CN104910372B - Aryl polyphenol and the injection of 1,3,5 s-triazine cross-linked polymer holes and transmission material and preparation method and application - Google Patents

Abstract

The invention discloses aryl polyphenol and the injection of 1,3,5 s-triazine cross-linked polymer holes and the preparation method and application of transmission material.During preparation, under the conditions of 0 DEG C~40 DEG C, in the aqueous solution that aryl polyphenol compound is added to alkali catalyst, 1,3,5 equal three polychlorostyrene piperazine quasi-molecule is dissolved in organic solvent, it is added drop-wise to dropwise in aryl polyphenol compound, 0.5h~48h is reacted under the conditions of 0 DEG C~100 DEG C；Reacting liquid pH value, filtration washing are directly adjusted after reaction with diluted acid.The phenolic hydroxyl structure of the present invention is oxidized easily, form free radical intermediate state, therefore possess hole injection and transmission performance, there is preferable dissolubility in the big polar solvent such as dimethyl sulfoxide (DMSO) and alcohols simultaneously, and such as toluene, chlorobenzene, dichloromethane, chloroform low polar solvent are insoluble in, its corrosion can be resisted, in organic electro-optic device, including organic electroluminescent LED, there is preferable application prospect in terms of organic solar batteries device.

Description

Hole injection and transport materials of aryl polyphenols and 1,3,5-s-triazine crosslinked polymers and Its preparation method and application

technical field

The invention relates to a hole injection and transport molecular material, in particular to a novel one-step synthesized soluble hole injection and transport material, a preparation method and its application in the field of organic optoelectronic devices.

Background technique

Since Tang and Van Slyke prepared multilayer thin-film electroluminescent devices in 1987 and invented organic light-emitting diodes (OLEDs), organic electronic materials and devices including organic light-emitting diodes have experienced nearly three decades of rapid development. At present, electroluminescent devices (OLEDs) of small molecular materials prepared by vacuum thermal evaporation film formation technology have been successfully applied to the display screens of some electronic products; Low-cost, large-area, flexible display, inkjet printing, etc. have great development prospects, and are the frontier and hot directions of basic research and applied research.

Organic polymer electroluminescent devices (PLEDs) based on solution processing technology, similar to multilayer evaporated thin film electroluminescent devices, need to prepare multilayer devices by solution processing. Therefore, the development of solution processable charge transport materials is of great significance for the industrial application of full solution processing. The primary problem faced by multi-layer solution processed devices is the erosion of the underlying material by the solvent. The current device structure: conductive glass (such as ITO, etc.)/hole injection and transport layer (HIL/HTL, hole injection/transport layer), The upper layer is a luminescent material dissolved in a weak polar solvent such as toluene, xylene or chlorobenzene to form a film. Therefore, hole injection/transport materials need to effectively overcome the attack of these solvents. Poly(3,4-ethylenedioxythiophene/polystyrene sulfonate) (PEDOT:PSS) is a water-soluble high-efficiency hole injection/transport material, but it has strong acidity and will corrode the anode material in the long run , reducing the lifetime of the device. Therefore, the development of sulfonate-free and good hole injection/transport properties is soluble in relatively large polar solvents, but insoluble or insoluble in other low-polarity organic solvents, such as toluene, chlorobenzene, dichloromethane, Hole injection/transport materials in solvents such as chloroform are of great significance.

Contents of the invention

The purpose of the present invention is to overcome the shortcomings and deficiencies of the prior art, and provide a novel type of hole injection and transport material cross-linked with soluble aryl polyphenols and 1,3,5-s-triazine and a preparation method thereof. Solubility has good solvent selectivity.

Another object of the present invention is to provide the application of hole injection and transport materials of aryl polyphenols and 1,3,5-s-triazine cross-linked polymers as hole injection and transport materials in organic optoelectronic devices.

