Amine compound and organic electroluminescent device containing same

Abstract

The invention provides an amine compound, belongs to the technical field of organic light-emitting materials, and also relates to an application of the compound in an organic light-emitting device. An amine compound is characterized in that the compound has a structure shown in a formula (1): # imgabs0 #, an organic electroluminescent element comprises a first electrode, a second electrode and one or more organic layers between the first electrode and the second electrode, and at least one organic layer contains the amine compound. According to the prepared organic electroluminescent device, the driving voltage can be reduced, the luminous efficiency of the device can be improved, and the service life is also well prolonged.

Description

Technical Field

[0001] The invention belongs to the technical field of optoelectronic materials, and in particular relates to an organic electroluminescent device of an amine compound and a preparation method thereof. Background Art

[0002] Organic light emitting diode (OLED) is a self-luminous display device based on organic electroluminescent materials. Unlike existing liquid crystal display devices, it does not require a backlight source and is thin, and is a technology suitable for flexible device devices (flexible light-emitting display devices). Organic electroluminescent devices that utilize organic light-emitting phenomena usually have a structure including an anode, a cathode, and an organic layer therebetween. In order to improve the efficiency and stability of organic electroluminescent devices, the organic layer is usually composed of a multilayer structure composed of various different substances, for example, a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, and an electron injection layer.

[0003] Currently, OLED display technology has been applied in smart phones, tablet computers and other fields, and will further expand to large-size application fields such as TVs. However, compared with the actual product application requirements, the luminous efficiency and service life of OLED devices need to be further improved. Research on improving the performance of OLED light-emitting devices includes: reducing the driving voltage of the device, improving the luminous efficiency of the device, and increasing the service life of the device. In order to continuously improve the performance of OLED devices, it is necessary not only to innovate the structure and manufacturing process of OLED devices, but also to continuously research and innovate OLED optoelectronic functional materials to create functional materials with higher performance OLEDs.

[0004] Many aromatic amine compounds can be used as hole transport materials in the hole transport layer. At present, although a large number of aromatic amine derivative materials with excellent performance have been developed, there are still many problems in this technology. How to design materials with better performance so that the device can achieve low voltage, high efficiency and long life has always been a problem that needs to be solved urgently by technicians in this field. Summary of the invention

[0005] The purpose of the present invention is to provide a luminescent material of an amine compound and the application of the compound in an organic electroluminescent device to achieve high luminescent efficiency, low driving voltage and long life of the organic electroluminescent device.

[0006] The present invention provides an amine compound having a structure shown in formula (1):

[0007]

[0008] wherein Cy is present or absent, and when Cy is present, it is selected from a 5-6 membered ring,

[0009] L 1 -L 2 are each independently selected from a single bond, a substituted or unsubstituted C6-C60 arylene group, and a substituted or unsubstituted C3-C60 heteroarylene group,

[0010] R 1 -R 3 each independently selected from hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C2-C10 heterocycloalkyl, substituted or unsubstituted C1-C10 alkoxy, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C3-C60 heteroaryl,

[0011] The substituents in the "substituted or unsubstituted" are each independently selected from one or a combination of deuterium, halogen, cyano, C1-C10 alkyl, C3-C10 cycloalkyl, C6-C30 aryl, C3-C30 heteroaryl,

[0012] The heteroatom of the heteroaryl group is selected from one or more of oxygen, sulfur and nitrogen.

[0013] Preferably, the compound has a structure shown in formula (2) or formula (3):

[0014]

[0015] More preferably, the compound has a structure shown in formula (4) or formula (5):

[0016]

[0017]

[0018] As a preference, L 1 -L 2 Each is independently selected from a single bond, a substituted or unsubstituted C6-C30 arylene group, and a substituted or unsubstituted C3-C25 O-containing heteroarylene group.

[0019] Preferably, the L 1 -L 2 each independently selected from a single bond, a substituted or unsubstituted phenylene group, a substituted or unsubstituted biphenylene group, a substituted or unsubstituted naphthylene group, a substituted or unsubstituted anthrylene group, a substituted or unsubstituted phenanthrylene group, a substituted or unsubstituted fluoranthenylene group, a substituted or unsubstituted pyrenylene group, a substituted or unsubstituted perylene group, a substituted or unsubstituted triphenyl ... pyrenylene group, a substituted or unsubstituted pyrenylene group, a substituted or unsubstituted fluorenylene, substituted or unsubstituted 9,9-dimethylfluorenylene, substituted or unsubstituted 9,9-diphenylfluorenylene, substituted or unsubstituted spirobifluorenylene, substituted or unsubstituted dibenzofuranylene, substituted or unsubstituted dibenzothiophenylene, substituted or unsubstituted carbazolylene.

[0020] Preferably, the L 1 -L 2 Each is independently selected from a single bond, a substituted or unsubstituted group: in Indicates the connection site.

[0021] As more preferably, the L 1 Selected from single bonds, substituted or unsubstituted groups: in Indicates the connection site.

[0022] As more preferably, the L 2 Select from single bonds.

[0023] As a preference, R 1- R 3 Each is independently selected from hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C6-C30 aryl, and substituted or unsubstituted C3-C25 O-containing heteroaryl.

