An olefin fluorene organic electroluminescent material, a synthesis method thereof, and application in electroluminescent devices

Abstract

The present invention discloses an alkenefluorene organic electroluminescent material, a synthesis method thereof, and an application in an electroluminescent device, wherein the structural formula is as follows: #imgabs0# wherein R1 and R2 are each independently a substituted or unsubstituted C6-C30 aromatic hydrocarbon group or a substituted or unsubstituted C5-C30 heteroaromatic hydrocarbon group; the fluorenyl group in the structural formula is connected to Ar by a double bond; Ar is a substituted or unsubstituted C6-C30 aromatic hydrocarbon group, and the substituent is selected from at least one of the following atoms or groups: deuterium, hydroxyl, cyano, monodeuteriomethyl, dideuteriomethyl, trideuteriomethyl, C1-C4 straight or branched alkyl group, C6-C18 aromatic hydrocarbon group, or C5-C24 heteroaromatic hydrocarbon group. The alkenefluorene organic electroluminescent material of the present invention is applied to an organic electroluminescent device, and at the same current density, the luminous efficiency is effectively improved, the starting voltage of the device is reduced, the power consumption of the device is significantly reduced, and the life of the device is improved.

Description

Technical Field

[0001] The invention belongs to the field of organic electroluminescent materials, and in particular relates to an enefluorene organic electroluminescent material, a synthesis method thereof, and application of the material in electroluminescent devices. Background Art

[0002] Organic light-emitting devices (OLEDs), also known as organic light-emitting diodes (OLEDs), are a type of all-solid-state flat-panel display technology developed in the 1980s. Organic electroluminescence (OLED) refers to the phenomenon in which organic semiconductor materials emit light through carrier injection, transport, recombination, and exciton decay under an electric field. OLEDs are displays based on this principle.

[0003] In OLEDs, the role of the hole transport layer is to improve the efficiency of hole transport in the device and block electrons in the light-emitting layer to achieve maximum carrier recombination. The hole transport layer can reduce the energy barrier of holes during injection, increase the hole injection efficiency, and improve the brightness and life of the device. For a good hole transport material, in addition to having a high hole mobility, it must also meet the following conditions: (1) be able to form a defect-free uniform amorphous film; (2) have good thermal stability and can remain amorphous under long-term operation. Although the aging mechanism of OLEDs is not very clear at present, studies have shown that changes in the physical morphology of the organic layer are one of its influencing factors, such as the melting and crystallization of the organic layer caused by the heat generated during device operation; (3) have a suitable highest occupied molecular orbital (HOMO) energy level to ensure the effective injection and transport of holes between various interfaces; and prevent the device from generating excessive Joule heat during operation, which causes the recrystallization of the material. This crystallization will destroy the uniformity of the film and destroy the good interface contact between the hole transport layer and the anode and the organic layer, thereby reducing the life of the device.

[0004] At present, since small molecule hole transport materials and polymer hole transport materials have their own advantages and disadvantages in their application performance, seeking new hole transport materials with excellent performance has always been a hot topic in research in this field. Summary of the Invention

[0005] In view of the above technical problems, the object of the present invention is to provide an olefinic fluorene organic electroluminescent material.

[0006] Another object of the present invention is to provide an organic electroluminescent device containing the above-mentioned olefinefluorene organic electroluminescent material.

[0007] In order to achieve the above-mentioned object of the invention, the technical solution adopted by the present invention is as follows:

[0008] An olefin fluorene organic electroluminescent material, the structural formula of which is shown below:

[0009]

[0010] wherein R1 and R2 are each independently a substituted or unsubstituted C6-C30 aromatic hydrocarbon group or a substituted or unsubstituted C5-C30 heteroaromatic hydrocarbon group;

[0011] The fluorenyl group in the structural formula is connected to Ar via a double bond;

[0012] Ar is a substituted or unsubstituted C6-C30 aromatic hydrocarbon group; preferably, the substituent of the C6-C30 aromatic hydrocarbon group is selected from at least one of the following atoms or groups: deuterium, hydroxyl, cyano, monodeuteriomethyl, dideuteriomethyl, trideuteriomethyl, C1-C4 straight or branched alkyl, C6-C18 aromatic hydrocarbon group, C5-C24 heteroaromatic hydrocarbon group.

[0013] Furthermore, R1 and R2 are each independently substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted anthracenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted phenanthrenyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted thiofuranyl, substituted or unsubstituted N-phenylcarbazolyl, substituted or unsubstituted 9,9-dimethylfluorenyl, substituted or unsubstituted 9,9-diphenylfluorenyl, or substituted or unsubstituted 9,9-spirobifluorenyl.

[0014] Further, R1 and R2 are each independently an unsubstituted phenyl, biphenyl, terphenyl, anthracenyl, naphthyl, phenanthrenyl, fluorenyl, dibenzofuranyl, thiobenzofuranyl, N-phenylcarbazolyl, 9,9-dimethylfluorenyl, 9,9-diphenylfluorenyl, 9,9-spirobifluorenyl, or a phenyl, biphenyl, terphenyl, anthracenyl, naphthyl, phenanthrenyl, fluorenyl, dibenzofuranyl, thiobenzofuranyl, N-phenylcarbazolyl, 9,9-dimethylfluorenyl, 9,9-diphenylfluorenyl, 9,9-spirobifluorenyl, in which at least one hydrogen is replaced by deuterium, methyl, monodeuterated methyl, bisdeuterated methyl, or trideuterated methyl.

[0015] Furthermore, Ar is an unsubstituted group of the following structural formula:

[0016]

[0017] Or it is any one of the groups in which at least one hydrogen in the above groups is replaced by deuterium, methyl, monodeuterated methyl, dideuterated methyl, or trideuterated methyl.

