CN105924395B - A kind of blue light dopant material, preparation method and organic electroluminescence device - Google Patents
A kind of blue light dopant material, preparation method and organic electroluminescence device Download PDFInfo
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Abstract
The present invention relates to a kind of blue light dopant material, preparation method and organic electroluminescence device, blue light dopant material therein is as shown in following formula I, and in following formula I, X is oxygen, sulphur or is not present, Ar1With Ar2For any one in aryl, condensed-nuclei aromatics base or aromatic heterocyclic radical, the Ar1With Ar2It is identical or different.The material not only has suitable HOMO and lumo energy, to have good hole transport performance, while film forming also with higher and stability, therefore can apply in organic electroluminescence device as blue light dopant material.
Description
Technical field
The present invention relates to a kind of machine optoelectronic materials technology more particularly to a kind of blue light dopant materials, preparation method
And organic electroluminescence device.
Background technique
Since reporting the electroluminescent diode based on organic material from Kodak doctor Deng Qingyun in 1987, nearly 30 years
Between, hundreds of efficient luminous organic material has been developed.
The development of organic electroluminescent LED is also because the difference of material can be divided into fluorescence OLED, phosphorescent OLED.First
Traditional fluorescent material is mainly used for OLED, and there is good device stability, but since conventional fluorescent material can only benefit
It is shone with singlet excitons, internal quantum efficiency only up to reach 25%.To make full use of triplet exciton, general woods in 1998
Professor Forrest of Si Dun university has developed second generation OLED material-phosphor material.Phosphor material due to that can utilize list simultaneously
Weight state exciton and triplet exciton, therefore its internal quantum efficiency theoretically can reach 100%, be 4 times of fluorescent material OLED.
But due to the factors such as phosphor material is expensive, blue light material is unstable, device efficiency decaying is serious, not yet
It is able to satisfy the demand of people.
Summary of the invention
Technical problem to be solved by the invention is to provide a kind of luminescent properties with higher, preferable film forming, and
At room temperature with the blue light dopant material of better stability.
The technical solution that the present invention solves above-mentioned technical problem is as follows：A kind of blue light dopant material, as shown in Formulas I：
Wherein, X is oxygen, sulphur or is not present, Ar1With Ar2Appointing respectively in aryl, condensed-nuclei aromatics base or aromatic heterocyclic radical
It anticipates one kind, the Ar1With Ar2It is identical or different.
The beneficial effects of the invention are as follows：Formulas I compound represented, due to drawing with spiro-cyclic groups and tertiary aromatic amine structure
Enter, improves the carrier mobility and luminous efficiency of the blue light dopant material, substantially increase its photoelectric characteristic, additionally due to
The introducing of spiro-cyclic groups is so that the compound can be used for the preparation of blue light dopant material with good luminescent properties.It is comprehensive and
Speech, blue light dopant material luminescent properties with higher provided by the invention, good film-forming property, and have at room temperature preferable steady
It is qualitative.
Based on the above technical solution, the present invention can also be improved as follows.
Further, the carbon atom number of the aryl is 6~20.Preferably, the carbon atom number of the aryl is 6~12.
Further, the carbon atom number of the condensed-nuclei aromatics base is 10~20.Preferably, the carbon atom of the condensed-nuclei aromatics base
Number is 10~14.
Further, the aromatic heterocyclic radical contains one of nitrogen-atoms, oxygen atom or sulphur atom or a variety of, and the virtue
The carbon atom number of race's heterocycle is 4~20.Preferably, the aromatic heterocyclic radical contains in nitrogen-atoms, oxygen atom or sulphur atom
It is one or more, and the carbon atom number of the aromatic heterocyclic radical is 4~18.
Another object of the present invention, which also resides in, provides a kind of preparation method of blue light dopant material described above comprising
Following steps：
S1, by 5- chloro-8-hydroxyquinoline and trifluoromethanesulfanhydride anhydride adding into dichloromethane, in the catalytic action of triethylamine
Lower reaction obtains the reaction system containing intermediate A, and intermediate A is as shown in Formula Il；
S2, the mixed solution that intermediate A, the bromo- phenyl boric acid of 2- methyl formate -3- and potassium carbonate are added to toluene and water
In, reaction obtains the reaction system containing intermediate B under the catalysis of four triphenyl phosphorus palladiums, is then added to intermediate B dense
It is reacted in sulfuric acid, obtains the reaction system containing intermediate C, wherein the structural formula of intermediate B following formula III, intermediate C
Shown in the following formula IV of structural formula；
S3, the following Formula VII compound represented of structural formula is added in tetrahydrofuran, is cooled down, addition contains normal-butyl
The hexane solution of lithium, is then added the tetrahydrofuran containing intermediate C to system, and reaction obtains the reaction containing intermediate D
System, wherein the X shown in the following Formula VIII of the structural formula of intermediate D, in the following Formula VII compound represented of structural formula
For oxygen, sulphur or it is not present, when X is oxygen, the following Formula VII compound represented of structural formula is 2- dibromodiphenyl ether, when X is sulphur,
The following Formula VII compound represented of structural formula is 2- bromine diphenyl sulfide, in the absence of X, is changed shown in the following Formula VII of structural formula
Conjunction object is 2- bromo biphenyl；
S4, intermediate D and concentrated hydrochloric acid are added in acetic acid and reacted, obtain the reaction system containing intermediate E, intermediate
Shown in the following Formula IX of E；
S5, after intermediate E, diaryl-amine and sodium tert-butoxide are added in mesitylene, make in the catalysis of four triphenyl phosphorus palladiums
With lower reaction, the reaction system containing Formulas I compound represented is obtained.
