CN107540663A - Soluble high glass-transition temperature bipolar host material and its preparation and application - Google Patents
Soluble high glass-transition temperature bipolar host material and its preparation and application Download PDFInfo
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Abstract
The invention belongs to the technical field of Organic Light Emitting Diode, discloses soluble high glass-transition temperature bipolar host material and its preparation and application.The structure of the bipolar host material such as formula I.Methods described is：(1) in catalyst system, by 3,6 two (tert-butyl group) carbazoles and 1,3 dibromobenzenes are reacted, and obtain the product containing 3 bromophenyls；(2) in the presence of alkalescence condition and catalyst, the product containing 3 bromophenyls and double boron of valeryl two is reacted, obtain the product containing borate；(3) in catalyst system and catalyzing, the product containing borate and 1 (3 bromobenzene) 2 (4 tert-butyl benzene) benzimidazole is subjected to coupling reaction, obtain bipolar host material.The bipolar host material has preferable dissolubility, is easy to solution processing；With higher glass transition temperature and higher triplet energy level；Efficiency of luminescent device and stability can be improved；It is readily synthesized.
Description
Technical field
It is more particularly to a kind of soluble high glass-transition temperature, bipolar the present invention relates to organic molecule material of main part
Property, high triplet energy level material of main part and its synthetic method and the application in luminescent device.
Background technology
Organic Light Emitting Diode (OLEDs) is before novel electroluminescent is shown and lighting field has important application
Scape.Prepared by current OLEDs is widely based on vacuum evaporation process, and stock utilization is relatively low.Thus, solution processing OLED, such as
Using inkjet technology, increase substantially stock utilization, show and illuminating device preparing large scale, with it is potential it is low into
This advantage.
But during solution processing preparation OLED, existing high-performance material of main part faces choosing in terms of synthesizing with purifying
War.In the present invention, carbazole and imidazole group, respectively with hole and electron transport property.On 3- the and 6- positions of carbazole, tertiary fourth
The introducing of base increases its dissolubility.Bipolar host material provided by the invention is a kind of soluble high glass for being easily-synthesized preparation
Change transition temperature, bipolarity, high triplet energy level bipolar host material.
The content of the invention
In order to overcome the disadvantages mentioned above of prior art and deficiency, it is an object of the invention to provide a kind of soluble high glass
Change transition temperature, bipolarity, high triplet energy level material of main part and preparation method thereof.The bipolar host material synthesis of the present invention
Route is simple, and comprehensive yied is high.
Another object of the present invention is to provide answering for above-mentioned soluble high glass-transition temperature bipolar host material
With.The bipolar host material is used to prepare Organic Light Emitting Diode, prepared by the mode processed especially by solution.
The purpose of the present invention is achieved through the following technical solutions：
A kind of soluble high glass-transition temperature bipolar host material, its structural formula such as formula I：
The soluble high glass-transition temperature bipolar host material be using 3,6- di-t-butyls -9- (3- (4,4,
5,5- tetramethyl -1,3,2-2- dioxaborinates base) phenyl) carbazole and 1- (3- bromobenzenes) -2- (4- tert-butyl benzenes)-benzimidazole
It is prepared for raw material；The bipolar host material being capable of solution processing.
