CN1403491A - Prepn of triphenylamine polymer as hole material - Google Patents
Prepn of triphenylamine polymer as hole material Download PDFInfo
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- CN1403491A CN1403491A CN 02139146 CN02139146A CN1403491A CN 1403491 A CN1403491 A CN 1403491A CN 02139146 CN02139146 CN 02139146 CN 02139146 A CN02139146 A CN 02139146A CN 1403491 A CN1403491 A CN 1403491A
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Abstract
The present invention relates to the preparation process of triphenylamine polymer as hole material. The triphenylamine polymer as hole material is prepared through the reaction with triphenylamine as material, hydrocarbon halide or nitrobenzene as solvent in the presence of Lewis acid and at the temperature of minus 30 to 70 deg.c. The present invention simplifies the preparation of phenylamine polymer to one single-step reaction process without the halogenation reaction of triphenylamine and the use of halogenating agent and noble catalyst and thus has lower production cost.
Description
Technical field
The present invention relates to a kind of triphenylamine polymkeric substance hole preparation methods.
Background technology
Triphenylamine and derivative thereof are used as hole transmission layer in electroluminescent device, its second-order transition temperature and positive correlation device lifetime.The multipolymer of the dimer of triphenylamine, polymer, star compound and other aromatic molecules all can be used as the hole transmission layer of electroluminescent device.
The method of synthetic triphenylamine star hole material has Grignard reagent method, Liv Ullmann (ulman) reaction method etc.The Grignard reagent method is difficult to industrialization.Document Chemistry letter, pp1145-1148,1989 have reported with the copper powder to be catalyzer, three iodo triphenylamine condensations obtain product, productive rate only 19%.European patent EP 0802173A1 is a catalyzer with palladium and trialkyl phosphine, and three bromo triphenylamine condensations obtain product, have improved productive rate.But raw material and catalyzer are all very expensive.Chinese patent application number is the preparation method that 99119031.9 patent application discloses a kind of star hole transfering material, at first with raw material triphenylamine, halogenating agent iodine or bromine, catalyzer aluminum chloride and solvent methyl-sulphoxide, halogenating reaction is carried out in intensification, products therefrom and 3 methyl diphenylamine are the Preparation of Catalyst star hole transfering material as raw material with Palladous chloride and triphenyl phosphine.Used halogenating agent iodine of this method or bromine price are higher, and the toxicity of bromine is bigger, easily contaminate environment.And use tellurian narrow resources precious metal palladium, production cost is increased.
Summary of the invention
The present invention provides a kind of triphenylamine polymkeric substance hole preparation methods at the problems referred to above exactly, and this method is easy to suitability for industrialized production, and the preparation cost of gained material is lower.
Technical scheme provided by the invention is: a kind of triphenylamine polymkeric substance hole preparation methods is that raw material, halohydrocarbon or oil of mirbane are solvent with the triphenylamine, and in the presence of lewis acid ,-30 ℃～70 ℃ reactions obtain required triphenylamine polymkeric substance hole material.
In order to reconcile or improve product performance, also can add heteroaromatic compounds and/or carbocyclic aromatic and derivative thereof in above-mentioned reactant is second monomer or the 3rd monomer.
Above-mentioned heteroaromatic compounds can be selected from carbazole, alkyl carbazole, pyridine oxide, oxidation quinoline, thiophene or pyrroles etc., and carbocyclic aromatic is selected from benzene, naphthalene, anthracene, Stilbene or phenanthrene etc. and derivative thereof.
Above-mentioned lewis acid is iron trichloride, aluminum chloride or dichloride copper etc.
Above-mentioned solvent is methyl chloride, monochloroethane, chlorobenzene or oil of mirbane isopolarity solvent.
The present invention makes the preparation of aniline polymer be reduced to single step reaction, has saved the halogenating reaction of triphenylamine, has saved halogenating agents such as iodine, bromine; Save catalyzer precious metal palladium title complex, reduced production cost.
Because three phenyl ring of triphenylamine have identical reactive behavior, the hydrogen atom activity that is in the nitrogen-atoms contraposition is the highest, and product has tree structure.Thereby not needing to introduce alkyl as the hydrotropy group, the polymkeric substance of production has good solvability, can spin-coating film be processed into device.
