CN101698796A - Substituted 9,10-dinaphthyl anthracene blue light-emitting organic electro-luminescent material and method for preparing same - Google Patents
Substituted 9,10-dinaphthyl anthracene blue light-emitting organic electro-luminescent material and method for preparing same Download PDFInfo
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- CN101698796A CN101698796A CN200810203245A CN200810203245A CN101698796A CN 101698796 A CN101698796 A CN 101698796A CN 200810203245 A CN200810203245 A CN 200810203245A CN 200810203245 A CN200810203245 A CN 200810203245A CN 101698796 A CN101698796 A CN 101698796A
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Abstract
The invention relates to a blue light-emitting organic electro-luminescent material, in particular to the blue-light-emitting organic electro-luminescent material of 9,10-dinaphthyl anthracene derivatives, which has the following structural formula, wherein R1 and R2 can be methyl, ethyl, isopropyl, tertiary butyl, 4-metrylphenyl and the halides thereof, and can be either the same or different. The invention also provides a method for preparing the substituted anthracene blue light-emitting organic electro-luminescent material. In the invention, through a molecular designing method, some rigid radicals, such as the methyl, the ethyl or the tertiary butyl and the like, are introduced into a major structure of ADN so as to increase the steric hindrance of the ADN, which breaks the symmetry of the AND, increases intervals among molecules and can solve the problem of the shape of a thin film to make the image forms of the thin film of the material obtained better than that prior to and after annealing, achieve the effect of approaching dark blue light; and the efficiency of the material is remarkably improved and is 1.2 to 1.5 times of the traditional efficiency.
Description
Technical field
The present invention relates to a kind of blue organic electroluminescent material, particularly a kind of 9, the blue organic electroluminescent material of 10-dinaphthyl anthracene derivative.
Background technology
Organic light emitting display (be Organic Light Emitting Display, be called for short OLED), it belongs to the kind of new emergence on mobile phone screen, MP3, MP4 screen, be described as " dreamlike indicating meter ".The OLED technique of display is different with traditional LCD display mode, need not backlight, adopt extremely thin coating of organic material and glass substrate, when electric current passes through, these organic materialss will be luminous, therefore the OLED screen can be done lighter and thinnerly, and visible angle is bigger, and can significantly save electric energy.
Though blue light material research is many, existing blue light material all is in various degree in-problem, specific as follows:
(1) works long hours under electric field or in (95 ℃) tempering (annealing) program that heats up, the film morphology rather unstable of blue light material and crystallization easily are difficult to form unbodied film;
(2) the photochromic of classical blue light material all is that green partially (CIEx, y=0.20,0.26) is difficult to reach high color purity and dark blue light effect;
(3) fluorescence quantum efficiency of classical blue light material is all on the low side.
Summary of the invention
Technical problem to be solved by this invention is the problem that the easy crystallization of blue light material under ordinary method is difficult to form amorphous membrance, photochromic green partially problem and efficient problem on the low side.
In order to solve the problems of the technologies described above, replacement anthracene blue-ray organic electroluminescent material of the present invention, its general structure is as follows:
R1 wherein, R2 can be methyl, ethyl, sec.-propyl, the tertiary butyl, 4-aminomethyl phenyl and their halides can be the same or different.
The present invention also provides a kind of preparation method who replaces anthracene blue-ray organic electroluminescent material, may further comprise the steps:
Step 1,2-replace-9,10-two (the 6-halo tertiary butyl-2-naphthalene-)-9,10-glycol synthetic
With the 6-tertiary butyl-2-bromonaphthalene of 0.04-0.06mol, the THF of 40-60ml, blending and stirring, nitrogen protection; After being cooled to-78 ℃, begin to drip the n-Butyl Lithium/hexane solution of calculated amount, the control rate of addition keeps reacting liquid temperature below-70 ℃; Question response liquid during the turbid shape of yellowing, drips and finishes gradually, stirs standby;
The 2-substituted anthraquinone that in another container, adds 0.020-0.027mol, the THF of 70-90ml suffers from altogether and stirs nitrogen protection; After being cooled to-78 ℃, the reaction solution of step 1.1 slowly is transferred in the container of this step, the control reacting liquid temperature continues to stir below-70 ℃, allows it heat up naturally, and reaction is spent the night.
Step 2,9,10-two (the 6-halo tertiary butyl) naphthalene-2-replaces the synthetic of anthracene
0.03-0.04mol two hydrated stannous chloride heating for dissolving are in solvent, standby;
The 4a that in another container, adds 2-5mol, 8a, 9,9a, 10,10a-six hydrogen-2-replaces-9, and (dissolving with the stannous chloride solution impouring in the step 2.1 wherein, is warming up to 100 ℃ to 10-two, stirs for some time for the anthracene-9 of naphthalene-2-), 10-glycol; Filtered while hot, filter cake be with absolute ethanol washing twice, washing once, dry 9,10-two (the 6-tertiary butyl) naphthalene-2-replaces anthracene (1b, 2b, 3b).
