CN102199287B - Preparation method of polyaniline nanofibers - Google Patents
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Abstract
The invention provides a preparation method of polyaniline nanofibers, which comprises the following steps of: (a) mixing a phenylamine monomer and an inorganic acid to obtain a first mixed liquid, wherein the concentration of the phenylamine monomer in the first mixed liquid is 1 -3 mol/L; (b) mixing an oxidizing agent and the first mixed liquid to obtain a second mixed liquid, and polymerizing the phenylamine monomer in the second mixed liquor to obtain a first reaction product, wherein the oxidation-reduction potential Eox of the oxidizing agent is less than or equal to 0.8V and larger than or equal to 0.5V; and (c) cleaning, washing with alkali and drying the first reaction product to obtain the polyaniline nanofibers. Compared with the prior art, the preparation method provided by the invention has the advantages that the prepared polyaniline nanofibers have uniform diameter and high purity and are suitable for large-scale industrial production, and the production efficiency is increased.
Description
Technical field
The present invention relates to the synthetic field of polymkeric substance, relate in particular to a kind of preparation method of polyaniline nano fiber.
Background technology
Polyaniline is a kind of macromolecular material of conductivity excellence, and monomer whose is easy to get, and has diversified structure, unique mechanism of doping effect, good environmental stability, and technology application prospect widely, and causes scientist's concern.Drawbacks limit such as but polyaniline is poorly soluble, fusing point is high, poor in processability the suitability for industrialized production of polyaniline, so compositing conducting rate height, solvability is good, the nano polyaniline that particle diameter is little becomes the focus of current research.
At present, synthesizing nano polyaniline mainly contains two kinds of methods, a kind of is electrochemical method, Chinese patent CN 1958854A discloses a kind of nano polyaniline fiber preparation method, this patent adopts three-electrode system, the control temperature of reaction is that 10～30 ℃, reaction times are 10～30min, prepares polyaniline nano fiber by the constant potential method on working electrode.In addition, and people such as Liang (Angew.Chem.Int.Ed.2002,41 (19): 3665～3668, Chem.Eur.J.2003,9,604-611) with 0.02-0.08mAcm
-2Low current density, by electrochemical production polyaniline nano fiber.
Another is chemical oxidization method, and at present, the method for preparing polyaniline nano fiber by chemical oxidation method mainly comprises: (1) template, people (Science such as Martin for example, 1994,266,1961) be that template has prepared polyaniline nano fiber with the porous alumina; It is the technical scheme that template prepares polyaniline nano fiber that Chinese patent CN101302294B and CN 101284908A disclose with the fat-soluble Sucrose octaacetate that contains eight side chains and polyoxyethylene glycol respectively.(2) interfacial, for example people (J.Am.Chem.Soc.2003,125,314 such as Huang; J.Am.Chem.Soc.2004,126,851) reported and namely carried out interfacial polymerization method polymerization in oil/water termination and prepared polyaniline nano fiber; The preparation method of Chinese patent CN 101338031B, CN 100526367C, CN 101037504A and the disclosed nano polyaniline of CN 100480443C also by interfacial polymerization method, has prepared polyaniline nano fiber.(3) ultrasonic radiation method, for example the preparation method of Chinese CN 101870770A and the disclosed nano polyaniline of CN 1323199C all is the polyaniline nano fibers that prepared highly doped degree by ultrasonic method.(4) weak solution method, for example people (Adv.Mater.2005,17,1679 such as Epstein; Synth.Met.2005,153,69) reported that weak solution method prepares the technical scheme of polyaniline nano fiber, wherein the concentration of polyaniline is 0.008mol/L.(5) seeding polymerization method, for example people (J.Am.Chem.Soc.2004,126,4502 such as Manohar; Adv.Funct.Mater.2006,16,1145) reported the technical scheme of utilizing the seeding polymerization legal system to be equipped with polyaniline nano fiber.Yet the present following problem of method ubiquity for the preparation of polyaniline nano fiber: (1) template exists template and is difficult for removing, the problem that aftertreatment is loaded down with trivial details, and cause polyaniline nano fiber to damage in the last handling process easily; (2) to exist the organic solvent usage quantity big for interfacial polymerization, causes environmental pollution problems; (3) electrochemical method, ultrasonic radiation method and seeding polymerization method exist the requirement for experiment condition height, are not suitable for the problem of scale operation; (4) weak solution method has caused this method to yield poorly because polyaniline concentration is very low, is not suitable for the industry mass production.
