Organic compounds and polymers, inks and electronic devices

Abstract

The application relates to the field of organic materials, and provides an organic compound, a polymer, ink and an electronic device. The organic compound has a structure as shown in formula 1. The organic compound is a low-molecular-weight cross-linkable compound. In the preparation of a light-emitting device, cross-linking groups on the molecules of the compound can be cross-linked in situ, so that a network polymer structure resistant to solvents is formed.

Description

Technical Field

[0001] This application relates to the field of organic materials, and in particular to an organic compound and polymer, as well as inks and electronic devices. Background Technology

[0002] Research on organic light-emitting diodes (OLEDs) began in the 1960s with Pope et al.'s first report on the electroluminescence of anthracene single crystals under high pressure, marking the beginning of organic solid-state light emission. In 1987, researchers at Kodak, including CWTang et al., selected triarylamine derivatives and 8-hydroxyquinoline aluminum complex (Alq3), which possessed good film-forming properties, as the hole transport layer and the light-emitting layer (also serving as the electron transport layer), respectively, resulting in an organic electroluminescent device with high brightness and low driving voltage (less than 10V). In 1990, RHFriend et al. at the Cavendish Laboratory at Cambridge University fabricated a polymer electroluminescent device using poly(p-phenylenevinyl chloride) (PV) as the light-emitting layer material via solution processing. These two breakthroughs made scientists realize the significant potential of light-emitting devices in the display field, sparking a surge in research on light-emitting devices for displays.

[0003] Typically, OLED devices incorporate an electron transport layer (such as an electron injection layer and / or an electron transport layer) between the emissive layer and the cathode, and a hole transport layer (such as a hole transport layer) between the emissive layer and the anode, thereby achieving a balance between electrons and holes in the emissive layer. Currently, OLED devices are mainly manufactured using two processes: vapor deposition and inkjet printing. Inkjet printing achieves a material utilization rate as high as 90%, while vapor deposition only reaches about 30%–40%. Furthermore, inkjet printing does not require a vacuum environment, resulting in lower equipment and consumable costs compared to OLED panels manufactured using vapor deposition. However, inkjet printing technology still faces some challenges that urgently need to be addressed.

[0004] To fabricate OLEDs using inkjet printing, the hole transport material needs to be solvent-resistant to prevent interlayer mixing during the inkjet printing process. Traditional methods to avoid interlayer mixing include: thermal or photochemical crosslinking before applying the second layer; forming a self-assembled layer on ITO; and utilizing the solubility differences between polar and non-polar solvents. However, these methods suffer from complex processes, low polymer synthesis efficiency, and low device quality. Summary of the Invention

[0005] Based on this, the purpose of this application is to provide an organic compound, a polymer, an ink, and an electronic device. The organic compound is a low-molecular-weight, crosslinkable compound. During the fabrication of a light-emitting device, the crosslinking groups on the compound molecules can undergo in-situ crosslinking, thereby forming a solvent-resistant network polymer structure.

[0006] In a first aspect, this application provides an organic compound having the structure shown in Formula 1:

[0007]

[0008] X represents O, S, or C(R). 1 R 2 ), R 1 and R 2 They may be the same or different, and each is independently hydrogen or methyl;

[0009] L1, L2, L3, and L4 may be the same or different, and each independently represents: a single bond, O, an alkylene group with 1-4 carbon atoms, an alkene group with 1-4 carbon atoms, a substituted or unsubstituted arylene group with 6-18 carbon atoms, a substituted or unsubstituted arylene group with 6-18 carbon atoms, a group formed by a single bond connecting an alkylene group with 1-4 carbon atoms and a phenylene group, or a group formed by a single bond connecting an alkene group with 1-4 carbon atoms and a phenylene group.

[0010] R1, R2, R3 and R4 may be the same or different, and each is independently selected from H or vinyl, and at least two of R1, R2, R3 and R4 are vinyl;

[0011] Ar represents a substituted or unsubstituted triarylamine group with 18-40 carbon atoms, a substituted or unsubstituted aryl group with 6-40 carbon atoms, or a substituted or unsubstituted heteroaryl group with 12-40 carbon atoms.

[0012] In L1, L2, L3, L4 and Ar, the substituents are the same or different, and each is independently selected from D, halogen, alkyl with 1-4 carbon atoms, aryl with 6-12 carbon atoms or heteroaryl with 5-12 carbon atoms.

[0013] Secondly, this application provides a polymer whose monomers include the aforementioned organic compounds.

[0014] Thirdly, this application provides an ink comprising a solvent and a crosslinkable hole transport material dissolved in the solvent, wherein the crosslinkable hole transport material comprises the organic compound.

