WO2016176955A1

WO2016176955A1 - Polyarylphenol and 1,3,5-triazine crosslinked polymer hole injection/transport material, preparation method for same, and applications thereof

Info

Publication number: WO2016176955A1
Application number: PCT/CN2015/090685
Authority: WO
Inventors: 李�远; 邱学青; 薛雨源; 杨东杰; 武颖
Original assignee: 华南理工大学
Priority date: 2015-05-07
Filing date: 2015-09-25
Publication date: 2016-11-10
Also published as: CN104910372A; CN104910372B

Abstract

Disclosed are a preparation method for a polyarylphenol and 1,3,5-triazine crosslinked polymer hole injection/transport material and applications thereof. During preparation, in a condition of 0 °C to 40 °C, a polyarylphenol compound is added into an aqueous solution of an alkali catalyst, 1,3,5-trichloroazine molecules are dissolved in an organic solvent, pipetted drop-by-drop into the polyarylphenol compound, and reacted for 0.5 h to 48 h in a condition of 0 °C to 100 °C; and after the reaction, the pH of the reaction solution is regulated directly using a diluted acid, followed by filtering and washing to complete the process. The phenolic hydroxyl group structure of the present invention can be oxidized easily to form a radical intermediate state, thus providing hole injection and transport properties, at the same time, provides improved solubility in high polarity solvents such as dimethyl sulfoxide and alcohols, is difficult to be dissolved in low polarity solvents such as toluene, chlorobenzene, methylene chloride, and chloroform and capable of withstanding corrosion thereby, and has great application prospects in organic solar cell devices such as organic electroluminescent diodes.

Description

Hole injecting and transporting material of aryl polyphenol and 1,3,5-s-triazine cross-linking polymer, preparation method and application thereof

Technical field

The invention relates to hole injection and transport molecular materials, in particular to a novel one-step synthesis of soluble hole injection and transport materials, a preparation method thereof and the use thereof in the field of organic optoelectronic devices.

Background technique

Since the fabrication of multilayer thin-film electroluminescent devices by Tang and Van Slyke in 1987, organic light-emitting diodes (OLEDs) have been invented, and organic electronic materials and devices, including organic light-emitting diodes, have experienced rapid development for nearly three decades. At present, the electroluminescent device (OLED) for preparing small molecular materials by vacuum thermal evaporation film forming technology has been successfully applied to the display screen of some electronic products; and the solution processing type organic polymer electroluminescent device (PLED) is Low cost, large area, flexible display, inkjet printing, etc. have great development prospects, and are the frontier and hotspot of basic research and applied research.

Organic polymer electroluminescent devices (PLEDs) based on solution processing techniques, like multilayer vapor-deposited thin film electroluminescent devices, require the preparation of multilayer devices by solution processing. Therefore, the development of solution-processable charge transport materials is of great significance for industrial applications that achieve full solution processing. The primary problem faced by multi-layer solution processing devices is the solvent erosion of the underlying material. The current device structure: conductive glass (such as ITO, etc.) / hole injection/transport layer (HIL/HTL, hole injection/transport layer), Further, the upper layer is a luminescent material in which a weakly polar solvent such as toluene, xylene or chlorobenzene is dissolved to form a film. Therefore, hole injection/transport materials need to effectively overcome the erosion of these solvents. Poly 3,4-ethylenedioxythiophene/polystyrene sulfonate (PEDOT:PSS) is a water-soluble high-efficiency hole injection/transport material, however it has strong acidity and will corrode the anode material in the long run. , reducing the life of the device. Therefore, the development of sulfonate-free, while having good hole injection / transport properties, soluble in relatively large polar solvents, but insoluble or insoluble in other low-polar organic solvents, such as toluene, chlorobenzene, dichloromethane, The hole injection/transport material of a solvent such as chloroform is very important.

Summary of the invention

The present invention aims to overcome the shortcomings and deficiencies of the prior art, and provides a novel hole injection and transport material for crosslinking a soluble aryl polyphenol with 1,3,5-s-triazine, and a preparation method thereof. Solubility has good solvent selectivity.

