CN104448304A - Soluble conductive polyaniline nano fiber and preparation method thereof - Google Patents
Soluble conductive polyaniline nano fiber and preparation method thereof Download PDFInfo
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Abstract
The invention discloses soluble conductive polyaniline nano fiber and a preparation method thereof. According to the preparation method, a soap-free emulsion polymerization method is adopted, macromolecule protonic acid fumaric acid is adopted as a doping agent for doping polyaniline, because of the surface activation function of the macromolecule protonic acid fumaric acid, the solubility of polyaniline is improved, and the conformation in and between molecules of polyaniline is relatively beneficial for delocalization of charges on molecule chains, so that the conductivity of a product is improved. The doping process is completed 'at a time', and no tedious aftertreatment procedure is needed after reaction. Therefore, the soluble conductive polyaniline nano fiber is simple in process, easy to control, free of pollution, relatively high in yield, low in cost and applicable to large-scale and industrial production; the prepared polyaniline nano fiber is relatively high in conductivity, thermal stability and solubility, and is applicable to application in fields such as chemical sensors, batteries, molecular electronic devices, anti-corrosion materials, separation membranes, light emitting diode display devices, electromagnetic shielding materials and energy storage devices.
Description
Technical field
The present invention relates to a kind of polyaniline nano fiber and preparation method thereof, particularly relate to a kind of fusible conductive polyaniline nanofiber and preparation method thereof.
Background technology
Polyaniline because of have raw material cheap and easy to get, synthesize easy, good thermostability and chemical stability, unique mechanism of doping effect, adjustable specific conductivity, lighter density, can carry out fast with reversible redox reaction, can the advantages such as highdensity electric charge be stored, and become the conductive polymers being hopeful to obtain practical application at present most.The polyaniline of one dimension Nano structure combines the advantage of organic conductor and One-dimensional System, creates significant physical and chemical performance, has potential using value.
Polyaniline nano fiber has the electronics, optics, chemistry and the thermal characteristics that are different from body polyaniline, the structure electronics of nanoscale, photoelectron, electrochemistry and electro-mechanical devices be interconnected with functional unit etc. in there is important effect.Compared with plain particles polyaniline, polyaniline nano fiber has higher sensitivity and response speed, higher capacity and more Charge/Discharge Cycles, higher photo-thermal conversion efficiency and low thermal conductivity, stable Flied emission behavior, lower critical emitting voltage and higher emission.Therefore polyaniline nano fiber has a very wide range of application prospect in chemistry and biosensor, artificial-muscle, corrosion protection coating, electrical condenser, ion-exchange, secondary cell, electrochromism etc.
In prior art, the preparation method of polyaniline nano fiber can be divided into physical route and the large class of chemistry route two.Wherein, physical route has the shortcomings such as equipment complexity, output is little, is difficult to prepare on a large scale;
Chemistry route can be divided into electrochemical process and chemical method.Wherein, electrochemical polymerization method can pass through controlled oxidization recovery voltage, and accurately control size and the rate of polymerization of nanofiber, synthesis ratio electric capacity is higher, the better micrometer/nanometer structure polyaniline of stability.But its major defect is limited by electrode area, is difficult to obtain a large amount of products, is not suitable for scale operation;
Chemical method can be divided into again template and without template, wherein, template comprises again hard template method and soft template method.Although hard template method prepares the effective ways of polyaniline nano fiber, the last handling process of removing template is more numerous and diverse and easily cause the destruction of polyaniline nano structure in template.Soft template method is a kind of method of synthesized polyaniline nanofiber under the existence of surfactant molecule, macromole acid or DNA molecular etc., but aftertreatment trouble and productive rate is lower.Common comprises interfacial polymerization, short mix method, supersonic polymerization method etc. without template.Wherein interfacial polymerization needs the organic solvent of at substantial, is difficult to the needs adapting to large-scale production; Short mix method is only applicable to synthesized polyaniline nanofiber in dilute solution, and low temperature, stirring etc. are unfavorable for the generation of nanofiber; Although supersonic polymerization method preparation process is comparatively simple, hyperacoustic shearing action can cause the polyaniline nano fiber length that obtains very limited.Such as:
Chinese patent application CN 102050947 B discloses a kind of emulsion polymer and preparation method of polyaniline nano fiber, it take ammonium persulphate as oxygenant, be reaction medium with the electronegative negatively charged ion Sodium dodecylbenzene sulfonate template that is letex polymerization, with water with the system of water-soluble micella, cause aniline monomer at oil and aqueous phase interface place by oxygenant and be polymerized and form polyaniline nano fiber.
