CN102191042A - Triarylamine hole transport material and preparation method thereof - Google Patents
Triarylamine hole transport material and preparation method thereof Download PDFInfo
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- CN102191042A CN102191042A CN2011100639628A CN201110063962A CN102191042A CN 102191042 A CN102191042 A CN 102191042A CN 2011100639628 A CN2011100639628 A CN 2011100639628A CN 201110063962 A CN201110063962 A CN 201110063962A CN 102191042 A CN102191042 A CN 102191042A
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- hole transport
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- triarylamine
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Abstract
The invention provides a high-stability triarylamine hole transport material capable of providing brightness efficiency and service life of a device, and a preparation method thereof. The triarylamine hole transport material provided by the invention comprises a compound N,N'-diphenyl-N,N'-di(4-(9H-carbazolyl)biphenyl)-1,1'-biphenyl-4,4'-diamine. Since the inside of the triarylamine hole transport material does not contain a high-symmetry structure and can enhance the amorphous stability of the film, the triarylamine hole transport material can enhance the transport rate of the holes in the device and effectively obstruct electrons to the inside of the luminescent layer when being used as a hole transport layer in an organic electroluminescent device, thereby implementing the maximum compounding of the current carrier, reducing the energy barrier of the holes in the implantation process and further improving the brightness efficiency and service life of the device.
Description
Technical field
The present invention relates to a kind of organic material and preparation method thereof of giving out light, especially a kind of triarylamine analog hole transport materials and preparation method thereof.
Background technology
At present, organic electroluminescence device is used more and more widely aspect the plate color demonstration, after the Tang of Kodak company C.W. utilizes double-deck organic assembly to realize that successfully low driving is luminous, the researchist has obtained a large amount of progress in field of organic electroluminescent materials, we can say that luminescent device has stepped into the commercialization eve of large screen display.
The focus of hole investigation of materials at present concentrates on the stability that improves luminous efficiency and increase device, and the hole injection barrier of reduction hole mobile material, improving carrier mobility then is an important means that improves luminous efficiency, simultaneously, big quantity research discloses, it is a major reason of component failure that hole transmission layer lost efficacy under heat effect, and the carrier mobility of raising hole mobile material can prevent effectively that this inefficacy from taking place.
Because arylamine class material has low ionization tendency, form radical cation (hole) easily, and can be by the vacuum-evaporation film forming, therefore be the hole mobile material that a class has good carrier mobility performance, but existing arylamine class material has high symmetric structure mostly, make that the morphological stability of film is very low, easily crystallization, thus influence the life-span and the performance of device.
Summary of the invention
The invention provides the triarylamine analog hole transport materials in a kind of good stability, the luminance efficiency that device can be provided and life-span and preparation method thereof.
Realize the triarylamine analog hole transport materials of one of the object of the invention, comprise following compound:
Wherein the locational R base of N is benzene or alkylbenzene.
Realize the preparation method of two the triarylamine analog hole transport materials of the object of the invention, step is as follows:
(1) with N, the N-diphenylamine is raw material and bromo-iodobenzene is carried out ullmann reaction under certain condition synthesize N, N '-phenylbenzene-N, N '-two (4-bromophenyl)-1,1 '-biphenyl-4,4 '-diamines.
(2) with the carbazole be main raw material, elder generation and paradibromobenzene reaction generate 4-(9H-carbazole) bromobenzene, are carrying out butyllithium reaction generation 4-(9H-carbazole) phenylo boric acid.
(3) with the final product N of step (1), N '-phenylbenzene-N, N '-two (4-bromophenyl)-1,1 '-biphenyl-4, suzuki reaction takes place and generates N in the final product 4-of 4 '-diamines and step (2) (9H-carbazole) phenylo boric acid, N '-phenylbenzene-N, N '-two (4-(9H-carbazole) xenyl)-1,1 '-biphenyl-4,4 '-diamines.
Raw material N in the described step (1), the N-diphenylamine substitutes with the alkylbenzene benzidine.
Triarylamine analog hole transport materials of the present invention, because its material internal does not contain high symmetry structure, can improve the stability of film amorphous state, therefore, be applied to organic electroluminescence device, can improve the transfer rate of hole in device as hole transmission layer, and effectively electronics is blocked in the luminescent layer, realize the maximum compound of current carrier, reduce the energy barrier of hole in injection process simultaneously, thereby improve the luminance efficiency and the life-span of device.
