Diamine monomer containing pyrene and triphenylamine structure and preparation method thereof, polyimide and preparation method thereof and application thereof

Abstract

The present invention discloses a diamine monomer containing pyrene and triphenylamine structure and a preparation method thereof, a polyimide and a preparation method thereof and an application thereof, wherein triphenylamine is used as a core and as a medium-strength electron donor (D), a derivative of pyrene is used as a weak electron acceptor (A), and the D-A molecule has a distorted spatial conformation and a hybridized localized charge transfer characteristic (HLCT). Adjusting the electron-donating and electron-withdrawing characteristics of the substituents on pyrene can adjust the ratio of LE to CT excited states, which is conducive to achieving efficient luminescence of the monomer. Based on the diamine monomer, a series of luminescent polyimide polymer materials can be prepared, and such polyimide has excellent solubility, high glass transition temperature and thermal stability, and has obvious fluorescence characteristics and high luminescence intensity. Further, such polyimide is used as a light-emitting layer, and an organic light-emitting device with excellent device performance is prepared by a simple solution spin coating method.

Description

Technical Field

[0001] The invention relates to the field of material science and technology, belonging to the field of organic optoelectronic polymers, and specifically to a novel diamine monomer containing pyrene and triphenylamine structures and a preparation method thereof, polyimide and a preparation method and application thereof. Background Art

[0002] Organic light-emitting devices (OLEDs) have the advantages of being light, thin, low driving voltage, wide viewing angle, high brightness, high efficiency, and high and low temperature resistance, and have attracted widespread attention. In particular, OLED technology can achieve flexible and transparent displays. In terms of device manufacturing, most OLEDs with excellent performance are usually manufactured using vacuum deposition technology. However, this technology has problems such as complex procedures, strict requirements, high production costs, and low material utilization, which limits the commercial development of OLEDs. In addition, vacuum deposition technology is also difficult to achieve large-area device and flexible device manufacturing. In contrast, solution-processed solution processes (such as spin coating, inkjet printing, and screen printing) have low manufacturing costs and simple preparation processes, allowing fine control of doping concentrations, which is conducive to the development of large-area device manufacturing processes, especially flexible devices. However, most small molecule OLEDs with excellent performance manufactured by vacuum deposition technology perform poorly when prepared by solution processes. The main reason is that most small molecules have poor solubility and poor film-forming properties, and are prone to crystallization when the solution is spin-coated into a film. To solve this problem, the design strategies for solution-processed OLED small molecules mainly include the introduction of alkyl chains such as tert-butyl, long alkyl chains, and dovetail chains, as well as the introduction of bulky structures such as adamantyl substitution, dendrimers or oligomers. However, there are problems such as complex synthesis process, expensive raw materials, and poor thermal performance. Most importantly, the strong electron donating ability of the alkyl chain usually causes the emission of the material to red-shift, which is not conducive to the manufacture of deep blue OLEDs (Dyes and Pigments., 2016, 132, 94; Advanced Optical Materials., 2016, 4, 1236; ACS Applied Materials&Interfaces., 2019, 11, 44474; Applied Materials&Interfaces., 2021, 13, 12305.).

[0003] Compared with small molecule materials, polymer materials usually have good thermal stability and film-forming ability, and are very suitable for wet processes. In 1990, polymer light-emitting diodes (PLEDs) with polystyrene (PPV) as a single semiconductor layer were first reported (Nature., 1990, 347, 539.), and since then PLEDs have received increasing attention. The Heeger group (Nature., 1992, 357, 477.) used polyethylene terephthalate as a substrate, soluble polyaniline as a hole injection electrode, substituted poly (1,4-styrene-vinyl) as an electroluminescent layer, and calcium as an electron injection layer to prepare a fully flexible PLED. The device can be bent sharply without damage, has a start-up voltage of 2-3V, and an external quantum efficiency of about 1%. In 2011, the Adachi group (Applied Physics Letters., 2011, 98, 083302.) reported the first pure aromatic polymer with efficient thermally activated delayed fluorescence (TADF) characteristics. The device prepared with this polymer as the luminescent material showed a maximum external quantum efficiency of 5.3% at low current density. The Nikolaenko group (Adv. Mater., 2015, 27, 7236.) first reported a new type of soluble non-conjugated polymer material with a main chain containing a TADF luminescent unit. By introducing a non-conjugated monomer with high triplet energy to separate the TADF unit to prevent the quenching of triplet excitons, the device external quantum efficiency can reach 10.1%. The Bryce group (Advanced Optical Materials., 4, 2016, 597.) prepared a conjugated polymer luminescent material using benzothiazine as a donor and dibenzothiophene as an acceptor. The maximum external quantum efficiency of the prepared doped PLED can reach 11.05%. Although many polymers have achieved remarkable performance as luminescent materials in PLEDs, there are still many problems. On the one hand, the main chain structure of conjugated polymers is single, and the triplet energy level of the conjugated main chain is often low, which cannot effectively suppress energy dissipation. In addition, the inevitable red shift of emission caused by conjugation still makes it difficult to obtain blue light devices; and the solubility of conjugated polymers is poor. In the design process of conjugated polymers, flexible alkyl dovetail chains must be introduced to improve the solubility of polymers. In addition, luminescent polymers are greatly affected by the degree of polymerization of the polymer main chain. The spectra obtained with different degrees of polymerization are quite different, and the purity of the luminescent color is often difficult to control. Compared with conjugated polymers, non-conjugated polymers use non-conjugated chains as the skeleton, and there are pendant luminescent units on the main chain, which ensures that the main chain has a higher triplet energy and avoids the transfer of excess triplet energy from the luminescent unit to the main chain, but the transmission is poor.At present, non-conjugated polymer connection strategies can be divided into three types: ① directly connecting two components in the form of a single bond (Macromolecules., 52, 2019, 2296.); ② connecting the light-emitting unit with a long alkyl chain (Macromolecules., 51, 2018, 1598.); ③ utilizing the spatial charge transfer between the donor and the acceptor (Journal of the American Chemical Society., 139, 2017, 17739.; Angewandte Chemie International Edtion., 59, 2020, 20174.). However, the preparation process of these polymers is complicated and requires metal catalysts to participate in the reaction. The metal catalysts are difficult to completely remove in the later stage, which may affect the stability and practicality of the equipment.

