CN102127223A - Preparation method of micro/nano polyaniline - Google Patents
Preparation method of micro/nano polyaniline Download PDFInfo
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- CN102127223A CN102127223A CN2010100341101A CN201010034110A CN102127223A CN 102127223 A CN102127223 A CN 102127223A CN 2010100341101 A CN2010100341101 A CN 2010100341101A CN 201010034110 A CN201010034110 A CN 201010034110A CN 102127223 A CN102127223 A CN 102127223A
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Abstract
The invention relates to a preparation method of micro/nano polyaniline. According to the preparation method, an aniline monomer solution and an oxidizing agent solution are introduced to a supergravity reactor and are rapidly mixed to carry out a chemical oxidization reaction under the condition of supergravity, wherein the aniline monomer concentration in the reaction solution is 0.1mol/L to 1.0mol/L, the mol ratio of the aniline monomer to the oxidizing agent is 1:1-8:1, the reaction temperature and the reaction time are respectively 0-80 DEG C and 25-120min, and the supergravity level of the reactor is controlled to be 0.33g-830g; and the micro-nano polyaniline is obtained through the posttreatment processes of ageing, separating, filtering, washing and drying. With the method, the rapid, microscopic and even mixing on the solutions with higher reaction monomer concentration can be realized, and therefore, nanometer polyanilines in different shapes are obtained through carrying out the chemical oxidization reaction on the solutions in the absence of a template reagent and a surfactant. The preparation method has a simple and convenient process, is easy for scale enlargement, and realizes the purpose of preparing the micro-nano polyaniline in an industrial scale by adopting a liquid-liquid rapid mixing method.
Description
Technical field
The present invention relates to a kind of preparation method of conducting polymer composite, concrete is to adopt liquid liquid short mix legal system to be equipped with the micro-/ nano polyaniline.Also belong to the application of high-gravity technology in the prepared in reaction field of nanoparticles.
Background technology
Polyaniline is a kind of macromolecular material; raw material is easy to get, synthesis technique is easy, higher electroconductibility and potential solution, melt-processed possibility and good environmental stability are arranged owing to having; be applied at many high-technology fields; as with electrically conductive polyaniline as base mateiral, be used for many fields such as metal anti-corrosive paint, rechargeable battery, electrically conducting coating and conducting film, electromagnetic shielding, antistatic protection, electroluminescent material, solar cell, sensor component, electrochemistry and catalytic material, stealthy technique and electrochromism and all obtained impressive progress.In recent years, the nano-conductive polyaniline material becomes the another important research direction of conducting polymer materials, with body mutually polyaniline compare, nano polyaniline particularly nano polyaniline fiber integrates electroconductibility and nano material is functional, have specific surface area big, in water good dispersity, good film-forming property, be easy to and characteristics such as nano particle such as metal is compound, the processing characteristics and the application performance of body phase polyaniline have not only been improved greatly, but also expanded the Application Areas of polyaniline, be with a wide range of applications.
