CN104629730A - Blue light organic electroluminescent material, preparation method and applications thereof - Google Patents

Abstract

The invention belongs to the field of organic electroluminescent materials, and discloses a blue light organic electroluminescent material, a preparation method and applications thereof, wherein the structure formula of the material is defined in the instruction. According to the blue light organic electroluminescent material of the present invention, the luminescence is at the blue light region, the material has the high fluorescence quantum yield, and the luminous efficiency of the organic electroluminescent device adopting the material as the luminous layer material is high.

Description

Blue-ray organic electroluminescent material and its preparation method and application

Technical field

The present invention relates to field of organic electroluminescent materials, particularly relate to a kind of blue-ray organic electroluminescent material and its preparation method and application.

Background technology

Since the first times such as C.W.Tang report Organic Light Emitting Diode (OLED), no matter be small molecules or polymer LED, all achieved huge development.Its potential application is full color flat-panel monitor and solid-state white illumination.In three primary colours, ruddiness and green diode are all close to the requirement of practical application, but blue light material is due to greater band gap, and lower highest occupied molecular orbital (HOMO) energy level, therefore there is larger carrier injection energy barrier; Meanwhile, because emitted energy is high, unstable, easily energy trasfer occurs and cause transmitting look impure, so development is relatively slow.The blue light emitting material of research and development high-level efficiency, high stable performance, remains a difficult problem.

In the exploitation of material, have two kinds of thinkings available, one is research and develop novel blue phosphor materials, and another is the blue fluorescent material of development of new.One large advantage of fluorescent material is stable, and efficiency decay is severe unlike phosphorescent devices.Many novel blue fluorescent materials have been had to be seen in report, as: toluylene benzene class (DSA), pyridine beryllium title complex, many phenyl substituted benzene, fluorenes class, especially with spiral shell fluorene derivatives, anthracene derivative and fluorenes anthracene hybrid.Recently, Lyu etc. report the anthracene derivative that a class take tetraphenyl-silicon as core, and this compounds has higher second-order transition temperature (T _g=102 ~ 177 DEG C), and there is higher purity of color, its doping device efficiency is up to 7.5cd/A, and emission peak is at 460nm.Although many blue light materials are in the news, high-level efficiency, the material that emitting performance is stable or few.

Summary of the invention

Problem to be solved by this invention is better heat stability and the higher blue-ray organic electroluminescent material of luminous efficiency.

For achieving the above object, blue-ray organic electroluminescent material provided by the invention, its structure is such as formula as follows:

i.e. 10,10 '-(benzo [k] fluoranthene-7,12-bis-base) two (N, N-diphenylanthrancene-9-amine).

Another object of the present invention is to provide the preparation method of the blue-ray organic electroluminescent material that a kind of synthetic route is simple, material is cheap and easy to get, described preparation method comprises the steps:

The compd A providing following structural formula to represent respectively and B,

Under oxygen-free environment, compd A and B are added in the organic solvent containing catalyzer and alkaline solution and dissolve, compd A and B mol ratio are 1:2 ~ 2.4, the mixing solutions obtained after dissolving carries out Suzuki coupling reaction 12 ~ 48 hours at 70 ~ 130 DEG C, stopped reaction cool to room temperature, separating-purifying reaction solution, obtains blue-ray organic electroluminescent material described in following structural formula:

Wherein, described catalyzer is bis-triphenylphosphipalladium palladium dichloride or tetra-triphenylphosphine palladium; Or,

Described catalyzer is the mixture of organic palladium and organophosphorus ligand, and the mol ratio of described organic palladium and organophosphorus ligand is 1:4 ~ 8; Preferably, described organic palladium is palladium or three or two argon benzyl acetone two palladiums, and described organophosphorus ligand is three (o-methyl-phenyl-) phosphines or 2-dicyclohexyl phosphine-2 ', 6 '-dimethoxy-biphenyl; More preferably, described mixture is the mixture of palladium and tri-o-tolyl phosphine, or described mixture is three or two argon benzyl acetone two palladiums and 2-dicyclohexyl phosphine-2 ', the mixture of 6 '-dimethoxy-biphenyl.