It is a kind of 9 that the present invention provides in addition, the luminescent device that 10-two (the 6-tertiary butyl) naphthalene-2-tert-butyl anthracene constitutes, and the thickness of each material is in the device: NPB, 30nm; 2,6-di-t-butyl-9,10-two (the 2-tertiary butyl-6-naphthyl-) anthracene, 30nm; Alq3,30nm; LiF, 0.5nm.
The present invention provides a kind of 9 at last, the preparation method of the luminescent device that 10-two (the 6-tertiary butyl) naphthalene-2-tert-butyl anthracene constitutes, may further comprise the steps: with NPB is hole transmission layer, 9, naphthalene-the 2-tert-butyl anthracene is as luminescent layer for 10-two (the 6-tertiary butyl), and Alq3 is as electron transfer layer, with the ito glass is anode, lithium fluoride is an electron injecting layer, and aluminium is negative electrode, prepares luminescent device by the vacuum evaporation mode.
Pass through said structure, the present invention can reach following effect: pass through molecule design method, in the agent structure of ADN, introduce some rigid radicals, such as methyl, the ethyl or the tertiary butyl wait and increase that it is sterically hindered, destroyed the symmetry of ADN like this, increased the interval between the molecule, can solve the problem of film morphology, make the film image form of film before and after tempering of this material improve, and can reach effect near dark blue light, and material efficiency obviously increases, and can reach original 1.2-1.5 doubly.
Embodiment
Provide preferred embodiment of the present invention below, and described in detail, enable to understand better function of the present invention, characteristics.
In following examples, solvent for use, the catalyzer agent is Chemical Reagent Co., Ltd., Sinopharm Group's commodity, analytical pure AR level.
Product performance test event and testing tool: absorption spectrum is measured by Hitach 330 ultraviolet-visible absorption spectroscopy instrument; Fluorescence spectrum and fluorescence quantum yield are by Hitach F-4500 type fluorescent spectrophotometer assay.
Embodiment 1.1
R
1Be methyl, R
2Synthesis path for the 6-tertiary butyl-2-naphthyl substituted anthracene blue-ray organic electroluminescent material of the tertiary butyl:
(1) 2-methyl-9,10-two (the 6-tertiary butyl-2-naphthalene-)-9,10-glycol synthetic
In being connected to the four-hole round-bottomed flask of constant pressure funnel and thermometer, (15.79g, 0.06mol), THF (60ml) stirs nitrogen protection to add the 6-tertiary butyl-2-bromonaphthalene.The dry ice acetone bath cooling after question response liquid is cooled to-78 ℃, begins to drip the n-Butyl Lithium/hexane solution of calculated amount, and the control rate of addition keeps reacting liquid temperature below-70 ℃.Reaction solution is the turbid shape of yellowing gradually.Drip and finish, stir 0.5hr, standby.In another there-necked flask, add 2-methylanthraquinone (5.56g, 0.027mol), THF (90ml) stirs, nitrogen protection is cooled to-78 ℃ with dry ice acetone bath.With double-ended needle the reaction solution in the four-hole bottle slowly is transferred in the there-necked flask, controls reacting liquid temperature simultaneously below-70 ℃.About 1hr drips complete, continues to stir, and allows it heat up naturally, and reaction is spent the night.The TLC detection reaction.Aftertreatment: in reaction solution impouring 300ml water, with 200mL ethyl acetate extraction twice, merge organic layer, anhydrous magnesium sulfate drying filters, filtrate concentrate faint yellow solid 11.2g, yield 70%.
Synthesizing of (2) 9,10-two (the 6-tertiary butyl) naphthalene-2-methyl anthracene
In the single port bottle of 500mL, (10g 0.04mol), uses Glacial acetic acid (250mL) heating for dissolving, and is standby to add two hydrated stannous chlorides.In another 500mL single port bottle, add 2-methyl-9,10-two (the 6-tertiary butyl-2-naphthalene-)-9, the 10-glycol (18g, 0.03mol), with Glacial acetic acid (100mL) dissolving, with the tin protochloride glacial acetic acid solution impouring that configures wherein, be warming up to 100 ℃, stirred 1 hour.Filtered while hot, filter cake be with absolute ethanol washing twice, washing once, dry white powder 13.36g, yield 80%.
The spectrum property of (3) 9,10-two (the 6-tertiary butyl) naphthalene-2-methyl anthracene
Absorption spectrum λ max=235nm.
Fluorescence spectrum λ max=431nm
Fluorescence quantum yield Φ=1.2
Embodiment 1.2
(1) 2-methyl-9,10-two (the 6-tertiary butyl-2-naphthalene-)-9,10-glycol synthetic
Other condition is constant, changes the 6-tertiary butyl-2-bromonaphthalene into 0.04mol, and THF changes 40ml into, and 2-methylanthraquinone changes 0.022mol into, and the THF that occurs later changes 75ml into, and ethyl acetate changes 150ml into, makes faint yellow solid 7.4g, yield 68%.
Synthesizing of (2) 9,10-two (the 6-tertiary butyl) naphthalene-2-methyl anthracene
Other condition is constant, and two hydrated stannous chlorides change 0.03mol into, 2-methyl-9, and 10-two (the 6-tertiary butyl-2-naphthalene-)-9, the 10-glycol changes 0.03mol into, makes white powder 10.12g, yield 77%.