Beneficial effects of the present invention：The preparation method of blue light doping provided by the invention is simple and easy, easily operated, and at
This is cheap, is conducive to promote on a large scale.In addition, the blue light dopant material purity is high that the present invention is prepared, yield is high, and
Used raw material is conventional raw material during preparation, low in cost.
Further, in the step S1, the molar ratio of 5- chloro-8-hydroxyquinoline and trifluoromethanesulfanhydride anhydride be 1: 1.5~
3.0, it is 1: 1.5~3.0 that the additive amount of triethylamine, which meets triethylamine and the molar ratio of 5- chloro-8-hydroxyquinoline,；
In the step S2, the molar ratio 1: 1~1.5 of intermediate A and the bromo- phenyl boric acid of 2- methyl formate -3-, potassium carbonate
Additive amount to meet the molar ratio of potassium carbonate and intermediate A be 1.8~2.5: 1, the additive amount of four triphenyl phosphorus palladiums is intermediate A
Weight 0.3%~1%, the molar ratio of intermediate B and sodium hydroxide is 1: 3~6, the concentrated sulfuric acid that mass fraction is 98%
Additive amount is 2~6 times of the weight of intermediate B；
In the step S3, the molar ratio of intermediate C and raw material 1 is 1: 1~2, the additive amount of n-BuLi make its with
The molar ratio of intermediate C is 1: 1.05~1.2；
In the step S4, the molar ratio of concentrated hydrochloric acid and intermediate D that mass fraction is 36.5% is 2~10: 1；
In the step S5, the molar ratio of intermediate E and diaryl-amine is 1: 2.5~4, sodium tert-butoxide and intermediate E
Molar ratio is 3~5: 1, and the additive amount of four triphenyl phosphorus palladiums is the 2%~5% of the weight of intermediate E.
Further, in the step S1, the reaction system is reacted at 20 DEG C~80 DEG C；
In the step S2, intermediate A, the bromo- phenyl boric acid of 2- methyl formate -3- and potassium carbonate are added to toluene and water
Mixed solution in, and be added four triphenyl phosphorus palladium catalysts, by reaction system be heated to reflux react, by intermediate B
After being added in the concentrated sulfuric acid, reaction system is reacted at 40 DEG C~120 DEG C；
In the step S3, after cooling the temperature to -100 DEG C~-80 DEG C, it is molten that the n-hexane containing n-BuLi is added
Liquid, after the tetrahydrofuran containing intermediate C is added, reaction system is reacted at -100 DEG C~-80 DEG C；
In the step S4, after intermediate D and concentrated hydrochloric acid are added in acetic acid, it is anti-that reaction system is heated to reflux
It answers；
In the step S5, intermediate E, diaryl-amine, sodium tert-butoxide and four triphenyl phosphorus palladiums are added to reaction system
In, the reaction system is reacted at 100 DEG C~150 DEG C.
Further, in the step S1, the reaction time of the reaction system is 3~12 hours；
In the step S2, intermediate A, the bromo- phenyl boric acid of 2- methyl formate -3- and potassium carbonate are added to toluene and water
Mixed solution in, and after four triphenyl phosphorus palladium catalysts are added, reaction time of reaction system is 6h~12h, by intermediate B
After being added in the concentrated sulfuric acid, the reaction time of reaction system is 6h~10h；
In the step S3, after the tetrahydrofuran containing intermediate C being added, reaction time of reaction system be 2h~
6h；
In the step S4, the reaction time of the reaction system is 3h~8h；
In the step S5, the reaction time of the reaction system is 6h~12h.
It further, in the step S1, further include post-processing the reaction system containing intermediate A obtained
Step, specially：Water is added into the reaction system containing intermediate A of acquisition, it, later, will be organic by reaction system liquid separation
It is mutually spin-dried for, then column chromatography is selected to be purified, obtain intermediate A after purification；
In the step S2, further includes the steps that post-processing the reaction system containing intermediate B obtained, have
Body is：Organic phase is spin-dried for by the reaction system liquid separation containing intermediate B of acquisition later, then selects column chromatography progress pure
Change, obtains intermediate B after purification；
Further include the steps that post-processing the reaction system containing intermediate C obtained, specially：By containing for acquisition
There is the reaction system of intermediate C to pour into ice water, later, ethyl acetate extraction is added, organic phase is spin-dried for after liquid separation, is then selected
It is chromatographed with column, obtains intermediate C after purification；
In the step S3, further include the steps that post-processing the reaction system containing intermediate D obtained, have
Body is：Saturated aqueous ammonium chloride, liquid separation are added into the reaction system containing intermediate D of acquisition, then organic phase is spin-dried for,
Then acetone mashing stirring is added, filters, obtains intermediate D after purification；
In the step S4, further includes the steps that post-processing the reaction system containing intermediate E obtained, have
Body is：After removing solvent, ethyl acetate is added, then wash, organic phase is spin-dried for later, adds acetone, then at 50 DEG C
It is beaten, after suction filtration, obtains intermediate E；
In the step S5, further includes the steps that post-processing the reaction system containing intermediate G obtained, have
Body is：The reaction system containing intermediate G of acquisition is filtered, after organic phase crosses column, is spin-dried for, column chromatographic purifying is selected, is obtained
Formulas I compound represented after purification.
