CN108841379A - A kind of preparation method of the OLED hole transport new material suitable for solution processing - Google Patents
A kind of preparation method of the OLED hole transport new material suitable for solution processing Download PDFInfo
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Abstract
The present invention relates to field of new material preparation, particularly with regard to a kind of preparation method of OLED hole transport new material suitable for solution processing；A kind of preparation method of the OLED hole transport new material suitable for solution processing disclosed in the method for the present invention, a kind of OLED hole transport new material suitable for solution processing of this patent preparation has 12 hydroxyls of each molecule, the material has excellent solvent selection performance, under room temperature, solubility is very small in toluene, in low polar solvent, and larger to the highly polar Solvent Solubility of alcohols；Using the property, which can form high-quality thin film from alcoholic solution, and can prevent the phenomenon that adjacent functional interface layer dissolves each other.
Description
Technical field
The present invention relates to field of material preparation, particularly with regard to a kind of OLED hole transport new material suitable for solution processing
Preparation method.
Background technique
Early in the last century 60's, people just have begun organic electroluminescent phenomenon and research.Vacuum Heat steams
It is quite perfect to plate film technique, can easily prepare multilayer device by this method, there is no between layers
Mutual corrosion phenomenon, however this method is involved great expense and is dfficult to apply in the electroluminescent device of flexible base board.
201710463151.4 disclose a kind of dithieno cyclopentadiene derivant structure luminous organic material and its
Organic luminescent device belongs to organic photoelectrical material technical field.The derivative of the invention with 4-H- cyclopentadiene 1,4-Dithiapentalene 1,
Structure based on 1,7,7- tetroxide, by connecting the ligand groups of opposed polarity, so that the obtained derivative of the present invention
With stronger electrophilicity, charge transport ability and luminescent properties.Using the dithieno cyclopentadiene derivant system of the invention
Standby organic luminescent device, luminous efficiency is high, it is photochromic uniformly, have good membrane stability and thermal stability, can effectively solve
The unbalanced problem of unipolarity transmission material carrier in machine luminescent device.
201710031409.3 a kind of doping type navy blue luminous organic material and its preparation method and application is disclosed, it is described
Doping type navy blue luminous organic material includes material of main part and guest materials, its molecular structural formula of material of main part is as follows：Wherein,
R1 and R2 be and one of；Wherein, R1 and R2 is connected by 1,2,3 or No. 4 positions with anthracene；Its molecular structural formula of guest materials
It is as follows：Wherein, R3 and R4 be one of；Wherein, R3 and R4 by 1,2,3 or No. 4 positions with connect.The preparation side of the invention
Method simple process, prepared doping type navy blue luminous organic material, thermal stability is good, purity is high, and quantum efficiency is high, steady
It is qualitative good, solve the problems, such as that device performance prepared by existing blue-light fluorescent material is difficult to improve.
201710255040.4 providing a kind of luminous organic material and its organic illuminator based on bipolar phosphorescence derivative
Part belongs to organic photoelectrical material technical field.Solve organic photoelectrical material luminous efficiency is low in the prior art, service life is short etc.
The technical problem of luminescent properties difference.The invention is using dihydrophenazine group connection quinazoline group as core, so that having concurrently in structure
Electronics and power loss subbase group, to obtain a kind of novel electronics and hole bipolar transmission profile material.Compared with prior art, should
The organic luminescent device based on bipolar phosphorescence derivative of invention, luminous efficiency reach as high as 19.7cd/A, and luminescent lifetime is
210h@100mA/cm2 is a kind of excellent OLED material.
With the development of organic electroluminescent LED, the attention of researchers starts to low cost, large area, Yi Jia
Work etc. transfer.Solution processing be compared to thermal evaporation deposition preparation OLED device have it is convenient and efficient, equipment is simple, cost
Many advantages, such as cheap, but use in solution process, there is the phenomenon that dissolving each other in luminescent layer and adjacent functional interface layer,
Limit the development of the processing method.