[0015] Fourthly, this application provides an electronic device including an anode and a cathode disposed opposite to each other, and a hole transport layer disposed between the anode and the cathode, wherein the hole transport layer comprises the polymer.

[0016] In some embodiments, the electronic device is a photoelectric conversion device.

[0017] In other embodiments, the electronic device is an organic electroluminescent device.

[0018] The organic compound provided in this application is a low-molecular-weight, crosslinkable compound. This organic compound can be used to prepare a hole transport layer. During the formation of the hole transport layer, the crosslinking groups in the organic compound can undergo in-situ crosslinking, thereby forming a solvent-resistant network structure. This avoids the solvent erosion problem that occurs during inkjet printing of electronic devices (such as organic electroluminescent devices). Furthermore, using this organic compound as a crosslinkable hole transport layer material in organic electroluminescent devices can enable the devices to have higher luminous efficiency and longer lifespan.

[0019] Other features and advantages of this application will be described in detail in the following detailed description section. Attached Figure Description

[0020] Figure 1 The thermogravimetric curve of compound HT2 in this application;

[0021] Figure 2 DSC curves of compound HT2 from this application after two rounds of heating;

[0022] Figure 3 This is a schematic diagram of the structure of an organic electroluminescent device according to one embodiment.

[0023] Explanation of reference numerals in the attached figures

[0024] 100: Organic electroluminescent device; 1: Anode; 2: Hole injection layer; 3: Hole transport layer

[0025] 4: Organic light-emitting layer; 5: Electron transport layer; 6: Electron injection layer; 7: Cathode Detailed Implementation

[0026] To facilitate understanding of this application, a more complete description will be provided below with reference to the accompanying drawings. Preferred embodiments of this application are shown in the drawings. However, this application can be implemented in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided to provide a more thorough and complete understanding of the disclosure of this application.

[0027] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. The term "and / or" as used herein includes any and all combinations of one or more of the associated listed items.

[0028] A first aspect of this application provides an organic compound having the structure shown in Formula 1:

[0029]

[0030] X represents O, S, or C(R). 1 R 2 ), R 1 and R 2 They may be the same or different, and each is independently H or methyl;

[0031] L1, L2, L3, and L4 may be the same or different, and each independently represents: a single bond, O, an alkylene group with 1-4 carbon atoms, an alkene group with 1-4 carbon atoms, a substituted or unsubstituted arylene group with 6-18 carbon atoms, a substituted or unsubstituted arylene group with 6-18 carbon atoms, a group formed by a single bond connecting an alkylene group with 1-4 carbon atoms and a phenylene group, or a group formed by a single bond connecting an alkene group with 1-4 carbon atoms and a phenylene group.

[0032] R1, R2, R3 and R4 may be the same or different, and each is independently selected from H or vinyl, and at least two of R1, R2, R3 and R4 are vinyl;

[0033] Ar represents a substituted or unsubstituted triarylamine group with 18-40 carbon atoms, a substituted or unsubstituted aryl group with 6-40 carbon atoms, or a substituted or unsubstituted heteroaryl group with 12-40 carbon atoms.

[0034] In L1, L2, L3, L4 and Ar, the substituents are the same or different, and each is independently selected from D, halogen, alkyl with 1-4 carbon atoms, aryl with 6-12 carbon atoms or heteroaryl with 5-12 carbon atoms.

[0035] In this application, the term "substituted or unsubstituted" means that the functional group described after the term may or may not have substituents. For example, "substituted or unsubstituted phenyl" refers to a phenyl with substituents or an unsubstituted phenyl. The number of substituents can be one or more, such as deuterium (D), halogens, alkyl groups, aryl groups, heteroaryl groups, etc. It should be understood that when the functional group has substituents, the number of carbon atoms refers to the total number of carbon atoms of the functional group and its substituents. For example, in Formula 1, when Ar is a methyl-substituted phenyl, then the total number of carbon atoms in Ar is 7, that is, A is a methyl-substituted phenyl with 7 carbon atoms.

[0036] In this application, aryl refers to an aromatic hydrocarbon group derived from an aromatic ring compound by losing one hydrogen atom. Aryl can be a monocyclic aryl (such as phenyl), a fused-ring aryl (such as naphthyl), two or more monocyclic aryl groups (such as biphenyl) conjugated by carbon-carbon bonds, monocyclic and fused-ring aryl groups conjugated by carbon-carbon bonds, or two or more fused-ring aryl groups conjugated by carbon-carbon bonds. Specific examples of aryl include, but are not limited to, phenyl, naphthyl, anthracene, phenanthryl, biphenyl, terphenyl, benzo[9,10]phenanthryl, pyrene, benzofluoranthracene, etc. Alkyl, dibenzocycloalkyl (such as fluorenyl, dihydroanthracene), etc.

