CN107142103A - A kind of conjugated polymer electroluminescent organic material and its application and device comprising TADF monomers by skeleton of acridine - Google Patents

A kind of conjugated polymer electroluminescent organic material and its application and device comprising TADF monomers by skeleton of acridine Download PDF

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CN107142103A
CN107142103A CN201710267279.3A CN201710267279A CN107142103A CN 107142103 A CN107142103 A CN 107142103A CN 201710267279 A CN201710267279 A CN 201710267279A CN 107142103 A CN107142103 A CN 107142103A
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tadf
monomers
substitution
group
substituted
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李庆
吕公鑫
刘国升
石宇
慈振华
董仲毅
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Valiant Co Ltd
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Valiant Co Ltd
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Abstract

The invention discloses a kind of conjugated polymer electroluminescent organic material and its application and device comprising TADF monomers by skeleton of acridine, belong to organic photoelectrical material technical field.It has following structure:The invention also discloses the application of the above-mentioned conjugated polymer electroluminescent organic material comprising TADF monomers by skeleton of acridine and device.The conjugated polymer electroluminescent organic material for including TADF monomers by skeleton of acridine of the present invention, using acridine as skeleton, is mingled with TADF monomer structures, structure is novel, and photoelectric properties are excellent.

Description

A kind of hair of the conjugated polymer organic electroluminescence comprising TADF monomers by skeleton of acridine Luminescent material and its application and device
Technical field
The present invention relates to a kind of conjugated polymer electroluminescent organic material for including TADF monomers by skeleton of acridine And its application and device, belong to organic photoelectrical material technical field.
Background technology
Hot activation delayed fluorescence (TADF) is a kind of special fluorescence phenomenon, and its principle of luminosity is triplet state T1 excitons in heat Reverse intersystem crossing generation singlet S1 excitons under activation, S1 excitons radiation transistion produces fluorescence, due to the TADF of early stage Molecular fluorescence inefficiency, therefore enough attention are not obtained, 2009, Adachi seminars of Kyushu University existed first TADF phenomenons are observed in tin complex, and pass through unremitting effort, 2012, Adachi seminars were using carbazole as donor, two Cyano group benzene is acceptor, and design has synthesized a series of TADF molecules with different colours, and wherein green glow molecule 4CzIPN's is luminous Performance is the most superior, and the external quantum efficiency of device is 19.3 ± 1.5%, and the exciton utilization rate of device has reached 100%, and it is studied Achievement is published in the same year nature periodical.Afterwards, TADF causes the extensive concern of researcher, and Kim etc. is further optimized 4CzIPN device architecture so that the current efficiency of device has reached 94.5cd/A, power efficiency is 88.6lm/W, outer quantum effect Rate 29.6%, device efficiency has approached the best level of phosphorescent devices, is the efficiency highest fluorescent device reported so far.
The fluorescent brightness and photoelectric efficiency of polymer device have an obvious deficiency compared with small molecule devices, but its have it is excellent Big face can be made in different optical stability, good machining characteristics by the way of spin coating, printing or inkjet printing Product flexible panel, this be small molecule it is incomparable.
In order to make full use of the advantage of TADF organic materials high efficiency and polymer high stability, and be further desirable to can be with Printing, printing, prepare low cost, the OLED display panel of large area by way of spin coating, people attempt TADF materials and Polymer links together, it is desirable to can obtain high efficiency and suitable for the material of printing.
The content of the invention
An object of the present invention, is to provide a kind of conjugated polymer comprising TADF monomers by skeleton of acridine organic Electroluminescent material.The conjugated polymer electroluminescent organic material of the present invention, using acridine as skeleton, is mingled with TADF monomer knots Structure, structure is novel, and photoelectric properties are excellent, and film fluorescence quantum efficiency is located at 47%-77%, the outer quantum effect of prepared device Rate is up to 4.9%.Prepared TADF conjugated polymers Mw of the invention：8K-11K, the coefficient of dispersion is located at 1.6-2.0, heating power Learn performance stable, and good dissolubility is respectively provided with Conventional solvents, such as toluene, chlorobenzene, dimethylbenzene, can be by beating Print, printing, the mode of spin coating prepare device, are suitable as the luminescent layer of large-area flat-plate display.
The technical scheme that the present invention solves above-mentioned technical problem is as follows：It is a kind of by skeleton of acridine comprising TADF monomers Conjugated polymer electroluminescent organic material, with the structure shown in formula I:
Wherein, A, B are respectively and independently selected from C1~C10Straight chain or branched alkyl, C1~C10Straight chain containing alkoxy or Branched alkyl；Ar1Selected from C4~C40Substitution or non-substituted arylamine group, C4~C40Substitution or non-substituted carbazyl Group, C4~C40Substitution or non-substituted azophenlyene group, C4~C40Substitution or non-substituted phenthazine group, C4~C40Substitution Or non-substituted phenoxazine group, C4~C40Substitution or non-substituted acridine group or combinations thereof；Ar2Selected from C4 ~C40Substitution or non-substituted aryl；R is TADF monomer structures；0≤X≤0.5；N is 1-100.
On the basis of above-mentioned technical proposal, the present invention can also do following improvement.
Further, the Ar1Selected from C12~C36Substitution or non-substituted arylamine group, C12~C36Substitution non-takes Carbazole group, the C in generation12~C36Substitution or non-substituted azophenlyene group, C12~C36Substitution or non-substituted phenothiazinyl Group, C12~C36Substitution or non-substituted phenoxazine group, C12~C36Substitution or non-substituted acridine group or they Combination；Wherein, the substituted carbazole group, substitution azophenlyene group, substitution phenoxazine group, substituted phenothiazine group, substitution a word used for translation Substituent in piperidinyl group is C1~C10Straight chain or branched alkyl, C1~C10Straight chain containing alkoxy or branched alkyl.
Further, the Ar1For one kind in following structure：
In formula, R1For hydrogen, C1~C10Straight chain or branched alkyl, C1~C10Straight chain containing alkoxy or branched alkane Base.
Further, the Ar2Selected from C4~C30Substitution or non-substituted aryl or heteroaryl, wherein, the heteroaryl Middle hetero atom is the one or more in nitrogen, silicon, sulphur and oxygen.
Further, the Ar2For one kind in following structure：
Further, the TADF monomers are one kind in following structure：
In formula, R2For hydrogen, C1~C10Straight chain or branched alkyl, C1~C10Straight chain containing alkoxy or branched alkane Base.
It is using above-mentioned further beneficial effect：The materials synthesis and purifying process of the present invention is simple, it is easy to a large amount of systems It is standby, and with higher molecular weight, the narrower PDI coefficients of dispersion, good thermodynamic stability, and in Conventional solvents, For example in toluene, chlorobenzene, dimethylbenzene equal solvent there is good dissolubility, spin coating, inkjet printing or printing process can be passed through Film forming, film forming is splendid.