Another object of the present invention is to provide an application of an aryl polyphenol and a 1,3,5-s-triazine crosslinked polymer hole injecting and transporting material as a hole injecting and transporting material in an organic optoelectronic device.

The invention polymerizes aryl diphenol or aryl trisphenol with 1,3,5-homochloropyrazine by a one-step method, and directly reacts the product after the reaction. Adjust the pH value and filter to obtain it. The material of the present invention can undergo an oxidation reaction due to the arylphenolic hydroxyl group and the hydroxyl group in the structure of the tripolyzinic acid. This process has an electron transfer process and thus has hole injection and transport properties. The material of the invention has a phenolic hydroxyl structure, so it has good solubility in dimethyl sulfoxide and alcohol, and is insoluble in low-polar solvents such as toluene, chlorobenzene, dichloromethane, chloroform, etc., and can resist corrosion thereof. . Therefore, the hole injecting and transporting material can be used to prepare a multilayer device for solution processing, avoiding mutual erosion of the hole injecting/transporting layer and the active layer, and a multilayer thin film device can be prepared by a solution processing method. The novel hole injection and transport material is simple to prepare and can be processed into a film. In organic optoelectronic devices, including organic electroluminescent diodes, organic solar cells, organic field effect transistors, perovskite solar cells, dye sensitization There are application prospects in batteries, organic laser illumination and other devices, which is of great significance for the development and industrialization of all-solution processing of organic optoelectronic materials and devices.

The object of the invention is achieved by the following technical solutions:

An aryl polyphenol and a 1,3,5-s-triazine crosslinked polymer hole injecting and transporting material having one of the molecular structures of formula (I) or formula (II):

Wherein Ar ₁ is an aryl diphenol structure, Ar ₂ is an aryl trisphenol structure, and a wavy line represents a coupling structure of an aryl diphenol or an aryl trisphenol and a 1,3,5-s-triazine.

The preparation method of the aryl polyphenol and the 1,3,5-s-triazine crosslinked polymer hole injection and transport material comprises the following steps:

1) Adding an aryl polyphenol compound to an aqueous solution of a base catalyst at 0 ° C to 40 ° C, dissolving the 1,3,5 - homotrichloromethane molecule in an organic solvent, dropwise dropwise In the aryl polyphenols, the reaction is carried out at 0 ° C ~ 100 ° C for 0.5 h ~ 48 h;

The aryl polyphenol compound is an aryl diphenol or an aryl trisphenol compound; the aryl diphenol is an aryl compound containing two phenolic hydroxyl groups; the aryltriphenol is contained in three An aryl compound of a phenolic hydroxyl group;

The base catalyst is one or more of sodium hydroxide, triethylamine, diisopropylethylamine, potassium hydroxide, sodium carbonate, potassium carbonate and cesium carbonate;

According to the molar fraction of the substance, the composition of the raw material is: 1,3,5-homopolychloroazine 10 parts; aryl polyphenol monomer 5-50 parts; alkali catalyst 5~150 parts;

2) Pour the reaction mixture obtained in the step 1) into a large amount of deionized water, adjust the pH of the solution to neutral with a dilute acid solution, filter, wash with water and an organic solvent to obtain aryl polyphenol crosslinks 1, 3, 5 a hole injection and transport material of a homotriazine structure.

The molecular formula of the 1,3,5-homochloropyrazine is:

To further achieve the object of the present invention, preferably, the dilute acid solution is one or more of hydrochloric acid, sulfuric acid, acetic acid, and trifluoromethanesulfonic acid.

The aryl diphenol is one or more of the following structural formulae (1) to (12);

The aryltriphenol is the following structural formula (13) and / or (14);

The volume ratio of the organic solvent to water in the mixture of the organic solvent and water is 0.1-10:1.

The organic solvent is one or more of tetrahydrofuran, acetone, diethyl ether, acetonitrile and dioxane.

The use of the aryl polyphenol and the 1,3,5-s-triazine crosslinked polymer hole injecting and transporting material as a hole injecting and transporting material in an organic optoelectronic device; the organic optoelectronic device comprising Light-emitting diodes, organic heterojunction cells, perovskite solar cells, dye-sensitized cells, organic laser lighting devices.