[0037] In this application, the term "arylene" refers to a divalent group formed by the further loss of a hydrogen atom from an aryl group.

[0038] In this application, a heteroaryl group refers to a group formed by replacing at least one carbon atom on the aryl ring with a heteroatom. The heteroatom can be at least one of B, O, N, P, Si, Se, and S. The number of heteroatoms in a heteroaryl group can be 1, 2, 3, 4, 5, or more. A heteroaryl group can be a monocyclic heteroaryl, a fused-ring heteroaryl, or a group formed by connecting monocyclic and fused-ring heteroaryl groups through a single bond. Specific examples of heteroaryl groups include, but are not limited to, thiophene, furanyl, pyrrolyl, imidazolyl, thiazolyl, oxazolyl, oxadiazolyl, triazolyl, pyridyl, triazinyl, acridinel, pyridazinyl, quinolinyl, quinazolinyl, quinoxazinyl, phenothiazinyl, phthalazinyl, pyridopyrimidinyl, pyridopyrazinyl, isoquinolinyl, indolyl, carbazole, benzoxazolyl, benzimidazolyl, benzothiazolyl, benzocarbazole, benzothiaphenyl, dibenzothiaphenyl, thienothiaphenyl, benzofuranyl, phenanthrololinyl, isoxazolyl, thiadiazolyl, phenothiazinyl, phenothiazyl, dibenzo-p-dioxinyl, quinazolinone, benzothiadiazolyl, benzotriazolyl, thiathenyl, phenothiazinyl, phenothiazyl, N-phenylcarbazole, etc.

[0039] In this application, aryloxy group refers to a group with the structure -OAr1, where Ar1 is an aryl group, as defined above. Specific examples of aryloxy groups include, but are not limited to, methoxy groups.

[0040] In this application, aryloxy group refers to a divalent group formed by the loss of a hydrogen atom from the aryl group (Ar1) of the structure -OAr1.

[0041] In this application, the number of carbon atoms in the alkyl group is, for example, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10. Specific examples of alkyl groups include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, 1-butyl (n-Bu, n-butyl, -CH2CH2CH2CH3), 2-methyl-1-propyl (i-Bu, i-butyl, -CH2CH(CH3)2), 2-butyl (s-Bu, s-butyl, -CH(CH3)CH2CH3), 2-methyl-2-propyl (t-Bu, t-butyl, -C(CH3)3), and 1-pentyl. (n-pentyl, -CH2CH2CH2CH2CH3), 2-pentyl (-CH(CH3)CH2CH2CH3), 3-pentyl (-CH(CH2CH3)2), 2-methyl-2-butyl (-C(CH3)2CH2CH3), 3-methyl-2-butyl (-CH(CH3)CH(CH3)2), 3-methyl-1-butyl (-CH2CH2CH(CH3)2), 2-methyl-1-butyl ( -CH2CH(CH3)CH2CH3), 1-hexyl(-CH2CH2CH2CH2CH2CH3), 2-hexyl(-CH(CH3)CH2CH2CH2CH3), 3-hexyl(-CH(CH2CH3)(CH2CH2CH3)), 2-methyl-2-pentyl(-C(CH3)2CH2CH2CH3), 3-methyl-2-pentyl(-CH(CH3)CH(CH3)CH2CH3), 4-methyl-2-pentyl(-CH(CH3)CH2CH(CH3)2), 3-methyl-3-pentyl(-C(CH3)(CH2CH3)2), 2-methyl-3-pentyl(-CH(CH2CH3)CH(CH3)2), 2,3-dimethyl-2-butyl(-C(CH3)2CH(CH3)2), 3,3-dimethyl-2-butyl(-CH(CH3)C(CH3)3 and octyl.

[0042] In this application, alkylene refers to a divalent group formed by the further loss of a hydrogen atom from an alkyl group.

[0043] In this application, "alkoxy" refers to a group with the structure -OR, i.e., an alkyl group R as defined above, which is attached to an adjacent group via an oxygen atom. Phrases containing this term, such as "alkoxy group having 1-10 carbon atoms," mean that the alkyl moiety contains 1-10 carbon atoms. Examples of alkoxy groups include, but are not limited to: methoxy (-O-CH3 or -OMe), ethoxy (-O-CH2CH3 or -OEt), and tert-butoxy (-OC(CH3)3 or -OtBu).

[0044] In this application, alkylene refers to a divalent group formed by the further loss of a hydrogen atom from an alkyl group.

[0045] In this application, halogen groups include chlorine, fluorine, bromine, and iodine.

[0046] In this application, the aryl group used as a substituent may have 6-12 carbon atoms, for example 6, 10, or 12. Examples of aryl groups used as substituents include, but are not limited to, phenyl, naphthyl, or biphenyl.