There is provided the above-mentioned conjugated polymer Organic Electricity for including TADF monomers by skeleton of acridine for the second object of the present invention The application of electroluminescent material.The conjugated polymer electroluminescent organic material of the present invention is used for organic electroluminescence device, described Conjugated polymer film forming and can be used as the luminescent layer of device in the way of spin coating.
The technical scheme that the present invention solves above-mentioned technical problem is as follows：A kind of including by skeleton of acridine as described above Application of the conjugated polymer electroluminescent organic material of TADF monomers in organic electroluminescence device.
There is provided a kind of organic electroluminescence device for the third object of the present invention.The organic electroluminescence device of the present invention, tool Open that bright voltage is low, luminous efficiency is higher, stability good, service life is long, and then cause the polymer electroluminescence Material has good industrialization prospect.
The technical scheme that the present invention solves above-mentioned technical problem is as follows：A kind of organic electroluminescence device, it is supreme by lower floor Layer, be followed successively by ITO Conducting Glass, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer, Cathode layer, wherein, luminescent layer is related to the above-mentioned hair of the conjugated polymer organic electroluminescence comprising TADF monomers by skeleton of acridine Luminescent material.
The beneficial effects of the invention are as follows：
1. the conjugated polymer electroluminescent organic material for including TADF monomers by skeleton of acridine of the present invention, with a word used for translation Pyridine is skeleton, is mingled with TADF monomer structures, structure is novel, and photoelectric properties are excellent.
2. the conjugated polymer electroluminescent organic material for including TADF monomers by skeleton of acridine of the present invention, has Higher molecular weight, extraordinary thermodynamic stability, and there is good dissolubility in Conventional solvents, rotation can be passed through Painting, inkjet printing or printing process film forming, film forming are splendid.
3. the conjugated polymer electroluminescent organic material for including TADF monomers by skeleton of acridine of the present invention, fluorescence Quantum efficiency is higher, spectrum-stable, is suitable as the luminescent layer of large-area flat-plate display.
4. using the organic electroluminescence device for preparing of polymer organic electroluminescence material of the present invention, with opening The advantages of bright voltage is low, luminous efficiency is higher, stability is good, service life is long, and then cause the polymer electroluminescence material With good industrialization prospect.
Brief description of the drawings
The structural representation of organic electroluminescence device that Fig. 1 is prepared for the present invention, by lower floor to upper strata, be followed successively by 101, ITO Conducting Glass, 102, hole injection layer, 103, hole transmission layer, 104, luminescent layer, 105, electron transfer layer, 106, Electron injecting layer, 107, cathode layer, wherein, luminescent layer is related to electroluminescent organic material of the present invention.
Embodiment
The principle and feature of the present invention are described below in conjunction with specific accompanying drawing, example is served only for explaining this hair It is bright, it is not intended to limit the scope of the present invention.
Embodiment 1：Intermediate M1 preparation
9,9- dimethyl acridiniums (20.9g, 0.1mol), toluene (200mL), TBABr (0.64g, 2.0mmol) are introduced In 500mL three-necked flasks, dissolved clarification is stirred.The 50wt%NaOH aqueous solution (50mL) is poured into batches, prevents blunt temperature.Bath temperature is set to 100 DEG C, stirring heating.N-C is slowly added dropwise6H13Br (24.8g, 0.15mol) toluene solution (100mL), insulation reaction 10- 12h.Add water terminating reaction, and washing organic phase is to neutrality, point liquid, anhydrous sodium sulfate drying organic phase.Organic phase directly crosses post, removes Mechanical admixture, crosses post liquid desolventizing, obtains light yellow powder crude product, the isolated 26.2g white powders of silica gel column chromatography Solid, yield：89.4%.
Mass spectrum MS (m/e), molecular formula C21H27N, theoretical value 293.2, test value 294.1.
Elementary analysis (C21H27N), theoretical value：C, 85.95%；H, 9.27%；N, 4.77%；Measured value：C, 85.97%； H, 9.26%；N, 4.77%.
Embodiment 2：Intermediate M2 preparation
Intermediate M1 (14.7g, 0.05mol), dichloromethane (200mL) are introduced into 500mL three-necked flasks, 0 DEG C of condition Lower cooling stirring dissolved clarification.Insulated and stirred 2h under the conditions of NBS (19.6g, 0.11mol) DMF solution (20mL), 0 DEG C is slowly added dropwise, Plus reaction is quenched in the saturated sodium sulfite aqueous solution (50mL).Organic phase is washed to neutrality, point liquid, anhydrous sodium sulfate drying is organic Phase.Organic phase desolventizing, obtains off-white powder shape crude product, and the isolated 17.9g white powdery solids of silica gel column chromatography are received Rate：79.3%.
Mass spectrum MS (m/e), molecular formula C21H25Br2N, theoretical value 451.0, test value 452.1.
Elementary analysis (C21H25Br2N), theoretical value：C, 55.90%；H, 5.58%；N, 3.10%；Br, 35.42%；Actual measurement Value：C, 55.92%；H, 5.57%；N, 3.12%；Br, 35.39%.
Embodiment 3：Intermediate M3 preparation
Successively into 250mL there-necked flasks add intermediate M2 (9.0g, 0.02mol), double connection boric acid pinacol esters (11.2g, 0.044mol), KOAc (7.9g, 0.08mol), catalyst Pd (dppf) Cl2(146mg, 0.2mmol), 100mL toluene, nitrogen The lower back flow reaction 4.0h of protection.Suction filtration, filtrate is washed to neutrality, anhydrous sodium sulfate drying, desolventizing.Silica gel column chromatography is purified, Obtain white powdery solids 8.7g, yield 79.8%.
Mass spectrum MS (m/e), molecular formula C33H49B2NO4, theoretical value 545.4, test value 546.3.
Elementary analysis (C33H49B2NO4), theoretical value C, 72.68%；H, 9.06%；B, 3.96%；N, 2.57%；O, 11.73%；Measured value C, 72.70%；H, 9.05%；B, 3.92%；N, 2.59%；O, 11.74%.
Embodiment 4：Intermediate M4 preparation
Using the method similar with embodiment 3, intermediate M2 is replaced using two Bromo-intermediates of equivalent, other Part is constant, obtains intermediate M4, white crystal 9.7g, yield 84.6%.
Mass spectrum MS (m/e), molecular formula C35H53B2NO4, theoretical value 573.4, test value 574.3.
