CN105754589A - Electronic transmission material, preparation method thereof and organic electroluminescence device including electronic transmission material - Google Patents

Electronic transmission material, preparation method thereof and organic electroluminescence device including electronic transmission material Download PDF

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CN105754589A
CN105754589A CN201610217960.2A CN201610217960A CN105754589A CN 105754589 A CN105754589 A CN 105754589A CN 201610217960 A CN201610217960 A CN 201610217960A CN 105754589 A CN105754589 A CN 105754589A
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electron transport
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CN105754589B (en
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刘英瑞
石宇
尹胜
王晓磊
张婷婷
盖明慧
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Valiant Co Ltd
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Abstract

The invention relates to an electronic transmission material, a preparation method thereof and an organic electroluminescence device including the electronic transmission material. The electronic transmission material is represented by the formula I (shown in the specification), wherein R is selected from one of hydrogen and C1-C10 alkyl; Ar is selected from one of C6-C20 aryl, C10-C20 polycyclic aromatic hydrocarbon and C4-C20 aromatic heterocyclic radical containing at least one of nitrogen atoms, oxygen atoms and sulfur atoms. The electronic transmission material has a relatively large conjugate plane structure and therefore is beneficial to electronic transmission; the reduction potential is relatively low, so that the electronic transmission performance is good; and the film-forming property and the stability are good, so that the electronic transmission material can be applied to the organic electroluminescence device. The electronic transmission material is prepared by virtue of coupled reaction, cyclization reaction, low temperature metallization, cycling reaction and secondary coupled reaction. The preparation method has the beneficial effects that the operation is easy, the cost is low, and the purity of the prepared product is high. The preparation method is beneficial for large-scale popularization. The formula I is as shown in the specification.

Description

Electron transport material, its preparation method and include the organic electroluminescence device of this electron transport material
Technical field
The present invention relates to organic photoelectrical material technical field, particularly relate to a kind of electron transport material, its preparation method and include the organic electroluminescence device of this electron transport material.
Background technology
The origin of organic electroluminescence device (OLED) can trace back to nineteen sixties, Pope et al. makes it luminous with anthracene single crystal impressed DC voltage, but because driving voltage high (100V) and luminosity and efficiency are all relatively low, it does not have cause too many attention.Along with technology is updated. at the C.W.Tang et al. of Kodak Company in 1987 with oxine aluminum (AIq3) for luminescent material, adopt the method for vacuum evaporation to be made for double layer sandwich structure OLED, open bright voltage and only have several volts, brightness reaches as high as 1000cd/m2, mark OLED has stepped an important step towards practical, becomes an important milestone of field of organic electroluminescence.
Electron transfer layer is requisite ingredient in organic electroluminescence device, as a rule, electron transport material all has the plane aromatic compound of big conjugated structure, they have good electron acceptability mostly, under certain forward bias, can effectively transmit again electronics (referring to electroluminescent organic material and device introduction simultaneously, Huang Chunhui, Li Fuyou, Huang Wei, 143 pages).It is currently available that electron transport material and mainly has oxine aluminum compounds, furodiazole compound, glyoxaline compound, oxazole compounds, triazole class compounds, nitrogenous hexa-member heterocycle class, perfluorinate electron-like transmission material, silicone based electron transport material etc..
Design an electron transport material that organic electroluminescence device efficiency can be made to be obviously improved, need to possess following character: there is reversible electrochemical reduction and higher reduction potential；Need suitable highest occupied molecular orbital (HighestOccupiedMolecularOrbital, it is called for short HOMO) and lowest unoccupied molecular orbital (LowestUnoccupiedMolecularOrbital, it is called for short LUMO), electronics is made to have minimum injection energy gap, to reduce initial and operation voltage；Also need to higher electron mobility；The glass transition temperature having had and heat stability；There is noncrystalline thin film (referring to organic electroluminescent and element, Chen Jinxin, yellow filial piety literary composition are outstanding, 52 pages).
Summary of the invention
In order to solve the problems referred to above, the applicant has carried out studying with keen determination, found that: by introducing different modification groups on phenanthro-azaspiro fluorenes, make the material finally given not only have bigger conjugate planes structure, be beneficial to electric transmission, also there is relatively low reduction potential, thus having good electronic transmission performance, also there is higher film property and stability simultaneously, therefore, it is possible to be applied in organic electroluminescence device as electron transport material, thus completing the application.
Below by the present invention is described in detail, the feature of the application and advantage will illustrate along with these and become more apparent from, clearly.
It is an object of the invention to provide a kind of electron transport material, shown in following formula I.
In above-mentioned formula I, R one in hydrogen-based and alkyl that carbon number is 1～10；Ar is selected from the condensed-nuclei aromatics base that the aryl that carbon number is 6～20, carbon number are 10～20 and containing the one at least one in nitrogen-atoms, oxygen atom and sulphur atom and aromatic heterocyclic radical that carbon number is 4～20.
In above-mentioned formula I, substituent R and described under Ar.
Carbon number is the alkyl of 1～10, chain-like alkyl and cycloalkyl, and wherein chain-like alkyl includes again straight chained alkyl and branched alkyl, additionally, the hydrogen on chain-like alkyl also can be replaced by cycloalkyl, same, is positioned at the hydrogen in cycloalkyl and also can be replaced by alkyl.Preferably, selecting carbon number is the alkyl of 1～6, it is further preferred that selecting carbon number is the alkyl group of 1～4, carbon number is the cycloalkyl of 5～6.As the example of alkyl, specifically can enumerate: methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, the tert-butyl group.Substituent R is preferably hydrogen-based or the tert-butyl group.
Carbon number is the aryl of 6～20, for instance can enumerate phenyl, aralkyl, at least contain the aryl such as xenyl etc. of a phenyl.Preferably, selecting carbon number is the aryl of 6～12, it is further preferred that selecting carbon number is the aryl of 6～9.Enforcement as aryl, specifically can enumerate: phenyl, benzyl, xenyl, trityl, p-methylphenyl, an ethylbenzene, adjacent ethylbenzene, 3,5-xylyl, 2,6-diisopropylbenzyl, 3,5-bis-n-proplbenzene base, 2,6-bis-n-butyl benzene base, 3,5-bis-isobutylphenyls, 3,5-bis-2-methyl-2-phenylpropane bases.
Carbon number is the condensed-nuclei aromatics base of 10～20, for instance naphthyl, anthryl, phenanthryl etc..Preferably, the condensed-nuclei aromatics base selecting carbon number to be 10～16, it is further preferred that the condensed-nuclei aromatics base selecting carbon number to be 10～14, it is further preferred that the condensed-nuclei aromatics base selecting carbon number to be 10～12.As the enforcement of condensed-nuclei aromatics base, specifically can enumerate: 1-naphthyl, 2-naphthyl.
Carbon number is the aromatic heterocyclic radical of 4～20, it may include annelated heterocycles base, monocyclic aromatic heterocycle base, may also include polycyclic aromatic heterocyclic radical etc., wherein annelated heterocycles base, can be obtained by monocyclic aromatic or non-aromatic heterocyclic (heterocycle can be different) condensation.In described aromatic heterocyclic radical, the at least one atom in nitrogen-atoms, oxygen atom and sulphur atom can be contained, when containing above-mentioned hetero atom, heteroatomic number is not exposed to concrete restriction, can be such as 1,2,3,4,5,6 or 7, in addition, heteroatomic kind is also not subjected to concrete restriction, be selected from nitrogen-atoms, oxygen atom and sulphur atom any one or multiple, it addition, the hydrogen on monocyclic aromatic heterocycle base also can be replaced by other groups such as aryl, condensed-nuclei aromatics base or aromatic heterocyclic radical.Preferably, selecting carbon number is the aromatic heterocyclic radical of 4～18, it is further preferred that selecting carbon number is the aromatic heterocyclic radical of 4～17.
