CN1326910C - Method for preparing polyaniline without emulsified Nano granule - Google Patents
Method for preparing polyaniline without emulsified Nano granule Download PDFInfo
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Abstract
The present invention belongs to the field of a preparation method for polyaniline nanometer particles. The preparation method for non-emulsified nanometer particle polyaniline of the present invention has the following steps: aniline and sulfoacid phenylamine derivatives are added to acid media to sufficiently dissolve so as to form monomer solution; oxydant is added in the acid media to sufficiently dissolve to form oxydant solution; then, the oxydant solution is dropped in the monomer solution so that the polymerization is initiated until the reaction is complete. The preparation method of the present invention is simple, additives, such as emulsifying agents, or dispersing agents, etc., do not need to be added, and acquired nanometer particles are not required to wash and remove the additives. The preparation method provides a new path for the synthesis of polyaniline nanometer particles, and solves the machining problem of insoluble polyaniline. The yield of sulfonic polyaniline nanometer particles prepared by the present invention reaches 80.4%, the electric conductivity reaches 0.56 s/cm, and the particle diameter is 11 nm to 300 nm. The acquired nanometer particles can be directly applied to the preparation aspects of antistatic films, antistatic coatings, anticorrosion paint, electromagnetic shielding coating layers, etc.
Description
Technical field
The invention belongs to the preparing technical field of conducting polymer nano material, particularly do not having preparation polyaniline nano particulate preparation method under the outer doping condition.
Background technology
The polyaniline of traditional method preparation is an indissoluble, can only be dissolved in the high polar solvent of minority, and processing characteristics is very poor, has greatly limited the development of its industrial application.Therefore, the preparation of workability polyaniline becomes the target of numerous scientific worker's researchs.The processed and applied that is introduced as polyaniline of nanometer notion has been brought new life in the conducting polymer composite field, the polyaniline nano material integrates the characteristics such as surface effects, small-size effect and quantum effect of its electroconductibility and nano material, and excellent characteristic makes it have more wide application prospect.Yet Tortuous Development Process has also been experienced in the nanometer research of polyaniline.Traditional preparation process polyaniline nano particulate method has microemulsion polymerization method and dispersion copolymerization method, and electrochemical polymerization recently prepares the polyaniline nano particle also report.Micro-emulsion polymerization is the simple polymerization process of a kind of preparation 10～100nm polymer particle, and the microemulsion polymerization method that is used to prepare the nano level polyaniline at present mainly contains positive micro-emulsion polymerization, conversed phase micro emulsion copolymerization and ultrasonic auxiliary conversed phase micro emulsion copolymerization method.Not only particle diameter is little for the polyaniline nano particle that conversed phase micro emulsion copolymerization prepares, and degree of crystallinity is also high.But compare with the micro-emulsion polymerization of routine, the contained emulsifier content of micro-emulsion polymerization system of polyaniline is very big, its consumption is 15 to 52 times (weight multiples) of aniline monomer consumption, and gained polyaniline content is extremely low like this, and general polyaniline content is at (0.04～0.8) wt%.Sometimes also need add organic solvent in the conversed phase micro emulsion copolymerization method and make dispersion medium, this has not only increased cost greatly but also has caused environmental pollution.More fatal is, the existence of a large amount of emulsifying agents in the micro-emulsion polymerization system makes the products therefrom complicated component, usually need numerous and diverse aftertreatment (as: breakdown of emulsion, filtration, washing, product collection etc.), and product is difficult to purifying, directly influenced the physical and mechanical properties of product.Dispersion copolymerization method is also commonly used with preparation polyaniline nano particle, but all the particle diameter and the size distribution thereof of p-poly-phenyl amine have remarkably influenced for the concentration of several factors such as aniline monomer, stabilizer concentration and kind, temperature of reaction, stirring velocity, reaction times, medium, initiator type and concentration etc., the particle of gained polyaniline is bigger, is difficult to obtain nano polyaniline truly.The same with micro-emulsion polymerization, exist the drawback that the macromole stablizer of interpolation is difficult to remove equally.Nano particles of polyaniline as for the electrochemical process preparation only is to obtain specific nano-complex, is subjected to the restriction of electrode area simultaneously, is difficult to obtain a large amount of polyaniline nano particles, is unsuitable for large-scale commercial production.Therefore, be badly in need of seeking a kind of simple and preparation polyaniline nano particulate novel method of not containing outer doping with the industrialized process of promotion polyaniline.