This preparation method belongs to soft template method, and its main weak point is, aftertreatment trouble, productive rate are low.
Chinese patent application CN 1323199C discloses a kind of preparation method of conductive polymer polyanilinc nano fiber, and it, by introducing ultrasonic wave in common polyaniline chemical oxidising polymerisation process, has prepared the polyaniline nano fiber that diameter is 20 ~ 100nm.
But this preparation method must be the condition of reaction with ultrasonic wave, and reaction conditions is relatively harsh, and its technique is also more complicated.
Chinese patent application CN 103408754 A discloses a kind of preparation method of polyaniline nano fiber, it is by being strapped in thinner reaction tubes by aniline polymerization, by the orientation of the unrestricted flow of reaction solution induction polyaniline molecule chain, and then obtain the diameter of fiber and the controlled polyaniline nano fiber of length.
But this preparation method, technique is loaded down with trivial details and equipment requirements is high.
Chinese patent application CN 101942090 B discloses a kind of preparation method of Nano-fibrous PANI, and it for raw material, utilizes the oxypolymerization of electrochemistry unipolar pulse method to prepare nanometer fibrous polyaniline with aniline monomer and mineral acid at ambient temperature.
But this electrochemical production process is complicated, output is little.
And, in above-mentioned prior art, all adopt the technique means of small molecules protonic acid doping polyaniline, its stability and poorly soluble, and workability is poor, limits it and applies.
Summary of the invention
An object of the present invention is, provide a kind of solubleness in N-Methyl pyrrolidone high, conduct electricity very well, fusible conductive polyaniline nanofiber that thermal stability is good.
The technical scheme that the present invention is adopted for achieving the above object is, a kind of fusible conductive polyaniline nanofiber, it is characterized in that, structural formula is
Its solubleness in N-Methyl pyrrolidone is 2.8g/mL;
Specific conductivity is 1.8 × 10
-3-3.05 × 10
-2s/cm;
Diameter is 150 ± 25nm;
Below 200 DEG C, Absorbable organic halogens exists.
Above-mentioned polyaniline has the structure of nanofiber, in organic solvent there is good solubility, and possess higher specific conductivity and thermostability, be suitable for the application of the aspect such as chemical sensor, battery, molecular electronic device, anticorrosive and separatory membrane, light emitting diodde desplay device, electromagnetic shielding material, energy storage device.
What is more important, the solution of above-mentioned polyaniline nano fiber can adopt direct casting or spin-coating method to apply into the good film of snappiness, this workability can and the advantage of nanostructure can be it in the wide application space of the blazes such as coating, electromagnetic shielding material, secondary cell, lithium ion battery, electrical condenser, sensor, absorbing material, nano functional device.
Two of object of the present invention is, provides the preparation method of the fusible conductive polyaniline nanofiber that a kind of preparation technology is simple, reaction conditions is gentle, productive rate is higher.
The technical scheme that the present invention is adopted for achieving the above object is, a kind of preparation method of fusible conductive polyaniline nanofiber, is characterized in that, comprise the following steps:
The first step, material preparation step:
A. use deionized water, analytical pure ammonium persulphate and analytical pure FUMARIC ACID TECH GRADE, preparing volumetric molar concentration is respectively the ammonium persulfate solution of 0.25-1mol/L and the FUMARIC ACID TECH GRADE emulsion of volumetric molar concentration 0.25-1mol/L;
B. be the ratio of 4 ︰ 1-4 in aniline and fumaric mol ratio, the analytical pure aniline distilled joined in above-mentioned FUMARIC ACID TECH GRADE yogurt liquid, stir through secondary pressure, obtained aniline salt emulsion;
Second step, at room temperature, or in the cryogenic thermostat reactive tank of 5 DEG C, the step of synthesizing soluble electrically conductive polyaniline nano fiber:
A. be the ratio of 1-1.5 ︰ 1 in the mol ratio of ammonium persulphate and aniline, limit is stirred, above-mentioned ammonium persulfate solution is slowly added drop-wise in above-mentioned aniline salt emulsion by limit, and Keep agitation is until react completely;
B. carry out suction filtration with sand core funnel, and with deionized water wash to filtrate clear, colorless, obtain filter cake;
C. above-mentioned filter cake is placed in vacuum drying oven, at 60 DEG C of temperature, dry 24h, gets product.
The technique effect that technique scheme is directly brought is, on the one hand, adopts macromole protonic acid doping polyaniline, utilizes its surface activation, improve the solvability of polyaniline; And make in polyaniline molecule and conformation between molecule to be more conducive to electric charge on molecular chain delocalized, thus improve the specific conductivity of product.
