CN104003950A - Organic electroluminescence phosphorescence host material, preparation method thereof and organic electroluminescence device - Google Patents

Organic electroluminescence phosphorescence host material, preparation method thereof and organic electroluminescence device Download PDF

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CN104003950A
CN104003950A CN201310055323.6A CN201310055323A CN104003950A CN 104003950 A CN104003950 A CN 104003950A CN 201310055323 A CN201310055323 A CN 201310055323A CN 104003950 A CN104003950 A CN 104003950A
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organic
preparation
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compd
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周明杰
王平
梁禄生
张振华
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Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Engineering Co Ltd
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Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Engineering Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
    • C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
    • C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D251/14—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom
    • C07D251/24—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom to three ring carbon atoms
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H10K85/626—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing more than one polycyclic condensed aromatic rings, e.g. bis-anthracene
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
    • H10K85/633—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising polycyclic condensed aromatic hydrocarbons as substituents on the nitrogen atom
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/654—Aromatic compounds comprising a hetero atom comprising only nitrogen as heteroatom

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  • Materials Engineering (AREA)
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  • Electroluminescent Light Sources (AREA)

Abstract

The invention provides an organic electroluminescence phosphorescence host material, a preparation method thereof and an organic electroluminescence device. The organic electroluminescence phosphorescence host material is shown as the following structural formula (please see the formula in the specification), the structural formula of Ar is shown as follows in the specification, and the organic electroluminescence phosphorescence host material is obtained through a coupled reaction. The organic electroluminescence phosphorescence host material includes a triazine group and an aniline group, the material has good hole transport performance and electrical transmission performance, when the material is applied to the field of the organic electroluminescence device, the device has high heat stability and luminous efficiency, and the service life of the luminescent device can be better prolonged.

Description

A kind of organic electrophosphorescenpolymer material of main part and preparation method thereof and organic electroluminescence device
Technical field
The present invention relates to field of photovoltaic materials, particularly relate to a kind of organic electrophosphorescenpolymer material of main part and preparation method thereof and organic electroluminescence device.
Background technology
Along with the development of information age, the organic EL display (OLEDs) of efficient, energy-conservation, lightweight and big area white-light illuminating more and more receive people's concern.OLED technology is paid close attention to by global scientist, and relevant enterprise and laboratory are all in the research and development of carrying out this technology.As a kind of novel LED technology, there is active illuminating and light, thin, good contrast, energy consumption organic electroluminescence device low, that can be made into the features such as flexible device has proposed higher requirement to organic semiconductor material.
1987, the Tang of Eastman Kodak company of the U.S. and VanSlyke reported the breakthrough in organic electroluminescent research, and will realize the application purposes such as panchromatic demonstration and illumination, and luminescent device must have certain efficiency and life-span.Organic electrophosphorescenpolymer material of main part thermally-stabilised and that luminous efficiency is high lacks at present, and this has influence on life-span and the development thereof of organic electroluminescence device.
Summary of the invention
The problem lacking for solving the organic electrophosphorescenpolymer material of main part of above-mentioned efficient stable, the present invention aims to provide a kind of organic electrophosphorescenpolymer material of main part that contains triazine group and aniline group, this organic electrophosphorescenpolymer material of main part has good hole transport performance and electronic transmission performance, in the time being applied to organic electroluminescence device field, device has higher thermostability and luminous efficiency, is beneficial to the work-ing life that extends luminescent device.
The organic electroluminescence device that the present invention also provides the preparation method of this organic electrophosphorescenpolymer material of main part and contains this organic electrophosphorescenpolymer material of main part.
First aspect, the invention provides a kind of organic electrophosphorescenpolymer material of main part, and described organic electrophosphorescenpolymer material of main part is the compound M shown in following structural formula:
Wherein, Ar is
In the present invention, contain triazine group and aniline group in organic electrophosphorescenpolymer material of main part, triazine is the 6-membered heterocyclic compound containing 3 nitrogen-atoms, be a short of electricity daughter, and aniline structure is a kind of electron rich body; In a structure, contain electron rich and electron deficiency structure, this material has the performance of good transporting holes and electronics simultaneously; The material of main part that this organic electrophosphorescenpolymer material of main part can be used as blue light electroluminescence phosphorescence uses, and in the time being applied to organic electroluminescence device field, is conducive to the charge balance of current carrier at recombination region, makes device obtain high luminous efficiency; Triazine is connected with the mode that arylamine is connected with position between phenyl simultaneously, makes material there is higher triplet.