The spectrum property of (3) 9,10-two (the 6-tertiary butyl) naphthalene-2-methyl anthracene
With embodiment 1.1.
Embodiment 2
R
1Be ethyl, R
2Synthesis path for the replacement anthracene blue-ray organic electroluminescent material of the 6-tertiary butyl-2-naphthyl of the tertiary butyl:
(1) 2-ethyl-9,10-two (the 6-tertiary butyl-2-naphthalene-)-9,10-glycol synthetic
In being connected to the four-hole round-bottomed flask of constant pressure funnel and thermometer, add (15.79g, 0.06mol) the 6-tertiary butyl-2-bromonaphthalene, THF (60mL), stirring, nitrogen protection.The dry ice acetone bath cooling after question response liquid is cooled to-78 ℃, begins to drip the n-Butyl Lithium/hexane solution of calculated amount, and the control rate of addition keeps reacting liquid temperature below-70 ℃.Reaction solution is the turbid shape of yellowing gradually.Drip and finish, stir 0.5hr, standby.In another there-necked flask, add 2-ethyl-anthraquinone (5.56g, 0.027mol), THF (90mL) stirs, nitrogen protection is cooled to-78 ℃ with dry ice acetone bath.With double-ended needle the reaction solution in the four-hole bottle slowly is transferred in the there-necked flask, controls reacting liquid temperature simultaneously below-70 ℃.About 1hr drips complete, continues to stir, and allows it heat up naturally, and reaction is spent the night.The TLC detection reaction.Aftertreatment: in reaction solution impouring 300mL water, with 200mL ethyl acetate extraction twice, merge organic layer, anhydrous magnesium sulfate drying filters, filtrate concentrate faint yellow solid 11.5, yield 70%.
Synthesizing of (2) 9,10-two (the 6-tertiary butyl) naphthalene-2-ethyl anthracene
In the single port bottle of 500mL, (10g 0.04mol), uses Glacial acetic acid (250mL) heating for dissolving, and is standby to add two hydrated stannous chlorides.In another 500mL single port bottle, add 2-ethyl-9,10-two (the 6-tertiary butyl-2-naphthalene-)-9,10-glycol (18g) with Glacial acetic acid (100mL) dissolving, with the tin protochloride glacial acetic acid solution impouring that configures wherein, is warming up to 100 ℃, stirs 1 hour.Filtered while hot, filter cake be with absolute ethanol washing twice, washing once, dry white powder 13.5g, yield 80%.
The spectrum property of (3) 9,10-two (the 6-tertiary butyl) naphthalene-2-ethyl anthracene
Absorption spectrum λ max=235nm.
Fluorescence spectrum λ max=431nm
Embodiment 3
R
1Be sec.-propyl, R
2Synthesis path for the replacement anthracene blue-ray organic electroluminescent material of the 6-tertiary butyl-2-naphthyl of the tertiary butyl:
(1) 2-sec.-propyl-9,10-two (the 6-tertiary butyl-2-naphthalene-)-9,10-glycol synthetic
In being connected to the four-hole round-bottomed flask of constant pressure funnel and thermometer, add (15.79g, 0.06mol) the 6-tertiary butyl-2-bromonaphthalene, THF (60mL), stirring, nitrogen protection.The dry ice acetone bath cooling after question response liquid is cooled to-78 ℃, begins to drip the n-Butyl Lithium/hexane solution of calculated amount, and the control rate of addition keeps reacting liquid temperature below-70 ℃.Reaction solution is the turbid shape of yellowing gradually.Drip and finish, stir 0.5hr, standby.Adding 2-sec.-propyl anthraquinone in another there-necked flask (5.56g, 0.022mol), THF (90mL) stirs, and nitrogen protection is cooled to-78 ℃ with dry ice acetone bath.With double-ended needle the reaction solution in the four-hole bottle slowly is transferred in the there-necked flask, controls reacting liquid temperature simultaneously below-70 ℃.About 1hr drips complete, continues to stir, and allows it heat up naturally, and reaction is spent the night.The TLC detection reaction.Aftertreatment: in reaction solution impouring 300mL water, with 200mL ethyl acetate extraction twice, merge organic layer, anhydrous magnesium sulfate drying filters, filtrate concentrate faint yellow solid 9.59g, yield 70%.
Synthesizing of (2) 9,10-two (the 6-tertiary butyl) naphthalene-2-sec.-propyl anthracene
In the single port bottle of 500mL, (10g 0.04mol), uses Glacial acetic acid (250mL) heating for dissolving, and is standby to add two hydrated stannous chlorides.In another 500mL single port bottle, add 2-sec.-propyl-9,10-two (the 6-tertiary butyl-2-naphthalene-)-9, the 10-glycol (18g, 0.029mol), with Glacial acetic acid (100mL) dissolving, with the tin protochloride glacial acetic acid solution impouring that configures wherein, be warming up to 100 ℃, stirred 1 hour.Filtered while hot, filter cake be with absolute ethanol washing twice, washing once, dry white powder 13.5g, yield 70%.
The spectrum property of (3) 9,10-two (the 6-tertiary butyl) naphthalene-2-sec.-propyl anthracene
Absorption spectrum λ max=235nm.