[0024] Preferably, the R 1 -R 3 each independently selected from hydrogen, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted phenylnaphthyl, substituted or unsubstituted anthracenyl, substituted or unsubstituted phenanthrenyl, substituted or unsubstituted fluoranthenyl, substituted or unsubstituted pyrenyl, substituted or unsubstituted peryl, substituted or unsubstituted triphenylene, substituted or unsubstituted substituted or unsubstituted fluorenyl, substituted or unsubstituted 9,9-dimethylfluorenyl, substituted or unsubstituted 9,9-diphenylfluorenyl, substituted or unsubstituted spirobifluorenyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothiophenyl, substituted or unsubstituted carbazolyl.

[0025] Preferably, the R 1 -R 3 Each is independently selected from the following groups which may be substituted with hydrogen: in Indicates the connection site.

[0026] More preferably, the R1 Selected from the following substituted or unsubstituted groups: in Indicates the connection site.

[0027] More preferably, the R 2 Selected from hydrogen.

[0028] More preferably, the R 3 Selected from the following substituted or unsubstituted groups: in Indicates the connection site.

[0029] Preferably, the substituents in the "substituted or unsubstituted" are each independently selected from deuterium, halogen, cyano, methyl, ethyl, tert-butyl, cyclohexyl, phenyl, biphenyl, terphenyl, naphthyl, anthracenyl, phenanthrenyl, pyrene, fluoranthenyl, triphenylene, A combination of one or more of dibenzothiophene, dibenzofuranyl and dibenzothiophene.

[0030] In a specific embodiment of the present invention, the amine compound is selected from any one of the following compounds Nos. 1-1 to 1-42, 2-1 to 2-42:

[0031]

[0032]

[0033]

[0034]

[0035]

[0036]

[0037] A use of the compound of the invention as an organic electroluminescent material.

[0038] An organic electroluminescent element comprises a substrate, an anode, a hole transport region, a light-emitting layer, an electron transport region, and a cathode, wherein the light-emitting layer is located between the anode and the cathode, the hole transport region is located between the anode and the light-emitting layer, the electron transport region is located between the light-emitting layer and the cathode, and the hole transport region contains the amine compound described in the present invention.

[0039] Preferably, the hole transport region comprises at least one of a hole injection layer and a hole transport layer, and the hole transport layer comprises the amine compound of the present invention.

[0040] An electronic device comprises: one or more of a display, a monitor and a lighting device, including the organic electroluminescent element of the present invention; and a control unit for driving the display device.

[0041] The beneficial effects of the present invention are:

[0042] The amine compound of the present invention is applied to the hole transport layer, has good hole transport performance, has low molecular coplanarity, good solubility and good thermal stability. The prepared organic electroluminescent device can increase the hole movement speed, thereby improving the luminous efficiency of the device, and has a good improvement in both luminous efficiency and life. BRIEF DESCRIPTION OF THE DRAWINGS

[0043] Figure 1 It is a schematic diagram of the structure of the organic electroluminescent element described in Application Example 1, wherein: 1. anode; 2. hole injection layer; 3. hole transport layer; 4. luminescence auxiliary layer; 5. luminescent layer; 6. electron transport layer; 7. cathode. DETAILED DESCRIPTION

[0044] In order to more fully describe the present invention to those skilled in the art, embodiments of the present invention are provided. The scope of the present invention is not limited to the following embodiments. These embodiments can make the present invention more thorough and complete, and fully convey the viewpoints of the present invention to those skilled in the art.

[0045] By reference to the following specific embodiments and the examples contained therein, the disclosure can be more easily understood. Before disclosing and describing the compounds, devices and / or methods of the present invention, it should be understood that, unless otherwise stated, they are not limited to specific synthetic methods or specific reagents, because this can be varied. It should also be understood that the terms used in the present invention are only used to describe specific aspects and are not intended to be limiting. Although any methods and materials similar or equivalent to those described in the present invention can be used in this practice or test, exemplary methods and materials are now described.

[0046] Unless otherwise specified, the experimental methods used in the following examples are all conventional methods; the reagents, materials, etc. used in the following examples, unless otherwise specified, can be obtained from commercial channels.

[0047] As used herein, the term "halogen" may include fluorine, chlorine, bromine or iodine.

[0048] As used in the present invention, the term "C1-C10 alkyl" refers to a monovalent substituent derived from a straight or branched chain saturated hydrocarbon having 1 to 10 carbon atoms, examples of which include but are not limited to methyl, ethyl, propyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl and hexyl.

[0049] As used in the present invention, the term "C3-C10 cycloalkyl" refers to a monovalent substituent derived from a monocyclic or polycyclic non-aromatic hydrocarbon having 3 to 10 carbon atoms. Examples of such cycloalkyl include, but are not limited to, cyclopropane, cyclobutane, cyclopentane, cyclohexane, norbornyl, adamantane, and the like.

[0050] As used in the present invention, the term "C2-C10 heterocycloalkyl" is a monovalent substituent having a monocyclic or polycyclic ring of 2 to 10 carbon atoms, and the ring contains at least one heteroatom selected from O, S, N, P, and Si.