Summary of the invention
To solve the above-mentioned problems, the present invention provides a kind of OLED hole transport new materials suitable for solution processing
Preparation method.
A kind of preparation method of the OLED hole transport new material suitable for solution processing, technology of preparing scheme are as follows：
Step 1: according to mass fraction, by 5.6-10.8 parts by (6- THP trtrahydropyranyl -2- (the 2- tetrahydro-pyran oxy of 9,9- bis-
Ethyl) hexyl) -2,7- two (4,4,5,5- tetramethyl -1,3,2- dioxaborinate base) fluorenes, in 12.4-24.3 parts of highly branched chain
Mesosome, 0.01-0.1 parts of 6- amino -2,3- dihydro 1-Indanone, the three of 0.001-0.01 parts (dinaphthyl methylene) Dan Fei are coughed up
Quinoline europium, 0.02-0.2 part N- [(1,3- dimethyl -1H- pyrazoles -4- base) methyl]-N- ethamine, 80-100 parts of toluene, 40-50
The ethyl alcohol and 5-10 parts of aqueous sodium carbonate of part are added in reaction kettle, are vacuumized, with high pure nitrogen displaced air, are laid equal stress on
Again three times；0.01-0.05 parts of catalyst is added in reaction kettle under high pure nitrogen protection, 90-110 DEG C of temperature control, reflux
React 10-15h；It is extracted in three times after completing reaction using 300-500 parts of methylene chloride, merges organic phase, use deionized water
Washing is three times；Then it will be filtered after organic layer drying, the solvent in obtained solution steamed 150-250 parts, then will be left
Solution be added in reaction kettle, 5-10 parts of ethyl alcohol and 1.0-5.0 parts of concentrated hydrochloric acid is added, stirs 20- at room temperature
Then 30h is filtered, washed with methylene chloride and be dried in vacuo afterwards three times, and it is empty that a kind of OLED suitable for solution processing can be obtained
Transmit new material in cave.
The catalyst is tetrakis triphenylphosphine palladium or four (triphenylphosphine) platinum or four (triphenylphosphine) nickel.
The highly branched chain intermediate is prepared in accordance with the following methods：
According to mass fraction, the dimethyl sulfoxide of 12.5-25.0 parts of 2- bromine fluorenes and 60-80 part is added to thoroughly dry anti-
It answers in kettle, vacuumizes, with high pure nitrogen displaced air, and in triplicate；It is complete after stirring 20-30min under high pure nitrogen protection
25-30 parts of potassium hydroxide, is then added in reaction kettle, continues after being stirred to react 50-80min by portion's dissolution, ice-water bath item
Under part, by the bromo- 6- THP trtrahydropyranyl -2- of 38.7-51.6 parts of 1- (2- tetrahydro-pyran oxy ethyl) hexane, 0.02-0.2 part 1,
3,4,5- ttetrahydro-pyrans simultaneously [4,3-B] indoles, be slowly dropped in reaction kettle, react 7-12h；It completes reaction system is added
Precipitating in 200-300 parts of ice water uses after purifying water washing three times after filtering, is dried in vacuo 7-10h at 60-70 DEG C, obtains
To white solid；The white solid of obtained 12.6-24.8 part and 60-80 parts of tetrahydrofuran are added in reaction kettle, taken out
Vacuum, with high pure nitrogen displaced air, and in triplicate；It is cooled to subzero 70-80 DEG C with liquid nitrogen under high pure nitrogen protection, so
5.5-10.5 parts of n-butyllithium solution is added dropwise afterwards；40-60min is reacted after being added dropwise, and then will contain 4.4-10.8 parts of iodine
40-60 parts of tetrahydrofuran solution of simple substance are added in reaction kettle, are removed liquid nitrogen bath, are reacted 10- after being warming up to room temperature naturally
15h；After completing reaction, the aqueous solution containing 2.5-8.5 parts of sodium hydrogensulfites is added in reaction kettle, reacts 30-40min；
200-300 parts of water is added after completing reaction, it, will be organic laminated using 300-400 parts of methylene chloride aqueous layer extracted in three times
And then washed organic layer will be filtered after organic layer drying with desiccant, obtained solution is evaporated, by chromatography to neutrality
Highly branched chain intermediate can be obtained in separation.