The invention polymerizes aryl diphenols or aryl triphenols with 1,3,5-homotripolychlorazine through a one-step method, and directly adjusts the pH value of the product after the reaction, and can be obtained by filtering and washing. Because the aryl phenolic hydroxyl group and the hydroxyl group in the tripolyoxane acid structure can undergo oxidation reaction, the material of the present invention has electron transfer process, so it has hole injection and transport properties. The material of the present invention has a phenolic hydroxyl structure, so it has good solubility in dimethyl sulfoxide and alcohol, and is insoluble in low-polarity solvents such as toluene, chlorobenzene, methylene chloride, and chloroform, and can resist corrosion . Therefore, the hole injection and transport material can be used to prepare solution-processed multilayer devices, avoid mutual erosion between the hole injection/transport layer and the active layer, and can prepare multilayer thin film devices by solution processing. This new type of hole injection and transport material is simple to prepare and can be processed into a film by solution. Batteries, organic laser lighting and other devices have application prospects, which is of great significance for the development and industrialization of full solution processing organic optoelectronic materials and devices.

The object of the present invention is achieved through the following technical solutions:

The hole injection and transport material of aryl polyphenol and 1,3,5-s-triazine cross-linked polymer has one of the molecular structures such as formula (I) or formula (II):

Among them, Ar ₁ is the structure of aryl diphenol, Ar ₂ is the structure of aryl triphenol, and the wavy line represents the coupling structure of aryl diphenol or aryl triphenol and 1,3,5-s-triazine.

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

1) Under the condition of 0℃～40℃, add the aryl polyphenol compound into the aqueous solution of the alkali catalyst, dissolve the 1,3,5-tripolychlorazine molecules in the organic solvent, and add dropwise Into aryl polyphenol compounds, react at 0°C to 100°C for 0.5h to 48h;

The aryl polyphenol compounds are aryl diphenols or aryl triphenol compounds; the aryl diphenols are aryl compounds containing two phenolic hydroxyl groups; the aryl triphenols contain three Aryl compounds of phenolic hydroxyl groups;

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

According to the mole fraction of the substance, the raw material formula is composed of: 10 parts of 1,3,5-s-tripolychlorazine; 5-50 parts of aryl polyphenol monomer; 5-150 parts of alkali catalyst;

2) Pour the reaction mixture obtained in step 1) into a large amount of deionized water, adjust the pH value of the solution to neutrality with a dilute acid solution, filter, wash with water and an organic solvent, and obtain aryl polyphenol crosslinked 1,3,5 - Hole injection and transport materials with s-triazine structure.

The molecular formula of described 1,3,5-tripolychlorazine is:

To further realize the purpose 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 formulas (1)-(12);

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

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

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

The application of the aryl polyphenol and 1,3,5-s-triazine cross-linked polymer hole injection and transport material as a hole injection and transport material in an organic optoelectronic device; the organic optoelectronic device includes Light-emitting diodes, organic heterojunction cells, perovskite solar cells, dye-sensitized cells, organic laser lighting devices.

The aryl polyphenol and 1,3,5-s-triazine crosslinked polymer hole injection and transport material of the present invention are dissolved in large polar solvents such as dimethyl sulfoxide and alcohol, and then applied to the preparation of organic optoelectronic devices. As a hole injection and transport material.

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

1) The aryl polyphenol crosslinked 1,3,5-s-triazine hole injection and transport material of the present invention contains a plurality of phenolic hydroxyl structures, so that the prepared material is stable in dimethyl sulfoxide and It has good solubility in alcohol, but it is difficult to dissolve in other low-polarity organic solvents, such as toluene, chlorobenzene, methylene chloride, chloroform, etc. Therefore, the hole injection and transport material of the aryl polyphenol cross-linked 1,3,5-s-triazine structure described in the present invention can be used for the preparation of solution-processed multilayer devices, avoiding the hole injection and transport layer and the active layer. mutual erosion.