Further, after obtaining Formulas I compound represented after purification, further include it is carried out using vacuum sublimation it is pure
The step of change.
Another object of the present invention, which also resides in, provides a kind of organic electroluminescence device comprising anode, hole transmission layer,
Luminescent layer, electron transfer layer and cathode；Wherein, it has been sequentially stacked the hole transmission layer, luminescent layer, electronics on the anode
Transport layer and cathode；Wherein, the luminescent layer contains blue light dopant material described in any of the above embodiments.
The beneficial effects of the invention are as follows：To have compared with high luminescence energy, more carefully film forming, and have at room temperature preferable
After the blue light dopant material of stability is applied in organic electroluminescence device, organic electroluminescence device can be greatly improved
Stability, at the same time, additionally it is possible to which the driving voltage for reducing organic electroluminescence device greatly improves its service life.
Detailed description of the invention
Fig. 1 is the structural schematic diagram for the organic electroluminescence device that the embodiment of the present invention three provides.
In attached drawing, parts list represented by the reference numerals are as follows：
101- anode, 102- hole transmission layer, 103- luminescent layer, 104 electron transfer layers, 105- electron injecting layer, 106-
Cathode layer.
Specific embodiment
The principle and features of the present invention will be described below with reference to the accompanying drawings, and the given examples are served only to explain the present invention, and
It is non-to be used to limit the scope of the invention.
In following embodiments, comparative example, used 5- chloro-8-hydroxyquinoline, bromobenzene, aniline, 4- bromine dibenzo furan
Mutter, the compounds such as 4- bromodiphenylthiophene, 4- bromo biphenyl, 3- bromo biphenyl, 1- bromonaphthalene can at home Chemical market it is commercially available.
2- methyl formate -3- bromobenzeneboronic acid reacts institute according to document J.Org.Chem.1998, the synthesis of 63,2054-2055 report methods
Diaryl-amine is all made of corresponding bromo aromatic compound and arylamine and uses common organic synthesis side by the coupling coupling of carbon nitrogen
Method synthesis obtains.In addition, the reagent used, material and instrument such as not special explanation, are conventional reagent, routine
Material and conventional instrument, it is commercially available, involved in reagent can also pass through conventional synthesis process synthesis obtain.
Embodiment one
A kind of blue light dopant material is present embodiments provided, as shown in following formula I.
Wherein, X is oxygen, sulphur or is not present, Ar1With Ar2Appointing respectively in aryl, condensed-nuclei aromatics base or aromatic heterocyclic radical
It anticipates one kind, Ar1With Ar2It is identical or different.
X can be selected from oxygen, sulphur, there is no one of, when X is oxygen, the corresponding substance of structure shown in Formulas I is xanthene, X
When for sulphur, the corresponding compound of structure shown in Formulas I is thioxanthene, and when X is not deposited, the corresponding compound of structure shown in Formulas I is
Spiro fluorene.Ar therein1With Ar2It may be the same or different, can be selected from aryl or carbon atom that carbon atom number is 6~20 or 6~22
Number is 10~20 or 10~24 condensed-nuclei aromatics base, or contains one of nitrogen-atoms, oxygen atom or sulphur atom or a variety of virtues
Race's heterocycle, wherein the carbon atom number of aromatic heterocyclic radical is 4~20 or 4~18.
In the plurality of embodiment of the present embodiment, Ar1With Ar2It may be the same or different, Ar1With Ar2Structure can
For following structures：
Carbon atom number is 6~20 aryl, such as can enumerate phenyl, aralkyl, the aryl at least containing a phenyl such as
Xenyl etc..Preferably, select carbon atom number for 6~12 aryl, it is further preferred that selecting carbon atom number for 6
~9 aryl.As the example of aryl, it is specifically as follows：Phenyl, benzyl, xenyl, trityl, p-methylphenyl, ethylbenzene
Base, adjacent ethylbenzene, 3,5- xylyl, 2,6- diisopropylbenzyl, 3,5-, bis- n-proplbenzene base, 2,6-, bis- n-butyl benzene base, 3,5- bis-
Isobutylphenyl, 3,5-, bis- 2-methyl-2-phenylpropane base.
The condensed-nuclei aromatics base, such as naphthalene, anthryl, phenanthryl etc. that carbon atom number is 10~20.Preferably, selection carbon is former
Subnumber be 10~16 condensed-nuclei aromatics base, it is further preferred that select carbon atom number for 10~14 condensed-nuclei aromatics base, more into one
Step preferably, selects carbon atom number to be specifically as follows for 10~12 condensed-nuclei aromatics base as the example of condensed-nuclei aromatics base：1-
Naphthalene, 2- naphthalene.
Certainly, substituent A r1With Ar2Type be not so limited, can also for other include phenyl, pyridyl group, quinoline
The aromatic groups such as base, thiophene, furans.
As Ar1With Ar2Example, be specifically as follows with flowering structure：
As the example of blue light dopant material, it is specifically as follows with flowering structure：
Blue light dopant material provided in this embodiment, that is, Formulas I compound represented, due to spiro-cyclic groups and three
The introducing of arylamine structure improves the carrier mobility and luminous efficiency of the blue light dopant material, substantially increases its photoelectricity
Characteristic, additionally due to the introducing of spiro-cyclic groups is so that the compound can be used for blue light dopant material with good luminescent properties
Preparation.
Embodiment two
A kind of method for preparing blue light dopant material described in embodiment one is present embodiments provided, this gives
The specific preparation method of the exemplary some blue light dopant material of embodiment one.