The mol ratio of described catalyzer and described compd A is 1:20 ~ 1:100.

In described preparation method, described alkaline solution is selected from least one in sodium carbonate solution, solution of potassium carbonate and sodium hydrogen carbonate solution; In described alkaline solution, the mol ratio of alkali solute and described compd A is 20:1.

In a preferred embodiment, organic solvent is selected from least one in toluene, DMF, tetrahydrofuran (THF).

In a preferred embodiment, the temperature of reaction of Suzuki coupling reaction is 90 ~ 120 DEG C, and the reaction times is 24 ~ 36 hours.

In a preferred embodiment, described separating-purifying reaction solution comprises:

After Suzuki coupling reaction stops, with dichloromethane extraction reaction solution repeatedly and merge organic phase, after this organic phase is spin-dried for after anhydrous magnesium sulfate drying, obtain crude product, this crude product adopts volume ratio to be that sherwood oil and the ethyl acetate of 10:1 mixes leacheate and be separated through silica gel column chromatography and obtain crystalline substance, this crystalline substance, under vacuo after 50 DEG C of dry 24h, obtains described blue-ray organic electroluminescent material.

In described preparation method, oxygen-free environment is made up of at least one gas in argon gas, nitrogen.

Above-mentioned preparation method's principle is simple, easy and simple to handle, low for equipment requirements, can wide popularization and application.

Another object of the present invention is to provide the application of above-mentioned blue-ray organic electroluminescent material in organic electroluminescence device luminescent layer.

The structure of this organic electroluminescence device comprises conductive anode substrate and is sequentially laminated on the hole transmission layer of conductive anode substrate, luminescent layer, electric transmission/hole blocking layer, electron injecting layer, cathode layer; Wherein:

Conductive anode substrate comprises with substrate of glass, and is deposited on the conductive anode layer of glass basic surface, and the material changing conductive anode layer is indium tin oxide (ITO), and therefore, this conductive anode substrate is also called ito glass;

The material of hole transmission layer is N, N '-two [(1-naphthyl)-N, N '-phenylbenzene]-1,1 '-xenyl-4,4 '-diamines (NPD);

The material of luminescent layer is blue-ray organic electroluminescent material described above, namely 10,10 '-(benzo [k] fluoranthene-7,12-bis-base) two (N, N-diphenylanthrancene-9-amine) dopant mixture that forms of 4,4'-two [4-(di-p-tolyl is amino) styryl] biphenyl (DPAVBi) of 5% mass percent of adulterating;

The material of electric transmission/hole blocking layer is 2,9-dimethyl-4,7-phenylbenzene-1,10-phenanthroline (BCP);

The material of electron injecting layer is LiF;

The material of cathode layer is Al.

The present invention has the following advantages:

In blue-ray organic electroluminescent material provided by the invention, benzofluoranthrene has higher fluorescence quantum yield and good thermostability; Pentanoic has excellent hole transport performance.Therefore this blue-ray organic electroluminescent material emitted energy is high, and the device light emitting efficiency based on this material is higher.

The preparation method of above-mentioned blue-ray organic electroluminescent material, have employed better simply synthetic route, thus reduces technical process, and starting material are cheap and easy to get, and manufacturing cost is reduced:

Accompanying drawing explanation

Fig. 1 is the thermogravimetic analysis (TGA) figure of the blue-ray organic electroluminescent material that embodiment 1 obtains;

Fig. 2 is the organic electroluminescence device structural representation that embodiment 5 obtains.

Embodiment

In order to understand the content of patent of the present invention better, technology case of the present invention is further illustrated below by concrete example and legend, specifically comprise material preparation and device preparation, but these embodiments do not limit the present invention, wherein compd A, compd B are all purchased from scientific and technological in lark prestige.