Fluorescence spectrum λ max=431nm
Embodiment 4
R
1Be the tertiary butyl, R
2Synthesis path for the replacement anthracene blue-ray organic electroluminescent material of the 6-tertiary butyl-2-naphthyl of the tertiary butyl
(1) the 2-tertiary butyl-9,10-two (the 6-tertiary butyl-2-naphthalene-)-9,10-glycol synthetic
In being connected to the four-hole round-bottomed flask of constant pressure funnel and thermometer, (15.79g, 0.06mol), THF (60mL) stirs nitrogen protection to add the 6-tertiary butyl-2-bromonaphthalene.The dry ice acetone bath cooling after question response liquid is cooled to-78 ℃, begins to drip the n-Butyl Lithium/hexane solution of calculated amount, and the control rate of addition keeps reacting liquid temperature below-70 ℃.Reaction solution is the turbid shape of yellowing gradually.Drip and finish, stir 0.5hr, standby.Adding 2-tertiary butyl anthraquinone in another there-necked flask (5.56g, 0.027mol), THF (90mL) stirs, and nitrogen protection is cooled to-78 ℃ with dry ice acetone bath.With double-ended needle the reaction solution in the four-hole bottle slowly is transferred in the there-necked flask, controls reacting liquid temperature simultaneously below-70 ℃.About 1hr drips complete, continues to stir, and allows it heat up naturally, and reaction is spent the night.The TLC detection reaction.Aftertreatment: in reaction solution impouring water (300mL), with 200mL ethyl acetate extraction twice, merge organic layer, anhydrous magnesium sulfate drying filters, filtrate concentrate faint yellow solid 12g, yield 70%.
Synthesizing of (2) 9,10-two (the 6-tertiary butyl) naphthalene-2-tert-butyl anthracene
In the single port bottle of 500mL, (10g 0.04mol), uses Glacial acetic acid (250mL) heating for dissolving, and is standby to add two hydrated stannous chlorides.In another 500mL single port bottle, add the 2-tertiary butyl-9,10-two (the 6-tertiary butyl-2-naphthalene-)-9, the 10-glycol (18g, 0.028mol), with Glacial acetic acid (100mL) dissolving, with the tin protochloride glacial acetic acid solution impouring that configures wherein, be warming up to 100 ℃, stirred 1 hour.Filtered while hot, filter cake be with absolute ethanol washing twice, washing once, dry white powder 13.9g, yield 80%.
The spectrum property of (3) 9,10-two (the 6-tertiary butyl) naphthalene-2-tert-butyl anthracene
Absorption spectrum λ max=234nm.
Fluorescence spectrum λ max=431nm
Embodiment 5
R1 is a trifluoromethyl, and R2 is the synthesis path of replacement anthracene blue-ray organic electroluminescent material of the 6-tertiary butyl-2-naphthyl of the tertiary butyl:
(1), 2-(4-toluyl) is benzoic synthetic
The anhydrous phthalic anhydride, the aluminum chloride of 0.2mol and the phenylfluoroform of 0.6mol that in there-necked flask, add 0.1mol, 50 ℃ of reactions of controlled temperature 4 hours, then product is moved in the beaker 10% the dilute sulphuric acid that is added dropwise to slowly then that ice bath crosses, cooling back filtration under diminished pressure.Filter cake dissolves with 20% sodium hydroxide solution, removes toluene by steam distillation then, distillation back liquid after filtration, behind 10% the sulfuric acid acidation, crystallization filters, last vacuum-drying gets product, yield 91.85%.
(2), 2-trifluoromethyl anthraquinone is synthetic
In there-necked flask, add 2-(4-toluyl) phenylformic acid (0.13mol), with 1,2-ethylene dichloride (30ml), normal temperature drip off in following 30 minutes and add the 25ml vitriol oil, then with 130 ℃ of oil bath heating, react and steamed 1 in 3 hours, 2-ethylene dichloride, final product add in the 200ml frozen water, separate out filtration under diminished pressure behind the throw out, filter cake moves in the beaker, soaks 2 hours with 20% hydroxide, to remove unreacted 2-(4-toluyl) phenylformic acid.Pass through filtration under diminished pressure then, washing, dry yellow product 2-trifluoromethyl anthraquinone, the yield 88% of getting
(3) 2-trifluoromethyl-9,10-two (the 6-tertiary butyl-2-naphthalene-)-9,10-glycol synthetic
In being connected to the four-hole round-bottomed flask of constant pressure funnel and thermometer, (15.79g, 0.06mol), THF (60mL) stirs nitrogen protection to add the 6-tertiary butyl-2-bromonaphthalene.The dry ice acetone bath cooling after question response liquid is cooled to-78 ℃, begins to drip the n-Butyl Lithium/hexane solution of calculated amount, and the control rate of addition keeps reacting liquid temperature below-70 ℃.Reaction solution is the turbid shape of yellowing gradually.Drip and finish, stir 0.5hr, standby.Adding 2-trifluoromethyl anthraquinone in another there-necked flask (6.8g, 0.024mol), THF (90mL) stirs, and nitrogen protection is cooled to-78 ℃ with dry ice acetone bath.With double-ended needle the reaction solution in the four-hole bottle slowly is transferred in the there-necked flask, controls reacting liquid temperature simultaneously below-70 ℃.About 1hr drips complete, continues to stir, and allows it heat up naturally, and reaction is spent the night.In reaction solution impouring water (300mL), with 200mL ethyl acetate extraction twice, merge organic layer, anhydrous magnesium sulfate drying filters, filtrate concentrate faint yellow solid 10.9g, yield 70%.