The aryl polyphenol and the 1,3,5-s-triazine cross-linked polymer hole injection and transport material of the invention are dissolved in a large polar solvent such as dimethyl sulfoxide and alcohol, and then used for preparing an organic optoelectronic device. As a hole injection and transport material.

Compared with the prior art, the present invention has the following advantages and benefits:

1) The aryl polyphenol crosslinked 1,3,5-s-triazine structure of the hole injection and transport material of the present invention contains a plurality of phenolic hydroxyl structures, so that the prepared material is in dimethyl sulfoxide and Alcohol has good solubility, but it is hardly soluble in other low-polar organic solvents such as toluene, chlorobenzene, dichloromethane, chloroform and the like. Therefore, the hole injecting and transporting material of the aryl polyphenol crosslinked 1,3,5-s-triazine structure of the present invention can be used for preparing a multilayer device for solution processing, avoiding hole injection and transport layer and active layer. Mutual erosion.

2) The aryl polyphenol crosslinked 1,3,5-s-triazine structure of the hole injection and transport material of the present invention is combined with a conventional hole injection and transport material having a large conjugated system. 4-ethylenedioxythiophene/polystyrene sulfonate (PEDOT:PSS) is a non-conjugated structure because the aromatic ring and the 1,3,5-s-triazine unit are connected by an ether bond. Broader The gap absorbs very little light in visible light and infrared light, and does not reduce the light-emitting efficiency in the electroluminescent device, and is convenient for the preparation of a transparent electrode.

3) The aryl polyphenol crosslinked 1,3,5-s-triazine structure hole injection and transport material of the present invention is used to replace the conventional PEDOT:PSS in an indium tin oxide (ITO) conductive glass base. On-chip spin-coating is used as a hole injecting and transporting material, and the performance of the electroluminescent device is close to that of PEDOT:PSS as a device for hole injecting and transporting materials. Since phenol and arylphenols such as hydroquinone are easily oxidized, the oxidation process undergoes electron transfer to form a phenol radical intermediate, and the phenol radical intermediate can form a plurality of resonance tautomers. As a hole injection/transport material.

4) The method for preparing a hole injection and transport material of the aryl polyphenol crosslinked 1,3,5-s-triazine structure according to the present invention is simple and convenient to purify.

DRAWINGS

1, 2, 3, 4, 5, and 6 are the nuclear magnetic hydrogen spectra of the products of Examples 1, 2, 3, 4, 5, and 6, respectively;

Figure 7 is a matrix assisted laser desorption-time of flight mass spectrometry of Example 1.

Fig. 8 is a graph showing the maximum external current efficiency of the device of Example 1 (device structure: ITO/HIL/HTL/p-PPV/CsF/Al).

detailed description

The present invention will be further described with reference to the accompanying drawings and embodiments. It is to be understood that the embodiments are not intended to limit the scope of the invention.

Example 1

Hydroquinone (0.825 g, 7.5 mmol) was dissolved in 20 mL of an aqueous solution of sodium hydroxide (0.3 g, 7.5 mmol), and 1,3,5-petrochloropyridazine (0.25) was slowly added dropwise in the dark. M, 10 mL, 2.5 mmol) of tetrahydrofuran solution was poured into a reaction flask. After stirring at room temperature for 24 hours, tetrahydrofuran was removed by rotary distillation. The reaction mixture was poured into water (100 mL), pH was adjusted to neutral with dilute hydrochloric acid, filtered, and the filter cake was washed with water and dried to give 0.80 g of brown product.

Figure 1 and Figure 7 show nuclear magnetic resonance spectroscopy and matrix-assisted laser desorption-time-of-flight mass spectrometry, respectively. The results of nuclear magnetic resonance spectroscopy are: ¹ H NMR (d ₆ -DMSO, 400 MHz, δ / ppm): 6.55 (s, 2H), 6.67 - 6.81 (d, 7H), 6.94-7.09 (m, 7H), 7.25-7.41 (m, 7H), 11.11-11.24 (m, 4H). In the signal of the aromatic ring, it is a multiple peak, and compared with the raw material, it proves that it is not the signal of the raw material, which is consistent with the characteristics of the polymer, indicating that the sample is hydroquinone and 1,3,5-homopolychloroazine The polymer formed after the association. Figure 7 is the result of matrix-assisted laser desorption-time-of-flight mass spectrometry, the mass-to-charge ratio of the mass spectrum representing the molecular fragment peaks produced by the excitation of the polymer sample molecules under the test conditions, demonstrating that the molecular weight of the polymer of this example is 500- Between 1312, the molecular weight of the polymer itself is greater than the molecular weight corresponding to the fragment peak. The solubility of the polymer in common solvents for testing molecular weight is poor, and it is currently difficult to measure its exact molecular weight.