Embodiment
In reactor, add friedel-crafts reaction (Friedel-Crafts) catalyzer such as triphenylamine, polar solvent methyl chloride, monochloroethane, chlorobenzene or oil of mirbane etc., lewis acid such as iron trichloride, aluminum chloride or dichloride copper; under-30 ℃～70 ℃, argon gas or nitrogen protection, reacted 20～60 hours; filter, leach catalyzer.In the methyl alcohol or ethanol with 5 times of filtrate impourings, stir, have precipitation to generate, filter collecting precipitation, vacuum dehydrating at lower temperature gets required triphenylamine polymkeric substance hole material.
Three mouthfuls of reaction flasks of embodiment 1:100 milliliter are equipped with water condensing tube, argon gas ingress pipe.Argon gas is derived by the prolong top, and connects through a drying tower and the atmosphere that calcium chloride is housed.Place one in the bottle and stir magneton, reaction flask is put on the magnetic stirring apparatus.Earlier logical argon gas is three minutes before the reaction, under the argon gas stream protection, add triphenylamine 2.4 grams (0.01 mole) from another opening (clogging with grinding port plug before this) of there-necked flask, add 30 milliliters of chloroforms and make the triphenylamine dissolving, add FERRIC CHLORIDE ANHYDROUS 6.5 grams (0.04 mole) again; 25 ℃ are stirred stopped reaction after 48 hours under argon shield.Filtration under diminished pressure, the elimination iron trichloride in filtrate impouring 150 ml methanol, stirred 30 minutes.Decompress filter is used ethanol repetitive scrubbing filter residue once more; Filter residue 50 ℃ of dryings, is obtained canescence to yellow powder triphenylamine polymkeric substance hole material 0.65 gram, productive rate 35%.
Embodiment 2: reaction unit is with embodiment 1.In there-necked flask, add triphenylamine 2.4 grams (0.01 mole), Stilbene 1.8 grams (0.01 mole), anhydrous dichloride copper 8 grams, 50 milliliters in oil of mirbane.There-necked flask is in cryosel is bathed, and-20 ℃ were stirred 60 hours under the argon shield.In reaction flask, add 300 milliliters of ethanol, stirred 30 minutes, precipitation in a large number occurs.Filter collecting precipitation, use distilled water wash, suction filtration, repeated multiple times, colourless to filtrate, use washing with alcohol filter residue twice again, filter residue dry below 50 ℃, is obtained triphenylamine polymkeric substance hole material 2 grams.Product has hole transport and EL function.
Embodiment 3: reaction unit is with embodiment 1.1.2 gram (0.005 mole) triphenylamines and 0.35 gram pyrroles are added in the reaction flask, add 15 milliliters of chloroforms, stir and make its dissolving.In addition FERRIC CHLORIDE ANHYDROUS 3.2 grams, aluminum trichloride (anhydrous) 2.7 grams are scattered in 25 milliliters of chloroforms, pack into and be with the dropping funnel of voltage stabilizing tube, in reaction flask, slowly drip and keep stirring.Drip and finish, continue reaction 48 hours down for 50 degrees centigrade in argon shield and constant temperature.150 milliliters of ethanol of adding in reaction flask are finished in reaction, stir, and occur precipitation in the reaction flask.Filter collecting precipitation, water repetitive scrubbing filter residue is colourless to filtrate, uses washing with alcohol twice again, and dry filter residue in 50 ℃ of loft drier obtains triphenylamine polymkeric substance hole material.
Also can add other heteroaromatic compounds of the present invention and/or carbocyclic aromatic and derivative thereof in the foregoing description and be second monomer or the 3rd monomer to reconcile or to improve product performance.
Embodiment 4: the product purification method: in 250 milliliters of conical flasks thick product triphenylamine polymkeric substance 2 grams are dissolved in 100 milliliters of chloroforms, stirred 10 to 20 minutes.Filter, in the ethanol that the filtrate impouring is 400～50 milliliter 95%, stirred 30 minutes, filter on funnel, collecting precipitation dry below 50 ℃, obtains triphenylamine polymkeric substance straight product.