[0004] Polyimide is a type of heterocyclic macromolecular polymer with an imide ring structure in the main chain. It has good mechanical and thermal properties, excellent film-forming properties, dimensional stability and structural designability. It is widely used in organic electrical storage, nonlinear optical materials, liquid crystal display alignment film materials, liquid crystal display phase difference compensation film materials, electroluminescent diodes and other organic electronic devices. By rationally designing new diamine monomers, introducing different functional groups on diamine monomers with excellent structural designability, adjusting the composition ratio of diamine monomers with different functional structures, and through a simple room temperature polycondensation method with aliphatic dianhydrides, it is possible to polymerize polyimide materials with unique photoelectric properties, expanding its application in the field of OLEDs. Summary of the invention

[0005] In order to solve the above technical problems, the purpose of the present invention is to provide a diamine monomer containing pyrene and triphenylamine structures and a preparation method thereof, starting from the bromine substitution of pyrene, a monoamine compound containing a pyrene structure is prepared by Suzuki reaction, and a nitro structural unit is grafted using the active hydrogen of the monoamine compound and a new diamine monomer containing pyrene and triphenylamine structures is prepared by hydrogen reduction reaction, so that the monomer can emit light efficiently and the preparation process is simple.

[0006] Another object of the present invention is to provide a polyimide and a preparation method and application thereof, wherein the polyimide functionalized polymer is prepared by using the above-mentioned target diamine monomer containing pyrene and triphenylamine structure and other diamine and dianhydride monomers for mixed polycondensation or co-polycondensation reaction. The polyimide material prepared from the above-mentioned diamine monomer has good thermodynamic properties and electroluminescent properties, and a blue light device can be obtained.

[0007] The object of the present invention is achieved by: a diamine monomer containing pyrene and triphenylamine structure, characterized in that: the monomer structure is as follows:

[0008]

[0009] Preferably, in the formula, R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 , R 11 , R 12 , R 13 Select from any of the following structures:

[0010] -H, -OH, -CH3, -OCH3, -CF, -CN, -F,

[0011]

[0012] The method for preparing the diamine monomer containing pyrene and triphenylamine structure comprises the following steps:

[0013] (1) The 10 , R 11 , R 12 , R 13 The bromine-substituted pyrene of the structure is coupled with the amino-substituted phenylboronic acid containing the structures of R1, R2, R3, and R4 through Suzuki reaction to obtain the amino-substituted phenylpyrene structure compound;

[0014] (2) reacting the amino-substituted phenylpyrene structure compound prepared in step (1) with a p-fluoronitro group to prepare a 10 , R 11 , R 12 , R 13 The dinitro compounds of pyrene of structure;

[0015] Alternatively, the amino-substituted phenylpyrene structure compound prepared in step (1) is reacted with m-fluoronitrobenzene to prepare a 10 , R 11 , R 12 , R 13 The dinitro compounds of pyrene of structure;

[0016] (3) The dinitro compound prepared in step (2) is subjected to a hydrogen reduction reaction to obtain a compound containing R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 , R 11 , R 12 , R 13 Diamine monomer of structure;

[0017] A polyimide, whose molecular structure is as shown in general formula (I) or (II):

[0018]

[0019] In the formula: n and m represent the degree of polymerization, n is 5 to 10,000, m is 0 to 10,000, X and W are tetravalent aromatic hydrocarbon groups or aliphatic hydrocarbon groups, Z is a divalent aromatic hydrocarbon group or aliphatic hydrocarbon group, and Y is a divalent aromatic hydrocarbon group obtained after the polymerization reaction of the diamine monomer containing pyrene and triphenylamine structures, and the structure is as shown in the general formula (VI) or (VII);

[0020]

[0021] The preparation method of the polyimide containing pyrene and triphenylamine structure comprises the following steps: in a nitrogen or argon atmosphere, dissolving a diamine monomer containing a Y structure or a mixed diamine monomer containing both Y and Z structures and a dianhydride containing a X structure or a mixed dianhydride monomer containing both X and W structures in a polar aprotic organic solvent at a molar ratio of 1:(1-1.2), stirring and reacting for 24-48 hours at -10°C to 40°C to obtain a polyamic acid solution, and then imidizing by thermal imidization or chemical imidization to obtain a polyimide of the general formula (I) or (II).

[0022] Compared with the prior art, the present invention has the following beneficial effects:

[0023] The invention synthesizes a diamine compound containing pyrene and triphenylamine structures, and the preparation process is simple. Triphenylamine is used as a core and as a medium-strength electron donor (D), pyrene is used as a weak electron acceptor (A), and the DA molecule has a distorted spatial conformation and a hybrid localized charge transfer characteristic (HLCT). On the one hand, the DA molecule has a local excited state (LE), and partial orbital overlap is conducive to achieving a high radiation transition rate and enhancing the fluorescence quantum efficiency. On the other hand, the existence of a relatively weak charge transfer state (CT) is conducive to ensuring an efficient anti-system crossing rate and a high machine utilization rate. The ratio of the LE and CT excited states can be adjusted by adjusting the electron-donating and withdrawing characteristics of the substituents on the pyrene, which is conducive to achieving efficient monomer luminescence.

[0024] Based on the diamine monomer, a series of novel luminescent polyimide polymer materials can be prepared by mixed polycondensation or co-polycondensation. The polyimide material synthesized with it as a monomer has excellent solubility and high thermal stability, and the glass transition temperature can be as high as 300°C to 350°C. Compared with most other polymers such as polyethylene polymers, when the glass transition temperature is higher than 200°C, the monomer is prone to breakage during polymerization. The polymer obtained by the present invention has obvious advantages. In particular, when it is used as a monomer to polymerize with aliphatic dianhydride to prepare polyimide, the imide structure with weak electron-withdrawing ability can inhibit charge transfer within and between molecules, maintain the luminescent color of the DA molecule itself, and has obvious fluorescence characteristics and high luminescence intensity, and can obtain blue light devices, so that it can be widely used in the preparation of light-emitting layer materials, photoluminescent materials, and flexible electroluminescent devices OLED in optical equipment. An organic light-emitting device with excellent device performance is prepared by a simple solution spin coating method, which solves the technical problems in the prior art that there is a strong interaction between the main chains, between the side groups, or between the main chain and the side groups of polyimide, the number of charge transfer complexes cannot be reduced, and the charge transfer effect is still strong.

[0025] The method of the present invention has extremely high step economy and atom economy, and its main features are simple experimental operation, low design difficulty, diverse combination methods and good reaction region selectivity. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] Figure 1 The infrared spectra of polyimide PI-1 and PI-2 prepared in Examples 6-9 of the present invention are shown in FIG. As can be clearly seen from the figure, the film PI-I and PI-2 have a wave number of 1780 cm -1 and 1720cm -1 The asymmetric stretching vibration and symmetric stretching vibration absorption peaks of the carbonyl C=O bond appear, indicating the formation of polyimide polymer;

[0027] Figure 2 is a thermogravimetric graph of polyimides PI-1 and PI-2 prepared in Examples 6-9 of the present invention;

[0028] Figure 3 It is the fluorescence spectra of polyimide PI-1 and PI-2 prepared in Examples 6-9 of the present invention;

[0029] Figure 4 Schematic diagram of the structure of the organic optoelectronic device prepared in Examples 6-9 of the present invention, wherein EML is the light-emitting layer in each example.