That is, solution polyaniline is deliquescent while, improve the specific conductivity of polyaniline nano fiber.
On the other hand, in technique scheme, adopt surfactant-free emulsion polymerization to take FUMARIC ACID TECH GRADE as doping agent, prepared polyaniline is adulterated, and this doping process " step " completes; After reaction terminates, without the need to loaded down with trivial details postprocessing working procedures.Thus, technique is simple, easy to control, productive rate is higher, cost is low, is suitable for suitability for industrialized production;
And reaction medium is water, cheap and easy to get, and pollution-free;
In addition, reaction process is without the need to special equipment.
In sum, the present invention, relative to prior art, has technique and simply, easily controls, and reaction conditions is gentle, and productive rate is higher, and cost is low, pollution-free, be suitable for large-scale production; Prepared soluble polyaniline nanofiber has higher specific conductivity and thermostability, is suitable for the beneficial effects such as the application of the aspect such as chemical sensor, battery, molecular electronic device, anticorrosive and separatory membrane, light emitting diodde desplay device, electromagnetic shielding material, energy storage device.
Accompanying drawing explanation
The field emission scanning electron microscope figure of the finished product FUMARIC ACID TECH GRADE doped polyaniline nanofiber of Fig. 1 prepared by the embodiment of the present invention 5;
The infrared spectrogram of the finished product FUMARIC ACID TECH GRADE doped polyaniline nanofiber of Fig. 2 prepared by the embodiment of the present invention 5;
The ultraviolet spectrogram of the finished product FUMARIC ACID TECH GRADE doped polyaniline nanofiber of Fig. 3 prepared by the embodiment of the present invention 5;
The thermogravimetric curve figure of the finished product FUMARIC ACID TECH GRADE doped polyaniline nanofiber of Fig. 4 prepared by the embodiment of the present invention 5.
Embodiment
Below in conjunction with embodiment, preparation method of the present invention is described in detail.
Embodiment 1
The first step, material preparation step:
A. use deionized water, analytical pure ammonium persulphate and analytical pure FUMARIC ACID TECH GRADE, preparing volumetric molar concentration is respectively the ammonium persulfate solution of 0.25mol/L and the FUMARIC ACID TECH GRADE emulsion of volumetric molar concentration 0.75mol/L;
B. be the ratio of 2 ︰ 1 in aniline and fumaric mol ratio, the analytical pure aniline distilled joined in above-mentioned FUMARIC ACID TECH GRADE yogurt liquid, stir through secondary pressure, obtained aniline salt emulsion;
Second step, at room temperature, the step of synthesizing soluble electrically conductive polyaniline nano fiber:
A. be the ratio of 1 ︰ 1 in the mol ratio of ammonium persulphate and aniline, limit stirred, limit by above-mentioned ammonium persulfate solution with the every two seconds speed of one, be slowly added drop-wise in above-mentioned aniline salt emulsion, Keep agitation 27 hours, until react completely;
B. carry out suction filtration with sand core funnel, and with deionized water wash to filtrate clear, colorless, obtain filter cake;
C. above-mentioned filter cake is placed in vacuum drying oven, at 60 DEG C of temperature, dry 24h, gets product.
Embodiment 2
The first step, material preparation step:
A. use deionized water, analytical pure ammonium persulphate and analytical pure FUMARIC ACID TECH GRADE, preparing volumetric molar concentration is respectively the ammonium persulfate solution of 0.5mol/L and the FUMARIC ACID TECH GRADE emulsion of volumetric molar concentration 1.0mol/L;
B. be the ratio of 4 ︰ 1 in aniline and fumaric mol ratio, the analytical pure aniline distilled joined in above-mentioned FUMARIC ACID TECH GRADE yogurt liquid, stir through secondary pressure, obtained aniline salt emulsion;
Second step, at room temperature, the step of synthesizing soluble electrically conductive polyaniline nano fiber:
A. be the ratio of 1 ︰ 1 in the mol ratio of ammonium persulphate and aniline, limit stirred, limit by above-mentioned ammonium persulfate solution with the every two seconds speed of one, be slowly added drop-wise in above-mentioned aniline salt emulsion, Keep agitation 20 hours, until react completely;
All the other are with embodiment 1.