For fear of the problems referred to above, people such as Wang Xianhong (Syn.Met., 2009,159,1508～1511) reported that the high rare method of a kind of vacation prepares polyaniline nano fiber, be oxygenant with the ammonium persulphate, the aniline monomer protonic acid solution of 0.4mol/L is prepared the polyaniline nano fiber that diameter is 18～110nm by the high rare method of vacation.But there is the problem of following two aspects in this method: the diameter heterogeneity of (1) polyaniline nano fiber, and purity is not high, and size is difficult to control; (2) concentration of aniline monomer is lower, with traditional concentration 1mol/L old a certain distance still, and can't industrialization production.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is to provide a kind of preparation method of polyaniline nano fiber, compared to existing technology, and the polyaniline nano fiber diameter homogeneous of preparation, purity height.
In order to solve the problem that prior art exists, the invention provides a kind of preparation method of polyaniline nano fiber, comprising:
A) aniline monomer is mixed with mineral acid, obtain first mixed solution; Aniline monomer concentration is 1～3mol/L in described first mixed solution;
B) oxygenant is mixed with described first mixed solution, obtain second mixing solutions, the aniline monomer polymerization in described second mixing solutions obtains first reaction product; The redox potential E of described oxygenant
OxBe 0.5V≤E
Ox≤ 0.8V;
C) will obtain polyaniline nano fiber after the washing of described first reaction product process, alkali cleaning, the drying.
Preferably, described mineral acid is one or more in hydrochloric acid, sulfuric acid, nitric acid, perchloric acid and the boric acid.
Preferably, described oxygenant is one or more in iron nitrate, iron trichloride, ferric sulfate and the cupric chloride.
Preferably, the time of aniline monomer polymerization is 14～32h in the step b).
Preferably, described aniline monomer and described oxygenant are 1 in molar ratio: (1.2～15).
Preferably, the concentration of oxide compound is 0.5～3mol/L in described second mixing solutions.
Preferably, the concentration of mineral acid is 0.5～1.5mol/L in described first mixed solution.
Preferably, step b) is specially:
B1) oxygenant is dissolved in the deionized water, obtaining concentration is 1～3mol/L aqueous oxidizing agent solution; The redox potential E of described oxygenant
OxBe 0.5V≤E
Ox≤ 0.8V;
B2) described aqueous oxidizing agent solution is mixed with the speed of 15～50mL/min respectively with described first mixed solution, obtain second mixing solutions;
B3) aniline monomer in described second mixing solutions carries out the radical cation polymerization-30～10 ℃ of static placements down, obtains first reaction product.
Preferably, step d) is specially:
C1) water, methyl alcohol and deionized water wash are colourless to filtrate respectively with described first reaction product;
C2) with step c1) product that obtains soaks 2～24h with the ammoniacal liquor of 0.5～1mol/L, and is colourless to filtrate with deionized water wash then;
C3) with step c2) the product vacuum-drying that obtains obtains polyaniline nano fiber; The described vacuum-drying time is 24～36h.
Preferably, described vacuum drying vacuum tightness is 0.6MPa～0.9MPa, and drying temperature is 45 ℃～90 ℃.