The n-butyllithium solution is that concentration is 2.0-2.5mol/L.
The chromatography is petroleum ether and ethyl acetate according to 9.5-12.5 with eluent:1 ratio is formulated.
A kind of preparation method of the OLED hole transport new material suitable for solution processing disclosed in the method for the present invention, this is specially
A kind of OLED hole transport new material suitable for solution processing of benefit preparation has 12 hydroxyls of each molecule, which has
Excellent solvent selection performance, under room temperature, solubility is very small in toluene, in low polar solvent, and highly polar to alcohols
Solvent Solubility is larger；Using the property, which can form high-quality thin film from alcoholic solution, and can prevent adjacent
The phenomenon that function interface layer dissolves each other.
Specific embodiment
The invention is described further below by specific embodiment：
Embodiment 1
A kind of preparation method of the OLED hole transport new material suitable for solution processing, technology of preparing scheme are as follows：
Step 1: according to mass fraction, by 6.2 parts by the (6- THP trtrahydropyranyl -2- (2- tetrahydro-pyran oxy ethyl) of 9,9- bis-
Hexyl) -2,7- two (4,4,5,5- tetramethyl -1,3,2- dioxaborinate base) fluorenes, 13.2 parts of highly branched chain intermediate, 0.03
The single phenanthroline europium of 6- amino -2,3- dihydro 1-Indanone, the three of 0.005 part (dinaphthyl methylenes), 0.1 part of N- [(1,3- of part
Dimethyl -1H- pyrazoles -4- base) methyl]-N- ethamine, 90 parts of toluene, 45 parts of ethyl alcohol and 8 parts of aqueous sodium carbonate add
Enter into reaction kettle, vacuumize, with high pure nitrogen displaced air, and in triplicate；By 0.03 part under high pure nitrogen protection
Catalyst is added in reaction kettle, and 100 DEG C of temperature control, back flow reaction 13h；400 parts of methylene chloride is used to divide three after completing reaction
Secondary extraction merges organic phase, is washed with deionized three times；Then it will be filtered after organic layer drying, it will be in obtained solution
Solvent steams 200 parts, and then remaining solution is added in reaction kettle, and 8 parts of ethyl alcohol and 1.5 parts of concentrated hydrochloric acid is added,
25h is stirred under room temperature, is then filtered, is washed with methylene chloride and is dried in vacuo afterwards three times, can be obtained a kind of suitable for molten
The OLED hole transport new material of liquid processing.
The catalyst is four (triphenylphosphine) nickel.
The highly branched chain intermediate is prepared in accordance with the following methods：
According to mass fraction, 13.8 parts of 2- bromine fluorenes and 70 parts of dimethyl sulfoxide are added in thoroughly dry reaction kettle,
It vacuumizes, with high pure nitrogen displaced air, and in triplicate；It is all dissolved after stirring 25min under high pure nitrogen protection, then
28 parts of potassium hydroxide is added in reaction kettle, is continued after being stirred to react 70min, under the conditions of ice-water bath, by 39.8 parts of 1-
Bromo- 6- THP trtrahydropyranyl -2- (2- tetrahydro-pyran oxy ethyl) hexane, 0.08 part 1,3,4,5- ttetrahydro-pyrans simultaneously [4,3-B] Yin
Diindyl is slowly dropped in reaction kettle, reacts 10h；Reaction is completed by precipitating in 260 parts of system addition of ice water, is used after filtering
After purifying water washing three times, it is dried in vacuo 8h at 65 DEG C, obtains white solid；By obtain 13.4 parts of white solid and 70
Part tetrahydrofuran be added in reaction kettle, vacuumize, with high pure nitrogen displaced air, and in triplicate；It is protected in high pure nitrogen
Subzero 75 DEG C are cooled to liquid nitrogen under shield, 5 parts of n-butyllithium solution is then added dropwise；50min is reacted after being added dropwise, and then will
50 parts of tetrahydrofuran solution containing 5.6 parts of elemental iodines are added in reaction kettle, remove liquid nitrogen bath, are warming up to after room temperature naturally instead
Answer 13h；After completing reaction, the aqueous solution containing 2.9 parts of sodium hydrogensulfites is added in reaction kettle, reacts 35min；It completes anti-
250 parts of water should be added afterwards, using 350 parts of methylene chloride aqueous layer extracted in three times, organic layer is merged, washed organic layer is extremely
Then neutrality will be filtered after organic layer drying with desiccant, obtained solution is evaporated, can be obtained more by chromatography
Chain intermediate.