Embodiment 3
The first step, material preparation step:
A. use deionized water, analytical pure ammonium persulphate and analytical pure FUMARIC ACID TECH GRADE, preparing volumetric molar concentration is respectively the ammonium persulfate solution of 0.75mol/L and the FUMARIC ACID TECH GRADE emulsion of volumetric molar concentration 0.25mol/L;
B. be the ratio of 1 ︰ 1 in aniline and fumaric mol ratio, the analytical pure aniline distilled joined in above-mentioned FUMARIC ACID TECH GRADE yogurt liquid, stir through secondary pressure, obtained aniline salt emulsion;
Second step, at room temperature, the step of synthesizing soluble electrically conductive polyaniline nano fiber:
A. be the ratio of 1 ︰ 1 in the mol ratio of ammonium persulphate and aniline, limit stirred, limit by above-mentioned ammonium persulfate solution with the every two seconds speed of one, be slowly added drop-wise in above-mentioned aniline salt emulsion, Keep agitation 13 hours, until react completely;
All the other are with embodiment 1.
Embodiment 4
The first step, material preparation step:
A. use deionized water, analytical pure ammonium persulphate and analytical pure FUMARIC ACID TECH GRADE, preparing volumetric molar concentration is respectively the ammonium persulfate solution of 1.0mol/L and the FUMARIC ACID TECH GRADE emulsion of volumetric molar concentration 0.5mol/L;
B. be the ratio of 4 ︰ 3 in aniline and fumaric mol ratio, the analytical pure aniline distilled joined in above-mentioned FUMARIC ACID TECH GRADE yogurt liquid, stir through secondary pressure, obtained aniline salt emulsion;
Second step, at room temperature, the step of synthesizing soluble electrically conductive polyaniline nano fiber:
A. be the ratio of 1 ︰ 1 in the mol ratio of ammonium persulphate and aniline, limit stirred, limit by above-mentioned ammonium persulfate solution with the every two seconds speed of one, be slowly added drop-wise in above-mentioned aniline salt emulsion, Keep agitation 6 hours, until react completely;
All the other are with embodiment 1.
Embodiment 5
The first step, material preparation step:
A. use deionized water, analytical pure ammonium persulphate and analytical pure FUMARIC ACID TECH GRADE, preparing volumetric molar concentration is respectively the ammonium persulfate solution of 0.5mol/L and the FUMARIC ACID TECH GRADE emulsion of volumetric molar concentration 1.0mol/L;
B. be the ratio of 1 ︰ 1 in aniline and fumaric mol ratio, the analytical pure aniline distilled joined in above-mentioned FUMARIC ACID TECH GRADE yogurt liquid, stir through secondary pressure, obtained aniline salt emulsion;
Second step, at room temperature, the step of synthesizing soluble electrically conductive polyaniline nano fiber:
A. be the ratio of 1 ︰ 1 in the mol ratio of ammonium persulphate and aniline, limit stirred, limit by above-mentioned ammonium persulfate solution with the every two seconds speed of one, be slowly added drop-wise in above-mentioned aniline salt emulsion, Keep agitation 20 hours, until react completely;
All the other are with embodiment 1.
Embodiment 6
The first step, material preparation step:
A. use deionized water, analytical pure ammonium persulphate and analytical pure FUMARIC ACID TECH GRADE, preparing volumetric molar concentration is respectively the ammonium persulfate solution of 0.25mol/L and the FUMARIC ACID TECH GRADE emulsion of volumetric molar concentration 1.0mol/L;
B. be the ratio of 4 ︰ 3 in aniline and fumaric mol ratio, the analytical pure aniline distilled joined in above-mentioned FUMARIC ACID TECH GRADE yogurt liquid, stir through secondary pressure, obtained aniline salt emulsion;
Second step, at room temperature, the step of synthesizing soluble electrically conductive polyaniline nano fiber:
A. be the ratio of 3 ︰ 2 in the mol ratio of ammonium persulphate and aniline, limit stirred, limit by above-mentioned ammonium persulfate solution with the every two seconds speed of one, be slowly added drop-wise in above-mentioned aniline salt emulsion, Keep agitation 13 hours, until react completely;
All the other are with embodiment 1.