2) The aryl polyphenol cross-linked 1,3,5-s-triazine structure hole injection and transport material described in the present invention is different from the traditional hole injection and transport material poly 3, Compared with 4-ethylenedioxythiophene/polystyrene sulfonate (PEDOT:PSS), since the aromatic ring and the 1,3,5-s-triazine unit are connected by an ether bond, it is a non-conjugated structure, so It has a wide band gap, has very weak absorption in visible light and infrared light, does not reduce the light extraction efficiency in electroluminescent devices, and is convenient for the preparation of transparent electrodes.

3) The aryl polyphenol cross-linked 1,3,5-s-triazine structure hole injection and transport material of the present invention is used to replace the traditional PEDOT:PSS, on the indium tin oxide (ITO) conductive glass substrate The on-chip spin-coating film is used as the hole injection and transport material, and the performance of the electroluminescent device is close to that of the device using PEDOT:PSS as the hole injection and transport material. Because aryl polyphenols such as phenol and hydroquinone are prone to oxidation reactions, electron transfer occurs during the oxidation process to generate phenol radical intermediates, and the phenol radical intermediates can form multiple resonance interconversions, potentially as a hole injection/transport material.

4) The hole injection and transport material with aryl polyphenol crosslinked 1,3,5-s-triazine structure described in the present invention has a simple preparation method and convenient purification.

Description of drawings

Fig. 1, 2, 3, 4, 5, 6 are respectively the proton nuclear magnetic spectra of embodiment 1, 2, 3, 4, 5, 6 products;

FIG. 7 is the matrix-assisted laser desorption-time-of-flight mass spectrum of Example 1. FIG.

FIG. 8 is a diagram of 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 below in conjunction with the accompanying drawings and examples. It should be noted that the examples do not limit the protection scope of the present invention.

Example 1

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

Figure 1 and Figure 7 are H NMR spectrum and matrix-assisted laser desorption-time-of-flight mass spectrometry respectively. The H NMR spectrum test results are: ¹ HNMR(d ₆ -DMSO,400MHz,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). Among the signals of the aromatic ring, they are all multiple peaks, and compared with the raw material, it proves that it is not the signal of the raw material, which conforms to the characteristics of the polymer, indicating that the sample is hydroquinone and 1,3,5-tripolychlorazine. The resulting polymer. Fig. 7 is the result of matrix-assisted laser desorption-time-of-flight mass spectrometry, and the mass-to-charge ratio of this mass spectrum represents under this testing condition, the molecular fragmentation peak that polymer sample molecule is excited produces, proves that the molecular weight of this embodiment polymer is in 500- 1312, and the molecular weight of the polymer itself is greater than the corresponding molecular weight of the fragment peak. Polymers are poorly soluble in common solvents used to measure molecular weight, making it difficult to measure their exact molecular weight.

Example 2

Dissolve 2,5-di-tert-butylhydroquinone (1.67g, 7.5mmol) in 20mL of sodium hydroxide (0.9g, 22.5mmol) aqueous solution, slowly add 1,3,5 - Dioxane solution of s-tripolychlorazine (0.25M, 10 mL, 2.5 mmol) into the reaction vial. After stirring at 60°C for 24 hours, the reaction mixture was poured into 500 mL of water, the pH was adjusted to neutral with dilute sulfuric acid, filtered, and the filter cake was washed with water and acetone, and dried to obtain 1.5 g of off-white product.

Figure 2 is the proton NMR spectrum of Example 2, ¹ HNMR (d ₆ -DMSO, 400MHz, δ/ppm): 0.75-1.57 (m, 23H), 6.20-7.38 (m, 10H), 8.38-8.88 (m, 2H), 9.23(s, 1H). Among the signals of the aromatic ring, there are multiple peaks, and compared with the raw material, it proves that it is not the signal of the raw material, which conforms to the characteristics of the polymer. The results show that the samples are 2,5-di-tert-butylhydroquinone and 1,3 , 5-tripolychlorazine coupling generated polymer.