[0030] The following examples are given to illustrate the present invention in more detail. It is necessary to point out that the implementation cases cannot be interpreted as limiting the scope of protection of the invention. Some non-essential improvements and adjustments made to the present invention based on the above-mentioned invention content by technically skilled personnel in this field should still fall within the scope of protection of the present invention. DETAILED DESCRIPTION

[0031] The present invention discloses a diamine monomer containing pyrene and triphenylamine structure, which is a DA type diamine with a large substituted side group. The monomer structure is as shown in the general formula (I) or (II):

[0032]

[0033] Preferably, in the formula, R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 , R 11 , R 12 , R 13 Select from any of the following structures:

[0034] -H, -OH, -CH3, -OCH3, -CF3, -CN, -F,

[0035]

[0036] The diamine monomer containing pyrene and triphenylamine structure of the present invention has obvious fluorescence characteristics and high luminescence intensity. Its DA type diamine molecule has a distorted spatial conformation and a hybrid localized charge transfer characteristic (HLCT). On the one hand, the DA molecule has a local excited state (LE), and the partial overlap of orbits is conducive to achieving a high radiation transition rate and enhancing the fluorescence quantum efficiency. On the other hand, the existence of a relatively weak charge transfer state (CT) is conducive to ensuring an efficient anti-system crossing rate and a high exciton utilization rate. The ratio of the LE and CT excited states can be adjusted by adjusting the electron-donating and withdrawing characteristics of the substituents on the pyrene, which is conducive to achieving efficient luminescence of the monomer.

[0037] The method for preparing the diamine monomer containing pyrene and triphenylamine structure comprises the following steps:

[0038] (1) The 10 , R 11 , R 12 , R 13 The bromine-substituted pyrene of the structure is coupled with the amino-substituted phenylboronic acid containing the structures of R1, R2, R3, and R4 through Suzuki reaction to obtain the amino-substituted phenylpyrene structure compound;

[0039] (2) reacting the amino-substituted phenylpyrene structure compound prepared in step (1) with p-fluoronitrobenzene to prepare a 10 , R 11 , R 12 , R 13 The dinitro compounds of pyrene of structure;

[0040] Alternatively, the amino-substituted phenylpyrene structure compound prepared in step (1) is reacted with m-fluoronitrobenzene to prepare a 10 , R 11 , R 12 , R 13 The dinitro compounds of pyrene of structure;

[0041] (3) The dinitro compound prepared in step (2) is subjected to a hydrogen reduction reaction to obtain a compound containing R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 , R 11 , R 12 , R 13 Diamine monomer with structure.

[0042] Preferably, in the step (1), R5, R6, R7, R8, R9, R 10 , R 11 , R 12 , R 13 A bromine-substituted product of pyrene having a structure, an amino-substituted phenylboronic acid having structures R1, R2, R3, and R4, and potassium carbonate are added to a reaction container, and a tetrahydrofuran solution and deionized water are added, stirred and argon is introduced, and then tetrakistriphenylphosphine palladium is added, the temperature is raised and stirred for reaction, and the reaction solution is cooled, poured into water for precipitation, extracted, separated to obtain an organic layer, spin-dried, and purified by column chromatography to obtain an amino-substituted phenylpyrene structure compound having a structure as shown in general formula (III); more preferably, in the step (1): containing R5, R6, R7, R8, R9, R 10 , R 11 , R 12 , R 13 The molar ratio of the bromine substituted product of pyrene with structure, the amino substituted phenylboronic acid containing R1, R2, R3, R4 structure, and potassium carbonate is 1:1-1.2:1.5-2, the volume ratio of tetrahydrofuran and deionized water is 2-3:1, 0.02-0.05g of tetrakistriphenylphosphine palladium is added for every 50mol of bromine substituted product of pyrene, the reaction temperature is 90°C, the reaction time is 12-24h, and the extractant is ethyl acetate.

[0043]

[0044] Preferably, in the step (2), the amino-substituted phenylpyrene structure compound prepared in step (1), p-fluoronitrobenzene or m-fluoronitrobenzene, and cesium fluoride are placed in a reaction container, anhydrous DMSO is added, stirred and argon is introduced, the temperature is raised to react, the reaction solution is cooled, the reaction solution is poured into water for precipitation, filtered, washed with an organic solvent, and recrystallized to obtain a product containing R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 , R 11 , R 12 , R 13 A dinitro compound of pyrene having a structure such as the general formula (IV) or (V); more preferably, in the step (2), the molar ratio of the amino-substituted phenylpyrene structure compound, p-fluoronitrobenzene or m-fluoronitrobenzene, and cesium fluoride is 1:3-4:3-4, the reaction temperature is 130°C, the reaction time is 12-24h, the washing solvent is ethanol, and the recrystallization solvent is dichloromethane and petroleum ether,

[0045]

[0046] Preferably, in the step (3): the dinitro compound prepared in the step (2) is subjected to a hydrogen reduction reaction to obtain a product containing R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 , R 11 , R 12 , R 13 Diamine monomers of the structure;

[0047] A polyimide, whose molecular structure is as shown in general formula (I) or (II):

[0048]

[0049] In the formula: n and m represent the degree of polymerization, n is 5 to 10,000, m is 0 to 10,000, X and W are tetravalent aromatic hydrocarbon groups or aliphatic hydrocarbon groups, Z is a divalent aromatic hydrocarbon group or aliphatic hydrocarbon group, and Y is a divalent aromatic hydrocarbon group obtained by polymerization of the aforementioned diamine monomer containing pyrene and triphenylamine structures, and the structure is as shown in general formula (VI) or (VII);

[0050]

[0051] Preferably, Z can be selected from the following structures:

[0052]

[0053] X and W may be the same or different and are selected from the following structures:

[0054]

[0055] The preparation method of the polyimide containing pyrene and triphenylamine structure comprises the following steps: in a nitrogen or argon atmosphere, dissolving a diamine monomer containing a Y structure or a mixed diamine monomer containing both Y and Z structures and a dianhydride containing an X structure or a mixed dianhydride monomer containing both X and W structures in a polar aprotic organic solvent at a molar ratio of 1:1 to 1.2, stirring and reacting for 24 to 48 hours at -10°C to 40°C to obtain a polyamic acid solution, and then imidizing by thermal imidization or chemical imidization to obtain a polyimide having a structure such as general formula (I) or (II).

[0056] Preferably, the total mass of the diamine monomer containing the Y structure or the mixed diamine monomer containing the Y and Z structures and the dianhydride monomer containing the X structure or the dianhydride monomer containing the X and W structures accounts for 5-50% of the total mass of the reaction materials.