The n-butyllithium solution is that concentration is 2.3mol/L.
The chromatography is petroleum ether and ethyl acetate according to 10.5 with eluent:1 ratio is formulated.
Embodiment 2
A kind of preparation method of the OLED hole transport new material suitable for solution processing, technology of preparing scheme are as follows：
Step 1: according to mass fraction, by 5.6 parts by the (6- THP trtrahydropyranyl -2- (2- tetrahydro-pyran oxy ethyl) of 9,9- bis-
Hexyl) -2,7- two (4,4,5,5- tetramethyl -1,3,2- dioxaborinate base) fluorenes, 12.4 parts of highly branched chain intermediate, 0.01
Part 6- amino -2,3- dihydro 1-Indanone, the single phenanthroline europium of the three of 0.001 part (dinaphthyl methylenes), 0.02 part of N- [(1,
3- dimethyl -1H- pyrazoles -4- base) methyl]-N- ethamine, 80 parts of toluene, 40 parts of ethyl alcohol and 5-10 parts of sodium carbonate
Solution is added in reaction kettle, is vacuumized, with high pure nitrogen displaced air, and in triplicate；It will under high pure nitrogen protection
0.01-0.05 parts of catalyst is added in reaction kettle, and 90 DEG C of temperature control, back flow reaction 10h；300 parts are used after completing reaction
Methylene chloride extracts in three times, merges organic phase, is washed with deionized three times；Then it will be filtered after organic layer drying, will
To solution in solvent steam 150 parts, then remaining solution is added in reaction kettle, be added 5 parts ethyl alcohol and 1 part
Concentrated hydrochloric acid stirs 20h at room temperature, then filters, and is washed with methylene chloride and is dried in vacuo afterwards three times, one kind can be obtained
OLED hole transport new material suitable for solution processing.
The catalyst is four (triphenylphosphine) platinum.
The highly branched chain intermediate is prepared in accordance with the following methods：
According to mass fraction, 12.5 parts of 2- bromine fluorenes and 60 parts of dimethyl sulfoxide are added in thoroughly dry reaction kettle,
It vacuumizes, with high pure nitrogen displaced air, and in triplicate；It is all dissolved after stirring 20min under high pure nitrogen protection, then
25 parts of potassium hydroxide is added in reaction kettle, is continued after being stirred to react 50min, under the conditions of ice-water bath, by 38.7 parts of 1-
Bromo- 6- THP trtrahydropyranyl -2- (2- tetrahydro-pyran oxy ethyl) hexane, 0.02 part 1,3,4,5- ttetrahydro-pyrans simultaneously [4,3-B] Yin
Diindyl is slowly dropped in reaction kettle, reaction 7；Reaction is completed by precipitating in 200 parts of system addition of ice water, using pure after filtering
After changing water washing three times, it is dried in vacuo 10h at 60 DEG C, obtains white solid；By obtain 12.6 parts of white solid and 60
Part tetrahydrofuran be added in reaction kettle, vacuumize, with high pure nitrogen displaced air, and in triplicate；It is protected in high pure nitrogen
Subzero 70 DEG C are cooled to liquid nitrogen under shield, 5.5 parts of n-butyllithium solution is then added dropwise；40min is reacted after being added dropwise, then
40 parts of tetrahydrofuran solution containing 4.4 parts of elemental iodines are added in reaction kettle, liquid nitrogen bath are removed, after being warming up to room temperature naturally
React 10h；After completing reaction, the aqueous solution containing 2.5 parts of sodium hydrogensulfites is added in reaction kettle, reacts 30min；It completes
200 parts of water is added after reaction, using 300 parts of methylene chloride aqueous layer extracted in three times, organic layer is merged, washed organic layer
To neutrality, it then will be filtered after organic layer drying with desiccant, obtained solution be evaporated, can be obtained by chromatography more
Branch intermediate.