The preparation method of the soluble high glass-transition temperature bipolar host material, comprises the following steps：
(1) in catalyst system, (tert-butyl group) carbazoles of 3,6- bis- and 1,3- dibromobenzene is reacted, obtained containing 3-
The product of bromophenyl；
The structural formula of 3,6- bis- (tert-butyl group) carbazole isThe product of the 3- bromophenyls
Structure is
(2) in the presence of alkalescence condition and catalyst, the product containing 3- bromophenyls and double boron of valeryl two are carried out instead
Should, obtain the product containing borate；
The structure of the product containing borate is
(3) in catalyst system and catalyzing, by the product containing borate and 1- (3- bromobenzenes) -2- (4- tert-butyl benzenes)-benzo miaow
Azoles carries out coupling reaction, obtains bipolar host material；
The structural formula of 1- (3- bromobenzenes) -2- (4- the tert-butyl benzenes)-benzimidazole is：
The condition reacted described in step (1) is to react 12~16h in 200~250 DEG C；Catalytic body described in step (1)
System includes catalyst, and the catalyst is cuprous iodide；Catalyst system and catalyzing includes alkali compounds, the alkali described in step (1)
Property compound is preferably potassium carbonate or sodium carbonate；The catalyst system and catalyzing also includes 18 six ethers of hat；3,6- bis- described in step (1)
The mol ratio of (tert-butyl group) carbazole and 1,3- dibromobenzenes is 1：(1.2~1.3)；It is described to react using organic solvent as reaction medium,
The organic solvent is preferably DMPU；
Using organic solvent as reaction medium, organic solvent is preferably DMF for reaction described in step (2)；Described in step (2)
Alkalescence condition refers to add alkali compounds in reaction system, and the alkali compounds is preferably potassium acetate or sodium acetate；Step
Suddenly the product containing 3- bromophenyls described in (2) and double boron mol ratios of valeryl two are (1:1.3~1.5), the catalyst is palladium
Catalyst, the palladium catalyst are preferably double (triphenylphosphine) palladium chlorides；The temperature reacted described in step (2) be 200~
250 DEG C, the time of reaction is 6~8h；
Catalyst system and catalyzing described in step (3) includes catalyst, and the catalyst is palladium catalyst, and the palladium catalyst is four
(triphenylphosphine) palladium；Catalyst system and catalyzing described in step (3) also includes alkaline aqueous solution and consisting of phase-transferring agent, and the alkaline aqueous solution is
Solution of potassium carbonate or aqueous sodium carbonate, the consisting of phase-transferring agent are ethanol；The temperature reacted described in step (3) is 100~120
DEG C, the time of reaction is 3~8h；- the 2- of 1- (3- bromobenzenes) described in step (3) (4- tert-butyl benzenes)-benzimidazoles are with containing boron
The product molar ratio of acid esters is 1:(1.3~1.5).Using organic solvent as reaction medium, the organic solvent is preferred for the reaction
For toluene.
3,6- bis- (tert-butyl group) carbazole described in step (1) is prepared by the following method to obtain：In alchlor or chlorination
In the presence of zinc, carbazole and tertiary butyl chloride are reacted, obtain 3,6- bis- (tert-butyl group) carbazole.The reaction is with organic solvent
For reaction medium, the organic solvent is dichloromethane or nitromethane, and the temperature of the reaction is 0~20 DEG C, the reaction
Time be 8~12h.
1- (3- bromobenzenes) described in step (3) -2- (4- tert-butyl benzenes)-benzimidazole is prepared by the following method to obtain：
(a) under catalyst system and catalyzing, ortho-nitraniline and a bromo-iodobenzene are reacted, obtain the hexichol containing bromine and nitro
Amine intermediate product；
The structure of the intermediate product is
The condition of the reaction is in 150~250 DEG C of (being preferably 150~180 DEG C) 10~12h of reaction；The adjacent nitro
The mol ratio of aniline and a bromo-iodobenzene is 1：(1.1~1.2)；The catalyst system and catalyzing includes catalyst, and the catalyst is iodate
It is cuprous；The catalyst system and catalyzing includes alkali compounds, and the alkali compounds is potassium carbonate or sodium carbonate；The catalyst system and catalyzing is also
Including 18 six ethers of hat；Using organic solvent as reaction medium, organic solvent is preferably DMPU for the reaction；
(b) in the presence of reducing agent, nitro in the diphenylamines intermediate product containing bromine and nitro of step (a) is reduced
Into amino, obtain containing amino and brominated intermediate product；The reducing agent is two hydrated stannous chlorides, containing bromine and nitro
The mol ratio of diphenylamines and reducing agent is 1：(5~6)；The temperature of the reaction is 0~100 DEG C (being preferably 0~20 DEG C), is reacted
Time be 6~12h, it is described reaction using ethanol as reaction medium；
(c) under organic solvent and condition of ice bath, by the diphenylamines intermediate product and 4- containing bromine and nitro of step (b)
Tert-butyl benzoyl chloride is reacted, and obtains the intermediate product containing acyl group；
The structure of the intermediate product containing acyl group is
The time of the reaction is 6~8h；The diphenylamines intermediate product containing bromine and nitro and 4- tert-butyl benzene first
The mol ratio of acyl chlorides is 1：(1.1~1.2)；The organic solvent is the mixture of dichloromethane and triethylamine；
(d) under conditions of glacial acetic acid, the intermediate product containing acyl group of step (c) is subjected to ring-closure reaction, obtains 1- (3-
Bromobenzene) -2- (4- tert-butyl benzenes)-benzimidazole.The temperature of the reaction is 80~100 DEG C, and the reaction time is 6~12h.