The invention provides a kind of preparation method of polyaniline nano fiber, comprising: a) aniline monomer is mixed with mineral acid, obtain first mixed solution; Aniline monomer concentration is 1～3mol/L in described first mixed solution; B) oxygenant is mixed with described first mixed solution, obtain second mixing solutions, the aniline monomer polymerization in described second mixing solutions obtains first reaction product; The redox potential E of described oxygenant
OxBe 0.5V≤E
Ox≤ 0.8V; C) will obtain polyaniline nano fiber after the washing of described first reaction product process, alkali cleaning, the drying.Compared to existing technology, the present invention uses the lower oxygenant of redox potential to be used for causing the aniline monomer polymerization, obtains the polyaniline nano fiber of diameter homogeneous; In addition the raw material major part used of the present invention as inorganics, do not use template and any organic solvent, solved the pollution problem of aftertreatment.The present invention uses the method for " false high rare " to use the stock liquid of high density, has reduced the use of solvent, has reduced cost, is fit to large-scale industrial production.
Description of drawings
The sem photograph of the polyaniline nano fiber of Fig. 1 embodiment of the invention 1 preparation;
The transmission electron microscope picture of the polyaniline nano fiber of Fig. 2 embodiment of the invention 1 preparation;
The sem photograph of the polyaniline nano fiber of Fig. 3 embodiment of the invention 2 preparations;
The transmission electron microscope picture of the polyaniline nano fiber of Fig. 4 embodiment of the invention 2 preparations;
The sem photograph of the polyaniline nano fiber of Fig. 5 embodiment of the invention 3 preparations;
The transmission electron microscope picture of the polyaniline nano fiber of Fig. 6 embodiment of the invention 3 preparations;
The sem photograph of the polyaniline nano fiber of Fig. 7 embodiment of the invention 4 preparations;
The transmission electron microscope picture of the polyaniline nano fiber of Fig. 8 embodiment of the invention 4 preparations;
The sem photograph of the polyaniline nano fiber of Fig. 9 embodiment of the invention 5 preparations;
The transmission electron microscope picture of the polyaniline nano fiber of Figure 10 embodiment of the invention 5 preparations;
The transmission electron microscope picture of the polyaniline nano fiber of Figure 11 comparative example preparation of the present invention.
Embodiment
In order further to understand the present invention, be described below in conjunction with the preferred embodiments of the invention of embodiment, but should be appreciated that the just restriction for further specifying the features and advantages of the present invention rather than patent of the present invention being required of these descriptions.
The invention provides a kind of preparation method of polyaniline nano fiber, comprising: a) aniline monomer is mixed with mineral acid, obtain first mixed solution; Aniline monomer concentration is 1～3mol/L in described first mixed solution; B) oxygenant is mixed with described first mixed solution, obtain second mixing solutions, the aniline monomer polymerization in described second mixing solutions obtains first reaction product; The redox potential E of described oxygenant
OxBe 0.5V≤E
Ox≤ 0.8V; C) will obtain polyaniline nano fiber after the washing of described first reaction product process, alkali cleaning, the drying.
According to the present invention, " false high rare " technology is a kind of a kind of technology of building high rare reaction conditions by the method for control reaction soln concentration.Reactant is made into denseer solution, then reactant solution slowly is added drop-wise in the reaction system, along with the continuous generation of oligopolymer, make the unreacted end group of reactant remain on extremely low concentration.And the reaction end group of low concentration is conducive to the generation of polyaniline nano fiber, can control concentration of reactants by the control rate of addition, has avoided the use of a large amount of solvents.The present invention is decided to be 1～3mol/L with the concentration of the aniline monomer in described first mixing solutions, and the aniline monomer concentration 0.4mol/L in greatly improves compared to existing technology, has therefore improved reaction and has carried out the central stability of process, has reduced the usage quantity of solvent.
