CN107540663B - Soluble bipolar host material with high glass transition temperature, and preparation and application thereof - Google Patents
Soluble bipolar host material with high glass transition temperature, and preparation and application thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of organic light emitting diodes, and discloses a soluble bipolar main body material with high glass transition temperature, and preparation and application thereof. The bipolarThe structure of the sexual main material is shown as formula I. The method comprises the following steps: (1) in a catalyst system, 3, 6-di (tert-butyl) carbazole reacts with 1, 3-dibromobenzene to obtain a product containing 3-bromophenyl; (2) under the action of alkaline conditions and catalysts, reacting a product containing 3-bromophenyl with bis (valeryl) diboron to obtain a product containing borate; (3) in a catalytic system, a product containing boric acid ester and 1- (3-bromobenzene) -2- (4-tert-butyl benzene) -benzimidazole are subjected to coupling reaction to obtain the bipolar main body material. The bipolar main body material has better solubility and is easy to process solution; the glass transition temperature and the triplet state energy level are higher; the efficiency and the stability of the light-emitting device can be improved; is easy to synthesize.
Description
Technical Field
The invention relates to an organic small molecule host material, in particular to a soluble high-glass transition temperature, bipolar and high-triplet-state energy level host material, a synthetic method thereof and application thereof in a light-emitting device.
Background
Organic Light Emitting Diodes (OLEDs) have important application prospects in the fields of novel electroluminescent displays and lighting. Currently, the preparation of OLEDs is widely based on a vacuum evaporation process, and the material utilization rate is low. Therefore, the solution processing OLED device, such as the utilization of an ink-jet printing technology, greatly improves the material utilization rate, and has the potential advantage of low cost in the preparation of large-size display and lighting devices.
However, when solution processing is used to prepare OLED devices, the existing high-performance host materials face synthetic and purification challenges. In the present invention, carbazole and imidazole groups have hole and electron transport properties, respectively. The introduction of tertiary butyl groups at the 3-and 6-positions of the carbazole increases its solubility. The bipolar host material provided by the invention is a soluble bipolar host material with high glass transition temperature, bipolar property and high triplet state energy level, which is easy to synthesize and prepare.
Disclosure of Invention
In order to overcome the above disadvantages and shortcomings of the prior art, the present invention aims to provide a soluble high glass transition temperature, bipolar, high triplet state energy level host material and a preparation method thereof. The bipolar main body material has simple synthetic route and high comprehensive yield.
Another object of the present invention is to provide the application of the above soluble bipolar host material with high glass transition temperature. The bipolar host material is used for preparing an organic light-emitting diode, particularly by a solution processing mode.
The purpose of the invention is realized by the following technical scheme:
a soluble bipolar host material with high glass transition temperature has a structural formula shown as a formula I:
the soluble bipolar host material with high glass transition temperature is prepared by adopting 3, 6-di-tert-butyl-9- (3- (4,4,5, 5-tetramethyl-1, 3, 2-dioxaboronyl) phenyl) carbazole and 1- (3-bromobenzene) -2- (4-tert-butyl benzene) -benzimidazole as raw materials; the bipolar host material is solution processable.