Second aspect, the invention provides the preparation method of above-mentioned organic electrophosphorescenpolymer material of main part, comprises the steps:
The compd A and the compd B that provide respectively following structural formula to represent:
Wherein, Ar is
In atmosphere of inert gases, described compd A and described compd B for joining in organic solvent, 1:3～1:4.5 are dissolved in molar ratio, then add successively catalyzer and basic solution to form reaction solution, reaction solution is 75～185 DEG C in temperature and carries out linked reaction 24～72 hours, make the following organic electrophosphorescenpolymer material of main part of structural formula, i.e. compound M:
Wherein, Ar is
Preferably, described catalyzer is copper (Cu), cuprous iodide (CuI) or organic palladium.
Preferably, described organic palladium is two (dibenzalacetone) palladium (Pd (dba) 2) or palladium (Pd (OAc) 2), when catalyzer is Pd (dba) 2time, add tri-butyl phosphine (Pt-Bu 3) as promotor, when catalyzer is Pd (OAc) 2time, add three tertiary butyl phosphorus a tetrafluoro borates (t-Bu) 3pHBF 4) as promotor.
Preferably, described Pd (dba) 2and Pt-Bu 3mol ratio be 1:2～1:5, described Pd (OAc) 2(t-Bu) 3pHBF 4mol ratio be 1:2～1:5.
Preferably, in the time that catalyzer is Cu, add 18-hat-6 as promotor, described 18-hat-6 is 1:3～1:9 with the mol ratio of Cu.
Preferably, in the time that catalyzer is CuI, add phenanthroline as promotor, the mol ratio of described phenanthroline and CuI is 2:1～4:1.
Preferably, the mol ratio of described Cu, CuI or organic palladium and compd A is 0.01: 1～1.5:1.
Preferably, described basic solution is potassium hydroxide (KOH), salt of wormwood (K 2cO 3), sodium tert-butoxide (t-BuONa) or potassium tert.-butoxide (t-BuOK); The solute mole dosage of described basic solution is 1.8～7 times of compd A mole dosage.
Preferably, described organic solvent is toluene or o-Xylol.
More preferably, in the time that organic solvent is o-Xylol, can add orthodichlorobenzene as secondary solvent.
Preferably, the gas in described atmosphere of inert gases is nitrogen or argon gas.
Preferably, the preparation method of described organic electrophosphorescenpolymer material of main part further comprises the step of separation and purification, and described separation and purification does not affect the preparation of organic electrophosphorescenpolymer material of main part.
Preparation method's technique of organic electrophosphorescenpolymer material of main part provided by the invention is simple, be easy to control.
The third aspect, the invention provides a kind of organic electroluminescence device, comprise successively glass substrate, anode, hole transmission layer, luminescent layer, hole blocking layer, electron transfer layer, buffer layer and negative electrode, the material of described luminescent layer is the mixture of material of main part and guest materials, wherein material of main part is the organic electrophosphorescenpolymer material of main part shown in following structural formula, i.e. compound M:
Wherein, Ar is described guest materials is that three (2-phenylpyridines) close iridium (Ir (ppy) 3), two (2-phenylpyridine) (methyl ethyl diketones) close iridium (Ir (ppy) 2acac) or three [2-(p-methylphenyl) pyridines] close iridium (Ir (mppy) 3).
Preferably, the mass ratio of described guest materials and described material of main part is 0.05:1～0.12:1.
A kind of organic electrophosphorescenpolymer material of main part provided by the invention and preparation method thereof and organic electroluminescence device, have following beneficial effect:
Organic electrophosphorescenpolymer material of main part of the present invention has the performance of good transporting holes and electronics; The material of main part that can be used as blue light electroluminescence phosphorescence uses, and in the time being applied to organic electroluminescence device field, is conducive to the charge balance of current carrier at recombination region, makes device obtain high luminous efficiency; Triazine is connected with the mode that arylamine is connected with position between phenyl simultaneously, makes material there is higher triplet;
In addition, organic electrophosphorescenpolymer material of main part of the present invention has good solubility property and film forming properties in common solvent (as toluene, methylene dichloride, trichloromethane or tetrahydrofuran (THF)), and can regulate its dissolving and film forming properties by aliphatic chain substituting group;
Preparation method of the present invention is simple and ripe, mild condition, and product is easy to control.
Brief description of the drawings
Fig. 1 is the structural representation of the organic electroluminescence device that contains organic electrophosphorescenpolymer material of main part of Application Example one;
Fig. 2 is the electroluminescent spectrum figure of the organic electroluminescence device that contains organic electrophosphorescenpolymer material of main part of Application Example one.
Embodiment
The following stated is the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications are also considered as protection scope of the present invention.
