CN105482106B - A kind of preparation method of heteropoly acid inorganic acid mixing acid doped polyaniline/silver composite material - Google Patents
A kind of preparation method of heteropoly acid inorganic acid mixing acid doped polyaniline/silver composite material Download PDFInfo
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- CN105482106B CN105482106B CN201510887636.7A CN201510887636A CN105482106B CN 105482106 B CN105482106 B CN 105482106B CN 201510887636 A CN201510887636 A CN 201510887636A CN 105482106 B CN105482106 B CN 105482106B
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Abstract
The invention discloses a kind of preparation method of heteropoly acid inorganic acid mixing acid doped polyaniline/silver composite material：Under ultraviolet light initiation conditions, by silver nitrate and aniline reaction, polyaniline/argentum nano material is made；Polyaniline/argentum nano material, aniline, heteropoly acid inorganic acid mixed acid and DBSA are added in deionized water; under nitrogen protection; reacted after ammonium persulfate solution is slowly added dropwise under stirring condition; filtered after products therefrom demulsification, Washing of Filter Cake, the polyaniline/argentum composite for being drying to obtain heteropoly acid inorganic acid mixing acid doping.Heteropoly acid inorganic acid mixing acid doped polyaniline/silver composite material provided by the invention has high conductivity, preferably deliquescent water solubility, meets now to the industrial requirement of material, is advantageous to its industrial applications.
Description
(1) technical field
The present invention relates to a kind of preparation method of heteropoly acid-inorganic acid mixing acid doped polyaniline/silver composite material.
(2) background technology
Polyaniline (PANI) is due to the electricity of simple synthetic method, preferable stability, adjustable conductance and uniqueness
Chemical property and in anti-corrosion of metal, fuel cell, clang ion secondary battery, ultra-capacitor, detection of gas, life science, medical science
Diagnosis and Ultrahigh-Density Data Storage etc. have widely application prospect in field.But it is still faced with actual applications
Some problems, excellent ground processing characteristics and preferably electric conductivity can not be taken into account by being concentrated mainly on.In order to improve these problems, section
Scholars have done substantial amounts of research work, main to use synthesis substitution PANI and macromolecular function protonic acid doping PANI to improve
Its dissolubility in a solvent；And with different matrix, metal, small molecule acid and ion doping to improve its chemical property.
On the one hand, silver nano material be used to make due to having the advantages that the electric conductivity that fusing point is low, agglutinating property is good, good
In the polyaniline nano material (polyaniline/argentum nano material) of standby Ag doping, resulting materials have excellent chemical property, have
Prestige is widely used in the fields such as biology, catalysis, electronic component.
The method for preparing polyaniline/argentum nano composite material is a lot, such as anti-sol method and in-situ compositing etc..Its Central Plains
The application of position composite algorithm is relatively broad.The polyphenyl of different-shape using the step fabricated in situ of method one that quickly mixes such as high mountain
Amine/argentum nano composite material.Test result indicates that：Polyaniline/argentum can be made by the amount ratio for the material for changing aniline and silver nitrate
The pattern of nano composite material is changed into one-dimensional nano line by three-dimensional manometer ball, and the presence of silver particles can change polyaniline
Molecular structure；The polyaniline/argentum nano nanofiber of gained has most excellent anti-microbial property.Li Zhihua etc. uses the method for fractional steps, first
Silver nanoparticle colloidal sol is prepared using microemulsion method, polyaniline/argentum nano composite material is then prepared using situ aggregation method.Experiment
As a result show, gained composite is hud typed spherical nano composite material, dispersiveness of the Nano silver grain in polyaniline
It is improved, so as to which its Electrical Conductivity of Composites also increases.