Summary of the invention
Purpose of the present invention is exactly in order to overcome and to solve the prior art problem, provides a kind of efficient height, technology is simple, products therefrom is pure, environmentally friendly polyaniline nano particulate preparation method.
The present invention is not a kind ofly having under the conditions such as outer doping such as emulsifying agent or dispersion agent preparation polyaniline nano particulate preparation method.The present invention relates to sulfonation aniline internal stabilizer, implement means, add in nothing under the situation of emulsifying agent and stablizer and make polyaniline particle direct nanometer when synthetic by sedimentation type heterogeneous phase chemistry oxidative polymerization method.
Method for preparing polyaniline without emulsified Nano granule of the present invention is as follows:
1, preparation monomer solution: monomer aniline and comonomer are joined fully dissolving in the acid medium, form monomer solution, temperature of reaction is 0～50 ℃;
2, preparation oxidizing agent solution: oxygenant is joined fully dissolving in the acid medium, form oxidizing agent solution, temperature of reaction is 0～50 ℃;
3, oxidizing agent solution is splashed into initiated polymerization in the monomer solution, it is reacted completely promptly get the deep green polymers soln that contains the nano level copolymer pellet.
The comonomer of nano polyaniline is the sulfoacid aniline derivative shown in chemical formula (1), (2) among the present invention:
Wherein R be selected from-H ,-CH
3,-C
2H
5,-C
6H
5SO
3H or-C
6H
5SO
3Na; R
1, R
2, R
3, R
4, R
5Be selected from-H ,-CH
3,-NO
2,-F ,-Cl ,-OCH
3,-C
2H
5,-Br ,-I ,-SO
3H or-SO
3Na.
The volumetric molar concentration of reaction monomers is 0.025～0.5M among the present invention, and more excellent concentration is 0.1M～0.2M.
Among the present invention, employed acid medium is: HCl, H
2SO
4, H
3PO
4, HNO
3, CH
3COOH, HClO
4The concentration of acid medium is 0.2～3.0M, and more excellent concentration is 0.75～1.5M.
The volumetric molar concentration of oxygenant is 0.025～0.5M among the present invention, and more excellent concentration is 0.05M～0.25M.
Employed oxygenant is among the present invention: Potassium Persulphate (KPS), ammonium persulphate (APS), Sodium Persulfate, H
2O
2/ FeCl
2Oxygenant and monomeric mol ratio are 1: 4～5: 4, and more excellent mol ratio is 1: 4～5: 4.
Beneficial effect of the present invention: preparation method of the present invention is simple, need not to add additives such as emulsifying agent or dispersion agent, simplified synthesis technique, the nanoparticle that what is more important obtained is pure, need not washing and remove additive, for the preparation of polyaniline nano particulate provides new way, solved the forming process problem of indissoluble polyaniline, for its industrial application lays the first stone.Productive rate height by the sulfonated polyaniline nano particle of the present invention preparation can reach 80.4%, and the product specific conductivity can reach 0.56S/cm, and particle diameter is 11nm～300nm.The nano particle of gained can directly apply to the preparation aspect of antistatic film, antistatic coating, protective system and coating for EMI shielding etc.
Description of drawings
Figure one is 1 synthetic nano polyaniline of embodiment particle AFM photo: (a) shape appearance figure; (b): 3 dimensional drawing
Figure two is 4 synthetic nano polyanilines of embodiment particle AFM photos: (a) shape appearance figure; (b): 3 dimensional drawing
Figure three is 5 synthetic nano polyanilines of embodiment particle AFM photos: (a) shape appearance figure; (b): 3 dimensional drawing
Figure four is 7 synthetic nano polyanilines of embodiment particle AFM photos: (a) shape appearance figure; (b): 3 dimensional drawing
Embodiment
Embodiment 1
Take by weighing 2.20g aniline-2,5-disulfonic acid and 5.60g ammonium persulphate join respectively in 250mL, the 150mL vial, adding 75mL and 25mL concentration more respectively is the hydrochloric acid soln of 1.0M, stirring makes it abundant dissolving, the aniline monomer of then measuring 1.20mL joins aniline-2, in the 5-disulfonic acid solution, stirs, with vial seal put into 25 ℃ the reaction water-baths, constant temperature is more than half an hour under the high degree of agitation.