In following examples, compd A is can the disclosed method of reference literature (Organic Electronics, 2012,13:1937 – 1947) synthetic to be obtained, and compd B from the market (Aladdin reagent) is bought and obtained.
Embodiment mono-
A kind of organic electrophosphorescenpolymer material of main part, i.e. 3-(two (3-(phenyl amine) phenyl)-1,3,5-triazines-2-yls of 4,6-)-N, N-phenylbenzene aniline (called after TDPPz), the compound M1 for shown in following structural formula:
The preparation method of above-mentioned organic electrophosphorescenpolymer material of main part compound M1, comprises the steps:
(1) compd A (2-(4-bromophenyl)-1-phenyl-1H-phenanthro-[9,10-d] imidazoles) and the compound B-11 (pentanoic) that provide respectively following structural formula to represent,
(2) under nitrogen protection, in reaction flask, add successively compound A-13 mmol, compound B-11 9.0mmol, toluene 25mL forms mixing solutions, then under agitation in mixing solutions, adds Pd (OAc) 20.09mmol, t-BuONa5.4mmol, (t-Bu) 3pHBF 40.27mmol obtains reaction solution, and stirring reaction 48h refluxes reaction solution at 110 DEG C.After reaction finishes, cooling, reaction solution is poured in the aqueous solution of saturated ammonium chloride, dichloromethane extraction three times, organic phase is washed with sodium chloride aqueous solution, dry, revolve steaming and obtain crude product except after desolventizing, through silica gel column chromatography separating-purifying, finally obtain M1 solid product.
The productive rate of the present embodiment M1 is 69%.Mass spectrometric measurement result MALDI-TOF-MS:m/z811 (M +), results of elemental analyses is C, 84.49; H, 5.28; N, 10.37, corresponding molecular formula is C 57h 42n 6.By the molecular structure of mass spectrometric measurement, results of elemental analyses and reactant, confirm that product has described structure.
Embodiment bis-
A kind of organic electrophosphorescenpolymer material of main part, i.e. compound M1, the preparation method of compound M1, comprises the steps:
(1) provide respectively compd A (2-(4-bromophenyl)-1-phenyl-1H-phenanthro-[9,10-d] imidazoles) and compound B-11 (pentanoic);
(2) under nitrogen protection, in reaction flask, add successively compound A-13 mmol, compound B-11 9.0mmol, toluene 25mL forms mixing solutions, then under agitation in mixing solutions, adds Pd (OAc) 20.09mmol, t-BuONa5.4mmol, (t-Bu) 3pHBF 40.18mmol obtains reaction solution, and stirring reaction 48h refluxes reaction solution at 110 DEG C.After reaction finishes, cooling, reaction solution is poured in the aqueous solution of saturated ammonium chloride, dichloromethane extraction three times, organic phase is washed with sodium chloride aqueous solution, dry, revolve steaming and obtain crude product except after desolventizing, through silica gel column chromatography separating-purifying, finally obtain M1 solid product.
Embodiment tri-
A kind of organic electrophosphorescenpolymer material of main part, i.e. compound M1, the preparation method of compound M1, comprises the steps:
(1) provide respectively compd A (2-(4-bromophenyl)-1-phenyl-1H-phenanthro-[9,10-d] imidazoles) and compound B-11 (pentanoic);
(2) under nitrogen protection, in reaction flask, add successively compound A-13 mmol, compound B-11 9.0mmol, toluene 25mL forms mixing solutions, then under agitation in mixing solutions, adds Pd (OAc) 20.09mmol, t-BuONa5.4mmol, (t-Bu) 3pHBF 40.45mmol obtains reaction solution, and stirring reaction 48h refluxes reaction solution at 110 DEG C.After reaction finishes, cooling, reaction solution is poured in the aqueous solution of saturated ammonium chloride, dichloromethane extraction three times, organic phase is washed with sodium chloride aqueous solution, dry, revolve steaming and obtain crude product except after desolventizing, through silica gel column chromatography separating-purifying, finally obtain M1 solid product.