Example 1, the specific preparation method for the blue light dopant material 1 that preparation embodiment one provides：
The preparation of step (1), intermediate A
Successively weigh 179g (1mol) 5- chloro-8-hydroxyquinoline, 282g (1mol) trifluoromethanesulfanhydride anhydride, 1500g dichloromethane
Alkane, 150g (1.5mol) triethylamine are stirred at room temperature under 12h in 2L there-necked flask, the addition 500g water into reaction system, liquid separation,
The water of organic phase 500g, washing three times, are spin-dried for, and with petroleum ether: ethyl acetate=4: 1 crosses column, and 280.6g fine work is prepared
Compound A, yield 90.2%, product purity GC are 99.5%.
The preparation of step (2), intermediate B and intermediate C
Successively weigh 105g (0.5mol) compound A, 129g (0.5mol) 2- methyl formate -3- bromobenzeneboronic acid, 800g first
The solution of benzene, 207g potassium carbonate and 500g water under nitrogen protection, is stirred at room temperature, after 20min, into system in 2L there-necked flask
Addition tetra- triphenyl phosphorus palladium of 1g, back flow reaction 12h, then liquid separation, organic phase cross column, and efflux is spin-dried for obtaining white intermediate B.
After the Crude Intermediate B of acquisition is added in the concentrated sulfuric acid that 500g mass percent is 98%, stirred at 60 DEG C
Reaction 5h is mixed, reaction system is poured into 3000g ice water later, 500g ethyl acetate is added and is extracted, will be had after liquid separation
Machine is mutually spin-dried for, and column chromatography is then selected to be purified, and in column chromatography, selects petroleum ether and ethyl acetate to carry out intermediate pure
Change, wherein the volume ratio of petroleum ether and ethyl acetate is petroleum ether: ethyl acetate=4: 1, finally prepare among 160.6g
Body C, intermediate C are yellow solid.Intermediate C learns that purity is 99% after gas-chromatography (referred to as GC) test, receives
Rate is 93.3%.
In addition, intermediate B and intermediate C are shown below：
The preparation of step (3), intermediate D
After 116.5g (0.5mol) 2- bromo biphenyl is added in 800g tetrahydrofuran, system is cooled to -90 DEG C, then is added dropwise
227ml contains the hexane solution of n-BuLi, wherein molar concentration of the n-BuLi in hexane solution is 2.2mol/
L, control system temperature are no more than -80 DEG C, the hexane solution containing n-BuLi are added dropwise in 1 hour, then keeps the temperature
Reaction 1 hour is added dropwise in 1 hour into reaction system later under conditions of control system temperature is no more than -80 DEG C
Tetrahydrofuran containing intermediate C wherein obtains in step (2) in the tetrahydrofuran of 300g containing 172g (0.5mol)
Intermediate C after being added dropwise, system is moved to and is reacted at 25 DEG C 4 hours, later, 200g is added into reaction system and is saturated chlorine
Change aqueous ammonium, after continuing stirring at room temperature 1 hour, organic phase is spin-dried for by liquid separation, 500g acetone is added, at 60 DEG C
Mashing stirring 1 hour, finally filters, and obtaining intermediate D after purification is 199.5g, and intermediate D is white solid, and intermediate
D is shown below.Intermediate D learns that purity is 99.2% after liquid chromatogram (referred to as HPLC) test, product yield
It is 80%.
The preparation of step (4), intermediate E
It is 36.5% concentrated hydrochloric acid by intermediate D and the 10ml mass percent obtained in 149.6g (0.3mol) step (3)
After being added in 1200g acetic acid, system is heated to insulation reaction 5h under reflux state, later, removing solvent obtains 150g palm fibre
Red oil adds 1000g ethyl acetate, after system is entirely molten, is washed with water three times, and each water is 500ml, then incites somebody to action
To organic phase be spin-dried for, obtain 110g yellow solid, add 600g acetone, 1h is beaten at 50 DEG C, is filtered later, obtain
Mesosome E is 106.2g, is yellow powder, and the purity for learning intermediate E by high performance liquid chromatography (abbreviation HPLC) detection is
99.6%, yield 73.5%；
Intermediate E is shown below.
The preparation of step (5), material 1
By 96g (0.2mol) intermediate E, 84.5g (0.5mol) diaryl-amine, 57.6g sodium tert-butoxide is added to 1200g equal three
In toluene, tetra- triphenyl phosphorus palladium of 1.5g is added under nitrogen protection, reacts 6h at 150 DEG C, later, 600g water is added, liquid separation is organic
Mutually three times, each water is 600g for washing, and organic phase is crossed column, is spin-dried for, and is purified using column chromatography, in column chromatography, is selected
Petroleum ether and ethyl acetate purify intermediate, and wherein the volume ratio of petroleum ether and ethyl acetate is petroleum ether: acetic acid second
Ester=1: 1, material 106.8g is prepared, is yellow powder, learns material by high performance liquid chromatography (abbreviation HPLC) detection
The purity of material 1 is 99.6%, yield 75.9%.