Claims (5)
1. a triphenylamine polymkeric substance hole preparation methods is that raw material, halohydrocarbon or oil of mirbane are solvent with the triphenylamine, and in the presence of lewis acid ,-30 ℃～70 ℃ reactions obtain required triphenylamine polymkeric substance hole material.
2. preparation method according to claim 1 is characterized in that: also can add heteroaromatic compounds and/or carbocyclic aromatic and derivative thereof in above-mentioned reactant is second monomer or the 3rd monomer.
3. preparation method according to claim 2 is characterized in that: above-mentioned heteroaromatic compounds can be selected from carbazole, alkyl carbazole, pyridine oxide, oxidation quinoline, thiophene or pyrroles, and carbocyclic aromatic is selected from benzene, naphthalene, anthracene, Stilbene or phenanthrene and derivative thereof.
4. according to claim 1 or 2 or 3 described preparation methods, it is characterized in that: above-mentioned lewis acid is iron trichloride, aluminum chloride or dichloride copper.
5. according to claim 1 or 2 or 3 described preparation methods, it is characterized in that: above-mentioned organic solvent is methyl chloride, monochloroethane, chlorobenzene or oil of mirbane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021391467A CN1168760C (en) | 2002-10-09 | 2002-10-09 | Prepn of triphenylamine polymer as hole material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021391467A CN1168760C (en) | 2002-10-09 | 2002-10-09 | Prepn of triphenylamine polymer as hole material |
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| Publication Number | Publication Date |
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| CN1403491A true CN1403491A (en) | 2003-03-19 |
| CN1168760C CN1168760C (en) | 2004-09-29 |
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| Application Number | Title | Priority Date | Filing Date |
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| CNB021391467A Expired - Fee Related CN1168760C (en) | 2002-10-09 | 2002-10-09 | Prepn of triphenylamine polymer as hole material |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1331914C (en) * | 2005-10-18 | 2007-08-15 | 武汉大学 | Method for synthesizing polymer of poly-triphenylamine |
| CN102585176A (en) * | 2012-03-02 | 2012-07-18 | 河北联合大学 | Heterocycle-modified polytriphenylamine organic hole transport material for all-solid-state quantum dot sensitized solar cell |
| CN103396531A (en) * | 2013-07-19 | 2013-11-20 | 苏州纳埃净化科技有限公司 | Preparation method of porous aromatic skeleton compound |
| CN106471057A (en) * | 2014-05-29 | 2017-03-01 | Az电子材料（卢森堡）有限公司 | Space formation compositionss, possess the space being formed using said composition semiconductor device and employ said composition semiconductor device manufacture method |
-
2002
- 2002-10-09 CN CNB021391467A patent/CN1168760C/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1331914C (en) * | 2005-10-18 | 2007-08-15 | 武汉大学 | Method for synthesizing polymer of poly-triphenylamine |
| CN102585176A (en) * | 2012-03-02 | 2012-07-18 | 河北联合大学 | Heterocycle-modified polytriphenylamine organic hole transport material for all-solid-state quantum dot sensitized solar cell |
| CN102585176B (en) * | 2012-03-02 | 2013-11-13 | 河北联合大学 | Heterocycle-modified polytriphenylamine organic hole transport material for all-solid-state quantum dot sensitized solar cell |
| CN103396531A (en) * | 2013-07-19 | 2013-11-20 | 苏州纳埃净化科技有限公司 | Preparation method of porous aromatic skeleton compound |
| CN103396531B (en) * | 2013-07-19 | 2016-03-16 | 苏州纳埃净化科技有限公司 | A kind of preparation method of porous aromatic skeleton compound |
| CN106471057A (en) * | 2014-05-29 | 2017-03-01 | Az电子材料（卢森堡）有限公司 | Space formation compositionss, possess the space being formed using said composition semiconductor device and employ said composition semiconductor device manufacture method |
| US10435555B2 (en) | 2014-05-29 | 2019-10-08 | Az Electronic Materials (Luxembourg) S.A.R.L | Void forming composition, semiconductor device provided with voids formed using composition, and method for manufacturing semiconductor device using composition |
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| Publication number | Publication date |
|---|---|
| CN1168760C (en) | 2004-09-29 |
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