CN105482106A - Preparation method of heteropoly acid-inorganic acid mixed acid doped polyaniline / silver composite - Google Patents
Preparation method of heteropoly acid-inorganic acid mixed acid doped polyaniline / silver composite Download PDFInfo
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- CN105482106A CN105482106A CN201510887636.7A CN201510887636A CN105482106A CN 105482106 A CN105482106 A CN 105482106A CN 201510887636 A CN201510887636 A CN 201510887636A CN 105482106 A CN105482106 A CN 105482106A
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Abstract
The present invention discloses a preparation method of heteropoly acid-inorganic acid mixed acid doped polyaniline / silver composite. The method is as below: under UV irradiation conditions, reacting silver nitrate with aniline to prepare a polyaniline / silver nano material; adding a polyaniline / silver nano material, aniline, heteropoly acid-inorganic acid mixed acid and dodecylbenzenesulfonic acid into deionized water, slowly dropwise adding with stirring an ammonium sulfate solution under nitrogen protection for reaction, demulsifying the product, conducting pumping filtration, washing and drying a filter cake to obtain the heteropoly acid-inorganic acid mixed acid doped polyaniline / silver composite. The heteropoly acid-inorganic acid mixed acid doped polyaniline / silver composite provided by the present invention has high electrical conductivity and good water solubility, and is in line with the industrial requirements for material and beneficial to the industrial application.
Description
(1) technical field
The present invention relates to the preparation method of a kind of heteropolyacid-mineral acid mixing acid doped polyaniline/silver composite material.
(2) background technology
Polyaniline (PANI) has application prospect widely due to the chemical property of simple synthetic method, preferably stability, adjustable electric conductivity and uniqueness in the fields such as anti-corrosion of metal, fuel cell, clang ion secondary battery, ultra-capacitor, gas detection, life science, medical diagnosis and Ultrahigh-Density Data Storage.But it is still faced with some problems in actual applications, mainly concentrates on and cannot take into account excellent ground processing characteristics and conductivity preferably.In order to improve these problems, scientists has done a large amount of research work, main adopts synthesis to replace PANI and macromole function protonic acid doping PANI to improve its solvability in a solvent; And with different matrix, metal, small molecules acid and ion doping to improve its chemical property.
On the one hand, silver nano material is the advantage such as fusing point is low, coking property good, good electroconductibility and be used to prepare in the polyaniline nano material (polyaniline/argentum nano material) of Ag doping owing to having, resulting materials has excellent chemical property, is expected to be widely used in the fields such as biology, catalysis, electronic component.
The method preparing polyaniline/argentum nano composite material is a lot, such as anti-sol method and in-situ compositing etc.Wherein the application of in-situ compositing is comparatively extensive.High mountains etc. adopt the method one step fabricated in situ of the short mix polyaniline/argentum nano composite material of different-shape.Experimental result shows: change one-dimensional nano line than making the pattern of polyaniline/argentum nano composite material by three-dimensional manometer ball with the amount of substance of Silver Nitrate by changing aniline, and the existence of silver particles can change the molecular structure of polyaniline; The polyaniline/argentum nano nanofiber of gained has the most excellent anti-microbial property.Li Zhihua etc. adopt the method for fractional steps, first utilize microemulsion method to prepare silver nanoparticle colloidal sol, then adopt situ aggregation method to prepare polyaniline/argentum nano composite material.Experimental result shows, gained matrix material is hud typed spherical nano composite material, and the dispersiveness of Nano silver grain in polyaniline is improved, thus its Electrical Conductivity of Composites also increases.