The material 1 for weighing the above-mentioned acquisition of 4g, is placed in vacuum sublimation instrument, and setting distillation parameter is as follows：Distil vacuum degree
It is 2 × 10-5Pa, three area's temperature of distillation are 360 DEG C, and two area's temperature of distillation are 260 DEG C, and one area's temperature of distillation is 160 DEG C, each
Qu Zhong, established temperature are gradient increased temperature, and every 15min increases 50 DEG C, after being increased to target temperature, and heat preservation distillation 5h, distillation is altogether
It is 3.6g with the material 1 obtained after purification.Learn that the purity of material 1 is by high performance liquid chromatography (abbreviation HPLC) detection
99.5%, yield 90%, and learnt by high resolution mass spectrum, theoretical value [M+1] is 702.2826, and test value is
702.2831。
Example 2, the specific preparation method for the blue light dopant material 2 that preparation embodiment one provides：
Using with identical preparation method and raw material proportioning that material 1 is prepared in example 1, wherein only in step (3)
Middle that 2- bromo biphenyl is replaced with 2- dibromodiphenyl ether, remaining is constant.(referred to as by high performance liquid chromatography by the material 2 finally obtained
HPLC) detection learns that the purity of material 2 is 99.6%, and learns by high resolution mass spectrum, and theoretical value [M+1] is 717.2780,
Test value is 717.2776.
Example 3, the specific preparation method for the blue light dopant material 3 that preparation embodiment one provides：
Using with identical preparation method and raw material proportioning that material 1 is prepared in example 1, wherein only in step (3)
Middle that 2- bromo biphenyl is replaced with 2- bromine diphenyl sulfide, remaining is constant.By the material 2 finally obtained by high performance liquid chromatography (letter
HPLC) detection learns that the purity of material 2 is referred to as 99.6%, and learns that theoretical value [M+1] is by high resolution mass spectrum
734.2552 test value 734.2556.
Example 4, the specific preparation method for the blue light dopant material 4 that preparation embodiment one provides：
Using with identical preparation method and raw material proportioning that material 1 is prepared in example 1, wherein only in step (5)
Middle that diphenylamines is replaced with two (4- tert-butyl) aniline, remaining is constant.The material 7 finally obtained is passed through into high performance liquid chromatography
(abbreviation HPLC) detection learns that the purity of material 7 is 99.2%, and learns by high resolution mass spectrum, theoretical value [M+1]
926.5335 test value 926.5336.
Example 5, the specific preparation method for the blue light dopant material 5 that preparation embodiment one provides：
Using with identical preparation method and raw material proportioning that material 2 is prepared in example 2, wherein only in step (5)
Middle that diphenylamines is replaced with two (4- tert-butyl) aniline, remaining is constant.The material 8 finally obtained is passed through into high performance liquid chromatography
(abbreviation HPLC) detection learns that the purity of material 8 is 99.3%, and learns by high resolution mass spectrum, theoretical value [M+1]
942.5284 test value 942.5286.
Example 6, the specific preparation method for the blue light dopant material 9 that preparation embodiment one provides：
Using with identical preparation method and raw material proportioning that material 3 is prepared in example 3, wherein only in step (5)
Middle that diphenylamines is replaced with two (4- tert-butyl) aniline, remaining is constant.The material 9 finally obtained is passed through into high performance liquid chromatography
(abbreviation HPLC) detection learns that the purity of material 9 is 99.3%, and learns by high resolution mass spectrum, theoretical value [M+1]
957.5056 test value 957.5052.
Example 7, the specific preparation method for the blue light dopant material 10 that preparation embodiment one provides：
Using with identical preparation method and raw material proportioning that material 1 is prepared in example 1, wherein only in step (5)
Middle that diphenylamines is replaced with N- phenyl-1-naphthylamine, remaining is constant.By the material 10 finally obtained by high performance liquid chromatography (letter
HPLC) detection learns that the purity of material 10 is referred to as 99.8%, and learns by high resolution mass spectrum, theoretical value [M+1] 802.3144,
Test value is 802.3146.
Example 8, the specific preparation method for the blue light dopant material 14 that preparation embodiment one provides：
Using with identical preparation method and raw material proportioning that material 2 is prepared in example 2, wherein only in step (5)
Middle that diphenylamines is replaced with N- phenyl -4- dibenzofurans, remaining is constant.The material 14 finally obtained is passed through into high-efficient liquid phase color
Spectrum (abbreviation HPLC) detection learns that the purity of material 14 is 99.8%, and learns by high resolution mass spectrum, theoretical value [M+1]
898.2991 test value 898.2988.
Example 9, the specific preparation method for the blue light dopant material 16 that preparation embodiment one provides：
Using with identical preparation method and raw material proportioning that material 1 is prepared in example 1, wherein only in step (5)
Middle that diphenylamines is replaced with N- phenyl -4- dibenzothiophenes, remaining is constant.The material 16 finally obtained is passed through into high-efficient liquid phase color
Spectrum (abbreviation HPLC) detection learns that the purity of material 16 is 99.7%, and learns by high resolution mass spectrum, theoretical value [M+1]
914.2585 test value 914.2588.
Example 10, the specific preparation method for the blue light dopant material 20 that preparation embodiment one provides：
Using with identical preparation method and raw material proportioning that material 2 is prepared in example 2, wherein only in step (5)
Middle that diphenylamines is replaced with N- (4- tert-butyl-phenyl) -4- dibenzofurans, remaining is constant.The material 20 finally obtained is passed through
High performance liquid chromatography (abbreviation HPLC) detection learns that the purity of material 20 is 99.7%, and learns by high resolution mass spectrum, theoretical
It is worth [M+1] 1010.4243, test value 1010.4246.