[0018] Furthermore, the olefinefluorene organic electroluminescent material is any one of the following compounds:

[0019]

[0020]

[0021]

[0022]

[0023]

[0024]

[0025]

[0026]

[0027]

[0028]

[0029]

[0030]

[0031]

[0032] Furthermore, the preparation method of the above-mentioned olefin fluorene organic electroluminescent material is as follows: (1)

[0034]

[0035] Under an inert atmosphere, first cool ethanol to -10 to -5°C, then add compound I and sodium ethoxide, stir mechanically to mix, cool liquid nitrogen to -78°C, add dropwise the ethanol solution of compound II, and naturally warm to room temperature after the addition is complete, stir and react for 5-10 hours, add acetic acid and hydrochloric acid dropwise in sequence, and after the addition is complete, heat the mixture to reflux and react for 5-10 hours, stop the reaction and cool to room temperature, concentrate the reaction solution, add appropriate amounts of dichloromethane and water for extraction and separation, wash the dichloromethane phase with water until neutral and then dry, pass through a silica gel funnel and concentrate under reduced pressure to obtain compound III. Preferably, the molar ratio of compound I, sodium ethoxide and compound II is 1:1-1.2:0.8-0.9; the amount of ethanol used when cooling the ethanol to -10 to -5°C is 10 to 20 times the mass of compound II, the amount of ethanol in the ethanol solution of compound II is 10 to 20 times the mass of compound II; the amount of acetic acid used is 5 to 6 times the mass of compound II; and the molar ratio of hydrochloric acid to compound II is 1:4 to 5. (2)

[0037]

[0038] Under an inert atmosphere, compound III, compound IV, potassium or sodium tert-butoxide, tris(dibenzylideneacetone)dipalladium, tri-tert-butylphosphine, and toluene are mixed, heated to reflux for 5-10 hours, cooled to room temperature, added with water and stirred, the reaction solution filtered, the organic phase separated, dried, and then spin-dried, and purified by column chromatography to obtain the enefluorene organic electroluminescent material. Preferably, the molar ratio of compound III to compound IV is 1:1.1-1.5; the molar ratio of compound III, potassium or sodium tert-butoxide, tris(dibenzylideneacetone)dipalladium, and tri-tert-butylphosphine is 1:1.1-1.5:0.05-0.1:0.05-0.1.

[0039] Application of the above-mentioned olefinefluorene organic electroluminescent material in the preparation of organic electroluminescent devices.

[0040] The present invention also discloses the above-mentioned organic electroluminescent device, comprising: an anode, a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, an electron injection layer and a cathode stacked in sequence; the hole transport layer contains at least one of the above-mentioned olefinic organic electroluminescent materials.

[0041] Furthermore, the present invention also discloses an organic electroluminescent display device containing the organic electroluminescent device.

[0042] Furthermore, the present invention also discloses an organic electroluminescent lighting device comprising the organic electroluminescent device.

[0043] The room temperature described in the present invention is 25±5°C.

[0044] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0045] The organic electroluminescent material of the present invention is a blue luminescent compound and can be used as a blue fluorescent host material in organic electroluminescent devices to reduce driving voltage and improve luminous efficiency, brightness, thermal stability, color purity and device life.

[0046] The application of the organic electroluminescent material of the present invention in the preparation of a light-emitting device, wherein the above-mentioned blue light-emitting compound is applied to the light-emitting device, can improve the luminous efficiency and service life of the light-emitting device.

[0047] The organic electroluminescent device provided by the present invention uses the above-mentioned organic electroluminescent material as a hole transport layer material, so that the organic electroluminescent device has excellent performances of high efficiency and long life. BRIEF DESCRIPTION OF THE DRAWINGS

[0048] Figure 1 A schematic structural diagram of an organic electroluminescent device provided by the present invention;

[0049] The numbers in the figure represent: 1-anode, 2-hole injection layer, 3-hole transport layer, 4-electron blocking layer, 5-light-emitting layer, 6-hole blocking layer, 7-electron transport layer, 8-electron injection layer, 9-cathode.

[0050] Figure 2 HPLC chart and diagrammatic illustration of the organic electroluminescent material (26) in the embodiment of the present invention.

[0051] Figure 3 is the DSC spectrum of the organic electroluminescent material (6) in the embodiment of the present invention, Figure 3 It can be seen that the Tm value of compound 6 is 210.52°C.

[0052] Figure 4 is the TGA spectrum of the organic electroluminescent material (6) in the embodiment of the present invention, Figure 4 It can be seen that the thermal gravimetric loss temperature Td value of compound 6 is 378.24°C. DETAILED DESCRIPTION

[0053] The following further illustrates and describes embodiments of various aspects. It should be understood that the description herein is not intended to limit the claims to the specific aspects described. On the contrary, it is intended to cover alternatives, modifications, and equivalents that may be included within the spirit and scope of the present disclosure as defined by the appended claims.

[0054] In "deuterated" or "undeuterated", the term "deuterated" means that at least one hydrogen in the group is re-coordinated with deuterium. The term "undeuterated" means that none of the hydrogens in the group are re-coordinated with deuterium.

[0055] As used herein, "aromatic group," "aryl," or "aromatic radical" refers to a group containing one or more aromatic rings, including but not limited to benzene, naphthalene, phenanthrene, fluorene, acenaphthene, pyridine, pyrimidine, pyrrole, furan, and thiophene. The C6-C30 in a C6-C30 aromatic group refers to the number of carbon atoms in the group. In a C6-C20 aromatic group substituted with a C1-C10 alkyl group, the C1-C10 refers to the number of carbon atoms in the substituent, and the C6-C20 refers to the number of carbon atoms in the aromatic group without a substituent. Aromatic groups can be divided into monocyclic aromatic groups and polycyclic aromatic groups. Specific aromatic groups in the present invention include but are not limited to phenyl, biphenyl, terphenyl, anthracenyl, naphthyl, phenanthrenyl, fluorenyl, dibenzofuranyl, dibenzothiophenyl, 9,9-spirobifluorenyl, 9,9-dimethylfluorenyl, or 9,9-diphenylfluorenyl. Aromatic groups can be substituted or unsubstituted.

[0056] As used herein, "cycloalkyl" refers to a monocyclic or fused ring group ("fused" ring means that each ring in the system shares a pair of adjacent carbon atoms with the other rings in the system) that is entirely carbon, wherein one or more rings are saturated alicyclic rings, generally having 3 to 20 carbon atoms, preferably 3 to 12 carbon atoms, and more preferably 3 to 10 carbon atoms. Cycloalkyl groups can be divided into monocyclic alkyl groups having only one ring and fused cyclic alkyl groups having multiple rings. Examples of monocyclic alkyl groups include, but are not limited to, cyclopropane, cyclobutane, cyclopentane, cyclohexane, and cycloheptane. Cycloalkyl groups can be substituted or unsubstituted.

[0057] As used herein, "cycloalkenyl" refers to a monocyclic or fused ring group ("fused" ring means that each ring in the system shares a pair of adjacent carbon atoms with the other rings in the system) that is entirely carbon, wherein one or more rings do not have a completely connected π electron system and contain at least one alkenyl group, which generally has 3-20 carbon atoms, preferably 3-12 carbon atoms, and more preferably 3-10 carbon atoms. Examples of cycloalkenyl groups include, but are not limited to, cyclopentene, cyclohexene, cyclohexadiene, and cycloheptatriene. Cycloalkenyl groups may be substituted or unsubstituted.