Body gathering aniline synthesis method commonly used at present has the synthetic and electrochemical synthesis two big classes of chemical oxidation.The a large amount of electric energy of electrochemical process consumption, and electrolytic solution had relatively high expectations, only be applicable to synthetic be pilot, be unsuitable for mass-producing.What the research of chemical oxidation synthesis method was more mainly is solution polymerization and letex polymerization.Though letex polymerization has plurality of advantages, even etc. as rate of polymerization height, molecular weight of product height and product particle diameter, emulsion polymerization need add more tensio-active agent and organic solvent, and the feature of environmental protection is poor, and the product aftertreatment is loaded down with trivial details.The method that adopts the solution chemistry oxidation style to prepare nano polyaniline mainly is divided into template and no template.Template has product size and controllability is good, realize advantages such as nano-structural ordered arrangement easily, but process cost height, the use of template makes the preparation process relative very complicated that becomes, and the removing of template has not only increased reactions steps also can cause certain destruction to the pattern and the structure of product.No template mainly comprises radiation method, ultrasonic method, liquid liquid short mix method, interfacial polymerization and micella self-assembly method etc.The ultrasonic method preparation is as Chinese patent " a kind of method for preparing conductive polyaniline salt in controllable grain size " (application number 20,071,001 1+9349.X, publication number CN101020748A), the polyaniline particle diameter that makes is bigger, this can cause the decline of the conductivity of polyaniline, and to use the higher ultrasound emission equipment of energy consumption in the preparation process, too high energy consumption is unsuitable for scale operation.Interfacial polymerization prepares nano polyaniline, the bigger than normal and skewness of fibrous polyaniline particle diameter that obtains, and to use organic solvents such as a large amount of deleterious benzene, toluene in the reaction.Liquid liquid short mix method is the novel method of a kind of synthesizing nano polyaniline of occurring in recent years.This is owned by France in the solution chemistry oxidative polymerization, do not need to use template and tensio-active agent, concrete implementing process is that monomer and oxygenant are dissolved in respectively in the dopant acid aqueous solution, preparation monomer solution and oxidizing agent solution, in two kinds of same containers of solution impouring, use stirring rake, magnetic stirring apparatus to mix fast, and stop to stir before being controlled at the induction period of polymerization end, to obtain the nano polyaniline of fibrous texture.This method synthesis technique is easy, and the products obtained therefrom aftertreatment does not also have additive method loaded down with trivial details like that.But this method requires to finish the full and uniform mixing of monomer and oxygenant before decomposition induction time finishes, and just can reach the needed homogeneous nucleation condition of preparation nano polyaniline, and conventional stirring tank is difficult to finish so high mixing requirement.Therefore use conventional stirring tank to carry out the amplification process that liquid liquid short mix prepares nano polyaniline and have fairly obvious scale effect; usually mix on the inhomogeneous nanofiber that causes polyaniline to generate in early days and carry out a large amount of " diauxic growth "; the final big polyaniline particle that forms serious reunion can't the preparation of industrialization nano polyaniline.And liquid liquid short mix reaction method reaction monomers concentration can not be too high, in the strong solution of monomer concentration greater than 0.4mol/L, thorough mixing is to reach the homogeneous nucleation condition before also being difficult to be implemented in the induction period in polymerization end, polymerisate then produces irregular macrobead and coacervate (Li Yu, Zheng Jianlong, well is newly sharp. and chemical oxidising polymerisation prepares micro polyaniline progress [J]. New Chemical Materials, 2009,37 (11): 18-21, therefore with conventional stirring reaction method, the nano polyaniline that can not primary first-order equation obtains the larger process amount, influence the industrialization promotion of this method, nano polyaniline can only be synthetic in a small amount with liquid liquid short mix method in the laboratory at present.In the existing nano polyaniline production technology, still use template and tensio-active agent mostly to obtain the uniform nano polyaniline of pattern on a large scale.
Supergravity reactor is a kind of reactor that can be used for strengthening reaction process of developing in recent years, being developed of success is applied to kinds of reaction and prepares nano material, it is fast to have speed of response, the synthetic grain graininess is little and even, be easy to characteristics such as industrialization, 95105343.4) etc. (patent No.: series of patents proposes to carry out the chemosynthesis of nano particle with hypergravity swinging bed device as: Chinese patent " preparation method of ultrafine particle " (application number 95105344.2) and " preparation method of calcium carbonate superfine powder ", high-gravity technology is applied to the precipitin reaction system, single step reaction is prepared nano particle, and realizes the suitability for industrialized production nano particle.Chinese patent " preparation method of calcium sulfonate with high base number detergent for lubricating oil " in addition, (patent No. CN 1271183C) and " preparation method of ultrafine aluminium hydroxide ", (application number 200510032296.6) is applied to complicated reaction process such as neutralization reaction, carbonating, phase inversion with the high-gravity technology success, prepare calcium sulfonate with high base number purification agent, nano-aluminum hydroxide etc. little/receive particle.Above-mentioned patent certificate high-gravity technology has changed the traditional chemical reaction process of many chemical reaction processes, shows outstanding effect.And adopt high-gravity technology to be applied to the solution chemistry oxidative polymerization, realize that liquid liquid short mix legal system is equipped with nano polyaniline and does not appear in the newspapers as yet.