Synthesizing of (4) 9,10-two (the 6-tertiary butyl) naphthalene-2-trifluoromethyl anthracene
In the single port bottle of 500mL, (10g 0.04mol), uses Glacial acetic acid (250mL) heating for dissolving, and is standby to add two hydrated stannous chlorides.In another 500mL single port bottle, add 2-trifluoromethyl-9,10-two (the 6-tertiary butyl-2-naphthalene-)-9,10-glycol (18g) with Glacial acetic acid (100mL) dissolving, with the tin protochloride glacial acetic acid solution impouring that configures wherein, is warming up to 100 ℃, stirs 1 hour.Filtered while hot, filter cake be with absolute ethanol washing twice, washing once, dry white powder 13.55g, yield 80%.
The spectrum property of (5) 9,10-two (the 6-tertiary butyl) naphthalene-2-tertiary butyl base anthracene:
Absorption spectrum λ max=234nm.
Fluorescence spectrum λ max=440nm
Embodiment 6
The R1 perfluor tertiary butyl, R2 are the synthesis path of replacement anthracene blue-ray organic electroluminescent material of the 6-tertiary butyl-2-naphthyl of the tertiary butyl:
(1) the 2-perfluor tertiary butyl-9,10-two (the 6-tertiary butyl-2-naphthalene-)-9,10-glycol synthetic
In being connected to the four-hole round-bottomed flask of constant pressure funnel and thermometer, (15.79g, 0.06mol), THF (60mL) stirs nitrogen protection to add the 6-tertiary butyl-2-bromonaphthalene.The dry ice acetone bath cooling after question response liquid is cooled to-78 ℃, begins to drip the n-Butyl Lithium/hexane solution of calculated amount, and the control rate of addition keeps reacting liquid temperature below-70 ℃.Reaction solution is the turbid shape of yellowing gradually.Drip and finish, stir 0.5hr, standby.Adding 2-perfluor tertiary butyl anthraquinone in another there-necked flask (6.8g, 0.016mol), THF (90mL) stirs, and nitrogen protection is cooled to-78 ℃ with dry ice acetone bath.With double-ended needle the reaction solution in the four-hole bottle slowly is transferred in the there-necked flask, controls reacting liquid temperature simultaneously below-70 ℃.About 1hr drips complete, continues to stir, and allows it heat up naturally, and reaction is spent the night.In reaction solution impouring water (300mL), with 200mL ethyl acetate extraction twice, merge organic layer, anhydrous magnesium sulfate drying filters, filtrate concentrate faint yellow solid 8.88g, yield 70%.
Synthesizing of (2) 9,10-two (the 6-tertiary butyl) naphthalene-2-perfluor tert-butyl anthracene
In the single port bottle of 500mL, (10g 0.04mol), uses Glacial acetic acid (250mL) heating for dissolving, and is standby to add two hydrated stannous chlorides.In another 500mL single port bottle, add the 2-perfluor tertiary butyl-9,10-two (the 6-tertiary butyl-2-naphthalene-)-9, the 10-glycol (18g, 0.022mol), with Glacial acetic acid (100mL) dissolving, with the tin protochloride glacial acetic acid solution impouring that configures wherein, be warming up to 100 ℃, stirred 1 hour.Filtered while hot, filter cake be with absolute ethanol washing twice, washing once, dry white powder 13.7g, yield 80%.
The spectrum property of (3) 9,10-two (the 6-tertiary butyl) naphthalene-2-perfluor tert-butyl anthracene:
Absorption spectrum λ max=230nm.
Fluorescence spectrum λ max=445nm
Embodiment 7
R1, R2 is the synthesis path of the blue-ray organic electroluminescent material of the perfluoro tertiary butyl:
(1) the 2-perfluor tertiary butyl-9,10-two (the 6-perfluoro tertiary butyl-2-naphthalene-)-9,10-glycol synthetic
In being connected to the four-hole round-bottomed flask of constant pressure funnel and thermometer, (25.5g, 0.06mol), THF (60mL) stirs nitrogen protection to add the 6-perfluoro tertiary butyl-2-bromonaphthalene.The dry ice acetone bath cooling after question response liquid is cooled to-78 ℃, begins to drip the n-Butyl Lithium/hexane solution of calculated amount, and the control rate of addition keeps reacting liquid temperature below-70 ℃.Reaction solution is the turbid shape of yellowing gradually.Drip and finish, stir 0.5hr, standby.Adding 2-perfluor tertiary butyl anthraquinone in another there-necked flask (6.8g, 0.016mol), THF (90mL) stirs, and nitrogen protection is cooled to-78 ℃ with dry ice acetone bath.With double-ended needle the reaction solution in the four-hole bottle slowly is transferred in the there-necked flask, controls reacting liquid temperature simultaneously below-70 ℃.About 1hr drips complete, continues to stir, and allows it heat up naturally, and reaction is spent the night.In reaction solution impouring water (300mL), with 200mL ethyl acetate extraction twice, merge organic layer, anhydrous magnesium sulfate drying filters, filtrate concentrate faint yellow solid 47.15g, yield 70%.