[0058] If the specific conditions are not specified in the examples, the experiments were carried out under conventional conditions or those recommended by the manufacturer. All reagents or instruments used, if the manufacturer is not specified, are commercially available conventional products.

[0059] Example 1

[0060]

[0061] The preparation method of the organic electroluminescent material (3) is as follows: (1)

[0063]

[0064] Under nitrogen protection, ethanol (20 g, 20 times the mass of compound 1-b) was first cooled to -5 ° C, and then compound 1-a (1.2 eq, 0.37 g, 80.06 g / mol, 4.65 mmol) and sodium ethoxide (1.2 eq, 0.32 g, 68.05 g / mol, 4.65 mmol) were added. After mechanical stirring and mixing, liquid nitrogen was cooled to -78 ° C and compound 1-b (1 eq, 1 g, 257.97 g / mol, 3.88 mmol) in ethanol (20 times the mass of compound 1-b) was added dropwise. ) solution, after the addition is completed, the temperature is naturally raised to room temperature and stirred for 10 hours, acetic acid (5g, 5 times the mass of compound 1-b) and hydrochloric acid (5eq, 3.88ml, 5mol / L, 19.38mmol) are added dropwise in sequence, and after the addition is completed, the temperature is raised to reflux for 10 hours, the reaction is stopped and cooled to room temperature, the reaction solution is concentrated, and appropriate amounts of dichloromethane and water are added for extraction and separation, the dichloromethane phase is washed with water to neutrality and then dried, passed through a silica gel funnel and concentrated under reduced pressure to obtain compound 1-c (0.8g, yield 64.3%), MS (EI): 320 (M + ); (2)

[0066]

[0067] Under nitrogen protection, compound 1-c (0.6 g, 320.02 g / mol, 1.87 mmol), compound 1-d (1.1 eq, 0.66 g, 321.15 g / mol, 2.06 mmol), sodium tert-butoxide (1.1 eq, 0.2 g, 96.1 g / mol, 2.06 mmol), tris(dibenzylideneacetone)dipalladium (0.05 eq, 0.089 g, 915 g / mol, 0.094 mmol), tri-tert-butylphosphine (0.05 eq, 0.089 g, 915 g / mol, 0.094 mmol), and 1-d were added to the mixture. q, 0.02 g, 202.32 g / mol, 0.094 mol), and toluene (12 ml) were added to the reaction flask. After the addition was completed, the temperature was raised to reflux for reaction for 5 h. After the reaction was completed, the temperature was lowered to room temperature, 12 ml of water was added, and the mixture was stirred for 15 min. The filtrate was filtered to obtain a filtrate. The filtrate was filtered through diatomaceous earth and separated to obtain an organic phase. The organic phase was dried over anhydrous magnesium sulfate and then dried by spin drying. After purification by column chromatography, an organic electroluminescent material (3) (0.94 g, yield 89.6%) was obtained. MS (EI): 561 (M + ).

[0068] Example 2

[0069]

[0070] The preparation method of the organic electroluminescent material (6) is as follows:

[0071]

[0072] Under nitrogen protection, compound 2-a (1 g, 320.02 g / mol, 3.12 mmol), compound 2-b (1.1 eq, 1.66 g, 483.2 g / mol, 3.44 mmol), sodium tert-butoxide (1.1 eq, 0.33 g, 96.1 g / mol, 3.44 mmol), tris(dibenzylideneacetone)dipalladium (0.05 eq, 0.14 g, 915 g / mol, 0.156 mmol), tri-tert-butylphosphine (0.05 eq, 0.032 g, 202.32 g / mol, 0.156 mol), and toluene (20 ml) were added to a reaction flask. After the addition was completed, the temperature was raised to reflux for reaction for 10 h. After the reaction was completed, the temperature was lowered to room temperature, 20 ml of water was added, and the mixture was stirred for 15 min. The filtrate was filtered to obtain a filtrate. The filtrate was filtered through diatomaceous earth and separated to obtain an organic phase. The organic phase was dried over anhydrous magnesium sulfate and then dried by spin drying. After purification by column chromatography, an organic electroluminescent material (6) (1.94 g, yield 86.1%) was obtained. MS (EI): 723 (M + ).

[0073] Example 3

[0074]

[0075] The preparation method of the organic electroluminescent material (26) is as follows: (1)

[0077]

[0078] Under nitrogen protection, ethanol (20 g, 20 times the mass of compound 3-b) was first cooled to -10 ° C, and then compound 3-a (1.2 eq, 0.5 g, 108.09 g / mol, 4.65 mmol) and sodium ethoxide (1.2 eq, 0.32 g, 68.05 g / mol, 4.65 mmol) were added. After mechanical stirring and mixing, liquid nitrogen was cooled to -78 ° C and compound 3-b (1 eq, 1 g, 257.97 g / mol, 3.88 mmol) in ethanol (20 times the mass of compound 3-b) was added dropwise. After the addition was completed, the temperature was naturally raised to room temperature and stirred for 5 hours. Acetic acid (5 g, 5 times the mass of compound 3-b) and hydrochloric acid (5 eq, 3.88 ml, 5 mol / L, 19.38 mmol) were added dropwise in sequence. After the addition was completed, the temperature was raised to reflux for 5 hours. The reaction was stopped and cooled to room temperature. After the reaction solution was concentrated, appropriate amounts of dichloromethane and water were added for extraction and separation. The dichloromethane phase was washed with water until neutral and then dried. After passing through a silica gel funnel, it was concentrated under reduced pressure to obtain compound 3-c (0.74 g, yield 59.3%), MS (EI): 320 (M + ); (2)

[0080]

[0081] Under nitrogen protection, compound 3-c (0.6 g, 348.05 g / mol, 1.72 mmol), compound 3-d (1.1 eq, 0.68 g, 361.18 g / mol, 1.9 mmol), sodium tert-butoxide (1.1 eq, 0.18 g, 96.1 g / mol, 1.9 mmol), tris(dibenzylideneacetone)dipalladium (0.05 eq, 0.079 g, 915 g / mol, 0.086 mmol), tri-tert-butylphosphine (0.05 eq, 0.079 g, 915 g / mol, 0.086 mmol), , 0.017 g, 202.32 g / mol, 0.086 mol), toluene (12 ml) were added to the reaction flask, and after the addition was completed, the temperature was raised to reflux for reaction for 10 h. After the reaction was completed, the temperature was lowered to room temperature, 12 ml of water was added, and the mixture was stirred for 15 min and filtered to obtain a filtrate. The filtrate was filtered through diatomaceous earth and separated to obtain an organic phase. The organic phase was dried over anhydrous magnesium sulfate and then dried by spin drying. After purification by column chromatography, an organic electroluminescent material (26) (1.1 g, yield 88.4%) was obtained, MS (EI): 723 (M + ).