Ammonium persulfate solution is moved in the separating funnel, splash in the monomer solution initiated polymerization with 1/3 seconds speed.After oxygenant dropwises, continue reaction 24 hours, it is reacted completely.After reaction finishes, obtain containing the deep green polymers soln of nano-scale particle.Pipette the 2mL reaction solution and be diluted to 200mL, stir, leave standstill, precipitation, repetitive scrubbing, in washings, do not have SO with deionized water
4 2-(BaCl
2Check), do particle diameter test and atomic force microscope test with this sample, average particle size is 64nm, sees Fig. 1.Reacting liquid filtering, thorough washing with remainder obtain the deep green polymkeric substance, 50 ℃ of following dry weeks, get product 1.8g (polymerization yield rate is 52.7%), and its specific conductivity is 0.15S/cm.
Embodiment 2
Taking by weighing 0.87g ORTHO AMINO PHENOL SULPHONIC and 1.14g ammonium persulphate joins respectively in 250mL, the 150mL vial, the hydrochloric acid soln that adds 100mL and 50mL concentration more respectively and be 1.0M stirs and makes it abundant dissolving, the aniline monomer of then measuring 0.46mL joins in the ORTHO AMINO PHENOL SULPHONIC solution, stir, with vial seal put into 30 ℃ the reaction water-baths, constant temperature is more than half an hour under the high degree of agitation.
Ammonium persulfate solution is moved in the separating funnel, splash in the monomer solution initiated polymerization with 1/3 seconds speed.After oxygenant dropwises, continue reaction 24 hours, it is reacted completely.After reaction finishes, obtain containing the deep green polymers soln of nano level copolymer pellet.Pipette the 2mL reaction solution and be diluted to 200mL, stir, leave standstill, precipitation, repetitive scrubbing, in washings, do not have SO with deionized water
4 2-(BaCl
2Check), do the particle diameter test with this sample, it is 88.6nm that laser particle analyzer records average particle size.Reacting liquid filtering, thorough washing with remainder obtain the deep green polymkeric substance, and 50 ℃ of following dry weeks, getting its specific conductivity of product 0.39g (polymerization yield rate is 27.0%) is 0.090S/cm.
Embodiment 3
Take by weighing 2.20g aniline-2,5-disulfonic acid and 5.60g ammonium persulphate join respectively in 250mL, the 150mL vial, adding 75mL and 25mL concentration more respectively is the hydrochloric acid soln of 1.0M, stirring makes it abundant dissolving, the aniline monomer of then measuring 1.20mL joins aniline-2, in the 5-disulfonic acid solution, stirs, with vial seal put into 45 ℃ the reaction water-baths, constant temperature is more than half an hour under the high degree of agitation.
Ammonium persulfate solution is moved in the separating funnel, splash in the monomer solution initiated polymerization with 1/3 seconds speed.After oxygenant dropwises, continue reaction 24 hours, it is reacted completely.After reaction finishes, obtain containing the deep green polymers soln of nano level copolymer pellet., do the particle diameter test with the method sample thief among the embodiment 2, getting average particle size is 232nm, gets product 1.7g (polymerization yield rate is 50.2%), its specific conductivity is 0.12S/cm.
Embodiment 4
Taking by weighing 0.87g ORTHO AMINO PHENOL SULPHONIC and 1.14g ammonium persulphate joins respectively in 250mL, the 150mL vial, adding 100mL and 50mL concentration more respectively is the hydrochloric acid soln of 1M, stirring makes it abundant dissolving, the aniline monomer of then measuring 0.46mL joins in the ORTHO AMINO PHENOL SULPHONIC solution, stir, with vial seal put into 40 ℃ the reaction water-baths, constant temperature is more than half an hour under the high degree of agitation.
Ammonium persulfate solution is moved in the separating funnel, splash in the monomer solution initiated polymerization with 1/3 seconds speed.After oxygenant dropwises, continue reaction 24 hours, it is reacted completely.After reaction finishes, obtain containing the deep green polymers soln of nano level copolymer pellet.Do the particle diameter test with the method sample thief among the embodiment 2, getting average particle size is 89nm, sees Fig. 2, gets product 0.35g (polymerization yield rate is 23.7%), and its specific conductivity is 0.083S/cm.
