CN104498986A - Polyaniline single crystal film with long-term stable existence in atmospheric environment - Google Patents
Polyaniline single crystal film with long-term stable existence in atmospheric environment Download PDFInfo
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- CN104498986A CN104498986A CN201410802585.9A CN201410802585A CN104498986A CN 104498986 A CN104498986 A CN 104498986A CN 201410802585 A CN201410802585 A CN 201410802585A CN 104498986 A CN104498986 A CN 104498986A
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Abstract
A polyaniline material is high in chemical stability, however, the polyaniline material serving as an electronic device is low in environmental tolerance, and the service life of the whole device or the battery is restricted. If the problem can be solved, rapid development of new materials and new energy technology can be effectively promoted. The invention discloses a method for preparing a conductive polyaniline single crystal film material with long-term stable existence in an atmospheric environment. The method is simple in process, slight in environmental pollution and high in yield, the industrial production is easily realized, and the obtained polyaniline single crystal film is high in electric conductivity.
Description
Technical field
The present invention relates to the preparation method of a kind of semiconducting polymer monocrystal thin films material, specifically, relate to the preparation method that long-time stable under a kind of atmospheric environment exists polyaniline monocrystal thin films material.
Background technology
The polyaniline of π-pi-conjugated structure not only has the density of plastics, there is again the workability of plastics and the electroconductibility etc. of metal, also possessed electrochemistry and chemical property that metal and plastics are short of, the performance by means of its brilliance has huge application prospect in lithium ion battery, fuel cell, ultracapacitor, solar cell, photochemical catalysis, stealth material, impregnating material, many hot fields such as antistatic simultaneously.
Although polyaniline material chemical stability is better, as electron device, environmental resistance difference is still govern to the life-span of whole battery or device, if the fast development that this difficult problem effectively will promote new energy technology undoubtedly can be solved.
Current adulterating method mainly contains three major types: (one) is emulsion polymerization, and (two) are interfacial synthesis methods, is namely to adopt at organic phase and aqueous phase interface place polymerization reaction take place.(3) mass polymerization.Three kinds of above methods can prepare common polyaniline material, but it is helpless to there is electrically conductive polyaniline monocrystal thin films material for long-time stable under a kind of atmospheric environment of preparation electronic industry urgent need.So prepare overstable electrically conductive polyaniline crystalline material no matter for stability and the reliability of the electron device of electronic industry, or comprehensive industrial prospect of semiconducting polymer has great meaning.
Summary of the invention
In order to solve the more weak shortcoming of current polyaniline material atmospheric environment stability inferior, there is provided that a kind of technique is simple, environmental pollution is little, productive rate is high, be easy to realize suitability for industrialized production, and product crystallization better, electrically conductive polyaniline monocrystal thin films preparation method that specific conductivity is higher.
Technical scheme:
Under a kind of atmospheric environment of the present invention there is the preparation method of electrically conductive polyaniline monocrystal thin films material in long-time stable, by a certain amount of aniline monomer and have water and organic proton acid to mix, then electrochemical polymerization film forming on a silicon substrate, finally be placed on slow epitaxy in non-polar organic solvent, its key step is as follows:
First by water used in quantitative aniline and deionized water, mixing 0.01-3N organic proton acid and water mixed solvent are placed in reactor and fully stir, then 1-100mA electrochemical polymerization 1-24 hour film forming on a silicon substrate, finally be placed on the slow epitaxy 1-12 month in non-polar organic solvent, under the matter detergent obtained can being obtained atmospheric environment there is electrically conductive polyaniline monocrystal thin films in long-time stable.
Wherein: described organic proton acid is stearic acid, tartrate, sulfuric acid, hydrochloric acid, nitric acid, citric acid, phenylformic acid, camphorsulfonic acid, glacial acetic acid; Described organic solvent is acetone, cresols, hexane, octane, benzene, toluene, tetracol phenixin, ethanol, methyl alcohol, hexanaphthene.
Embodiment:
Under atmospheric environment there is the preparation of electrically conductive polyaniline crystalline material in long-time stable.First, aniline monomer, deionized water, organic acid are placed in electrolyzer and carry out electrochemical polymerization, temperature is-10 DEG C-80 DEG C, and polymerization reaction time is 1-24 hour, after stopped reaction, silicon substrate forms polyaniline film.Finally, place in organic solvent the slowly epitaxy 1-12 month, under the matter detergent obtained can being obtained atmospheric environment there is electrically conductive polyaniline monocrystal thin films in long-time stable.Wherein: described organic solvent is acetone, cresols, hexane, octane, benzene, toluene, tetracol phenixin, ethanol, methyl alcohol, hexanaphthene; Described organic proton acid is citric acid, phenylformic acid, camphorsulfonic acid, glacial acetic acid; Concentration of aniline is 0.1-2N, and the concentration of organic proton acid is 0.1-3N.