Embodiment 1: the blue-ray organic electroluminescent material of the present embodiment, i.e. 10,10 '-(benzo [k] fluoranthene-7,12-bis-base) two (N, N-diphenylanthrancene-9-amine), preparation process is as follows:

Under argon shield, 7,12-dibromo benzo [k] fluoranthene (82mg, 0.2mmol), 10-(diphenylamine) anthracene-9-boric acid (156mg, 0.4mmol) adds in the flask filling 10ml toluene solvant, by salt of wormwood (2mL after fully dissolving, 2mol/L) solution joins in flask, vacuumize deoxygenation and be filled with argon gas, then adding bis-triphenylphosphipalladium palladium dichloride (5.6mg, 0.008mmol); Flask is heated to 120 DEG C and carries out Suzuki coupling reaction 24h.Stopped reaction cool to room temperature, with dichloromethane extraction reaction solution repeatedly and merge organic phase, after this organic phase is spin-dried for after anhydrous magnesium sulfate drying, obtain crude product, this crude product adopts volume ratio to be that sherwood oil and the ethyl acetate of 10:1 mixes leacheate and be separated through silica gel column chromatography and obtain crystalline substance, this crystalline substance, under vacuo after 50 DEG C of dry 24h, obtains described blue-ray organic electroluminescent material.Productive rate is 81%.Mass spectrum: m/z939.2(M ⁺+ 1); Ultimate analysis (%) C ₇₂h ₄₆n ₂: theoretical value: C92.08, H4.94, N2.98; Measured value: C92.15, H4.89, N2.92.

Fig. 1 is the thermogravimetic analysis (TGA) figure of the blue-ray organic electroluminescent material that embodiment 1 obtains; Thermogravimetic analysis (TGA) is completed by the measurement of Perkin-Elmer Series7 Thermo System, and all measurements all complete in atmosphere at room temperature.As shown in Figure 1, the thermal weight loss temperature (T of blue-ray organic electroluminescent material 5% _d) be 407 DEG C.

Embodiment 2: the blue-ray organic electroluminescent material of the present embodiment, its structure is 10,10 '-(benzo [k] fluoranthene-7,12-bis-base) two (N, N-diphenylanthrancene-9-amine), and preparation process is as follows:

Under nitrogen and argon gas gas mixture are protected; by 7; 12-dibromo benzo [k] fluoranthene (123mg; 0.3mmol), 10-(diphenylamine) anthracene-9-boric acid (257mg; 0.66mmol) add in the two-mouth bottle of 50mL specification with 15mL tetrahydrofuran (THF); after the gas mixture air-discharging passing into nitrogen and argon gas after abundant dissolving is about 20min; then by tetra-triphenylphosphine palladium (4mg; 0.003mmol) add wherein; sodium bicarbonate (3mL, 2mol/L) solution is added again after abundant dissolving.After the gas mixture air-discharging of fully logical nitrogen and argon gas is about 10min again, two-mouth bottle is joined 70 DEG C and carry out Suzuki coupling reaction 48h.Stopped reaction cool to room temperature, with dichloromethane extraction reaction solution repeatedly and merge organic phase, after this organic phase is spin-dried for after anhydrous magnesium sulfate drying, obtain crude product, this crude product adopts volume ratio to be that sherwood oil and the ethyl acetate of 10:1 mixes leacheate and be separated through silica gel column chromatography and obtain crystalline substance, this crystalline substance, under vacuo after 50 DEG C of dry 24h, obtains described blue-ray organic electroluminescent material.Productive rate is 77%.

Embodiment 3: the blue-ray organic electroluminescent material of the present embodiment, its structure is 10,10 '-(benzo [k] fluoranthene-7,12-bis-base) two (N, N-diphenylanthrancene-9-amine), and preparation process is as follows:

Under nitrogen protection, by 7,12-dibromo benzo [k] fluoranthene (123mg, 0.3mmol), 10-(diphenylamine) anthracene-9-boric acid (280mg, 0.72mmol), palladium (3.5mg, 0.015mmol) He three (o-methyl-phenyl-) phosphine (21mg, 0.06mmol) join the N filling 12mL, in the flask of dinethylformamide, salt of wormwood (3mL is added after abundant dissolving, 2mol/L) solution, after in flask, logical nitrogen purge gas is about 30min subsequently; Flask is heated to 130 DEG C and carries out Suzuki coupling reaction 12h.Stopped reaction cool to room temperature, with dichloromethane extraction reaction solution repeatedly and merge organic phase, after this organic phase is spin-dried for after anhydrous magnesium sulfate drying, obtain crude product, this crude product adopts volume ratio to be that sherwood oil and the ethyl acetate of 10:1 mixes leacheate and be separated through silica gel column chromatography and obtain crystalline substance, this crystalline substance, under vacuo after 50 DEG C of dry 24h, obtains described blue-ray organic electroluminescent material.Productive rate is 80%.