Embodiment tetra-
A kind of organic electrophosphorescenpolymer material of main part, be N-(3-(4, two (3-(naphthyl-2-base-phenyl amine) phenyl)-1 of 6-, 3,5-triazine-2-yl) phenyl)-N-phenylnaphthalene-2-amine (called after TN2PPz), the compound M2 for shown in following structural formula:
The preparation method of above-mentioned organic electrophosphorescenpolymer material of main part compound M2, comprises the steps:
(1) compd A (2-(4-bromophenyl)-1-phenyl-1H-phenanthro-[9,10-d] imidazoles) and the compd B 2(N-phenylnaphthalene-2-amine that provide respectively following structural formula to represent),
(2) under nitrogen protection; in reaction flask, add successively compound A-13 mmol; compd B 210.5mmol; o-Xylol 25mL forms mixing solutions; then under agitation in mixing solutions, add CuI0.03mmol, phenanthroline 0.09mmol, KOH18.0mmol to form reaction solution, by reaction solution return stirring linked reaction 40h at 130 DEG C.After reaction finishes, cooling, reaction solution is poured in dilute hydrochloric acid solution, toluene extraction, organic phase is washed with sodium chloride aqueous solution, dry, revolves to steam except after desolventizing to obtain crude product, through silica gel column chromatography separating-purifying, finally obtains M2 solid product.
In the present embodiment, the productive rate of M2 is 61%, and mass spectrometric measurement result is MALDI-TOF-MS:m/z962 (M +), results of elemental analyses is C, 86.17; H, 5.05; N, 8.79, corresponding molecular formula is C 69h 48n 6.By the molecular structure of mass spectrometric measurement, results of elemental analyses and reactant, confirm that product has described structure.
Embodiment five
A kind of organic electrophosphorescenpolymer material of main part, i.e. compound M2, the preparation method of compound M2, comprises the steps:
(1) provide respectively compd A (2-(4-bromophenyl)-1-phenyl-1H-phenanthro-[9,10-d] imidazoles) and compd B 2(N-phenylnaphthalene-2-amine);
(2) under nitrogen protection; in reaction flask, add successively compound A-13 mmol; compd B 210.5mmol; o-Xylol 25mL forms mixing solutions; then under agitation in mixing solutions, add CuI0.03mmol, phenanthroline 0.06mmol, KOH18.0mmol to form reaction solution, by reaction solution return stirring linked reaction 40h at 130 DEG C.After reaction finishes, cooling, reaction solution is poured in dilute hydrochloric acid solution, toluene extraction, organic phase is washed with sodium chloride aqueous solution, dry, revolves to steam except after desolventizing to obtain crude product, through silica gel column chromatography separating-purifying, finally obtains M2 solid product.
Embodiment six
A kind of organic electrophosphorescenpolymer material of main part, i.e. compound M2, the preparation method of compound M2, comprises the steps:
(1) provide respectively compd A (2-(4-bromophenyl)-1-phenyl-1H-phenanthro-[9,10-d] imidazoles) and compd B 2(N-phenylnaphthalene-2-amine);
(2) under nitrogen protection; in reaction flask, add successively compound A-13 mmol; compd B 210.5mmol; o-Xylol 25mL forms mixing solutions; then under agitation in mixing solutions, add CuI0.03mmol, phenanthroline 0.12mmol, KOH18.0mmol to form reaction solution, by reaction solution return stirring linked reaction 40h at 130 DEG C.After reaction finishes, cooling, reaction solution is poured in dilute hydrochloric acid solution, toluene extraction, organic phase is washed with sodium chloride aqueous solution, dry, revolves to steam except after desolventizing to obtain crude product, through silica gel column chromatography separating-purifying, finally obtains M2 solid product.
Embodiment seven
A kind of organic electrophosphorescenpolymer material of main part, be N-(3-(4, two (3-(naphthyl-1-base-phenyl amine) phenyl)-1 of 6-, 3,5-triazine-2-yl) phenyl)-N-phenylnaphthalene-1-amine (called after TN1PPz), the compound M3 for shown in following structural formula:
The preparation method of above-mentioned organic electrophosphorescenpolymer material of main part (being compound M3), comprises the steps:
(1) compd A (2-(4-bromophenyl)-1-phenyl-1H-phenanthro-[9,10-d] imidazoles) and the compd B 3(N-phenylnaphthalene-1-amine that provide respectively following structural formula to represent),
(2) under argon shield, in reaction flask, add successively compd A 4.0mmol, compd B 318.0mmol, o-Xylol 25mL forms mixing solutions, then under agitation in mixing solutions, adds Cu powder 6mmol, 18-hat-61.0mmol, K 2cO 328.0mmol, 15mL orthodichlorobenzene form reaction solution, by reaction solution return stirring linked reaction 48h at 185 DEG C.After reaction finishes, reaction solution, by a short silicagel column heat filtering, is revolved after organic solvent is removed in steaming and obtains crude product, then pass through silica gel column chromatography separating-purifying, finally obtain M3 solid product.
In the present embodiment, M3 productive rate is 64%.Mass spectrometric measurement result is MALDI-TOF-MS:m/z961 (M +), ultimate analysis fruit is C, 87.59; H, 4.94; N, 7.56, corresponding molecular formula is C 81h 54n 6.By the molecular structure of mass spectrometric measurement, results of elemental analyses and reactant, confirm that product has described structure.