[0047] In this application, the number of carbon atoms in the heteroaryl group used as a substituent can be 5-12, for example 5, 6, 10 or 12. Examples of heteroaryl groups used as substituents include, but are not limited to, pyridinyl, pyrimidinyl, quinolinyl, piperazineyl or carbazoleyl.

[0048] In this application, The term "linking bond" refers to a non-positioned linking bond that extends from the ring system. This indicates that one end of the linker can connect to any position in the ring system it traverses, and the other end connects to the rest of the molecule. For example, as shown in equation (Q), the naphthyl group represented by equation (Q) is connected to other positions in the molecule via two non-positional linkers that traverse different benzene rings, representing any possible connection configuration shown in equations (Q-1) to (Q-6):

[0049]

[0050] For another example, as shown in equation (Z), the naphthyl group represented by equation (Z) is connected to other positions in the molecule via a non-positional linker extending from the middle of one side of the benzene ring. This can represent any of the connection methods shown in equations (Z-1) and (Z-2):

[0051]

[0052] In this application, a non-orienting substituent refers to a substituent connected by a single bond extending from the center of the ring system, indicating that the substituent can be attached to any possible position in the ring system. For example, as shown in the following formula (E), the substituent R in formula (E) is connected to the naphthalene ring by a non-orienting linking bond, which means that it includes any of the possible connection methods shown in formulas (E-1) to (E-14):

[0053]

[0054] In this application, the number of carbon atoms in the substituted or unsubstituted aryl group can be 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39 or 40.

[0055] In this application, the number of carbon atoms in the substituted or unsubstituted heteroaryl group can be 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39 or 40.

[0056] In this application, the structure of the triarylamine group can be represented as follows: Where L is arylene or heteroarylene, Ar a and Ar b They may be the same or different, and each is independently aryl or heteroaryl. Specific examples of L include, but are not limited to, phenylene, naphthylene, or biphenylene. Ar a and Ar b Specific examples of each include, but are not limited to, phenyl, naphthyl, or biphenyl.

[0057] In some embodiments, the structure of the organic compound is shown as any one of Formulas 1-1 to 1-3:

[0058]

[0059] Alternatively, the structure of the organic compound is shown in Formula 1-1. In this case, the organic compound can be used to form a hole transport layer to further improve the lifespan of the organic electroluminescent device.

[0060] In some implementations, two of R1, R2, R3, and R4 are vinyl groups, and the remainder are hydrogen groups.

[0061] In other embodiments, three of R1, R2, R3, and R4 are vinyl groups, and the remainder are hydrogen groups.

[0062] In some other embodiments, R1, R2, R3 and R4 are all vinyl groups.

[0063] In some embodiments, in L1, L2, L3 and L4, the substituents are the same or different, and each is independently selected from D, fluorine, bromine, chlorine, alkyl, phenyl or naphthyl with 1-4 carbon atoms.

[0064] In some embodiments, L1, L2, L3, and L4 may be the same or different, and each independently represents: a single bond, O, methylene, ethylene, methyleneoxy, ethoxy, or a group W substituted or unsubstituted by one or more substituents Z1, wherein group W is selected from any of the following groups:

[0065]

[0066] m1 is 1 or 2, m2 is 0, 1 or 2;

[0067] Each substituent Z1 is independently selected from D, fluorine, bromine, chlorine, methyl, ethyl, n-propyl, isopropyl, tert-butyl, phenyl, or naphthyl.

[0068] Optionally, L1, L2, L3, and L4 may be the same or different, and each independently represents a single bond, O, methylene, ethylene, methyleneoxy, ethoxy, or any one of the following groups:

[0069]

[0070] In some implementations... At least two of them are independently selected from any one of the following groups:

[0071]

[0072] m3 can be 0, 1, 2, 3 or 4, and m4 can be 0, 1, 2, 3 or 4.

[0073] In some embodiments, Ar is a substituted or unsubstituted aromatic amino group with 18-25 carbon atoms, a substituted or unsubstituted aryl group with 6-25 carbon atoms, or a substituted or unsubstituted heteroaryl group with 12-24 carbon atoms.

[0074] In some embodiments, Ar is selected from any of the following groups: substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted biphenyl, substituted or unsubstituted phenanthyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted dibenzothiophene, substituted or unsubstituted dibenzofuran, substituted or unsubstituted carbazolyl, substituted or unsubstituted phenoxthial, substituted or unsubstituted xanthanel, substituted or unsubstituted thioxanthyl, substituted or unsubstituted phenoxazinyl, substituted or unsubstituted phenthiaazinyl, substituted or unsubstituted triphenylamino.

