CN102174196B - Method for preparing high-molecular-weight conducting polyaniline material - Google Patents
Method for preparing high-molecular-weight conducting polyaniline material Download PDFInfo
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- CN102174196B CN102174196B CN 201110058271 CN201110058271A CN102174196B CN 102174196 B CN102174196 B CN 102174196B CN 201110058271 CN201110058271 CN 201110058271 CN 201110058271 A CN201110058271 A CN 201110058271A CN 102174196 B CN102174196 B CN 102174196B
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Abstract
The invention discloses a novel method for synthesizing high-molecular-weight conducting polyaniline, which comprises the following steps of: mixing p-phenylenediamine with an organic mutually-soluble system of a 1,4-dioxane-acetic acid/sodium acetate buffer solution and stirring at N2 atmosphere and the water bath of 40 DEG C till the mixture is completely dissolved; slowly adding Fe3O4 magnetic nano particles and an initiator hydrogen peroxide solution, then continuously reacting for 12 hours; after a polymerized product precipitates, filtering, washing, reprecipitating, removing Fe3O4 magnetic nano particles by utilizing a strong magnet and filtering a suspension; dissolving sediments into DMF (Dimethyl Formamide); slowly dropwise adding into anhydrous ethanol so that a polymer is precipitated; and filtering and drying the sediments in vacuum to obtain the high-molecular-weight eigenstate black product conducting polyaniline. The method has the advantages of simple synthesis conditions, easiness in control and simple and convenient postprocessing processes, such as separation, purification, and the like; the magnetic nano particles are easy for magnetic separation; and the eigenstate conducting polyaniline has superhigh molecular weight, is easy to dissolve in a common organic solvent and has the characteristics of favorable oxidoreduction reversibility and heat stability.
Description
Technical field
The present invention relates to a kind of preparation method of high molecular eigenstate conducting polymer composite.Relate in particular a kind of preparation method of high-molecular-weight conducting polyaniline material.
Background technology
Polyaniline is the conducting polymer conjugated polymers that a class has longer π-electron conjugated main chain, has good chemical property, specific conductivity, stability and Coulomb effect etc., is used widely in electrochemistry, materialogy and field of biology.Its molecular designing and polymerization process are the focuses of polymer chemistry research.
The prior synthesizing method of polyaniline has chemical polymerization, electrochemical polymerization method, template synthesis method etc.These methods have that synthesis condition is complicated and be difficult to control, and the last handling processes such as separating-purifying are loaded down with trivial details, and molecular weight of product is little, molecular distribution is wide, and are simple in structure and be insoluble in the shortcoming such as ordinary organic solvents.
Summary of the invention
The object of the invention is to overcome the shortcoming of conventional conductive method for preparing polyaniline; provide that a kind of synthesis condition is simple and easy to control, aftertreatment technology is simple, have good industrial scale application prospect, product has the green novel preparation method of high molecular, better deliquescent electrically conductive polyaniline.
Technical scheme is as follows:
A kind of preparation method of high-molecular-weight conducting polyaniline material may further comprise the steps: Ursol D is mixed with the organic system of dissolving each other of Isosorbide-5-Nitrae-dioxane-acetic acid/sodium-acetate buffer, and in N2 atmosphere, be stirred to fully dissolving under 40 ℃ of water-baths; After slowly adding Fe3O4 magnetic nano-particle and initiator solution, continue reaction 12h, after polymerisate is precipitated out, suction filtration, washing is heavily analysed, utilize kicker magnet to remove the Fe3O4 magnetic nano-particle, the filtration suspension will be precipitated and dissolved in DMF, slowly be added drop-wise to polymkeric substance is separated out, filter, precipitation vacuum-drying is obtained the eigenstate black product electrically conductive polyaniline of high molecular.
Described method, described initiator solution are superoxol
Described method, the synthetic method of described Fe3O4 magnetic nano-particle is: under 63 ℃ of water-baths, N2 atmosphere the molysite mixing solutions is joined in the strong base solution, continuous stirring reaction 1h, namely get the Fe3O4 magnetic nano-particle of particle diameter 10nm, reaction is chilled to room temperature after finishing, and at room temperature cleans with ultrapure water, then uses the absolute ethanol washing several times, until Fe3O4 magnetic nano-particle solution is neutral, adjust its concentration.
Described method, described molysite mixing solutions are the mixing solutions of FeSO4 and FeCl3, and the amount of substance ratio is 0.5～1.
Described method, described strong base solution are NaOH solution.
Described method, described washing specific practice is: use 50% acetone-water mixing solutions washing precipitation 2～3 times.