The present invention compared with prior art has following advantage: (one) the inventive method adopts electrochemical polymerization, freely can control the size of strength of current, reaction times, silicon substrate, for different size and polyaniline film, slowly be polymerized at-10 DEG C of-80 DEG C of temperature, gained polyaniline good film-forming property.(2) adopt the polyaniline monocrystal thin films that in Secondary Organic solvent prepared by slow epitaxy, its atmospheric environment stability, specific conductivity, degree of crystallinity are all better than the product obtained by prior art, and specific performance data are in table 1.
Table 1.
Below by embodiment, the invention will be further described, but it does not affect protection scope of the present invention:
Embodiment 1
(1) by 1 gram of aniline monomer, 0-50ml deionized water, 0-50ml camphorsulfonic acid be placed in there-necked flask, stir, be placed in electrolyzer and carry out electrochemical polymerization, temperature is-10 DEG C-80 DEG C, polymerization reaction time is 1-24 hour, after stopped reaction, silicon substrate is formed one deck polyaniline film, productive rate is 38.22%.(2) be placed on by the polyaniline film obtained in 0-50ml benzene and leave standstill the 1-12 month, under namely the matter detergent obtained obtains atmospheric environment there is electrically conductive polyaniline monocrystal thin films in long-time stable.It is 101.81S/cm that four probe method test obtains its specific conductivity, tests its crystallization situation, calculate its degree of crystallinity is greater than 92.65% with XRD.
Claims (1)
1. under an atmospheric environment there is the preparation method of polyaniline monocrystal thin films material in long-time stable, the key step of described method is: first quantitative aniline and aqueous phase are placed in reactor and fully stir, the acid of mixing 0.01-4N organic proton, then 1-100mA electrochemical polymerization 1-24 hour film forming on a silicon substrate, is finally placed on slow epitaxy in non-polar organic solvent.Wherein: described organic proton acid is citric acid, phenylformic acid, camphorsulfonic acid, glacial acetic acid, Phenylsulfonic acid, oxysuccinic acid, o-hydroxy-benzoic acid, acetylsalicylic acid, p-aminosallcylic acid, pyruvic acid, B-batanone acid, α-one succinic acid; Concentration of aniline is 0.1-2N.2. the method for claim 1, it is characterized in that polyaniline monocrystal thin films, productive rate is high.Wherein said organic solvent is acetone, cresols, hexanaphthene, hexane, octane, benzene, toluene, tetracol phenixin.
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Citations (9)
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| CN101492536A (en) * | 2008-08-04 | 2009-07-29 | 南京理工大学 | Nano-polyaniline material with morphology inheritance and electrochemical preparation method |
| CN101942090A (en) * | 2010-09-10 | 2011-01-12 | 太原理工大学 | Preparation method of nano-fiber poly-aniline |
| CN102071433A (en) * | 2010-11-25 | 2011-05-25 | 武汉大学 | Interfacial polymerization method for conductive polymers |
| CN102134317A (en) * | 2010-01-27 | 2011-07-27 | 中国科学院合肥物质科学研究院 | Preparation method of carbon nano tube/polyaniline nano composite conductive powder |
| CN102604087A (en) * | 2012-03-08 | 2012-07-25 | 长春工业大学 | Preparation method of water-soluble conductive polyaniline |
| CN103304808A (en) * | 2013-07-05 | 2013-09-18 | 上海市七宝中学 | Electric synthesizing method of polyaniline |
| CN103396547A (en) * | 2013-08-08 | 2013-11-20 | 安徽理工大学 | Preparation method of doped state polyaniline crystals |
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2014
- 2014-12-22 CN CN201410802585.9A patent/CN104498986A/en active Pending
Patent Citations (9)
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| CN1415645A (en) * | 2002-11-14 | 2003-05-07 | 华东理工大学 | Method for preparing fusible conductive polyaniline |
| CN1831030A (en) * | 2006-03-02 | 2006-09-13 | 扬州大学 | Electrochemical synthesis method for producing homogeneous and odered aniline nanometer particles |
| CN101492536A (en) * | 2008-08-04 | 2009-07-29 | 南京理工大学 | Nano-polyaniline material with morphology inheritance and electrochemical preparation method |
| CN102134317A (en) * | 2010-01-27 | 2011-07-27 | 中国科学院合肥物质科学研究院 | Preparation method of carbon nano tube/polyaniline nano composite conductive powder |
| CN101942090A (en) * | 2010-09-10 | 2011-01-12 | 太原理工大学 | Preparation method of nano-fiber poly-aniline |
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| CN102604087A (en) * | 2012-03-08 | 2012-07-25 | 长春工业大学 | Preparation method of water-soluble conductive polyaniline |
| CN103304808A (en) * | 2013-07-05 | 2013-09-18 | 上海市七宝中学 | Electric synthesizing method of polyaniline |
| CN103396547A (en) * | 2013-08-08 | 2013-11-20 | 安徽理工大学 | Preparation method of doped state polyaniline crystals |
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Application publication date: 20150408 |