Certainly, the kind of substituent A r is not so limited, and also can include the aromatic groups such as phenyl, pyridine radicals, quinolyl for other.
As the example of Ar, specifically can enumerate:
Discovery is studied through the present inventor, electron transport material provided by the invention, the namely compound shown in formula I, owing to having bigger conjugate planes structure, thus making it have high electron mobility, improve carrier mobility and the luminous efficiency of this electron transport material, substantially increasing its photoelectric characteristic, this electron transport material also has relatively low reduction potential in addition, is beneficial to reception electronics, improve charge transporting ability, thus also having good electronic transmission performance.It addition, this electron transport material also has higher film property.Comprehensive, electron transport material provided by the invention has higher electronic transmission performance, good film-forming property, and at room temperature there is good stability, after this electron transport material is applied in organic electroluminescence device, it is possible to be greatly improved the stability of organic electroluminescence device, meanwhile, the driving voltage of organic electroluminescence device can also be reduced, be greatly improved its service life.
As the example of electron transport material, specifically can enumerate:
Another object of the present invention is to provide a kind of method preparing electron transport material provided by the invention, including following seven steps.
Step (1), 2-bromopyridine, the bromo-2-carboxylate methyl ester phenylboric acid of 3-and potassium carbonate are joined after in the mixed solvent containing water and toluene, react under the catalytic action of four triphenyl phosphorus palladiums, obtaining the reaction system containing intermediate A, intermediate A is such as shown in following formula 1.
In above-mentioned steps (1), the mol ratio of 2-bromopyridine and 3-bromo-2-carboxylate methyl ester phenylboric acid is preferably 2-bromopyridine: bromo-2-carboxylate methyl ester phenylboric acid=1:1～1.5 of 3-, further, 2-bromopyridine is preferably 2-bromopyridine with the mol ratio of 3-bromo-2-carboxylate methyl ester phenylboric acid: bromo-2-carboxylate methyl ester phenylboric acid=1:1～1.1 of 3-；Potassium carbonate is as alkali, and it is potassium carbonate that its addition is preferably the mol ratio making itself and 2-bromopyridine: 2-bromopyridine=1.8～2.5:1, and further, it is potassium carbonate that the addition of potassium carbonate is preferably the mol ratio making itself and 2-bromopyridine: 2-bromopyridine=2:1；The addition of four triphenyl phosphorus palladiums is preferably the 0.3～1% of the weight of 2-bromopyridine, and further, the addition of four triphenyl phosphorus palladiums is preferably the 0.4～0.7% of the weight of 2-bromopyridine；Additionally, the addition of solvent can carry out selecting and regulating according to practical situation, as long as can by stock dispersion wherein, it is preferable that the weight ratio of water and toluene is water: toluene=1:1～2, further, the weight ratio of water and toluene is preferably water: toluene=1:1.2～1.5.
In above-mentioned steps (1), system reacts at 50～120 DEG C, and further, system reacts at 60～100 DEG C；Additionally, the response time of system is preferably 15～36 hours, further, the response time of system is preferably 20～26 hours.
In above-mentioned steps (1), system reacts preferably under noble gas such as nitrogen atmosphere.
In above-mentioned steps (1), four triphenyl phosphorus palladiums can be added drop-wise in system, it is also possible to together joins in system with other raw materials.
In above-mentioned steps (1), can by whether thin layer chromatography (being called for short TLC) detection compound 2-bromopyridine reacts completely, after question response is complete, reaction system containing intermediate A is carried out following post processing: reaction system is carried out separatory, afterwards, organic facies is spin-dried for, petroleum ether and ethyl acetate is selected to carry out column chromatography purification again, obtain the intermediate A after purification, when column chromatography, select suitable petroleum ether and ethyl acetate proportioning according to practical situation.
Step (2), intermediate A and sodium hydroxide are joined in dehydrated alcohol, reaction obtains the reaction system containing intermediate B, then intermediate B is joined in concentrated sulphuric acid and react, obtain the reaction system containing intermediate C, wherein, intermediate B and intermediate C are successively as shown in following formula 2, formula 3.
In above-mentioned steps (2), the mol ratio of intermediate A and sodium hydroxide is preferably intermediate A: sodium hydroxide=1:3～6, and further, the mol ratio of intermediate A and sodium hydroxide is preferably intermediate A: sodium hydroxide=1:4～5；The addition of dehydrated alcohol is not exposed to concrete restriction, as long as the stock dispersion that can add is opened, the addition of dehydrated alcohol is preferably 5～10 times of the weight of intermediate A, and further, the addition of dehydrated alcohol is preferably 6～8 times of the weight of intermediate A；The addition of concentrated sulphuric acid is preferably 2～6 times of the weight of intermediate B, further, the addition of concentrated sulphuric acid is preferably 3～4 times of the weight of intermediate B, in addition, the mass percent of selected concentrated sulphuric acid is preferably 80～98%, further, the mass percent of selected concentrated sulphuric acid is preferably 90～98%.
In above-mentioned steps (2), intermediate A and sodium hydroxide are joined after in dehydrated alcohol, system heating is reacted to backflow；The time of reaction is preferably 2～6 hours, and further, the time of system reaction is preferably 3～5 hours.
In above-mentioned steps (2), intermediate B is joined after in concentrated sulphuric acid, system is heated to 40～90 DEG C and reacts, further, it is preferable that system is heated to 60～80 DEG C and reacts；Additionally, the time of reaction is preferably 3～8 hours, further, the time of reaction is preferably 5～7 hours.
In above-mentioned steps (2), preferably the reaction system containing intermediate B is carried out following post processing: after elimination ethanol, hydrochloric acid is added in reaction system, then system precipitates out a large amount of white solids, it is sequentially carried out sucking filtration, drying again, dry particularly preferably in 70～90 DEG C, finally obtain intermediate B, wherein, it is preferable that the mass percent of hydrochloric acid is 8～20%, further, the mass percent of preferred hydrochloric acid is 10～15%, additionally, the addition of hydrochloric acid is preferably 4～10 times of intermediate A, further, the addition of hydrochloric acid is preferably 6～8 times of intermediate A.It should be noted that intermediate B need not be carried out further purification, can directly react under concentrated sulphuric acid effect.
In above-mentioned steps (2), the reaction system containing intermediate C obtained is carried out following post processing: reaction system poured in frozen water, the addition of frozen water is 4～10 times of the weight of concentrated sulphuric acid, further, preferably 5～6 times of the weight of concentrated sulphuric acid, afterwards, add extraction into ethyl acetate, after separatory, organic facies is spin-dried for, then column chromatography purification is selected, obtain the intermediate C after purification, wherein during column chromatography, intermediate A is purified by preferred petroleum ether and ethyl acetate, in addition, suitable Solvent Gradient can be selected according to the actual requirements to be purified, the volume ratio of preferred petroleum ether and ethyl acetate is petroleum ether: ethyl acetate=4:1.
Step (3), raw material 1 is joined in oxolane (referred to as THF), cooling, add the hexane solution containing n-BuLi, then adding the oxolane containing intermediate C to system, reaction obtains the reaction system containing intermediate D, wherein, raw material 1 and intermediate D are successively as shown in following formula 4, formula 5, in the raw material 1 shown in formula 4, substituent R as illustrated as the former, so repeating no more.
In above-mentioned steps (3), the mol ratio of intermediate C and raw material 1 is preferably 1:1～2, and further, the mol ratio of intermediate C and raw material 1 is preferably 1:1～1.5；The addition of n-BuLi makes the mol ratio of n-BuLi and intermediate C be preferably n-BuLi: intermediate C=ratio is 1:1.05～1.2；In addition, before n-BuLi is joined system, n-BuLi is dispersed in hexane solution, preferred n-BuLi molar concentration in hexane solution is 1.5～3.0mol/L, further, molar concentration is preferably 1.5～2.5mol/L, is joined in system by the hexane solution containing intermediate C.The addition of solvents tetrahydrofurane is conventional addition, is not exposed to concrete restriction.