According to the present invention, preferably under agitation condition, described aniline monomer to be mixed with mineral acid, purpose is to carry out in order to make to be reflected under the acidic conditions, makes the radical cation polyreaction stable, improves the oxidation efficiency of initiation of oxygenant.The mineral acid that the present invention uses is preferably one or more in hydrochloric acid, sulfuric acid, nitric acid, perchloric acid and the boric acid, more preferably one or more in hydrochloric acid, nitric acid, perchloric acid and the boric acid.The present invention preferably is dissolved in described mineral acid in the deionized water, forms acidic aqueous solution, more described aniline monomer is mixed with described acidic aqueous solution.According to the present invention, the concentration of aniline monomer is 1～3mol/L in described first mixing solutions, is preferably 1.2～2mol/L, more preferably 1.5～2mol/L.The concentration of mineral acid is preferably 0.1～3mol/L in described first mixing solutions, and more preferably 0.5～1.5mol/L most preferably is 1～1.2mol/L.The purpose of using deionized water preparation acidic aqueous solution is for aniline monomer and mineral acid being dissolved in the same system, forming the aniline monomer salts solution.Organic solvent compared to existing technology, the deionized water environmental protection, cheap, be applicable to all reaction conditionss.
The present invention uses the lower oxygenant of oxidizing potential to replace traditional ammonium persulphate on the basis of " false high rare " technology, causes aniline monomer and carries out polymerization, the preparation polyaniline nano fiber.Redox potential is the ammonium persulphate of 2.01V in the prior art of comparing, the redox potential of the described oxygenant that the present invention uses is lower, oxidisability a little less than, causing the reaction of polyaniline carries out milder, so polyaniline nano fiber diameter homogeneous that forms, experimental result proves, the diameter of the polyaniline nano fiber of preparation method's preparation provided by the invention is 10～24nm, the polyaniline nano fiber diameter 10～110nm of the prior art for preparing of comparing, the polyaniline nano fiber diameter of the inventive method preparation is homogeneous more.
According to the present invention, preferably under agitation condition, described oxygenant is mixed with first mixing solutions, hybrid mode preferably uses dropping funnel well known in the art to drip mixing or manual dropping of dropper mixed, the present invention more preferably dropping funnel drips mixing, respectively first mixing solutions and oxygenant are added on respectively in the different separating funnels, drip mixing with identical speed, described dropping mixing velocity is preferably 15～50mL/min, it is slow for what mixing velocity was tried one's best selecting such speed, thereby the carrying out of delayed response makes reaction more stable.
According to the present invention, described oxygenant is preferably one or more in iron nitrate, iron trichloride, ferric sulfate and the cupric chloride.The mol ratio of described aniline monomer and described oxygenant is preferably 1: (1.2～15), more preferably 1: (2.5～10) most preferably are 1: (5～10).Described oxygenant preferably uses deionized water dissolving, obtains aqueous oxidizing agent solution, helps oxygenant to form ionic forms, and multivalence attitude metal ion can disperse in deionized water, and does not have the redundant impurities ion, and the ionic polymerization meeting is more stable.According to the present invention, the concentration of described aqueous oxidizing agent solution is preferably 0.5～3mol/L, more preferably 1～2.5mol/L.
Described aqueous oxidizing agent solution and described first mixing solutions are dropped in the conversion unit, provide first condition to make described aniline monomer generation radical cation polyreaction, described first condition low-temp reaction, temperature are preferably-30～10 ℃, more preferably-5～5 ℃.Reaction times is preferably 14～64h, more preferably 24～32h.After finishing, reaction obtains first reaction product.Low-temp reaction can make reaction as far as possible slowly, can reduce the generation of by product, is conducive to the polyaniline of generating structure homogeneous, can obtain the polyaniline nano fiber of diameter homogeneous.
According to the present invention, water, methyl alcohol and deionized water wash are colourless to filtrate respectively with described first reaction product; Obtain second reaction product, the neutralize acidic substance on the described second reaction product surface, the present invention preferably uses ammoniacal liquor to soak described second reaction product, and the concentration of described ammoniacal liquor is preferably 0.5～1mol/L, soak time is preferably 2～24h, and is colourless to filtrate with deionized water wash then; Obtain the 3rd reaction product drying, obtain polyaniline nano fiber, the described dry drying means well known in the art that uses preferably uses vacuum-drying, infrared drying or spontaneous evaporation.Vacuum-drying more preferably.According to the present invention, the described vacuum-drying time is preferably 24～36h, more preferably 28～32h.It is 0.6MPa～0.9MPa that vacuum drying vacuum tightness is preferably vacuum tightness, and drying temperature is preferably 45 ℃～90 ℃.Equipment the present invention that vacuum-drying is used does not do restriction.