[0075] In some embodiments, in Ar, the substituents are each independently selected from fluorine, bromine, chlorine, methyl, ethyl, n-propyl, isopropyl, tert-butyl, phenyl, naphthyl, or carbazole.

[0076] In some embodiments, Ar is a group V that is substituted or unsubstituted by one or more substituents Z2, wherein group V is selected from any of the following groups:

[0077]

[0078]

[0079] Each substituent Z2 is independently selected from D, fluorine, methyl, ethyl, n-propyl, isopropyl, tert-butyl, or phenyl.

[0080] Optionally, Ar is selected from any of the following groups:

[0081]

[0082] Furthermore, Ar is selected from any one of the following groups:

[0083]

[0084] In some embodiments, the organic compound is any one of the following compounds:

[0085]

[0086]

[0087]

[0088] This application does not specifically limit the synthetic methods of the provided organic compounds. Those skilled in the art can determine suitable synthetic methods based on the organic compounds provided in this application and the preparation methods provided in the Synthesis Examples section below. In other words, the Synthesis Examples section of this application provides exemplary methods for preparing organic compounds, and the raw materials used can be obtained commercially or by methods well known in the art. Those skilled in the art can obtain all the organic compounds provided in this application based on these exemplary methods. All specific preparation methods for these organic compounds will not be detailed here, and the Synthesis Examples below should not be construed as limiting this application.

[0089] A second aspect of this application provides a polymer whose monomers include the aforementioned organic compounds.

[0090] In some embodiments, the polymer is formed by the monomer under crosslinking conditions, the crosslinking conditions including a temperature of 150°C-250°C and a time of 5 min-60 min.

[0091] Thirdly, this application provides an ink comprising a solvent and a crosslinkable hole transport material dissolved in the solvent. The crosslinkable hole transport material includes the organic compound.

[0092] This application describes the use of inks containing the aforementioned organic compounds in solution processing methods such as spin coating and inkjet printing to prepare hole transport layers. The solvents and their content in the ink can be selected with reference to existing technologies, and this application does not impose any particular limitations. For example, the solvents may include chlorobenzene, xylene, etc., and the mass content of the organic compounds in the ink can be 1%-20%. During the fabrication of electronic devices, the organic compounds undergo in-situ polymerization to form a network structure of the polymer, thereby preventing solvent corrosion.

[0093] Fourthly, this application provides an electronic device including an anode and a cathode disposed opposite to each other, and a hole transport layer disposed between the anode and the cathode, wherein the hole transport layer comprises the polymer.

[0094] In this application, the electronic device is, for example, a photoelectric conversion device or an organic electroluminescent device.

[0095] This application does not particularly limit the material of the anode, and it can be any anode material capable of transporting holes. Anode materials include, for example, one or a combination of metals, metal oxides, and conductive polymers. In some embodiments, the anode material is selected from at least one of indium tin oxide (ITO), indium zinc oxide (IZO), and indium gallium zinc oxide (IGZO).

[0096] This application does not specifically limit the material of the cathode; it can be any cathode material capable of transporting electrons. The cathode material may include metals, such as one or more of magnesium (Mg), calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum (Al), silver (Ag), tin, and lead, or an alloy of at least two of these. In some embodiments, the cathode material is selected from at least one of Al, Ag, Mg, and Mg-Ag alloys.

[0097] In some embodiments, the electronic device is a photoelectric conversion device. Specific examples of such photoelectric conversion devices include, but are not limited to, organic solar cells (OPVs) or organic photodetectors (OPDs).

[0098] In other embodiments, the electronic device is an organic electroluminescent device. The organic electroluminescent device may be a blue light-emitting device, a red light-emitting device, or a green light-emitting device.

[0099] In some implementations, such as Figure 3 As shown, the organic electroluminescent device 100 includes an anode 1, a hole injection layer 2, a hole transport layer 3, an organic light-emitting layer 4, an electron transport layer 5, an electron injection layer 6, and a cathode 7, which are sequentially stacked. The hole transport layer 3 comprises the polymer, which is formed by a crosslinking reaction of one or more of the organic compounds described in this application.

[0100] In this application, the material of the hole injection layer 2 can be a benzidine derivative, a starburst-shaped aryl amine compound, a phthalocyanine derivative, or a conductive polymer, etc., and this application does not impose any special restrictions on it. For example, the material of the hole injection layer 2 is PEDOT:PPS.

[0101] In some embodiments, the organic light-emitting layer 4 may include a host material and a guest material. This application does not particularly limit the host material and guest material, and they can be selected with reference to existing organic electroluminescent devices. The host material is, for example, ADN (CAS No.: 122648-99-1), and the guest material is, for example, BD-1 (structure shown below).