In above-mentioned steps (3), after cooling the temperature to-100～-80 DEG C, add the hexane solution containing n-BuLi, the mode wherein added can be disposable addition, it is possible to for dripping, when adopting the mode of dropping, the time of dropping according to circumstances selects, the time of dropping is 0.5～2 hour, and further, the time of dropping is preferably 1～1.5 hour.In addition, before intermediate C is joined system, also it is dispersed in oxolane, then the oxolane containing intermediate C is joined in system, as long as wherein intermediate C is scatter by the addition of oxolane, it is preferable that the mode of dropping joins in system, the time of dropping is preferably 0.5～3 hour, further, the time of dropping is preferably 1～2 hour.
In above-mentioned steps (3), after adding the oxolane containing intermediate C, system reacts at 15～40 DEG C, and further, system reacts at 20～30 DEG C；The time of reaction is preferably 2～6 hours, and further, the time of reaction is preferably 3～5 hours.It is pointed out that and preferably in the way of dropping, the oxolane containing intermediate C is joined in system.
In above-mentioned steps (3), reaction system containing intermediate D is carried out following post processing: in reaction system, add saturated aqueous ammonium chloride, at room temperature stir, it is preferable that 1～4 hour time of stirring, after stirring, separatory, then organic facies is spin-dried for, it is subsequently adding acetone, making beating stirring at 60 DEG C, preferably stirring 1～3 hour, sucking filtration, it is thus achieved that the intermediate D after purification.Wherein, the addition of saturated aqueous ammonium chloride is preferably 1～3 times of the weight of intermediate C, further, it is preferred to 1～2 times of the weight of intermediate C；And the addition of acetone is preferably 2～5 times of weight of intermediate C, further, the addition of acetone is preferably 3～4 times of the weight of intermediate C.
Intermediate D and concentrated hydrochloric acid are joined in acetic acid by step (4) to react, obtain the reaction system containing intermediate E, again intermediate E is joined in oxolane, after system being lowered the temperature, being sequentially added into the hexane solution containing n-BuLi and methyl borate. in oxolane, reaction obtains the reaction system containing intermediate F, wherein intermediate E and intermediate F are successively as shown in following formula 6, formula 7, in formula 6 and formula 7, substituent R as illustrated as the former, so repeating no more.
In above-mentioned steps (4), the mol ratio of concentrated hydrochloric acid and intermediate D is concentrated hydrochloric acid: intermediate D=2～10:1, the mass percent of concentrated hydrochloric acid is preferably 20～37%, it is further preferred that the mass percent of concentrated hydrochloric acid is 30～37%；The addition of acetic acid is preferably 8～12 times of the weight of intermediate D, further, it is preferred to 9～10 times of the weight of intermediate D.The mol ratio of intermediate E and n-BuLi is preferably intermediate E: n-BuLi=1:0.9～1.3, further, therebetween mol ratio is preferably 1:0.9～1, it should further be noted that, n-BuLi molar concentration in hexane solution is preferably 1.5～3mol/L, further, molar concentration is preferably 2～2.5mol/L；The mol ratio of methyl borate. and intermediate E is preferably methyl borate.: intermediate E=1.5～3:1, and further, the mol ratio of methyl borate. and intermediate E is preferably methyl borate.: intermediate E=1.5～2:1.Same, the addition of oxolane is conventional addition, can select according to the actual requirements.
In above-mentioned steps (4), intermediate D and concentrated hydrochloric acid are joined after in acetic acid, by system heating to back flow reaction；The time of system reaction is preferably 3～8 hours, and further, the time of system reaction is preferably 4～6 hours.
In above-mentioned steps (4), after adding intermediate E in oxolane, system being down to-100～-80 DEG C, is subsequently adding the hexane solution containing n-BuLi, the mode wherein added can be disposable addition, it is alternatively dropping, when adopting the mode of dropping, the time of dropping according to circumstances selects, and the time of dropping is 0.5～2 hour, further, the time of dropping is preferably 1～1.5 hour.Additionally, the mode that methyl borate. can drip joins in system, the time of dropping is preferably 0.5～3 hour, and further, the time of dropping is preferably 1～2 hour.
In above-mentioned steps (4), after adding methyl borate., system reacts at-100～-80 DEG C, and the time of reaction is preferably 0.5～1.5 hour；Afterwards, system being reacted at 20～30 DEG C, the time of reaction is preferably 1.5～3 hours.
In above-mentioned steps (4), after adding intermediate E, system reacts in a nitrogen atmosphere, and wherein, the draft speed of nitrogen is preferably 30～60ml/min.
In above-mentioned steps (4), it is preferable that the reaction system containing intermediate E is carried out following post processing, then the intermediate E through post processing is carried out next step reaction: desolvation, it is subsequently adding ethyl acetate, the addition of ethyl acetate makes system scatter, then washes, and the number of times of washing is preferably three times, afterwards organic facies is spin-dried for, adding acetone, then pulling an oar at 50 DEG C, the time of making beating is preferably 1～3 hour, sucking filtration after making beating, it is thus achieved that intermediate E.
In above-mentioned steps (4), it is preferable that the reaction system containing intermediate F is carried out following post processing: adding mass percent in system is the hydrochloric acid of 10%, at room temperature stirs, the time of stirring is preferably 0.5～2 hour, desolvation afterwards, after adding water, pulls an oar at 60 DEG C, it is subsequently adding petroleum ether, pull an oar at 60 DEG C again, wherein, when water and petroleum ether, all preferably making beating is 1～3 hour, it is thus achieved that the intermediate F after purification.
Step (5), by intermediate F, 2,2 '-'-dibromobiphenyl and potassium carbonate join after in the mixed solvent of water and toluene, react, it is thus achieved that containing the reaction system of intermediate G under the catalytic action of four triphenyl phosphorus palladiums, wherein, intermediate G is such as shown in following formula 8.
In above-mentioned steps (5), intermediate F and 2, the mol ratio of 2 '-'-dibromobiphenyl is preferably intermediate F:2,2 '-'-dibromobiphenyl=1:1～2, further, intermediate F and 2, the mol ratio of 2 '-'-dibromobiphenyl is preferably intermediate F:2,2 '-'-dibromobiphenyl=1:1～1.5；The mol ratio of potassium carbonate and intermediate F is preferably potassium carbonate: intermediate F=2～3:1, and further, the mol ratio of potassium carbonate and intermediate F is preferably potassium carbonate: intermediate F=2～2.5:1；The addition of four triphenyl phosphorus palladiums is preferably the 2～5% of the weight of intermediate F, and further, the addition of four triphenyl phosphorus palladiums is preferably the 2.5～3.5% of the weight of intermediate F.It addition, the weight ratio of water and toluene is preferably water: toluene=1:1～3, further, the weight ratio of water and toluene is preferably water: toluene=1:1.5～2.
In above-mentioned steps (5), system reacts at 50～100 DEG C, further, it is preferable that react at 60～80 DEG C；The time of reaction is preferably 3～7 hours, and further, the time of reaction is preferably 4～6 hours.
In above-mentioned steps (5), system reacts in a nitrogen atmosphere.
In above-mentioned steps (5), the reaction system containing intermediate G is preferably performed following process: by system sucking filtration, adds toluene, pull an oar at 60 DEG C, the time of making beating is preferably 1～3 hour, sucking filtration again after big slurry, it is thus achieved that the intermediate G after purification.
Step (6), intermediate G and ferric chloride are joined in dichloromethane react, it is thus achieved that containing the reaction system of intermediate H, wherein, intermediate H is such as shown in following formula 8.