Summary of the invention
The present invention is directed to liquid liquid short mix and prepare the technical problem that nano polyaniline exists; utilize supergravity reactor to realize that the quick microcosmic of solution mixes; can before finishing, finish this decomposition induction time the full and uniform mixing of monomer and oxygenant; reach the needed homogeneous nucleation condition of preparation nano polyaniline; thereby scale preparation nano polyaniline in the strong solution of being implemented in (monomer concentration is greater than 0.4mol/L); thereby a kind of commercial scale production that is suitable for is provided, method simple and easy to control the preparation method of micro-/ nano polyaniline.
The preparation method of micro-/ nano polyaniline provided by the invention, aniline solution and oxidizing agent solution are fed in the supergravity reactor, under the hypergravity effect, the solution short mix is carried out chemical oxidation reaction, aniline monomer concentration is 0.1mol/L to 1.0mol/L in the reaction soln, the mol ratio of aniline monomer and oxygenant is 1: 1 to 8: 1, temperature of reaction keeps 0 ℃ to 80 ℃, reaction times is 25min to 120min, during reaction the hypergravity level of controlling reactor be 0.33g to 830g, reaction product is through ageing, separate, filter, postprocessing working procedures such as washing and drying obtain the micro-/ nano polyaniline.
Aniline monomer solution of the present invention and oxidizing agent solution be according to common collocation method, and aniline, oxygenant are dissolved in respectively obtain aniline monomer solution, oxidizing agent solution in the dopant acid aqueous solution, wherein:
Described oxygenant comprises persulphate, superoxide, dichromate, hypochlorite, permanganate, iodate or their mixture, preferred persulphate, superoxide, hypochlorite or their mixture, more preferably ammonium persulphate, hydrogen peroxide, clorox or their mixture;
Described dopant acid is this area mineral acid and organic acid commonly used, one or more mixtures in preferred hydrochloric acid, sulfuric acid, nitric acid, perchloric acid, phosphoric acid, the acid or glacial acetic acid, more preferably one or more mixtures in hydrochloric acid, sulfuric acid or the perchloric acid.With dopant acid aqueous solution configuration monomer solution and oxidizing agent solution, acid participates in reaction in the chemical oxidising polymerisation reaction process, wherein proton is attached on the superpolymer chain, make the polymer molecular chain positively charged, for keeping the electric neutrality of molecular chain, acid group is as on the imino-that negatively charged ion is attached in the polyaniline in eigenstate molecular chain, to obtain doped polyaniline.
The dopant acid concentration of using is in the molar weight of this acid molecule in the unit volume acid solution, in 0.5mol/L to 3.0mol/L scope.Preferred mineral acid is the hydrochloric acid of 1mol/L, and preferred organic acid is formic acid or the acetic acid of 1mol/L.
Aniline monomer solution of the present invention and oxidizing agent solution can first premixs, add short mix reaction in the supergravity reactor then, also can pump in the supergravity reactor respectively, and collide hybrid reaction in reactor.
Supergravity reactor of the present invention is disclosed hypergravity swinging bed device, the rotating packed bed reactor (application reference number 91109255.2,91111028.3,01268009.5,200520100685.3,02114174.6 and 200510032296.6) that comprises forms such as bed of packings, deflector type, helical channel, preferred hypergravity is rotary packed bed.