The preparation method of the soluble bipolar host material with high glass transition temperature comprises the following steps:
(1) in a catalyst system, 3, 6-di (tert-butyl) carbazole reacts with 1, 3-dibromobenzene to obtain a product containing 3-bromophenyl;
the structural formula of the 3, 6-di (tert-butyl) carbazole is shown in the specification
The product of the 3-bromophenyl group has the structure
(2) Under the action of alkaline conditions and catalysts, reacting a product containing 3-bromophenyl with bis (valeryl) diboron to obtain a product containing borate;
the borate containing product has the structure
(3) In a catalytic system, a product containing boric acid ester and 1- (3-bromobenzene) -2- (4-tert-butyl benzene) -benzimidazole are subjected to coupling reaction to obtain a bipolar main body material;
the structural formula of the 1- (3-bromobenzene) -2- (4-tert-butyl benzene) -benzimidazole is as follows:
the reaction condition in the step (1) is that the reaction is carried out for 12-16 h at 200-250 ℃; the catalytic system in the step (1) comprises a catalyst, wherein the catalyst is cuprous iodide; the catalytic system in the step (1) comprises a basic compound, and the basic compound is preferably potassium carbonate or sodium carbonate; the catalytic system further comprises octadecatetraenoic hexaether; in the step (1), the molar ratio of the 3, 6-di (tert-butyl) carbazole to the 1, 3-dibromobenzene is 1: (1.2-1.3); the reaction takes an organic solvent as a reaction medium, and the organic solvent is preferably DMPU;
in the reaction in the step (2), an organic solvent is used as a reaction medium, and the organic solvent is preferably DMF; the alkaline condition in the step (2) is that an alkaline compound is added into a reaction system, and the alkaline compound is preferably potassium acetate or sodium acetate; the molar ratio of the product containing the 3-bromophenyl group to the bis (valeryl) diboron in the step (2) is (1: 1.3-1.5), the catalyst is a palladium catalyst, and the palladium catalyst is preferably bis (triphenylphosphine) palladium dichloride; the reaction temperature in the step (2) is 200-250 ℃, and the reaction time is 6-8 h;
the catalytic system in the step (3) comprises a catalyst, wherein the catalyst is a palladium catalyst, and the palladium catalyst is tetrakis (triphenylphosphine) palladium; the catalytic system in the step (3) further comprises an alkaline aqueous solution and a phase transfer agent, wherein the alkaline aqueous solution is a potassium carbonate solution or a sodium carbonate aqueous solution, and the phase transfer agent is ethanol; the reaction temperature in the step (3) is 100-120 ℃, and the reaction time is 3-8 h; in the step (3), the molar ratio of the 1- (3-bromobenzene) -2- (4-tert-butyl benzene) -benzimidazole to the product containing the boric acid ester is 1 (1.3-1.5). The reaction takes an organic solvent as a reaction medium, and the organic solvent is preferably toluene.
The 3, 6-di (tert-butyl) carbazole in the step (1) is prepared by the following method: reacting carbazole with tert-butyl chloride under the action of aluminum trichloride or zinc chloride to obtain 3, 6-di (tert-butyl) carbazole. The reaction takes an organic solvent as a reaction medium, the organic solvent is dichloromethane or nitromethane, the reaction temperature is 0-20 ℃, and the reaction time is 8-12 hours.
The 1- (3-bromobenzene) -2- (4-tert-butyl benzene) -benzimidazole in the step (3) is prepared by the following method:
(a) reacting o-nitroaniline with m-bromoiodobenzene in a catalytic system to obtain a diphenylamine intermediate product containing bromine and nitro;
the structure of the intermediate product is
The reaction condition is that the reaction is carried out for 10-12 h at 150-250 ℃ (preferably 150-180 ℃); the molar ratio of the o-nitroaniline to the m-bromoiodobenzene is 1: (1.1-1.2); the catalytic system comprises a catalyst, and the catalyst is cuprous iodide; the catalytic system comprises an alkaline compound, and the alkaline compound is potassium carbonate or sodium carbonate; the catalytic system further comprises octadecatetraenoic hexaether; the reaction takes an organic solvent as a reaction medium, and the organic solvent is preferably DMPU;
(b) reducing the nitro group in the diphenylamine intermediate product containing bromine and nitro group in the step (a) into amino group under the action of a reducing agent to obtain an intermediate product containing amino group and bromine; the reducing agent is stannous chloride dihydrate, and the molar ratio of the diphenylamine containing bromine and nitro to the reducing agent is 1: (5-6); the reaction temperature is 0-100 ℃ (preferably 0-20 ℃), the reaction time is 6-12 h, and ethanol is used as a reaction medium in the reaction;
(c) reacting the diphenylamine intermediate product containing bromine and nitro in the step (b) with 4-tert-butylbenzoyl chloride under the conditions of an organic solvent and ice bath to obtain an acyl-containing intermediate product;
the structure of the intermediate product containing acyl is
The reaction time is 6-8 h; the molar ratio of the diphenylamine intermediate product containing bromine and nitro to 4-tert-butylbenzoyl chloride is 1: (1.1-1.2); the organic solvent is a mixture of dichloromethane and triethylamine;
(d) and (c) carrying out ring closure reaction on the intermediate product containing the acyl in the step (c) under the condition of glacial acetic acid to obtain 1- (3-bromobenzene) -2- (4-tert-butyl benzene) -benzimidazole. The reaction temperature is 80-100 ℃, and the reaction time is 6-12 h.