On the other hand, acid doping is also one of common method improving polyaniline solvability and electroconductibility.Conventional acid have the acid of mineral acid, organic proton and macromole sour, such as hydrochloric acid, sulfuric acid, perchloric acid dodecyl sodium sulfonate, dodecyl camphorsulfonic acid, naphthene sulfonic acid and 2,4 dinitrobenzene naphthols-7 sulfonic acid and heteropolyacid etc.Though wherein mineral acid can improve its electric conductivity but its volatility limits its application prospect.The doping of organic proton acid comparatively ideal can improve its solvability and stability simultaneously.And heteropolyacid is as a class polynuclear coordination compound, have the double characteristic of title complex and metal oxide concurrently, have again unique oxidation-reduction quality and strongly-acid, the dual-function catalyst that can be used as transmitting proton and electronics uses.Therefore using heteropolyacid as the polyaniline study hotspot that become this year one of of doping agent for the synthesis of acid doping.Products therefrom has good solvability and electric conductivity.It is oxygenant that Luo Yun waits with ammonium peroxydisulfate clearly, is successfully synthesized the electrically conductive polyaniline nano fiber of heteropolyacid doping by liquid-solid phase chemical oxidative polymerization method.WangFunchun etc. have utilized seed pattern legal system for the polyaniline fiber of heteropolyacid doping.Experimental result shows, the pattern of gained polyaniline conjugated fibre is subject to the impact of template fiber clearly, and its size is unaffected; In addition, the electroconductibility of gained polyaniline nano fiber improves comparatively obvious.
In sum, if with the polyaniline of Ag doping for matrix, be aided with the doping of heteropolyacid-mineral acid mixing acid, in conjunction with the excellent electroconductibility of silver and the oxidation-reduction quality of heteropolyacid uniqueness and strongly-acid, the acidity that mineral acid is stronger, be expected to preparation and there is high conductivity, better deliquescent water-soluble doped polyaniline, thus meet the requirement on industrial application of p-poly-phenyl amine.And the preparation of this kind of doped polyaniline and the research of exploration have no report at home and abroad.
(3) summary of the invention
In order to effectively silver and heteropolyacid-mineral acid mixing acid are doped into polyaniline matrix, while making prepared polyaniline have high electrical conductivity simultaneously, can have again water-soluble preferably, the object of the present invention is to provide the polyaniline/argentum matrix material of a kind of novel heteropolyacid-mineral acid mixing acid doping.
The technical solution used in the present invention is:
The invention provides the preparation method of a kind of heteropolyacid-mineral acid mixing acid doped polyaniline/silver composite material, said method comprising the steps of:
(1) under UV-light initiation conditions, be that 0.25 ~ 1.5:1 mix with aniline by the ratio of amount of substance by Silver Nitrate, in deionized water, stirring at room temperature reaction 24h ~ 96h, solid-liquid separation obtains cyan product, through washing, dry obtained polyaniline/argentum nano material;
(2) polyaniline/argentum nano material, aniline, heteropolyacid-mineral acid mixing acid in mass ratio 5:2:5 ~ 25 mixes, add in Witco 1298 Soft Acid and deionized water, in gained mixed solution, the mass concentration of Witco 1298 Soft Acid is 0.02 ~ 0.04g/mL, polyaniline/argentum nano material, total mass concentration of aniline and heteropolyacid-mineral acid mixing acid is 0.05 ~ 0.15g/mL, mixed solution is stirred under nitrogen protection, at 0 ~ 5 DEG C of temperature, the ammonium persulfate solution of slow dropping 0.3 ~ 0.6mol/L, drip off rear reaction 8 ~ 16 hours, suction filtration is carried out after products therefrom ethanol-acetone mixing solutions breakdown of emulsion, filter cake washing, drying i.e. obtained described heteropolyacid-mineral acid mixing acid doped polyaniline/silver composite material, described mineral acid is phosphoric acid, and described heteropolyacid is tungstosilicic acid, and in described heteropolyacid-mineral acid mixing acid, the volume ratio of heteropolyacid and mineral acid is 5 ~ 10:1,
In described step (1), the preferred 8W ~ 20W of light intensity of UV-light.
In described step (1), the consumption of deionized water is generally counts 40 ~ 120mL/g with the quality of aniline.
In described step (1), cyan product generally washs with distilled water, acetone and anhydrous diethyl ether by described washing successively.
In described step (2), in mixed solution, total mass concentration of polyaniline/argentum nano material, aniline and heteropolyacid-mineral acid mixing acid is preferably 0.07 ~ 0.11g/mL.
In described step (2), in ammonium persulfate solution, the quality of ammonium persulphate and the mass ratio of aniline are 3 ~ 8:1.