Example 11, the specific preparation method for the blue light dopant material 22 that preparation embodiment one provides：
Using with identical preparation method and raw material proportioning that material 1 is prepared in example 1, wherein only in step (5)
Middle that diphenylamines is replaced with N- (4- tert-butyl-phenyl) -4- dibenzothiophenes, remaining is constant.The material 22 finally obtained is passed through
High performance liquid chromatography (abbreviation HPLC) detection learns that the purity of material 22 is 99.7%, and learns by high resolution mass spectrum, theoretical
It is worth [M+1] 1026.3837, test value 1026.3836.
Example 12, the specific preparation method for the blue light dopant material 23 that preparation embodiment one provides：
Using with identical preparation method and raw material proportioning that material 2 is prepared in embodiment 2, wherein only in step
(5) diphenylamines is replaced with into N- (4- tert-butyl-phenyl) -4- dibenzothiophenes in, remaining is constant.The material 23 that will finally obtain
The purity that material 21 is learnt by high performance liquid chromatography (abbreviation HPLC) detection is 99.7%, and is learnt by high resolution mass spectrum,
Theoretical value [M+1] 1042.3787, test value 1042.3786.
Example 13, the specific preparation method for the blue light dopant material 26 that preparation embodiment one provides：
Using with identical preparation method and raw material proportioning that material 2 is prepared in example 2, wherein only in step (5)
Middle that diphenylamines is replaced with N- phenyl -3- biphenyl, remaining is constant.By the material 26 finally obtained by high performance liquid chromatography (letter
HPLC) detection learns that the purity of material 22 is referred to as 99.7%, and learns by high resolution mass spectrum, test value [M+1] 870.3408,
Theoretical value is 870.3406.
Example 14, the specific preparation method for the blue light dopant material 30 that preparation embodiment one provides：
Using with identical preparation method and raw material proportioning that material 3 is prepared in example 3, wherein only in step (5)
Middle that diphenylamines is replaced with N- phenyl -2- biphenyl, remaining is constant.By the material 27 finally obtained by high performance liquid chromatography (letter
HPLC) detection learns that the purity of material 30 is referred to as 99.7%, and learns by high resolution mass spectrum, theoretical value [M+1] 886.3178,
Test value is 886.3176.
Example 15, the specific preparation method for the blue light dopant material 31 that preparation embodiment one provides：
Using with identical preparation method and raw material proportioning that material 2 is prepared in example 2, wherein only in step (5)
Middle that diphenylamines is replaced with N-2- furyl aniline, remaining is constant.By the material 31 finally obtained by high performance liquid chromatography (letter
HPLC) detection learns that the purity of material 31 is referred to as 99.7%, and learns that theoretical value [M+1] is by high resolution mass spectrum
698.2365 test value 698.2366.
Example 16, the specific preparation method for the blue light dopant material 35 that preparation embodiment one provides：
Using with identical preparation method and raw material proportioning that material 2 is prepared in example 2, wherein only in step (5)
Middle that diphenylamines is replaced with N-2- thienyl aniline, remaining is constant.By the material 32 finally obtained by high performance liquid chromatography (letter
HPLC) detection learns that the purity of material 32 is referred to as 99.7%, and learns by high resolution mass spectrum, theoretical value [M+1] 730.1909,
Test value is 730.1916.
High performance liquid chromatography and high resolution mass spectrum detection are carried out by the material obtained to above-described embodiment, it is known that
The blue light dopant material as shown in Formulas I has successfully been obtained in the present invention, and purity is high and yield are high.
Embodiment three
As shown in Figure 1, present embodiments providing a kind of organic electroluminescence device comprising anode 101, hole transmission layer
102, luminescent layer 103, electron transfer layer 104 and cathode layer 106；Wherein, the hole has been sequentially stacked on the anode 101
Transport layer 102, luminescent layer 103, electron transfer layer 104 and cathode 106；Wherein, the luminescent layer 103 contains by one institute of embodiment
The blue light that the preparation method of the blue light dopant material and/or the blue light dopant material as described in embodiment two stated is prepared and obtained is mixed
Miscellaneous material.
It is following to give the example of 14 organic electroluminescence devices of preparation, in following organic electroluminescence devices that prepare
In example and comparative example, used reagent material is as follows：
1, material 1, material 2, material 3, material 7, material 8, material 9, the material 10, material by being provided in embodiment one
14, material 16, material 20, material 22, material 30, material 31, material 35 are the organic electroluminescent being prepared in example
Blue light dopant material in device；
Further relate to following material：Wherein DNTPD and α-NPD is used for hole transmission layer 102, AND as Blue-light emitting host material,
LiQ and RD201 is as electron transfer layer 104.
2, selecting glass is substrate layer, and tin indium oxide (referred to as ITO) is anode material, NPB as hole mobile material,
For LiF as electron injection material, Al is cathode material.