Below with specific embodiment and comparative example technical scheme of the present invention is described, but protection scope of the present invention and being not limited by the following examples.Need to prove that raw material and reagent source that the present invention uses are: aniline, iron nitrate, iron trichloride, ferric sulfate and cupric chloride are all from Tianjin fine chemistry industry institute product.Hydrochloric acid, sulfuric acid, nitric acid, perchloric acid and boric acid are from Beijing chemical reagent work product.
Embodiment 1:
Step 2, under agitation condition, iron nitrate is dissolved in the deionized water iron nitrate aqueous solution B that forms 1mol/L;
After step 4, the reaction product that step 3 is obtained were filtered, water, methyl alcohol and deionized water wash were colourless to filtrate respectively;
Step 5, product that step 4 is obtained soak 24h with the ammoniacal liquor of 0.5mol/L, and be colourless to filtrate with deionized water wash then;
Step 6, the product vacuum-drying that step 5 is obtained obtain polyaniline nano fiber, vacuum-drying 24h.
Present embodiment is prepared polyaniline nano fiber detect, the result shows that the diameter of the polyaniline that present embodiment obtains is 15～23nm, and length is 3～5 μ m.The polyaniline nano fiber of embodiment 1 preparation observed in scanning electron microscope and transmission electron microscope and the scanning electron microscope that obtains and the polyaniline nano fiber diameter in the transmission electron microscope picture are carried out statistical study, the result as shown in Figure 1 and Figure 2, polyaniline nano fiber diameter homogeneous, purity height, the distribution homogeneous of present embodiment 1 preparation.
Embodiment 2:
Step 2, under agitation condition, iron nitrate is dissolved in the deionized water iron nitrate aqueous solution B that forms 3mol/L;
After step 4, the reaction product that step 3 is obtained were filtered, water, methyl alcohol and deionized water wash were colourless to filtrate respectively;
Step 5, product that step 4 is obtained soak 10h with the ammoniacal liquor of 1mol/L, and be colourless to filtrate with deionized water wash then;
Step 6, the product vacuum-drying that step 5 is obtained obtain polyaniline nano fiber, vacuum-drying 36h.
Present embodiment is prepared polyaniline nano fiber to be detected, the result shows, the diameter of the polyaniline that present embodiment obtains is 13～22nm, length is 5-7 μ m, the polyaniline nano fiber of embodiment 2 preparation observed in scanning electron microscope and transmission electron microscope and the scanning electron microscope that obtains and the polyaniline nano fiber diameter in the transmission electron microscope picture are carried out statistical study, the result as shown in Figure 3, Figure 4, polyaniline nano fiber diameter homogeneous, purity height, the distribution homogeneous of present embodiment 2 preparation.
Embodiment 3:
Step 2, under agitation condition, iron trichloride is dissolved in the deionized water ferric chloride aqueous solutions B that forms 1.5mol/L;
After step 4, the reaction product that step 3 is obtained were filtered, water, methyl alcohol and deionized water wash were colourless to filtrate respectively;
Step 5, product that step 4 is obtained soak 20h with the ammoniacal liquor of 0.81mol/L, and be colourless to filtrate with deionized water wash then;
Step 6, the product vacuum-drying that step 5 is obtained obtain polyaniline nano fiber, vacuum-drying 30h.
Present embodiment is prepared polyaniline nano fiber to be detected, the result shows, the diameter of the polyaniline that present embodiment obtains is 16～24nm, length is 4-6 μ m, the polyaniline nano fiber of embodiment 3 preparation observed in scanning electron microscope and transmission electron microscope and the scanning electron microscope that obtains and the polyaniline nano fiber diameter in the transmission electron microscope picture are carried out statistical study, result such as Fig. 5, shown in Figure 6, polyaniline nano fiber diameter homogeneous, purity height, the distribution homogeneous of present embodiment 3 preparations.