Hypergravity level of the present invention is meant the size of the centrifugal acceleration that hypergravity swinging bed device rotor rotation produces, and represents with the multiple of gravity acceleration g usually, and the rotating speed of main and rotor and the interior external diameter of rotor are relevant.The horizontal g of hypergravity
rCan represent with following formula:
In the formula: n is the rotating speed of rotor per minute
r
1, r
2Be respectively the inside and outside footpath of rotor
Hypergravity level of the present invention is controlled at certain limit according to the needs of chemical oxidising polymerisation reaction process, to guarantee that decomposition induction time finishes to finish before the full and uniform mixing of monomer and oxygenant, thereby reach the needed homogeneous nucleation condition of preparation nano polyaniline, the hypergravity level is crossed low thorough mixing that can't the realization response thing, and reach after certain hypergravity level, the raising of hypergravity level has not also had too big influence to reaction.Experimental result of the present invention is that the hypergravity level is high more in restricted portion, will reach ideal homogeneous nucleation condition more in the short more time, obtains the uniform nano polyaniline of pattern, and the preferred 33g of hypergravity level is to 206g.
Monomer concentration is in certain limit in the reaction soln of the present invention, and monomer concentration is low, though the product pattern is even, output very little; If excessive concentration easily produces sudden and violent gathering, cause before finishing inductive phase, reaching the condition of homogeneous nucleation, can't obtain the uniform nano polyaniline of pattern.Monomer concentration is preferably 0.8mol/L in the reaction soln of the present invention.
The molar ratio of monomer and oxygenant was 1: 1 to 8: 1 range regulation in the reaction soln of the present invention.If this ratio is too small, and then the polymerization velocity long response time is long, and product production is low; Over oxidation occurs if cross conference, cause product electric conductivity energy variation, and reaction mixture material thickness, be difficult to handle.
Temperature of reaction of the present invention remains on 0 ℃ to 80 ℃ scope, preferred 40 ℃.It is slow that reaction temperature is spent low monomer polymerization speed, is unfavorable for forming pattern homogeneous fibre shape nano polyaniline; Polymerization velocity is fast during high temperature, can react completely rapidly to reach the homogeneous nucleation condition rapidly, utilizes and the relative homogeneous fibre shape of formation pattern nano polyaniline; But if temperature is too high, polymerization rate is accelerated, and induction period in polymerization shortens, and causes reaching before finishing inductive phase the condition of homogeneous nucleation, can't obtain the uniform nano polyaniline of pattern.
Postprocessing working procedures such as separation of the present invention, filtration, washing and drying are conventional treatment process.
The micro-/ nano polyaniline of the present invention's preparation is fibrous or particulate state different-shape nano polyaniline.
Beneficial effect of the present invention: the present invention is applied to the chemical oxidising polymerisation reaction process to high-gravity technology and prepares the micro-/ nano polyaniline, utilize the highly enriched microcosmic of supergravity reactor to mix ability and control corresponding technological conditions, reach the be beyond one's reach requirement of liquid liquid short mix of conventional tank reactor, make at the reaction soln monomer concentration higher, temperature of reaction is higher, under the big condition of reaction scale, material still can be finished quick microcosmic uniform mixing before induction period of polymerization finishes, reach polymerization and prepare the needed homogeneous nucleation condition of nano polyaniline, and technology is controlled easily, the scale effect influence is not obvious, and then be implemented under the condition of no template and tensio-active agent, prepare the nano polyaniline of different-shape by liquid liquid short mix method industrially scalable.Method technology of the present invention is easy, the efficient height, and the scale that is easy to is amplified.
Description of drawings
Fig. 1 is the synoptic diagram of the simplification reaction process of one embodiment of the invention.
Fig. 2 is the stereoscan photograph of micro-/ nano polyaniline prepared under the different condition of the present invention.
Embodiment
Below in conjunction with accompanying drawing the present invention is further specified.
The present invention can adopt the rhythmic reaction operating method, that is: with aniline monomer solution and oxidizing agent solution process supergravity reactor short mix, the still aging then chemical oxidising polymerisation reaction process of finishing, reaction mass obtains the micro-/ nano polyaniline through aftertreatment technology.The present invention also can be according to reaction needed, adopt the circulating reaction operating method, solution chemistry oxidative polymerization process is finished in the circulation repeatedly in supergravity reactor with aniline monomer solution and oxidizing agent solution process, obtains the micro-/ nano polyaniline through aftertreatment technology then.