[0057] Preferably, the polar aprotic organic solvent is selected from one or a mixture of two or more of N-methylpyrrolidone, N,N'-dimethylformamide, N,N'-dimethylacetamide, dimethyl sulfoxide, dimethyl sulfone, 1,4-dioxane, tetrahydrofuran, and m-cresol.

[0058] Preferably, the specific steps of preparing polyimide by the chemical imidization method are: adding acetic anhydride and pyridine as a dehydrating agent and a catalyst respectively to a polyamic acid solution, stirring at room temperature for 24 to 48 hours, adding the obtained solution dropwise to anhydrous methanol or ethanol solution for precipitation, filtering and drying to obtain a polyimide powder.

[0059] The polyimide is used in organic photodiodes or optical information storage device materials.

[0060] Preferably, the device structure includes a first electrode, a second electrode and a light-emitting layer sandwiched between the first electrode and the second electrode, wherein the light-emitting layer includes a polyimide having a molecular structure of the general formula (I). More preferably, at least one layer of a hole injection layer, a hole transport layer, a hole blocking layer, an electron blocking layer, an electron transport layer and an electron injection layer is further included between the first electrode and the second electrode. Most preferably, the organic light-emitting device structure comprising the above-mentioned polyimide is layered, in order: first electrode / hole injection layer / light-emitting layer / electron transport layer / electron injection layer / second electrode.

[0061] Now, various exemplary embodiments of the present invention are described in detail, and this detailed description should not be considered as a limitation of the present invention, but should be understood as a more detailed description of certain aspects, characteristics and embodiments of the present invention. It should be understood that the terms described in the present invention are only for describing specific embodiments and are not used to limit the present invention.

[0062] In addition, for the numerical range in the present invention, it is understood that each intermediate value between the upper and lower limits of the range is also specifically disclosed. Each smaller range between the intermediate value in any stated value or stated range and any other stated value or intermediate value in the range is also included in the present invention. The upper and lower limits of these smaller ranges can be independently included or excluded in the scope.

[0063] Unless otherwise indicated, all technical and scientific terms used herein have the same meanings as those generally understood by those skilled in the art. Although the present invention describes only preferred methods and materials, any methods and materials similar or equivalent to those described herein may also be used in the implementation or testing of the present invention. All documents mentioned in this specification are incorporated by reference to disclose and describe the methods and / or materials associated with the documents. In the event of a conflict with any incorporated document, the content of this specification shall prevail.

[0064] It will be apparent to those skilled in the art that various modifications and variations may be made to the specific embodiments of the present invention description without departing from the scope or spirit of the present invention. Other embodiments derived from the present invention description will be apparent to those skilled in the art. The present invention description and examples are exemplary only.

[0065] Example 1 (Synthesis of diamine monomer A)

[0066]

[0067] 1-Bromopyrene (28.1 g, 0.1 mol), p-aminophenylboronic acid (20.8 g, 0.12 mol), and potassium carbonate (27.6 g, 0.2 mol) were added to a 250 mL three-necked flask, and tetrahydrofuran (100 mL) solution and deionized water were added, stirred and argon was introduced, and then tetrakistriphenylphosphine palladium was added, the temperature was raised and stirred to react, and the reaction solution was cooled. The reaction solution was poured into water for precipitation, extracted, and the organic layer was separated, which was spin-dried and purified by dichloromethane / petroleum ether mixed solvent column chromatography to obtain a pale white solid intermediate product 1.

[0068]

[0069] Take the intermediate product 1 (29.3 g, 0.1 mol), p-fluoronitrobenzene (42.3 g, 0.3 mol), and cesium fluoride (60.7 g, 0.4 mol) and add them into a 250 mL three-necked flask, add 50 mL of anhydrous DMSO, stir and pass argon, heat reflux at 130 ° C for 24 h, cool, pour the reaction solution into water for precipitation, filter, wash with ethanol, filter and recrystallize from dichloromethane / petroleum ether to obtain an orange-yellow solid intermediate product 2.

[0070]

[0071] Take the intermediate product 2 (52.7 g, 0.1 mol), add THF (100 mL) and 10% palladium carbon (2.6 g), evacuate at low temperature and fill with hydrogen to react for 72 hours. After the reaction is completed, filter and purify by dichloromethane / petroleum ether mixed solvent column chromatography to obtain a light yellow diamine monomer A.

[0072] Example 2 (Synthesis of diamine monomer B)

[0073]

[0074] 1-Bromopyrene (28.1 g, 0.1 mol), m-aminophenylboronic acid (16.1 g, 0.12 mol), and potassium carbonate (27.6 g, 0.2 mol) were added to a 250 mL three-necked flask, and tetrahydrofuran (100 mL) solution and deionized water were added, stirred and argon was introduced, and then tetrakistriphenylphosphine palladium was added, the temperature was raised and stirred to react, and the reaction solution was cooled. The reaction solution was poured into water for precipitation, extracted, and the organic layer was separated, which was spin-dried and purified by dichloromethane / petroleum ether mixed solvent column chromatography to obtain a pale white solid intermediate product 3.

[0075]

[0076] Take the intermediate product 3 (29.3 g, 0.1 mol), m-fluoronitrobenzene (42.3 g, 0.3 mol), and cesium fluoride (60.7 g, 0.4 mol) and add them into a 250 mL three-necked flask, add 50 mL of anhydrous DMSO, stir and pass argon, heat reflux at 130 ° C for 24 h, cool, pour the reaction solution into water for precipitation, filter, wash with ethanol, filter and recrystallize from dichloromethane / petroleum ether to obtain an orange-yellow solid intermediate product 4.

[0077]

[0078] Take the intermediate product 4 (52.7 g, 0.1 mol), add THF (100 mL) and 10% palladium carbon (2.6 g), evacuate at low temperature and fill with hydrogen to react for 72 hours. After the reaction is completed, filter and purify by dichloromethane / petroleum ether mixed solvent column chromatography to obtain a light yellow diamine monomer B.

[0079] Example 3 (Synthesis of diamine monomer C)

[0080]

[0081] 1-Bromopyrene (28.1 g, 0.1 mol), 2-aminophenylboronic acid (20.8 g, 0.12 mol), and potassium carbonate (27.6 g, 0.2 mol) were added to a 250 mL three-necked flask, and tetrahydrofuran (100 mL) solution and deionized water were added. The mixture was stirred and argon was introduced. Then, tetrakistriphenylphosphine palladium was added, and the temperature was raised and stirred to react. The mixture was cooled, and the reaction solution was poured into water for precipitation. The mixture was extracted and separated to obtain an organic layer, which was spin-dried. The mixture was purified by column chromatography using a mixed solvent of dichloromethane / petroleum ether to obtain a pale white solid intermediate product 5.