In above-mentioned steps (6), the weight ratio of intermediate G and ferric chloride is preferably intermediate G: ferric chloride=1:1～3, and further, the weight ratio of intermediate G and ferric chloride is preferably intermediate G: ferric chloride=1:1～1.5；The weight ratio of intermediate G and dichloromethane is preferably intermediate G: dichloromethane=1:15～20, and further, the weight ratio of intermediate G and dichloromethane is preferably intermediate G: ferric chloride=1:17～19.
In above-mentioned steps (6), system is reacted at 20～40 DEG C, further, it is preferable that react at 20～30 DEG C；The response time of system is preferably 20～48 hours, and further, the response time of system is preferably 20～26 hours.
In above-mentioned steps (6), reaction system containing intermediate H is preferably performed following process: after system sucking filtration, filtrate is spin-dried for, in the material obtained after being spin-dried for, adds oxolane, then cross post, after again effluent being spin-dried for, adding toluene, then pull an oar at 70 DEG C, the time of making beating is preferably 1～3 hour, sucking filtration after making beating, it is thus achieved that intermediate H.
Step (7), by intermediate H, wet chemical and Ar-B (OH)2Join after in toluene, react under the catalytic action of four triphenyl phosphorus palladiums, it is thus achieved that containing the reaction system of the compound shown in formula I, namely obtain the reaction system containing electron transport material provided by the invention, at Ar-B (OH)2In, described in substituent A r is such as aforementioned, do not repeat one by one at this.
In above-mentioned steps (7), intermediate H and Ar-B (OH)2Mol ratio be preferably intermediate H:Ar-B (OH)2=1:1～2, further, intermediate H and Ar-B (OH)2Mol ratio be preferably intermediate H:Ar-B (OH)2=1:1～1.5；It is potassium carbonate that the addition of wet chemical is preferably such that the mol ratio of potassium carbonate and intermediate H: intermediate H=2～6:1, further, the mol ratio of potassium carbonate and intermediate H is preferably potassium carbonate: intermediate H=2～3:1, in addition, the molar concentration of wet chemical is preferably 1～4mol/L, further, the molar concentration of wet chemical is preferably 1～2mol/L；The addition of four triphenyl phosphorus palladiums is preferably the 2～5% of the weight of intermediate H, and further, the addition of four triphenyl phosphorus palladiums is preferably the 3～4% of the weight of intermediate H.
In above-mentioned steps (7), system is reacted at 60～100 DEG C, and further, system is reacted at 70～85 DEG C；The time of system reaction is preferably 1～4 hour, and further, the time of system reaction is preferably 1～2 hour.
In above-mentioned steps (4), system reacts in a nitrogen atmosphere, and wherein, the draft speed of nitrogen is preferably 30～60ml/min.
In above-mentioned steps (7), reaction system containing the compound shown in formula I is preferably performed following post processing: after reacting completely through thin layer chromatography (being called for short TLC) detection system, system separatory, select ethyl acetate washing aqueous phase again, the number of times selecting ethyl acetate washing according to circumstances selects, preferably washing three times, after merging organic facies, select column chromatography purification to remove catalyst, obtain the compound shown in formula I after purification, wherein during column chromatography, compound shown in formula I is purified by preferred petroleum ether and ethyl acetate, namely electron transport material provided by the present invention is purified, in addition, suitable Solvent Gradient can be selected according to the actual requirements to be purified, the volume ratio of preferred petroleum ether and ethyl acetate is petroleum ether: ethyl acetate=4:1.
In order to improve the purity of electron transport material further, select vacuum sublimation to being purified, for instance can be selected for vacuum sublimation instrument and electron transport material is purified, actual conditions parameter is as follows: distillation vacuum is 2 × 10-5Pa, the three district's temperature that distil are 260 DEG C, and the two district's temperature that distil are 160 DEG C, and the district's temperature that distils is 100 DEG C, in each district, established temperature is gradient increased temperature, and every 15min raises 50 DEG C, after being increased to target temperature, insulation distillation 6.0 hours, distillation obtains final products.It is 99.5% that the final compound shown in formula I obtained detects purity through high performance liquid chromatography (HPLC), and distillation yield may be up to 90%.
In the preparation method of above-mentioned offer, electron transport material passes through coupling reaction, and cyclization, low temperature metalization, cyclization and again coupling reaction prepare.
The preparation method of electron transport material provided by the invention is simple and easy, it is easy to operation, and with low cost, is conducive to large-scale popularization.Additionally, the electron transport material purity that the present invention prepares is high, productivity is high, and the raw material used in the process of preparation is convenient source, with low cost.
A further object of the present invention is in that to provide a kind of organic electroluminescence device, including anode, hole transmission layer, luminescent layer, hole blocking layer, electron transfer layer, negative electrode, anode has been sequentially stacked hole transmission layer, luminescent layer, hole blocking layer, electron transfer layer and negative electrode, wherein, electron transfer layer is made up of electron transport material provided by the invention.
In above-mentioned organic electroluminescence device, also including electron injecting layer 106, electron injecting layer 106 is between electron transfer layer 105 and negative electrode 107.
In above-mentioned organic electroluminescence device, anode preferential oxidation indium stannum (referred to as ITO) electro-conductive glass.
Organic electroluminescence provided by the invention selects conventional method to prepare, and there is no special demand.
In organic electroluminescence provided by the invention, due to containing electron transport material provided by the invention, it is possible to be greatly improved the electric current density of organic electroluminescence, electric current and brightness, meanwhile, also reduce driving voltage, significantly improve the life-span of organic electroluminescence.
Accompanying drawing explanation
Fig. 1 is the structural representation of organic electroluminescence provided by the invention.
Drawing reference numeral illustrates:
101-anode, 102-hole transmission layer, 103-luminescent layer, 104-hole blocking layer, 105-electron transfer layer, 106-electron injecting layer, 107-negative electrode.
Detailed description of the invention
The application is further described below by way of instantiation.But these examples are only exemplary, the protection domain of the application do not constituted any restriction.
In following embodiment, comparative example, used 2-bromopyridine, the bromo-2-carboxylic acid methyl phenylboric acid of 3-, 2,2 '-'-dibromobiphenyl, the compound such as 2-bromo biphenyl all can Chemical market be commercially available at home.Phenylboric acid, 1-naphthalene boronic acids, furan boronic acid, thienyl boric acid, 4-boric acid dibenzofurans, 4-boric acid dibenzothiophenes, 2-pyridine boronic acid, the pyridine boronic acid of 3-pyridine boronic acid and replacement all adopts the synthesis of common methodology of organic synthesis to obtain.It addition, the reagent used, material and instrument be not as having special explanation, being conventional reagent, conventional material and conventional instrument, all commercially available, wherein involved reagent obtains also by conventional synthesis process synthesis.
Embodiment one, prepare electron transport material
Embodiment 1The material 1 that preparation is previously mentioned
Step (1), intermediate A preparation
2-bromopyridine by 157.9g (1mol), 284.6g the bromo-2-carboxylate methyl ester phenylboric acid of 3-and the potassium carbonate of 276g (2mol) (1.1mol) join after in the mixed solvent containing 600g water and 800g toluene, under nitrogen protection, at room temperature stir 20min, it is subsequently adding 1g tetra-triphenyl phosphorus palladium, under the catalytic action of four triphenyl phosphorus palladiums, and at 80 DEG C, insulation reaction 24h, it is then passed through TLC detection compound 2-bromopyridine to react completely, afterwards by system separatory, again organic facies is spin-dried for, then petroleum ether and ethyl acetate is adopted to carry out column chromatography, obtaining the intermediate A after purification is 268.6g, intermediate A is shown below.This intermediate A learns that purity is 99% after gas chromatogram (referred to as GC) is tested, and yield is 91.9%.