The application of the soluble bipolar host material is used for preparing a light-emitting device, in particular to a light-emitting device prepared by a solution processing method.
The principle of the invention is as follows:
according to the invention, a carbazole group for giving electrons and an imidazole group for attracting electrons are introduced at the same time, so that the organic molecular host material has a bipolar property; meanwhile, the design of the compound also enables the molecule to have a higher triplet energy level; on the basis, tertiary butyl is respectively introduced into benzene rings connected with 3, 6-position of carbazole and C-position of imidazole to improve the solubility of carbazole, so that the carbazole has good film-forming property and is easy to process solution; in addition, a series of reactions adopted by the invention are relatively mature, and higher yield can be realized.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the 3, 6-di (tert-butyl) carbazole reacts with 1, 3-dibromobenzene with high selectivity, and different from unsubstituted carbazole, the monosubstituted yield is high.
(2) The main body material has bipolarity, simultaneously has better electron transmission and hole transmission performance, is beneficial to improving the efficiency and the stability of a light-emitting device, and is suitable for solution processing.
(3) The main material capable of being processed by the solution is introduced with three tert-butyl groups, has good solubility and can be suitable for solution processing and ink-jet printing.
(4) The bipolar main body material capable of being processed by the solution has the advantages of simple synthesis, easy purification, high-purity product obtained by wet column chromatography separation, good thermal stability, film shape stability and the like, and is favorable for meeting the requirements of practical application of OLED devices.
(5) High triplet energy level ET＝2.71eV。
Drawings
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of the bipolar host material t-BuCz-m-NPBI prepared in example 1;
FIGS. 2a and 2b are thermogravimetric and differential scanning calorimetry curves of the bipolar host material t-BuCz-m-NPBI prepared in example 1, respectively;
FIG. 3 is the UV absorption and phosphorescence emission spectra of the bipolar host material t-BuCz-m-NPBI prepared in example 1;
FIG. 4 is a low temperature phosphorescence spectrum of t-BuCz-m-NPBI as a bipolar host material prepared in example 1.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the present invention is not limited thereto. The reaction is preferably carried out in an inert atmosphere.
Example 1
The structure of the bipolar host material of this embodiment is as follows:
the preparation method of the soluble bipolar host material t-BuCz-m-NPBI of the embodiment comprises the following steps:
step 1: preparation of 3, 6-di (tert-butyl) carbazole (1), equation:
carbazole (5g,0.03mmol) is dissolved in dichloromethane, after discharging air for 30 minutes, aluminum trichloride (4g,0.03mmol) is added, the temperature is cooled to 0 ℃, tert-butyl chloride (5.8g,0.063mmol) is added, and the reaction is stirred overnight (12 hours); after the reaction is finished, adding a sodium hydroxide aqueous solution to neutralize excessive aluminum trichloride, removing the solvent under reduced pressure, pouring the reaction mixture into water, and extracting with dichloromethane; the organic layer was dried over anhydrous magnesium sulfate, filtered, the solvent was removed under reduced pressure, and then separated by a silica gel column, eluting with a mixed solvent of petroleum ether and dichloromethane (volume ratio is preferably 2:1) to obtain a pale yellow solid, and recrystallized from ethanol to obtain a white solid.