Example 2

2,5-di-tert-butyl hydroquinone (1.67 g, 7.5 mmol) was dissolved in 20 mL of sodium hydroxide (0.9 g, 22.5 mmol) aqueous solution, and slowly added 1, 3, 5 in the dark. - A solution of tetrachlorolimazine (0.25 M, 10 mL, 2.5 mmol) in dioxane to the reaction flask. After stirring at 60 ° C for 24 h, the reaction mixture was poured into 500 mL of water, pH was adjusted to neutral with dilute sulfuric acid, filtered, and the filter cake was washed with water and acetone, and dried to give 1.5 g of an off white product.

Figure 2 is a nuclear magnetic resonance spectrum of Example 2, ¹ H NMR (d _{6 -} DMSO, 400 MHz, δ / ppm): 0.75-1.57 (m, 23H), 6.20-7.38 (m, 10H), 8.38-8.88 (m, 2H), 9.23 (s, 1H). In the signal of the aromatic ring, it is a multiple peak, and compared with the raw material, it proves that it is not the signal of the raw material, and it conforms to the characteristics of the polymer. The result shows that the sample is 2,5-di-tert-butyl hydroquinone and 1,3. , a polymer formed after 5-monochlorotriazine coupling.

Example 3

Dissolve 1,4-dihydroxynaphthalene (1.2 g, 7.5 mmol) in 20 mL of sodium carbonate (0.8 g, 7.5 mmol) in an aqueous solution, and slowly add 1,3,5-petrochlorochloride in the dark. (0.25 M, 10 mL, 2.5 mmol) in tetrahydrofuran solution into a reaction flask. After stirring at 60 ° C for 24 h, the reaction mixture was poured into 100 mL of water, pH was adjusted to neutral with dilute acetic acid, filtered, and the filter cake was washed with water and acetone, and dried to give 1.1 g of brown product.

3 is a nuclear magnetic resonance spectrum of Example 3, ¹ H NMR (d ₆ -DMSO, 400 MHz, δ/ppm): 4.52 (s, 1H), 6.90-8.04 (m, 21H), 9.83 (s, 1H). In the signal of the aromatic ring, it is a multiple peak, and compared with the raw material, it proves that it is not the signal of the raw material, and it conforms to the characteristics of the polymer. The result shows that the sample is 1,4-dihydroxynaphthalene and 1,3,5-all three. A polymer formed after coupling with polychlorazine.

Example 4

Hydroquinone (0.85 g, 7.5 mmol) was dissolved in 20 mL of an aqueous solution of triethylamine (1.51 g, 15 mmol), and 1,3,5-petrochloropyridazine (0.75 M) was slowly added dropwise in the dark. , 10 mL, 7.5 mmol) of dioxane solution into the reaction flask. After stirring at room temperature for 24 hours, the acetone was rotary distilled off, the reaction mixture was poured into 100 mL of water, pH was adjusted to neutral with dilute hydrochloric acid, filtered, and the filter cake was washed with water and acetone, and dried to give 2.3 g of a white solid product.

Figure 4 is a nuclear magnetic resonance spectrum of Example 4, ¹ H NMR (d _{6 -} DMSO, 400 MHz, δ / ppm): 4.46 (s, 9H), 6.62 - 6.92 (m, 2H), 6.91 - 7.11 (m, 3H) , 7.28-7.48 (m, 5H), 11.20 (s, 1H). In the signal of the aromatic ring, it is a multiple peak, and compared with the raw material, it proves that it is not the signal of the raw material, and it conforms to the characteristics of the polymer. The result shows that the sample is 1,4-dihydroxynaphthalene and 1,3,5-all three. A polymer formed after the combination of polychlorazine.