[0082]

[0083] Take the intermediate product 5 (29.3 g, 0.1 mol), p-fluoronitrobenzene (42.3 g, 0.3 mol), and cesium fluoride (60.7 g, 0.4 mol) and add them into a 250 mL three-necked flask, add 50 mL of anhydrous DMSO, stir and pass argon, heat reflux at 130 ° C for 24 h, cool, pour the reaction solution into water for precipitation, filter, wash with ethanol, filter and recrystallize with dichloromethane / petroleum ether to obtain an orange-yellow solid intermediate product 6.

[0084]

[0085] Take the intermediate product 6 (52.7 g, 0.1 mol), add THF (100 mL) and 10% palladium carbon (2.6 g), evacuate at low temperature and fill with hydrogen to react for 72 hours. After the reaction is completed, filter and purify by dichloromethane / petroleum ether mixed solvent column chromatography to obtain a light yellow diamine monomer C.

[0086] Example 4 (Synthesis of diamine monomer D)

[0087]

[0088] 1-Bromo-7-(tert-butyl)pyrene (33.7 g, 0.1 mol), p-aminophenylboronic acid (16.1 g, 0.12 mol), and potassium carbonate (27.6 g, 0.2 mol) were added to a 250 mL three-necked flask, and tetrahydrofuran (100 mL) solution and deionized water were added, stirred and argon was introduced, and then tetrakistriphenylphosphine palladium was added, the temperature was raised and stirred to react, and the reaction mixture was cooled. The reaction mixture was poured into water for precipitation, extracted, and the organic layer was separated, which was spin-dried and purified by dichloromethane / petroleum ether mixed solvent column chromatography to obtain a pale white solid intermediate product 7.

[0089]

[0090] Take the intermediate product 7 (34.9 g, 0.1 mol), p-fluoronitrobenzene (42.3 g, 0.3 mol), and cesium fluoride (60.7 g, 0.4 mol) and add them into a 250 mL three-necked flask, add 50 mL of anhydrous DMSO, stir and pass argon, heat reflux at 130 ° C for 24 h, cool, pour the reaction solution into water for precipitation, filter, wash with ethanol, filter and recrystallize from dichloromethane / petroleum ether to obtain an orange-yellow solid intermediate product 8.

[0091]

[0092] Take the intermediate product 8 (59.2 g, 0.1 mol), add THF (100 mL) and 10% palladium carbon (3.0 g), evacuate at low temperature and fill with hydrogen to react for 72 hours. After the reaction is completed, filter and purify by dichloromethane / petroleum ether mixed solvent column chromatography to obtain yellow diamine monomer D.

[0093] Example 5 (Synthesis of diamine monomer E)

[0094]

[0095] 1,6-Dibromopyrene (36.0 g, 0.1 mol), 4-triphenylamine borate (14.5 g, 0.05 mol), and potassium carbonate (27.6 g, 0.2 mol) were added into a 250 mL three-necked flask, and toluene and ethanol were added to obtain a mixed solution (100 / 20 mL) solution and deionized water. The solution was stirred and argon was introduced. Tetrakistriphenylphosphine palladium was then added, and the temperature was raised and stirred to react. The reaction was cooled, and the reaction solution was poured into water for precipitation. The organic layer was separated after extraction and spin-dried to obtain a pale white solid intermediate product 9.

[0096]

[0097] The intermediate product 9 (53.7 g, 0.1 mol), p-aminophenylboronic acid (16.1 g, 0.12 mol), and potassium carbonate (27.6 g, 0.2 mol) were added to a 250 mL three-necked flask, and tetrahydrofuran (100 mL) solution and deionized water were added, stirred and argon was introduced, and then tetrakistriphenylphosphine palladium was added, the temperature was raised and stirred to react, and the reaction solution was cooled. The reaction solution was poured into water for precipitation, extracted, and the organic layer was separated, which was spin-dried and purified by tetrahydrofuran / petroleum ether mixed solvent column chromatography to obtain a light yellow solid intermediate product 10.

[0098]

[0099] Take the intermediate product 10 (53.7 g, 0.1 mol), p-fluoronitrobenzene (42.3 g, 0.3 mol), and cesium fluoride (60.7 g, 0.4 mol) and add them into a 250 mL three-necked flask, add 50 mL of anhydrous DMSO, stir and introduce argon, heat and reflux at 130 ° C for 24 h, cool, pour the reaction solution into water for precipitation, filter, wash with ethanol, filter and recrystallize from dichloromethane / petroleum ether to obtain a brown-yellow solid intermediate product 11.

[0100]

[0101] Take the intermediate product 11 (77.9 g, 0.1 mol), add THF (100 mL) and 10% palladium carbon (3.9 g), evacuate at low temperature and fill with hydrogen to react for 72 hours. After the reaction is completed, filter and purify by dichloromethane / petroleum ether mixed solvent column chromatography to obtain yellow diamine monomer E.

[0102] Example 6 (Synthesis of polyimide PI-1 and preparation of organic photoelectric device 1)

[0103] Under nitrogen protection, diamine A (14.2680 g, 30 mmol) was added to the reaction bottle, N, N-dimethylacetamide DMAc (48.56 mL) was added, stirred at room temperature until dissolved, and then hydrogenated pyromellitic anhydride (HPMDA) (6.5436 g, 30 mmol) was slowly added, and stirred at room temperature overnight to obtain a homogeneous, transparent, and viscous polyimide acid solution. 120 mL of acetic anhydride and 60 mL of pyridine were added to the polyimide acid solution, and after continuing to stir at room temperature for 24 hours, it was slowly poured into high-speed stirring ethanol to obtain a blocky polyimide precipitate, extracted with tetrahydrofuran Soxhlet for 24 hours, filtered and dried to obtain the target polyimide PI-1. The absolute fluorescence quantum yield of the polymer PI-1 in toluene solution is about 94.7%, and the absolute fluorescence quantum yield of the spin-coated film is about 24.7%. The wavelength corresponding to the strongest fluorescence peak is 468 nm, the 5% thermal weight loss temperature is 559 ° C, and the glass transition temperature is 357 ° C. PI-1 has good solubility in strong polar organic solvents such as N,N'-dimethylformamide, N,N'-dimethylacetamide, and dimethyl sulfoxide.