Embodiment
The preparation method embodiment of triarylamine analog hole transport materials of the present invention is as follows:
Embodiment 1
Triarylamine analog hole transport materials compound of the present invention:
The locational R base of N is the preparation method of phenyl, and step is as follows:
(1) with N, the N-diphenylamine is raw material and bromo-iodobenzene is carried out ullmann reaction under certain condition synthesize N, N '-phenylbenzene-N, N '-two (4-bromophenyl)-1,1 '-biphenyl-4,4 '-diamines.
Concrete preparation method is:
A) in the 1L four-hole bottle, add acetate 200 grams, 400 milliliters in water, sulfuric acid 150 grams, pentanoic 0.4mol.Stirring cools to 5 degree, slowly drips the saturated aqueous solution of potassium bichromate of 0.2mol, dropwises, under this temperature, stir half an hour, filter washing then, crude product with dimethyl formamide and toluene recrystallization to off-white color elaboration compound N, N-diphenylamine 20 grams (HPLC:98.5%).
Concrete synthetic route is as follows:
B) under nitrogen protection, digest compound N, the N-diphenylamine with 20; 50 grams are to bromo-iodobenzene, 100 milliliters of KOH9 gram and orthodichlorobenzenes and 1, and 10-phenanthroline 0.2 restrains; cuprous chloride 0.3 gram, reflux 8 hours, cold filtration; cross pillar (column chromatography for separation) and obtain compound N, N '-phenylbenzene-N, N '-two (4-bromophenyl)-1; 1 '-biphenyl-4; 4 '-diamines 22 gram, wherein, the chromatography solvent is methylene dichloride and oil fan 1: 6.
Concrete reaction scheme is as follows:
(2) with the carbazole be main raw material, elder generation and paradibromobenzene reaction generate 4-(9H-carbazole) bromobenzene, are carrying out butyllithium reaction generation 4-(9H-carbazole) phenylo boric acid.
Concrete preparation method is:
A) under nitrogen protection; carbazole with 0.5mol; paradibromobenzene with 0.7mol; 800 milliliters of perhydronaphthalenes, K2CO3 0.7mol reflux 10 hours, cooling; filter; decompression is desolvated, and residue is crossed silicagel column with 1: 3 methylene dichloride and oil fan, obtains elaboration 4-(9H-carbazole) bromobenzene 110 grams (HPLC:98.4%).
Concrete reaction scheme is as follows:
B) under nitrogen protection; with 0.2mol compound 4-(9H-carbazole) bromobenzene; THF1000ml joins in the 3000ml four-hole bottle; cool to-80 degree; drip 85 milliliters of the n-Butyl Lithium hexane solutions of 2.5L/mol in 30 minutes; dropwise; insulated and stirred 30 minutes; spend the tetrahydrofuran (THF) mixing solutions that drips 0.25mol triisopropyl borate ester and 100ml again-80, about 30 minutes of dropping time, dripped off insulated and stirred 1 hour; 2N hydrochloric acid hydrolysis PH=5-6 then; static layering, water merges organic phase twice with extracted with diethyl ether, with twice of saturated salt washing; decompression is desolvated then; obtain crude product,, obtain product compound 4-(9H-carbazole) phenylo boric acid 38.2 grams with ethanol water recrystallization.
Concrete reaction scheme is as follows:
(3) with the final product N of step (1), N '-phenylbenzene-N, N '-two (4-bromophenyl)-1,1 '-biphenyl-4, suzuki reaction takes place and generates N in the final product 4-of 4 '-diamines and step (2) (9H-carbazole) phenylo boric acid, N '-phenylbenzene-N, N '-two (4-(9H-carbazole) xenyl)-1,1 '-biphenyl-4,4 '-diamines.
Concrete preparation method is as follows:
Under nitrogen protection; in the 2000ml four-hole bottle, add the 0.1mol compound N; N '-phenylbenzene-N; N '-two (4-bromophenyl)-1,1 '-biphenyl-4,4 '-diamines; 0.05mol compound 4-(9H-carbazole) phenylo boric acid; 0.3mol K2CO3, toluene 800ml, water 200mol; 1.5 restrain four (triphenyl phosphorus) palladium reflux 10 hours; the cooling layering, the phase of anhydrating, organic phase wash 200ml*2 with water twice; anhydrous sodium sulfate drying; boil off toluene, residue is crossed silicagel column with 1: 4 methylene dichloride sherwood oil, obtains the light yellow solid compound N; N '-phenylbenzene-N; N '-two (4-(9H-carbazole) xenyl)-1,1 '-biphenyl-4,4 '-diamines, 22 grams (HPLC:99%).