[0082] Example 4

[0083]

[0084] The preparation method of the organic electroluminescent material (31) is as follows:

[0085]

[0086] Under nitrogen protection, compound 4-a (1 g, 348.05 g / mol, 2.87 mmol), compound 4-b (1.1 eq, 0.64 g, 203.16 g / mol, 3.16 mmol), sodium tert-butoxide (1.1 eq, 0.3 g, 96.1 g / mol, 3.16 mmol), tris(dibenzylideneacetone)dipalladium (0.05 eq, 0.13 g, 915 g / mol, 0.144 mmol), tri-tert-butylphosphine (0.05 eq, 0 0.029 g, 202.32 g / mol, 0.144 mol), and toluene (20 ml) were added to the reaction flask. After the addition was completed, the temperature was raised to reflux for reaction for 10 h. After the reaction was completed, the temperature was lowered to room temperature, 20 ml of water was added, and the mixture was stirred for 15 min. The filtrate was filtered to obtain a filtrate. The filtrate was filtered through diatomaceous earth and separated to obtain an organic phase. The organic phase was dried over anhydrous magnesium sulfate and then dried by spin drying. After purification by column chromatography, an organic electroluminescent material (31) (1.24 g, yield 91.5%) was obtained. MS (EI): 471 (M + ).

[0087] Example 5

[0088]

[0089] The preparation method of the organic electroluminescent material (43) is as follows: (1)

[0091]

[0092] Under nitrogen protection, ethanol (20 g, 20 times the mass of compound 5-b) was first cooled to -10 ° C, and then compound 5-a (1.2 eq, 0.43 g, 92.06 g / mol, 4.65 mmol) and sodium ethoxide (1.2 eq, 0.32 g, 68.05 g / mol, 4.65 mmol) were added. After mechanical stirring and mixing, liquid nitrogen was cooled to -78 ° C and compound 5-b (1 eq, 1 g, 257.97 g / mol, 3.88 mmol) in ethanol (20 times the mass of compound 5-b) was added dropwise. After the addition was completed, the temperature was naturally raised to room temperature and stirred for 5 hours. Acetic acid (5 g, 5 times the mass of compound 5-b) and hydrochloric acid (5 eq, 3.88 ml, 5 mol / L, 19.38 mmol) were added dropwise in sequence. After the addition was completed, the temperature was raised to reflux for 5 hours. The reaction was stopped and cooled to room temperature. After the reaction solution was concentrated, appropriate amounts of dichloromethane and water were added for extraction and separation. The dichloromethane phase was washed with water until neutral and then dried. After passing through a silica gel funnel, it was concentrated under reduced pressure to obtain compound 5-c (0.81 g, yield 62.9%), MS (EI): 332 (M + ); (2)

[0094]

[0095] Under nitrogen protection, compound 5-c (0.6 g, 332.02 g / mol, 1.81 mmol), compound 5-d (1.1 eq, 0.67 g, 335.13 g / mol, 1.99 mmol), sodium tert-butoxide (1.1 eq, 0.19 g, 96.1 g / mol, 1.99 mmol), tris(dibenzylideneacetone)dipalladium (0.05 eq, 0.081 g, 915 g / mol, 0.09 mmol), tri-tert-butylphosphine (0.05 eq, 0.081 g, 915 g / mol, 0.09 mmol), q, 0.018 g, 202.32 g / mol, 0.09 mol), and toluene (12 ml) were added to the reaction flask. After the addition was completed, the temperature was raised to reflux for reaction for 10 h. After the reaction was completed, the temperature was lowered to room temperature, 12 ml of water was added, and the mixture was stirred for 15 min. The filtrate was filtered to obtain a filtrate. The filtrate was filtered through diatomaceous earth and separated to obtain an organic phase. The organic phase was dried over anhydrous magnesium sulfate and then dried by spin drying. After purification by column chromatography, an organic electroluminescent material (43) (0.9 g, yield 84.7%) was obtained. MS (EI): 587 (M + ).

[0096] Example 6

[0097]

[0098] The preparation method of the organic electroluminescent material (64) is as follows: (1)

[0100]

[0101] Under nitrogen protection, ethanol (20 g, 20 times the mass of compound 6-b) was first cooled to -10 ° C, and then compound 6-a (1.2 eq, 0.89 g, 192.09 g / mol, 4.65 mmol) and sodium ethoxide (1.2 eq, 0.32 g, 68.05 g / mol, 4.65 mmol) were added. After mechanical stirring and mixing, liquid nitrogen was cooled to -78 ° C and compound 6-b (1 eq, 1 g, 257.97 g / mol, 3.88 mmol) in ethanol (20 times the mass of compound 6-b) was added dropwise. After the addition was completed, the temperature was naturally raised to room temperature and stirred for 5 hours. Acetic acid (5 g, 5 times the mass of compound 6-b) and hydrochloric acid (5 eq, 3.88 ml, 5 mol / L, 19.38 mmol) were added dropwise. After the addition was completed, the temperature was raised to reflux for 5 hours. The reaction was stopped and cooled to room temperature. After the reaction solution was concentrated, appropriate amounts of dichloromethane and water were added for extraction and separation. The dichloromethane phase was washed with water until neutral and then dried. After passing through a silica gel funnel, it was concentrated under reduced pressure to obtain compound 6-c (1.02 g, yield 60.6%), MS (EI): 432 (M + ); (2)

[0103]

[0104] Under nitrogen protection, compound 6-c (0.8 g, 432.05 g / mol, 1.85 mmol), compound 6-d (1.1 eq, 0.84 g, 410.18 g / mol, 2.04 mmol), sodium tert-butoxide (1.1 eq, 0.2 g, 96.1 g / mol, 2.04 mmol), tris(dibenzylideneacetone)dipalladium (0.05 eq, 0.085 g, 915 g / mol, 0.093 mmol), tri-tert-butylphosphine (0.05 eq, 0.085 g, 915 g / mol, 0.093 mmol), , 0.019 g, 202.32 g / mol, 0.093 mol), toluene (16 ml) were added to the reaction flask, and after the addition was completed, the temperature was raised to reflux for reaction for 10 h. After the reaction was completed, the temperature was lowered to room temperature, 16 ml of water was added, and the mixture was stirred for 15 min and filtered to obtain a filtrate. The filtrate was filtered through diatomaceous earth and separated to obtain an organic phase. The organic phase was dried over anhydrous magnesium sulfate and then dried by spin drying. After purification by column chromatography, an organic electroluminescent material (64) (1.03 g, yield 73.3%) was obtained, MS (EI): 762 (M + ).

