CN101215418A - Method for preparing polyaniline/attapulgite clay nano conductive composite material - Google Patents
Method for preparing polyaniline/attapulgite clay nano conductive composite material Download PDFInfo
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Abstract
The invention relates to a process for preparing polyaniline/concave-convex soil conducting nanocomposites, the process comprises first adding concave-convex soil raw material in deionized water to prepare slurry, adding aniline in the slurry under the condition of continuously stirring, and further adding inorganic acid and oxidation agent solution to have an oxidative polymerization, and preparing polyaniline/concave-convex soil conducting nanocomposites which is doped with inorganic acid, second, removing the waste of the preparing polyaniline/concave-convex soil conducting nanocomposites which is doped with inorganic acid, and then pumping and filtering, and washing with deionized water till filter liquor takes achromatic color and neutrality, and getting eigen state polyaniline/concave-convex soil conducting nanocomposites, third, newly dispersing in water to form slurry body, and then adding organic acid in the slurry to dope, finally, pumping and filtering, flushing off free organic acid with deionized water, placing in 40-80 DEG C to dry, at last getting atrovirens powder body through grinding. The invention lowers production cost, and the performance of polyaniline/concave-convex soil conducting nanocomposites which is prepared is more excellent.
Description
Technical field
The present invention relates to the preparation field in conducing composite material field, specifically, relate to a kind of preparation method of polyaniline/attapulgite nano-electric conducting composite material.
Background technology
Polyaniline (PANI) have structure variation, doping attitude and unadulterated environmental stability good, be easy to synthesize, advantage such as physicals excellence, monomer are cheap and easy to get, particularly it has unique Protonic Acid Doping Mechanism and good conductivity, and being considered to has one of conductive polymers of actual application prospect most.But the polyaniline comprehensive mechanical property is poor, solvability and meltability extreme difference and the bad shortcoming of rheological property make its method that is difficult to adopt traditional forming process, and this has just seriously hindered its large-scale promotion application in every field.Therefore, processing characteristics how to improve polyaniline is the key that promotes polyaniline practicability.People have carried out unremitting effort for this reason, find that the composite modification technology of polyaniline and inorganic materials can overcome the shortcoming of its poor in processability, and obtain to have multiple functional matrix material, fields such as these functional materialss can be widely used in that electricity is led, magnetic conductance, electric demonstration, electrostatic shielding, microwave absorbing, anti-corrosion of metal and photochemical catalysis.
The preparation method of polyaniline/inorganic nano conducing composite material has electrochemical synthesis method, situ aggregation method, emulsion polymerization and blending method etc.Wherein, the chemical oxidation situ aggregation method is widely adopted because of industrial applicability is convenient.For example: one step in-situ oxidizing-polymerizing aniline prepares the adulterated fibrous polyaniline/diatomite nano-conductive composite material of mineral acid on the diatomite surface in Chinese patent ZL 200510023159.6 propositions, but the thermostability of the adulterated conductive nano composites of mineral acid is not good enough, and its conductivity can prolong and variation gradually in time.The polyaniline that Chinese patent ZL 200510095422.2 proposes to coat through in-situ polymerization on whiskers such as potassium titanate prepares conductive whiskers, the shortcoming that the adulterated conductive whiskers of its mineral acid exists conductivity to descend gradually equally, and there is doping problem bigger than normal in organic acid doped conductive whiskers.The polyaniline that Chinese patent ZL 200510057168.7 proposes to coat through in-situ polymerization on inorganic oxide conductive powder prepares conductive polymer composite, but the aniline amount and the dopant acid amount that add are all too big, the cost costliness.For the resistance toheat that makes polyaniline/inorganic nano conducing composite material improves a lot, dopant acid (particularly Ang Gui organic acid) consumption significantly reduces, has excellent conductivity simultaneously, the present invention has adopted " dopings-Tuo assorted-doping again " prepared organic acid doped polyaniline/attapulgite nano-electric conducting composite material.