Step 2: preparation of 9- (3-bromophenyl) -3, 6-di-tert-butylcarbazole (2) according to the following equation:
in N2Under an atmosphere, 3, 6-di-tert-butylcarbazole (2g,7.16mmol), 1, 3-dibromobenzene (2.18g,8.59mmol), potassium carbonate (6g,43.0mol), octadecanohexaether (0.20g, 0.716mmol), cuprous iodide (0.14g,0.716mmol) and DMPU (4ml) were added to a three-necked flask, and the reaction was heated to 250 ℃ and stirred overnight (12 h); after the reaction was completed, the solvent was removed under reduced pressure, and the reaction mixture was poured into water and extracted with dichloromethane; the organic layer was dried over anhydrous magnesium sulfate, filtered, the solvent was removed under reduced pressure, and then separated by a silica gel column, eluting with a mixed solvent of petroleum ether and dichloromethane (the volume ratio of petroleum ether to dichloromethane is preferably 1:1), and recrystallized from ethanol to obtain a white powder (compound 2).
And step 3: preparation of 3, 6-di-tert-butyl-9- (3- (4,4,5, 5-tetramethyl-1, 3, 2-dioxabornyl) phenyl) carbazole (3) according to the following equation:
in N2Bis (triphenylphosphine) palladium dichloride (80mg,0.11mmol) was added to a mixture of compound (2) (2.3g,5.30mmol), bis (valeryl) diboron (2.02g,7.94mmol), potassium acetate (3.12g,31.8mmol), and dimethylformamide (30mL) under an atmosphere, heated to reflux for reaction for 3 hours, cooled to room temperature, the solvent was removed under reduced pressure, and the reaction mixture was added to water and extracted with dichloromethane; the organic layer was dried over anhydrous magnesium sulfate, filtered, and the solvent was removed under reduced pressure, and then separated by a silica gel column, and the eluent was a mixed solvent of petroleum ether and dichloromethane (petroleum ether: dichloromethane ═ 1:1 to 1:4), to give a white powder (compound 3) in a yield of 92% (2.35 g).
Step 4, preparation of N- (3-bromophenyl) -2-nitroaniline (4), the reaction equation is as follows:
in N22-nitroaniline (6g,43.4mmol), m-bromoiodobenzene (13.5g,47.8mmol), potassium carbonate (18g,0.13mol), octadecanohexaether (1.2g, 4.34mmol), cuprous iodide (0.827g,4.34mmol) and DMPU (4ml) were added to a three-necked flask under atmosphere, the reaction was heated to 250 ℃ and stirred for 12 h; after the reaction is finished, removing the solvent under reduced pressure, adding water, and extracting with dichloromethane; the organic layer was dried over anhydrous magnesium sulfate, filtered, and the solvent was removed under reduced pressure, and then separated by a silica gel column, and the eluent was a mixed solvent of petroleum ether and dichloromethane (petroleum ether: dichloromethane ═ 1:4 to 1:1), to obtain an orange-yellow liquid (compound 4, i.e., N- (3-bromophenyl) -2-nitroaniline).
Step 5, preparation of N- (3-bromophenyl) -1, 2-diphenylamine (5), equation:
to a solution of compound (4) (4.3g,14.5mmol) in ethanol (60mL) was added stannous chloride dihydrate (19.6g,87mmol) and stirred at 100 ℃ for 12 h; after the reaction was completed, an aqueous sodium hydroxide solution was slowly dropped into the reaction mixture to neutralize excess tin chloride, and extraction was performed with ethyl acetate, and the organic layer was subjected to solvent removal under reduced pressure to obtain a white powder (compound 5, i.e., N- (3-bromophenyl) -1, 2-diphenylamine) in a yield of 98% (3.8 g).
Step 6, preparation of N- (2- ((3-bromophenyl) amino) phenyl) -4-tert-butylbenzamide (6), equation:
under the ice-bath condition, adding N- (3-bromophenyl) -1, 2-diphenylamine (3.8g,14.5mmol) into a mixed solution of dichloromethane and triethylamine (volume ratio 1:1), slowly dropwise adding 4-tert-butylbenzoyl chloride (3.1g,16.0mmol), continuously stirring for reacting for 8h after the dropwise adding reaction is completed to room temperature, removing the solvent under reduced pressure, and recrystallizing the reaction mixture twice with ethanol to obtain white powder (compound 6, namely N- (2- ((3-bromophenyl) amino) phenyl) -4-tert-butylbenzoamide) with the yield of 89% (5.5 g).