[0102] In this application, the material of the electron transport layer 5 may typically include metal complexes and / or nitrogen-containing heterocyclic derivatives, specific examples including but not limited to TPBi, BCP, Bphen, NBphen, DBimiBphen, BimiBphen, etc.

[0103] In this application, an electron injection layer 6 is provided between the electron transport layer 5 and the cathode 7 to enhance the ability of the cathode 7 to inject electrons into the electron transport layer 5. The material of the electron injection layer may include inorganic materials such as alkali metal sulfides and alkali metal halides, or may include complexes of alkali metals and organic materials. For example, the material of the electron injection layer 6 is CsF, LiQ, or LiF.

[0104] Using the organic compounds of this application as raw materials to prepare the hole transport layer of electronic devices can improve the luminous efficiency and other performance properties of the devices.

[0105] The present application will be described below with specific synthesis examples and embodiments.

[0106] 1. Preparation of intermediate IM I-3

[0107]

[0108] (1) Under nitrogen protection, Sub 1 (3.66 g, 20 mmol), N-bromosuccinimide (14.25 g, 80 mmol) and 100 mL of dichloromethane were added to a 250 mL reaction flask and stirred at room temperature in the dark for 24 h. After the reaction was completed, the product was extracted with dichloromethane, the organic phase was washed with saturated sodium chloride aqueous solution, the solvent was evaporated under reduced pressure, and the crude product was purified by column chromatography using a mixed solvent (petroleum ether: dichloromethane = 6:1 (v / v)) as the eluent to obtain a white solid, namely intermediate IM I-1 (4.48 g, yield 45%).

[0109]

[0110] (2) Under nitrogen protection, IM I-1 (9.98 g, 20 mmol), 2-tributyltinylthiophene (29.85 g, 80 mmol), tetrakis(triphenylphosphine)palladium (1.16 g, 1 mmol) and 200 mL of anhydrous tetrahydrofuran were added to the reaction flask. The mixture was heated to reflux and reacted for 12 h. After the reaction was completed, the product was extracted with dichloromethane. The organic phase was washed with saturated sodium chloride aqueous solution until the aqueous layer was clear. The solvent was removed under reduced pressure. The crude product was purified by column chromatography using a mixed solvent (petroleum ether: dichloromethane = 7:1 (v / v)) as the eluent to obtain a white solid, namely intermediate IM I-2 (5.42 g, yield 53%).

[0111]

[0112] (3) Under nitrogen protection, IM I-2 (10.23 g, 20 mmol) and cobalt phthalocyanine (COPC, 91 mg, 0.16 mmol) were added to the reaction flask, dissolved in 50 mL of acetonitrile at room temperature, stirred, and irradiated with 254 nm ultraviolet light for 24 h. After the reaction was completed, the product was extracted with dichloromethane, and the organic phase was washed five times with saturated sodium chloride aqueous solution until the aqueous layer was clear. The solvent was removed under reduced pressure, and the crude product was purified by column chromatography using a mixed solvent (petroleum ether: dichloromethane = 7:1 (v / v)) as the eluent to obtain a white solid, namely IM I-3 (6.09 g, yield 60%).

[0113] 2. Prepare the intermediates IM X-3 listed in Table 1 according to the method of IM I-3, except that the raw material Sub 1 is replaced with raw material 1. The intermediates and the total yield are shown in Table 1.

[0114] Table 1

[0115]

[0116] 3. Preparation of intermediate IM 2-1

[0117]

[0118] IM I-3 (10.15 g, 20 mmol), Sub a-1 (4-bromotriphenylamine, 12.97 g, 40 mmol), potassium carbonate (5.53 g, 40 mmol), and tetrakis(triphenylphosphine)palladium (0.46 g, 0.4 mmol) were added to a 300 mL reaction flask, along with 20 mL of water and 40 mL of 1,4-dioxane. The mixture was heated to 85 °C and stirred for 12 h. After the reaction was complete, the product was extracted with dichloromethane, washed with a saturated sodium chloride aqueous solution, and the solvent was removed under reduced pressure. The crude product was purified by column chromatography using a mixed solvent (petroleum ether:dichloromethane = 3:1 (v / v)) as the eluent to obtain a white solid, namely intermediate IM 2-1 (9.01 g, yield 60%).

[0119] 4. Synthesize the intermediates listed in Table 2, IM 2-X, according to the method of IM 2-1, except that raw material 2 is used instead of IM 2-3 and raw material 3 is used instead of Sub a-1. The synthesized intermediates and their yields are shown in Table 2.