The application of described soluble bipolar host material, for preparing luminescent device, is processed especially by solution
Method prepare luminescent device.
The principle of the present invention is as follows：
The present invention introduces the carbazole group of electron, electrophilic imidazole group simultaneously so that organic molecule material of main part
With bipolarity；Meanwhile the design of compound also causes molecule to have higher triplet energy level；On this basis, in carbazole
3,6- positions, introduce the tert-butyl group respectively on the phenyl ring that is connected with imidazoles C positions and can increase its dissolubility, make good film-forming property, be easy to molten
Liquid is processed；In addition, series reaction all relative maturities that the present invention is taken, it is possible to achieve higher yield.
Compared with prior art, the present invention has advantages below and beneficial effect：
(tert-butyl group) carbazole of (1) 3,6- bis- and the high selectivity of 1,3- dibromobenzene reaction, different from unsubstituted carbazole,
Monosubstituted yield is high.
(2) material of main part of the invention has bipolarity, while has preferable electric transmission and hole transport performance, has
Beneficial to efficiency of luminescent device and stability is improved, processed suitable for solution.
(3) material of main part of solution processable of the invention introduces three tert-butyl groups, and dissolubility is good, and applicable solution adds
Work and inkjet printing.
(4) bipolar host material of solution processable of the invention has synthesis simple, is easily purified, passes through wet method post layer
Analysis separation, you can obtain high purity product, and the advantages that good heat endurance, film morphological stability, be advantageous to meet
The demand of OLED practical application.
(5) high triplet energy level ET=2.71eV.
Brief description of the drawings
Fig. 1 is bipolar host material t-BuCz-m-NPBI prepared by embodiment 1 proton nmr spectra；
Fig. 2 a, 2b are respectively that bipolar host material t-BuCz-m-NPBI prepared by embodiment 1 thermal weight loss and differential are swept
Retouch calorimetric curve；
Fig. 3 is bipolar host material material t-BuCz-m-NPBI prepared by embodiment 1 UV absorption and phosphorescent emissions
Spectrum；
Fig. 4 is bipolar host material t-BuCz-m-NPBI prepared by embodiment 1 antenna effect spectrum.
Embodiment
With reference to embodiment and accompanying drawing, the present invention is described in further detail, but embodiments of the present invention are not
It is limited to this.The reaction is carried out preferably in inert atmosphere.
Embodiment 1
The structural formula of the bipolar host material of the present embodiment is as follows：
The soluble bipolar host material t-BuCz-m-NPBI of the present embodiment preparation method, comprises the following steps：
Step 1：The preparation of 3,6- bis- (tert-butyl group) carbazoles (1), equation are as follows：
Carbazole (5g, 0.03mmol) is dissolved with dichloromethane, and air-discharging is after 30 minutes, add alchlor (4g,
0.03mmol), 0 DEG C is cooled to, adds tertiary butyl chloride (5.8g, 0.063mmol), stirring reaction is overnight (12h)；Question response terminates
Add alchlor in sodium hydrate aqueous solution and excessive afterwards, after removal of solvent under reduced pressure, reactant mixture is poured into water, and
Extracted with dichloromethane；Organic layer is dried with anhydrous magnesium sulfate, filtered, silica gel post separation is used after removal of solvent under reduced pressure, is eluted
Agent is that (volume ratio is preferably 2 for the mixed solvent of petroleum ether and dichloromethane:1) faint yellow solid, is obtained, uses ethyl alcohol recrystallization
Afterwards, white solid is obtained.