In described step (2), the preferred 0.4mol/L of concentration of ammonium persulfate solution.
In described step (2), the volume ratio of ethanol, acetone preferably 0.5 ~ 2:1, more preferably 1:1 in ethanol-acetone mixing solutions.
In described step (2), filter cake washing generally uses distilled water, washing with acetone successively.
In described step (2), described filtration cakes torrefaction preferably at 40 ~ 50 DEG C dry 10 ~ 15 hours.
The heteropolyacid that the present invention also provides aforesaid method to prepare-mineral acid mixing acid doped polyaniline/silver composite material, described heteropolyacid-mineral acid mixing acid doped polyaniline/silver composite material comprises polyaniline matrix and is doped in the active ingredient in matrix, and described active ingredient is argent and heteropolyacid-mineral acid mixing acid.In order to improve the consistency of polyaniline/argentum matrix material and polyaniline matrix and heteropolyacid-mineral acid mixing acid can be made to be doped into obtained target product in polyaniline matrix, the present invention adopts the method for fractional steps to prepare the polyaniline/argentum matrix material of heteropolyacid-mineral acid mixing acid doping, and is regulated size and the electric conductivity of gained matrix material by the reaction conditions such as mol ratio, reaction times of the mol ratio, heteropolyacid-mineral acid mixing acid and the aniline that change Silver Nitrate and aniline.
Compared with prior art, the polyaniline/argentum nano composite material of the heteropolyacid that the present invention utilizes the method for fractional steps to prepare-mineral acid mixing acid doping, can be adulterated heteropolyacid-mineral acid mixing acid and silver nano material simultaneously, heteropolyacid provided by the invention-mineral acid mixing acid doped polyaniline/silver composite material, with the polyaniline of Ag doping for matrix, be aided with the doping of heteropolyacid-mineral acid mixing acid again, in conjunction with the excellent electroconductibility of silver and the oxidation-reduction quality of heteropolyacid uniqueness and strongly-acid, the acidity that mineral acid is stronger, prepare and there is high conductivity, better deliquescent water-soluble doped polyaniline, thus meet the requirement on industrial application of p-poly-phenyl amine.
Beneficial effect of the present invention is:
The present invention, by doped polyaniline/argentum nano composite material, not only can improve the electric conductivity of material but also can strengthen the consistency of silver nano material and polyaniline matrix; And the specific conductivity that the doping of the acidic components such as heteropolyacid-mineral acid mixing acid then both can improve gained polyaniline can improve, and it is water-soluble; The present invention makes product have good electroconductibility and water-soluble concurrently, meets the industrial requirement now to material, is conducive to its industrial applications.
(4) accompanying drawing explanation
The scanning electron microscope (SEM) photograph of the polyaniline/argentum matrix material of heteropolyacid-mineral acid mixing acid doping that Fig. 1 embodiment 1 is obtained.
The grain size distribution of the polyaniline/argentum matrix material of heteropolyacid-mineral acid mixing acid doping that Fig. 2 embodiment 1 is obtained.
(5) embodiment
With specific embodiment, technical scheme of the present invention is described below, but protection scope of the present invention is not limited thereto.