Example 3

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

Fig. 3 is the proton NMR spectrum of Example 3, ¹ HNMR (d ₆ -DMSO, 400MHz, δ/ppm): 4.52 (s, 1H), 6.90-8.04 (m, 21H), 9.83 (s, 1H). Among the signals of the aromatic ring, there are multiple peaks, and compared with the raw material, it proves that it is not the signal of the raw material, which is in line with the characteristics of the polymer. The results show that the samples are 1,4-dihydroxynaphthalene and 1,3,5-same Polymers produced after polychlorazine coupling.

Example 4

Hydroquinone (0.85g, 7.5mmol) was dissolved in 20mL of triethylamine (1.51g, 15mmol) aqueous solution, and 1,3,5-s-tripolychlorazine (0.75M , 10mL, 7.5mmol) of dioxane solution into the reaction flask. After stirring at room temperature for 24 hours, the acetone was removed by rotary distillation, the reaction mixture was poured into 100 mL of water, the pH was adjusted to neutral with dilute hydrochloric acid, filtered, the filter cake was washed with water and acetone, and dried to obtain 2.3 g of a gray solid product.

Figure 4 is the proton NMR spectrum of Example 4, ¹ HNMR (d ₆ -DMSO, 400MHz, 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). Among the signals of the aromatic ring, there are multiple peaks, and compared with the raw material, it proves that it is not the signal of the raw material, which is in line with the characteristics of the polymer. The results show that the samples are 1,4-dihydroxynaphthalene and 1,3,5-same A polymer formed after polychlorazine coupling.

Example 5

Dissolve 1,4-dihydroxynaphthalene (1.2g, 7.5mmol) in 20mL of an aqueous solution of cesium carbonate (4.88g, 22.5mmol), and slowly add 1,3,5-trimeric chloride dropwise under dark conditions A solution of oxazine (0.75M, 10 mL, 7.5 mmol) in acetonitrile was added to the reaction vial. 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 obtain 1.1 g of a brown solid product.

Figure 5 is the NMR spectrum of Example 5, ¹ HNMR (d ₆ -DMSO, 400MHz, δ/ppm): 4.56 (s, 1H), 6.77-7.95 (m, 14H), 9.20-9.67 (d, 1H) , 10.06(s, 1H). Among the signals of the aromatic ring, there are multiple peaks, and compared with the raw material, it proves that it is not the signal of the raw material, which is in line with the characteristics of the polymer. The results show that the samples are 1,4-dihydroxynaphthalene and 1,3,5-same Polymers produced after polychlorazine coupling.

Example 6

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

Figure 6 is the NMR spectrum of Example 6, ¹ HNMR (d ₆ -DMSO, 400MHz, 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). Among the signals of the aromatic ring, there are multiple peaks, and compared with the raw material, it proves that it is not the signal of the raw material, which is in line with the characteristics of the polymer. The results show that the sample is bisphenol A and 1,3,5-tripolychlorazine. The resulting polymer.

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

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

The indium tin oxide (ITO) conductive glass substrate was ultrasonically cleaned with acetone, detergent, deionized water and isopropanol in sequence, 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:

Dissolve the three aryl polyphenols and 1,3,5-s-triazine crosslinked polymer hole injection and transport materials obtained in Examples 1, 2, and 3 in dimethyl sulfoxide, and form a film by spin coating In the same way, three aryl polyphenols and 1,3,5-s-triazine cross-linked polymer hole-injecting polymers obtained in Examples 1, 2, and 3 were separately coated on three treated ITO glass sheets. and transport material thin film, wherein the hole injection and transport layer is represented by HIL/HTL (hole injection/transport layer), and the thickness of HTL is about 30nm. The substrate was dried in a vacuum oven at 80° C. for 8 hours to remove the solvent, and the green luminescent material p-PPV was dissolved in xylene (o-xylene). Next, the p-PPV solution was spin-coated on the ITO glass coated with the sample films of Examples 1, 2, and 3. In addition, device No. 1 is a control device without a hole injection/transport layer. Metal CsF (1nm)/Al (100nm) cathodes were vapor-deposited on the above four sheets under a vacuum of 4×10 ^-4 Pa.