Elementary analysis (C35H53B2NO4), theoretical value C, 73.31%；H, 9.32%；B, 3.77%；N, 2.44%；O, 11.16%；Measured value C, 73.32%；H, 9.34%；B, 3.75%；N, 2.44%；O, 11.15%.
Embodiment 5：Intermediate M5 preparation
9,9- dimethyl acridiniums (20.9g, 0.05mol), toluene (100mL), TBABr (0.32g, 1.0mmol) are introduced In 500mL three-necked flasks, dissolved clarification is stirred.The 50wt%NaOH aqueous solution (30mL) is poured into batches, prevents blunt temperature.Bath temperature is set to 100 DEG C, stirring heating.The toluene solution (100mL) of 1,6- dibromos n-hexane (36.6g, 0.15mol) is slowly added dropwise, insulation is anti- 10 are answered to 12h.Add water terminating reaction, and washing organic phase is to neutrality, point liquid, anhydrous sodium sulfate drying organic phase.Organic phase is direct Post is crossed, except mechanical admixture, post liquid desolventizing, the isolated 16.7g white powdery solids of silica gel column chromatography, yield is crossed： 89.8%.
Mass spectrum MS (m/e), molecular formula C21H26BrN, theoretical value 371.1, test value 372.1.
Elementary analysis (C21H26BrN), theoretical value：C, 67.74%；H, 7.04%；N, 3.76%；Br, 21.46%；Actual measurement Value：C, 67.75%；H, 7.05%；N, 3.77%；Br, 21.43%.
Embodiment 6：Intermediate M6 preparation
By 3,6- dimethyl -9H- carbazoles (1.95g, 0.01mol), dry DMF solution (20mL) introducing tri- mouthfuls of burnings of 100mL In bottle, dissolved clarification, nitrogen protection are stirred.NaH (440mg, 0.011mol) is added in batches, blunt temperature is prevented, 25 DEG C of room temperature, stirring is anti- Answer 2h.Intermediate M5 (3.7g, 0.01mol) THF solution (30mL), completion of dropping, 50 DEG C of reaction 12h of bath temperature are slowly added dropwise. Room temperature is down to, reaction solution is poured into terminating reaction in 100mL frozen water, off-white powder is separated out.Suction filtration, washes filter cake to neutrality, Suction filtration after absolute ethyl alcohol and stirring 30min, filter cake is recrystallized using toluene/absolute ethyl alcohol, obtains 4.2g white powdery solids, is received Rate：86.4%.
Mass spectrum MS (m/e), molecular formula C35H38N2, theoretical value 486.3, test value 487.3.
Elementary analysis (C35H38N2), theoretical value：C, 86.37%；H, 7.87%；N, 5.76%；Measured value：C, 86.35%； H, 7.88%；N, 5.77%.
Embodiment 7：Intermediate M7 preparation
Using the method similar with embodiment 6,3,6- bis- is replaced using 3, the 6- di-t-butyl -9H- carbazoles of equivalent Methyl -9H- carbazoles, other conditions are constant, obtain intermediate M7, white crystal 4.3g, yield 75.4%.
Mass spectrum MS (m/e), molecular formula C41H50N2, theoretical value 570.4, test value 571.3.
Elementary analysis (C41H50N2), theoretical value：C, 86.26%；H, 8.83%；N, 4.91%；Measured value：C, 86.27%； H, 8.84%；N, 4.89%.
Embodiment 8：Intermediate M8 preparation
Intermediate M6 (4.9g, 0.01mol), dichloromethane (100mL) are introduced into 250mL three-necked flasks, under the conditions of 0 DEG C Cooling stirring dissolved clarification.Insulated and stirred 2h under the conditions of NBS (3.9g, 0.022mol) DMF solution (10mL), 0 DEG C is slowly added dropwise, plus Reaction is quenched in the saturated sodium sulfite aqueous solution (50mL).Organic phase is washed to neutrality, point liquid, anhydrous sodium sulfate drying organic phase. Organic phase desolventizing, obtains off-white powder shape crude product, the isolated 5.8g white powdery solids of silica gel column chromatography, yield： 90.1%.
Mass spectrum MS (m/e), molecular formula C35H36Br2N2, theoretical value 642.1, test value 643.2.
Elementary analysis (C35H36Br2N2), theoretical value：C, 65.23%；H, 5.63%；N, 4.35%；Br, 24.80%；It is real Measured value：C, 65.24%；H, 5.64%；N, 4.32%；Br, 24.80%.
Embodiment 9：Intermediate M9 preparation
Using the method similar with embodiment 8, intermediate M6 is replaced using the intermediate M7 of equivalent, intermediate is obtained M9, white solid 5.7g, yield 78.3%.
Mass spectrum MS (m/e), molecular formula C41H48Br2N2, theoretical value 726.2, test value 727.2.
Elementary analysis (C41H48Br2N2), theoretical value C, 67.58%；H, 6.64%；Br, 21.93%；N, 3.84%；Actual measurement Value C, 67.60%；H, 6.63%；Br, 21.91%；N, 3.86%.
Embodiment 10：TADF monomers T1 preparation
TADF monomers T1-A preparation：Under nitrogen environmental protection, successively into 100mL there-necked flasks add phenoxazine (2.0g, 0.011mol), the bromo- 4- of 1- ((4- fluorophenyls) sulfuryl) benzene (3.15g, 0.01mol), ortho-xylene (50mL), sodium tert-butoxide (1.92g, 0.02mol), is stirred at room temperature after 15min, adds palladium (23mg, 0.1mmol), 2- dicyclohexyl phosphines -2', 6'- Dimethoxy-biphenyl (S-phos) (84mg, 0.2mmol).Bath temperature is set to 110-120 DEG C, stirred under nitrogen atmosphere reaction 6- Room temperature is cooled to after 10.0h, TLC monitoring raw material reaction completely.Organic phase is washed to neutrality, point liquid, anhydrous sodium sulfate drying has Machine phase, suction filtration, filtrate desolventizing.Column chromatography is purified, and purification ＆ isolation obtains 3.8g light yellow powder solids, yield 91.1%.
Mass spectrum MS (m/e), molecular formula C24H16FNO3S, theoretical value 417.1, test value 418.0.
Elementary analysis (C24H16FNO3S), theoretical value C, 69.05%；H, 3.86%；F, 4.55%；N, 3.36%；O, 11.50%；S, 7.68%；Measured value C, 69.07%；H, 3.85%；F, 4.58%；N, 3.32%；O, 11.51%；S, 7.67%.