Concrete reaction scheme is as follows:
Embodiment 2
Triarylamine analog hole transport materials compound of the present invention:
The locational R base of N is the preparation method of alkylbenzene, and basic identical with the preparation method of embodiment 1, different is: with the raw material N in the step (1), the N-diphenylamine substitutes with the alkylbenzene benzidine.
Triarylamine analog hole transport materials of the present invention and preparation method thereof advantage is as follows:
1, to have changed the degree of crystallinity of hole mobile material in the past low for triarylamine analog hole transport materials of the present invention, material is unfavorable for the crystalline shortcoming, can form non-crystalline state preferably in evaporate process, and it is smooth to help film morphology, improved the plated film yield rate, reduced cost.
2, the employed catalyzer of the preparation method of triarylamine analog hole transport materials of the present invention is by metal halide/1,10-phenanthroline/mineral alkali, and cuprous chloride, formulated by a certain percentage, make the reaction conditions gentleness, the reaction times shortens, and yield improves.And the catalyzer of using in the present synthetic method is that palladium metal, Palladous chloride or palladium are catalyzer, not only cost an arm and a leg, and necessary anhydrous, the anaerobic system of reaction conditions, be not suitable for industrialization.
3, reaction raw materials and the catalyzer among the preparation method of triarylamine analog hole transport materials of the present invention is easy to get; and price is lower, and purification process is simple, thereby greatly reduces production cost; be a breakthrough in large-scale production, be suitable for scale operation and application.
Claims (3)
1. triarylamine analog hole transport materials comprises following compound:
Wherein the locational R base of N is benzene or alkylbenzene.
2. the preparation method of a triarylamine analog hole transport materials comprises the steps:
(1) with N, the N-diphenylamine is raw material and bromo-iodobenzene is carried out ullmann reaction under certain condition synthesize N, N '-phenylbenzene-N, N '-two (4-bromophenyl)-1,1 '-biphenyl-4,4 '-diamines.
(2) with the carbazole be main raw material, elder generation and paradibromobenzene reaction generate 4-(9H-carbazole) bromobenzene, are carrying out butyllithium reaction generation 4-(9H-carbazole) phenylo boric acid.
(3) with the final product N of step (1), N '-phenylbenzene-N, N '-two (4-bromophenyl)-1,1 '-biphenyl-4, suzuki reaction takes place and generates N in the final product 4-of 4 '-diamines and step (2) (9H-carbazole) phenylo boric acid, N '-phenylbenzene-N, N '-two (4-(9H-carbazole) xenyl)-1,1 '-biphenyl-4,4 '-diamines.
3. the preparation method of a kind of triarylamine analog hole transport materials according to claim 2 is characterized in that: the raw material N in the described step (1), the N-diphenylamine substitutes with the alkylbenzene benzidine.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2011100639628A CN102191042A (en) | 2011-03-17 | 2011-03-17 | Triarylamine hole transport material and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111116946A (en) * | 2019-12-31 | 2020-05-08 | 深圳市华星光电半导体显示技术有限公司 | Hole transport material, display panel and manufacturing method thereof |
| US11798763B2 (en) | 2019-03-22 | 2023-10-24 | Supergrid Institute | Current cut-off device for high-voltage direct current with resonator and switching |
-
2011
- 2011-03-17 CN CN2011100639628A patent/CN102191042A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11798763B2 (en) | 2019-03-22 | 2023-10-24 | Supergrid Institute | Current cut-off device for high-voltage direct current with resonator and switching |
| CN111116946A (en) * | 2019-12-31 | 2020-05-08 | 深圳市华星光电半导体显示技术有限公司 | Hole transport material, display panel and manufacturing method thereof |
| CN111116946B (en) * | 2019-12-31 | 2022-11-08 | 深圳市华星光电半导体显示技术有限公司 | Hole transport material, display panel and manufacturing method thereof |
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