[0104] The transient PL decay curve test and the emission spectrum experimental characterization under different polar solvents confirmed that PI-1 has obvious HLCT characteristics and can be used for the preparation of optoelectronic devices. Therefore, the polyimide PI-1 prepared above was prepared into a 10 mg / mL DMF solution, and then 10 mg 9,9'-(l,3-phenyl)di-9H-carbazole (mCP) was added, and the solution was fully dissolved and stored at low temperature. The ITO glass sheet was washed with deionized water, isopropanol, and acetone in turn, and dried for use. The poly(3,4-ethylenedioxythiophene)-poly(styrene sulfonic acid) (PEDOT:PSS) aqueous solution was spin-coated on the ITO glass at a speed of 2000 r / s, the spin-coating time was 60s, and the residual solvent was removed by heating at 120°C for 30min; after cooling to room temperature, the DMF solution of the above PI-1 was spin-coated on it at a speed of 2000 r / s, the spin-coating time was 60s, and the residual solvent was removed by heating at 150°C for 30min. After cooling, the device was transferred to a vapor deposition chamber, and 1,3,5-tri(1-phenyl-1H-benzimidazol-2-yl)benzene (TPBi), lithium fluoride (LiF) and aluminum (Al) were sequentially vapor deposited to prepare an organic light-emitting device 1, wherein the first electrode / hole injection layer / light-emitting layer / electron transport layer / electron injection layer / second electrode in the structure was specifically: ITO / PEDOT:PSS / PI-1:mCP / TPBi / LiF / Al;

[0105] The device has a turn-on voltage of 3.7V and a maximum lumen brightness of 2400cd / m 2 , the maximum external quantum efficiency is as high as 9.1%.

[0106] The molecular structure of the electroluminescent polyimide PI-1 in this embodiment is as follows:

[0107]

[0108] Example 7 (Synthesis of polyimide PI-1 and preparation of organic photoelectric device 2)

[0109] The preparation process of polyimide PI-1 containing diamine A is the same as that of Example 6;

[0110] The polyimide PI-1 prepared above was prepared into a 10 mg / mL DMF solution, and then 10 mg 4,4',4"-tri(carbazole-9-yl)triphenylamine (TCTA) was added. After fully dissolved, it was stored at low temperature. The ITO glass sheet was washed with deionized water, isopropanol, and acetone in turn, and dried for use. The poly(3,4-ethylenedioxythiophene)-poly(styrene sulfonic acid) (PEDOT:PSS) aqueous solution was spin-coated on the ITO glass at a speed of 2000 r / s for 60 s, and the residual solvent was removed by heating at 120°C for 30 min; after cooling to room temperature, the DMF solution of the PI-1 was spin-coated at a speed of 2000 r / s. The organic light-emitting device 2 is prepared by spin coating at a high speed for 60 seconds and heating at 150°C for 30 minutes to remove the residual solvent. After cooling, the organic light-emitting device 2 is transferred to a vapor deposition chamber, and 1,3,5-tris(1-phenyl-1H-benzimidazol-2-yl)benzene (TPBi), lithium fluoride (LiF) and aluminum (Al) are sequentially vapor-deposited to obtain an organic light-emitting device 2, wherein the first electrode / hole injection layer / luminescent layer / electron transport layer / electron injection layer / second electrode are specifically: ITO / PEDOT:PSS / PI-1:TCTA / TPBi / LiF / Al;

[0111] The device has a turn-on voltage of 3.7V and a maximum lumen brightness of 2000cd / m 2 , the maximum external quantum efficiency is as high as 5.4%.

[0112] Example 8 (Synthesis of polyimide PI-2 and preparation of organic photoelectric device 3)

[0113] Under nitrogen protection, diamine A (14.2680 g, 30 mmol) was added to the reaction bottle, N, N-dimethylacetamide DMAc (54.73 mL) was added, stirred at room temperature until dissolved, and then hydrogenated biphenyl dicarboxylic anhydride (HBPDA) (9.1893 g, 30 mmol) was slowly added, and stirred at room temperature overnight to obtain a homogeneous, transparent, and viscous polyimide acid solution. 120 mL of acetic anhydride and 60 mL of pyridine were added to the polyimide acid solution, and after continuing to stir at room temperature for 24 hours, it was slowly poured into high-speed stirring ethanol to obtain a blocky polyimide precipitate, extracted with tetrahydrofuran Soxhlet for 24 hours, filtered and dried to obtain the target polyimide PI-2. The absolute fluorescence quantum yield of the polymer PI-2 in toluene solution is about 98.1%, and the absolute fluorescence quantum yield of the spin-coated film is about 28.4%. The wavelength corresponding to the strongest fluorescence peak is 466 nm, the 5% thermal weight loss temperature is 538 ° C, and the glass transition temperature is 290 ° C. PI-2 has good solubility in strong polar organic solvents such as N,N'-dimethylformamide, N,N'-dimethylacetamide, and dimethyl sulfoxide.

[0114] The transient PL decay curve test and the emission spectrum experimental characterization under different polar solvents confirmed that PI-2 has obvious HLCT characteristics and can be used for the preparation of optoelectronic devices. Therefore, the polyimide PI-2 prepared above was prepared into a 10 mg / mL DMF solution, and then 10 mg 9,9'-(l,3-phenyl)di-9H-carbazole (mCP) was added, and the solution was fully dissolved and stored at low temperature. The ITO glass sheet was washed with deionized water, isopropanol, and acetone in turn, and dried for use. The poly(3,4-ethylenedioxythiophene)-poly(styrene sulfonic acid) (PEDOT:PSS) aqueous solution was spin-coated on the ITO glass at a speed of 2000 r / s, the spin-coating time was 60s, and the residual solvent was removed by heating at 120°C for 30min; after cooling to room temperature, the DMF solution of the above PI-2 was spin-coated on it at a speed of 2000 r / s, the spin-coating time was 60s, and the residual solvent was removed by heating at 150°C for 30min. After cooling, the device was transferred to a vapor deposition chamber, and 1,3,5-tri(1-phenyl-1H-benzimidazol-2-yl)benzene (TPBi), lithium fluoride (LiF) and aluminum (Al) were sequentially vapor deposited to prepare an organic light-emitting device 3, wherein the first electrode / hole injection layer / light-emitting layer / electron transport layer / electron injection layer / second electrode in the structure was specifically: ITO / PEDOT:PSS / PI-2:mCP / TPBi / LiF / Al;

[0115] The device has a turn-on voltage of 4.2V and a maximum lumen brightness of 2700cd / m 2 , the maximum external quantum efficiency is as high as 9.9%.