TADF monomers T1-B preparation：By 9,9- dimethyl acridiniums (2.09g, 0.01mol), dry DMF solution (20mL) It is introduced into 100mL three-necked flasks, stirs dissolved clarification, nitrogen protection.NaH (440mg, 0.011mol) is added in batches, prevents blunt temperature, 25 DEG C of room temperature, stirring reaction 2h.TADF monomers T1-A (4.17g, 0.01mol) THF solution (30mL) is slowly added dropwise, drips Finish, 50 DEG C of reaction 12h of bath temperature.Room temperature is down to, reaction solution is poured into terminating reaction in 100mL frozen water, light yellow solid is separated out.Take out Suction filtration after filter, washing filter cake to neutrality, absolute ethyl alcohol and stirring 30min, column chromatography purification ＆ isolation obtains 5.2g light yellow powders Solid, yield：85.8%.
Mass spectrum MS (m/e), molecular formula C39H30N2O3S, theoretical value 606.2, test value 606.9.
Elementary analysis (C39H30N2O3S), theoretical value：C, 77.20%；H, 4.98%；N, 4.62%；O, 7.91%；S, 5.28%；Measured value：C, 77.21%；H, 4.99%；N, 4.60%；O, 7.89%；S, 5.31%.
TADF monomers T1 preparation：TADF monomers T1-B (6.06g, 0.01mol), DMF (100mL) are introduced into 250mL tri- In mouth flask, cooling stirring dissolved clarification, is slowly added dropwise NBS (3.9g, 0.022mol) DMF solution (20mL) under the conditions of 0 DEG C, is added dropwise Finish, reaction solution is poured into water by insulated and stirred 5h under the conditions of 25 DEG C of room temperature, separate out yellow mercury oxide.Suction filtration, washing filter cake is into Property, absolute ethyl alcohol and stirring 30min is added, suction filtration, obtains yellow powder crude product again.Silica gel column chromatography purification ＆ isolation obtains 4.6g Light yellow powder solid, yield：60.2%.
Mass spectrum MS (m/e), molecular formula C39H28Br2N2O3S, theoretical value 762.0, test value 763.0.
Elementary analysis (C39H28Br2N2O3S), theoretical value：C, 61.27%；H, 3.69%；Br, 20.90%；N, 3.66%； O, 6.28%；S, 4.19%；Measured value：C, 61.28%；H, 3.70%；Br, 20.87%；N, 3.68%；O, 6.24%；S, 4.23%.
Embodiment 11：TADF monomers T2 preparation
TADF monomers T2-A preparation：Using with embodiment 10, method similar TADF monomers T1-A is used etc. and worked as The carbazole of amount replaces phenoxazine, obtains TADF monomer T2-A, light yellow solid 3.5g, yield 87.3%.
The preparation of the bromo- 9,9- dimethyl-acridans of 2,7- bis-：By 9,9- dimethyl acridiniums (2.09g, 0.01mol), DMF (30mL) is introduced into 100mL three-necked flasks, under the conditions of 0 DEG C cooling stirring dissolved clarification, be slowly added dropwise NBS (3.9g, Insulated and stirred 2h under the conditions of DMF solution (15mL) 0.022mol), completion of dropping, 25 DEG C of room temperature, reaction solution is poured into water, Separate out white precipitate.Suction filtration, filter cake uses absolute ethyl alcohol and stirring 30min, and suction filtration, obtains white powder crude product again.Silicagel column The isolated white powdery solids 3.0g of Chromatographic purification, yield：81.7%.
TADF monomers T2 preparation：Using with embodiment 10, method similar TADF monomers T1-B uses equivalent Bromo- 9,9- dimethyl -9, the 10- acridans of 2,7- bis- replace 9,9- dimethyl acridiniums, use the TADF monomers T2- of equivalent A obtains TADF monomer T2, light yellow solid 5.7g, yield 76.2% instead of TADF monomers T1-A.
Mass spectrum MS (m/e), molecular formula C39H28Br2N2O2S, theoretical value 746.0, test value 747.1.
Elementary analysis (C39H28Br2N2O2S), theoretical value：C, 62.58%；H, 3.77%；Br, 21.35%；N, 3.74%； O, 4.27%；S, 4.28%；Measured value：C, 62.60%；H, 3.76%；Br, 21.33%；N, 3.76%；O, 4.28%；S, 4.27%.
Embodiment 12：TADF monomers T3 preparation
TADF monomers T3-A preparation：Under nitrogen environmental protection, 3,6- di-t-butyls are added into 100mL there-necked flasks successively Carbazole (3.07g, 0.011mol), 4,4'- dibromobenzenes sulfone (3.76g, 0.01mol), ortho-xylene (50mL), sodium tert-butoxide (1.92g, 0.02mol), is stirred at room temperature after 15min, adds palladium (23mg, 0.1mmol), 2- dicyclohexyl phosphines -2', 6'- Dimethoxy-biphenyl (S-phos) (84mg, 0.2mmol).Bath temperature is set to 110-120 DEG C, stirred under nitrogen atmosphere reaction 6.0- Room temperature is cooled to after 10.0h, TLC monitoring raw material reaction completely.Organic phase is washed to neutrality, point liquid, anhydrous sodium sulfate drying has Machine phase, suction filtration, filtrate desolventizing.Column chromatography is purified, and purification ＆ isolation obtains 2.1g light yellow powder solids, yield 36.6%.
TADF monomers T3-B preparation：Under nitrogen environmental protection, 9,9- dimethyl a word used for translations are added into 100mL there-necked flasks successively Pyridine (2.30g, 0.011mol), TADF monomers T3-A (5.74g, 0.01mol), ortho-xylene (80mL), sodium tert-butoxide (1.92g, 0.02mol), it is stirred at room temperature after 15min, adds palladium (23mg, 0.1mmol), 2- dicyclohexyl phosphine -2', 6'- dimethoxys Biphenyl (S-phos) (84mg, 0.2mmol).Bath temperature is set to 110-120 DEG C, and stirred under nitrogen atmosphere reacts 6.0-10.0h, Room temperature is cooled to after TLC monitoring raw material reactions completely.Organic phase is washed to neutrality, point liquid, anhydrous sodium sulfate drying organic phase is taken out Filter, filtrate desolventizing.Column chromatography is purified, and purification ＆ isolation obtains 6.4g light yellow powder solids, yield 91.2%.
TADF monomers T3 preparation：TADF monomers T3-B (7.02g, 0.01mol), DMF (100mL) are introduced into 250mL tri- In mouth flask, cooling stirring dissolved clarification, is slowly added dropwise NBS (3.9g, 0.022mol) DMF solution (20mL) under the conditions of 0 DEG C, is added dropwise Finish, reaction solution is poured into water by insulated and stirred 5h under the conditions of 25 DEG C of room temperature, separate out yellow mercury oxide.Suction filtration, washing filter cake is into Property, absolute ethyl alcohol and stirring 30min is added, suction filtration, obtains yellow powder crude product again.Silica gel column chromatography purification ＆ isolation obtains pale yellow Color pulverulent solids 7.4g, yield：86.0%.