[0051] As used in the present invention, the term "alkoxy" refers to a straight chain, a branched chain or a cyclic chain. The number of carbon atoms of the alkoxy group is not particularly limited herein, but the alkoxy group preferably has 1 to 10 carbon atoms. Specific examples thereof include, but are not limited to, methoxy, ethoxy, n-propoxy, isopropoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, sec-butoxy, n-pentoxy, neopentoxy, isopentyloxy, n-hexyloxy, and benzyloxy.

[0052] As used in the present invention, the term "C6-C60 aryl" refers to a monovalent substituent derived from an aromatic hydrocarbon having a monocyclic ring or a combination of two or more rings and having 6 to 60 carbon atoms. Further, such an aryl may have a form in which two or more rings are simply lateral or fused to each other. Examples of such aryl groups include, but are not limited to, phenyl, biphenyl, naphthyl, phenanthrenyl, anthracenyl, pyrenyl, triphenylene, fluoranthenyl, dimethyl 9,9-dimethylfluorene, 9,9-diphenylfluorene, spirobifluorenyl, etc.

[0053] As used herein, the term "arylene group" refers to a divalent aromatic group derived from an "aryl group" by removing a hydrogen atom. For example, a phenyl group is substituted by removing a hydrogen atom to form a phenylene group, and a naphthyl group is substituted by removing a hydrogen atom to form a naphthylene group.

[0054] As used in the present invention, the term "C3-C60 heteroaryl group" refers to a monovalent substituent derived from a monocyclic heterocyclic or polycyclic aromatic hydrocarbon having 3 to 60 carbon atoms. In this connection, at least one carbon, preferably 1 to 3 carbons in the ring are substituted with a heteroatom such as N, O, S, P, B or Si. In addition, this heteroaryl group may have a form in which two or more rings are simply lateral to each other or fused to each other or fused to an aromatic group. Examples of such heteroaryl groups include pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, triazinyl, indolizinyl, indolyl, indolopyridinyl, purinyl, phenanthroline, quinolyl, isoquinolyl, quinazolinyl, quinoxalinyl, thiazolyl, imidazolyl, oxazolyl, furanyl, thienyl, benzofuranyl, benzothienyl, benzothiazolyl, benzimidazolyl, benzoxazolyl, carbazolyl, dibenzofuranyl, dibenzothienyl and the like, but the present invention is not limited thereto.

[0055] As used in the present invention, the term "heteroarylene" refers to a divalent heteroaryl group derived from a "heteroaryl" by removing a hydrogen atom. For example, a pyridyl group is derived from a pyridylene group by removing a hydrogen atom.

[0056] As used in the present invention, the "carbon number is AA-BB" in the expression "Z group having carbon atoms AA-BB" or "Z group having C(AA-BB)" means the carbon number of the Z group when it is unsubstituted, and does not include the carbon number of the substituent when it is substituted. For example, a C6-C30 aryl group means that when it is unsubstituted, the number of carbon atoms in the aryl group is any integer between 6 and 30, that is, the number of carbon atoms when it is unsubstituted can be 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20...30.

[0057] As used in the present invention, the term "single bond" refers to a direct connection of groups, for example, in formula (1), Medium 1 is a single bond, which means

[0058] As used in the present invention, "Cy is present or absent", when absent,

[0059] As used in the present invention, "Cy is selected from a 5-6 membered ring" as shown in the following structure The “-*” indicates the same as L 2 Connection site.

[0060] As used in the present invention, the term "substituted" means that a hydrogen atom in a compound is replaced by another substituent. The position where the substitution occurs can be the position where the hydrogen atom is replaced. That is, the position is not limited to a specific position, as long as the hydrogen at the position can be replaced by a substituent. For example, carbazolyl includes any of the following groups, but is not limited thereto, as long as it is not otherwise described in this specification,

[0061] Indicates the position of substitution. "Unsubstituted" means that hydrogen atoms remain, in this case, hydrogen atoms include protium, deuterium, tritium.

[0062] As used herein, the term "phenylene naphthyl" refers to

[0063] As used herein, the term "phenylnaphthyl" includes

[0064] Refers to the replacement position.

[0065] When two or more substituents are present, the two or more substituents may be the same or different.

[0066] As used in the present invention, hydrogen atoms include protium, deuterium and tritium. The compounds of the present invention may contain deuterium atoms of natural origin, or may introduce deuterium atoms by deuterating a portion or all of the raw material compounds. If deuterium atoms are introduced from the raw materials, the deuteration rate may be 100%, or may be less than 100%, or less than 95%, or less than 90%, or less than 80%, and the deuteration rate may also be more than 1%, or more than 5%, or more than 10%. If the deuteration rate is not 100%, it means a mixture of deuterated compounds and undeuterated compounds, or a mixture of completely deuterated compounds and incompletely deuterated compounds, or a mixture of completely deuterated compounds and undeuterated compounds and incompletely deuterated compounds.

[0067] As used in the present invention, terms such as first, second, A, B, etc. are used. The above terms are only used to distinguish components, and do not limit the nature or order of the components to which the terms correspond.