Step 2：The preparation of 9- (3- bromophenyls) -3,6- di-t-butyls carbazole (2), equation are as follows：
In N2Under atmosphere, by 3,6- di-t-butyls carbazole (2g, 7.16mmol), 1,3- dibromobenzenes (2.18g,
8.59mmol), potassium carbonate (6g, 43.0mol), 18 hat six ethers (0.20g, 0.716mmol), cuprous iodide (0.14g,
0.716mmol) added with DMPU (4ml) in there-necked flask, reaction is heated to 250 DEG C and is stirred overnight (12h)；Question response terminates,
After removal of solvent under reduced pressure, reactant mixture is poured into water, and extracted with dichloromethane；Organic layer is done with anhydrous magnesium sulfate
It is dry, filter, silica gel post separation is used after removal of solvent under reduced pressure, eluant, eluent is the mixed solvent (petroleum ether of petroleum ether and dichloromethane：
The volume ratio of dichloromethane is preferably 1:1), with ethyl alcohol recrystallization, white powder (compound 2) is obtained.
Step 3：3,6- di-t-butyls -9- (3- (4,4,5,5- tetramethyl -1,3,2-2- dioxaborinates base) phenyl) click
The preparation of azoles (3), equation are as follows：
In N2Under atmosphere, will double (triphenylphosphine) palladium chlorides (80mg, 0.11mmol) be added to compound (2) (2.3g,
5.30mmol), double boron of valeryl two (2.02g, 7.94mmol), potassium acetate (3.12g, 31.8mmol), dimethylformamide
In the mixed liquor of (30mL), heating reflux reaction 3 hours is cooled to room temperature, and after removal of solvent under reduced pressure, reactant mixture is added
In water, and extracted with dichloromethane；Organic layer is dried with anhydrous magnesium sulfate, filtered, with silicagel column point after removal of solvent under reduced pressure
From eluant, eluent is the mixed solvent (petroleum ether of petroleum ether and dichloromethane：Dichloromethane=(1:1~1:4) white powder), is obtained
Last (compound 3), yield 92% (2.35g).
Step 4, the preparation of N- (3- bromophenyls) -2- nitroanilines (4), reaction equation are as follows：
In N2Under atmosphere, by 2- nitroanilines (6g, 43.4mmol), a bromo-iodobenzene (13.5g, 47.8mmol), potassium carbonate
(18g, 0.13mol), 18 six ethers of hat (1.2g, 4.34mmol), cuprous iodide (0.827g, 4.34mmol) and DMPU (4ml)
Add in there-necked flask, reaction is heated to 250 DEG C and stirs 12h；Question response terminates, and after removal of solvent under reduced pressure, is added to the water, is used in combination
Dichloromethane extracts；Organic layer is dried with anhydrous magnesium sulfate, filtered, silica gel post separation, eluant, eluent are used after removal of solvent under reduced pressure
For petroleum ether and the mixed solvent (petroleum ether of dichloromethane：Dichloromethane=(1:4~1:1) orange-yellow liquid (chemical combination), is obtained
Thing 4 is N- (3- bromophenyls) -2- nitroanilines).
Step 5, the preparation of N- (3- bromophenyls) -1,2- diphenylamines (5), equation are as follows：
Added into ethanol (60mL) solution of compound (4) (4.3g, 14.5mmol) two hydrated stannous chlorides (19.6g,
87mmol), 12h is stirred at 100 DEG C；Question response terminates, and sodium hydrate aqueous solution is slowly dropped into reactant mixture in
With the stannic chloride of excess, and it is extracted with ethyl acetate, after organic layer removal of solvent under reduced pressure, obtaining white powder, (compound 5 is i.e.
N- (3- bromophenyls) -1,2- diphenylamines), yield 98% (3.8g).