Embodiment 5
Taking by weighing 1.35g sodium diphenylaminesulfonate and 0.57g ammonium persulphate joins respectively in 150mL, the 100mL vial, add the hydrochloric acid soln that 25mL concentration is 1.0M more respectively, stirring makes it abundant dissolving, the aniline monomer of then measuring 0.46mL joins in the diphenylamine sulfonic acid sodium solution, stir, with vial seal put into 25 ℃ the reaction water-baths, constant temperature is more than half an hour under the high degree of agitation.
Ammonium persulfate solution is moved in the separating funnel, splash in the monomer solution initiated polymerization with 1/3 seconds speed.After oxygenant dropwises, continue reaction 24 hours, it is reacted completely.After reaction finishes, obtain containing the deep green polymers soln of nano level copolymer pellet.Do the particle diameter test with the method sample thief among the embodiment 2, it is 95.1nm that laser particle analyzer records average particle size.Atomic force microscope studies show that the median size of polymer beads is 60.2nm, and minimum grain size is 11nm, as shown in Figure 3.Reacting liquid filtering, thorough washing with remainder obtain the deep green polymkeric substance, 50 ℃ of following dry weeks, get product 0.50g, and (polymerization yield rate is 27.8%), its specific conductivity is 1.3 * 10
-3S/cm.
Embodiment 6
Taking by weighing 0.40g O-methoxy-5-sulfoacid aniline and 4.56g ammonium persulphate joins respectively in 250mL, the 150mL vial, adding 70mL and 30mL concentration more respectively is the hydrochloric acid soln of 1.0M, stirring makes it abundant dissolving, the aniline monomer of then measuring 1.64mL joins in O-methoxy-5-sulfoacid aniline solution, stir, with vial seal put into 25 ℃ the reaction water-baths, constant temperature is more than half an hour under the high degree of agitation.
Ammonium persulfate solution is moved in the separating funnel, splash in the monomer solution initiated polymerization with 1/3 seconds speed.After oxygenant dropwises, continue reaction 24 hours, it is reacted completely.After reaction finishes, obtain containing the deep green polymers soln of nano level copolymer pellet.Do the particle diameter test with the method sample thief among the embodiment 2, it is 278nm that laser particle analyzer records average particle size.Reacting liquid filtering, thorough washing with remainder obtain the deep green polymkeric substance, 50 ℃ of following dry weeks, get product 1.63 (polymerization yield rate is 80.4%), and its specific conductivity is 0.30S/cm.
Embodiment 7
Taking by weighing 2.03g O-methoxy-5-sulfoacid aniline and 5.71g ammonium persulphate joins respectively in 250mL, the 150mL vial, adding 70mL and 30mL concentration more respectively is the hydrochloric acid soln of 1.0M, stirring makes it abundant dissolving, the aniline monomer of then measuring 0.91mL joins in O-methoxy-5-sulfoacid aniline solution, stir, with vial seal put into 25 ℃ the reaction water-baths, constant temperature is more than half an hour under the high degree of agitation.
Ammonium persulfate solution is moved in the separating funnel, splash in the monomer solution initiated polymerization with 1/3 seconds speed.After oxygenant dropwises, continue reaction 24 hours, it is reacted completely.After reaction finishes, obtain containing the deep green polymers soln of nano level copolymer pellet.Do the particle diameter test with the method sample thief among the embodiment 2, atomic force microscope test particle median size is 78nm, as shown in Figure 4.Reacting liquid filtering, thorough washing with remainder obtain the deep green polymkeric substance, 50 ℃ of following dry weeks, get product 1.73g (polymerization yield rate is 59.5%), and its specific conductivity is 0.13S/cm.
Embodiment 8
Take by weighing the 2.71g sodium diphenylaminesulfonate and join in the 250mL vial, take by weighing 2mg FeCl
24H
2O, measure the 0.52mL hydrogen peroxide and join in the 100mL vial, add the hydrochloric acid soln that 50mL concentration is 1.0M more respectively, stirring makes it abundant dissolving, the aniline monomer of then measuring 0.91mL joins in the diphenylamine sulfonic acid sodium solution, stir, with vial seal put into 25 ℃ the reaction water-baths, constant temperature is more than half an hour under the high degree of agitation.