The effective light-emitting area of the device is 0.17 cm ² , and the film thickness is measured with a Tencor Alfa Step-500 surface profiler. The deposition rate and thickness of the metal electrode vapor deposition were measured with Sycon Instrument's Thickness/Speed Meter STM-100. Except that the spin-coating process of the aryl polyphenol and 1,3,5-s-triazine crosslinked polymer hole injection/transport layer film was completed in the atmosphere, all other steps were completed in a nitrogen atmosphere glove box . The source of materials corresponding to the numbers of the obtained devices is shown in Table 1.

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

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

Table 1 shows the hole injection/transport properties of the materials obtained in Examples 1, 2 and 3 (the device structure is: ITO/HIL/HTL/p-PPV/CsF/Al)

Table 1 result shows, application embodiment 1,2,3 material, adopt solution spin-coating method to form a film, prepare the hole injection and transport layer of organic electroluminescence diode, maximum current efficiency and maximum external quantum efficiency (2.6%) Compared with the efficiency (0.98%) of the device without the hole injection/transport layer, the improvement effect is obvious. The method is used to prepare the hole injection/transport layer of the organic electroluminescence diode by the spin coating method, and the turn-on voltage is very low, and the maximum current efficiency is 6.50cd/A. This is the first report on the application of aryl polyphenols and 1,3,5-s-triazine crosslinked polymer hole injection and transport materials in organic electroluminescent diode devices.

Example 8: Application performance of aryl polyphenol and 1,3,5-s-triazine crosslinked polymer hole injection and transport materials in blue organic light-emitting diode devices

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

The indium tin oxide (ITO) conductive glass substrate was ultrasonically cleaned with acetone, detergent, deionized water and isopropanol in sequence, 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:

Devices 1 and 2: spin-coat PEDOT:PSS films (40nm ), then the material of embodiment 1 is dissolved with dimethyl sulfoxide, and the material film of embodiment 1 is coated on 2 pieces of ITO glass that have been coated with PEDOT:PSS layer respectively in the mode of spin-coating film , with a thickness of 10 nm and 30 nm, respectively. The above substrate was dried in a vacuum oven at 80°C for 8 hours to remove the solvent, and then polyvinylcarbazole (PVK, 35nm) was spin-coated on the material film of Example 1. Next, the blue luminescent material PSF is dissolved in xylene (o-xylene), and the PSF solution is spin-coated on the PVK layer. Finally, the metal CsF (1nm)/Al (100nm) cathode is vapor-deposited under a vacuum of 4×10-4Pa, and the device is completed.

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

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

No. 5 device, in the preparation process, the material of embodiment 1 is spin-coated with spin-coating mode on ITO glass, and thickness is 20nm, then spin-coats polyvinylcarbazole layer (PVK, 35nm) on the material layer of embodiment 1 , and then spin-coat the luminescent material PSF layer (10nm) on the PVK layer.

The effective light-emitting area of the device is 0.17 cm ² , and the film thickness is measured with a Tencor Alfa Step-500 surface profiler. The deposition rate and thickness of the metal electrode vapor deposition were measured with Sycon Instrument's Thickness/Speed Meter STM-100. Except that the spin-coating process of the aryl polyphenol and 1,3,5-s-triazine crosslinked polymer hole injection/transport material film was completed in the atmosphere, all other steps were completed in a nitrogen atmosphere glove box .

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

Where 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 performance of the material obtained in Example 1 (the device structure is: ITO/HIL/HTL/PSF/CsF/Al)

Table 2 result shows, with the embodiment material of the present invention, solution spin-coating method forms a film, prepares the hole injection and transport layer of organic electroluminescent diode, maximum current efficiency and maximum external quantum efficiency (4.26%) are more traditional The efficiency (2.75%) of the device with PEDOT/PVK as the hole injection and transport layer is significantly improved.