A kind of implementing process by as shown in Figure 1 further specifies embodiments of the present invention:
The aniline monomer solution and the oxidizing agent solution that prepare are on demand added respectively in storage tank 1 and the storage tank 5, monomer solution is delivered to rotating bed by pump 2, valve 3, under meter 4 in the reaction process, and oxidizing agent solution is delivered to the rotary packed bed reactor 9 of hypergravity by pump 6, valve 7, under meter 8.After starting rotary drill reactor 9, in rotor rotation process, behind two-way raw material process liquid distributor premix, spray to the inner edge of packing layer 12, under action of centrifugal force, flow to outer rim, in packing layer 12 by inner edge, monomer and oxygenant carry out sufficient microcosmic to be mixed, the reaction mixture body enters through discharge gate and proceeds the solution chemistry oxidative polymerization in the aging reactor 10, and then to the reaction mass aftertreatment, periodical operation prepares the micro-/ nano polyaniline.
In the above-mentioned technology, also can according to the reaction needs, with the mixture in the aging reactor through pump, valve, under meter, be transported to once more in the rotating bed, be circulated to the reaction times that needs repeatedly, then stopped reaction, carry out aftertreatment technology, prepare required micro-/ nano polyaniline.
The preferred hypergravity of rotating bed super gravity reactor of the present invention is rotary packed bed, and the filler in the packing layer 12 includes, but are not limited to: the silk screen of metallic substance and non-metallic material, porous plate, waved plate, foam materials or structured packing.
In the method for preparing the micro-/ nano polyaniline of the present invention, the hypergravity level of supergravity reactor be 0.33g to about 830g, preferred 33g to 206g.
Embodiment
It below is the non-limiting example that the present invention prepares the micro-/ nano polyaniline.The present invention also should comprise, the various changes that those of ordinary skills can carry out under the condition that does not deviate from the scope of the invention.
Embodiment 1: as shown in Figure 1: by metering, get 18.6 gram aniline, be dissolved in the 1000mL hydrochloric acid, make aniline monomer solution; Take by weighing 11.4 gram ammonium persulphates (APS), be dissolved in the 1000mL hydrochloric acid, make oxidizing agent solution.HCl concentration is 1mol/L in the used hydrochloric acid, the monomer solution and the oxidizing agent solution that prepare are joined respectively in storage tank 1 and 5, ejector priming, two strands of feedstock pumps are entered the mouth to rotating bed, behind the liquid distributor premix, be sprayed onto packing layer 12 inner edges, wherein conditioned reaction device hypergravity level is 33g, and temperature of reaction is room temperature (25 ℃), and the mol ratio of monomer and oxygenant is 4: 1.Mixture enters in the aging reactor 10 (do not open and stir) still aging 25 minutes by behind the rotating bed through discharge port.After ageing finishes, collect the product feed liquid, after filtration, washing, drying obtain the nano polyaniline product through aging reactor.Gained nano polyaniline product, through scanning electron microscope analysis, as Fig. 2 (a), for fibrous, the about 30～50nm of diameter is about length 400 nanometers.
Embodiment 2: except that following variation, all the other processes are with embodiment 1.The hypergravity level is elected 0.33g as, and digestion time is 120 minutes, and making the polyaniline product is the about 50～80nm of nanofibrous structures diameter, about length 300 nanometers.
Embodiment 3: except that following variation, all the other processes are with embodiment 1.The hypergravity level is elected 830g as, and temperature of reaction is 40 ℃, and making the polyaniline product is the about 20～40nm of nanofibrous structures diameter, about length 600 nanometers.
Embodiment 4: except that following variation, all the other processes are with embodiment 1.The aniline consumption is 149 grams, and the APS consumption is 81.8 grams, is mixed with monomer solution (concentration 0.8mol/L) and oxidizing agent solution respectively.Temperature of reaction is adjusted to 60 ℃.Product be the nano polyaniline of fibrous texture, as Fig. 2 (b).