The preparation method of polyaniline/argentum nano materials all in the embodiment of the present invention is as follows:
Embodiment 1
Under UV-light (light intensity is at 8W) initiation conditions, by 0.43g Silver Nitrate and 0.93g aniline in molar ratio 0.25:1 add in 50mL deionized water, stir, under room temperature, reaction 24h, centrifugation obtains cyan product, and products therefrom is successively with obtained polyaniline/argentum nano material 1.1g dry after the washing of distilled water, acetone and anhydrous diethyl ether;
Embodiment 2
Under UV-light (light intensity is at 20W) initiation conditions, by 0.86g Silver Nitrate and 0.93g aniline in molar ratio 0.5:1 add in 50mL deionized water, stir, under room temperature, reaction 48h, centrifugation obtains cyan product, and products therefrom is successively with obtained polyaniline/argentum nano material 1.38g dry after the washing of distilled water, acetone and anhydrous diethyl ether;
Embodiment 3
Under UV-light (light intensity is at 20W) initiation conditions, by 2,58g Silver Nitrate and 0.95g aniline in molar ratio 1.5:1 add in 100mL deionized water, stir, under room temperature, reaction 96h, centrifugation obtains cyan product, and products therefrom is successively with obtained polyaniline/argentum nano material 2.17g dry after the washing of distilled water, acetone and anhydrous diethyl ether;
Embodiment 4
2.0g Witco 1298 Soft Acid is joined in 50mL deionized water, and then add the polyaniline/argentum nano material and 1.17g aniline that 2.92g prepared by embodiment 1 method, 2.92g tungstosilicic acid-phosphoric acid mixing acid (polyaniline/argentum nano material, aniline, the mass ratio of tungstosilicic acid-phosphoric acid mixing acid is 5:2:5) and 50mL deionized water, in tungstosilicic acid-phosphoric acid mixing acid, the volume ratio 10:1 of tungstosilicic acid and phosphoric acid, under nitrogen protection, in ice bath, slowly start under agitation condition to drip the ammonium persulfate solution that 50mL volumetric molar concentration is 0.4mol/L, drip off rear reaction 8 hours, products therefrom volume ratio is carry out suction filtration after the ethanol-acetone mixing solutions breakdown of emulsion of 1:1, filter cake uses distilled water successively, after washing with acetone, namely the baking oven inner drying placing 40 DEG C again obtains the polyaniline/argentum matrix material 3 of heteropolyacid-mineral acid mixing acid doping for 12 hours, 15g.
Embodiment 5
3.0g Witco 1298 Soft Acid is joined in 50mL deionized water, and then add 2.35g according to the obtained polyaniline/argentum nano material of embodiment 2 method, 0.95g aniline, 4.70g tungstosilicic acid-phosphoric acid mixing acid (polyaniline/argentum nano material, aniline, the mass ratio of tungstosilicic acid-phosphoric acid mixing acid is 5:2:10) and 50mL deionized water, in tungstosilicic acid-phosphoric acid mixing acid, the volume ratio 10:1 of tungstosilicic acid and phosphoric acid, under nitrogen protection, in ice bath, slowly start under agitation condition to drip the ammonium persulfate solution that 50mL volumetric molar concentration is 0.4mol/L, drip off rear reaction 12 hours, products therefrom volume ratio is carry out suction filtration after the ethanol-acetone mixing solutions breakdown of emulsion of 1:1, filter cake uses distilled water successively, after washing with acetone, namely the baking oven inner drying placing 40 DEG C again obtains the polyaniline/argentum matrix material 3.92g of heteropolyacid-mineral acid mixing acid doping for 12 hours.
Embodiment 6
4.0g Witco 1298 Soft Acid is joined in 50mL deionized water, and then add 1.56g by the obtained polyaniline/argentum nano material of embodiment 3 method, 0.63g aniline, 7.81g tungstosilicic acid-phosphoric acid mixing acid (polyaniline/argentum nano material, aniline, the mass ratio of tungstosilicic acid-phosphoric acid mixing acid is 5:2:25) and 50mL deionized water, in tungstosilicic acid-phosphoric acid mixing acid, the volume ratio 5:1 of tungstosilicic acid and phosphoric acid, under nitrogen protection, in ice bath, slowly start under agitation condition to drip the ammonium persulfate solution that volumetric molar concentration is 50mL0.4mol/L, drip off rear reaction 16 hours, products therefrom volume ratio is carry out suction filtration after the ethanol-acetone mixing solutions breakdown of emulsion of 1:1, filter cake uses distilled water successively, after washing with acetone, namely the baking oven inner drying placing 40 DEG C again obtains the polyaniline/argentum matrix material 1 of heteropolyacid-mineral acid mixing acid doping for 12 hours, 95g.
The scanning electron microscope (SEM) photograph of the polyaniline/argentum matrix material of heteropolyacid-mineral acid mixing acid doping that embodiment 1 is obtained as shown in Figure 1.Grain size distribution as shown in Figure 2.