[0068] Organic electroluminescent element

[0069] The structure of the organic electroluminescent element of the present invention is a disclosed structure, comprising an anode, a cathode and an organic layer located between the anode and the cathode, wherein the organic layer comprises a light-emitting layer, and at least one layer of the organic layer comprises the compound of the present invention.

[0070] The organic layer further includes one or more of a hole injection layer, a hole transport layer, a light-emitting auxiliary layer, a hole blocking layer, an electron transport layer, and an electron injection layer, but is not limited thereto.

[0071] The light-emitting element of the present invention may emit fluorescence or phosphorescence or a combination thereof. The light-emitting element may emit light alone or in series with multiple light-emitting units.

[0072] As simple light emitting elements, the following may be cited, but are not limited thereto:

[0073] (1) hole transport layer / fluorescent light emitting layer / electron transport layer;

[0074] (2) hole transport layer / phosphorescent light emitting layer / electron transport layer;

[0075] (3) hole transport layer / first fluorescent light-emitting layer / second fluorescent light-emitting layer / electron transport layer;

[0076] (4) hole transport layer / first phosphorescent light-emitting layer / second phosphorescent light-emitting layer / electron transport layer;

[0077] (5) hole transport layer / fluorescent emitting layer / spacer layer / phosphorescent emitting layer / electron transport layer;

[0078] (6) hole transport layer / luminescence auxiliary layer / fluorescent light emitting layer / electron transport layer;

[0079] (7) hole transport layer / luminescence auxiliary layer / fluorescent light-emitting layer / hole blocking layer / electron transport layer;

[0080] (8) hole transport layer / luminescence auxiliary layer / phosphorescent light emitting layer / electron transport layer;

[0081] (9) hole transport layer / luminescence auxiliary layer / phosphorescent light emitting layer / hole blocking layer / electron transport layer;

[0082] (10) hole injection layer / hole transport layer / phosphorescent light emitting layer / electron transport layer / electron injection layer;

[0083] (11) hole injection layer / hole transport layer / fluorescent light emitting layer / electron transport layer / electron injection layer;

[0084] (12) hole injection layer / hole transport layer / luminescence auxiliary layer / phosphorescent light emitting layer / electron transport layer / electron injection layer;

[0086] (13) hole injection layer / hole transport layer / luminescence auxiliary layer / fluorescent light emitting layer / electron transport layer / electron injection layer;

[0087] The phosphorescent / fluorescent light-emitting layers mentioned above can each emit light of a different color.

[0088] As a tandem type organic electroluminescent element, it can be an anode / first light-emitting unit / intermediate layer / second light-emitting unit / cathode. The intermediate layer can also be generally called a charge generation layer, an electron extraction layer, a connecting layer, etc. For example, when stacking a fluorescent light-emitting layer and a phosphorescent light-emitting layer, an intermediate layer is placed between the fluorescent light-emitting layer and the phosphorescent light-emitting layer in order to prevent the excitons generated by the phosphorescent light-emitting layer from diffusing to the fluorescent light-emitting layer or to adjust the balance of carriers.

[0089] When the organic light emitting element includes a plurality of organic material layers, the organic material layers may be formed of the same material or different materials.

[0090] The organic electroluminescent element of the present specification can be manufactured by materials and methods known in the art, except that one or more of the organic material layers is prepared by using a compound comprising the formula (1).

[0091] As the anode material, a material having a relatively large work function may be used, and a transparent conductive oxide, a metal, a conductive polymer, or the like may be used.

[0092] As the cathode material, a material having a low work function is generally used to facilitate electron injection into the organic material layer, and metals, metal oxides, conductive polymers, etc. can be used.

[0093] The hole injection layer is a layer that injects holes from the electrodes and has the ability to transport holes. In order to reduce the energy level difference between the electrodes, the hole injection layer is mainly prepared based on aromatic amine compounds, and other materials with hole transport ability can also be used.

[0094] The hole transport layer is a layer that receives holes from the hole injection layer and transports the holes to the light emitting layer, and the hole transport material is suitably a material having high hole mobility that can receive holes from the anode or the hole injection layer and transfer the holes to the light emitting layer.

[0095] The luminescent auxiliary layer is a layer that blocks electrons from reaching the anode. It can adjust the energy difference between the hole transport region and the luminescent layer, facilitate holes to enter the luminescent layer, and reduce the probability of electrons entering the hole transport region from the luminescent layer. Aromatic amine derivatives are commonly used.

[0096] The luminescent material is a material that receives holes and electrons from the hole transport layer and the electron transport layer, respectively, and combines the holes and electrons to emit light in the visible light region. The luminescent layer material includes a host material and a doping material. Red, green or blue luminescent materials can be used, and two or more luminescent materials can be mixed as needed. As the luminescent material, a fluorescent material can be used, and a phosphorescent material can also be used. As the luminescent material, a single component material can be used, and a multi-component material can also be used.