The n-butyllithium solution is that concentration is 2.0mol/L.
The chromatography is petroleum ether and ethyl acetate according to 9.5 with eluent:1 ratio is formulated.
Embodiment 3
A kind of preparation method of the OLED hole transport new material suitable for solution processing, technology of preparing scheme are as follows：
Step 1: according to mass fraction, by 10.8 parts by (6- THP trtrahydropyranyl -2- (the 2- tetrahydro-pyran oxy second of 9,9- bis-
Base) hexyl) -2,7- two (4,4,5,5- tetramethyl -1,3,2- dioxaborinate base) fluorenes, 24.3 parts of highly branched chain intermediate,
The single phenanthroline europium of 0.1 part of 6- amino -2,3- dihydro 1-Indanone, the three of 0.01 part (dinaphthyl methylenes), 0.2 part of N- [(1,
3- dimethyl -1H- pyrazoles -4- base) methyl]-N- ethamine, 100 parts of toluene, 50 parts of ethyl alcohol and 10 parts of sodium carbonate it is water-soluble
Liquid is added in reaction kettle, is vacuumized, with high pure nitrogen displaced air, and in triplicate；By 0.05 under high pure nitrogen protection
The catalyst of part is added in reaction kettle, and 110 DEG C of temperature control, back flow reaction 15h；Complete the methylene chloride after reacting using 500 parts
It extracts in three times, merges organic phase, be washed with deionized three times；Then it will be filtered after organic layer drying, the solution that will be obtained
In solvent steam 250 parts, then remaining solution is added in reaction kettle, 10 parts of ethyl alcohol and 5 parts of concentrated hydrochloric acid is added,
30h is stirred at room temperature, is then filtered, is washed with methylene chloride and is dried in vacuo afterwards three times, and one kind can be obtained and be suitable for
The OLED hole transport new material of solution processing.
The catalyst is tetrakis triphenylphosphine palladium.
The highly branched chain intermediate is prepared in accordance with the following methods：
According to mass fraction, 25.0 parts of 2- bromine fluorenes and 80 parts of dimethyl sulfoxide are added in thoroughly dry reaction kettle,
It vacuumizes, with high pure nitrogen displaced air, and in triplicate；It is all dissolved after stirring 30min under high pure nitrogen protection, then
30 parts of potassium hydroxide is added in reaction kettle, is continued after being stirred to react 80min, under the conditions of ice-water bath, by 51.6 parts of 1-
Bromo- 6- THP trtrahydropyranyl -2- (2- tetrahydro-pyran oxy ethyl) hexane, 0.2 part 1,3,4,5- ttetrahydro-pyrans simultaneously [4,3-B] Yin
Diindyl is slowly dropped in reaction kettle, reacts 12h；Reaction is completed by precipitating in 300 parts of system addition of ice water, is used after filtering
After purifying water washing three times, it is dried in vacuo 10h at 70 DEG C, obtains white solid；By obtain 24.8 parts of white solid and
80 parts of tetrahydrofuran is added in reaction kettle, is vacuumized, with high pure nitrogen displaced air, and in triplicate；In high pure nitrogen
Subzero 80 DEG C are cooled to liquid nitrogen under protection, 10.5 parts of n-butyllithium solution is then added dropwise；60min is reacted after being added dropwise,
Then 60 parts of tetrahydrofuran solution containing 10.8 parts of elemental iodines are added in reaction kettle, remove liquid nitrogen bath, is warming up to naturally
15h is reacted after room temperature；After completing reaction, the aqueous solution containing 8.5 parts of sodium hydrogensulfites is added in reaction kettle, is reacted
40min；300 parts of water is added after completing reaction, using 400 parts of methylene chloride aqueous layer extracted in three times, organic layer is merged,
Then washed organic layer will be filtered after organic layer drying with desiccant, obtained solution is evaporated, by chromatography to neutrality
Highly branched chain intermediate can be obtained.