[0120] Table 2

[0121]

[0122]

[0123] 5. Preparation of intermediate IM 3-1

[0124]

[0125] Under nitrogen protection, IM 2-1 (15.02 g, 20 mmol), N-bromosuccinimide (14.25 g, 80 mmol), and 200 mL of dichloromethane were added to a 250 mL reaction flask. The mixture was stirred at room temperature and protected from light for 24 h. After the reaction was complete, the product was extracted with dichloromethane, the organic phase was washed with saturated sodium chloride aqueous solution, the solvent was evaporated under reduced pressure, and the crude product was purified by column chromatography using a mixed solvent (petroleum ether:dichloromethane = 6:1 (v / v)) as the eluent to give a white solid, namely IM 3-1 (9.17 g, yield 43%).

[0126] 6. Synthesize the intermediates listed in Table 3, IM 3-X, using the same method as IM 3-1, except that raw material 4 is used instead of IM 2-1. The synthesized intermediates and their yields are shown in Table 3.

[0127] Table 3

[0128]

[0129]

[0130] Synthesis Example 1: Synthesis of Compound HT2

[0131]

[0132] IM 3-1 (10.67 g, 10 mmol), p-vinylphenylboronic acid (6.21 g, 42 mmol), potassium carbonate (2.78 g, 20 mmol), and tetrakis(triphenylphosphine)palladium (0.28 g, 0.25 mmol) were added to a 300 mL reaction flask, along with 15 mL of water and 60 mL of 1,4-dioxane. The mixture was heated to 85 °C and stirred for 12 h. After the reaction was complete, the product was extracted with dichloromethane, washed with a saturated sodium chloride aqueous solution, and the solvent was removed under reduced pressure. The crude product was purified by column chromatography using a mixed solvent (petroleum ether:dichloromethane = 3:1 (v / v)) as the eluent to give a white solid, compound HT2 (6.02 g, yield 52%), with a mass spectrometry m / z of 1159.3 [M+H]. + . Figure 1 The thermogravimetric curve of HT2 is shown. The test conditions were a slow heating from 30℃ to 600℃ at a heating rate of 20℃ / min. The graph shows that the thermogravimetric temperature at which HT2 experiences a 5% mass loss is approximately 400℃, indicating that HT2 has good thermal stability. The DSC curves of the first and second heating cycles for compound HT2 are shown below. Figure 2 As shown, the first round of heating shows a significant exothermic peak at approximately 200℃, indicating the temperature of the first crosslinking. The second round of heating shows no significant exothermic peak, indicating that the crosslinking is complete.

[0133] Synthesis example 2-10

[0134] The compounds listed in Table 4 were synthesized according to the method of Synthesis Example 1, except that starting material 5 was used instead of IM3-1 and starting material 6 was used instead of p-vinylphenylboronic acid. The synthesized compounds and their yields are shown in Table 4.

[0135] Table 4

[0136]

[0137]

[0138]

[0139] Example 1: Fabrication of Organic Electroluminescent Devices

[0140] First, the ITO substrate (50nm thick) was cleaned in the following order: ultrasonication with 5wt% KOH solution for 15min, ultrasonication with pure water for 15min, ultrasonication with isopropanol for 15min, and drying in an oven for 1h; then the substrate was transferred to a UV-OZONE device for surface treatment for 15min.

[0141] PEDOT:PSS was spin-coated onto a clean ITO substrate and annealed at 120°C for 12 min to form a hole injection layer (HIL) with a thickness of 40 nm.

[0142] The hole injection layer was spin-coated with an ink containing compound HT2 (composed of compound HT2 and xylene, with a concentration of 10 wt%), and annealed at 210 °C for 30 min to form a hole transport layer (HTL) with a thickness of 20 nm.

[0143] On the hole transport layer, ADN and BD-1 (mass ratio 98:2) are spin-coated to form an organic light-emitting layer (EML) with a thickness of 30 nm.

[0144] Then, DBimiBphen is vacuum-deposited on the organic light-emitting layer to form an electron transport layer (ETL) with a thickness of 20 nm.

[0145] LiQ was vacuum-deposited on the electron transport layer to form an electron injection layer (EIL) with a thickness of 8 nm.

[0146] Next, Ag is vacuum-deposited onto the electron injection layer to form a cathode with a thickness of 110 nm. This process yields an OLED device.

[0147] Example 2-10

[0148] Organic electroluminescent devices were prepared according to the method of Example 1, except that, when forming the hole transport layer, the compounds listed in Table 5 ("crosslinkable HTM" column) were used instead of compound HT2 in Example 1.

[0149] Comparative Example 1

[0150] Organic electroluminescent devices were prepared according to the method of Example 1, except that compound A was used instead of compound HT2 in Example 1 when forming the hole transport layer.

[0151] In the above embodiments and comparative examples, the structures of some materials are shown below:

[0152]

[0153] The performance of the organic electroluminescent devices prepared in the examples and comparative examples was analyzed. The performance of the devices was tested under the condition of 1000 ints, and the results are shown in Table 5.