Example 5

1,4-Dihydroxynaphthalene (1.2 g, 7.5 mmol) was dissolved in 20 mL of an aqueous solution of cesium carbonate (4.88 g, 22.5 mmol), and 1,3,5-trimeric chloride was slowly added dropwise in the dark. Azine (0.75M, 10mL, 7.5mmol) in acetonitrile to In the reaction bottle. After stirring at 60 ° C for 24 h, the reaction mixture was poured into 100 mL of water, filtered, and the filter cake was washed with water and acetone, and dried to give 1.1 g of brown solid product.

Figure 5 is a nuclear magnetic resonance spectrum of Example 5, ¹ H NMR (d _{6 -} DMSO, 400 MHz, δ / ppm): 4.56 (s, 1H), 6.77 - 7.95 (m, 14H), 9.20 - 9.67 (d, 1H) , 10.06 (s, 1H). In the signal of the aromatic ring, it is a multiple peak, and compared with the raw material, it proves that it is not the signal of the raw material, and it conforms to the characteristics of the polymer. The result shows that the sample is 1,4-dihydroxynaphthalene and 1,3,5-all three. A polymer formed after coupling with polychlorazine.

Example 6

Dissolve bisphenol A (0.95 g, 7.5 mmol) in 20 mL of diisopropylethylamine (1.94 g, 15 mmol) in an aqueous solution, and slowly add 1,3,5-petrochlorochloride in the dark. (0.25 M, 10 mL, 2.5 mmol) in tetrahydrofuran solution into a reaction flask. After stirring under reflux for 24 h, tetrahydrofuran was removed by rotary distillation. The reaction mixture was poured into 100 mL of water, pH was adjusted to neutral with dilute sulfuric acid, filtered, and the filter cake was washed with water and tetrahydrofuran, and dried to give 1.3 g of a white solid product.

Figure 6 is a nuclear magnetic resonance spectrum of Example 6, ¹ H NMR (d _{6 -} DMSO, 400 MHz, δ / ppm): 1.04-1.33 (s, 1H), 1.43-1.75 (m, 18H), 6.62 (d, 7H) , 7.04-7.38 (m, 17H), 11.22 (s, 1H), 10.06 (s, 1H). In the signal of the aromatic ring, there are multiple peaks, and compared with the raw materials, it proves that it is not the signal of the raw material, which is consistent with the characteristics of the polymer. The results show that the sample is bisphenol A and 1,3,5-homopolychloroazine. The polymer formed after the association.

Example 7: Application of aryl polyphenols and 1,3,5-s-triazine cross-linked polymer hole injection and transport materials in green organic electroluminescent diode devices:

Preparation of aryl polyphenols and 1,3,5-s-triazine cross-linked polymer hole injection and transport materials in green organic electroluminescent diodes (p-PPV):

The indium tin oxide (ITO) conductive glass substrate was ultrasonically cleaned successively with acetone, detergent, deionized water and isopropyl alcohol, and after drying in an oven, it was treated with PLASMA (oxygen plasma) for 4 minutes to further clean the conductive glass.

The hole injection and transport layer involved in the following preparation process is represented by HIL/HTL (hole injection/transport layer), and the specific preparation methods of the five devices are as follows:

The three aryl polyphenols obtained in Examples 1, 2, and 3 and the 1,3,5-s-triazine cross-linked polymer hole injecting and transporting materials were respectively dissolved in dimethyl sulfoxide to form a film by spin coating. The three aryl polyphenols obtained in Examples 1, 2, and 3 and the 1,3,5-s-triazine cross-linked polymer are injected into the three treated ITO glass sheets, respectively. The film of the transport material, wherein the hole injection and transport layer is represented by HIL/HTL (hole injection/transport layer), has a thickness of about 30 nm. The substrate was dried in a vacuum oven at 80 ° C for 8 hours to remove the solvent, and the green light-emitting material p-PPV was dissolved in x-xylene. Next, the p-PPV solution was spin-coated on the ITO glass to which the sample films of Examples 1, 2, and 3 were applied. In addition, the No. 1 device was a control device, and no hole injection/transport layer was added. The four wafers described above were vapor-deposited with a metal CsF (1 nm) / Al (100 nm) cathode under a vacuum of 4 × 10 ^-4 Pa.