The n-butyllithium solution is that concentration is 2.5mol/L.
The chromatography is petroleum ether and ethyl acetate according to 12.5 with eluent:1 ratio is formulated.
Comparative example 1
6- amino -2,3- dihydro 1-Indanone, the other the same as in Example 1 is not added.
Comparative example 2
The single phenanthroline europium of three (dinaphthyl methylenes), the other the same as in Example 1 is not added.
Comparative example 3
Four (triphenylphosphine) nickel, the other the same as in Example 1 is not added.
Comparative example 4
N- [(1,3- dimethyl -1H- pyrazoles -4- base) methyl]-N- ethamine, the other the same as in Example 1 is not added.
Comparative example 5
1,3,4,5- ttetrahydro-pyrans simultaneously [4,3-B] indoles, the other the same as in Example 1 is not added.
Table：The performance for the photoelectric device that the test specimen that different process is made is made compares.
Claims (5)
1. a kind of preparation method of the OLED hole transport new material suitable for solution processing, technology of preparing scheme are as follows：
Step 1: according to mass fraction, by 5.6-10.8 parts by (6- THP trtrahydropyranyl -2- (the 2- tetrahydro-pyran oxy of 9,9- bis-
Ethyl) hexyl) -2,7- two (4,4,5,5- tetramethyl -1,3,2- dioxaborinate base) fluorenes, in 12.4-24.3 parts of highly branched chain
Mesosome, 0.01-0.1 parts of 6- amino -2,3- dihydro 1-Indanone, the three of 0.001-0.01 parts (dinaphthyl methylene) Dan Fei are coughed up
Quinoline europium, 0.02-0.2 part N- [(1,3- dimethyl -1H- pyrazoles -4- base) methyl]-N- ethamine, 80-100 parts of toluene, 40-50
The ethyl alcohol and 5-10 parts of aqueous sodium carbonate of part are added in reaction kettle, are vacuumized, with high pure nitrogen displaced air, are laid equal stress on
Again three times；0.01-0.05 parts of catalyst is added in reaction kettle under high pure nitrogen protection, 90-110 DEG C of temperature control, reflux
React 10-15h；It is extracted in three times after completing reaction using 300-500 parts of methylene chloride, merges organic phase, use deionized water
Washing is three times；Then it will be filtered after organic layer drying, the solvent in obtained solution steamed 150-250 parts, then will be left
Solution be added in reaction kettle, 5-10 parts of ethyl alcohol and 1.0-5.0 parts of concentrated hydrochloric acid is added, stirs 20- at room temperature
Then 30h is filtered, washed with methylene chloride and be dried in vacuo afterwards three times, and it is empty that a kind of OLED suitable for solution processing can be obtained
Transmit new material in cave.
2. a kind of preparation method of OLED hole transport new material suitable for solution processing according to claim 1,
It is characterized in that：The catalyst is tetrakis triphenylphosphine palladium or four (triphenylphosphine) platinum or four (triphenylphosphine) nickel.