Mass spectrum MS (m/e), molecular formula C47H44Br2N2O2S, theoretical value 858.1, test value 859.0.
Elementary analysis (C47H44Br2N2O2S), theoretical value：C, 65.58%；H, 5.15%；Br, 18.57%；N, 3.25%； O, 3.72%；S, 3.73%；Measured value：C, 65.59%；H, 5.15%；Br, 18.59%；N, 3.23%；O, 3.70%；S, 3.74%.
Embodiment 13：TADF monomers T4 preparation
TADF monomers T4-A preparation：Using with embodiment 12, method similar TADF monomers T3-A is used etc. and worked as Amount phenoxazines replace 3,6- di-t-butyl carbazoles, use 3,7- dibromos dibenzo [b, d] thiophene 5 of equivalent, 5- dioxos TADF monomer T4-A are obtained for 4,4'- dibromobenzene sulfones, yellow-brown solid 3.1g, yield 65.1% is obtained.
TADF monomers T4-B preparation：Using with embodiment 12, method similar TADF monomers T3-B is used etc. and worked as The TADF monomers T4-A of amount replaces TADF monomer T3-A, obtains yellow solid 5.2g, yield 86.1%.
TADF monomers T4 preparation：Using with embodiment 12, method similar TADF monomers T3 uses equivalent TADF monomers T4-B replaces TADF monomer T3-B, obtains yellow solid 5.4g, yield 70.9%.
Mass spectrum MS (m/e), molecular formula C39H26Br2N2O3S, theoretical value 760.0, test value 761.0.
Elementary analysis (C39H26Br2N2O3S), theoretical value：C, 61.43%；H, 3.44%；Br, 20.96%；N, 3.67%； O, 6.29%；S, 4.21%；Measured value：C, 61.45%；H, 3.47%；Br, 20.90%；N, 3.68%；O, 6.27%；S, 4.23%.
Embodiment 14：TADF monomers T5 preparation
TADF monomers T5-A preparation：Under nitrogen environmental protection, intermediate C1 is added into 100mL there-necked flasks successively (3.88g, 0.01mol), 9,9- dimethyl acridiniums (2.30g, 0.011mol), ortho-xylene (50mL), sodium tert-butoxide (1.92g, 0.02mol), be stirred at room temperature after 15min, add palladium (23mg, 0.1mmol), tri-butyl phosphine tetrafluoroborate (58mg, 0.2mmol).Bath temperature is set to 120-140 DEG C, and stirred under nitrogen atmosphere reaction 10.0-12.0h, TLC monitoring raw material reaction is complete After be cooled to room temperature.Organic phase is washed to neutrality, point liquid, anhydrous sodium sulfate drying organic phase, suction filtration, filtrate desolventizing.Post layer Analysis purification, purification ＆ isolation obtains 3.7g yellow greenish powder shape solids, yield 71.6%.
TADF monomers T5 preparation：TADF monomers T5-A (5.16g, 0.01mol), DMF (150mL) are introduced into 250mL tri- In mouth flask, cooling stirring dissolved clarification, is slowly added dropwise NBS (3.9g, 0.022mol) DMF solution (20mL) under the conditions of 0 DEG C, is added dropwise Finish, reaction solution is poured into water by insulated and stirred 5-6h under the conditions of 25 DEG C of room temperature, separate out brown color precipitation.Suction filtration, washes filter cake To neutrality, filter cake uses absolute ethyl alcohol and stirring 30min, and suction filtration, obtains light brown powder shape solid again.Silica gel column chromatography is purified Isolated yellow greenish powder shape solid 5.8g, yield：86.1%.
Mass spectrum MS (m/e), molecular formula C35H22Br2N4O, theoretical value 672.0, test value 673.0.
Elementary analysis (C35H22Br2N4O), theoretical value：C, 62.33%；H, 3.29%；Br, 23.70%；N, 8.31%；O, 2.37%；Measured value：C, 62.34%；H, 3.30%；Br, 23.67%；N, 8.30%；O, 2.39%.
Embodiment 15：TADF monomers T6 preparation
TADF monomers T6-A preparation：Using with embodiment 14, method similar TADF monomers T5-A is used etc. and worked as The intermediate C2 of amount replaces intermediate C1, obtains light yellow or off-white powder 4.6g, yield 89.1%.
TADF monomers T6 preparation：Using with embodiment 14, method similar TADF monomers T5 uses equivalent TADF monomers T6-A replaces TADF monomer T5-A, obtains light yellow solid 6.0g, yield 89.0%.
Mass spectrum MS (m/e), molecular formula C36H26Br2N4, theoretical value 672.0, test value 672.9.
Elementary analysis (C36H26Br2N4), theoretical value：C, 64.11%；H, 3.89%；Br, 23.70%；N, 8.31%；It is real Measured value：C, 64.14%；H, 3.90%；Br, 23.68%；N, 8.28%.
Embodiment 16：TADF monomers T7 preparation
TADF monomers T7-A preparation：Using with embodiment 14, method similar TADF monomers T5-A is used etc. and worked as The intermediate C3 of amount replaces intermediate C1, obtains yellow solid 5.9g, yield 67.8%.
TADF monomers T7 preparation：Using with embodiment 14, method similar TADF monomers T5 uses equivalent TADF monomers T7-A replaces TADF monomer T5-A, obtains yellow solid 8.1g, yield 78.8%.
Mass spectrum MS (m/e), molecular formula C62H53Br2N5, theoretical value 1025.3, test value 1026.2.
Elementary analysis (C62H53Br2N5), theoretical value：C, 72.44%；H, 5.20%；Br, 15.55%；N, 6.81%；It is real Measured value：C, 72.45%；H, 5.21%；Br, 15.52%；N, 6.82%.
Embodiment 17：TADF monomers T8 preparation
TADF monomers T8-A preparation：Using with embodiment 14, method similar TADF monomers T5-A is used etc. and worked as The intermediate C4 of amount replaces intermediate C1, obtains white solid 6.9g, yield 78.5%.
TADF monomers T8 preparation：Using with embodiment 14, method similar TADF monomers T5 uses equivalent TADF monomers T8-A replaces TADF monomer T5-A, obtains white solid 7.8g, yield 75.2%.
Mass spectrum MS (m/e), molecular formula C60H40Br2N6O2, theoretical value 1034.2, test value 1035.1.
Elementary analysis (C60H40Br2N6O2), theoretical value：C, 69.51%；H, 3.89%；Br, 15.41%；N, 8.11%； O, 3.09%；Measured value：C, 69.54%；H, 3.90%；Br, 15.38%；N, 8.10%；O, 3.08%.