Embodiment eight
A kind of organic electrophosphorescenpolymer material of main part, i.e. compound M3, the preparation method of compound M3, comprises the steps:
(1) provide respectively compd A (2-(4-bromophenyl)-1-phenyl-1H-phenanthro-[9,10-d] imidazoles) and compd B 3(N-phenylnaphthalene-1-amine);
(2) under argon shield, in reaction flask, add successively compd A 4.0mmol, compd B 318.0mmol, o-Xylol 25mL forms mixing solutions, then under agitation in mixing solutions, adds Cu powder 6mmol, 18-hat-62.0mmol, K 2cO 328.0mmol, 15mL orthodichlorobenzene form reaction solution, by reaction solution return stirring linked reaction 48h at 185 DEG C.After reaction finishes, reaction solution, by a short silicagel column heat filtering, is revolved after organic solvent is removed in steaming and obtains crude product, then pass through silica gel column chromatography separating-purifying, finally obtain M3 solid product.
Embodiment nine
A kind of organic electrophosphorescenpolymer material of main part, i.e. compound M3, the preparation method of compound M3, comprises the steps:
(1) provide respectively compd A (2-(4-bromophenyl)-1-phenyl-1H-phenanthro-[9,10-d] imidazoles) and compd B 3(N-phenylnaphthalene-1-amine);
(2) under argon shield, in reaction flask, add successively compd A 6.0mmol, compd B 318.0mmol, o-Xylol 25mL forms mixing solutions, then under agitation in mixing solutions, adds Cu powder 9.0mmol, 18-hat-61.0mmol, K 2cO 328.0mmol, 15mL orthodichlorobenzene form reaction solution, by reaction solution return stirring linked reaction 48h at 185 DEG C.After reaction finishes, reaction solution, by a short silicagel column heat filtering, is revolved after organic solvent is removed in steaming and obtains crude product, then pass through silica gel column chromatography separating-purifying, finally obtain M3 solid product.
Embodiment ten
A kind of organic electrophosphorescenpolymer material of main part, be N-(3-(4, two (3-(dinaphthyl-2-base amine) phenyl)-1 of 6-, 3,5-triazine-2-yl) phenyl)-N-(naphthalene-2-yl) naphthalene-2-amine (called after TDN11Pz), the compound M4 for shown in following structural formula:
The preparation method of above-mentioned organic electrophosphorescenpolymer material of main part (being compound M4), comprises the steps:
(1) compd A (2-(4-bromophenyl)-1-phenyl-1H-phenanthro-[9,10-d] imidazoles) and compd B 4(N-(naphthalene-2-yl) naphthalene-1-amine that provide respectively following structural formula to represent),
(2) under argon shield, in reaction flask, add successively compound A-13 .0mmol, compd B 412mmol, toluene 25mL forms mixing solutions, then under agitation in mixing solutions, adds Pd (dba) 20.12mmol, t-BuOK7.2mmol, Pt-Bu 30.36mmol forms reaction solution, by reaction solution return stirring linked reaction 24h at 110 DEG C.After reaction finishes, reaction solution, by a short silicagel column heat filtering, is revolved after organic solvent is removed in steaming and obtains crude product, then pass through silica gel column chromatography separating-purifying, finally obtain M4 solid product.
In the present embodiment, M4 productive rate is 70%, and mass spectrometric measurement result is MALDI-TOF-MS:m/z1111 (M +), results of elemental analyses is C, 87.58; H, 4.94; N, 7.52, corresponding molecular formula is C81H54N6.By the molecular structure of mass spectrometric measurement, results of elemental analyses and reactant, confirm that product has described structure.
Embodiment 11
A kind of organic electrophosphorescenpolymer material of main part, be N-(3-(4, two (3-(dinaphthyl-1-base amine) phenyl)-1 of 6-, 3,5-triazine-2-yl) phenyl)-N-(naphthalene-1-yl) naphthalene-2-amine (called after TDN12Pz), the compound M5 for shown in following structural formula:
The preparation method of above-mentioned organic electrophosphorescenpolymer material of main part (being compound M5), comprises the steps:
(1) compd A (2-(4-bromophenyl)-1-phenyl-1H-phenanthro-[9,10-d] imidazoles) and the compd B 5(dinaphthyl-2-base amine that provide respectively following structural formula to represent),
(2) under argon shield, add successively compound A-13 .0mmol, compd B 512mmol, toluene 25mL forms mixing solutions, then under agitation in mixing solutions, adds Pd (dba) 20.12mmol, t-BuOK7.2mmol, Pt-Bu 30.24mmol forms reaction solution, by reaction solution return stirring linked reaction 72h at 75 DEG C.After reaction finishes, reaction solution, by a short silicagel column heat filtering, is revolved after organic solvent is removed in steaming and obtains crude product, then pass through silica gel column chromatography separating-purifying, finally obtain M5 solid product.