Step 6, the preparation of N- (2- ((3- bromophenyls) ammonia) phenyl) -4- t-butylbenzamides (6), equation are as follows：
Under condition of ice bath, by N- (3- bromophenyls) -1,2- diphenylamines (3.8g, 14.5mmol) be added to dichloromethane and
Triethylamine (volume ratio 1:1) in mixed liquor, then 4- tert-butyl benzoyl chlorides (3.1g, 16.0mmol) are slowly added dropwise, drip
Reaction is to continuing stirring reaction 8h after room temperature, and after removal of solvent under reduced pressure, twice of ethyl alcohol recrystallization of reactant mixture obtains white
Color powder (compound 6 is N- (2- ((3- bromophenyls) ammonia) phenyl) -4- t-butylbenzamides), yield 89% (5.5g).
Step 7, the preparation of 1- (3- bromophenyls) -2- (4- tert-butyl-phenyls) benzimidazoles (7), equation are as follows：
N- (2- ((3- bromophenyls) ammonia) phenyl) -4- t-butylbenzamides (5.5g, 13mmol) are dissolved with glacial acetic acid,
The stirring reaction 12h at 100 DEG C, obtain closed loop product (compound 7 i.e. 1- (3- bromophenyls) -2- (4- tert-butyl-phenyls) benzo
Imidazoles), for white powder (compound 7 is 1- (3- bromophenyls) -2- (4- tert-butyl-phenyls) benzimidazole), yield 92%
(4.8g)。
Step 8, bipolar host material t-BuCz-m-NPBI (8) preparation, equation are as follows：
In N2Under atmosphere, by compound (3) (840mg, 2.08mmol) be added to compound (7) (1.2g, 2.49mmol),
2M solution of potassium carbonate (4mL), toluene (80mL), ethanol (4mL), tetrakis triphenylphosphine palladium (72mg) mixed liquor in, heat back
Flow and react 3 hours, be cooled to room temperature, after removal of solvent under reduced pressure, reactant mixture is added to the water, and is extracted with dichloromethane
Take；Organic layer is dried with anhydrous magnesium sulfate, filtered, use silica gel post separation after removal of solvent under reduced pressure, eluant, eluent be petroleum ether with
Mixed solvent (two petroleum ethers of dichloromethane：The volume ratio of dichloromethane is (2:1~1:1) it is i.e. bipolar), to obtain white powder
Property material of main part t-BuCz-m-NPBI, yield 92% (1.3g).
Soluble bipolar host material t-BuCz-m-NPBI manufactured in the present embodiment is tested below：
1st, proton nmr spectra：
1H NMR (500MHz, CDCl3) δ 8.15 (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 bipolar host material t-BuCz-m-NPBI prepared by embodiment 1 proton nmr spectra.
2nd, macroscopic property：
Thermogravimetic analysis (TGA) (TGA) is to lead to nitrogen protection on TGA2050 (TA instruments) thermogravimetric analyzer with 20
DEG C/min determination of heating rate；Differential scanning calorimetric analysis (DSC) use NETZSCH DSC204F1 thermal analyzers, in nitrogen
In gas atmosphere, with 10 DEG C/min heating rate to 280 DEG C since -30 DEG C, -30 DEG C then are cooled to 20 DEG C/min, perseverance
Warm 5min, again with 10 DEG C/min heating rate to 280 DEG C of tests.Test result is as shown in Figure 2；Fig. 2 a, 2b are respectively real
Apply the bipolar host material t-BuCz-m-NPBI of the preparation of example 1 thermal weight loss and differential scanning calorimetric curve.
Shown by Fig. 2 a thermogravimetric curves, novel soluble bipolar host material t-BuCz-m-NPBI weightlessness 5% when
Temperature is 402 DEG C, has higher heat endurance.
Shown by Fig. 2 b differential scanning calorimetric curves, heated in the first round, novel soluble processing bipolar host material
There is obvious melting peak in t-BuCz-m-NPBI, and in first round cooling and the second wheel heating, t-BuCz-m-NPBI does not have
Peak crystallization and melting peak are occurred, and shows obvious glass transition, corresponding glass transition temperature is 137 DEG C.This
Show that material can form stable amorphous state, there is good film morphological stability.
3rd, optical performance test：
Fig. 3 is bipolar host material material t-BuCz-m-NPBI prepared by embodiment 1 UV absorption and phosphorescent emissions
Spectrum.Absorption spectrum in Fig. 3, it can determine that optical band gap is 3.32eV according to ABSORPTION EDGE；It can be calculated by emission spectrum
Go out singlet energy level Es=3.23eV.