Described method, the described heavy specific practice of analysing is: the tetrahydrofuran (THF)-aqueous solution of use 50% carries out resuspended to washed polymerisate.
Described method, described slowly being added drop-wise to makes polymkeric substance separate out dehydrated alcohol in the dehydrated alcohol, adopt the dehydrated alcohol of 5～20 times of volumes.
The present invention has compared following advantage with the conventional art means: (1) the inventive method has overcome the control of traditional method synthesis condition complicated difficult, the last handling processes such as separating-purifying are loaded down with trivial details, molecular weight of product is little, molecular distribution is wide, simple in structure and be insoluble in the shortcomings such as ordinary organic solvents, the green novel method that provide that a kind of synthesis condition is simple and easy to control, aftertreatment technology is simple, has good industrial scale application prospect, the polyaniline of preparing have high molecular, characteristics that resolvability is high; (2) the inventive method adopts the Fe that coprecipitation synthesis has the Mimetic Peroxidase catalytic activity
3O
4MNPs, and adopt and under organic system of dissolving each other, utilize Fe
3O
4The catalytic activity of MNPs successfully catalyzes and synthesizes out the polyaniline in eigenstate of high molecular.Utilize the eigenstate electrically conductive polyaniline of the method preparation to have good redox reversible and thermostability etc.; (3) the present invention adopts Mimetic Peroxidase active catalytic high molecular eigenstate electrically conductive polyaniline synthetic of magnetic nano-particle, compare with the catalyzer that traditional method is used, have the advantages such as low cost, high-level efficiency, recyclable, easy realization, the present invention provides a kind of novel method for the green of high molecular eigenstate electrically conductive polyaniline is synthetic.
Embodiment
Below in conjunction with specific embodiment, the present invention is described in detail.
Embodiment 1
(1) Fe
3O
4Synthesizing of magnetic nano-particle (MNPs)
At first, at 63 ℃ of water-baths, N
2Under the atmosphere molysite mixing solutions is joined in the strong base solution, continuous stirring reaction 1h namely gets the Fe of particle diameter 10nm
3O
4Magnetic nano-particle.Wherein: the molysite mixing solutions is FeSO
4With FeCl
3Mixing solutions, the amount of substance ratio is 0.5～1; Strong base solution is NaOH.Constantly stirring reaction is chilled to room temperature after the reaction end, at room temperature repeatedly cleans several times with ultrapure water, then uses the absolute ethanol washing several times, until Fe3O4 magnetic nano-particle solution is neutral, adjusts its concentration.
(2) preparation of fusible conductive polyaniline
Ursol D is mixed with the organic system of dissolving each other of Isosorbide-5-Nitrae-dioxane-acetic acid/sodium-acetate buffer, and at N
2Atmosphere is stirred to fully dissolving under 40 ℃ of water-baths.Slowly adding Fe
3O
4Continue reaction 12h behind magnetic nano-particle and the initiator superoxol, after polymerisate is precipitated out, suction filtration, washing is heavily analysed, and removes Fe
3O
4Magnetic nano-particle, filter suspension, in precipitation, add DMF (N, dinethylformamide) to fully dissolving of precipitation, slowly being added drop-wise in the dehydrated alcohol of 5～20 times of volumes separates out polymkeric substance, filter, precipitation vacuum-drying is obtained the eigenstate black product electrically conductive polyaniline of high molecular.。
Embodiment 2
(1) at 63 ℃ of water-baths, N
2Under the atmosphere with FeSO
46H
2O (0.5M 20mL) and FeCl
37H
2O (0.5M 30mL) solution joins in the 4M NaOH solution after mixing, constantly stirring reaction 1h.(2) reaction is chilled to room temperature after finishing, with ultrapure water (dd H
2O) repeatedly clean 5～7 times, then use absolute ethanol washing 2～3 times, until Fe
3O
4It is neutral that MNPs solution becomes, and adjusting its concentration is 0.01g/mL.(3) take by weighing 1.08g (approximately 0.01mol) Ursol D in reaction vessel, add 15% (V/V) Isosorbide-5-Nitrae-dioxane-organic system 40mL that dissolves each other of acetic acid/sodium-acetate buffer (pH 3.6), at 40 ℃ of water-baths, N
2Atmosphere also dissolves it under constantly stirring fully, then adds 4mg Fe
3O
4MNPs, the H of final concentration 2%
2O
2(slowly dripping in the 2h) continues reaction 12h.Treat that polymerisate is precipitated out from reaction solution gradually, the suction filtration reaction solution is collected product.With 50% acetone-water mixing solutions washing precipitation 2～3 times, remove unreacted monomer and low-molecular weight oligo body, then be resuspended in 50% tetrahydrofuran (THF)-water mixed solution, repeatedly remove Fe with kicker magnet again
3O
4MNPs.Filter suspension, add DMF (DMF) in the precipitation to fully dissolving of precipitation, slowly be added drop-wise in the dehydrated alcohol of 5～20 times of volumes polymkeric substance is separated out, filter, precipitation vacuum-drying is obtained the eigenstate black product electrically conductive polyaniline of high molecular.The number-average molecular weight of polymerisate
And molecular distribution (D) is respectively 38088 and 1.20, improved 70 times than polymericular weight synthetic under water.Have more stable electrochemical activity, thermostability high (when temperature is increased to 1000 ℃, still keeping more than 40%).