Ammonium persulfate solution is moved in the separating funnel, splash in the monomer solution initiated polymerization with 1/3 seconds speed.After oxygenant dropwises, continue reaction 24 hours, it is reacted completely.After reaction finishes, obtain containing the deep green polymers soln of nano level copolymer pellet.Do the particle diameter test with the method sample thief among the embodiment 2, it is 164nm that laser particle analyzer records average particle size.Reacting liquid filtering, thorough washing with remainder obtain the deep green polymkeric substance, 50 ℃ of following dry weeks, get product 1.08g, and (polymerization yield rate is 30.2%), its specific conductivity is 2.1 * 10
-3S/cm.
Embodiment 9
Taking by weighing 1.35g sodium diphenylaminesulfonate and 0.57g ammonium persulphate joins respectively in 150mL, the 100mL vial, add the hydrochloric acid soln that 25mL concentration is 0.2M more respectively, stirring makes it abundant dissolving, the aniline monomer of then measuring 0.46mL joins in the diphenylamine sulfonic acid sodium solution, stir, with vial seal put into 25 ℃ the reaction water-baths, constant temperature is more than half an hour under the high degree of agitation.
Ammonium persulfate solution is moved in the separating funnel, splash in the monomer solution initiated polymerization with 1/3 seconds speed.After oxygenant dropwises, continue reaction 24 hours, it is reacted completely.After reaction finishes, obtain containing the deep green polymers soln of nano level copolymer pellet.Do the particle diameter test with the method sample thief among the embodiment 2, it is 173nm that laser particle analyzer records average particle size.Reacting liquid filtering, thorough washing with remainder obtain the deep green polymkeric substance, 50 ℃ of following dry weeks, get product 0.45g, and (polymerization yield rate is 26.4%), its specific conductivity is 7.73 * 10
-4S/cm.
Embodiment 10
Taking by weighing 2.03g O-methoxy-5-sulfoacid aniline and 5.71g ammonium persulphate joins respectively in 250mL, the 150mL vial, adding 70mL and 30mL concentration more respectively is the hydrochloric acid soln of 3.0M, stirring makes it abundant dissolving, the aniline monomer of then measuring 0.91mL joins in O-methoxy-5-sulfoacid aniline solution, stir, with vial seal put into 25 ℃ the reaction water-baths, constant temperature is more than half an hour under the high degree of agitation.
Ammonium persulfate solution is moved in the separating funnel, splash in the monomer solution initiated polymerization with 1/3 seconds speed.After oxygenant dropwises, continue reaction 24 hours, it is reacted completely.After reaction finishes, obtain containing the deep green polymers soln of nano level copolymer pellet.Do the particle diameter test with the method sample thief among the embodiment 2, it is 181nm that laser particle analyzer records average particle size.Reacting liquid filtering, thorough washing with remainder obtain the deep green polymkeric substance, 50 ℃ of following dry weeks, get product 1.2g (polymerization yield rate is 41.4%), and its specific conductivity is 0.56S/cm.
Embodiment 11
Taking by weighing 2.03g O-methoxy-5-sulfoacid aniline and 5.71g ammonium persulphate joins respectively in 250mL, the 150mL vial, adding 70mL and 30mL concentration more respectively is the sulphuric acid soln of 1.0M, stirring makes it abundant dissolving, the aniline monomer of then measuring 0.91mL joins in O-methoxy-5-sulfoacid aniline solution, stir, with vial seal put into 25 ℃ the reaction water-baths, constant temperature is more than half an hour under the high degree of agitation.
Ammonium persulfate solution is moved in the separating funnel, splash in the monomer solution initiated polymerization with 1/3 seconds speed.After oxygenant dropwises, continue reaction 24 hours, it is reacted completely.After reaction finishes, obtain containing the deep green polymers soln of nano level copolymer pellet.Do the particle diameter test with the method sample thief among the embodiment 2, it is 148nm that laser particle analyzer records average particle size.Reacting liquid filtering, thorough washing with remainder obtain the deep green polymkeric substance, 50 ℃ of following dry weeks, get product 1.73g (polymerization yield rate is 60.8%), and its specific conductivity is 0.13S/cm.
Embodiment 12
Taking by weighing 1.02g O-methoxy-5-sulfoacid aniline and 2.85g ammonium persulphate joins respectively in 150mL, the 100mL vial, adding 30mL and 20mL concentration more respectively is the acetic acid solution of 1.0M, stirring makes it abundant dissolving, the aniline monomer of then measuring 0.46mL joins in O-methoxy-5-sulfoacid aniline solution, stir, with vial seal put into 25 ℃ the reaction water-baths, constant temperature is more than half an hour under the high degree of agitation.