Embodiment 4:
Step 2, under agitation condition, ferric sulfate dissolving is formed the ferric sulfate aqueous solution B of 2mol/L in deionized water;
After step 4, the reaction product that step 3 is obtained were filtered, water, methyl alcohol and deionized water wash were colourless to filtrate respectively;
Step 5, product that step 4 is obtained soak 20h with the ammoniacal liquor of 1mol/L, and be colourless to filtrate with deionized water wash then;
Step 6, the product vacuum-drying that step 5 is obtained obtain polyaniline nano fiber, vacuum-drying 28h.
Present embodiment is prepared polyaniline nano fiber to be detected, the result shows, the diameter of the polyaniline that present embodiment obtains is 11-15nm, length is 2-3 μ m, the polyaniline nano fiber of embodiment 4 preparation observed in scanning electron microscope and transmission electron microscope and the scanning electron microscope that obtains and the polyaniline nano fiber diameter in the transmission electron microscope picture are carried out statistical study, result such as Fig. 7, shown in Figure 8, polyaniline nano fiber diameter homogeneous, purity height, the distribution homogeneous of present embodiment 4 preparations.
Embodiment 5:
Step 2, under agitation condition, cupric chloride is dissolved in the deionized water copper chloride solution B that forms 1.2mol/L;
After step 4, the reaction product that step 3 is obtained were filtered, water, methyl alcohol and deionized water wash were colourless to filtrate respectively;
Step 5, product that step 4 is obtained soak 2h with the ammoniacal liquor of 1mol/L, and be colourless to filtrate with deionized water wash then;
Step 6, the product vacuum-drying that step 5 is obtained obtain polyaniline nano fiber, vacuum-drying 30h.
Present embodiment is prepared polyaniline nano fiber to be detected, the result shows, the diameter of the polyaniline that present embodiment obtains is 10-13nm, length is 1-3 μ m, the polyaniline nano fiber of embodiment 5 preparation observed in scanning electron microscope and transmission electron microscope and the scanning electron microscope that obtains and the polyaniline nano fiber diameter in the transmission electron microscope picture are carried out statistical study, result such as Fig. 9, shown in Figure 10, polyaniline nano fiber diameter homogeneous, purity height, the distribution homogeneous of present embodiment 5 preparations.
Comparative example 1
Ammonium persulphate (E with high redox potential
Ox=2.01V) be oxygenant, according to prior art (Syn.Met., 2009,159,1508～1511) preparation polyaniline nano fiber.The aniline salt aqueous acid of 0.8M and the ammonium persulphate aqueous hydrochloric acid of 0.2M are added drop-wise in the reaction vessel with constant speed under the speed room temperature of 5mL/min, drip the static placement of back room temperature 18h.Filter, washing filtrate obtains polyaniline nano fiber to colourless after the vacuum-drying.Its transmission electron microscope picture such as Figure 11.The diameter of polyaniline is 20-65nm as can be seen, and length is 150-800nm, compare with the present invention, and the diameter heterogeneity of polyaniline, purity is not high.And the concentration of aniline is compared with 1-3M of the present invention, and relatively low, output is less.
Compared to existing technology, the present invention uses the lower oxygenant of redox potential to be used for causing the aniline monomer polymerization, obtains the polyaniline nano fiber of diameter homogeneous; In addition the raw material major part used of the present invention as inorganics, do not use template and any organic solvent, solved the pollution problem of aftertreatment.The present invention uses the method for " false high rare " to use the stock liquid of high density, has reduced the use of solvent, has reduced cost, is fit to large-scale industrial production.