[0116] The molecular structure of the electroluminescent polyimide PI-2 in this embodiment is as follows:

[0117]

[0118] Example 9 (Synthesis of polyimide PI-2 and preparation of organic photoelectric device 4)

[0119] The preparation process of polyimide PI-2 containing diamine A is the same as that of Example 8;

[0120] The polyimide PI-2 prepared above was prepared into a 10 mg / mL DMF solution, and then 10 mg 4,4',4"-tri(carbazole-9-yl)triphenylamine (TCTA) was added. After fully dissolved, it was stored at low temperature. The ITO glass sheet was washed with deionized water, isopropanol, and acetone in turn, and dried for use. The poly(3,4-ethylenedioxythiophene)-poly(styrene sulfonic acid) (PEDOT:PSS) aqueous solution was spin-coated on the ITO glass at a speed of 2000 r / s for 60 s, and heated at 120°C for 30 min to remove the residual solvent; after cooling to room temperature, the DMF solution of the above PI-2 was spin-coated on it at a speed of 2000 r / s for 60 s, and heated at 150°C for 30 min to remove the residual solvent. After cooling, the mixture was transferred to a vapor deposition chamber, and 1,3,5-tri(1-phenyl-1H-benzimidazol-2-yl)benzene (TPBi), lithium fluoride (LiF) and aluminum (Al) were sequentially vapor deposited to prepare an organic light-emitting device 4, in which the first electrode / hole injection layer / luminescent layer / electron transport layer / electron injection layer / second electrode were specifically: ITO / PEDOT:PSS / PI-2:TATC / TPBi / LiF / Al. The turn-on voltage of the obtained device was 4.6 V, and the maximum lumen brightness could reach 900 cd / m 2 , the maximum external quantum efficiency is as high as 3.7%.

[0121] The polyimide luminescent materials prepared in Examples 6-9 of polyimide synthesis and organic optoelectronic device preparation were subjected to infrared detection, thermal gravimetric test and fluorescence test. The results are as follows: Figure 1 , Figure 2 , Figure 3 The results are shown in Table 1. The results show that the films PI-I and PI-2 have a wave number of 1780 cm -1 and 1720cm -1 The asymmetric stretching vibration and symmetric stretching vibration absorption peaks of the carbonyl C=O bond appear at a wave number of There is no characteristic absorption peak of stretching vibration of NH bond in amino group in the range. The 5% thermal weight loss temperature of film PI-I and PI-2 is 559℃ and 538℃ respectively, and the maximum emission wavelength is 468nm and 466nm respectively. Figure 4 shown.

[0122] Example 10 (Synthesis of polyimide PI-3 and preparation of organic photoelectric device 5)

[0123] Under nitrogen protection, diamine D (15.9381 g, 30 mmol) was added to the reaction bottle, N, N-dimethylacetamide DMAc (52.46 mL) was added, and hydrogenated pyromellitic anhydride (HPMDA) (6.5436 g, 30 mmol) was slowly added, and stirred at room temperature overnight to obtain a homogeneous, transparent, and viscous polyimide acid solution. 120 mL of acetic anhydride and 60 mL of pyridine were added to the polyimide acid solution, and after continuing to stir at room temperature for 24 hours, it was slowly poured into high-speed stirring ethanol to obtain a blocky polyimide precipitate, and extracted with tetrahydrofuran Soxhlet for 24 hours, filtered and dried to obtain the target polyimide PI-3. The absolute fluorescence quantum yield of the polymer PI-3 in toluene solution is about 97.8%, and the absolute fluorescence quantum yield of the spin-coated film is about 30.3%. The wavelength corresponding to the strongest fluorescence peak is 470 nm, the 5% thermal weight loss temperature is 530 ° C, and the glass transition temperature is 320 ° C. PI-3 has good solubility in strong polar organic solvents such as N,N'-dimethylformamide, N,N'-dimethylacetamide, and dimethyl sulfoxide.

[0124] The transient PL decay curve test and the emission spectrum experimental characterization under different polar solvents confirmed that PI-3 has obvious HLCT characteristics and can be used for the preparation of optoelectronic devices. Therefore, the polyimide PI-3 prepared above was prepared into a 10 mg / mL DMF solution, and then 10 mg 9,9'-(l,3-phenyl)di-9H-carbazole (mCP) was added, and the solution was fully dissolved and stored at low temperature. The ITO glass was washed with deionized water, isopropanol, and acetone in turn, and dried for use. The poly(3,4-ethylenedioxythiophene)-poly(styrene sulfonic acid) (PEDOT:PSS) aqueous solution was spin-coated on the ITO glass at a speed of 2000 r / s, the spin-coating time was 60s, and the residual solvent was removed by heating at 120°C for 30min; after cooling to room temperature, the DMF solution of the above PI-3 was spin-coated on it at a speed of 2000 r / s, the spin-coating time was 60s, and the residual solvent was removed by heating at 150°C for 30min. After cooling, the device is transferred to a vapor deposition chamber, and 1,3,5-tri(1-phenyl-1H-benzimidazol-2-yl)benzene (TPBi), lithium fluoride (LiF) and aluminum (Al) are sequentially vapor deposited to prepare an organic light-emitting device 5, wherein the first electrode / hole injection layer / light-emitting layer / electron transport layer / electron injection layer / second electrode are specifically: ITO / PEDOT:PSS / PI-3:mCP / TPBi / LiF / Al;

[0125] The device has a turn-on voltage of 5.5V and a maximum lumen brightness of 1000cd / m 2 , the maximum external quantum efficiency is as high as 4.1%.

[0126] The molecular structure of the electroluminescent polyimide PI-3 in this example is as follows:

[0127]

[0128] Example 11 (Synthesis of polyimide PI-4 and preparation of organic photoelectric device 6)

[0129] Under nitrogen protection, diamine E (7.9916 g, 15 mmol), 4,4'-diaminodiphenyl ether (3.0036 g, 15 mmol) were added to the reaction bottle, N,N-dimethylacetamide DMAc (40.92 mL) was added, and hydrogenated pyromellitic anhydride (HPMDA) (6.5436 g, 30 mmol) was slowly added at room temperature and stirred overnight to obtain a homogeneous, transparent, viscous polyimide acid solution. 120 mL of acetic anhydride and 60 mL of pyridine were added to the polyimide acid solution, and after continuing to stir at room temperature for 24 hours, it was slowly poured into ethanol with high-speed stirring to obtain a blocky polyimide precipitate, extracted with tetrahydrofuran Soxhlet for 24 hours, and filtered and dried to obtain the target polyimide PI-4. The absolute fluorescence quantum yield of the polymer PI-4 in toluene solution is about 84.2%, and the absolute fluorescence quantum yield of the spin-coated film is about 6.9%. The wavelength corresponding to the strongest fluorescence peak is 485nm, the 5% thermal weight loss temperature is 485℃, and the glass transition temperature is 297℃. PI-4 has good solubility in strong polar organic solvents such as N,N'-dimethylformamide, N,N'-dimethylacetamide, and dimethyl sulfoxide.