[0097] The electron transport layer receives electrons from the electron injection layer and transports the electrons to the light-emitting layer, and the electron transport material can receive electrons from the cathode and transfer the electrons to the light-emitting layer. The metal complexes of triazine derivatives, oxadiazole derivatives, benzoquinone and its derivatives, naphthoquinone and its derivatives, anthraquinone and its derivatives, fluorenone derivatives, diphenyl dicyanoethylene and its derivatives, 8-hydroxyquinoline and its derivatives, etc. can be used, and polymer materials and small molecule materials can also be used.

[0098] The electron injection layer is a layer that injects electrons from the electrode.

[0099] The organic light-emitting element of the present specification may be a top-emitting element, a bottom-emitting element, or a dual-emission element depending on the materials used.

[0100] Synthesis formula: The following general formula is only one method for synthesizing the compounds of the present invention. The compounds of the present invention can also be synthesized by other methods.

[0101]

[0102] Where X represents halogen, different substitution positions can be synthesized using the same method, Cy, L 1 , L 2 , R1 -R 3 The same meaning as in claim 1.

[0103] Compound Preparation Examples

[0104] The present invention is specifically described by way of compound examples 1-14.

[0105] Compound Example 1: Preparation of Compound 1-1

[0106]

[0107] 1-1-1 (42.0 g, 149.46 mmol) was dissolved in ethyl acetate (500 mL), and Raney nickel (20 g) was then added and reacted at room temperature for 48 hours. After TLC confirmed that the reaction was complete, a diatomaceous earth column was used to remove the catalyst. At room temperature, pd / C (10 g) catalyst was added, and hydrogen reaction was carried out under a hydrogen pressure of about 100 psi. After 72 hours, the reaction was complete, and the solvent was removed under reduced pressure to obtain 1-1-2 (35.7 g, 83% yield) by column chromatography.

[0108] LC-MS (APCI) (M+H) + :285.82

[0109]

[0110] Under a nitrogen atmosphere, compounds 1-1-3 (26.83 g, 93.45 mmol) and 1-1-4 (17.89 g, 93.45 mmol) were added to a three-necked flask, THF (150 mL) and water (50.0 mL) were added to dissolve, potassium carbonate (19.4 g, 140.58 mmol) and tetrakistriphenylphosphine palladium (2.15 g, 1.87 mmol) were added, and the mixture was heated to 70-80 ° C for reaction. After the reaction was completed, the liquid was extracted and separated, and the organic phase was dried over anhydrous sodium sulfate, filtered and concentrated, and the intermediate compound 1-1-5 (25.00 g, yield 67%) was obtained by column chromatography.

[0111] LC-MS (APCI) (M+H) + :354.36

[0112]

[0113] Under nitrogen atmosphere, compound 1-1-5 (14.37 g, 50.37 mmol) and compound 1-1-6 (4.69 g, 50.37 mmol) were dissolved in 150 mL of toluene, tri(dibenzylacetone)dipalladium (0) (0.92 g, 1.01 mmol), tri-tert-butylphosphine (2.01 mL, 2.01 mmol), sodium tert-butoxide (14.50 g, 151.04 mmol) were added, and refluxed for 5 h. After the reaction was completed, 200 mL of dichloromethane and 200 mL of water were added, and then the dichloromethane layer was extracted, and the intermediate 1-1-7 (16.46 g, yield 75%) was obtained by column chromatography (petroleum ether: ethyl acetate volume ratio = 5:1).

[0114] LC-MS (APCI) (M+H) + :411.32

[0115]

[0116] Under a nitrogen atmosphere, compound 1-1-2 (10.00 g, 35.21 mmol) and compound 1-1-7 (14.30 g, 35.21 mmol) were dissolved in 250 mL of toluene, and then sodium tert-butoxide (16.90 g, 176.05 mmol)), tri(dibenzylacetone)dipalladium(0) (0.64 g, 0.70 mmol) and tri-tert-butylphosphine (0.14 g, 0.70 mmol) were added. After stirring at 90 ° C for 4 hours, it was extracted with dichloromethane and water, the organic layer was collected, and the target compound 1-1 (11.64 g, yield 54%) was obtained by column chromatography.

[0117] LC-MS (APCI) (M+H) + :615.77

[0118] Compound Example 2: Preparation of Compound 1-9

[0119]

[0120] Prepared according to the same synthesis method as the above compound Example 1, replacing compound 1-1-6 with compound 1-9-6, and synthesizing compound 1-9 (13.91 g, yield 56%, the yield is the synthesis yield of the reaction of 1-1-2 and 1-9-7) according to the above synthesis route.

[0121] LC-MS (APCI) (M+H) + :705.37

[0122] Compound Example 3: Preparation of Compound 1-16

[0123]

[0124] Prepared according to the same synthesis method as the above compound Example 1, replacing compound 1-1-5 with compound 1-16-5, compound 1-16 (14.60 g, yield 60%, the yield is the synthesis yield of the reaction of 1-1-2 and 1-16-7) can be synthesized according to the above synthesis route.

[0125] LC-MS (APCI) (M+H) + :691.04

[0126] Compound Example 4: Preparation of Compound 1-19

[0127]

[0128] Prepared according to the same synthesis method as the above-mentioned compound Example 1, replacing compound 1-1-5 with compound 1-16-5, and compound 1-1-6 with compound 1-19-6, compound 1-19 (14.36 g, yield 55%, the yield of the reaction of 1-1-2 and 1-19-7) can be synthesized according to the above-mentioned synthesis route.