Silver can be found out with the form of nano silver wire by polyaniline-coated wherein by the scanning electron microscope (SEM) photograph of the polyaniline/argentum matrix material observing gained heteropolyacid-mineral acid mixing acid doping.The solubleness of products therefrom in water reaches as high as 11% (mass concentration), the electric conductivity of products therefrom is also ideal, the polyaniline/argentum matrix material of heteropolyacid-mineral acid mixing acid doping is made into the aqueous solution that mass concentration is 0.6g/L, and its specific conductivity reaches as high as 135 μ S/cm.
Claims (8)
1. a preparation method for heteropolyacid-mineral acid mixing acid doped polyaniline/silver composite material, is characterized in that said method comprising the steps of:
(1) under UV-light initiation conditions, be that 0.25 ~ 1.5:1 mix with aniline by the ratio of amount of substance by Silver Nitrate, in deionized water, stirring at room temperature reaction 24h ~ 96h, solid-liquid separation obtains cyan product, through washing, dry obtained polyaniline/argentum nano material;
(2) polyaniline/argentum nano material, aniline, heteropolyacid-mineral acid mixing acid in mass ratio 5:2:5 ~ 25 mixes, add in Witco 1298 Soft Acid and deionized water, in gained mixed solution, the mass concentration of Witco 1298 Soft Acid is 0.02 ~ 0.04g/mL, polyaniline/argentum nano material, total mass concentration of aniline and heteropolyacid-mineral acid mixing acid is 0.05 ~ 0.15g/mL, mixed solution is stirred under nitrogen protection, at 0 ~ 5 DEG C of temperature, the ammonium persulfate solution of slow dropping 0.3 ~ 0.6mol/L, drip off rear reaction 8 ~ 16 hours, suction filtration is carried out after products therefrom ethanol-acetone mixing solutions breakdown of emulsion, filter cake washing, drying i.e. obtained described heteropolyacid-mineral acid mixing acid doped polyaniline/silver composite material, described mineral acid is phosphoric acid, and described heteropolyacid is tungstosilicic acid, and in described heteropolyacid-mineral acid mixing acid, the volume ratio of heteropolyacid and mineral acid is 5 ~ 10:1.
2. the method for claim 1, is characterized in that in described step (1), and the light intensity of UV-light is 8W ~ 20W.
3. the method for claim 1, is characterized in that, in described step (1), the consumption of deionized water counts 40 ~ 120mL/g with the quality of aniline.
4. the method for claim 1, is characterized in that, in described step (2), in described mixed solution, total mass concentration of polyaniline/argentum nano material, aniline and heteropolyacid-mineral acid mixing acid is 0.07 ~ 0.11g/mL.
5. the method for claim 1, is characterized in that in described step (2), and in ammonium persulfate solution, the quality of ammonium persulphate and the mass ratio of aniline are 3 ~ 8:1.
6. the method for claim 1, is characterized in that in described step (2), and the concentration of ammonium persulfate solution is 0.4mol/L.
7. the method for claim 1, is characterized in that, in described step (2), in ethanol-acetone mixing solutions, the volume ratio of ethanol, acetone is 1:1.
8. the heteropolyacid that the method as described in one of claim 1 ~ 7 prepares-mineral acid mixing acid doped polyaniline/silver composite material.
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Cited By (2)
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| CN106149460A (en) * | 2016-07-06 | 2016-11-23 | 福建农林大学 | High intensity high antibiotic property water proof type conductive paper and preparation method thereof |
| CN110255674A (en) * | 2019-07-03 | 2019-09-20 | 辽宁科技学院 | A kind of anode material and preparation method for wastewater treatment |
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| CN101838391A (en) * | 2010-06-12 | 2010-09-22 | 中南大学 | Polyaniline/silver conductive nanocomposite material and preparation method thereof |
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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 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106149460A (en) * | 2016-07-06 | 2016-11-23 | 福建农林大学 | High intensity high antibiotic property water proof type conductive paper and preparation method thereof |
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| CN110255674A (en) * | 2019-07-03 | 2019-09-20 | 辽宁科技学院 | A kind of anode material and preparation method for wastewater treatment |
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