On the other hand, acid doping is also one of common method for improving polyaniline dissolubility and electric conductivity.Conventional acid has
Inorganic acid, organic proton acid and macromolecular acid, such as hydrochloric acid, sulfuric acid, perchloric acid dodecyl sodium sulfonate, dodecyl camphor sulphur
Acid, naphthalene sulfonic acids and 2, the sulfonic acid of 4 dinitro naphthols -7 and heteropoly acid etc..Wherein though inorganic acid can improve its conductance but it is waved
Hair property limits its application prospect.The doping comparatively ideal of organic proton acid can improve its dissolubility and stably simultaneously
Property.And heteropoly acid has the double characteristic of complex and metal oxide concurrently, has unique oxygen again as a kind of polynuclear complex
Change reproducibility and highly acid, can be used as transmitting proton and the bifunctional catalyst of electronics uses.Therefore using heteropoly acid as dopant
Polyaniline for synthesizing acid doping turns into one of study hotspot come this year.Products therefrom has preferable dissolubility and conduction
Rate.Luo Yun is waited using ammonium peroxydisulfate as oxidant clearly, successfully synthesizes heteropoly acid by liquid-solid phase chemical oxidative polymerization method
The electrically conductive polyaniline nano fiber of doping.Wang Funchun etc. are prepared for the polyaniline of heteropoly acid doping using seed pattern method
Fiber.Test result indicates that the pattern of gained polyaniline composite fibre is influenceed clearly by template fiber, and its size is not
It is impacted；In addition, the electric conductivity raising of gained polyaniline nano fiber is more obvious.
In summary, if using the polyaniline of Ag doping as matrix, it is being aided with the doping of heteropoly acid-inorganic acid mixed acid, is tying
The oxidation-reduction quality and highly acid of the excellent electric conductivity of silver and heteropoly acid uniqueness are closed, the stronger acidity of inorganic acid, is expected to prepare tool
There are high conductivity, preferably deliquescent water-soluble doped polyaniline, so as to meet the requirement on industrial application to polyaniline.And this
The research of preparation and the exploration of class doped polyaniline at home and abroad has no report.
(3) content of the invention
In order to which silver and heteropoly acid-inorganic acid mixed acid effectively are doped into polyaniline matrix, while cause prepared
Polyaniline while there is high electrical conductivity, and can has preferably water-soluble, and object of the present invention is to provide one kind
The polyaniline/argentum composite of new heteropoly acid-inorganic acid mixing acid doping.
The technical solution adopted by the present invention is：
The present invention provides a kind of preparation method of heteropoly acid-inorganic acid mixing acid doped polyaniline/silver composite material, described
Method comprises the following steps：
(1) under ultraviolet light initiation conditions, it is 0.25~1.5 that silver nitrate and aniline are pressed to the ratio between amount of material:1 mixing,
In deionized water, reaction 24h~96h is stirred at room temperature, separation of solid and liquid obtains blackish green product, scrubbed, dry to be made poly-
Aniline/silver nano material；
(2) polyaniline/argentum nano material, aniline, heteropoly acid-inorganic acid mixed acid in mass ratio 5:2:5~25 mixing, add
Enter in DBSA and deionized water, in gained mixed liquor the mass concentration of DBSA be 0.02~
0.04g/mL, total mass concentration of polyaniline/argentum nano material, aniline and heteropoly acid-inorganic acid mixed acid for 0.05~
0.15g/mL, mixed liquor is stirred under nitrogen protection, at a temperature of 0~5 DEG C, 0.3~0.6mol/L persulfuric acid is slowly added dropwise
Ammonium salt solution, reacted 8~16 hours after dripping off, products therefrom is filtered after being demulsified with ethanol-acetone mixed solution, and filter cake is washed
Wash, dry the i.e. obtained heteropoly acid-inorganic acid mixing acid doped polyaniline/silver composite material；The inorganic acid is phosphoric acid, institute
It is tungstosilicic acid to state heteropoly acid, and the volume ratio of heteropoly acid and inorganic acid is 5~10 in the heteropoly acid-inorganic acid mixed acid：1；
In the step (1), the preferred 8W/m of light intensity of ultraviolet light2~20W/m2。
In the step (1), the dosage of deionized water is generally calculated as 40~120mL/g with the quality of aniline.