Ammonium persulfate solution is moved in the separating funnel, splash in the monomer solution initiated polymerization with 1/3 seconds speed.After oxygenant dropwises, continue reaction 24 hours, it is reacted completely.After reaction finishes, obtain containing the deep green polymers soln of nano level copolymer pellet.Do the particle diameter test with the method sample thief among the embodiment 2, it is 127nm that laser particle analyzer records average particle size.Reacting liquid filtering, thorough washing with remainder obtain the deep green polymkeric substance, 50 ℃ of following dry weeks, get product 0.87g (polymerization yield rate is 61.2%), and its specific conductivity is 0.20S/cm.
Taking by weighing 2.71g sodium diphenylaminesulfonate and 1.14g ammonium persulphate joins respectively in 150mL, the 100mL vial, add the salpeter solution that 25mL concentration is 1.0M more respectively, stirring makes it abundant dissolving, the aniline monomer of then measuring 0.91mL joins in the diphenylamine sulfonic acid sodium solution, stir, with vial seal put into 25 ℃ the reaction water-baths, constant temperature is more than half an hour under the high degree of agitation.
Ammonium persulfate solution is moved in the separating funnel, splash in the monomer solution initiated polymerization with 1/3 seconds speed.After oxygenant dropwises, continue reaction 24 hours, it is reacted completely.After reaction finishes, obtain containing the deep green polymers soln of nano level copolymer pellet.Do the particle diameter test with the method sample thief among the embodiment 2, it is 156nm that laser particle analyzer records average particle size.Reacting liquid filtering, thorough washing with remainder obtain the deep green polymkeric substance, 50 ℃ of following dry weeks, get product 0.92g, and (polymerization yield rate is 25.6%), its specific conductivity is 1.12 * 10
-3S/cm.
More than raw material that each embodiment uses and main technical details see Table one, experimental result sees Table two.
Table one raw material used herein and technical parameter
In the following table
A is an aniline-2, and 5-disulfonic acid B is an ORTHO AMINO PHENOL SULPHONIC
C is that sodium diphenylaminesulfonate D is O-methoxy-5-sulfoacid aniline
| Embodiment | Aniline ml | The aniline sulfonic acid | Oxygenant | Acid medium | Temperature ℃ |
| Embodiment 1 | 1.2 | A 2.20g | APS 5.60g | HCl 1.0M | 25 |
| Embodiment 2 | 0.46 | B 0.87g | APS 1.14g | HCl 1.0M | 30 |
| Embodiment 3 | 1.2 | A 2.20g | APS 5.60g | HCl 1.0M | 45 |
| Embodiment 4 | 0.46 | B 0.87g | APS 1.14g | HCl 1.0M | 40 |
| Embodiment 5 | 0.46 | C 1.35g | APS 0.57g | HCl 1.0M | 25 |
| Embodiment 6 | 1.64 | D 0.40g | APS 4.56g | HCl 1.0M | 25 |
| Embodiment 7 | 0.91 | D 2.03g | APS 5.71g | HCl 1.0M | 25 |
| Embodiment 8 | 0.91 | C 2.71g | FeCl 2·4H 2O2mg H 2O 2 0.52mL | HCl 1.0M | 25 |
| Embodiment 9 | 0.46 | C 1.35g | APS 0.57g | HCl 0.2M | 25 |
| Embodiment 10 | 0.91 | D 2.03g | APS 5.71g | HCl 3.0M | 25 |
| Embodiment 11 | 0.91 | D 2.03g | APS 5.71g | H 2SO 4 1.0M | 25 |
| Embodiment 12 | 0.46 | D 1.02g | APS 2.85g | HAc 1.0M | 25 |
| |
0.91 | C 2.71g | APS 1.14g | HNO 3 1.0M | 25 |
The conductive polyaniline nanometer particle performance test that table two the present invention is prepared
| Embodiment | Product particle diameter nm | Polymerization yield rate | Specific conductivity (s/cm) |
| Embodiment 1 | 64 | 52.7％ | 0.15 |
| Embodiment 2 | 88.6 | 27.0％ | 0.09 |
| Embodiment 3 | 232 | 50.2％ | 0.12 |
| Embodiment 4 | 89 | 23.7％ | 0.083 |
| Embodiment 5 | 95.1 | 27.8％ | 1.3×10 -3 |
| Embodiment 6 | 278 | 80.4％ | 0.30 |
| Embodiment 7 | 78 | 59.5％ | 0.13 |
| Embodiment 8 | 164 | 30.2％ | 2.1×10 -3 |
| Embodiment 9 | 173 | 26.4％ | 7.73×10 -4 |