Step 7, preparation of 1- (3-bromophenyl) -2- (4-tert-butylphenyl) benzimidazole (7), equation:
n- (2- ((3-bromophenyl) amino) phenyl) -4-tert-butylbenzamide (5.5g,13mmol) was dissolved in glacial acetic acid and stirred at 100 ℃ for 12h to give the ring-closed product (compound 7, 1- (3-bromophenyl) -2- (4-tert-butylphenyl) benzimidazole) as a white powder (compound 7, 1- (3-bromophenyl) -2- (4-tert-butylphenyl) benzimidazole) in 92% yield (4.8 g).
Step 8, preparing the bipolar host material t-BuCz-m-NPBI (8), wherein the equation is as follows:
in N2Under an atmosphere, compound (3) (840mg,2.08mmol) was added to a mixture of compound (7) (1.2g,2.49mmol), 2M potassium carbonate solution (4mL), toluene (80mL), ethanol (4mL), tetrakis (triphenylphosphine) palladium (72mg), heated under reflux and reacted for 3 hours, cooled to room temperature, the solvent was removed under reduced pressure, and then the reaction mixture was added to water and extracted with dichloromethane; the organic layer was dried over anhydrous magnesium sulfate, filtered, and the solvent was removed under reduced pressure, and then separated by a silica gel column, eluting with a mixed solvent of petroleum ether and dichloromethane (the volume ratio of the two petroleum ethers to dichloromethane was 2:1 to 1:1), to obtain a white powder, i.e., bipolar host material t-BuCz-m-NPBI, with a yield of 92% (1.3 g).
The soluble bipolar host material t-BuCz-m-NPBI prepared in this example was tested as follows:
1. hydrogen nuclear magnetic resonance spectroscopy:
1H NMR(500MHz,CDCl3)δ8.15(d,J＝1.7Hz,2H),7.92(d,J＝7.6Hz,1H),7.72(d,J＝8.2Hz,1H),7.64–7.58(m,3H),7.57–7.50(m,4H),7.49–7.44(m,3H),7.42–7.39(m,1H),7.38–7.32(m,4H),7.28(m,2H),1.47(s,18H),1.18(s,9H).
FIG. 1 is the NMR spectrum of the bipolar host material t-BuCz-m-NPBI prepared in example 1.
2. Thermodynamic properties:
thermogravimetric analysis (TGA) was determined on a TGA2050(TA instruments) thermogravimetric analyzer with nitrogen blanket at a temperature rise rate of 20 ℃/min; differential Scanning Calorimetry (DSC) Using a NETZSCH DSC204F1 thermal analyzer, in a nitrogen atmosphere, from-30 deg.C, the temperature is raised to 280 deg.C at a rate of 10 deg.C/min, then lowered to-30 deg.C at a rate of 20 deg.C/min, and the temperature is maintained for 5min, and then the temperature is raised to 280 deg.C at a rate of 10 deg.C/min. The test results are shown in fig. 2; FIGS. 2a and 2b are thermogravimetry and differential scanning calorimetry curves of the bipolar host material t-BuCz-m-NPBI prepared in example 1, respectively.
As shown in FIG. 2a, the thermal weight loss curve shows that the temperature of the novel soluble bipolar host material t-BuCz-m-NPBI at 5% weight loss is 402 ℃, and the thermal stability is high.
As shown in fig. 2b, the differential scanning calorimetry curve shows that in the first heating cycle, the novel soluble processing bipolar host material t-BuCz-m-NPBI has a distinct melting peak, while in the first cooling cycle and the second heating cycle, the t-BuCz-m-NPBI has no crystallization peak and no melting peak, and shows a distinct glass transition, corresponding to a glass transition temperature of 137 ℃. This indicates that the material can form a stable amorphous state with good film morphology stability.