Embodiment 5: except that following variation, all the other processes are with embodiment 1.The aniline consumption is 186.2 grams, and the APS consumption is 57.1 grams, is mixed with monomer solution (concentration 1.0mol/L) and oxidizing agent solution respectively, and the mol ratio of monomer and oxygenant is 8: 1.Temperature of reaction is adjusted to 80 ℃, and the hypergravity level is elected 830g as, and the product that obtains is the fibrous nano polyaniline through scanning electron microscope analysis, as Fig. 2 (c).
Embodiment 6: except that following variation, all the other are with embodiment 1.Be reflected in the ice-water bath and carry out (0～5 ℃), the product that obtains is the fibrous nano polyaniline through scanning electron microscope analysis, and the about 70-90nm of nanofibrous structures diameter is about length 500 nanometers.
Embodiment 7: except that following variation, all the other are with embodiment 1.Oxygenant clorox consumption is 11.4 grams, and promptly the mol ratio of monomer and oxygenant is 4: 1, and it is the fibrous texture nano polyaniline that reaction obtains product.About 20～the 40nm of diameter is about length 400 nanometers.
Embodiment 8: except that following variation, all the other are with embodiment 1.The oxidant hydrogen peroxide consumption is 45.6 grams, and promptly the mol ratio of monomer and oxygenant is 1: 1, and it is the fibrous texture nano polyaniline that reaction obtains product.The about 70-90nm of nanofibrous structures diameter is about length 500 nanometers.
Embodiment 9: except that following variation, all the other are with embodiment 1.HCl concentration is 3mol/L in the used hydrochloric acid of preparation monomer solution and oxidizing agent solution.Making the polyaniline product is nanofibrous structures.The about 100nm of nanofibrous structures diameter is about length 500 nanometers.
Embodiment 10: except that following variation, all the other are with embodiment 1.Used dopant acid solution is the sulphuric acid soln of 1mol/L, and making the polyaniline product is nanofibrous structures.About 40～the 60nm of diameter is about length 400 nanometers
Embodiment 11: except that following variation, all the other are with embodiment 1.Used dopant acid solution is the acetum of 2mol/L, and making the polyaniline product is nanofibrous structures.About 40～the 60nm of diameter, length 400 nanometers
Embodiment 12: present embodiment is the method that continuous circulating reaction prepares nano polyaniline, technical process referring to Fig. 1, press the collocation method of embodiment 1, with concentration be that the aqueous hydrochloric acid of 1mol/L is prepared monomer solution and oxidizing agent solution respectively, monomer solution and oxidizing agent solution concentration are respectively aniline and the ammonium persulphate of 1mol/L, monomer solution and the oxidizing agent solution that to prepare are joined respectively in storage tank 1 and 5, ejector priming, two strands of feedstock pumps are entered the mouth to rotating bed, be sprayed onto behind the premix on the packing layer 12, mixture enters in the aging reactor 10 of opening stirring through discharge port by behind the rotating bed.After the raw material charging finishes, open pump and valve, mixture is pumped into rotating bed once more, so constantly circulation.Behind the 15min, stopped reaction is emitted the product feed liquid from aging reactor discharge gate 11, obtains the polyaniline product through conventional aftertreatment.Wherein, temperature of reaction is 20 ℃.Through scanning electron microscope analysis, products obtained therefrom is the particulate state nano polyaniline of particle diameter less than 100nm, as Fig. 2 (d).
Embodiment 13: except that following variation, all the other are with embodiment 12.Temperature of reaction is 40 ℃, and be 10 minutes cycling time, and through scanning electron microscope analysis, products obtained therefrom is irregularly shaped polyaniline particle, as Fig. 2 (e) and Fig. 2 (f).