| Embodiment 10 | 181 | 41.4％ | 0.56 |
| Embodiment 11 | 148 | 60.8％ | 0.13 |
| Embodiment 12 | 127 | 61.2％ | 0.2 |
| |
156 | 25.6％ | 1.12×10 -3 |
Claims (9)
1, the preparation method of nano particle polyaniline, this method steps is as follows:
(1), preparation monomer solution: monomer aniline and comonomer are joined fully dissolving in the acid medium, form monomer solution, temperature of reaction is 0～50 ℃;
(2), preparation oxidizing agent solution: oxygenant is joined fully dissolving in the acid medium, form oxidizing agent solution, temperature of reaction is 0～50 ℃;
(3), oxidizing agent solution is splashed into initiated polymerization in the monomer solution, it is reacted completely promptly get the deep green polymers soln that contains the nano level copolymer pellet;
Comonomer described in the step (1) is the sulfoacid aniline derivative shown in chemical formula (1) or (2):
Wherein R be selected from-H ,-CH
3-C
2H
5-C
6H
5SO
3H or-C
6H
5SO
3Na; R
1, R
2, R
3, R
4, R
5Be selected from-H ,-CH
3,-NO
2,-F ,-Cl ,-OCH
3,-C
2H
5,-Br ,-I ,-SO
3H or-SO
3Na.
2, the preparation method of nano particle polyaniline as claimed in claim 1, the volumetric molar concentration that it is characterized in that reaction monomers is 0.025～0.5M.
3, the preparation method of nano particle polyaniline as claimed in claim 2, the volumetric molar concentration that it is characterized in that reaction monomers is 0.1～0.2M.
4, the preparation method of nano particle polyaniline as claimed in claim 1 is characterized in that employed oxygenant is: Potassium Persulphate, ammonium persulphate, Sodium Persulfate or H
2O
2And FeCl
2
5, the preparation method of nano particle polyaniline as claimed in claim 4, the volumetric molar concentration that it is characterized in that oxygenant is 0.025～0.5M.
6, the preparation method of nano particle polyaniline as claimed in claim 5, the volumetric molar concentration that it is characterized in that oxygenant is 0.05M～0.25M.
7, the preparation method of nano particle polyaniline as claimed in claim 1 is characterized in that employed acid medium is: HCl, H
2SO
4, H
3PO
4, HNO
3, CH
3COOH or HClO
4
8, the preparation method of nano particle polyaniline as claimed in claim 7, the concentration that it is characterized in that employed acid medium is 0.2～3.0M.
9, the preparation method of nano particle polyaniline as claimed in claim 8, the concentration that it is characterized in that employed acid medium is 0.75～1.5M.
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|---|---|---|---|---|
| CN100526367C (en) * | 2007-08-28 | 2009-08-12 | 厦门大学 | Method for preparing polyaniline nano thread |
| CN101643544B (en) * | 2009-09-03 | 2011-05-04 | 余姚中国塑料城塑料研究院有限公司 | Sulfonated polyaniline and a preparation method thereof |
| CN101983978B (en) * | 2010-10-21 | 2012-10-10 | 中国科学院苏州纳米技术与纳米仿生研究所 | Preparation method of monodisperse conducting polymer microballoon |
| CN102250344A (en) * | 2011-06-03 | 2011-11-23 | 重庆大学 | Aniline/2,3-dimethylaniline copolymer |
| US9217725B2 (en) | 2011-11-25 | 2015-12-22 | Tongji University | Compositions and methods for detecting lead ions |
| CN103937486B (en) * | 2014-01-26 | 2016-03-02 | 南京大学 | A kind of fluorescent nano probe and its preparation method and application |
| CN103936983B (en) * | 2014-04-10 | 2017-06-06 | 东华大学 | A kind of method that application PLA regulation and control prepare polyaniline micro/nano structure |
| CN105949459B (en) * | 2016-05-19 | 2019-02-19 | 合肥师范学院 | A kind of netted polyaniline nano piece and preparation method thereof |
| CN109281177A (en) * | 2018-08-31 | 2019-01-29 | 黄勇 | A kind of dedicated easy antistatic cleaning finishing agent of dacron |
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