In the step (1), the washing typically washes blackish green product with distilled water, acetone and absolute ether successively
Wash.
In the step (2), polyaniline/argentum nano material, aniline and heteropoly acid-inorganic acid mixed acid is total in mixed liquor
Mass concentration be preferably 0.07~0.11g/mL.
In the step (2), the mass ratio of the quality of ammonium persulfate and aniline is 3~8 in ammonium persulfate solution：1.
In the step (2), the preferred 0.4mol/L of concentration of ammonium persulfate solution.
In the step (2), the volume ratio preferably 0.5~2 of ethanol, acetone in ethanol-acetone mixed solution：1, more preferably
1：1.
In the step (2), Washing of Filter Cake is typically washed with distilled water, acetone successively.
In the step (2), the filtration cakes torrefaction is dried 10~15 hours preferably at 40~50 DEG C.
The present invention also provides heteropoly acid-inorganic acid mixing acid doped polyaniline/silver-colored composite wood that the above method is prepared
Material, described heteropoly acid-inorganic acid mixing acid doped polyaniline/silver composite material include polyaniline matrix and are doped in matrix
Active component, described active component is argent and heteropoly acid-inorganic acid mixed acid.It is compound in order to improve polyaniline/argentum
The compatibility of material and polyaniline matrix simultaneously can make heteropoly acid-inorganic acid mixed acid be doped into polyaniline matrix obtained target production
Thing, the present invention prepares the polyaniline/argentum composite of heteropoly acid-inorganic acid mixing acid doping using the method for fractional steps, and passes through change
The reaction conditions such as the mol ratio of silver nitrate and aniline, the mol ratio of heteropoly acid-inorganic acid mixed acid and aniline, reaction time are adjusted
The size and conductance of gained composite.
Compared with prior art, the present invention using the method for fractional steps prepare heteropoly acid-inorganic acid mixing acid doping polyaniline/
Argentum nano composite material, can adulterate heteropoly acid-inorganic acid mixed acid and silver nano material simultaneously, and heteropoly acid provided by the invention-
Inorganic acid mixing acid doped polyaniline/silver composite material, using the polyaniline of Ag doping as matrix, then it is aided with heteropoly acid-inorganic acid
The doping of mixed acid, it is stronger with reference to the excellent electric conductivity of silver and heteropoly acid unique oxidation-reduction quality and highly acid, inorganic acid
Acidity, it is prepared with high conductivity, preferably deliquescent water-soluble doped polyaniline, so as to meet the industry to polyaniline
Change application requirement.
The beneficial effects of the present invention are：
The present invention can not only be improved the conductance of material but also can be strengthened by doped polyaniline/argentum nano composite material
The compatibility of silver nano material and polyaniline matrix；And the doping of the acidic components such as heteropoly acid-inorganic acid mixed acid then both can be with
Its water solubility can be improved again by improving the electrical conductivity of gained polyaniline；The present invention makes product have good electric conductivity and water-soluble concurrently
Property, meet now to the industrial requirement of material, be advantageous to its industrial applications.
(4) illustrate
The ESEM of the polyaniline/argentum composite of heteropoly acid made from Fig. 1 embodiments 1-inorganic acid mixing acid doping
Figure.
The particle diameter distribution of the polyaniline/argentum composite of heteropoly acid made from Fig. 2 embodiments 1-inorganic acid mixing acid doping
Figure.
(5) embodiment
Technical scheme, but protection scope of the present invention not limited to this are illustrated with specific embodiment below.