It should be noted that the examples do not limit the protection scope of the present invention, and any modifications, equivalent replacements and improvements made within the spirit and principles of the present invention shall be included in the protection scope of the present invention.

Claims (8)

1. aryl polyphenol and 1, the injection of 3,5- s-triazine cross-linked polymer holes and transmission material, it is characterised in that with such as formula Or one kind in the molecular structure of formula (II) (I)：

Wherein Ar₁For aryl diphenol structure, Ar₂For aryl triphenol structure, wave represents aryl diphenol or aryl triphenol and 1, and 3, The coupled structures of 5- s-triazine.

2. aryl polyphenol described in claim 1 injects the preparation side with transmission material with 1,3,5- s-triazine cross-linked polymers hole Method, it is characterised in that comprise the following steps：

1) it is equal by 1,3,5- in the aqueous solution that aryl polyphenol compound is added to alkali catalyst under the conditions of 0 DEG C~40 DEG C Three polychlorostyrene piperazine quasi-molecules are dissolved in organic solvent, are added drop-wise to dropwise in aryl polyphenol compound, under the conditions of 0 DEG C~100 DEG C React 0.5h~48h；

Described aryl polyphenol compound is aryl diphenol or the phenolic compounds of aryl three；Described aryl diphenol is containing two phenol The aryl compound of hydroxyl；Described aryl triphenol is the aryl compound containing three phenolic hydroxyl groups；

Described alkali catalyst be sodium hydroxide, triethylamine, diisopropyl ethyl amine, potassium hydroxide, sodium carbonate, potassium carbonate and One or more in cesium carbonate；

According to the molfraction meter of material, composition of raw materials composition is：10 parts of the equal three polychlorostyrene piperazines of 1,3,5-；Aryl Polyphenols monomer 5 ~50 parts；5~150 parts of base catalyst；

2) by step 1) obtained reaction mixture poured into a large amount of deionized waters, and solution ph is adjusted to neutral with dilute acid soln, Filtering, with water and organic solvent washing, obtains hole injection and transmission material that aryl polyphenol is crosslinked 1,3,5- s-triazine structures Material.

3. aryl polyphenol according to claim 2 injects and transmission material with 1,3,5- s-triazine cross-linked polymers hole Preparation method, it is characterised in that the dilute acid soln is the one or more in hydrochloric acid, sulfuric acid, acetic acid and trifluoromethanesulfonic acid.

4. aryl polyphenol according to claim 2 injects and transmission material with 1,3,5- s-triazine cross-linked polymers hole Preparation method, it is characterised in that described aryl diphenol is the one or more in following structural formula (1)-(12)；

。

5. aryl polyphenol according to claim 2 injects and transmission material with 1,3,5- s-triazine cross-linked polymers hole Preparation method, it is characterised in that described aryl triphenol is following structural formula (13) and/or (14)；

。

6. aryl polyphenol according to claim 2 injects and transmission material with 1,3,5- s-triazine cross-linked polymers hole Preparation method, it is characterised in that the volume ratio 0.1-10 of organic solvent and water in described organic solvent and the mixed liquor of water:1.

7. the aryl polyphenol according to claim 2 or 6 is injected with transmitting material with 1,3,5- s-triazine cross-linked polymers hole The preparation method of material, it is characterised in that described organic solvent is in tetrahydrofuran, acetone, ether, acetonitrile and dioxane It is one or more.

8. the aryl polyphenol described in claim 1 is injected with transmission material organic with 1,3,5- s-triazine cross-linked polymers hole In optoelectronics device the application with transmission material is injected as hole；The organic optoelectronic device includes light-emitting diodes Pipe, organic heterojunction battery, perovskite solar cell, dye-sensitized cell or organic laser illuminating device.