More than the preparation method of a kind of polyaniline nano fiber provided by the invention is described in detail; having used specific case herein sets forth principle of the present invention and embodiment; the explanation of above embodiment just is used for helping to understand method of the present invention and core concept thereof; should be understood that; for those skilled in the art; under the prerequisite that does not break away from the principle of the invention; can also carry out some improvement and modification to the present invention, these improvement and modification also fall in the protection domain of claim of the present invention.
Claims (8)
1. the preparation method of a polyaniline nano fiber is characterized in that, comprising:
A) aniline monomer is mixed with mineral acid, obtain first mixed solution; Aniline monomer concentration is 1～3mol/L in described first mixed solution;
B1) oxygenant is dissolved in the deionized water, obtaining concentration is 1～3mol/L aqueous oxidizing agent solution; The redox potential E of described oxygenant
OxBe 0.5V≤E
Ox≤ 0.8V;
B2) described aqueous oxidizing agent solution is mixed with the speed of 15～50mL/min respectively with described first mixed solution, obtain second mixing solutions;
B3) aniline monomer in described second mixing solutions carries out the radical cation polymerization-30～10 ℃ of static placements down, obtains first reaction product;
C1) water, methyl alcohol and deionized water wash are colourless to filtrate respectively with described first reaction product;
C2) with step c1) product that obtains soaks 2～24h with the ammoniacal liquor of 0.5～1mol/L, and is colourless to filtrate with deionized water wash then;
C3) with step c2) the product vacuum-drying that obtains obtains polyaniline nano fiber; The described vacuum-drying time is 24～36h.
2. preparation method according to claim 1 is characterized in that, described mineral acid is one or more in hydrochloric acid, sulfuric acid, nitric acid, perchloric acid and the boric acid.
3. preparation method according to claim 1 is characterized in that, described oxygenant is one or more in iron nitrate, iron trichloride, ferric sulfate and the cupric chloride.
4. preparation method according to claim 1 is characterized in that, step b3) in time of aniline monomer polymerization be 14～32h.
5. preparation method according to claim 1 is characterized in that, described aniline monomer and described oxygenant are 1:(1.2～15 in molar ratio).
6. preparation method according to claim 1 is characterized in that, the concentration of oxide compound is 0.5～3mol/L in described second mixing solutions.
7. preparation method according to claim 1 is characterized in that, the concentration of mineral acid is 0.5～1.5mol/L in described first mixed solution.
8. preparation method according to claim 1 is characterized in that, described vacuum drying vacuum tightness is 0.6MPa～0.9MPa, and drying temperature is 45 ℃～90 ℃.
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| CN103936984B (en) * | 2014-04-10 | 2016-06-08 | 东华大学 | The method of polyaniline nano fiber is prepared in the regulation and control of a kind of using electric field |
| CN105348523B (en) * | 2015-12-03 | 2017-11-17 | 中国科学院长春应用化学研究所 | The preparation method of polyaniline nano fiber |
| CN105295039B (en) * | 2015-12-03 | 2018-06-15 | 中国科学院长春应用化学研究所 | Dendroid polyaniline nano fiber and preparation method thereof |
| CN105801852B (en) * | 2016-05-06 | 2018-05-15 | 东华大学 | A kind of preparation method of micrometer/nanometer structure polyaniline |
| CN110684194B (en) * | 2019-10-14 | 2021-07-20 | 东华大学 | Polyaniline nano-belt and preparation method thereof |
| CN112064136B (en) * | 2020-09-16 | 2022-07-19 | 中国石油大学(华东) | Hollow-structure nanofiber aerogel and preparation method and application thereof |
| CN113789584B (en) * | 2021-08-02 | 2022-10-21 | 安徽理工大学 | Cluster-shaped magnetic polyaniline ultrafine nanofiber and preparation method and application thereof |
| CN113663659A (en) * | 2021-08-30 | 2021-11-19 | 安徽理工大学 | Catching agent and preparation method and application thereof |
| CN114160079A (en) * | 2021-12-06 | 2022-03-11 | 吉林省陆柒肆伍贰科技有限公司 | Neutral treatment process and equipment for polyaniline product after synthesis |
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