a ring; L1, L2are independently from each other selected from a chemical bond, substituted and unsubstituted C6-C10aryl, substituted and unsubstituted C5-C10heteroaryl; 30 substituted and unsubstituted C5-C10heteroaryl; 30 substituted and unsubstituted C5-C10heteroaryl; R 9 , R 10 are independently of one another selected from the group consisting of hydrogen, deuterium, substituted and unsubstituted C6-C 30 aromatic radicals, substituted and unsubstituted C5-C 30 heteroaryl radicals; Ar1is selected from substituted and unsubstituted C6-C10aryl, substituted and unsubstituted C5-C10heteroaryl; 30 30 substituted and unsubstituted C5-C10heteroaryl;​ the heteroatoms on the heteroaryl group are each independently selected from O, S, N; The hydrogen atoms on the aromatic and heteroaryl groups can be independently replaced by Ra, which are independently selected from deuterium, halogen, nitro, cyano, C1-C4 alkyl, C5-C 20 Cycloalkyl, phenyl, biphenyl, terphenyl, naphthyl.

2. The oxaspirobifluorene substituted arylamine compound according to claim 1, characterized by L1, L2are independently of each other selected from a chemical bond, unsubstituted and substituted with Ra, phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, triphenylene, fluorenyl, dibenzofuranyl, dibenzothiophenyl, 9,9-dimethylfluorenyl, spirofluorenyl.

3. The oxaspirobifluorene substituted arylamine compound according to claim 1, wherein R 1 -R 8 are independently of each other selected from the group consisting of hydrogen, deuterium, hydroxyl, thiol, methyl, ethyl, isopropyl, tert-butyl, cyclopentyl, cyclohexyl, the following groups which are unsubstituted and substituted with Ra: phenyl, biphenyl, naphthyl, phenanthryl, fluorenyl, dibenzofuranyl, dibenzothiophenyl, carbazolyl, anilino.

4. The oxaspirobifluorene substituted arylamine compound according to claim 1, wherein R 9 , R 10 are independently from each other selected from the group consisting of hydrogen, deuterium, unsubstituted and substituted with Ra: phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, triphenylenyl, fluorenyl, dibenzofuranyl, dibenzothiophenyl, 9,9-dimethylfluorenyl, spirofluorenyl.

5. The oxaspirobifluorene substituted arylamine compound according to claim 1, wherein Ar1is selected from unsubstituted and substituted with Ra, phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, triphenylene, fluorenyl, benzofuranyl, dibenzofuranyl, benzothiophenyl, dibenzothiophenyl, 9,9-dimethylfluorenyl, spirofluorenyl, arylamine, carbazolyl.

6. The oxaspirobifluorene substituted arylamine compound according to claim 1, wherein selected from the group consisting of compounds A1-A20:

7. A hole transporting material, characterized by, comprising at least one of the oxaspirobifluorene-substituted arylamine compounds of any one of claims 1-6.

8. An organic electroluminescent device, characterized by comprising at least one of the hole transport materials of claim 7.

9. A display device, characterized by comprising: comprising the organic electroluminescence device of claim 8.

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