Should be understood that, for those of ordinary skills, can be improved according to the above description or conversion, and all these improvement and conversion all should belong to the protection domain of claims of the present invention.
Claims (5)
1. the preparation method of a high-molecular-weight conducting polyaniline material is characterized in that, may further comprise the steps: Ursol D is mixed with the organic system of dissolving each other of Isosorbide-5-Nitrae-dioxane-acetic acid/sodium-acetate buffer, and at N
2Atmosphere is stirred to fully dissolving under 40 ℃ of water-baths; Slowly adding Fe
3O
4Continue reaction 12h behind magnetic nano-particle and the initiator solution, after polymerisate is precipitated out, suction filtration, washing is heavily analysed, and utilizes kicker magnet to remove Fe
3O
4Magnetic nano-particle filters suspension, will be precipitated and dissolved in DMF, slowly is added drop-wise to polymkeric substance is separated out, and filters, and precipitation vacuum-drying is obtained the eigenstate black product electrically conductive polyaniline of high molecular; The described heavy specific practice of analysing is: the tetrahydrofuran (THF)-aqueous solution of use 50% carries out resuspended to washed polymerisate; Described initiator solution is superoxol; Described Fe
3O
4The synthetic method of magnetic nano-particle is: at 63 ℃ of water-baths, N
2Under the atmosphere molysite mixing solutions is joined in the strong base solution, continuous stirring reaction 1h namely gets the Fe of particle diameter 10nm
3O
4Magnetic nano-particle, reaction is chilled to room temperature after finishing, and at room temperature cleans with ultrapure water, then uses the absolute ethanol washing several times, until Fe
3O
4It is neutral that magnetic nano-particle solution is, and adjusts its concentration.
2. the method for claim 1 is characterized in that, described molysite mixing solutions is FeSO
4With FeCl
3Mixing solutions, the amount of substance ratio is 0.5～1.
3. the method for claim 1 is characterized in that, described strong base solution is NaOH solution.
4. the method for claim 1 is characterized in that, described washing specific practice is: use 50% acetone-water mixing solutions washing precipitation 2～3 times.
5. the method for claim 1 is characterized in that, described slowly being added drop-wise to makes polymkeric substance separate out dehydrated alcohol in the dehydrated alcohol, adopts the dehydrated alcohol of 5～20 times of volumes.
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| CN102718966B (en) * | 2012-06-28 | 2014-04-09 | 沈阳理工大学 | Electrochemical synthesis method for preparing cobalt oxide/polyaniline composite material |
| CN103772694B (en) * | 2014-01-24 | 2016-08-31 | 邢台蓝天精细化工股份有限公司 | The preparation method of block type high polymerization degree polymeric monomer methyl thiazolinyl polyoxyethylene poly-oxygen propylene aether |
| CN105949459B (en) * | 2016-05-19 | 2019-02-19 | 合肥师范学院 | A kind of netted polyaniline nano piece and preparation method thereof |
| CN109251326B (en) * | 2018-08-17 | 2021-04-09 | 西南交通大学 | Preparation method of conductive high-molecular polymer nanoparticles with good water phase dispersibility |
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Non-Patent Citations (4)
| Title |
|---|
| Cristina D Pina et al."Conductive materials by metal catalyzed polymerization".《Catalysis Today》.2010,第160卷第22页第4-7段. |
| 张东霞等."HRP催化对苯二胺合成聚苯胺低聚物".《宝鸡文理学院学报（自然科学版）》.2006,第26卷(第2期),第110页第1.2部分. |
| 张东霞等."HRP催化对苯二胺合成聚苯胺低聚物".《宝鸡文理学院学报(自然科学版)》.2006,第26卷(第2期),第110页第1.2部分. * |
| 黄美荣等."聚邻苯二胺的合成及多功能性".《功能材料》.2008,(第1期),第9页2.2部分第2段第7-9行. |
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