Attapulgite be a kind of layer of chain-like structure contain Shuifu County's zeopan clay mineral, its crystal is needle-like, fibrous agrregate, the diameter of single fiber crystalline substance is about 20nm, length can reach several μ m, is a kind of natural monodimension nanometer material.At present, be nucleome with the nano-attapulgite, adopt the polyaniline/attapulgite nano-electric conducting composite material of " doping-Tuo mixes-mixes " prepared excellent electric conductivity to yet there are no report.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of polyaniline/attapulgite nano-electric conducting composite material, this method has reduced manufacturing cost, and the polyaniline/attapulgite nano-electric conducting composite material of preparing has good electrical conductivity and thermostability.
The technical scheme that realizes above-mentioned purpose is: a kind of preparation method of polyaniline/attapulgite nano-electric conducting composite material, and processing step is as follows:
1) preparation of attapulgite slurry: in deionized water, add the attapulgite raw material, make the account for slurry of ionized water quality 3%～25% of attapulgite quality;
2) preparation of mineral acid doped polyaniline/attapulgite clay nano conductive composite material: under continuous stirring condition, in slurry, add aniline, the aniline quality accounts for 20%～80% of attapulgite quality, in slurry, add mineral acid again, the mol ratio of mineral acid and aniline is 3.8～15.5: 1, in above-mentioned slurry, slowly splash into the oxidizing agent solution that concentration is 0.42～1.72mol/L then, the mol ratio of oxygenant and aniline is 0.5～2.0: 1, oxypolymerization 2～24 hours, polymerization temperature are 10～60 ℃;
3) mineral acid doped polyaniline/attapulgite clay nano conductive composite material take off assorted: take off assorted with taking off assorted agent to the adulterated polyaniline/attapulgite nano-electric conducting composite material of mineral acid, suction filtration then, and be washed till filtrate with deionized water and be colourless neutrality, obtain polyaniline in eigenstate/attapulgite clay nano composite material;
4) preparation of organic acid doped polyaniline/attapulgite clay nano conductive composite material: polyaniline in eigenstate/attapulgite clay nano composite material is dispersed in again forms slurry in the water, adding organic acid then in slurry mixes again, the mol ratio of organic acid and aniline is 0.24～1.20: 1, doping time is 2～24 hours again, the temperature of mixing again is 10～60 ℃, during constantly stir;
5) aftertreatment: with the polyaniline/attapulgite nano-electric conducting composite material slurries suction filtration of organic acid doped gained, and with deionized water with free (promptly mix reaction) organic acid flush away, place 40～80 ℃ of dryings down then, obtain blackish green powder through pulverizing.
Aniline among the present invention can be the aniline of aniline or replacement.
Wherein said oxygenant is a kind of in persulfuric acid salt, dichromic acid salt, iodates, bromic acid salt, chloric acid salt, chlorous acid salt, hydrogen peroxide and the iron(ic) chloride.When using ammonium persulphate as oxygenant, speed of response is milder, is easy to control so initiator system of ammonium persulfate of the present invention.
The wherein said the 2nd) Bu mineral acid is a kind of in hydrochloric acid, sulfuric acid, nitric acid and the phosphoric acid.
The wherein said the 3rd) the assorted agent of taking off in step is a kind of in ammoniacal liquor, sodium hydroxide and the potassium hydroxide.
The wherein said the 4th) Bu organic acid is one or more in p-methyl benzenesulfonic acid, camphorsulfonic acid, sulphosalicylic acid, Witco 1298 Soft Acid, naphthene sulfonic acid, dinonylnaphthalene sulfonic acid and the dibutyl naphthene sulfonic acid.
After adopting technique scheme, polyaniline and attapulgite are carried out compound preparation polyaniline/attapulgite nano-electric conducting composite material can realize organic phase and inorganic compound on nanoscale, reduce the cost of conductive nano composites, and give the conductivity of this matrix material excellence.Not only give full play to different specialities organic and inorganic materials, combined the characteristic of nano material again, realized mutual supplement with each other's advantages.
Along with the prolongation of time, the electroconductibility of the adulterated conductive nano composites of mineral acid can descend gradually, so poor heat stability.This technology is taken off assorted to the mineral acid doped polyaniline/attapulgite clay nano conductive composite material of gained, and then mix again with high boiling point, macromolecule organic acid, obtain organic acid doped polyaniline/attapulgite nano-electric conducting composite material at last, effectively improved the thermostability of matrix material.In addition, compare with disposable organic acid doped technology, this technology can obtain the polyaniline/attapulgite nano-electric conducting composite material of conductivity excellence under less organic acid doped amount, thereby has saved expensive organic acid consumption, has reduced cost.