The preparation method of all polyaniline/argentum nano materials is as follows in the embodiment of the present invention：
Embodiment 1
In ultraviolet light, (light intensity is in 8W/m2) under initiation conditions, by 0.43g silver nitrates and 0.93g aniline in molar ratio 0.25:
1 adds in 50mL deionized waters, stirring, at room temperature, reacts 24h, the product for centrifuging blackish green, products therefrom is used successively
Obtained polyaniline/argentum nano material 1.1g is dried after distilled water, acetone and absolute ether washing；
Embodiment 2
In ultraviolet light, (light intensity is in 20W/m2) under initiation conditions, by 0.86g silver nitrates and 0.93g aniline in molar ratio 0.5:
1 adds in 50mL deionized waters, stirring, at room temperature, reacts 48h, the product for centrifuging blackish green, products therefrom is used successively
Obtained polyaniline/argentum nano material 1.38g is dried after distilled water, acetone and absolute ether washing；
Embodiment 3
In ultraviolet light, (light intensity is in 20W/m2) under initiation conditions, by 2,58g silver nitrates and 0.95g aniline in molar ratio 1.5:
1 adds in 100mL deionized waters, stirring, at room temperature, reacts 96h, the product for centrifuging blackish green, products therefrom is successively
Obtained polyaniline/argentum nano material 2.17g is dried after being washed with distilled water, acetone and absolute ether；
Embodiment 4
2.0g DBSAs are added in 50mL deionized waters, then add 2.92g by the method for embodiment 1
The polyaniline/argentum nano material of preparation and 1.17g aniline, 2.92g tungstosilicic acids-phosphoric acid mixed acid (polyaniline/argentum nano material,
The mass ratio of aniline, tungstosilicic acid-phosphoric acid mixed acid is 5:2:5) and 50mL deionized waters, in tungstosilicic acid-phosphoric acid mixed acid, tungsten silicon
The volume ratio 10 of acid and phosphoric acid:1, under nitrogen protection, slowly starting dropwise addition 50mL molar concentrations in ice bath, under stirring condition is
0.4mol/L ammonium persulfate solution, reacted 8 hours after dripping off, products therefrom volume ratio is 1:1 ethanol-acetone mixing is molten
Filtered after liquid demulsification, after filter cake washs with distilled water, acetone successively, then place in 40 DEG C of baking oven 12 hours of drying i.e.
Obtain the polyaniline/argentum composite 3,15g of heteropoly acid-inorganic acid mixing acid doping.
Embodiment 5
3.0g DBSAs are added in 50mL deionized waters, then add 2.35g according to the side of embodiment 2
Polyaniline/argentum nano material made from method, 0.95g aniline, 4.70g tungstosilicic acids-phosphoric acid mixed acid (polyaniline/argentum nano material,
The mass ratio of aniline, tungstosilicic acid-phosphoric acid mixed acid is 5:2:10) and 50mL deionized waters, in tungstosilicic acid-phosphoric acid mixed acid, tungsten
The volume ratio 10 of silicic acid and phosphoric acid:1, under nitrogen protection, slowly start that 50mL molar concentrations are added dropwise in ice bath, under stirring condition
For 0.4mol/L ammonium persulfate solution, reacted 12 hours after dripping off, products therefrom volume ratio is 1:1 ethanol-acetone mixes
Filtered after closing solution demulsification, after filter cake washs with distilled water, acetone successively, then place dried in 40 DEG C of baking oven it is 12 small
When produce the polyaniline/argentum composite 3.92g of heteropoly acid-inorganic acid mixing acid doping.
Embodiment 6
4.0g DBSAs are added in 50mL deionized waters, then add 1.56g by the method for embodiment 3
Obtained polyaniline/argentum nano material, 0.63g aniline, 7.81g tungstosilicic acids-phosphoric acid mixed acid (polyaniline/argentum nano material, benzene
The mass ratio of amine, tungstosilicic acid-phosphoric acid mixed acid is 5:2:25) and 50mL deionized waters, in tungstosilicic acid-phosphoric acid mixed acid, tungsten silicon
The volume ratio 5 of acid and phosphoric acid:1, under nitrogen protection, slowly starting dropwise addition molar concentration in ice bath, under stirring condition is
50mL0.4mol/L ammonium persulfate solution, reacted 16 hours after dripping off, products therefrom volume ratio is 1:1 ethanol-acetone
Filtered after mixed solution demulsification, after filter cake washs with distilled water, acetone successively, then place drying 12 in 40 DEG C of baking oven
Hour produces the polyaniline/argentum composite 1,95g of heteropoly acid-inorganic acid mixing acid doping.