Embodiment 18：TADF monomers T9 preparation
TADF monomers T9-A preparation：Using with embodiment 12, method similar TADF monomers T3-A is used etc. and worked as 4, the 4'- dibromobenzo-phenones of amount replace 4,4'- dibromobenzene sulfones, and 3,6- di-t-butyl clicks are replaced using equivalent phenoxazines Azoles, obtains white solid 2.6g, yield 58.8%.
TADF monomers T9-B preparation：Using with embodiment 12, method similar TADF monomers T3-B is used etc. and worked as The TADF monomers T9-A of amount replaces TADF monomer T3-A, obtains white solid 4.6g, yield 80.7%.
TADF monomers T9 preparation：Using with embodiment 12, method similar TADF monomers T3 uses equivalent TADF monomers T9-B replaces TADF monomer T3-B, obtains yellow solid 6.3g, yield 86.5%.
Mass spectrum MS (m/e), molecular formula C40H28Br2N2O2, theoretical value 726.1, test value 727.0.
Elementary analysis (C40H28Br2N2O2), theoretical value：C, 65.95%；H, 3.87%；Br, 21.94%；N, 3.85%； O, 4.39%；Measured value：C, 65.90%；H, 3.89%；Br, 21.95%；N, 3.86%；O, 4.40%.
Embodiment 19：TADF monomers T10 preparation
TADF monomers T10-A preparation：Using with embodiment 12, method similar TADF monomers T3-A is used The bromo- 9H- xanthenes -9- ketone of 3,6- bis- of equivalent replaces 4,4'- dibromobenzene sulfones, obtains off-white powder 2.4g, yield 43.5%.
TADF monomers T10-B preparation：Using with embodiment 12, method similar TADF monomers T3-B is used The TADF monomers T10-A of equivalent replaces TADF monomer T3-A, obtains off-white powder 5.2g, yield 76.5%.
TADF monomers T10 preparation：Using with embodiment 12, method similar TADF monomers T3 uses equivalent TADF monomers T10-B replace TADF monomer T3-B, obtain white solid 7.6g, yield 90.7%.
Mass spectrum MS (m/e), molecular formula C48H42Br2N2O2, theoretical value 836.2, test value 837.1.
Elementary analysis (C48H42Br2N2O2), theoretical value：C, 68.74%；H, 5.05%；Br, 19.05%；N, 3.34%； O, 3.82%；Measured value：C, 68.75%；H, 5.07%；Br, 19.01%；N, 3.35%；O, 3.82%.
Embodiment 20：TADF monomers T11 preparation
TADF monomers T11-A preparation：Using with embodiment 12, method similar TADF monomers T3-A is used 2,7- dibromoanthracene -9,10- diketone of equivalent replaces 4,4'- dibromobenzene sulfones, obtains off-white powder 2.1g, yield 37.2%.
TADF monomers T11-B preparation：Using with embodiment 12, method similar TADF monomers T3-B is used The TADF monomers T11-A of equivalent replaces TADF monomer T3-A, obtains yellow solid 5.7g, yield 82.4%.
TADF monomers T11 preparation：Using with embodiment 12, method similar TADF monomers T3 uses equivalent TADF monomers T11-B replace TADF monomer T3-B, obtain yellow solid 5.2g, yield 61.3%.
Mass spectrum MS (m/e), molecular formula C49H42Br2N2O2, theoretical value 848.2, test value 849.2.
Elementary analysis (C49H42Br2N2O2), theoretical value：C, 69.18%；H, 4.98%；Br, 18.79%；N, 3.29%； O, 3.76%；Measured value：C, 69.17%；H, 4.97%；Br, 18.77%；N, 3.31%；O, 3.78%.
Embodiment 21：TADF monomers T12 preparation
TADF monomers T12-A preparation：Using with embodiment 12, method similar TADF monomers T3-A is used 3,5- bis- (4- bromophenyls) -4- phenyl -4H-1 of equivalent, 2,4- triazoles replace 4,4'- dibromobenzene sulfones, obtain greenish yellow solid 1.9g, yield 29.1%.
TADF monomers T12-B preparation：Using with embodiment 12, method similar TADF monomers T3-B is used The TADF monomers T12-A of equivalent replaces TADF monomer T3-A, obtains yellow solid 6.1g, yield 78.0%.
TADF monomers T12 preparation：Using with embodiment 12, method similar TADF monomers T3 uses equivalent TADF monomers T12-B replace TADF monomer T3-B, obtain yellow solid 7.5g, yield 79.8%.
Mass spectrum MS (m/e), molecular formula C55H49Br2N5, theoretical value 937.2, test value 938.2.
Elementary analysis (C55H49Br2N5), theoretical value：C, 70.29%；H, 5.26%；Br, 17.00%；N, 7.45%；It is real Measured value：C, 70.30%；H, 5.28%；Br, 17.03%；N, 7.39%.
Embodiment 22：TADF monomers T13 preparation
TADF monomers T13-A preparation：Using with embodiment 12, method similar TADF monomers T3-A is used 2, the 5- bis- (4- bromophenyls) -1 of equivalent, 3,4- thiadiazoles replace 4,4'- dibromobenzene sulfones, and 3 are replaced using the phenthazine of equivalent, 6- di-t-butyl carbazoles obtain yellow-brown solid 2.8g, yield 54.5%.
TADF monomers T13-B preparation：Using with embodiment 12, method similar TADF monomers T3-B is used The TADF monomers T13-A of equivalent replaces TADF monomer T3-A, obtains dark yellow solid 5.7g, yield 88.8%.
TADF monomers T13 preparation：Using with embodiment 12, method similar TADF monomers T3 uses equivalent TADF monomers T13-B replace TADF monomer T3-B, obtain yellow solid 6.3g, yield 78.7%.
Mass spectrum MS (m/e), molecular formula C41H28Br2N4S2, theoretical value 798.0, test value 799.1.
Elementary analysis (C41H28Br2N4S2), theoretical value：C, 61.51%；H, 3.53%；Br, 19.96%；N, 7.00%； S, 8.01%；Measured value：C, 61.54%；H, 3.50%；Br, 19.97%；N, 7.01%；S, 7.98%.
Embodiment 23：The preparation of polymer P 1
X=0.05.