Embodiment 4: the blue-ray organic electroluminescent material of the present embodiment, its structure is 10,10 '-(benzo [k] fluoranthene-7,12-bis-base) two (N, N-diphenylanthrancene-9-amine), and preparation process is as follows:

Under nitrogen protection; by 7; 12-dibromo benzo [k] fluoranthene (123mg; 0.3mmol), 10-(diphenylamine) anthracene-9-boric acid (280mg; 0.72mmol), three or two argon benzyl acetone two palladium (9mg; 0.009mmol) with 2-dicyclohexyl phosphine-2 '; 6 '-dimethoxy-biphenyl (29mg; 0.072mmol) join the N filling 12mL; in the flask of dinethylformamide; sodium carbonate (3mL, 2mol/L) solution is added after abundant dissolving.After in flask, logical nitrogen purge gas is about 30min subsequently; Flask is heated to 90 DEG C and carries out Suzuki coupling reaction 36h.Stopped reaction cool to room temperature, with dichloromethane extraction reaction solution repeatedly and merge organic phase, after this organic phase is spin-dried for after anhydrous magnesium sulfate drying, obtain crude product, this crude product adopts volume ratio to be that sherwood oil and the ethyl acetate of 10:1 mixes leacheate and be separated through silica gel column chromatography and obtain crystalline substance, this crystalline substance, under vacuo after 50 DEG C of dry 24h, obtains described blue-ray organic electroluminescent material.Productive rate is 87%.

Embodiment 5:

The present embodiment is organic electroluminescence device, and the material of main part of its luminescent layer is the blue-ray organic electroluminescent material that the present invention obtains, i.e. 10,10 '-(benzo [k] fluoranthene-7,12-bis-base) two (N, N-diphenylanthrancene-9-amine).

As shown in Figure 2, the structure of this organic electroluminescence device comprises conductive anode substrate 1 and is sequentially laminated on the hole transmission layer 2 of conductive anode substrate, luminescent layer 3, electric transmission/hole blocking layer 4, electron injecting layer 5, cathode layer 6; Wherein:

Conductive anode substrate 1 comprises with substrate of glass, and is deposited on the conductive anode layer of glass basic surface, and the material changing conductive anode layer is indium tin oxide (ITO), and therefore, this conductive anode substrate is also called ito glass;

The material of hole transmission layer 2 is N, N '-two [(1-naphthyl)-N, N '-phenylbenzene]-1,1 '-xenyl-4,4 '-diamines (NPD);

The material of luminescent layer 3 is with 10,10 '-(benzo [k] fluoranthene-7,12-bis-base) two (N, N-diphenylanthrancene-9-amine) (representing with P) be material of main part, to adulterate 4 of 5% mass percent, the dopant mixture of the guest materials composition of 4'-two [4-(di-p-tolyl is amino) styryl] biphenyl (DPAVBi), is expressed as P:DPAVBi;

The material of electric transmission/hole blocking layer 4 is 2,9-dimethyl-4,7-phenylbenzene-1,10-phenanthroline (BCP);

The material of electron injecting layer 5 is LiF;

The material of cathode layer 6 is Al.

The concrete grammar that electroluminescent device makes is:

Evaporation hole transmission layer (NPD), luminescent layer (P:DPAVBi) is stacked gradually, electric transmission/hole blocking layer (BCP), electron injecting layer (LiF), cathode layer (Al) on conductive anode layer (ITO) surface of the conductive anode substrate through cleaning.Therefore also can being expressed as of this organic electroluminescence device structure:

Glass/ITO(150nm)/NPD (20nm)/P:DPAVBi(20nm)/BCP (30nm)/LiF (1.5nm)/Al (150nm); Wherein, brace represents laminate structure, and the numerical value in bracket is the one-tenth-value thickness 1/10 of each functional layer.