Embodiment
The present invention is further detailed explanation below in conjunction with embodiment.
The mensuration of conductive nano composites powder volume specific resistance among the present invention: be with in the graduated polyacrylic ester Glass tubing one, put into 10.0g polyaniline/attapulgite nano-electric conducting composite material powder, pressure with 1MPa is pressed in the conductive nano composites powder between the two metal sheets, measure resistance between two metal sheets with universal meter, the volume specific resistance that is calculated as follows the conductive nano composites powder according to the thickness and the sectional area of conductive nano composites powder layer.
R
sp＝R×A/L
In the formula: R
SpBe volume specific resistance (Ω cm) that R is actual measurement resistance (Ω), A is the internal diameter sectional area (cm of Glass tubing
2), L is the height (cm) of conductive nano composites powder layer.
Embodiment 1: the slurry that 8g attapulgite and 50g deionized water is made, HCl solution and the 2.4g aniline of 150mL2.0mol/L join in the there-necked flask, stir; The 5.9g ammonium persulphate is dissolved in the 30mL deionized water, and dropwise splashes into initiated polymerization in the slurry with dropping funnel; Stir oxypolymerization 4 hours down at 20 ℃; Suction filtration takes off assortedly with 1.0mol/L ammoniacal liquor, be washed till filtrate with deionized water again and be colourless neutrality; The 2.0g Witco 1298 Soft Acid is dissolved in the 100mL deionized water, manages slurry with bluish voilet polyaniline in eigenstate/attapulgite composite material and join in the three-necked flask, stir under 20 ℃ and mix, doping time is 3 hours again; Suction filtration is used deionized water wash, and is dry in 40 ℃ of baking ovens, obtains blackish green powder through grinding.The volume specific resistance of prepared polyaniline/attapulgite nano-electric conducting composite material is 500 Ω cm.
Embodiment 2: among the embodiment 1, except that Witco 1298 Soft Acid was 10.0g, other operations were identical with embodiment 1.The volume specific resistance of prepared polyaniline/attapulgite nano-electric conducting composite material is 100 Ω cm.
Embodiment 3: the slurry that 8g attapulgite and 32g deionized water is made, HCl solution and the 1.6g aniline of 150mL2.0mol/L join in the there-necked flask, stir; The 3.9g ammonium persulphate is dissolved in the 20mL deionized water, and dropwise splashes into initiated polymerization in the slurry with dropping funnel; Stir oxypolymerization 5 hours down at 20 ℃; Suction filtration takes off assortedly with 2.0mol/L ammoniacal liquor, be washed till filtrate with deionized water again and be colourless neutrality; The 2.4g Witco 1298 Soft Acid is dissolved in the 100mL deionized water, manages slurry with bluish voilet polyaniline in eigenstate/attapulgite composite material and join in the three-necked flask, stir under 20 ℃ and mix, doping time is 4 hours again; Suction filtration is used deionized water wash, and is dry in 50 ℃ of baking ovens, obtains blackish green powder through grinding.The volume specific resistance of prepared polyaniline/attapulgite nano-electric conducting composite material is 2000 Ω cm.
Embodiment 4: the slurry that 8g attapulgite and 267g deionized water is made, HCl solution and the 6.4g aniline of 150mL2.0mol/L join in the there-necked flask, stir; The 15.7g ammonium persulphate is dissolved in the 80mL deionized water, and dropwise splashes into initiated polymerization in the slurry with dropping funnel; Stir oxypolymerization 5 hours down at 20 ℃; Suction filtration takes off assortedly with 2.0mol/L ammoniacal liquor, be washed till filtrate with deionized water again and be colourless neutrality; The 9.6g Witco 1298 Soft Acid is dissolved in the 100mL deionized water, manages slurry with bluish voilet polyaniline in eigenstate/attapulgite composite material and join in the three-necked flask, stir under 20 ℃ and mix, doping time is 4 hours again; Suction filtration is used deionized water wash, and is dry in 50 ℃ of baking ovens, obtains blackish green powder through grinding.The volume specific resistance of prepared polyaniline/attapulgite nano-electric conducting composite material is 1 Ω cm.