[0129] LC-MS (APCI) (M+H) + :741.32

[0130] Compound Example 5: Preparation of Compound 1-29

[0131]

[0132] Prepared according to the same synthesis method as the above-mentioned compound Example 1, replacing compound 1-1-3 with compound 1-29-3, compound 1-1-4 with compound 1-29-4, and compound 1-1-6 with compound 1-29-6, compound 1-29 (16.88 g, yield 55%, the yield being the synthesis yield of the reaction of 1-1-2 and 1-29-7) can be synthesized according to the above-mentioned synthesis route.

[0133] LC-MS (APCI) (M+H) + :871.66

[0134] Compound Example 6: Preparation of Compound 1-32

[0135]

[0136] Prepared according to the same synthesis method as the above-mentioned compound Example 1, replacing compound 1-1-4 with compound 1-32-4, and compound 1-1-6 with compound 1-32-6, compound 1-32 (17.30 g, yield 60%, the yield of the reaction of 1-1-2 and 1-32-7) can be synthesized according to the above-mentioned synthesis route.

[0137] LC-MS (APCI) (M+H) + :821.79

[0138] Compound Example 7: Preparation of Compound 1-40

[0139]

[0140]

[0141] Prepared according to the same synthesis method as the above-mentioned compound Example 1, replacing compound 1-1-3 with compound 1-29-3, compound 1-1-4 with compound 1-40-4, and compound 1-1-6 with compound 1-19-6, compound 1-40 (15.88 g, yield 57%, the yield of the reaction of 1-1-2 and 1-40-7) can be synthesized according to the above-mentioned synthesis route.

[0142] LC-MS (APCI) (M+H) + :791.43

[0143] Compound Example 8: Preparation of Compound 1-42

[0144]

[0145] Prepared according to the same synthesis method as the above-mentioned compound Example 1, replacing compound 1-1-3 with compound 1-29-3, compound 1-1-4 with compound 1-40-4, and compound 1-1-6 with compound 1-42-6, compound 1-42 (17.41 g, yield 57%, the yield of the reaction of 1-1-2 and 1-42-7) can be synthesized according to the above-mentioned synthesis route.

[0146] LC-MS (APCI) (M+H) + :867.53

[0147] Compound Example 9: Preparation of Compound 2-3

[0148]

[0149] Prepared according to the same synthesis method as the above compound Example 1, replacing compound 1-1-1 with compound 2-3-1, and compound 1-1-6 with compound 2-3-6, compound 2-3 (13.49 g, yield 60%, the yield of the reaction of 2-3-2 and 2-3-7) can be synthesized according to the above synthesis route.

[0150] LC-MS (APCI) (M+H) + :638.67

[0151] Compound Example 10: Preparation of Compound 2-11

[0152]

[0153] Prepared according to the same synthesis method as the above-mentioned compound Example 9, replacing compound 2-3-6 with compound 1-32-6, compound 2-11 (14.39 g, yield 58%, the yield is the synthesis yield of the reaction of 2-3-2 and 2-11-7) can be synthesized according to the above-mentioned synthesis route.

[0154] LC-MS (APCI) (M+H) + :705.29

[0155] Compound Example 11: Preparation of Compound 2-17

[0156]

[0157] Prepared according to the same synthesis method as the above-mentioned compound Example 9, replacing compound 1-1-5 with compound 2-17-5, and compound 2-3-6 with compound 2-17-6, compound 2-17 (15.14 g, yield 58%, the yield of the reaction of 2-3-2 and 2-11-7) can be synthesized according to the above-mentioned synthesis route.

[0158] LC-MS (APCI) (M+H) + :741.39

[0159] Compound Example 12: Preparation of Compound 2-24

[0160]

[0161] Prepared according to the same synthesis method as the above-mentioned compound Example 9, replacing compound 1-1-4 with compound 2-24-4, compound 2-24 (14.10 g, yield 56%, the yield is the synthesis yield of the reaction of 2-3-2 and 2-24-7) can be synthesized according to the above-mentioned synthesis route.

[0162] LC-MS (APCI) (M+H)+ :715.19

[0163] Compound Example 13: Preparation of Compound 2-31

[0164]

[0165] Prepared according to the same synthesis method as the above-mentioned compound Example 9, replacing compound 1-1-5 with compound 1-32-5, and compound 2-3-6 with compound 2-31-6, compound 2-31 (15.17 g, yield 56%, the yield of the reaction of 2-3-2 and 2-31-7) can be synthesized according to the above-mentioned synthesis route.

[0166] LC-MS (APCI) (M+H) + :769.35

[0167] Compound Example 14: Preparation of Compound 2-42

[0168]

[0169] Prepared according to the same synthesis method as the above-mentioned compound Example 9, replacing compound 2-3-7 with compound 1-42-7, and synthesizing compound 2-42 (16.29 g, yield 55%, the yield is the synthesis yield of the reaction of 2-3-2 and 2-42-7) according to the above-mentioned synthesis route.