3. a kind of preparation method of OLED hole transport new material suitable for solution processing according to claim 1,
It is characterized in that：The highly branched chain intermediate is prepared in accordance with the following methods：
According to mass fraction, the dimethyl sulfoxide of 12.5-25.0 parts of 2- bromine fluorenes and 60-80 part is added to thoroughly dry anti-
It answers in kettle, vacuumizes, with high pure nitrogen displaced air, and in triplicate；It is complete after stirring 20-30min under high pure nitrogen protection
25-30 parts of potassium hydroxide, is then added in reaction kettle, continues after being stirred to react 50-80min by portion's dissolution, ice-water bath item
Under part, by the bromo- 6- THP trtrahydropyranyl -2- of 38.7-51.6 parts of 1- (2- tetrahydro-pyran oxy ethyl) hexane, 0.02-0.2 part 1,
3,4,5- ttetrahydro-pyrans simultaneously [4,3-B] indoles, be slowly dropped in reaction kettle, react 7-12h；It completes reaction system is added
Precipitating in 200-300 parts of ice water uses after purifying water washing three times after filtering, is dried in vacuo 7-10h at 60-70 DEG C, obtains
To white solid；The white solid of obtained 12.6-24.8 part and 60-80 parts of tetrahydrofuran are added in reaction kettle, taken out
Vacuum, with high pure nitrogen displaced air, and in triplicate；It is cooled to subzero 70-80 DEG C with liquid nitrogen under high pure nitrogen protection, so
5.5-10.5 parts of n-butyllithium solution is added dropwise afterwards；40-60min is reacted after being added dropwise, and then will contain 4.4-10.8 parts of iodine
40-60 parts of tetrahydrofuran solution of simple substance are added in reaction kettle, are removed liquid nitrogen bath, are reacted 10- after being warming up to room temperature naturally
15h；After completing reaction, the aqueous solution containing 2.5-8.5 parts of sodium hydrogensulfites is added in reaction kettle, reacts 30-40min；
200-300 parts of water is added after completing reaction, it, will be organic laminated using 300-400 parts of methylene chloride aqueous layer extracted in three times
And then washed organic layer will be filtered after organic layer drying with desiccant, obtained solution is evaporated, by chromatography to neutrality
Highly branched chain intermediate can be obtained in separation.
4. a kind of preparation method of OLED hole transport new material suitable for solution processing according to claim 3,
It is characterized in that：The n-butyllithium solution is that concentration is 2.0-2.5mol/L.
5. a kind of preparation method of OLED hole transport new material suitable for solution processing according to claim 3,
It is characterized in that：The chromatography is petroleum ether and ethyl acetate according to 9.5-12.5 with eluent:1 ratio is formulated.
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| CN112531136A (en) * | 2020-12-08 | 2021-03-19 | 北京交通大学 | Preparation method of organic electroluminescent device multilayer film |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1696171A (en) * | 2005-05-20 | 2005-11-16 | 中国科学院长春应用化学研究所 | Alcohol soluble material in poly-fluorene group containing phosphate group in use for luminescent material |
| CN104163824A (en) * | 2014-07-04 | 2014-11-26 | 南开大学 | Gold-{2-(9-anthracene phenyl)dicyclohexylphosphine}-acetonitrile complex synthesis and application thereof |
-
2018
- 2018-07-23 CN CN201810814817.0A patent/CN108841379A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1696171A (en) * | 2005-05-20 | 2005-11-16 | 中国科学院长春应用化学研究所 | Alcohol soluble material in poly-fluorene group containing phosphate group in use for luminescent material |
| CN104163824A (en) * | 2014-07-04 | 2014-11-26 | 南开大学 | Gold-{2-(9-anthracene phenyl)dicyclohexylphosphine}-acetonitrile complex synthesis and application thereof |
Non-Patent Citations (4)
| Title |
|---|
| AYUMI MIYAO等: "Incorporation of fluorine-based emitting polymers into silica", 《JOURNAL OF POLYMER SCIENCE：PART A:POLYMER CHEMISTRY》 * |
| HOON-JE CHO 等: "Electroluminescent Polyhedral Oligomeric Silsesquioxane-Based Nanoparticle", 《CHEM. MATER.》 * |
| JIANPING LU 等: "High-efficiency multilayer polymeric blue light-emitting diodes using boronate esters as cross-linking linkages", 《J. MATER. CHEM.》 * |
| 朱同波: "含二羟基丙基芴基聚合物的合成及其光电性能研究", 《中国优秀硕士论文全文数据库 科技工程I辑》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112531136A (en) * | 2020-12-08 | 2021-03-19 | 北京交通大学 | Preparation method of organic electroluminescent device multilayer film |
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