Organic electroluminescence device 1~14 is all made of following methods and is prepared：
A) it selects cleaning agent to be cleaned by ultrasonic the substrate layer for being coated with anode material first, later, uses deionized water
It rinses, then selects the mixed solvent ultrasound oil removing of acetone and ethyl alcohol, be then baked under clean environment and completely remove moisture, then
With ultraviolet light and ozone clean, and with low energy positive electricity beamlet bombarded surface；
B) substrate layer for being coated with anode material is placed in vacuum chamber, then vacuumizes the pressure so that in vacuum chamber
For 9x10-5Pa is deposited DNTPD70nm and α-NPD 30nm on anode 101 with the evaporation rate of 0.05nm/s and obtains hole biography
Defeated layer 102, hole transmission layer 102 with a thickness of 100nm；
C) with the evaporation rate of 0.05nm/s, vacuum evaporation AND and blue light dopant material 1 (are mixed on hole transmission layer 102
Impurity level ratio be AND: material 1=97: 3), and obtain luminescent layer 103, luminescent layer 103 with a thickness of 25nm；
D) with the evaporation rate of 0.05nm/s on the light-emitting layer 103 vacuum evaporation electron transport material LiQ (50nm) and
RD201 (50nm), electron transfer layer 104 with a thickness of 100nm；
E) on electron transfer layer 104, vacuum evaporation LiF obtain electron injecting layer 105, electron injecting layer 105 with a thickness of
0.8nm；
F) on electron injecting layer 105, vacuum evaporation obtains cathode material Al and obtains cathode layer 106, obtains device,
In, cathode layer 106 with a thickness of 100nm.
In above-mentioned 1~14 organic electroluminescence device of preparation, used blue light dopant material is as shown in table 1 below：
Table 1
The preparation of comparative device 1#
The preparation of duplicate devices 1, only in step c), using BD as blue light dopant material, remaining is constant.
The device 1~14 of above-mentioned preparation and comparative device 1# are subjected to following tests：The brightness requirement of device is
1000cd/m2, the current density of device, brightness, voltage characteristic are by with corrected silicon photoelectric diode
What the source Keithley measuring system (236 source Measure Unit of Keithley) was completed, and all measurements are in room temperature
It is completed in atmosphere.
Voltage, current density and the electric current of the device 1~14 and comparative device 1# of testing above-mentioned preparation are such as the following table 2 institute
Show.
Table 2
By above-mentioned table 2 it is known that blue light dopant material provided by the present invention can be applied to organic electroluminescence device
In, and good excitation purity can be obtained.Compared with device 1#, the driving voltage of device 1~14 is substantially reduced, and excitation purity is bright
It is aobvious to improve.
In terms of comprehensive, blue light dopant material provided by the present invention is applied in organic electroluminescence device, so that having
Organic electroluminescence devices have excellent luminescent properties, to improve the stability of organic electroluminescence device and use the longevity
Life.
The foregoing is merely presently preferred embodiments of the present invention, is not intended to limit the invention, it is all in spirit of the invention and
Within principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (13)
1. a kind of preparation method of blue light dopant material, which is characterized in that include the following steps：
S1, by 5- chloro-8-hydroxyquinoline and trifluoromethanesulfanhydride anhydride adding into dichloromethane, it is anti-under the catalytic action of triethylamine
It answers, obtains the reaction system containing intermediate A, intermediate A is as shown in following formula II；
S2, intermediate A, the bromo- phenyl boric acid of 2- methyl formate -3- and potassium carbonate are added in the mixed solution of toluene and water,
Reaction obtains the reaction system containing intermediate B under the catalysis of four triphenyl phosphorus palladiums, and then intermediate B is added in the concentrated sulfuric acid
Reaction obtains the reaction system containing intermediate C, wherein the structural formula of intermediate B is as shown in following formula III, the structure of intermediate C
Formula is as shown in following formula IV；
S3, structural formula such as VII compound represented of following formula are added in tetrahydrofuran, are cooled down, is added containing n-BuLi just
Then the tetrahydrofuran containing intermediate C is added to system in hexane solution, reaction obtains the reaction system containing intermediate D, in
As shown in following formula VIII, the X in VII compound represented of the structural formula such as following formula is oxygen, sulphur or is not present the structural formula of mesosome D；
S4, intermediate D and concentrated hydrochloric acid are added in acetic acid and reacted, obtain the reaction system containing intermediate E, intermediate E is such as
Shown in following formula Ⅸ；
S5, after intermediate E, diaryl-amine and sodium tert-butoxide are added in mesitylene, under the catalytic action of four triphenyl phosphorus palladiums
Reaction, obtains the reaction system containing I compound represented of formula, and the structure shown in formula I is as follows：
Wherein, X is oxygen, sulphur or is not present, Ar1With Ar2For any one in aryl, condensed-nuclei aromatics base or aromatic heterocyclic radical, institute
State Ar1With Ar2It is identical or different.
2. the preparation method of blue light dopant material according to claim 1, which is characterized in that
In the step S1, the molar ratio of 5- chloro-8-hydroxyquinoline and trifluoromethanesulfanhydride anhydride is 1:1.5~3.0, triethylamine
It is 1 that additive amount, which meets triethylamine and the molar ratio of 5- chloro-8-hydroxyquinoline,:1.5~3.0；
In the step S2, the molar ratio 1 of intermediate A and the bromo- phenyl boric acid of 2- methyl formate -3-：1~1.5, potassium carbonate adds
It is 1.8~2.5 that dosage, which meets potassium carbonate and the molar ratio of intermediate A,:1, the additive amount of four triphenyl phosphorus palladiums is the weight of intermediate A
The 0.3%~1% of amount, the additive amount for the concentrated sulfuric acid that mass fraction is 98% is 2~6 times of the weight of intermediate B；
In the step S3, the molar ratio of intermediate C and compound VII is 1:1~2, the additive amount of n-BuLi meets just
The molar ratio of butyl lithium and intermediate C are 1:1.05~1.2；
In the step S4, the molar ratio of concentrated hydrochloric acid and intermediate D that mass fraction is 36.5% is 2~10:1；
In the step S5, the molar ratio of intermediate E and diaryl-amine is 1:2.5~4, mole of sodium tert-butoxide and intermediate E
Than being 3~5:1, the additive amount of four triphenyl phosphorus palladiums is the 2%~5% of the weight of intermediate E.