Under high pure nitrogen environmental protection, intermediate M3 (545mg, 1mmol), intermediate are added into 50mL autoclaves successively M9 (655mg, 0.9mmol), TADF monomers T1 (76mg, 0.1mmol), toluene (20mL), potassium carbonate (414mg, 3.0mmol), TBAB (32mg, 0.1mmol), deionized water (4mL), are stirred at room temperature after 15min, addition palladium (45mg, 0.2mmol), tri-butyl phosphine tetrafluoroborate (116mg, 0.4mmol), rear enclosed system is sufficiently displaced from using high pure nitrogen. Temperature setting is 100-110 DEG C, stirring reaction 48h.Phenyl boric acid (25mg, 0.2mmol) end-blocking is added, continues to react 12h, then add Enter bromobenzene (157mg, 1.0mmol) end-blocking, continue to react 12h, be cooled to room temperature.Silicagel column is crossed, mechanical admixture and salt, mistake is removed Post liquid desolventizing, is recrystallized using toluene/absolute ethyl alcohol, and suction filtration obtains brown-green solid.It is green that column chromatography purification ＆ isolation obtains 0.31g Color pulverulent solids, yield 35.9%.
Embodiment 24：The preparation of polymer P 2
X=0.1.
Using the method similar with embodiment 23, added successively into 50mL autoclaves intermediate M3 (545mg, 1mmol), intermediate M9 (582mg, 0.8mmol), TADF monomers T1 (153mg, 0.2mmol), other conditions are constant.Column chromatography Purification ＆ isolation obtains 0.46g yellow greenish powder shape solids, yield 53.1%.
Embodiment 25：The preparation of polymer P 3
X=0.05.
Using the method similar with embodiment 23, added successively into 50mL autoclaves intermediate M4 (573mg, 1mmol), intermediate M9 (655mg, 0.9mmol), TADF monomers T2 (75mg, 0.1mmol), other conditions are constant.Column chromatography is carried Pure isolated 0.53g green powders solid, yield 59.6%.
Embodiment 26：The preparation of polymer P 4
X=0.1.
Using the method similar with embodiment 23, added successively into 50mL autoclaves intermediate M4 (573mg, 1mmol), intermediate M9 (582mg, 0.8mmol), TADF monomers T2 (150mg, 0.2mmol), other conditions are constant.Column chromatography Purification ＆ isolation obtains 0.49g green powder solids, yield 54.9%.
Embodiment 27：The preparation of polymer P 5
X=0.1.
Using the method similar with embodiment 23, added successively into 50mL autoclaves intermediate M3 (545mg, 1mmol), intermediate M9 (582mg, 0.8mmol), TADF monomers T3 (172mg, 0.2mmol), other conditions are constant.Column chromatography Purification ＆ isolation obtains 0.62g green powder solids, yield 70.0%.
Embodiment 28：The preparation of polymer P 6
X=0.1.
Using the method similar with embodiment 23, added successively into 50mL autoclaves intermediate M3 (545mg, 1mmol), intermediate M9 (582mg, 0.8mmol), TADF monomers T6 (135mg, 0.2mmol), other conditions are constant.Column chromatography Purification ＆ isolation obtains 0.42g green powder solids, yield 49.5%.
Embodiment 29：The preparation of polymer P 7
X=0.05.
Using the method similar with embodiment 23, added successively into 50mL autoclaves intermediate M3 (545mg, 1mmol), intermediate M9 (582mg, 0.8mmol), TADF monomers T7 (206mg, 0.2mmol), other conditions are constant.Column chromatography Purification ＆ isolation obtains 0.49g green powder solids, yield 53.3%.
Embodiment 30：The preparation of polymer P 8
X=0.1.
Using the method similar with embodiment 23, added successively into 50mL autoclaves intermediate M4 (573mg, 1mmol), intermediate M9 (582mg, 0.8mmol), TADF monomers T8 (207mg, 0.2mmol), other conditions are constant.Column chromatography Purification ＆ isolation obtains 0.52g green powder solids, yield 54.7%.
Embodiment 31：The preparation of polymer P 9
X=0.1.
Using the method similar with embodiment 23, added successively into 50mL autoclaves intermediate M4 (573mg, 1mmol), intermediate M9 (582mg, 0.8mmol), TADF monomers T9 (146mg, 0.2mmol), other conditions are constant.Column chromatography Purification ＆ isolation obtains 0.33g green powder solids, yield 34.7%.
Embodiment 32：The preparation of polymer P 10
X=0.05.
Using the method similar with embodiment 23, added successively into 50mL autoclaves intermediate M4 (573mg, 1mmol), intermediate M9 (655mg, 0.9mmol), TADF monomers T13 (80mg, 0.1mmol), other conditions are constant.Column chromatography Purification ＆ isolation obtains 0.47g green powder solids, yield 52.6%.
Prepared TADF conjugated polymer luminescent materials composition and correlation performance parameters of the invention, as shown in table 1.
TADF conjugated polymer luminescent materials composition and correlation performance parameters prepared by table 1
As shown in Table 1, the coefficient of dispersion of the prepared TADF conjugated polymers of the present invention is located between 1.6-2.0, disperse system Number scope is narrower；Film fluorescence quantum efficiency is located between 47%-77%, and fluorescence quantum efficiency is higher.
Here is the device Application Example of the compounds of this invention：
Embodiment 33：Prepare device one
Preparation method：
A) ITO (tin indium oxide) glass is cleaned：It is cleaned by ultrasonic ito glass each 10 with deionized water, acetone, isopropanol respectively Minute, then handled 15 minutes in plasma cleaner；
B) polyethoxy thiophene (PEDOT of the spin coating doped with polystyrolsulfon acid on anode ito glass:PSS) film is thick Degree is about 60nm, and handles 15min on 150 DEG C of hot plate；
Polyethoxy thiophene (the PEDOT of polystyrolsulfon acid:PSS) as hole-injecting material；
C) in PEDOT:Spin coating PVK solution on PSS films, PVK solvents used are toluene, and solution concentration is 5mg/mL, thick Degree is about 30nm, and handles 30min on 150 DEG C of hot plate；
D) on PVK films, spin on polymers P1 chlorobenzene solution is as luminescent layer, solution concentration 15mg/mL, and thickness is about For 60nm, and 20min is handled on 150 DEG C of hot plate；
E) on luminescent layer, vacuum evaporation is as the TmPyPB of electron transfer layer, and thickness is 40nm；
F) on electron transfer layer, vacuum evaporation electron injecting layer LiF, thickness is 1nm；
G) on electron injecting layer, vacuum evaporation negative electrode Al, thickness is 100nm.