The scanning electron microscope (SEM) photograph of the polyaniline/argentum composite of heteropoly acid made from embodiment 1-inorganic acid mixing acid doping is such as
Shown in Fig. 1.Grain size distribution is as shown in Figure 2.
The scanning electron microscope (SEM) photograph of the polyaniline/argentum composite of heteropoly acid-inorganic acid mixing acid doping can as obtained by observation
By find out silver in the form of nano silver wire by polyaniline-coated wherein.Solubility of the products therefrom in water reaches as high as 11%
(mass concentration), the conductance of products therefrom is also ideal, and the polyaniline/argentum of heteropoly acid-inorganic acid mixing acid doping is answered
Condensation material is made into the aqueous solution that mass concentration is 0.6g/L, and its electrical conductivity reaches as high as 135 μ S/cm.
Claims (8)
- A kind of 1. preparation method of heteropoly acid-inorganic acid mixing acid doped polyaniline/silver composite material, it is characterised in that the side Method comprises the following steps：(1) under ultraviolet light initiation conditions, it is 0.25~1.5 that silver nitrate and aniline are pressed to the ratio between amount of material:1 mixing, is going In ionized water, reaction 24h~96h is stirred at room temperature, separation of solid and liquid obtains blackish green product, it is scrubbed, dry obtained polyaniline/ Silver nano material；(2) polyaniline/argentum nano material, aniline, heteropoly acid-inorganic acid mixed acid in mass ratio 5:2:5~25 mixing, add ten In dialkyl benzene sulfonic acids and deionized water, the mass concentration of DBSA is 0.02~0.04g/ in gained mixed liquor ML, total mass concentration of polyaniline/argentum nano material, aniline and heteropoly acid-inorganic acid mixed acid is 0.05~0.15g/mL, Mixed liquor is stirred under nitrogen protection, at a temperature of 0~5 DEG C, 0.3~0.6mol/L ammonium persulfate solution is slowly added dropwise, is dripped Reaction 8~16 hours after complete, products therefrom are filtered after being demulsified with ethanol-acetone mixed solution, Washing of Filter Cake, are dried and are made Obtain the heteropoly acid-inorganic acid mixing acid doped polyaniline/silver composite material；The inorganic acid is phosphoric acid, and the heteropoly acid is Tungstosilicic acid, the volume ratio of heteropoly acid and inorganic acid is 5~10 in the heteropoly acid-inorganic acid mixed acid：1.
- 2. the method as described in claim 1, it is characterised in that in the step (1), the light intensity of ultraviolet light is 8W/m2~20W/ m2。
- 3. the method as described in claim 1, it is characterised in that in the step (1), the dosage of deionized water is with the matter of aniline Amount is calculated as 40~120mL/g.
- 4. the method as described in claim 1, it is characterised in that in the step (2), polyaniline/argentum nano in the mixed liquor Total mass concentration of material, aniline and heteropoly acid-inorganic acid mixed acid is 0.07~0.11g/mL.
- 5. the method as described in claim 1, it is characterised in that in the step (2), ammonium persulfate in ammonium persulfate solution The mass ratio of quality and aniline is 3~8：1.
- 6. the method as described in claim 1, it is characterised in that in the step (2), the concentration of ammonium persulfate solution is 0.4mol/L。
- 7. the method as described in claim 1, it is characterised in that in the step (2), ethanol in ethanol-acetone mixed solution, The volume ratio of acetone is 1：1.
- 8. the heteropoly acid that the method as described in one of claim 1~7 is prepared-inorganic acid mixing acid doped polyaniline/silver Composite.
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