3. the preparation method of blue light dopant material according to claim 1 or 2, which is characterized in that
In the step S1, the reaction system is reacted at 20 DEG C~80 DEG C；
In the step S2, intermediate A, the bromo- phenyl boric acid of 2- methyl formate -3- and potassium carbonate are added to the mixed of toluene and water
It closes in solution, and four triphenyl phosphorus palladium catalysts is added, reaction system is heated to reflux and is reacted, intermediate B is added
After into the concentrated sulfuric acid, reaction system is reacted at 40 DEG C~120 DEG C；
In the step S3, after cooling the temperature to -100 DEG C~-80 DEG C, the hexane solution containing n-BuLi is added, adds
After entering the tetrahydrofuran containing intermediate C, reaction system is reacted at -100 DEG C~-80 DEG C；
In the step S4, after intermediate D and concentrated hydrochloric acid are added in acetic acid, reaction system is heated to back flow reaction；
In the step S5, intermediate E, diaryl-amine, sodium tert-butoxide and four triphenyl phosphorus palladiums are added in reaction system, institute
Reaction system is stated to be reacted at 100 DEG C~150 DEG C.
4. the preparation method of blue light dopant material according to claim 1 or 2, which is characterized in that
In the step S1, the reaction time of the reaction system is 3~12 hours；
In the step S2, intermediate A, the bromo- phenyl boric acid of 2- methyl formate -3- and potassium carbonate are added to the mixed of toluene and water
It closes in solution, and after four triphenyl phosphorus palladium catalysts of addition, the reaction time of reaction system is 6h~12h, and intermediate B is added
After into the concentrated sulfuric acid, the reaction time of reaction system is 6h~10h；
In the step S3, after the tetrahydrofuran containing intermediate C being added, the reaction time of reaction system is 2h~6h；
In the step S4, the reaction time of the reaction system is 3h~8h；
In the step S5, the reaction time of the reaction system is 6h~12h.
5. the preparation method of blue light dopant material according to claim 1 or 2, which is characterized in that
In the step S1, further include the steps that post-processing the reaction system containing intermediate A obtained, specifically
For：Water is added into the reaction system containing intermediate A of acquisition, later, organic phase is spin-dried for for reaction system liquid separation, then
It selects column chromatography to be purified, obtains intermediate A after purification；
In the step S2, further include the steps that post-processing the reaction system containing intermediate B obtained, specifically
For：Organic phase is spin-dried for by the reaction system liquid separation containing intermediate B of acquisition later, then column chromatography is selected to be purified,
Obtain intermediate B after purification；
Further include the steps that post-processing the reaction system containing intermediate C obtained, specially：It will be in the containing of acquisition
The reaction system of mesosome C is poured into ice water, later, ethyl acetate extraction is added, is spin-dried for organic phase after liquid separation, then selects column
Chromatography, obtains intermediate C after purification；
In the step S3, further include the steps that post-processing the reaction system containing intermediate D obtained, specifically
For：Saturated aqueous ammonium chloride, liquid separation are added into the reaction system containing intermediate D of acquisition, then organic phase is spin-dried for, so
Acetone mashing stirring is added afterwards, filters, obtains intermediate D after purification；
In the step S4, further include the steps that post-processing the reaction system containing intermediate E obtained, specifically
For：After removing solvent, ethyl acetate is added, then wash, organic phase is spin-dried for later, adds acetone, is then beaten at 50 DEG C
It starches, after suction filtration, obtains intermediate E；
In the step S5, further include the steps that post-processing the reaction system containing formula I obtained, specially：It will
The reaction system containing formula I obtained filters, and after organic phase crosses column, is spin-dried for, and selects column chromatographic purifying, obtains formula I after purification
Compound represented.
6. the preparation method of blue light dopant material according to claim 5, which is characterized in that obtaining formula I after purification
After compound represented, further include the steps that purifying it using vacuum sublimation.
7. a kind of preparation method of blue light dopant material according to claim 1, which is characterized in that the blue light adulterates material
Material is as shown in claim 1 Chinese style I.
8. a kind of preparation method of blue light dopant material according to claim 7, which is characterized in that the carbon atom of the aryl
Number is 6~20.
9. a kind of preparation method of blue light dopant material according to claim 8, which is characterized in that the carbon atom of the aryl
Number is 6~12.
10. a kind of preparation method of blue light dopant material according to claim 7, which is characterized in that the condensed-nuclei aromatics base
Carbon atom number be 10~20.
11. a kind of preparation method of blue light dopant material according to claim 10, which is characterized in that the condensed-nuclei aromatics base
Carbon atom number be 10~14.
12. a kind of preparation method of blue light dopant material according to claim 1, which is characterized in that the aromatic heterocyclic radical
Containing one of nitrogen-atoms, oxygen atom or sulphur atom or a variety of, and the carbon atom number of the aromatic heterocyclic radical is 4~20.
13. a kind of preparation method of blue light dopant material according to claim 12, which is characterized in that the aromatic heterocyclic radical
Containing one of nitrogen-atoms, oxygen atom or sulphur atom or a variety of, and the carbon atom number of the aromatic heterocyclic radical is 4~18.
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| CN105408303A (en) * | 2012-10-10 | 2016-03-16 | 大州电子材料株式会社 | Spiro-type organic material, and organic electroluminescent device using same |
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