Embodiment 7
The first step, material preparation step:
A. use deionized water, analytical pure ammonium persulphate and analytical pure FUMARIC ACID TECH GRADE, preparing volumetric molar concentration is respectively the ammonium persulfate solution of 0.5mol/L and the FUMARIC ACID TECH GRADE emulsion of volumetric molar concentration 0.75mol/L;
B. be the ratio of 1 ︰ 1 in aniline and fumaric mol ratio, the analytical pure aniline distilled joined in above-mentioned FUMARIC ACID TECH GRADE yogurt liquid, stir through secondary pressure, obtained aniline salt emulsion;
Second step, at room temperature, the step of synthesizing soluble electrically conductive polyaniline nano fiber:
A. be the ratio of 3 ︰ 2 in the mol ratio of ammonium persulphate and aniline, limit stirred, limit by above-mentioned ammonium persulfate solution with the every two seconds speed of one, be slowly added drop-wise in above-mentioned aniline salt emulsion, Keep agitation 6 hours, until react completely;
All the other are with embodiment 1.
Embodiment 8
The first step, material preparation step:
A. use deionized water, analytical pure ammonium persulphate and analytical pure FUMARIC ACID TECH GRADE, preparing volumetric molar concentration is respectively the ammonium persulfate solution of 1.0mol/L and the FUMARIC ACID TECH GRADE emulsion of volumetric molar concentration 0.25mol/L;
B. be the ratio of 2 ︰ 1 in aniline and fumaric mol ratio, the analytical pure aniline distilled joined in above-mentioned FUMARIC ACID TECH GRADE yogurt liquid, stir through secondary pressure, obtained aniline salt emulsion;
Second step, at room temperature, the step of synthesizing soluble electrically conductive polyaniline nano fiber:
A. be the ratio of 3 ︰ 2 in the mol ratio of ammonium persulphate and aniline, limit stirred, limit by above-mentioned ammonium persulfate solution with the every two seconds speed of one, be slowly added drop-wise in above-mentioned aniline salt emulsion, Keep agitation 20 hours, until react completely;
All the other are with embodiment 1.
Embodiment 9
The first step, material preparation step:
A. use deionized water, analytical pure ammonium persulphate and analytical pure FUMARIC ACID TECH GRADE, preparing volumetric molar concentration is respectively the ammonium persulfate solution of 0.5mol/L and the FUMARIC ACID TECH GRADE emulsion of volumetric molar concentration 1.0mol/L;
B. be the ratio of 1 ︰ 1 in aniline and fumaric mol ratio, the analytical pure aniline distilled joined in above-mentioned FUMARIC ACID TECH GRADE yogurt liquid, stir through secondary pressure, obtained aniline salt emulsion;
Second step, in the cryogenic thermostat reactive tank of 5 DEG C, the step of synthesizing soluble electrically conductive polyaniline nano fiber:
A. be the ratio of 1 ︰ 1 in the mol ratio of ammonium persulphate and aniline, limit stirred, limit by above-mentioned ammonium persulfate solution with the every two seconds speed of one, be slowly added drop-wise in above-mentioned aniline salt emulsion, Keep agitation 20 hours, until react completely;
All the other are with embodiment 1.
The productive rate of embodiment 1-9 and specific conductivity are in table 1.
The productive rate of table 1 embodiment 1-9 and specific conductivity
| Embodiment | Productive rate | Specific conductivity (S/cm) |
| 1 | 77.5％ | 2.05×10 -3 |
| 2 | 81.6％ | 1.47×10 -2 |
| 3 | 117.6％ | 1.62×10 -3 |
| 4 | 120.6％ | 4.33×10 -3 |
| 5 | 146.5％ | 1.56×10 -2 |
| 6 | 108.8％ | 1.80×10 -3 |
| 7 | 145.1％ | 7.21×10 -3 |
| 8 | 108.3％ | 5.5×10 -3 |
| 9 | 175％ | 3.05×10 -2 |
In upper table, the method for calculation of productive rate are: the prepared quality of finished product FUMARIC ACID TECH GRADE doped polyaniline nanofiber and the percent value of raw material aniline quality.
With embodiment 5 for representing embodiment, respectively by the fusible conductive polyaniline nanofiber obtained by embodiment 5 through field emission scanning electron microscope, XRD, ultraviolet spectral analysis and thermogravimetric analysis, detected result is as follows:
As shown in Figure 1, prepared fusible conductive polyaniline nanofiber:
Microtexture is nanofiber shape, length heterogeneity, surface irregularity, and dense arrangement the spheroidal particle that diameter is about 50nm, and Fibre diameter is substantially within the scope of 150 ± 25nm.