The preparation of step (2), intermediate B and intermediate C
The intermediate A that will obtain in 146g (0.5mol) step (1), 80g (2mol) sodium hydroxide joins in 1000g dehydrated alcohol, after system heating to back flow reaction 3h, elimination ethanol, adding 1000g mass percent again in reaction system is the dilute hydrochloric acid of 10%, now system precipitates out a large amount of white solids, then sucking filtration, obtain white solid, 5h is dried afterwards at 80 DEG C, obtaining 135.6g intermediate B, intermediate B is white solid, and the crude yield being computed its intermediate B is 97%.
The intermediate B that 139.1g (0.5mol) obtains is joined after in the concentrated sulphuric acid that 500g mass percent is 98%, stirring reaction 5h at 60 DEG C, afterwards reaction system is poured in 3000g frozen water, add 500g ethyl acetate to extract, after separatory, organic facies is spin-dried for, then column chromatography is selected to be purified, when column chromatography, select petroleum ether and ethyl acetate that intermediate is purified, wherein the volume ratio of petroleum ether and ethyl acetate is petroleum ether: ethyl acetate=4:1, finally preparing 128.6g intermediate C, intermediate C is yellow solid.This intermediate C learns that purity is 99% after gas chromatogram (referred to as GC) is tested, and yield is 98.9%.
It addition, intermediate B and intermediate C are shown below:
Step (3), intermediate D preparation
null116.5g (0.5mol) 2-bromo biphenyl is joined after in 800g oxolane，System is cooled to-90 DEG C，Drip the 227ml hexane solution containing n-BuLi again，Wherein，N-BuLi molar concentration in hexane solution is 2.2mol/L，Control system temperature less than-80 DEG C，1 hour dropwises the hexane solution containing n-BuLi，Then insulation reaction 1 hour，Afterwards when controlling system temperature less than-80 DEG C，In reaction system, the oxolane containing intermediate C is dropwised in 1 hour，The oxolane of 200g wherein contains the intermediate C obtained in step (2) of 130g (0.5mol)，After dropwising，System is moved to and reacts 4 hours at 25 DEG C，Afterwards，200g saturated aqueous ammonium chloride is added in reaction system，After at room temperature continuing stirring 1 hour，Separatory，Organic facies is spin-dried for，Add 500g acetone，Making beating stirring 1 hour at 60 DEG C，Last sucking filtration，Obtaining the intermediate D after purification is 165.7g，Intermediate D is white solid，And intermediate D is shown below.This intermediate D learns that purity is 99.2% after gas chromatogram (referred to as GC) is tested, product yield 80%.
The preparation of step (4), intermediate E and intermediate F
It is that 36.5% concentrated hydrochloric acid joins after in 1200g acetic acid by middle for 124.3g (0.3mol) step (3) the intermediate D obtained and 10ml mass percent, by system heating to insulation reaction 5h under reflux state, afterwards, desolvation obtains 150g brownish red grease, add 1000g ethyl acetate, after system is entirely molten, wash three times with water, each water is 500ml, then the organic facies obtained is spin-dried for, obtain 110g yellow solid, add 600g acetone, pull an oar 1h at 50 DEG C, sucking filtration afterwards, obtaining intermediate E is 82.6, it is yellow powder, learn that the purity of intermediate E is 99.6% through high performance liquid chromatography (being called for short HPLC) detection, yield is 70.1%；
nullWhen nitrogen is 50ml/min，39.6g (0.1mol) intermediate E obtained is added in 600g oxolane，When control volume ties up to less than-80 DEG C afterwards，The 45ml hexane solution containing n-BuLi is dripped in system，Wherein，N-BuLi molar concentration in hexane solution is 2.2mol/L，After adding n-BuLi，Architecture heat preservation reaction 1h，And backward reaction system adds 15.6g (0.15mol) methyl borate.，After insulation reaction 1h，System is moved to 25 DEG C of reaction 2h，After reaction terminates，Dripping 200ml mass fraction in reaction system is the hydrochloric acid of 10%，At room temperature stir 1h，Solvent is deviate from rotation steaming，Obtain white solid，Add 600g water，Pull an oar 1h at 60 DEG C，Add 600g petroleum ether，Pull an oar 1h at 60 DEG C，It is 30.2g that sucking filtration obtains intermediate F，It is white powder solid.Learning that the purity of intermediate F is 99.6% through high performance liquid chromatography (being called for short HPLC) detection, yield is 83.6%.
It addition, intermediate E and intermediate F are shown below successively.
Step (5), intermediate G preparation
The intermediate G that will obtain in 36.1g (0.1mol) step (4), 31.1g (0.1mol) 2, 2 '-'-dibromobiphenyl and 27.6g (0.2mol) potassium carbonate join in the mixed solvent of 600g toluene and 300g water, then under nitrogen protection, 30min is stirred at room temperature, then add 1g tetra-triphenyl phosphorus palladium, then insulation reaction 5h at 70 DEG C, after question response system precipitates out a large amount of yellow solids, sucking filtration, filter cake adds 500g toluene, pull an oar 1h at 60 DEG C, afterwards, sucking filtration again, obtaining the intermediate G after purification is 42.6g, it is glassy yellow powder, intermediate G is shown below.Learning that the purity of intermediate G is 98.6% through high performance liquid chromatography (being called for short HPLC) detection, yield is 77.7%.
Step (6), intermediate H preparation
54.8g (0.1mol) intermediate G is joined in 1000g dichloromethane, after system is clarified, in reaction system, at room temperature add 80g ferric chloride, 24h is stirred at 25 DEG C, afterwards by reaction system sucking filtration, and after filtrate is spin-dried for, add 1000g oxolane by be spin-dried for the product of acquisition entirely molten after, cross post, after effluent is spin-dried for again, obtaining yellow solid, add 1000g toluene, pull an oar 1h at 70 DEG C, sucking filtration, obtaining intermediate H is 26.9g, and it is yellow powder, and intermediate H is shown below.Learning that the purity of intermediate H is 98.8% through high performance liquid chromatography (being called for short HPLC) detection, yield is 49.3%.
Step (7), material 1 preparation
When nitrogen flow rate is 50mL/min, 5.5g (0.01mol) intermediate H, 1.3g (0.011mol) phenylboric acid and wet chemical are joined after in 100g toluene, at room temperature stir 20min, afterwards, in system, add 0.2g tetra-triphenyl phosphorus palladium, at 85 DEG C, react 2h, wherein, potassium carbonate is 0.03mol, and potassium carbonate molar concentration in aqueous is 2M/L.After TLC detection is learnt and is reacted completely, system separatory, wash aqueous phase by 100mL ethyl acetate, merge organic facies, select column chromatography to remove catalyst, when column chromatography, selecting petroleum ether and ethyl acetate that the compound shown in formula I is purified, wherein the volume ratio of petroleum ether and ethyl acetate is petroleum ether: ethyl acetate=4:1, and chromatographic solution is steamed in rotation, obtaining material 1 is 4.6g, and it is pale yellow powder.Learning that the purity of material 1 is 97.9% through high performance liquid chromatography (being called for short HPLC) detection, yield is 84.7%.
Weigh the material 1 of the above-mentioned acquisition of 4g, be placed in vacuum sublimation instrument, it is as follows that distillation parameter is set: distillation vacuum is 2 × 10-5Pa, the three district's temperature that distil are 260 DEG C, and the two district's temperature that distil are 160 DEG C, and the district's temperature that distils is 100 DEG C, in each district, established temperature is gradient increased temperature, and every 15min raises 50 DEG C, after being increased to target temperature, insulation distillation 5h, it is 3.6g that distillation obtains the material 1 after purification jointly.Learning that the purity of material 1 is 99.5% through high performance liquid chromatography (being called for short HPLC) detection, yield is 90%, and learns through high resolution mass spectrum, and test value [M+1] is 544.1990, and theoretical value is 544.1986.