4th, triplet energy level is tested：
Triplet energy level is calculated by antenna effect spectrum, tested using solwution method, solvent is tetrahydrofuran, and solution is dense
Spend for 10-5mol L-1, excitation wavelength 300nm.Fig. 4 is bipolar host material t-BuCz-m-NPBI prepared by embodiment 1
Antenna effect spectrum.It is 2.71eV so as to which t-BuCz-m-NPBI triplet energy level be calculated.This shows that material has height
Triplet energy level, be advantageous to its application in the high efficiency device such as phosphorescence.
Above-described embodiment is the preferable embodiment of the present invention, but embodiments of the present invention are not by the embodiment
Limitation, other any Spirit Essences without departing from the present invention with made under principle change, modification, replacement, combine, simplification,
Equivalent substitute mode is should be, is included within protection scope of the present invention.
Claims (10)
- A kind of 1. soluble high glass-transition temperature bipolar host material, it is characterised in that：Its structural formula such as formula I：
- 2. the preparation method of soluble high glass-transition temperature bipolar host material according to claim 1, its feature It is：Comprise the following steps：(1) in catalyst system, (tert-butyl group) carbazoles of 3,6- bis- and 1,3- dibromobenzene is reacted, obtained containing 3- bromobenzenes The product of base；The structural formula of 3,6- bis- (tert-butyl group) carbazole isThe structure of the product of the 3- bromophenyls For(2) in the presence of alkalescence condition and catalyst, the product containing 3- bromophenyls and double boron of valeryl two is reacted, obtained To the product containing borate；The structure of the product containing borate is(3) in catalyst system and catalyzing, the product containing borate and 1- (3- bromobenzenes) -2- (4- tert-butyl benzenes)-benzimidazole are entered Row coupling reaction, obtains bipolar host material；The structural formula of 1- (3- bromobenzenes) -2- (4- the tert-butyl benzenes)-benzimidazole is
- 3. the preparation method of soluble high glass-transition temperature bipolar host material according to claim 2, its feature It is：Catalyst system and catalyzing includes catalyst described in step (1)；Catalyst system and catalyzing includes alkali compounds described in step (1)；It is described Catalyst system and catalyzing also includes 18 six ethers of hat；The reaction is using organic solvent as reaction medium；Reaction is using organic solvent as reaction medium described in step (2)；Alkalescence condition refers in reaction system described in step (2) Middle addition alkali compounds, catalyst described in step (2) are palladium catalyst；Catalyst system and catalyzing described in step (3) includes catalyst, and catalyst described in step (3) is palladium catalyst；Institute in step (3) Stating catalyst system and catalyzing also includes alkaline aqueous solution and consisting of phase-transferring agent；Reaction is using organic solvent as reaction medium described in step (3).
- 4. the preparation method of soluble high glass-transition temperature bipolar host material according to claim 3, its feature It is：Organic solvent described in step (1) is DMPU, and catalyst described in step (1) is cuprous iodide, described in step (1) Alkali compounds is potassium carbonate or sodium carbonate；Organic solvent is DMF in step (2), and alkali compounds described in step (2) is vinegar Sour potassium or sodium acetate；Palladium catalyst described in step (2) is preferably double (triphenylphosphine) palladium chlorides；Palladium described in step (3) Catalyst is tetrakis triphenylphosphine palladium, and alkaline aqueous solution described in step (3) is solution of potassium carbonate or aqueous sodium carbonate, described Consisting of phase-transferring agent is ethanol, and organic solvent described in step (3) is toluene.
- 5. the preparation method of soluble high glass-transition temperature bipolar host material according to claim 2, its feature It is：The mol ratio of (tert-butyl group) carbazoles of 3,6- bis- described in step (1) and 1,3- dibromobenzenes is 1：(1.2~1.3)；Step (2) product and double boron mol ratios of valeryl two containing 3- bromophenyls described in are (1:1.3~1.5)；The condition reacted described in step (1) is to react 12~16h in 200~250 DEG C；The temperature reacted described in step (2) For 200~250 DEG C, the time of reaction is 6~8h；The temperature reacted described in step (3) is 100~120 DEG C, the time of reaction For 3~8h；- the 2- of 1- (3- bromobenzenes) described in step (3) (4- tert-butyl benzenes)-benzimidazoles are with the product molar ratio containing borate 1:(1.3~1.5).