As shown in Figure 2, prepared fusible conductive polyaniline nanofiber:
In infrared spectra, correspond to the quinone ring of FUMARIC ACID TECH GRADE doped polyaniline and the C-C stretching vibration of phenyl ring, the absorption peak of the out-of-plane deformation vibration of Isosorbide-5-Nitrae substituted benzene ring appears at 1562cm respectively
-1, 1488cm
-1, 812cm
-1, illustrate that polyaniline molecule structure exists with state from beginning to end;
At 1230cm
-1place has the charateristic avsorption band of protonic acid doping polyaniline, describes FUMARIC ACID TECH GRADE p-poly-phenyl amine and is successfully made doping.
As shown in Figure 3, prepared fusible conductive polyaniline nanofiber:
In ultraviolet spectrogram, the absorption peak at 330nm and 630nm place represents the π-π * transition of phenyl ring and quinone ring respectively.
As shown in Figure 4, prepared fusible conductive polyaniline nanofiber:
Below 200 DEG C, substantially there is no weightlessness, illustrate that it has good thermostability.
Fusible conductive polyaniline nanofiber obtained by embodiment 5 is carried out solubleness detection, and its solubleness in N-Methyl pyrrolidone is 2.8Kg/L.
Claims (2)
1. a fusible conductive polyaniline nanofiber, is characterized in that, structural formula is
Its solubleness in N-Methyl pyrrolidone is 2.8Kg/L;
Specific conductivity is 1.8 × 10
-3-3.05 × 10
-2s/cm;
Diameter is 150 ± 25nm;
Below 200 DEG C, Absorbable organic halogens exists.
2. the preparation method of fusible conductive polyaniline nanofiber as claimed in claim 1, is characterized in that, comprise the following steps:
The first step, material preparation step:
A. use deionized water, analytical pure ammonium persulphate and analytical pure FUMARIC ACID TECH GRADE, preparing volumetric molar concentration is respectively the ammonium persulfate solution of 0.25-1mol/L and the FUMARIC ACID TECH GRADE emulsion of volumetric molar concentration 0.25-1mol/L;
B. be the ratio of 4 ︰ 1-4 in aniline and fumaric mol ratio, the analytical pure aniline distilled joined in above-mentioned FUMARIC ACID TECH GRADE yogurt liquid, stir through secondary pressure, obtained aniline salt emulsion;
Second step, at room temperature, or in the cryogenic thermostat reactive tank of 5 DEG C, the step of synthesizing soluble electrically conductive polyaniline nano fiber:
A. be the ratio of 1-1.5 ︰ 1 in the mol ratio of ammonium persulphate and aniline, limit is stirred, above-mentioned ammonium persulfate solution is slowly added drop-wise in above-mentioned aniline salt emulsion by limit, and Keep agitation is until react completely;
B. carry out suction filtration with sand core funnel, and with deionized water wash to filtrate clear, colorless, obtain filter cake;
C. above-mentioned filter cake is placed in vacuum drying oven, at 60 DEG C of temperature, dry 24h, gets product.
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| CN104072763A (en) * | 2014-06-17 | 2014-10-01 | 山东科技大学 | Preparation method of soluble polyaniline composite wave absorbing material |
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2014
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| EP0579027A1 (en) * | 1992-06-30 | 1994-01-19 | Nitto Denko Corporation | Organic polymer solution composition and process for producting electrically conductive organic polymer therefrom |
| KR20030082059A (en) * | 2002-04-16 | 2003-10-22 | 주식회사 옴니켐 | Novel process of polyaniline |
| CN104072763A (en) * | 2014-06-17 | 2014-10-01 | 山东科技大学 | Preparation method of soluble polyaniline composite wave absorbing material |
| CN104064358A (en) * | 2014-06-25 | 2014-09-24 | 福建国光电子科技股份有限公司 | Electrochemical polymerization solution for preparing solid electrolyte layer for solid electrolytic capacitor |
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| Title |
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| SUN CHUANYU ET AL: "Preparation of polyaniline nanostructures doped with different dicarboxylic acids through template-free method", 《MATERIALS SCIENCE-POLAND》, vol. 32, no. 3, 17 October 2014 (2014-10-17), pages 419 - 422 * |
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Application publication date: 20150325 |