[0105] Example 7

[0106]

[0107] The preparation method of the organic electroluminescent material (71) is as follows: (1)

[0109]

[0110] Under nitrogen protection, ethanol (20 g, 20 times the mass of compound 7-b) was first cooled to -10 ° C, and then compound 7-a (1.2 eq, 0.78 g, 168.09 g / mol, 4.65 mmol) and sodium ethoxide (1.2 eq, 0.32 g, 68.05 g / mol, 4.65 mmol) were added. After mechanical stirring and mixing, liquid nitrogen was cooled to -78 ° C and compound 7-b (1 eq, 1 g, 257.97 g / mol, 3.88 mmol) in ethanol (20 times the mass of compound 7-b) was added dropwise. After the addition was completed, the temperature was naturally raised to room temperature and stirred for 5 hours. Acetic acid (5 g, 5 times the mass of compound 7-b) and hydrochloric acid (5 eq, 3.88 ml, 5 mol / L, 19.38 mmol) were added dropwise in sequence. After the addition was completed, the temperature was raised to reflux for 5 hours. The reaction was stopped and cooled to room temperature. After the reaction solution was concentrated, appropriate amounts of dichloromethane and water were added for extraction and separation. The dichloromethane phase was washed with water until neutral and then dried. After passing through a silica gel funnel, it was concentrated under reduced pressure to obtain compound 7-c (1.02 g, yield 64.3%), MS (EI): 408 (M + ); (2)

[0112]

[0113] Under nitrogen protection, compound 7-c (0.8 g, 408.05 g / mol, 1.96 mmol), compound 7-d (1.1 eq, 0.74 g, 345.15 g / mol, 2.16 mmol), sodium tert-butoxide (1.1 eq, 0.21 g, 96.1 g / mol, 2.16 mmol), tris(dibenzylideneacetone)dipalladium (0.05 eq, 0.09 g, 915 g / mol, 0.098 mmol), tri-tert-butylphosphine (0.05 eq, 0.09 g, 915 g / mol, 0.098 mmol), , 0.02 g, 202.32 g / mol, 0.098 mol), toluene (16 ml) were added to the reaction flask, and after the addition was completed, the temperature was raised to reflux for reaction for 10 h. After the reaction was completed, the temperature was lowered to room temperature, 16 ml of water was added, and the mixture was stirred for 15 min and filtered to obtain a filtrate. The filtrate was filtered through diatomaceous earth and separated to obtain an organic phase. The organic phase was dried over anhydrous magnesium sulfate and then spin-dried. After purification by column chromatography, an organic electroluminescent material (71) (0.87 g, yield 65.7%) was obtained, MS (EI): 673 (M + ).

[0114] Example 8

[0115]

[0116] The preparation method of the organic electroluminescent material (97) is as follows: (1)

[0118]

[0119] Under nitrogen protection, ethanol (20 g, 20 times the mass of compound 8-b) was first cooled to -10 ° C, and then compound 8-a (1.2 eq, 0.84 g, 180.09 g / mol, 4.65 mmol) and sodium ethoxide (1.2 eq, 0.32 g, 68.05 g / mol, 4.65 mmol) were added. After mechanical stirring and mixing, the liquid nitrogen was cooled to -78 ° C and ethanol (20 times the mass of compound 8-b) of compound 8-b (1 eq, 1 g, 257.97 g / mol, 3.88 mmol) was added dropwise. The mixture was stirred for 5 h, and acetic acid (5 g, 5 times the mass of compound 8-b) and hydrochloric acid (5 eq, 3.88 ml, 5 mol / L, 19.38 mmol) were added dropwise. After the addition was completed, the mixture was heated to reflux for 5 h, the reaction was stopped and cooled to room temperature. The reaction solution was concentrated and extracted with appropriate amounts of dichloromethane and water. The dichloromethane phase was washed with water until neutral and then dried. After passing through a silica gel funnel, the mixture was concentrated under reduced pressure to obtain compound 8-c (1 g, yield 61.6%). MS (EI): 420 (M + ); (2)

[0121]

[0122] Under nitrogen protection, compound 8-c (0.8 g, 420.05 g / mol, 1.9 mmol), compound 8-d (1.1 eq, 0.35 g, 169.09 g / mol, 2.09 mmol), sodium tert-butoxide (1.1 eq, 0.2 g, 96.1 g / mol, 2.09 mmol), tris(dibenzylideneacetone)dipalladium (0.05 eq, 0.087 g, 915 g / mol, 0.095 mmol), tri-tert-butylphosphine (0.05 eq, 0.019 g, 202.32 g / mol, 0.095 mol), and toluene (16 ml) were added to the reaction flask. After the addition was completed, the temperature was raised to reflux for reaction for 10 h. After the reaction was completed, the temperature was lowered to room temperature, 16 ml of water was added, and the mixture was stirred for 15 min. The filtrate was filtered to obtain a filtrate. The filtrate was filtered through diatomaceous earth and separated to obtain an organic phase. The organic phase was dried over anhydrous magnesium sulfate and then spin-dried. After purification by column chromatography, an organic electroluminescent material (97) (0.83 g, yield 86.2%) was obtained. MS (EI): 509 (M + ).

[0123] Example 9

[0124]

[0125] The preparation method of the organic electroluminescent material (125) is as follows: (1)

[0127]

[0128] Under nitrogen protection, ethanol (20 g, 20 times the mass of compound 9-b) was first cooled to -10 ° C, and then compound 9-a (1.2 eq, 0.97 g, 208.13 g / mol, 4.65 mmol) and sodium ethoxide (1.2 eq, 0.32 g, 68.05 g / mol, 4.65 mmol) were added. After mechanical stirring and mixing, liquid nitrogen was cooled to -78 ° C and compound 9-b (1 eq, 1 g, 257.97 g / mol, 3.88 mmol) in ethanol (20 times the mass of compound 9-b) was added dropwise. After the addition was completed, the temperature was naturally raised to room temperature and stirred for 5 hours. Acetic acid (5 g, 5 times the mass of compound 9-b) and hydrochloric acid (5 eq, 3.88 ml, 5 mol / L, 19.38 mmol) were added dropwise in sequence. After the addition was completed, the temperature was raised to reflux for 5 hours. The reaction was stopped and cooled to room temperature. After the reaction solution was concentrated, appropriate amounts of dichloromethane and water were added for extraction and separation. The dichloromethane phase was washed with water until neutral and then dried. After passing through a silica gel funnel, it was concentrated under reduced pressure to obtain compound 9-c (1.03 g, yield 59.2%), MS (EI): 448 (M + ); (2)

[0130]