[0170] LC-MS (APCI) (M+H) + :841.37

[0171] Device Preparation Example

[0172] Application Example 1 illustrates the application effect of the compound of the present invention as a hole transport layer in a device.

[0173] Application Example 1

[0174] This embodiment provides an organic electroluminescent element, such as Figure 1 As shown, it includes 1, an anode, 2, a hole injection layer, 3, a hole transport layer, 4, a light-emitting auxiliary layer, 5, a light-emitting layer, 6, an electron transport layer and 7, a cathode, which are stacked from bottom to top.

[0175] The specific device structure is:

[0176] ITO / HATCN(5nm) / HT(60nm) / EB(5nm) / BH+BD(3wt%)(20nm) / ET(15nm) / Al(100nm).

[0177] Device preparation process:

[0178] HATCN was evaporated on the ITO substrate to form a A hole injection layer (HIL) is formed by evaporating HT on the hole injection layer to form a layer with a thickness of A hole transport layer (HTL) is formed by evaporating BP on the hole transport layer to form a layer with a thickness of The light-emitting auxiliary layer (EBL) is formed by evaporating BH+BD (3 wt %) on the light-emitting auxiliary layer to form a layer with a thickness of The light-emitting layer (EML) is deposited in the following order: The electron transport layer (ETL) of ) to form a cathode, thereby manufacturing an organic electroluminescent device. This is recorded as Comparative Example 1.

[0179]

[0180] Device Comparison Example 2

[0181] The hole transport layer 3 was prepared by using HT-1 instead of HT material, and the organic electroluminescent device was prepared by the same method as the embodiment of the comparative example 1 above.

[0182] Device Comparison Example 3

[0183] The hole transport layer 3 was prepared by using HT-2 instead of HT material, and the organic electroluminescent device was prepared by the same method as the embodiment of the comparative example 1 above.

[0184] Device Comparison Example 4

[0185] The hole transport layer 3 was prepared by using HT-3 instead of HT material, and the organic electroluminescent device was prepared by the same method as the embodiment of the comparative example 1 above.

[0186] Device Example 1

[0187] The hole transport layer 3 was prepared by using compound 1-1 instead of HT material, and the organic electroluminescent device was prepared by the same method as that of the embodiment of Comparative Example 1.

[0188] Device Example 2

[0189] The hole transport layer 3 was prepared by using compound 1-9 instead of HT material, and the organic electroluminescent device was prepared by the same method as the embodiment of the comparative example 1 above.

[0190] Device Example 3

[0191] The hole transport layer 3 was prepared by using compound 1-16 instead of HT material, and the organic electroluminescent device was prepared by the same method as the embodiment of the comparative example 1 above.

[0192] Device Example 4

[0193] The hole transport layer 3 was prepared by using compound 1-19 instead of HT material, and the organic electroluminescent device was prepared by the same method as the embodiment of the comparative example 1 above.

[0194] Device Example 5

[0195] The hole transport layer 3 was prepared by using compound 1-29 instead of HT material, and the organic electroluminescent device was prepared by the same method as that of the embodiment of Comparative Example 1 above.

[0196] Device Example 6

[0197] The hole transport layer 3 was prepared by using compound 1-32 instead of HT material, and the organic electroluminescent device was prepared by the same method as that of the embodiment of Comparative Example 1 above.

[0198] Device Example 7

[0199] The hole transport layer 3 was prepared by using compound 1-40 instead of HT material, and the organic electroluminescent device was prepared by the same method as that of the embodiment of Comparative Example 1 above.

[0200] Device Example 8

[0201] The hole transport layer 3 was prepared by using compound 1-42 instead of HT material, and the organic electroluminescent device was prepared by the same method as that of the embodiment of Comparative Example 1 above.

[0202] Device Example 9

[0203] The hole transport layer 3 was prepared by using compound 2-3 instead of HT material, and the organic electroluminescent device was prepared by the same method as the implementation scheme of the above-mentioned comparative example 1.

[0204] Device Example 10

[0205] The hole transport layer 3 was prepared by using compound 2-11 instead of HT material, and the organic electroluminescent device was prepared by the same method as the embodiment of the comparative example 1 above.

[0206] Device Example 11

[0207] The hole transport layer 3 was prepared by using compound 2-17 instead of HT material, and the organic electroluminescent device was prepared by the same method as the implementation scheme of the above-mentioned comparative example 1.

[0208] Device Example 12

[0209] The hole transport layer 3 was prepared by using compound 2-24 instead of HT material, and the organic electroluminescent device was prepared by the same method as that of the embodiment of Comparative Example 1 above.

[0210] Device Example 13

[0211] The hole transport layer 3 was prepared by using compound 2-31 instead of HT material, and the organic electroluminescent device was prepared by the same method as that of the embodiment of Comparative Example 1 above.

[0212] Device Example 14

[0213] The hole transport layer 3 was prepared by using compound 2-42 instead of HT material, and the organic electroluminescent device was prepared by the same method as that of the embodiment of Comparative Example 1 above.