Synthesizing of (2) 9,10-two (the 6-perfluoro tertiary butyl) naphthalene-2-perfluor tert-butyl anthracene
In the single port bottle of 500mL, (10g 0.04mol), uses Glacial acetic acid (250mL) heating for dissolving, and is standby to add two hydrated stannous chlorides.In another 500mL single port bottle, add the 2-perfluor tertiary butyl-9,10-two (the 6-perfluoro tertiary butyl-2-naphthalene-)-9, the 10-glycol (24.7g, 0.022mol), with Glacial acetic acid (100mL) dissolving, with the tin protochloride glacial acetic acid solution impouring that configures wherein, be warming up to 100 ℃, stirred 1 hour.Filtered while hot, filter cake be with absolute ethanol washing twice, washing once, dry white powder 19.1g, yield 80%.
The spectrum property of (3) 9,10-two (the 6-perfluoro tertiary butyl) naphthalene-2-perfluor tert-butyl anthracene:
Absorption spectrum λ max=238nm.
Fluorescence spectrum λ max=440nm
Embodiment 8
R1 is the 4-trifluoromethyl, and R2 is the synthesis path of replacement anthracene blue-ray organic electroluminescent material of the 6-tertiary butyl-2-naphthyl of the tertiary butyl:
(1) 2-(4-trifluoromethyl)-9,10-two (the 6-tertiary butyl-2-naphthalene-)-9,10-glycol synthetic
In being connected to the four-hole round-bottomed flask of constant pressure funnel and thermometer, (15.79g, 0.06mol), THF (60mL) stirs nitrogen protection to add the 6-tertiary butyl-2-bromonaphthalene.The dry ice acetone bath cooling after question response liquid is cooled to-78 ℃, begins to drip the n-Butyl Lithium/hexane solution of calculated amount, and the control rate of addition keeps reacting liquid temperature below-70 ℃.Reaction solution is the turbid shape of yellowing gradually.Drip and finish, stir 0.5hr, standby.Adding 4-trifluoromethyl anthraquinone in another there-necked flask (6.8g, 0.019mol), THF (90mL) stirs, and nitrogen protection is cooled to-78 ℃ with dry ice acetone bath.With double-ended needle the reaction solution in the four-hole bottle slowly is transferred in the there-necked flask, controls reacting liquid temperature simultaneously below-70 ℃.About 1hr drips complete, continues to stir, and allows it heat up naturally, and reaction is spent the night.In reaction solution impouring water (300mL), with 200mL ethyl acetate extraction twice, merge organic layer, anhydrous magnesium sulfate drying filters, filtrate concentrate faint yellow solid 9.7g, yield 70%.
Synthesizing of (2) 9,10-two (the 6-tertiary butyl) naphthalene-2-(4-trifluoromethyl) anthracene
In the single port bottle of 500mL, (10g 0.04mol), uses Glacial acetic acid (250mL) heating for dissolving, and is standby to add two hydrated stannous chlorides.In another 500mL single port bottle, add 2-(4-trifluoromethyl)-9,10-two (the 6-tertiary butyl-2-naphthalene-)-9, the 10-glycol (18g, 0.025mol), with Glacial acetic acid (100mL) dissolving, with the tin protochloride glacial acetic acid solution impouring that configures wherein, be warming up to 100 ℃, stirred 1 hour.Filtered while hot, filter cake be with absolute ethanol washing twice, washing once, dry white powder 13.64g, yield 80%.
The spectrum property of (3) 9,10-two (the 6-tertiary butyl) naphthalene-2-(4-trifluoromethyl) anthracene:
Absorption spectrum λ max=230nm.
Fluorescence spectrum λ max=445nm
In addition, other feasible embodiment are included in the table 1.
Embodiment 9
9, the making and the performance of the luminescent device that 10-two (the 6-tertiary butyl) naphthalene-2-tert-butyl anthracene constitutes
With NPB is hole transmission layer, 9, and 10-two (the 6-tertiary butyl) naphthalene-2-tert-butyl anthracene is as luminescent layer, and Alq3 is anode as electron transfer layer with the ito glass, and lithium fluoride is an electron injecting layer, and aluminium is negative electrode, prepares luminescent device by the vacuum evaporation mode.The thickness of each material is in the device: NPB, 30nm; 2,6-di-t-butyl-9,10-two (the 2-tertiary butyl-6-naphthyl-) anthracene, 30nm; Alq3,30nm; LiF, 0.5nm. are under the operating voltage of 10V, and emission 445nm blue light highly is 3000cd/m2.In the element manufacturing, the chemical structure of used hole transmission layer NPB and electron transfer layer Alq3 is:
Embodiment 10
9, the making and the performance of the luminescent device that 10-two (the 6-tertiary butyl) naphthalene-2-trifluoromethyl anthracene constitutes
The manufacture craft of device is with embodiment 9.Device performance is, under the operating voltage of 8V, and the blue light of emission 440nm, brightness is 5000cd/m2.