3. And (3) testing optical performance:
FIG. 3 shows the UV absorption and phosphorescence emission spectra of the bipolar host material t-BuCz-m-NPBI prepared in example 1. From the absorption spectrum in fig. 3, the optical band gap can be determined to be 3.32eV from the absorption edge; from the emission spectrum the singlet energy level E can be calculateds＝3.23eV。
4. Triplet state energy level test:
calculating triplet state energy level by low temperature phosphorescence spectrum, and testing with solution method, wherein the solvent is tetrahydrofuran, and the solution concentration is 10-5mol L-1The excitation wavelength was 300 nm. FIG. 4 is a low temperature phosphorescence spectrum of t-BuCz-m-NPBI as a bipolar host material prepared in example 1. The triplet energy level of t-BuCz-m-NPBI was calculated to be 2.71 eV. This shows that the material has high triplet energy level, which is beneficial to the application of the material in high-efficiency devices such as phosphorescence.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A soluble high glass transition temperature bipolar host material, characterized in that: the structural formula is shown as formula I:
2. the method for preparing the soluble high glass transition temperature bipolar host material according to claim 1, wherein: the method comprises the following steps:
(1) in a catalyst system, 3, 6-di (tert-butyl) carbazole reacts with 1, 3-dibromobenzene to obtain a product containing 3-bromophenyl;
the structural formula of the 3, 6-di (tert-butyl) carbazole is shown in the specification
The product of the 3-bromophenyl group has the structure
(2) Under the action of alkaline conditions and catalysts, reacting a product containing 3-bromophenyl with bis (valeryl) diboron to obtain a product containing borate;
the borate containing product has the structure
(3) In a catalytic system, a product containing boric acid ester and 1- (3-bromobenzene) -2- (4-tert-butyl benzene) -benzimidazole are subjected to coupling reaction to obtain a bipolar main body material;
the structural formula of the 1- (3-bromobenzene) -2- (4-tert-butyl benzene) -benzimidazole is shown in the specification
3. The method for preparing the soluble high glass transition temperature bipolar host material according to claim 2, wherein: the catalytic system in the step (1) comprises a catalyst; the catalytic system in the step (1) comprises a basic compound; the catalytic system further comprises octadecatetraenoic hexaether; the reaction takes an organic solvent as a reaction medium;
in the reaction in the step (2), an organic solvent is used as a reaction medium; the alkaline condition in the step (2) is that an alkaline compound is added into a reaction system, and the catalyst in the step (2) is a palladium catalyst;
the catalytic system in the step (3) comprises a catalyst, and the catalyst in the step (3) is a palladium catalyst; the catalytic system in the step (3) also comprises an alkaline aqueous solution and a phase transfer agent; in the reaction in the step (3), an organic solvent is used as a reaction medium.
4. The method for preparing the soluble high glass transition temperature bipolar host material according to claim 3, wherein: the organic solvent in the step (1) is DMPU, the catalyst in the step (1) is cuprous iodide, and the alkaline compound in the step (1) is potassium carbonate or sodium carbonate; the organic solvent in the step (2) is DMF, and the alkaline compound in the step (2) is potassium acetate or sodium acetate; the palladium catalyst in step (2) is preferably bis (triphenylphosphine) palladium dichloride; the palladium catalyst in the step (3) is tetrakis (triphenylphosphine) palladium, the alkaline aqueous solution in the step (3) is a potassium carbonate solution or a sodium carbonate aqueous solution, the phase transfer agent is ethanol, and the organic solvent in the step (3) is toluene.