[0214] Test Results

[0215] Life test method: Apply voltage to the obtained organic electroluminescent element so that the current density reaches 30mA / cm 2 The time until the brightness reaches 95% of the initial brightness (LT95 (unit: hour)) was measured, and the life of Comparative Example 1 was taken as 100%, and the relative life values ​​of each Comparative Example and Example were obtained.

[0216] The driving voltage is at a current density of 15 mA / cm 2 The following test was performed, with the driving voltage of Comparative Example 1 being 100%, to obtain relative values ​​of the driving voltages of the comparative examples and the embodiments.

[0217] Current efficiency at current density 15mA / cm 2 The following test was conducted, with the current efficiency of Comparative Example 1 being 100%, to obtain the relative values ​​of the current efficiency of each Comparative Example and the Example. The test results are shown in Table 1.

[0218] Table 1

[0219]

[0220]

[0221] It can be seen from the results shown in Table 1 that the amine compound of the present invention is applied to the hole transport layer, which can reduce the driving voltage of the organic electroluminescent device, improve the luminous efficiency and life, and is an excellent hole transport material.

[0222] The above shows and describes the basic principles, main features and advantages of the present invention. Those skilled in the art should understand that the present invention is not limited to the above embodiments. The above embodiments and descriptions are only for explaining the principles of the present invention. The present invention may be subject to various changes and improvements without departing from the spirit and scope of the present invention. These changes and improvements fall within the scope of the present invention. The scope of protection of the present invention is defined by the attached claims and their equivalents.

Claims

1. An amine compound, Features The compound has the structure shown in formula (1): wherein Cy is present or absent, and when Cy is present, it is selected from a 5-6 membered ring, L 1 -L 2 are each independently selected from a single bond, a substituted or unsubstituted C6-C60 arylene group, and a substituted or unsubstituted C3-C60 heteroarylene group, R 1 -R 3 each independently selected from hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C2-C10 heterocycloalkyl, substituted or unsubstituted C1-C10 alkoxy, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C3-C60 heteroaryl, The substituents in the "substituted or unsubstituted" are independently selected from one or a combination of deuterium, halogen, cyano, C1-C10 alkyl, C3-C10 cycloalkyl, C6-C30 aryl, C3-C30 heteroaryl, and the heteroatom of the heteroaryl is selected from one or more of oxygen, sulfur and nitrogen.

2. The amine compound according to claim 1, Features: The compound has the structure shown in formula (2) and formula (3):

3. The amine compound according to claim 1, Features: The L 1 -L 2 each independently selected from a single bond, a substituted or unsubstituted phenylene group, a substituted or unsubstituted biphenylene group, a substituted or unsubstituted naphthylene group, a substituted or unsubstituted anthrylene group, a substituted or unsubstituted phenanthrylene group, a substituted or unsubstituted fluoranthenylene group, a substituted or unsubstituted pyrenylene group, a substituted or unsubstituted perylene group, a substituted or unsubstituted triphenyl ... pyrenylene group, a substituted or unsubstituted pyrenylene group, a substituted or unsubstituted fluorenylene, substituted or unsubstituted 9,9-dimethylfluorenylene, substituted or unsubstituted 9,9-diphenylfluorenylene, substituted or unsubstituted spirobifluorenylene, substituted or unsubstituted dibenzofuranylene, substituted or unsubstituted dibenzothiophenylene, substituted or unsubstituted carbazolylene.

4. The amine compound according to claim 1, Features: The R 1 -R 3 each independently selected from hydrogen, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted phenylnaphthyl, substituted or unsubstituted anthracenyl, substituted or unsubstituted phenanthrenyl, substituted or unsubstituted fluoranthenyl, substituted or unsubstituted pyrenyl, substituted or unsubstituted peryl, substituted or unsubstituted triphenylene, substituted or unsubstituted substituted or unsubstituted fluorenyl, substituted or unsubstituted 9,9-dimethylfluorenyl, substituted or unsubstituted 9,9-diphenylfluorenyl, substituted or unsubstituted spirobifluorenyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothiophenyl, substituted or unsubstituted carbazolyl.

5. The amine compound according to claim 1, Features: The L 1 -L 2 Each is independently selected from a single bond, a substituted or unsubstituted group: in Indicates the connection site.

6. The amine compound according to claim 1, Features: The R 1 -R 3 Each is independently selected from the following groups which may be substituted with hydrogen: in Indicates the connection site.

7. The amine compound according to claim 1, Features The compound is selected from any one of the following compounds Nos. 1-1 to 1-42, 2-1 to 2-42:

8. Use of the amine compound according to claims 1-7 as an organic electroluminescent material.

9. An organic electroluminescent element, Features: The organic electroluminescent element comprises a substrate, an anode, a hole transport region, a light-emitting layer, an electron transport region, and a cathode, wherein the light-emitting layer is located between the anode and the cathode, the hole transport region is located between the anode and the light-emitting layer, and the electron transport region is located between the light-emitting layer and the cathode; The hole transport region comprises at least one of a hole injection layer and a hole transport layer; The hole transport layer comprises the amine compound according to any one of claims 1 to 7.

10. An electronic device, include: One or more of a display, a monitor, and a lighting device, comprising the organic electroluminescent element according to claim 9; and a control unit for driving the display device.

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