[0130] The transient PL decay curve test and the emission spectrum experimental characterization under different polar solvents confirmed that PI-4 has obvious HLCT characteristics and can be used for the preparation of optoelectronic devices. Therefore, the polyimide PI-4 prepared above was prepared into a 10 mg / mL DMF solution, and then 10 mg 9,9'-(l,3-phenyl)di-9H-carbazole (mCP) was added, and the solution was fully dissolved and stored at low temperature. The ITO glass sheet was washed with deionized water, isopropanol, and acetone in turn, and dried for use. The poly(3,4-ethylenedioxythiophene)-poly(styrene sulfonic acid) (PEDOT:PSS) aqueous solution was spin-coated on the ITO glass at a speed of 2000 r / s, the spin-coating time was 60s, and the residual solvent was removed by heating at 120°C for 30min; after cooling to room temperature, the DMF solution of the above PI-4 was spin-coated on it at a speed of 2000 r / s, the spin-coating time was 60s, and the residual solvent was removed by heating at 150°C for 30min. After cooling, the device was transferred to a vapor deposition chamber, and 1,3,5-tri(1-phenyl-1H-benzimidazol-2-yl)benzene (TPBi), lithium fluoride (LiF) and aluminum (Al) were sequentially vapor deposited to prepare an organic light-emitting device 6, wherein the first electrode / hole injection layer / light-emitting layer / electron transport layer / electron injection layer / second electrode in the structure was specifically: ITO / PEDOT:PSS / PI-4:mCP / TPBi / LiF / Al;

[0131] The device has a turn-on voltage of 7.2V and a maximum lumen brightness of 560cd / m 2 , the maximum external quantum efficiency is as high as 1.1%.

[0132] The molecular structure of the electroluminescent polyimide PI-4 in this example is as follows:

[0133]

[0134] Table 1: Summary of the photoelectric performance data and device data of the polyimide films prepared in polyimide synthesis examples 6-11

[0135]

Claims

1. A diamine monomer containing pyrene and triphenylamine structure, characterized in that: The monomer structure is as follows: Wherein, R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 , R 11 , R 12 , R 13 Select from any of the following structures: -H, -OH, -CH3, -OCH3, -CF3, -CN, -F, 2. The method for preparing the diamine monomer containing pyrene and triphenylamine structure according to claim 1, characterized in that The following steps are involved: (1) The 10 , R 11 , R 12 , R 13 The bromine substituted product of pyrene with the structure, the amino-substituted phenylboronic acid containing R1, R2, R3, R4 structures, and potassium carbonate are added to a reaction container, and a tetrahydrofuran solution and deionized water are added, stirred and argon is introduced, and then tetrakistriphenylphosphine palladium is added, the temperature is raised and stirred to react, and the reaction solution is cooled, poured into water for precipitation, extracted, separated to obtain an organic layer, spin-dried, and purified by column chromatography to obtain an amino-substituted phenylpyrene structure compound, the structure of which is as shown in the general formula (III): (2) placing the amino-substituted phenylpyrene structure compound prepared in step (1), p-fluoronitrobenzene or m-fluoronitrobenzene, and cesium fluoride in a reaction container, adding anhydrous DMSO, stirring and introducing argon, heating to react, cooling, pouring the reaction solution into water for precipitation, filtering, washing with an organic solvent, and recrystallizing to obtain a product containing R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 , R 11 , R 12 , R 13 The dinitro compound of pyrene of the structure is as shown in the general formula (IV) or (V): (3) The dinitro compound prepared in step (2) is subjected to a hydrogen reduction reaction to obtain a compound containing R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 , R 11 , R 12 , R 13 The diamine monomer has a structure such as the general formula (I) or (II).

3. The method for preparing a diamine monomer containing pyrene and triphenylamine structures according to claim 2, characterized in that: In the step (1): containing R5, R6, R7, R8, R9, R 10 , R 11 , R 12 , R 13 The molar ratio of the bromine substituted product of pyrene with a structure, the amino substituted phenylboronic acid containing R1, R2, R3, and R4 structures, and potassium carbonate is 1:1-1.2:1.5-2, the volume ratio of tetrahydrofuran and deionized water is 2-3:1, 0.02-0.05g of tetrakistriphenylphosphine palladium is added for every 50mol of the bromine substituted product of pyrene, the reaction temperature is 90°C, the reaction time is 12-24h, and the extractant is ethyl acetate.

4. The method for preparing a diamine monomer containing pyrene and triphenylamine structures according to claim 2, characterized in that: In the step (2), the molar ratio of the amino-substituted phenylpyrene structure compound, p-fluoronitrobenzene or m-fluoronitrobenzene, and cesium fluoride is 1:3-4:3-4, the reaction temperature is 130°C, the reaction time is 12-24h, the washing solvent is ethanol, and the recrystallization solvent is dichloromethane and petroleum ether.

5. A polyimide, whose molecular structure is as shown in general formula (I) or (II): In the formula: n and m represent the degree of polymerization, n is 5 to 10,000, m is 0 to 10,000, X and W are tetravalent aromatic hydrocarbon groups or aliphatic hydrocarbon groups, Z is a divalent aromatic hydrocarbon group or aliphatic hydrocarbon group, and Y is a divalent aromatic hydrocarbon group obtained after the polymerization reaction of the diamine monomer containing pyrene and triphenylamine structure as described in claim 1, and the structure is as shown in general formula (VI) or (VII); 6. The polyimide according to claim 5, characterized in that Z is selected from the following structures: X and W may be the same or different and are selected from the following structures:

7. The method for preparing a polyimide according to claim 5 or 6, characterized in that: The following steps are involved: In a nitrogen or argon atmosphere, a diamine monomer containing a Y structure or a mixed diamine monomer containing both Y and Z structures and a dianhydride containing an X structure or a mixed dianhydride monomer containing both X and W structures are dissolved in a polar aprotic organic solvent at a molar ratio of 1:1 to 1.2, wherein the polar aprotic organic solvent is selected from one or a mixture of two or more of N-methylpyrrolidone, N,N'-dimethylformamide, N,N'-dimethylacetamide, dimethyl sulfoxide, dimethyl sulfone, 1,4-dioxane, tetrahydrofuran, and m-cresol, and the total mass of the diamine monomer and the dianhydride monomer accounts for 5 to 50% of the total mass of the reaction materials; the reaction is continuously stirred at -10°C to 40°C for 24 to 48 hours to obtain a polyamic acid solution, and then imidization is carried out by thermal imidization or chemical imidization to obtain a polyimide having a structure such as general formula (I) or (II).

8. Use of the polyimide according to claim 5 or 6 in organic photodiodes or optical information storage device materials.

9. An organic light-emitting device comprising the polyimide according to claim 5 or 6, characterized in that: include: A first electrode, a second electrode and a light-emitting layer sandwiched between the first electrode and the second electrode, wherein the light-emitting layer is the polyimide according to claim 5 or 6; and between the first electrode and the second electrode, there is also included at least one layer of a hole injection layer, a hole transport layer, a hole blocking layer, an electron blocking layer, an electron transport layer and an electron injection layer.

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