[0131] Under nitrogen protection, compound 9-c (0.8 g, 448.08 g / mol, 1.79 mmol), compound 9-d (1.1 eq, 0.63 g, 321.15 g / mol, 1.96 mmol), sodium tert-butoxide (1.1 eq, 0.19 g, 96.1 g / mol, 1.96 mmol), tris(dibenzylideneacetone)dipalladium (0.05 eq, 0.082 g, 915 g / mol, 0.089 mmol), tri-tert-butylphosphine (0.05 eq, 0.082 g, 915 g / mol, 0.089 mmol), , 0.018 g, 202.32 g / mol, 0.089 mol), and toluene (16 ml) were added to the reaction flask. After the addition was completed, the temperature was raised to reflux for reaction for 10 h. After the reaction was completed, the temperature was lowered to room temperature, 16 ml of water was added, and the mixture was stirred for 15 min. The filtrate was filtered to obtain a filtrate. The filtrate was filtered through diatomaceous earth and separated to obtain an organic phase. The organic phase was dried over anhydrous magnesium sulfate and then dried by spin drying. After purification by column chromatography, an organic electroluminescent material (125) (0.92 g, yield 74.7%) was obtained. MS (EI): 689 (M + ).

[0132] Example 10

[0133]

[0134] The preparation method of the organic electroluminescent material (154) is as follows: (1)

[0136]

[0137] Under nitrogen protection, ethanol (20 g, 20 times the mass of compound 10-b) was first cooled to -10 ° C, and then compound 10-a (1.2 eq, 1 g, 214.16 g / mol, 4.65 mmol) and sodium ethoxide (1.2 eq, 0.32 g, 68.05 g / mol, 4.65 mmol) were added. After mechanical stirring and mixing, liquid nitrogen was cooled to -78 ° C and compound 10-b (1 eq, 1 g, 257.97 g / mol, 3.88 mmol) in ethanol (20 times the mass of compound 10-b) was added dropwise. After the addition was completed, the temperature was naturally raised to room temperature and stirred for 5 hours. Acetic acid (5 g, 5 times the mass of compound 10-b) and hydrochloric acid (5 eq, 3.88 ml, 5 mol / L, 19.38 mmol) were added dropwise in sequence. After the addition was completed, the temperature was raised to reflux for 5 hours. The reaction was stopped and cooled to room temperature. After the reaction solution was concentrated, appropriate amounts of dichloromethane and water were added for extraction and separation. The dichloromethane phase was washed with water until neutral and then dried. After passing through a silica gel funnel, it was concentrated under reduced pressure to obtain compound 10-c (1.19 g, yield 67.4%), MS (EI): 454 (M + ); (2)

[0139]

[0140] Under nitrogen protection, compound 10-c (1 g, 454.12 g / mol, 2.2 mmol), compound 10-d (1.1 eq, 0.87 g, 361.18 g / mol, 2.42 mmol), sodium tert-butoxide (1.1 eq, 0.23 g, 96.1 g / mol, 2.42 mmol), tris(dibenzylideneacetone)dipalladium (0.05 eq, 0.1 g, 915 g / mol, 0.11 mmol), tri-tert-butylphosphine (0.05 eq, 0 0.022 g, 202.32 g / mol, 0.11 mol), and toluene (20 ml) were added to the reaction flask. After the addition was completed, the temperature was raised to reflux for reaction for 10 h. After the reaction was completed, the temperature was lowered to room temperature, 20 ml of water was added, and the mixture was stirred for 15 min. The filtrate was filtered to obtain a filtrate. The filtrate was filtered through diatomaceous earth and separated to obtain an organic phase. The organic phase was dried over anhydrous magnesium sulfate and then spin-dried. After purification by column chromatography, an organic electroluminescent material (154) (0.99 g, yield 61.5%) was obtained. MS (EI): 735 (M + ).

[0141] Example 11

[0142]

[0143] The preparation method of the organic electroluminescent material (195) is as follows: (1)

[0145]

[0146] Under nitrogen protection, ethanol (20 g, 20 times the mass of compound 10-b) was first cooled to -10 ° C, and then compound 11-a (1.2 eq, 0.77 g, 166.08 g / mol, 4.65 mmol) and sodium ethoxide (1.2 eq, 0.32 g, 68.05 g / mol, 4.65 mmol) were added. After mechanical stirring and mixing, liquid nitrogen was cooled to -78 ° C and compound 11-b (1 eq, 1 g, 257.97 g / mol, 3.88 mmol) in ethanol (20 times the mass of compound 11-b) was added dropwise. The mixture was stirred for 5 h, and acetic acid (5 g, 5 times the mass of compound 11-b) and hydrochloric acid (5 eq, 3.88 ml, 5 mol / L, 19.38 mmol) were added dropwise. After the addition was completed, the mixture was heated to reflux for 5 h, the reaction was stopped and cooled to room temperature. The reaction solution was concentrated and extracted with appropriate amounts of dichloromethane and water. The dichloromethane phase was washed with water until neutral and then dried. After passing through a silica gel funnel, the mixture was concentrated under reduced pressure to give compound 11-c (1.03 g, yield 65.5%). MS (EI): 406 (M + ); (2)

[0148]

[0149] Under nitrogen protection, compound 11-c (1 g, 406.04 g / mol, 1.97 mmol), compound 11-d (1.1 eq, 0.7 g, 321.15 g / mol, 2.17 mmol), sodium tert-butoxide (1.1 eq, 0.21 g, 96.1 g / mol, 2.17 mmol), tris(dibenzylideneacetone)dipalladium (0.05 eq, 0.09 g, 915 g / mol, 0.099 mmol), tri-tert-butylphosphine (0.05 eq, 0.09 g, 915 g / mol, 0.099 mmol), and 11-d (1.1 eq, 0.7 g, 321.15 g / mol, 2.17 mmol) were added. q, 0.02 g, 202.32 g / mol, 0.099 mol), and toluene (20 ml) were added to the reaction flask. After the addition was completed, the temperature was raised to reflux for reaction for 10 h. After the reaction was completed, the temperature was lowered to room temperature, 20 ml of water was added, and the mixture was stirred for 15 min. The filtrate was filtered to obtain a filtrate. The filtrate was filtered through diatomaceous earth and separated to obtain an organic phase. The organic phase was dried over anhydrous magnesium sulfate and then dried by spin drying. After purification by column chromatography, an organic electroluminescent material (195) (1 g, yield 78.3%) was obtained. MS (EI): 647 (M + ).