- 6. the preparation method of soluble high glass-transition temperature bipolar host material according to claim 2, its feature It is：3,6- bis- (tert-butyl group) carbazole described in step (1) is prepared by the following method to obtain：In alchlor or zinc chloride Under effect, carbazole and tertiary butyl chloride are reacted, obtain 3,6- bis- (tert-butyl group) carbazole.
- 7. the preparation method of soluble high glass-transition temperature bipolar host material according to claim 6, its feature It is：The reaction is using organic solvent as reaction medium, and the organic solvent is dichloromethane or nitromethane, the reaction Temperature is 0~20 DEG C, and the time of the reaction is 8~12h.
- 8. the preparation method of soluble high glass-transition temperature bipolar host material according to claim 2, its feature It is：1- (3- bromobenzenes) described in step (3) -2- (4- tert-butyl benzenes)-benzimidazole is prepared by the following method to obtain：(a) under catalyst system and catalyzing, ortho-nitraniline and a bromo-iodobenzene are reacted, obtained in the diphenylamines containing bromine and nitro Between product；The structure of the intermediate product is(b) in the presence of reducing agent, nitro in the diphenylamines intermediate product containing bromine and nitro of step (a) is reduced into ammonification Base, obtain containing amino and brominated intermediate product；(c) under organic solvent and condition of ice bath, by the diphenylamines intermediate product containing bromine and nitro of step (b) and the tertiary fourths of 4- Base chlorobenzoyl chloride is reacted, and obtains the intermediate product containing acyl group；The structure of the intermediate product containing acyl group is(d) under conditions of glacial acetic acid, the intermediate product containing acyl group of step (c) is subjected to ring-closure reaction, obtains 1- (3- bromines Benzene) -2- (4- tert-butyl benzenes)-benzimidazole.
- 9. the preparation method of soluble high glass-transition temperature bipolar host material according to claim 8, its feature It is：The condition reacted described in step (a) is to react 10~12h in 150~250 DEG C；The ortho-nitraniline and a bromine iodine The mol ratio of benzene is 1：(1.1~1.2)；The catalyst system and catalyzing includes catalyst, and the catalyst is cuprous iodide；Including alkalescence Compound, the alkali compounds are potassium carbonate or sodium carbonate；The catalyst system and catalyzing also includes 18 six ethers of hat；It is described reaction with Organic solvent is reaction medium；Reducing agent described in step (b) is two hydrated stannous chlorides, the mol ratio of diphenylamines and reducing agent containing bromine and nitro For 1：(5~6)；The temperature of the reaction is 0~100 DEG C, and the time of reaction is 6~12h, and the reaction is situated between by reaction of ethanol Matter；The time reacted described in step (c) is 6~8h；The diphenylamines intermediate product containing bromine and nitro and the 4- tert-butyl groups The mol ratio of chlorobenzoyl chloride is 1：(1.1~1.2)；The organic solvent is the mixture of dichloromethane and triethylamine；The temperature reacted described in step (d) is 80~100 DEG C, and the reaction time is 6~12h.
- 10. the application of soluble high glass-transition temperature bipolar host material, its feature exist according to claim 1 In：The soluble bipolar host material is used to prepare luminescent device, and the method processed by solution prepares luminescent device.
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| US20140027744A1 (en) * | 2012-07-25 | 2014-01-30 | Idemitsu Kosan Co., Ltd. | Organic electroluminescence device |
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| US20140027744A1 (en) * | 2012-07-25 | 2014-01-30 | Idemitsu Kosan Co., Ltd. | Organic electroluminescence device |
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| CN106232591A (en) * | 2014-04-29 | 2016-12-14 | 罗门哈斯电子材料韩国有限公司 | Electron transport material and the Organnic electroluminescent device comprising it |
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