The structure of device is ITO/PEDOT:PSS (60nm)/PVK (30nm)/Inventive polymers P1 (60nm)/TmPyPB (40nm)/LiF (1nm)/Al (100nm), spin coating process is carried out in the glove box of high pure nitrogen environment, vacuum evaporation process In, pressure<4.0×10-4Pa。
Embodiment 34：Prepare device two
Preparation method：
A) ITO (tin indium oxide) glass is cleaned：It is cleaned by ultrasonic ito glass each 10 with deionized water, acetone, isopropanol respectively Minute, then handled 15 minutes in plasma cleaner；
B) polyethoxy thiophene (PEDOT of the spin coating doped with polystyrolsulfon acid on anode ito glass:PSS) film is thick Degree is about 60nm, and handles 15min on 150 DEG C of hot plate；
Polyethoxy thiophene (the PEDOT of polystyrolsulfon acid:PSS) as hole-injecting material；
C) in PEDOT:Spin coating PVK solution on PSS films, PVK solvents used are toluene, and solution concentration is 5mg/mL, thick Degree is about 30nm, and handles 30min on 150 DEG C of hot plate；
D) on PVK films, spin coating luminescent layer mCP:The chlorobenzene solution of 20%wt polymer Ps 1, solution concentration 10mg/mL, Thickness is about 60nm, and handles 20min on 180 DEG C of hot plate；
E) on luminescent layer, vacuum evaporation is as the TmPyPB of electron transfer layer, and thickness is 40nm；
F) on electron transfer layer, vacuum evaporation electron injecting layer LiF, thickness is 1nm；
G) on electron injecting layer, vacuum evaporation negative electrode Al, thickness is 100nm.
The structure of device is ITO/PEDOT:PSS(60nm)/PVK(30nm)/mCP:20%wt polymer Ps 1 (50nm)/ TmPyPB (40nm)/LiF (1nm)/Al (100nm), spin coating process is carried out in the glove box of high pure nitrogen environment, and vacuum is steamed During plating, pressure<4.0×10-4Pa, the test result of obtained device is shown in Table 2.
The device photoelectric tables of data of table 2
As shown in table 2, device one：Using polymer P 1 as single emitting layer material, device opens bright voltage for 3.9V, maximum Current efficiency is 8.7cd/A, and maximum power efficiency 4.2lm/W, highest external quantum efficiency is 3.2%, in polymer electroluminescence It is excellent that photoelectric properties are showed in material category；Meanwhile, as a comparison, device two：With mCP:20%wt polymer Ps 1 are used as hair Photosphere, device opens bright voltage for 4.0V, opens that bright magnitude of voltage is close with undoped device one, and maximum current efficiency is 12.4cd/A, Maximum power efficiency 5.9lm/W, highest external quantum efficiency is 4.9%, and device photoelectric performance is stable to be lifted.
Preferred embodiments of the present invention are the foregoing is only, are not limitation of the present invention.The present invention is intended to provide one The conjugated polymer electroluminescent organic material that TADF monomers are included by skeleton of acridine is planted, with material system provided by the present invention The electroluminescent device of work, device performance has the space further lifted, other it is any without departing from the present invention Spirit Essences with Change, modification, replacement, combination, the simplification made under principle should be equivalent substitute mode, such as be replaced using other materials PVK is replaced TmPyPB as electron transfer layer, made using other modes adulterated as hole transmission layer using other materials Luminescent layer etc., similar improvement is all it should be understood that belong to the protection category of the present invention.

Claims (8)

1. a kind of conjugated polymer electroluminescent organic material for including TADF monomers by skeleton of acridine, it is characterised in that With the structure shown in formula I:
Wherein, A, B are respectively and independently selected from C1~C10Straight chain or branched alkyl, C1~C10Straight chain containing alkoxy or side chain Alkyl；Ar1Selected from C4~C40Substitution or non-substituted arylamine group, C4~C40Substitution or non-substituted carbazole group, C4~ C40Substitution or non-substituted azophenlyene group, C4~C40Substitution or non-substituted phenthazine group, C4~C40Substitution is non- Substituted phenoxazine group, C4~C40Substitution or non-substituted acridine group or combinations thereof；Ar2Selected from C4~C40Take Generation or non-substituted aryl or heteroaryl；R is TADF monomer structures；0≤X≤0.5；N is 1-100.
2. a kind of hair of the conjugated polymer organic electroluminescence comprising TADF monomers by skeleton of acridine according to claim 1 Luminescent material, it is characterised in that the Ar1Selected from C12~C36Substitution or non-substituted arylamine group, C12~C36Substitution is non- Substituted carbazole group, C12~C36Substitution or non-substituted azophenlyene group, C12~C36Substitution or non-substituted phenothiazinyl Group, C12~C36Substitution or non-substituted phenoxazine group, C12~C36Substitution or non-substituted acridine group or they Combination；Wherein, the substituted carbazole group, substitution azophenlyene group, substitution phenoxazine group, substituted phenothiazine group, substitution a word used for translation Substituent in piperidinyl group is C1~C10Straight chain or branched alkyl, C1~C10Straight chain containing alkoxy or branched alkyl.
3. a kind of conjugated polymer Organic Electricity for including TADF monomers by skeleton of acridine according to claim 1 or 2 Electroluminescent material, it is characterised in that the Ar1One kind in following structure：
In formula, R1For hydrogen, C1~C10Straight chain or branched alkyl, C1~C10Straight chain containing alkoxy or branched alkyl.
4. a kind of hair of the conjugated polymer organic electroluminescence comprising TADF monomers by skeleton of acridine according to claim 1 Luminescent material, it is characterised in that the Ar2Selected from C4~C30Substitution or non-substituted aryl or heteroaryl, wherein, the heteroaryl Hetero atom is the one or more in nitrogen, silicon, sulphur and oxygen in base.
5. a kind of conjugated polymer Organic Electricity for including TADF monomers by skeleton of acridine according to claim 1 or 4 Electroluminescent material, it is characterised in that the Ar2One kind in following structure：
6. a kind of hair of the conjugated polymer organic electroluminescence comprising TADF monomers by skeleton of acridine according to claim 1 Luminescent material, it is characterised in that the one kind of the TADF monomers in following structure：
In formula, R2For hydrogen, C1~C10Straight chain or branched alkyl, C1~C10Straight chain containing alkoxy or branched alkyl.
7. a kind of conjugated polymer for including TADF monomers by skeleton of acridine as described in any one of claim 1,2,4,6 Application of the electroluminescent organic material in organic electroluminescence device.
8. a kind of organic electroluminescence device, it is characterised in that by lower floor to upper strata, is followed successively by ITO Conducting Glass, hole Implanted layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer, cathode layer, wherein, luminescent layer is related to right will Seek the conjugated polymer electroluminescent organic material for including TADF monomers by skeleton of acridine described in 1,2,4,6 any one.
CN201710267279.3A 2017-04-21 2017-04-21 A kind of conjugated polymer electroluminescent organic material and its application and device comprising TADF monomers by skeleton of acridine Pending CN107142103A (en)

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