The effective illuminating area of the device was 0.17 cm ² and the film thickness was measured using a Tencor Alfa Step-500 surface profiler. The deposition rate of the metal electrode evaporation and its thickness were measured using a Sycon Instrument thickness/speed meter STM-100. Except that the spin coating process of the aryl polyphenol and the 1,3,5-s-triazine crosslinked polymer hole injection/transport layer film is completed in the atmosphere, all other steps are completed in a glove box in a nitrogen atmosphere. . The source of the material corresponding to the number of the obtained device is shown in Table 1.

The polymer involved in Example 7 is a commercial product, and the molecular structure of the polymer p-PPV is:

Wherein m, n, and p represent the relative amounts (in %) of the amounts of the three monomers in the polymer p-PPV, respectively, and are between 0 and 100.

Table 1 shows the hole injection/transport properties of the materials obtained in Examples 1, 2 and 3.

(Device structure is: ITO/HIL/HTL/p-PPV/CsF/Al)

The results in Table 1 show that the materials of Examples 1, 2, and 3 were formed by solution spin coating to prepare the hole injection and transport layer of the organic electroluminescent diode, and the maximum current efficiency and maximum external quantum efficiency (2.6%). The efficiency of the device with less hole injection/transport layer (0.98%) is improved. The hole injection/transport layer of the organic electroluminescent diode was prepared by a spin coating method, and the ignition voltage was low, and the maximum current efficiency was 6.50 cd/A. This is the first report on the application of aryl polyphenols and 1,3,5-s-triazine cross-linked polymer hole injection and transport materials in organic electroluminescent diode devices.

Example 8: Application performance of aryl polyphenols and 1,3,5-s-triazine cross-linked polymer hole injection and transport materials in blue organic electroluminescent diode devices

No.1 and No.2 devices: A solution of poly 3,4-ethylenedioxythiophene/polystyrene sulfonate (PEDOT:PSS) was separately coated on two treated ITO glass sheets by PEDOT:PSS film (40 nm). Then, the material of Example 1 was dissolved in dimethyl sulfoxide, and a layer of the material film of Example 1 was separately coated on two ITO glasses which had been coated with a PEDOT:PSS layer by spin coating. The thicknesses are 10 nm and 30 nm, respectively. The substrate was dried in a vacuum oven at 80 ° C for 8 hours to remove the solvent, and polyvinylcarbazole (PVK, 35 nm) was spin-coated on the material film of Example 1. Next, the blue light-emitting material PSF was dissolved in x-xylene, and the PSF solution was spin-coated on the PVK layer. Finally, a metal CsF (1 nm) / Al (100 nm) cathode was vapor-deposited under a vacuum of 4 × 10 -4 Pa, and the device was fabricated.

No. 3 device: In the preparation process, a PEDOT:PSS (40 nm)/PVK (35 nm) layer was prepared by spin coating, and then a PSF layer (10 nm) was prepared on the PEDOT:PSS/PVK layer.

No. 4 device: During the preparation, a PVK layer (35 nm) was prepared by spin coating, and then a luminescent material PSF was spin-coated on polyvinyl carbazole (PVK) to prepare a PSF layer (10 nm).

No. 5 device, during the preparation process, the material of Example 1 was spin-coated on ITO glass to a thickness of 20 nm, and then a polyvinyl carbazole layer (PVK, 35 nm) was spin-coated on the material layer of Example 1. Then, a luminescent material PSF layer (10 nm) was spin-coated on the PVK layer.

The effective illuminating area of the device was 0.17 cm ² and the film thickness was measured using a Tencor Alfa Step-500 surface profiler. The deposition rate of the metal electrode evaporation and its thickness were measured using a Sycon Instrument thickness/speed meter STM-100. Except that the spin coating process of the aryl polyphenol and the 1,3,5-s-triazine cross-linked polymer hole injection/transport material film is completed in the atmosphere, all other steps are completed in a glove box in a nitrogen atmosphere. .

The polymer involved in the embodiment 8 is a commercial product, and the molecular structure of the polymer PSF is:

Wherein n represents the number of repeating units of the monomer in the polymer PSF, and the value is between 5 and 500.