Wiping is carried out to the current versus brightness-voltage characteristic of this organic electroluminescence device, test completes by with Keithley source measuring system (Keithley2400Sourcemeter, Keithley2000Cuirrentmeter) correcting silicon photoelectric diode, and all measurements all complete in atmosphere at room temperature.Test result shows: the trigger voltage of device is 3.9V, at 1000cd/m ²brightness under, luminous efficiency is 4.2lm/W.

The above embodiment only have expressed several embodiment of the present invention, and it describes comparatively concrete and detailed, but therefore can not be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be as the criterion with claims.

Claims (10)

1. a blue-ray organic electroluminescent material, is characterized in that, its structure is such as formula as follows:

2. a preparation method for blue-ray organic electroluminescent material as claimed in claim 1, is characterized in that, its step is as follows:

The compd A providing following structural formula to represent respectively and B,

Under oxygen-free environment, compd A and B are added in the organic solvent containing catalyzer and alkaline solution and dissolve, compd A and B mol ratio are 1:2 ~ 2.4, the mixing solutions obtained carries out Suzuki coupling reaction 12 ~ 48 hours at 70 ~ 130 DEG C, stopped reaction cool to room temperature, separating-purifying reaction solution, obtains the described blue-ray organic electroluminescent material described in following structural formula:

3. the preparation method of blue-ray organic electroluminescent material according to claim 2, is characterized in that, described catalyzer is bis-triphenylphosphipalladium palladium dichloride or tetra-triphenylphosphine palladium; The mol ratio of described catalyzer and described compd A is 1:20 ~ 1:100.

4. the preparation method of blue-ray organic electroluminescent material according to claim 2, is characterized in that, described catalyzer is the mixture of organic palladium and organophosphorus ligand, and the mol ratio of described organic palladium and organophosphorus ligand is 1:4 ~ 8; The mol ratio of described catalyzer and described compd A is 1:20 ~ 1:100.

5. the preparation method of blue-ray organic electroluminescent material according to claim 4, it is characterized in that, described organic palladium is palladium or three or two argon benzyl acetone two palladiums, described organophosphorus ligand is three (o-methyl-phenyl-) phosphines or 2-dicyclohexyl phosphine-2 ', 6 '-dimethoxy-biphenyl.

6. the preparation method of blue-ray organic electroluminescent material according to claim 5, it is characterized in that, described mixture is the mixture of palladium and tri-o-tolyl phosphine, or described mixture is three or two argon benzyl acetone two palladiums and 2-dicyclohexyl phosphine-2 ', the mixture of 6 '-dimethoxy-biphenyl.

7. the preparation method of blue-ray organic electroluminescent material according to claim 2, is characterized in that, described alkaline solution is selected from least one in sodium carbonate solution, solution of potassium carbonate and sodium hydrogen carbonate solution; In described alkaline solution, the mol ratio of alkali solute and described compd A is 20:1.

8. the preparation method of blue-ray organic electroluminescent material according to claim 2, is characterized in that, described organic solvent is selected from as at least one in toluene, DMF, tetrahydrofuran (THF).

9. the preparation method of blue-ray organic electroluminescent material according to claim 2, is characterized in that, described separating-purifying reaction solution comprises:

After Suzuki coupling reaction stops, with dichloromethane extraction reaction solution repeatedly and merge organic phase, after this organic phase is spin-dried for after anhydrous magnesium sulfate drying, obtain crude product, this crude product adopts volume ratio to be that sherwood oil and the ethyl acetate of 10:1 mixes leacheate and be separated through silica gel column chromatography and obtain crystalline substance, this crystalline substance, under vacuo after 50 DEG C of dry 24h, obtains described blue-ray organic electroluminescent material.

10. the application of blue-ray organic electroluminescent material as claimed in claim 1 in organic electroluminescence device luminescent layer.