In the present embodiment, M5 productive rate is 70%.Mass spectrometric measurement result is MALDI-TOF-MS:m/z1111 (M +).Results of elemental analyses is C, 87.61; H, 4.92; N, 7.55, corresponding molecular formula is C 81h 54n 6.By the molecular structure of mass spectrometric measurement, results of elemental analyses and reactant, confirm that product has described structure.
Embodiment 12
A kind of organic electrophosphorescenpolymer material of main part, i.e. compound M5, the preparation method of compound M5, comprises the steps:
(1) provide respectively compd A (2-(4-bromophenyl)-1-phenyl-1H-phenanthro-[9,10-d] imidazoles) and compd B 5(dinaphthyl-2-base amine);
(2) under argon shield, add successively compound A-13 .0mmol, compd B 512mmol, toluene 25mL forms mixing solutions, then under agitation in mixing solutions, adds Pd (dba) 20.12mmol, t-BuOK7.2mmol, Pt-Bu 30.6mmol forms reaction solution, by reaction solution return stirring linked reaction 72h at 75 DEG C.After reaction finishes, reaction solution, by a short silicagel column heat filtering, is revolved after organic solvent is removed in steaming and obtains crude product, then pass through silica gel column chromatography separating-purifying, finally obtain M5 solid product.
Test implementation example
For supporting beneficial effect of the present invention, provide heat stability testing method and the data of organic electrophosphorescenpolymer material of main part of the present invention below.
The compound M1 by thermogravimetric analyzer (TGA) being prepared by the embodiment of the present invention one, compound M2 prepared by embodiment tetra-, compound M3 prepared by embodiment seven, the compound M5 of compound M4 prepared by embodiment ten and embodiment 11 preparations detects, analysis condition is nitrogen atmosphere, sweep velocity is 10 DEG C/min, and test 5% thermal weight loss temperature, the results are shown in Table 1.
The heat decomposition temperature of table 1 organic electrophosphorescenpolymer material of main part of the present invention
Compound M1 M2 M3 M4 M5
5% thermal weight loss temperature/DEG C 431 440 439 454 454
From table 1 data, 5% thermal weight loss temperature of organic electrophosphorescenpolymer material of main part prepared by the present invention, more than 431 DEG C, illustrates that organic electrophosphorescenpolymer material of main part of the present invention has extraordinary thermostability.
(2) hole and electronic transmission performance test: by time of flight method (Time ofFlight, TOF) the compound M1 that prepared by test above-described embodiment one, compound M2 prepared by embodiment tetra-, compound M3 prepared by embodiment seven, the hole of compound M5 and the mobility of electronics of compound M4 prepared by embodiment ten and embodiment 11 preparations, the results are shown in Table 2;
Table 2 organic electrophosphorescenpolymer material of main part of the present invention field-effect hole and electronic mobility
From table 2 data, organic electrophosphorescenpolymer material of main part prepared by the present invention is 6.5 × 10 at electric field 5vcm -1time, the hole mobility of compound is 2.6 × 10 -5above, electronic mobility is 1.0 × 10 -6cm 2(Vs) -1above, illustrate that organic electrophosphorescenpolymer material of main part prepared by the present invention has good hole and electronic transmission performance.
Application Example one
An organic electroluminescence device that contains organic electrophosphorescenpolymer material of main part is the compound M5(TDN12Pz of the application embodiment of the present invention 11 preparations) as the electroluminescent device of luminescent layer material, Fig. 1 is shown in by structure iron.General organic electroluminescence device comprises anode, functional layer, luminescent layer and negative electrode, and functional layer comprises hole injection layer, hole transmission layer, electron supplying layer and electron injecting layer, and luminescent layer is between hole transmission layer and electron supplying layer.