Major advantage of the present invention is:
1. synthetic product has been avoided the concentration quenching under high doping that most of electroluminescent organic materials exist, can be directly as the main body luminescent material, thereby can simplify device preparation technology, make device have stability preferably.
2. by the introducing of rigid radical, making the film morphology after the film forming of material is amorphous state, and fluorescence quantum efficiency improves.
3. cost of material is cheap, and reaction is simple, is fit to mass production.
Above-described, be preferred embodiment of the present invention only, be not in order to limiting scope of the present invention, the above embodiment of the present invention can also be made various variations.Be that every simple, equivalence of doing according to the claims and the description of the present patent application changes and modification, all fall into the claim protection domain of patent of the present invention.
Claims (26)
1. one kind replaces anthracene blue-ray organic electroluminescent material, and its general structure is as follows:
R1 wherein, R2 is a methyl, ethyl, sec.-propyl, the tertiary butyl, 4-aminomethyl phenyl or their halides can be the same or different.
2. replacement anthracene blue-ray organic electroluminescent material according to claim 1 is characterized in that, described R1 is a methyl, and R2 is a methyl, ethyl, sec.-propyl, the tertiary butyl, 4-aminomethyl phenyl or their halides.
3. replacement anthracene blue-ray organic electroluminescent material according to claim 2 is characterized in that, described R1 is a methyl, and R2 is the tertiary butyl.
4. replacement anthracene blue-ray organic electroluminescent material according to claim 1 is characterized in that, described R1 is an ethyl, and R2 is a methyl, ethyl, sec.-propyl, the tertiary butyl, 4-aminomethyl phenyl or their halides.
5. replacement anthracene blue-ray organic electroluminescent material according to claim 4 is characterized in that, described R1 is an ethyl, and R2 is the tertiary butyl.
6. replacement anthracene blue-ray organic electroluminescent material according to claim 1 is characterized in that, described R1 is a sec.-propyl, and R2 is a methyl, ethyl, sec.-propyl, the tertiary butyl, 4-aminomethyl phenyl or their halides.
7. replacement anthracene blue-ray organic electroluminescent material according to claim 6 is characterized in that, described R1 is a sec.-propyl, and R2 is the tertiary butyl.
8. replacement anthracene blue-ray organic electroluminescent material according to claim 1 is characterized in that, described R1 is the tertiary butyl, and R2 is a methyl, ethyl, sec.-propyl, the tertiary butyl, 4-aminomethyl phenyl or their halides.
9. replacement anthracene blue-ray organic electroluminescent material according to claim 8 is characterized in that, described R1 is the tertiary butyl, and R2 is the tertiary butyl.
10. replacement anthracene blue-ray organic electroluminescent material according to claim 1 is characterized in that, described R1 is a trifluoromethyl, and R2 is a methyl, ethyl, sec.-propyl, the tertiary butyl, 4-aminomethyl phenyl or their halides.
11. replacement anthracene blue-ray organic electroluminescent material according to claim 10 is characterized in that, described R1 is a trifluoromethyl, and R2 is the tertiary butyl.
12. replacement anthracene blue-ray organic electroluminescent material according to claim 1 is characterized in that, described R1 is the perfluor tertiary butyl, and R2 is a methyl, ethyl, sec.-propyl, the tertiary butyl, 4-aminomethyl phenyl or their halides.
13. replacement anthracene blue-ray organic electroluminescent material according to claim 12 is characterized in that, described R1 is the perfluor tertiary butyl, and R2 is the tertiary butyl.
14. replacement anthracene blue-ray organic electroluminescent material according to claim 12 is characterized in that, described R1 is the perfluor tertiary butyl, and R2 is the perfluor tertiary butyl.
15. replacement anthracene blue-ray organic electroluminescent material according to claim 1 is characterized in that, described R1 is the 4-trifluoromethyl, and R2 is a methyl, ethyl, sec.-propyl, the tertiary butyl, 4-aminomethyl phenyl or their halides.
16. replacement anthracene blue-ray organic electroluminescent material according to claim 15 is characterized in that, described R1 is the 4-trifluoromethyl, and R2 is the tertiary butyl.
17. a preparation method who replaces anthracene blue-ray organic electroluminescent material may further comprise the steps:
Step 1,2-replace-9,10-two (the 6-halo tertiary butyl-2-naphthalene-)-9,10-glycol synthetic;
Step 2,9,10-two (the 6-halo tertiary butyl) naphthalene-2-replaces the synthetic of anthracene.