Embodiment 2The material 5 that preparation is previously mentioned
The identical preparation method adopted and prepare material 1 in embodiment 1 and proportioning raw materials, be wherein that phenylboric acid replaces with 3-pyridine boronic acid in step (7), and all the other are constant.Through high performance liquid chromatography (being called for short HPLC) detection, the material 5 finally obtained being learnt, the purity of material 5 is 99.6%, and learns through high resolution mass spectrum, test value [M+1] is 544.1990, and theoretical value is 544.1986.
Embodiment 3The material 6 that preparation is previously mentioned
The identical preparation method adopted and prepare material 1 in embodiment 1 and proportioning raw materials, be wherein that phenylboric acid replaces with 2-pyridine boronic acid in step (7), and all the other are constant.Through high performance liquid chromatography (being called for short HPLC) detection, the material 6 finally obtained being learnt, the purity of material 6 is 99.6%, and learns through high resolution mass spectrum, test value [M+1] is 544.1996, and theoretical value is 544.1986.
Embodiment 4The material 7 that preparation is previously mentioned
The identical preparation method adopted and prepare material 1 in embodiment 1 and proportioning raw materials, be wherein that phenylboric acid replaces with 3-phenyl-2-pyridine boronic acid in step (7), and all the other are constant.Through high performance liquid chromatography (being called for short HPLC) detection, the material 7 finally obtained being learnt, the purity of material 7 is 99.2%, and learns through high resolution mass spectrum, test value [M+1] 621.2256, theoretical value is 621.2252.
Embodiment 5The material 11 that preparation is previously mentioned
The identical preparation method adopted and prepare material 1 in embodiment 1 and proportioning raw materials, be wherein that phenylboric acid replaces with 4-quinoline boronic acid in step (7), and all the other are constant.Through high performance liquid chromatography (being called for short HPLC) detection, the material 11 finally obtained being learnt, the purity of material 11 is 99.3%, and learns through high resolution mass spectrum, test value [M+1] 595.2088, theoretical value is 595.2096.
Embodiment 6The material 12 that preparation is previously mentioned
The identical preparation method adopted and prepare material 1 in embodiment 1 and proportioning raw materials, be wherein, in step (7), phenylboric acid is replaced with 8-quinolineboronic acid, and all the other are constant.Through high performance liquid chromatography (being called for short HPLC) detection, the material 12 finally obtained being learnt, the purity of material 12 is 99.3%, and learns through high resolution mass spectrum, test value [M+1] 595.2089, theoretical value is 595.2096.
Embodiment 7The material 13 that preparation is previously mentioned
The identical preparation method adopted and prepare material 1 in embodiment 1 and proportioning raw materials, be wherein that phenylboric acid replaces with 3,5-diphenyl triazine boric acid in step (7), and all the other are constant.Through high performance liquid chromatography (being called for short HPLC) detection, the material 13 finally obtained being learnt, the purity of material 13 is 99.8%, and learns through high resolution mass spectrum, test value [M+1] 699.2466, theoretical value is 699.2470.
Embodiment 8The material 15 that preparation is previously mentioned
The identical preparation method adopted and prepare material 1 in embodiment 1 and proportioning raw materials, be wherein that phenylboric acid replaces with 4-dibenzofurans boric acid in step (7), and all the other are constant.Through high performance liquid chromatography (being called for short HPLC) detection, the material 15 finally obtained being learnt, the purity of material 15 is 99.8%, and learns through high resolution mass spectrum, test value [M+1] 634.2088, theoretical value is 634.2093.
Embodiment 9The material 16 that preparation is previously mentioned
The identical preparation method adopted and prepare material 1 in embodiment 1 and proportioning raw materials, be wherein that phenylboric acid replaces with 4-dibenzothiophenes boric acid in step (7), and all the other are constant.Through high performance liquid chromatography (being called for short HPLC) detection, the material 16 finally obtained being learnt, the purity of material 16 is 99.7%, and learns through high resolution mass spectrum, test value [M+1] 650.1866, theoretical value is 650.1864.
Embodiment 10The material 17 that preparation is previously mentioned
The identical preparation method adopted and prepare material 1 in embodiment 1 and proportioning raw materials, be wherein, in step (3), 2-bromo biphenyl is replaced with 4, and 4 '-di-t-butyl-2-bromo biphenyl, all the other are constant.Through high performance liquid chromatography (being called for short HPLC) detection, the material 17 finally obtained being learnt, the purity of material 17 is 99.7%, and learns through high resolution mass spectrum, test value [M+1] 656.3280, theoretical value is 656.3286.
Embodiment 11The material 19 that preparation is previously mentioned
The identical preparation method adopted and prepare material 17 in embodiment 10 and proportioning raw materials, be wherein that phenylboric acid replaces with 2-furan boronic acid in step (7), and all the other are constant.Through high performance liquid chromatography (being called for short HPLC) detection, the material 19 finally obtained being learnt, the purity of material 19 is 99.7%, and learns through high resolution mass spectrum, test value [M+1] 646.3026, theoretical value is 646.3032.
Embodiment 12The material 21 that preparation is previously mentioned
The identical preparation method adopted and prepare material 17 in embodiment 10 and proportioning raw materials, be wherein that phenylboric acid replaces with 3-pyridine boronic acid in step (7), and all the other are constant.Through high performance liquid chromatography (being called for short HPLC) detection, the material 21 finally obtained being learnt, the purity of material 21 is 99.7%, and learns through high resolution mass spectrum, test value [M+1] 657.3186, theoretical value is 657.3191.
Embodiment 13The material 22 that preparation is previously mentioned
The identical preparation method adopted and prepare material 17 in embodiment 10 and proportioning raw materials, be wherein that phenylboric acid replaces with 2-pyridine boronic acid in step (7), and all the other are constant.Through high performance liquid chromatography (being called for short HPLC) detection, the material 22 finally obtained being learnt, the purity of material 22 is 99.7%, and learns through high resolution mass spectrum, test value [M+1] 657.3188, theoretical value is 657.3191.
Embodiment 14The material 27 that preparation is previously mentioned
The identical preparation method adopted and prepare material 17 in embodiment 10 and proportioning raw materials, be wherein that phenylboric acid replaces with 4-quinoline boronic acid in step (7), and all the other are constant.Through high performance liquid chromatography (being called for short HPLC) detection, the material 27 finally obtained being learnt, the purity of material 27 is 99.7%, and learns through high resolution mass spectrum, test value [M+1] 707.3356, theoretical value is 707.3348.
Embodiment 15The material 31 that preparation is previously mentioned
The identical preparation method adopted and prepare material 17 in embodiment 10 and proportioning raw materials, be wherein that phenylboric acid replaces with 4-dibenzofurans boric acid in step (7), and all the other are constant.Through high performance liquid chromatography (being called for short HPLC) detection, the material 31 finally obtained being learnt, the purity of material 31 is 99.7%, and learns through high resolution mass spectrum, test value [M+1] 746.3346, theoretical value is 746.3345.
Embodiment 16The material 32 that preparation is previously mentioned
The identical preparation method adopted and prepare material 17 in embodiment 10 and proportioning raw materials, be wherein that phenylboric acid replaces with 4-dibenzothiophenes boric acid in step (7), and all the other are constant.Through high performance liquid chromatography (being called for short HPLC) detection, the material 32 finally obtained being learnt, the purity of material 32 is 99.7%, and learns through high resolution mass spectrum, test value [M+1] 762.3130, theoretical value is 762.3136.
Being carried out high performance liquid chromatography and high resolution mass spectrum detection by the material that above-described embodiment is obtained, it is possible to learn, the present invention have successfully been obtained the electron transport material shown in formula I, and purity is high and productivity is high.