Claims (8)
1. the preparation method of a micro-/ nano polyaniline, it is characterized in that, the solution and the oxidizing agent solution of aniline monomer are fed supergravity reactor, under the effect of hypergravity, the reaction of solution mixing carrying out chemical oxidising polymerisation, aniline monomer concentration is 0.1mol/L to 1.0mol/L in the reaction soln, the mol ratio of aniline monomer and oxygenant is 1: 1 to 8: 1, temperature of reaction keeps 0 ℃ to 80 ℃, reaction times is 25min to 120min, during reaction the hypergravity level of controlling reactor be 0.33g to 830g, reaction mass is through ageing, separate, filter, washing and dry postprocessing working procedures obtain the micro-/ nano polyaniline.
2. preparation method according to claim 1, it is characterized in that, aniline monomer solution and oxidizing agent solution are that aniline monomer, oxygenant are dissolved in respectively in the dopant acid aqueous solution, and wherein said dopant acid is one or more mixtures in hydrochloric acid, sulfuric acid, nitric acid, perchloric acid, phosphoric acid, the acid or glacial acetic acid.
3. preparation method according to claim 2 is characterized in that, the dopant acid of use is in the molar weight of this acid molecule in the unit volume acid solution, and concentration is in 0.5mol/L to 3.0mol/L scope.
4. preparation method according to claim 2 is characterized in that, the oxygenant that uses is one or more mixtures in ammonium persulphate, hydrogen peroxide or the clorox.
5. preparation method according to claim 1 is characterized in that, the hypergravity level of reactor is controlled at 33g to the 206g scope.
6. preparation method according to claim 1 is characterized in that, monomer concentration is 0.8mol/L in the reaction soln.
7. preparation method according to claim 1 is characterized in that the solution of aniline monomer and oxidizing agent solution once feed the supergravity reactor hybrid reaction, then through ageing and aftertreatment technology, obtains the micro-/ nano polyaniline.
8. preparation method according to claim 1 is characterized in that, the solution of aniline monomer and oxidizing agent solution circulation feed the supergravity reactor hybrid reaction, then through ageing and aftertreatment technology, obtain the micro-/ nano polyaniline.
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| CN103834265A (en) * | 2014-03-24 | 2014-06-04 | 中国科学院长春应用化学研究所 | Polyaniline anti-corrosive paint |
| CN103408754B (en) * | 2013-07-11 | 2015-10-28 | 东华大学 | A kind of preparation method of polyaniline nano fiber |
| CN105199082A (en) * | 2015-10-16 | 2015-12-30 | 北京化工大学 | Method for preparing porous covalent organic material by using ultra-gravity method |
| CN105330855A (en) * | 2014-07-08 | 2016-02-17 | 中国科学院宁波材料技术与工程研究所 | Polyaniline and preparation method thereof |
| CN105949459A (en) * | 2016-05-19 | 2016-09-21 | 合肥师范学院 | Meshed polyaniline nanosheet and preparation method thereof |
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| CN1038578C (en) * | 1995-05-26 | 1998-06-03 | 北京化工大学 | Ultra-fine calcium carbonate preparation method |
| CN100497440C (en) * | 2005-04-19 | 2009-06-10 | 中国科学院金属研究所 | Production of polyaniline micro/nanometer fibre |
| CN100462303C (en) * | 2005-10-25 | 2009-02-18 | 湘潭大学 | Preparation method of ultrafine aluminium hydroxide |
| CN1323199C (en) * | 2005-12-05 | 2007-06-27 | 西安交通大学 | Preparation method of conductive polymer polyanilinc nano fiber |
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| CN103834265A (en) * | 2014-03-24 | 2014-06-04 | 中国科学院长春应用化学研究所 | Polyaniline anti-corrosive paint |
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| CN105330855A (en) * | 2014-07-08 | 2016-02-17 | 中国科学院宁波材料技术与工程研究所 | Polyaniline and preparation method thereof |
| CN105199082A (en) * | 2015-10-16 | 2015-12-30 | 北京化工大学 | Method for preparing porous covalent organic material by using ultra-gravity method |
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| CN116516685B (en) * | 2023-04-19 | 2024-03-22 | 重庆文理学院 | Preparation method of physiological monitoring multifunctional sensor |
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