[0150] Example 12

[0151]

[0152] The preparation method of the organic electroluminescent material (202) is as follows:

[0153]

[0154] Under nitrogen protection, compound 12-a (1 g, 406.04 g / mol, 1.97 mmol), compound 12-b (1.1 eq, 0.7 g, 361.18 g / mol, 2.17 mmol), sodium tert-butoxide (1.1 eq, 0.21 g, 96.1 g / mol, 2.17 mmol), tris(dibenzylideneacetone)dipalladium (0.05 eq, 0.09 g, 915 g / mol, 0.099 mmol), tri-tert-butylphosphine (0.05 eq, 0.02 g, 202.32 g / mol, 0.099 mol), and toluene (20 ml) were added to a reaction flask. After the addition was completed, the temperature was raised to reflux for reaction for 10 h. After the reaction was completed, the temperature was lowered to room temperature, 20 ml of water was added, and the mixture was stirred for 15 min. The filtrate was filtered to obtain a filtrate. The filtrate was filtered through diatomaceous earth and separated to obtain an organic phase. The organic phase was dried over anhydrous magnesium sulfate and then dried by spin drying. After purification by column chromatography, an organic electroluminescent material (202) (0.85 g, yield 62.8%) was obtained. MS (EI): 687 (M + ).

[0155] Example 13

[0156]

[0157] The preparation method of the organic electroluminescent material (219) is as follows: (1)

[0159]

[0160] Under nitrogen protection, ethanol (20 g, 20 times the mass of compound 13-b) was first cooled to -10 ° C, and then compound 13-a (1.2 eq, 0.54 g, 116.06 g / mol, 4.65 mmol) and sodium ethoxide (1.2 eq, 0.32 g, 68.05 g / mol, 4.65 mmol) were added. After mechanical stirring and mixing, liquid nitrogen was cooled to -78 ° C and compound 13-b (1 eq, 1 g, 257.97 g / mol, 3.88 mmol) in ethanol (20 times the mass of compound 13-b) was added dropwise. The mixture was stirred for 5 h, and acetic acid (5 g, 5 times the mass of compound 11-b) and hydrochloric acid (5 eq, 3.88 ml, 5 mol / L, 19.38 mmol) were added dropwise. After the addition was completed, the mixture was refluxed for 5 h, the reaction was stopped and cooled to room temperature. The reaction solution was concentrated and extracted with appropriate amounts of dichloromethane and water. The dichloromethane phase was washed with water until neutral and then dried. After passing through a silica gel funnel, the mixture was concentrated under reduced pressure to give compound 13-c (1.02 g, yield 74.1%). MS (EI): 356 (M + ); (2)

[0162]

[0163] Under nitrogen protection, compound 13-c (0.8 g, 356.02 g / mol, 2.25 mmol), compound 13-d (1.1 eq, 0.83 g, 335.13 g / mol, 2.47 mmol), sodium tert-butoxide (1.1 eq, 0.24 g, 96.1 g / mol, 2.47 mmol), tris(dibenzylideneacetone)dipalladium (0.05 eq, 0.1 g, 915 g / mol, 0.11 mmol), tri-tert-butylphosphine (0.05 eq, 0.1 g, 915 g / mol, 0.11 mmol), , 0.023 g, 202.32 g / mol, 0.11 mol), toluene (16 ml) were added to the reaction flask, and after the addition was completed, the temperature was raised to reflux for reaction for 10 h. After the reaction was completed, the temperature was lowered to room temperature, 16 ml of water was added, and the mixture was stirred for 15 min and filtered to obtain a filtrate. The filtrate was filtered through diatomaceous earth and separated to obtain an organic phase. The organic phase was dried over anhydrous magnesium sulfate and then spin-dried. After purification by column chromatography, an organic electroluminescent material (219) (0.83 g, yield 60.4%) was obtained, MS (EI): 611 (M + ).

[0164] Example 14

[0165]

[0166] The preparation method of the organic electroluminescent material (231) is as follows: (1)

[0168]

[0169] Under nitrogen protection, ethanol (20 g, 20 times the mass of compound 14-b) was first cooled to -10 ° C, and then compound 14-a (1.2 eq, 0.54 g, 116.06 g / mol, 4.65 mmol) and sodium ethoxide (1.2 eq, 0.32 g, 68.05 g / mol, 4.65 mmol) were added. After mechanical stirring and mixing, liquid nitrogen was cooled to -78 ° C and compound 14-b (1 eq, 1 g, 257.97 g / mol, 3.88 mmol) in ethanol (20 times the mass of compound 14-b) was added dropwise. The mixture was stirred for 5 h, and acetic acid (5 g, 5 times the mass of compound 14-b) and hydrochloric acid (5 eq, 3.88 ml, 5 mol / L, 19.38 mmol) were added dropwise. After the addition was completed, the mixture was heated to reflux for 5 h, the reaction was stopped and cooled to room temperature. The reaction solution was concentrated and extracted with appropriate amounts of dichloromethane and water. The dichloromethane phase was washed with water until neutral and then dried. After passing through a silica gel funnel, the mixture was concentrated under reduced pressure to obtain compound 14-c (0.86 g, yield 62.3%). MS (EI): 356 (M + ); (2)

[0171]

[0172] Under nitrogen protection, compound 14-c (0.6 g, 356.02 g / mol, 1.69 mmol), compound 14-d (1.1 eq, 0.64 g, 345.15 g / mol, 1.85 mmol), sodium tert-butoxide (1.1 eq, 0.18 g, 96.1 g / mol, 1.85 mmol), tris(dibenzylideneacetone)dipalladium (0.05 eq, 0.077 g, 915 g / mol, 0.084 mmol), tri-tert-butylphosphine (0.05 eq, 0.077 g, 915 g / mol, 0.084 mmol), and 14-d (1.1 eq, 0.64 g, 345.15 g / mol, 1.85 mmol) were added. q, 0.017 g, 202.32 g / mol, 0.084 mol), and toluene (12 ml) were added to the reaction flask. After the addition was completed, the temperature was raised to reflux for reaction for 10 h. After the reaction was completed, the temperature was lowered to room temperature, 12 ml of water was added, and the mixture was stirred for 15 min. The filtrate was filtered to obtain a filtrate. The filtrate was filtered through diatomaceous earth and separated to obtain an organic phase. The organic phase was dried over anhydrous magnesium sulfate and then dried by spin drying. After purification by column chromatography, an organic electroluminescent material (231) (0.58 g, yield 55.3%) was obtained. MS (EI): 621 (M + ).

[0173] Material property testing

[0174] The thermal gravimetric temperature Td and melting point Tm of the olefinefluorene organic electroluminescent materials 3, 6, 26, 31, 43, 64, 71, 97, 125, 154, 195, 202, 219, and 231 of the present invention were measured using TGA (TGA-1500). The test results are shown in Table 1 below.