Embodiment two prepares organic electroluminescence device (hereinafter referred to as device)
In the following embodiment preparing organic electroluminescence device and comparative example, used reagent material is as follows:
1, it is the electron transport material in the organic electroluminescence device prepared in embodiment by the material 1 provided in embodiment one, material 5, material 11, material 12, material 15, material 16, material 17, material 19, material 22, material 27, material 31, material 32；
Further relate to following material:
2, selecting glass is substrate layer, and tin indium oxide (referred to as ITO) is anode material, and NPB is as hole mobile material, and LiF is as electron injection material, and Al is cathode material.
Embodiment 1～12The preparation of device 1～12
Device 1～12 all adopts following method to be prepared:
A) first select abluent that the substrate layer being coated with anode material is carried out ultrasonic cleaning, afterwards, with deionized water rinsing, select the ultrasonic oil removing of mixed solvent of acetone and ethanol again, then it is baked under clean environment and completely removes moisture, again by ultraviolet light and ozone clean, and with mental retardation positron bundle bombarded surface；
B) substrate layer being coated with anode material is positioned in vacuum chamber, and then evacuation makes the pressure in vacuum chamber be 9 × 10-5Pa, is deposited with NPB on anode with the evaporation rate of 0.05nm/s and obtains hole transmission layer, and the thickness of hole transmission layer is 40nm；
C) with the evaporation rate of 0.05nm/s vacuum evaporation EML on hole transmission layer, it is thus achieved that luminescent layer, the thickness of luminescent layer is 40nm；
D) with the evaporation rate of 0.05nm/s vacuum evaporation electron transport material on luminescent layer, the thickness of electron transfer layer is 30nm；
E) on the electron transport layer, vacuum evaporation obtains cathode material and obtains cathode layer, it is thus achieved that device, wherein, the thickness of cathode layer is 150nm.
The device prepared, as shown in fig. 1, including anode 101, hole transmission layer 102, luminescent layer 103, hole blocking layer 104, electron transfer layer 105, negative electrode 107, anode 101 has been sequentially stacked hole transmission layer 102, luminescent layer 103, hole blocking layer 104, electron transfer layer 105 and negative electrode 107.Wherein, electron transfer layer 105 is made up of electron transport material provided by the invention.
In the above-described embodiments, used in each embodiment electron transport material is as shown in table 1 below:
Table 1
Device number Electron transport material kind Device number Electron transport material kind
Device 1 Material 1 Device 7 Material 7
Device 2 Material 2 Device 8 Material 8
Device 3 Material 3 Device 9 Material 9
Device 4 Material 4 Device 10 Material 10
Device 5 Material 5 Device 11 Material 11
Device 6 Material 6 Device 12 Material 12
Comparative example 1The preparation of device 1#
Repeating the preparation of device 1 in embodiment 1, simply in step d), using BPhen as electron transport material, all the other are constant.
Test example
The device obtained in above-described embodiment and contrast 1 is all carried out following test: the brightness requirement of device is 5000cd/m2, the electric current density of device, brightness, voltage characteristic are all measured system (Keithley236sourceMeasureUnit) by the Keithley source with corrected silicon photoelectric diode to complete, and all measurements all complete in atmosphere at room temperature.
The voltage of device, electric current density and the electric current that obtain in test above-described embodiment and comparative example are all as shown in table 2 below.
Table 2
By above-mentioned table 2 it is known that electron transport material provided by the present invention can be applicable in organic electroluminescence device, and good performance can be obtained.Compared with device 1#, the driving voltage of device 1～10 substantially reduces, and electric current density and electric current are all significantly improved.
Comprehensive, electron transport material provided by the present invention is applied in organic electroluminescence device, organic electroluminescence device is made to have electronic transmission performance and the filming performance of excellence, thus improve stability and the service life of organic electroluminescence device.
The announcement of book according to the above description, above-mentioned embodiment can also be carried out suitable change and amendment by the application those skilled in the art.Therefore, the application is not limited to detailed description of the invention disclosed and described above, should also be as some modifications and changes of the application falling in the protection domain of claims hereof.

Claims (10)

1. an electron transport material, it is characterised in that shown in following formula I:
Wherein, R one in hydrogen-based and alkyl that carbon number is 1～10；Ar is selected from the condensed-nuclei aromatics base that the aryl that carbon number is 6～20, carbon number are 10～20 and containing the one at least one in nitrogen-atoms, oxygen atom and sulphur atom and aromatic heterocyclic radical that carbon number is 4～20.
2. electron transport material according to claim 1, it is characterised in that
R is the alkyl of 1～6 selected from carbon number；
Ar is the condensed-nuclei aromatics base of 10～14 selected from the aryl that carbon number is 6～12, carbon number and is the aromatic heterocyclic radical of 4～18 containing at least one and carbon number in nitrogen-atoms, oxygen atom and sulphur atom.
3. electron transport material according to claim 1, it is characterised in that
R one in methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl and the tert-butyl group；
Ar one in following radicals:
4. the preparation method of the electron transport material according to any one of a claims 1 to 3, it is characterised in that comprise the following steps:
(1), 2-bromopyridine, the bromo-2-carboxylate methyl ester phenylboric acid of 3-and potassium carbonate are joined after in the mixed solvent containing water and toluene, react under the catalytic action of four triphenyl phosphorus palladiums, obtaining the reaction system containing intermediate A, intermediate A is such as shown in following formula 1；
(2), intermediate A and sodium hydroxide are joined in dehydrated alcohol, reaction obtains the reaction system containing intermediate B, then intermediate B is joined in concentrated sulphuric acid and reacts, it is thus achieved that containing the reaction system of intermediate C, wherein, intermediate B and intermediate C are successively as shown in following formula 2, formula 3；
(3), raw material 1 is joined in oxolane, cooling, add the hexane solution containing n-BuLi, then the oxolane containing intermediate C is added to system, reaction obtains the reaction system containing intermediate D, and wherein, raw material 1 and intermediate D are successively as shown in following formula 4, formula 5；
(4) intermediate D and concentrated hydrochloric acid are joined in acetic acid and react, obtain the reaction system containing intermediate E, again intermediate E is joined in oxolane, after system is lowered the temperature, the hexane solution containing n-BuLi and methyl borate. it is sequentially added in system, reaction obtains the reaction system containing intermediate F, and wherein intermediate E and intermediate F are successively as shown in following formula 6, formula 7；
(5), by intermediate F, 2,2 '-'-dibromobiphenyl and potassium carbonate join after in the mixed solvent of water and toluene, react, it is thus achieved that containing the reaction system of intermediate G, wherein, intermediate G is such as shown in following formula 8 under the catalytic action of four triphenyl phosphorus palladiums；
(6), intermediate G and ferric chloride are joined in dichloromethane and react, it is thus achieved that containing the reaction system of intermediate H, wherein, intermediate H is such as shown in following formula 8；
(7), by intermediate H, wet chemical and Ar-B (OH)2Join after in toluene, react under the catalytic action of four triphenyl phosphorus palladiums, it is thus achieved that containing the reaction system of the compound shown in formula I.