5. The method for preparing the soluble high glass transition temperature bipolar host material according to claim 2, wherein: in the step (1), the molar ratio of the 3, 6-di (tert-butyl) carbazole to the 1, 3-dibromobenzene is 1: (1.2-1.3); the molar ratio of the product containing the 3-bromophenyl to the bis-valeryl diboron in the step (2) is (1: 1.3-1.5);
the reaction condition in the step (1) is that the reaction is carried out for 12-16 h at 200-250 ℃; the reaction temperature in the step (2) is 200-250 ℃, and the reaction time is 6-8 h; the reaction temperature in the step (3) is 100-120 ℃, and the reaction time is 3-8 h;
in the step (3), the molar ratio of the 1- (3-bromobenzene) -2- (4-tert-butyl benzene) -benzimidazole to the product containing the boric acid ester is 1 (1.3-1.5).
6. The method for preparing the soluble high glass transition temperature bipolar host material according to claim 2, wherein: the 3, 6-di (tert-butyl) carbazole in the step (1) is prepared by the following method: reacting carbazole with tert-butyl chloride under the action of aluminum trichloride or zinc chloride to obtain 3, 6-di (tert-butyl) carbazole.
7. The method for preparing the soluble high glass transition temperature bipolar host material according to claim 6, wherein: the reaction takes an organic solvent as a reaction medium, the organic solvent is dichloromethane or nitromethane, the reaction temperature is 0-20 ℃, and the reaction time is 8-12 hours.
8. The method for preparing the soluble high glass transition temperature bipolar host material according to claim 2, wherein: the 1- (3-bromobenzene) -2- (4-tert-butyl benzene) -benzimidazole in the step (3) is prepared by the following method:
(a) reacting o-nitroaniline with m-bromoiodobenzene in a catalytic system to obtain a diphenylamine intermediate product containing bromine and nitro;
the structure of the intermediate product is
(b) Reducing the nitro group in the diphenylamine intermediate product containing bromine and nitro group in the step (a) into amino group under the action of a reducing agent to obtain an intermediate product containing amino group and bromine;
(c) reacting the diphenylamine intermediate product containing bromine and nitro in the step (b) with 4-tert-butylbenzoyl chloride under the conditions of an organic solvent and ice bath to obtain an acyl-containing intermediate product;
the structure of the intermediate product containing acyl is
(d) And (c) carrying out ring closure reaction on the intermediate product containing the acyl in the step (c) under the condition of glacial acetic acid to obtain 1- (3-bromobenzene) -2- (4-tert-butyl benzene) -benzimidazole.
9. The method for preparing the soluble high glass transition temperature bipolar host material according to claim 8, wherein: the reaction condition in the step (a) is that the reaction is carried out for 10-12 h at 150-250 ℃; the molar ratio of the o-nitroaniline to the m-bromoiodobenzene is 1: (1.1-1.2); the catalytic system comprises a catalyst, and the catalyst is cuprous iodide; comprises an alkaline compound, wherein the alkaline compound is potassium carbonate or sodium carbonate; the catalytic system further comprises octadecatetraenoic hexaether; the reaction takes an organic solvent as a reaction medium;
in the step (b), the reducing agent is stannous chloride dihydrate, and the molar ratio of the diphenylamine containing bromine and nitro to the reducing agent is 1: (5-6); the reaction temperature is 0-100 ℃, the reaction time is 6-12 h, and ethanol is used as a reaction medium;
the reaction time in the step (c) is 6-8 h; the molar ratio of the diphenylamine intermediate product containing bromine and nitro to 4-tert-butylbenzoyl chloride is 1: (1.1-1.2); the organic solvent is a mixture of dichloromethane and triethylamine;
the reaction temperature in the step (d) is 80-100 ℃, and the reaction time is 6-12 h.
10. The use of the soluble high glass transition temperature bipolar host material of claim 1, wherein: the soluble bipolar host material is used for preparing a light-emitting device, and the light-emitting device is prepared by a solution processing method.
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| CN103804360A (en) * | 2012-11-08 | 2014-05-21 | 海洋王照明科技股份有限公司 | Bipolar blue phosphorescent compound, and preparation method and application thereof |
| KR102427918B1 (en) * | 2014-04-29 | 2022-08-03 | 롬엔드하스전자재료코리아유한회사 | Electron transport material and an organic electroluminescence device comprising the same |
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