[0175] Note: The thermal gravimetric temperature (Td) is the temperature at which the weight loss ratio is 5% in a nitrogen atmosphere, and is measured on a TGAN-1000 thermogravimetric analyzer with a nitrogen flow rate of 10 mL / min. The melting point (Tm) is determined by differential scanning calorimetry (DSC, Xinke DSC N-650) at a heating rate of 10°C / min.

[0176] Table 1

[0177] project Material Td / ℃ Tm / ℃ project Material Td / ℃ Tm / ℃ Example 01 3 356.23 237.12 Example 02 6 378.24 210.52 Example 03 26 358.49 226.79 Example 04 31 355.74 238.16 Example 05 43 346.25 259.41 Example 06 64 359.46 239.77 Example 07 71 379.15 285.69 Example 08 97 344.27 266.72 Example 09 125 398.95 263.13 Example 10 154 384.12 286.33 Example 11 195 374.88 283.31 Example 12 202 389.49 277.30 Example 13 219 377.41 233.16 Example 14 231 394.32 280.63

[0178] From the above data, it can be seen that the compounds synthesized in the present invention have excellent thermal stability, which means that the compounds conforming to the general structural formula of the present invention all have excellent thermal stability and can meet the requirements for use as organic electroluminescent materials.

[0179] Device performance test

[0180] Application Example 1

[0181] ITO was used as the reflective layer anode substrate material, and its surface was treated with water, acetone, and N2 plasma in sequence;

[0182] On top of the ITO anode substrate, a hole injection layer (HIL) was formed by depositing 3% wt HAT-CN with a thickness of 10 nm.

[0183] The organic electroluminescent compound 3 prepared in Example 1 of the present invention was evaporated on the hole injection layer (HIL) to form a hole transport layer (HTL) with a thickness of 85 nm;

[0184] EB-1 was vacuum evaporated on the hole transport layer (HTL) to form an electron blocking layer (EBL) with a thickness of 10 nm;

[0185] BH-1 as a blue light host material and BD-1 as a blue light dopant material (BD-1 dosage is 3% of the weight of ADN) were evaporated at different rates on the hole transport layer (HTL) to form a 20 nm thick light-emitting layer;

[0186] HB-1 was evaporated onto the light-emitting layer to obtain a hole blocking layer (HBL) with a thickness of 20 nm;

[0187] ET-1 was used as the electron transport layer material (ET) and evaporated onto the hole blocking layer (HBL) to obtain an electron transport layer (ETL) with a thickness of 30 nm. LiQ was evaporated on top of the electron transport layer (ETL) to form an electron injection layer (EIL).

[0188] Subsequently, magnesium (Mg) and silver (Ag) were mixed in a mass ratio of 9:1 and evaporated to form a cathode with a thickness of 15 nm. A 50 nm thick layer of DNTPD was deposited on the cathode sealing layer. Furthermore, the cathode surface was sealed with a UV-curable adhesive and a seal cap containing a desiccant to protect the organic electroluminescent device from oxygen or moisture in the atmosphere. Thus, an organic electroluminescent device was prepared.

[0189]

[0190]

[0191] Application Example 2-14

[0192] The olefinic organic electroluminescent materials 6, 26, 31, 43, 64, 71, 97, 125, 154, 195, 202, 219, and 231 in Examples 2-14 of the present invention are respectively used as hole transport layer materials, and the other parts are consistent with Application Example 1, thereby manufacturing the organic electroluminescent devices of Application Examples 2-14.

[0193] Comparative Examples 1 and 2

[0194] The difference between Control Examples 1 and 2 and Application Example 1 is that HTL-1 and HTL-2 are used as hole transport layer materials, and the rest are the same as Application Example 1.

[0195] The characteristics of the organic electroluminescent device manufactured in the above application example and the organic electroluminescent device manufactured in the comparative example are that the current density is 10mA / cm 2 The results were shown in Table 2.

[0196] Table 2:

[0197]

[0198]

[0199] As shown in Table 2 above, when the olefinefluorene organic electroluminescent material of the present invention is applied to an organic electroluminescent device, the luminous efficiency is significantly improved at the same current density, and the starting voltage of the device is reduced, and the power consumption of the device is relatively reduced, thereby significantly improving the life of the device.

[0200] The organic electroluminescent devices prepared in Control Examples 1-2 and Application Examples 1-14 were tested for luminescence lifetime to obtain T97% data (the time it takes for the luminescence brightness to drop to 97% of the initial brightness). The test equipment was a TEO light-emitting device lifetime test system. The results are shown in Table 9:

[0201] Table 3

[0202]

[0203] As can be seen from Table 3, when the compound of the present invention is used as a hole transport layer (HTL) in an organic electroluminescent device, the service life of the organic electroluminescent device prepared is greatly improved, so it has a very broad application prospect.

Claims

1. An olefin fluorene organic electroluminescent material, characterized in that: The olefinefluorene organic electroluminescent material is any one of the following structural compounds:

2. The olefinefluorene organic electroluminescent material according to claim 1, wherein The preparation method is as follows: (1) Under an inert atmosphere, first cool ethanol to -10 to -5°C, then add compound I and sodium ethoxide, stir mechanically to mix, cool liquid nitrogen to -78°C, add dropwise the ethanol solution of compound II, and naturally warm to room temperature after the addition is complete, stir and react for 5 to 10 hours, then add acetic acid and hydrochloric acid dropwise in sequence, and after the addition is complete, heat to reflux and react for 5 to 10 hours, stop the reaction and cool to room temperature, concentrate the reaction solution, add appropriate amounts of dichloromethane and water for extraction and separation, wash the dichloromethane phase with water until neutral and then dry, pass through a silica gel funnel and concentrate under reduced pressure to obtain compound III; (2) Under an inert atmosphere, compound III, compound IV, potassium tert-butoxide or sodium tert-butoxide, tris(dibenzylideneacetone)dipalladium, tri-tert-butylphosphine, and toluene are mixed, the temperature is raised to reflux for reaction for 5 to 10 hours, the mixture is cooled to room temperature, water is added and stirred, the reaction solution is filtered, the organic phase is separated, dried, and then spin-dried, and purified by column chromatography to obtain the enefluorene organic electroluminescent material.

3. An organic electroluminescent device, characterized in that: include: A structure in which an anode, a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, an electron injection layer and a cathode are stacked in sequence; the hole transport layer contains at least one olefinefluorene organic electroluminescent material as claimed in any one of claims 1.

4. An organic electroluminescent display device, characterized in that: Contains the organic electroluminescent device as claimed in claim 3.

5. An organic electroluminescent lighting device, characterized in that: Contains the organic electroluminescent device as claimed in claim 3.

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