As shown in Figure 1, the organic electroluminescence device of the present embodiment is straticulate structure, comprise successively glass substrate 1, anode 2, hole transmission layer 3, luminescent layer 4, hole blocking layer 5, electron transfer layer 6, buffer layer 7 and negative electrode 8, luminescent layer 4 adopts the compound M5 of the embodiment of the present invention 11 preparations as material of main part doping guest materials Ir (ppy) 3the matrix material that (three (2-phenylpyridines) close iridium) forms, Ir (ppy) 3with the mass ratio of material of main part be 0.09:1, except glass substrate, 2 ~ 8 material is followed successively by: ITO/NPB/M5:Ir (ppy) 3/ BCP/Alq 3/ LiF/Al.Wherein, the structural formula of the organic electrophosphorescenpolymer material of main part compound M5 of embodiment 11 preparations is:
In addition, the material of anode 2 is preferably ITO(tin indium oxide), thickness is 160nm, the material of hole transmission layer 3 is NPB, i.e. N, N '-bis-(Alpha-Naphthyl)-N, N '-phenylbenzene-4,4 '-diamines, thickness is 40nm, the material of hole blocking layer 5 is BCP, 2, and 9-dimethyl-4,7-phenylbenzene-9,10-phenanthroline, thickness is 9nm, the material of electron transfer layer 6 is Alq 3, i.e. three (oxine) aluminium, thickness is 40nm, the material of buffer layer 7 is LiF, i.e. lithium fluoride, thickness is 1nm, and the material of negative electrode 8 is aluminium (Al), and thickness is 110nm.
Above-mentioned organic electroluminescence device adopts the method preparation of vacuum evaporation, first evaporation anode 2 on glass substrate 1, then evaporation hole transmission layer 3 successively, blue light-emitting layer 4, hole blocking layer 5, electron transfer layer 6, buffer layer 7, last evaporation negative electrode 8, obtains organic electroluminescence device, and each layer can adopt existing method to form.
Under room temperature, atmospheric environment, test, this ruddiness OLED device has been obtained the light efficiency of 35cd/A, has higher luminous efficiency.
In organic electrophosphorescenpolymer material of main part, contain triazine group and aniline group, triazine is the 6-membered heterocyclic compound containing 3 nitrogen-atoms, be a short of electricity daughter, and aniline structure is a kind of electron rich body; In a structure, contain electron rich and electron deficiency structure, this material has the performance of good transporting holes and electronics simultaneously; The material of main part that this organic electrophosphorescenpolymer material of main part can be used as blue light electroluminescence phosphorescence uses, and in the time being applied to organic electroluminescence device field, is conducive to the charge balance of current carrier at recombination region, makes device obtain high luminous efficiency.
Fig. 2 is the electroluminescent spectrum figure of the present embodiment organic electroluminescence device, and its maximum emission wavelength is at 516nm place, with Ir (ppy) 3intrinsic emission peak consistent, illustrate that exciton energy fully transfers to guest materials luminous from material of main part.
Application Example two
An organic electroluminescence device that contains organic electrophosphorescenpolymer material of main part is the electroluminescent device of the compound M1 for preparing of the application embodiment of the present invention one as luminescent layer material; General organic electroluminescence device comprises anode, functional layer, luminescent layer and negative electrode, and functional layer comprises hole injection layer, hole transmission layer, electron supplying layer and electron injecting layer, and luminescent layer is between hole transmission layer and electron supplying layer.
The organic electroluminescence device of the present embodiment is straticulate structure, comprise successively glass substrate, anode, hole transmission layer, luminescent layer, hole blocking layer, electron transfer layer, buffer layer and negative electrode, compound M1 prepared by the luminescent layer employing embodiment of the present invention one is as material of main part doping guest materials Ir (ppy) 2acac(two (2-phenylpyridine) (methyl ethyl diketones) closes iridium) matrix material that forms, Ir (ppy) 2the mass ratio of acac and material of main part is 0.05:1, and except glass substrate, the material of other layers of device is followed successively by: ITO/NPB/M1:Ir (ppy) 2acac/BCP/Alq 3/ LiF/Al.Wherein, the structural formula of the organic electrophosphorescenpolymer material of main part compound M1 that prepared by embodiment mono-is:
In addition, the material of anode is preferably ITO, and thickness is 160nm, and the material of hole transmission layer is NPB, and thickness is 40nm, and the material of hole blocking layer is BCP, and thickness is 9nm, and the material of electron transfer layer is Alq 3, thickness is 40nm, and the material of buffer layer is LiF, and thickness is 1nm, and the material of negative electrode is Al, thickness is 110nm.
Application Example three
An organic electroluminescence device that contains organic electrophosphorescenpolymer material of main part is the electroluminescent device of the compound M2 for preparing of the application embodiment of the present invention four as luminescent layer material; General organic electroluminescence device comprises anode, functional layer, luminescent layer and negative electrode, and functional layer comprises hole injection layer, hole transmission layer, electron supplying layer and electron injecting layer, and luminescent layer is between hole transmission layer and electron supplying layer.