18. preparation method according to claim 17 is characterized in that, described step 1 specifically comprises:
Step 1.1, with the 6-tertiary butyl-2-bromonaphthalene of 0.04-0.06mol, the THF of 40-60ml, blending and stirring, nitrogen protection; After being cooled to-78 ℃, begin to drip the n-Butyl Lithium/hexane solution of calculated amount, the control rate of addition keeps reacting liquid temperature below-70 ℃; Question response liquid during the turbid shape of yellowing, drips and finishes gradually, stirs standby;
Step 1.2, add the 2-substituted anthraquinone of 0.020-0.027mol in another container, the THF of 70-90ml suffers from altogether and stirs nitrogen protection; After being cooled to-78 ℃, the reaction solution of step 1.1 slowly is transferred in the container of this step, the control reacting liquid temperature continues to stir below-70 ℃, allows it heat up naturally, and reaction is spent the night.
19. preparation method according to claim 18 is characterized in that, adds post-processing step 1.3 after step 1.2, comprising:
In reaction solution impouring water, with 150-200ml ethyl acetate extraction twice, merge organic layer, anhydrous magnesium sulfate drying filters, and filtrate concentrates to such an extent that 2-replaces-9,10-two (the 6-tertiary butyl-2-naphthalene-)-9,10-glycol.
20. preparation method according to claim 17 is characterized in that, described step 2 specifically comprises:
Step 2.1, with 0.03-0.04mol two hydrated stannous chloride heating for dissolving in solvent, standby;
Step 2.2, in another container, add the 4a of 0.02-0.03mol, 8a, 9,9a, 10,10a-six hydrogen-2-replace-9,10-two (anthracene-9 of naphthalene-2-), 10-glycol, dissolving with the stannous chloride solution impouring in the step 2.1 wherein, is warming up to 100 ℃, stirs for some time; Filtered while hot, filter cake be with absolute ethanol washing twice, washing once, dry 9,10-two (the 6-tertiary butyl) naphthalene-2-replaces anthracene (1b, 2b, 3b).
21. preparation method according to claim 18 is characterized in that, the 6-tertiary butyl-2-bromonaphthalene described in the step 1.1 is 0.06mol, and THF is 60ml; 2-substituted anthraquinone described in the step 1.2 is 0.027mol, and THF is 90ml.
22. method according to claim 20, its feature with, two hydrated stannous chlorides described in the step 2.1 are 0.04mol, the 4a described in the step 2.2,8a, 9,9a, 10,10a-six hydrogen-2-replace-9, and (anthracene-9 of naphthalene-2-), the 10-glycol is 0.028mol to 10-two.
23. according to the arbitrary described preparation method of claim 17-22, it is characterized in that, after step 2, also comprise:
Step 3, detection 9, the spectrum property of 10-two (the 6-halo tertiary butyl) naphthalene-2-sec.-propyl anthracene.
24. according to the described preparation method of claim 17-22, it is characterized in that, before step 1, comprise:
The benzoic synthetic and 2-trifluoromethyl anthraquinone of 2-(4-toluyl) synthetic.
25. one kind 9, the luminescent device that 10-two (the 6-tertiary butyl) naphthalene-2-tert-butyl anthracene constitutes, the thickness of each material is in the device: NPB, 30nm; 2,6-di-t-butyl-9,10-two (the 2-tertiary butyl-6-naphthyl-) anthracene, 30nm; Alq3,30nm; LiF, 0.5nm.
26. one kind 9, the preparation method of the luminescent device that 10-two (the 6-tertiary butyl) naphthalene-2-tert-butyl anthracene constitutes may further comprise the steps:
With NPB is hole transmission layer, 9, and 10-two (the 6-tertiary butyl) naphthalene-2-tert-butyl anthracene is as luminescent layer, and Alq3 is anode as electron transfer layer with the ito glass, and lithium fluoride is an electron injecting layer, and aluminium is negative electrode, prepares luminescent device by the vacuum evaporation mode.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101864295A (en) * | 2010-06-28 | 2010-10-20 | 彩虹集团公司 | Small molecular blue light material and preparation method thereof |
| CN101875595A (en) * | 2010-06-09 | 2010-11-03 | 黑龙江省科学院石油化学研究院 | Method for synthesizing 9,10-dinaphthyl anthracene |
| CN110627601A (en) * | 2018-06-22 | 2019-12-31 | 天津大学 | Organic photoelectric semiconductor material and preparation method and application thereof |
| CN112552137A (en) * | 2020-12-09 | 2021-03-26 | 黑龙江省科学院石油化学研究院 | Organic electroluminescent intermediate material and synthetic method thereof |
-
2008
- 2008-11-24 CN CN200810203245A patent/CN101698796A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101875595A (en) * | 2010-06-09 | 2010-11-03 | 黑龙江省科学院石油化学研究院 | Method for synthesizing 9,10-dinaphthyl anthracene |
| CN101864295A (en) * | 2010-06-28 | 2010-10-20 | 彩虹集团公司 | Small molecular blue light material and preparation method thereof |
| CN101864295B (en) * | 2010-06-28 | 2013-03-27 | 彩虹集团公司 | Small molecular blue light material and preparation method thereof |
| CN110627601A (en) * | 2018-06-22 | 2019-12-31 | 天津大学 | Organic photoelectric semiconductor material and preparation method and application thereof |
| CN112552137A (en) * | 2020-12-09 | 2021-03-26 | 黑龙江省科学院石油化学研究院 | Organic electroluminescent intermediate material and synthetic method thereof |
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Application publication date: 20100428 |