5. the preparation method of electron transport material according to claim 4, it is characterised in that
In described step (1), the mol ratio of 2-bromopyridine and 3-bromo-2-carboxylate methyl ester phenylboric acid is bromo-2-carboxylate methyl ester phenylboric acid=1:1～1.5 of 2-bromopyridine: 3-, the addition of potassium carbonate is the mol ratio making it with 2-bromopyridine is potassium carbonate: 2-bromopyridine=1.8～2.5:1, the 0.3～1% of the weight that addition is 2-bromopyridine of four triphenyl phosphorus palladiums；
In described step (2), the mol ratio of intermediate A and sodium hydroxide is intermediate A: sodium hydroxide=1:3～6, and the addition of concentrated sulphuric acid is 2～6 times of the weight of intermediate B；
In described step (3), the mol ratio of intermediate C and raw material 1 is 1:1～2, and the addition of n-BuLi makes the mol ratio of n-BuLi and intermediate C be n-BuLi: intermediate C=1:1.05～1.2；
In described step (4), the mol ratio of concentrated hydrochloric acid and intermediate D is concentrated hydrochloric acid and intermediate D=2～10:1, the mol ratio of intermediate E and n-BuLi is intermediate E: n-BuLi=1:0.9～1.3, and the mol ratio of methyl borate. and intermediate E is methyl borate.: intermediate E=1.5～3:1；
In described step (5), intermediate F and 2, the mol ratio of 2 '-'-dibromobiphenyl is intermediate F:2,2 '-'-dibromobiphenyl=1:1～2, the mol ratio of potassium carbonate and intermediate F is potassium carbonate: intermediate F=2～3:1, the 2～5% of the weight that addition is intermediate F of four triphenyl phosphorus palladiums；
In described step (6), the weight ratio of intermediate G and ferric chloride is intermediate G: ferric chloride=1:1～3；
In described step (7), intermediate H and Ar-B (OH)2Mol ratio be intermediate H:Ar-B (OH)2=1:1～2, it is potassium carbonate that the addition of wet chemical is preferably such that the mol ratio of potassium carbonate and intermediate H: intermediate H=2～6:1, the 2～5% of the weight that addition is intermediate H of four triphenyl phosphorus palladiums.
6. the preparation method of electron transport material according to claim 4, it is characterised in that
In described step (1), system reacts at 50～120 DEG C；
In described step (2), intermediate A and sodium hydroxide being joined after in dehydrated alcohol, system heating reacted to backflow, intermediate B joined after in concentrated sulphuric acid, system reacts at 40～120 DEG C；
In described step (3), after cooling the temperature to-100～-80 DEG C, adding the hexane solution containing n-BuLi, after adding the oxolane containing intermediate C, system reacts at-100～-80 DEG C；
In described step (4), intermediate D and concentrated hydrochloric acid are joined after in acetic acid, by system heating to back flow reaction, it is down under-100～-80 DEG C of conditions in system, it is sequentially added into the hexane solution containing n-BuLi and methyl borate., after adding methyl borate., system reacts at-100～-80 DEG C；
In described step (5), system reacts at 50～100 DEG C；
In described step (6), system reacts at 20～40 DEG C；
In described step (7), system reacts at 50～120 DEG C.
7. the preparation method of electron transport material according to claim 4, it is characterised in that
In described step (1), the response time of system is 3～12 hours；
In described step (2), intermediate A and sodium hydroxide being joined after in dehydrated alcohol, the time of the reaction of system is 2～6 hours, intermediate B is joined after in concentrated sulphuric acid, and the response time of system is 3～8 hours；
In described step (3), after adding the oxolane containing intermediate C, the response time of system is 2～6 hours；
In described step (4), intermediate D and concentrated hydrochloric acid being joined after in acetic acid, the response time of system is 3～8 hours, and after adding methyl borate., the response time of system is 0.5～1.5 hour；
In described step (5), the response time of system is 3～7 hours；
In described step (6), the response time of system is 20～48 hours；
In described step (7), the time of system reaction is 1～4 hour.
8. the preparation method of electron transport material according to claim 4, it is characterised in that
In described step (1), the reaction system containing intermediate A is carried out following post processing: by reaction system separatory, afterwards, organic facies be spin-dried for, then select column chromatography to be purified, it is thus achieved that the intermediate A after purification；
In described step (2), reaction system containing intermediate B is carried out following post processing: after elimination ethanol, in reaction system, add hydrochloric acid, then be sequentially carried out sucking filtration, drying, it is thus achieved that intermediate B, the reaction system containing intermediate C obtained is carried out following post processing: reaction system poured in frozen water, afterwards, add extraction into ethyl acetate, after separatory, organic facies is spin-dried for, then column chromatography is selected, it is thus achieved that the intermediate C after purification；
In described step (3), reaction system containing intermediate D is carried out following post processing: in reaction system, add saturated aqueous ammonium chloride, at room temperature after stirring, separatory, again organic facies is spin-dried for, is subsequently adding acetone, making beating stirring at 60 DEG C, sucking filtration, it is thus achieved that the intermediate D after purification；
In described step (4), reaction system containing intermediate E is carried out following post processing: after desolvation, add ethyl acetate, wash again, afterwards organic facies is spin-dried for, adds acetone, then pull an oar at 50 DEG C, after sucking filtration, obtain intermediate E, the reaction system containing intermediate F is carried out following post processing: adding mass percent in system is the hydrochloric acid of 10%, at room temperature stirs, desolvation afterwards, after being subsequently adding water, pull an oar at 60 DEG C, add petroleum ether, pull an oar at 60 DEG C, it is thus achieved that the intermediate F after purification；
In described step (5), the reaction system containing intermediate G is carried out following process: by reaction system sucking filtration, after adding toluene, pull an oar at 60 DEG C, afterwards, sucking filtration again, it is thus achieved that the intermediate G after purification；
In described step (6), reaction system containing intermediate H is carried out following process: after system sucking filtration, filtrate is spin-dried for, in the material obtained after being spin-dried for, add oxolane, then cross post, then after effluent is spin-dried for, add toluene, then pull an oar at 70 DEG C, sucking filtration, it is thus achieved that intermediate H；
In described step (7), reaction system containing the compound shown in formula I is preferably performed following post processing: after system separatory, then selects ethyl acetate washing aqueous phase, be then combined with organic facies, finally select column chromatography purification, it is thus achieved that the compound shown in formula I after purification.
9. the preparation method of electron transport material according to claim 8, it is characterised in that after the compound shown in formula I is purified, then select vacuum sublimation to being purified.
10. an organic electroluminescence device, it is characterised in that include anode, hole transmission layer, luminescent layer, hole blocking layer, electron transfer layer, negative electrode, has been sequentially stacked hole transmission layer, luminescent layer on anode, hole blocking layer, electron transfer layer and negative electrode, wherein, the electron transport material that described electron transfer layer electron transport material according to any one of claims 1 to 3 and/or the preparation method according to any one of claim 4～9 prepare is made.
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20110002156A (en) * 2009-07-01 2011-01-07 주식회사 엘지화학 New compounds and organic electronic device using the same
CN103718316A (en) * 2011-07-29 2014-04-09 默克专利有限公司 Compounds for electronic devices
WO2014104600A1 (en) * 2012-12-31 2014-07-03 제일모직 주식회사 Compound for organic optoelectronic device, organic light-emitting device containing same, and display apparatus including said organic light-emitting device
US20150318490A1 (en) * 2014-05-02 2015-11-05 Samsung Display Co., Ltd. Condensed cyclic compound and organic light-emitting device comprising the same
CN105440024A (en) * 2016-01-04 2016-03-30 京东方科技集团股份有限公司 Compound, preparation method thereof and organic light-emitting device

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20110002156A (en) * 2009-07-01 2011-01-07 주식회사 엘지화학 New compounds and organic electronic device using the same
CN103718316A (en) * 2011-07-29 2014-04-09 默克专利有限公司 Compounds for electronic devices
WO2014104600A1 (en) * 2012-12-31 2014-07-03 제일모직 주식회사 Compound for organic optoelectronic device, organic light-emitting device containing same, and display apparatus including said organic light-emitting device
US20150318490A1 (en) * 2014-05-02 2015-11-05 Samsung Display Co., Ltd. Condensed cyclic compound and organic light-emitting device comprising the same
CN105440024A (en) * 2016-01-04 2016-03-30 京东方科技集团股份有限公司 Compound, preparation method thereof and organic light-emitting device

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