The organic electroluminescence device of the present embodiment is straticulate structure, comprise successively glass substrate, anode, hole transmission layer, luminescent layer, hole blocking layer, electron transfer layer, buffer layer and negative electrode, compound M2 prepared by the luminescent layer employing embodiment of the present invention four is as material of main part doping guest materials Ir (mppy) 3the matrix material that (three [2-(p-methylphenyl) pyridines] close iridium) forms, Ir (mppy) 3with the mass ratio of material of main part be 0.12:1, except glass substrate, the material of other layers of device is followed successively by: ITO/NPB/M2:Ir (mppy) 3/ BCP/Alq 3/ LiF/Al.Wherein, the structural formula of the organic electrophosphorescenpolymer material of main part compound M2 that prepared by embodiment tetra-is:
In addition, the material of anode is preferably ITO, and thickness is 160nm, and the material of hole transmission layer is NPB, and thickness is 40nm, and the material of hole blocking layer is BCP, and thickness is 9nm, and the material of electron transfer layer is Alq 3, thickness is 40nm, and the material of buffer layer is LiF, and thickness is 1nm, and the material of negative electrode is Al, thickness is 110nm.
The above is the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications are also considered as protection scope of the present invention.

Claims (10)

1. an organic electrophosphorescenpolymer material of main part, is characterized in that, the compound M for shown in following structural formula:
Wherein, Ar is
2. a preparation method for organic electrophosphorescenpolymer material of main part, is characterized in that comprising the steps:
The compd A and the compd B that provide respectively following structural formula to represent:
Wherein, Ar is
In atmosphere of inert gases, described compd A and described compd B for joining in organic solvent, 1:3～1:4.5 are dissolved in molar ratio, then add successively catalyzer and basic solution to form reaction solution, reaction solution is 75～185 DEG C in temperature and carries out linked reaction 24～72 hours, make the following organic electrophosphorescenpolymer material of main part of structural formula, i.e. compound M:
Wherein, Ar is
3. the preparation method of organic electrophosphorescenpolymer material of main part as claimed in claim 2, is characterized in that, described catalyzer is copper, cuprous iodide or organic palladium.
4. the preparation method of organic electrophosphorescenpolymer material of main part as claimed in claim 3, it is characterized in that, described organic palladium is two (dibenzalacetone) palladium or palladium, in the time that catalyzer is two (dibenzalacetone) palladium, add tri-butyl phosphine as promotor, in the time that catalyzer is palladium, add three tertiary butyl phosphorus a tetrafluoro borates as promotor.
5. the preparation method of organic electrophosphorescenpolymer material of main part as claimed in claim 4, it is characterized in that, the mol ratio of described two (dibenzalacetone) palladiums and tri-butyl phosphine is 1:2～1:5, and the mol ratio of described palladium and three tertiary butyl phosphorus a tetrafluoro borates is 1:2～1:5.
6. the preparation method of organic electrophosphorescenpolymer material of main part as claimed in claim 3, is characterized in that, in the time that catalyzer is copper, adds 18-hat-6 as promotor, and described 18-hat-6 is 1:3～1:9 with the mol ratio of copper.
7. the preparation method of organic electrophosphorescenpolymer material of main part as claimed in claim 3, is characterized in that, in the time that catalyzer is cuprous iodide, adds phenanthroline as promotor, and the mol ratio of described phenanthroline and cuprous iodide is 2:1～4:1.
8. the preparation method of organic electrophosphorescenpolymer material of main part as claimed in claim 3, is characterized in that, the mol ratio of described copper, cuprous iodide or organic palladium and compd A is 0.01:1 ~ 1.5:1.
9. an organic electroluminescence device, comprise successively glass substrate, anode, hole transmission layer, luminescent layer, hole blocking layer, electron transfer layer, buffer layer and negative electrode, it is characterized in that, the material of described luminescent layer is the mixture of material of main part and guest materials, the wherein organic electrophosphorescenpolymer material of main part shown in the following structural formula of material of main part, i.e. compound M:
Wherein, Ar is described guest materials is that three (2-phenylpyridines) close iridium, two (2-phenylpyridine) (methyl ethyl diketones) close iridium or three [2-(p-methylphenyl) pyridine] and close iridium.
10. organic electroluminescence device as claimed in claim 9, is characterized in that, the mass ratio of described guest materials and described material of main part is 0.05:1～0.12:1.
CN201310055323.6A 2013-02-21 2013-02-21 Organic electroluminescence phosphorescence host material, preparation method thereof and organic electroluminescence device Pending CN104003950A (en)

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Application publication date: 20140827