[0154] Table 5

[0155]

[0156] As shown in Table 5, using the organic compounds of this application as crosslinkable hole transport materials enables the prepared organic electroluminescent devices to have high luminous efficiency and long service life.

[0157] The technical features of the above embodiments can be combined in any way. For the sake of brevity, not all possible combinations of the technical features in the above embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0158] The embodiments described above are merely illustrative of several implementation methods of this application, and while the descriptions are relatively specific and detailed, they should not be construed as limiting the scope of the invention patent. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of this application, and these all fall within the protection scope of this application. Therefore, the protection scope of this patent application should be determined by the appended claims.

Claims

1. An organic compound, characterized in that, The organic compound has the structure shown in Formula 1: Formula 1 X represents O, S, or C(R). 1 R 2 ), R 1 and R 2 They may be the same or different, and each is independently H or methyl; L1, L2, L3, and L4 may be the same or different, and each independently represents: a single bond, O, an alkylene group with 1-4 carbon atoms, an alkene group with 1-4 carbon atoms, a substituted or unsubstituted arylene group with 6-18 carbon atoms, a substituted or unsubstituted arylene group with 6-18 carbon atoms, a group formed by a single bond connecting an alkylene group with 1-4 carbon atoms and a phenylene group, or a group formed by a single bond connecting an alkene group with 1-4 carbon atoms and a phenylene group. R1, R2, R3 and R4 are all vinyl groups; Ar represents a substituted or unsubstituted triarylamine group with 18-40 carbon atoms, a substituted or unsubstituted aryl group with 6-40 carbon atoms, or a substituted or unsubstituted heteroaryl group with 12-40 carbon atoms. In L1, L2, L3, L4 and Ar, the substituents are the same or different, and each is independently selected from D, halogen, alkyl with 1-4 carbon atoms, aryl with 6-12 carbon atoms or heteroaryl with 5-12 carbon atoms.

2. The organic compound according to claim 1, characterized in that, The structure of the organic compound is shown in any one of Formulas 1-1 to 1-3:

3. The organic compound according to claim 1, characterized in that, Ar represents a substituted or unsubstituted triarylamine group with 18-25 carbon atoms, a substituted or unsubstituted aryl group with 6-25 carbon atoms, or a substituted or unsubstituted heteroaryl group with 12-24 carbon atoms.

4. The organic compound according to any one of claims 1-3, characterized in that, L1, L2, L3, and L4 may be the same or different, and each independently represents: a single bond, O, methylene, ethylene, methyleneoxy, ethoxy, or a group W substituted or unsubstituted by one or more substituents Z1, wherein group W is selected from any of the following groups: m1 is 1 or 2, m2 is 0, 1 or 2; Each substituent Z1 is independently selected from D, fluorine, bromine, chlorine, methyl, ethyl, n-propyl, isopropyl, tert-butyl, phenyl, or naphthyl.

5. The organic compound according to claim 4, characterized in that, L1, L2, L3, and L4 may be the same or different, and each is independently a single bond, O, methylene, ethylene, methyleneoxy, ethoxy, or any of the following groups:

6. The organic compound according to claim 4, characterized in that, , , and At least two of them are independently selected from any one of the following groups: m3 can be 0, 1, 2, 3 or 4, and m4 can be 0, 1, 2, 3 or 4.

7. The organic compound according to any one of claims 1-3, characterized in that, Ar is a group V that is substituted or unsubstituted by one or more substituents Z2, wherein group V is selected from any of the following groups: Each substituent Z2 is independently selected from D, fluorine, methyl, ethyl, n-propyl, isopropyl, tert-butyl, or phenyl.

8. The organic compound according to claim 1, characterized in that, Ar is selected from any one of the following groups:

9. The organic compound according to claim 1, characterized in that, The organic compound is any one of the following compounds:

10. A polymer, characterized in that, Its monomers include the organic compounds described in any one of claims 1-9.

11. The polymer according to claim 10, characterized in that, The polymer is formed by the monomer under crosslinking conditions, which include a temperature of 150℃-250℃ and a time of 5 min-60 min.

12. An ink, characterized in that, The ink comprises a solvent and a crosslinkable hole transport material dissolved in the solvent, wherein the crosslinkable hole transport material comprises an organic compound as described in any one of claims 1-9.

13. An electronic device, characterized in that, It includes an anode and a cathode disposed opposite to each other, and a hole transport layer disposed between the anode and the cathode, wherein the hole transport layer comprises the polymer of claim 10 or 11.

14. The electronic device according to claim 13, characterized in that, The electronic device is a photoelectric conversion device or an organic electroluminescent device.

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