Table 2 shows the hole injection/transport properties of the material obtained in Example 1 (device structure: ITO/HIL/HTL/PSF/CsF/Al)

The results in Table 2 show that the hole injecting and transporting layer of the organic electroluminescent diode is prepared by the solution spinning method of the material of the embodiment of the present invention, and the maximum current efficiency and the maximum external quantum efficiency (4.26%) are more conventional. The efficiency of PEDOT/PVK as a device for hole injection and transport layer (2.75%) is obvious.

It should be noted that the embodiments are not intended to limit the scope of the invention, and any modifications, equivalents, and improvements made within the spirit and scope of the invention are included in the scope of the invention.

Claims

An aryl polyphenol and a 1,3,5-s-triazine crosslinked polymer hole injection and transport material characterized by having one of the molecular structures of formula (I) or formula (II):

Wherein Ar 1 is an aryl diphenol structure, Ar 2 is an aryl trisphenol structure, and a wavy line represents a coupling structure of an aryl diphenol or an aryl trisphenol and a 1,3,5-s-triazine.
The method for preparing a hole injecting and transporting material of an aryl polyphenol and a 1,3,5-s-triazine crosslinked polymer according to claim 1, comprising the steps of:

1) Adding an aryl polyphenol compound to an aqueous solution of a base catalyst at 0 ° C to 40 ° C, dissolving the 1,3,5 - homotrichloromethane molecule in an organic solvent, dropwise dropwise In the aryl polyphenols, the reaction is carried out at 0 ° C ~ 100 ° C for 0.5 h ~ 48 h;

The aryl polyphenol compound is an aryl diphenol or an aryl trisphenol compound; the aryl diphenol is an aryl compound containing two phenolic hydroxyl groups; the aryltriphenol is contained in three An aryl compound of a phenolic hydroxyl group;

The base catalyst is one or more of sodium hydroxide, triethylamine, diisopropylethylamine, potassium hydroxide, sodium carbonate, potassium carbonate and cesium carbonate;

According to the molar fraction of the substance, the composition of the raw material is: 1,3,5-homopolychloroazine 10 parts; aryl polyphenol monomer 5-50 parts; alkali catalyst 5~150 parts;

2) Pour the reaction mixture obtained in step 1) into a large amount of deionized water, and adjust the pH of the solution to a medium with a dilute acid solution. The organic solvent was washed with water and an organic solvent to obtain a hole injecting and transporting material in which an arylpolyphenol crosslinked 1,3,5-s-triazine structure.
The method for preparing a hole injecting and transporting material of an aryl polyphenol and a 1,3,5-s-triazine crosslinked polymer according to claim 2, wherein the dilute acid solution is hydrochloric acid, sulfuric acid or acetic acid. And one or more of trifluoromethanesulfonic acid.
The method for preparing a hole injecting and transporting material of an aryl polyphenol and a 1,3,5-s-triazine crosslinked polymer according to claim 2, wherein the aryl diphenol is of the following structural formula ( One or more of 1)-(12):
The method for preparing a hole injecting and transporting material of an aryl polyphenol and a 1,3,5-s-triazine crosslinked polymer according to claim 2, wherein the aryltriphenol is of the following structural formula ( 13) and / or (14):
The method for preparing a hole injecting and transporting material of an aryl polyphenol and a 1,3,5-s-triazine crosslinked polymer according to claim 2, wherein the organic solvent and water are mixed The volume ratio of the organic solvent to water is from 0.1 to 10:1.
The method for preparing a hole injecting and transporting material of an aryl polyphenol and a 1,3,5-s-triazine crosslinked polymer according to claim 2 or 6, wherein the organic solvent is tetrahydrofuran or acetone. One or more of diethyl ether, acetonitrile and dioxane.
The use of the aryl polyphenol and the 1,3,5-s-triazine crosslinked polymer hole injecting and transporting material according to claim 1 as a hole injecting and transporting material in an organic optoelectronic device; said organic photoelectron Devices include light-emitting diodes, organic heterojunction cells, perovskite solar cells, dye-sensitized cells, or organic laser lighting devices.