Embodiment 5: the slurry that 8g attapulgite and 50g deionized water is made, HCl solution and the 2.4g aniline of 50mL2.0mol/L join in the there-necked flask, stir; The 5.9g ammonium persulphate is dissolved in the 30mL deionized water, and dropwise splashes into initiated polymerization in the slurry with dropping funnel; Stir oxypolymerization 6 hours down at 20 ℃; Suction filtration takes off assortedly with 3.0mol/L ammoniacal liquor, be washed till filtrate with deionized water again and be colourless neutrality; The 3.6g Witco 1298 Soft Acid is dissolved in the 100mL deionized water, manages slurry with bluish voilet polyaniline in eigenstate/attapulgite composite material and join in the three-necked flask, stir under 20 ℃ and mix, doping time is 5 hours again; Suction filtration is used deionized water wash, and is dry in 60 ℃ of baking ovens, obtains blackish green powder through grinding.The volume specific resistance of prepared polyaniline/attapulgite nano-electric conducting composite material is 40 Ω cm.
Embodiment 6: among the embodiment 5, except that the HCl solution of 2.0mol/L is the 200mL, other operations are identical with embodiment 5, and the volume specific resistance of prepared polyaniline/attapulgite nano-electric conducting composite material is 25 Ω cm.
Embodiment 7: the slurry that 8g attapulgite and 50g deionized water is made, HCl solution and the 2.4g aniline of 100mL2.0mol/L join in the there-necked flask, stir; The 2.9g ammonium persulphate is dissolved in the 30mL deionized water, and dropwise splashes into initiated polymerization in the slurry with dropping funnel; Stir oxypolymerization 3 hours down at 20 ℃; Suction filtration takes off assortedly with 2.0mol/L ammoniacal liquor, be washed till filtrate with deionized water again and be colourless neutrality; The 3.6g Witco 1298 Soft Acid is dissolved in the 100mL deionized water, manages slurry with bluish voilet polyaniline in eigenstate/attapulgite composite material and join in the three-necked flask, stir under 20 ℃ and mix, doping time is 6 hours again; Suction filtration is used deionized water wash, and is dry in 70 ℃ of baking ovens, obtains blackish green powder through grinding.The volume specific resistance of prepared polyaniline/attapulgite conducing composite material is 850 Ω cm.
Embodiment 8: among the embodiment 7, removing ammonium persulphate is 11.8g, is dissolved in outside the 30mL deionized water, and other operations are identical with embodiment 7, and the volume specific resistance of prepared polyaniline/attapulgite nano-electric conducting composite material is 2000 Ω cm.
Embodiment 9: the slurry that 8g attapulgite and 50g deionized water is made, HCl solution and the 2.4g aniline of 100mL2.0mol/L join in the there-necked flask, stir; The 5.9g ammonium persulphate is dissolved in the 30mL deionized water, and dropwise splashes into initiated polymerization in the slurry with dropping funnel; Stir oxypolymerization 24 hours down at 10 ℃; Suction filtration takes off assortedly with 2.0mol/L ammoniacal liquor, be washed till filtrate with deionized water again and be colourless neutrality; The 3.6g Witco 1298 Soft Acid is dissolved in the 100mL deionized water, managing slurry with bluish voilet polyaniline in eigenstate/attapulgite composite material joins in the three-necked flask, stir under 10 ℃ and mix, doping time is 24 hours again, obtains the blackish green slurry of sticky starchiness; Suction filtration is used deionized water wash, and is dry in 80 ℃ of baking ovens, obtains blackish green powder through grinding.The volume specific resistance of prepared polyaniline/attapulgite nano-electric conducting composite material is 20 Ω cm.
Embodiment 10: among the embodiment 9, remove the polymerization and the temperature of mixing again and be 60 ℃, polymerization and again doping time be outside 2 hours, other operations are identical with embodiment 9, the volume specific resistance of prepared polyaniline/attapulgite nano-electric conducting composite material is 1000 Ω cm.
Embodiment 11: the slurry that 8g attapulgite and 50g deionized water is made, HCl solution and the 2.4g aniline of 100mL2.0mol/L join in the there-necked flask, stir; The 5.9g ammonium persulphate is dissolved in the 30mL deionized water, and dropwise splashes into initiated polymerization in the slurry with dropping funnel; Stir oxypolymerization 4 hours down at 20 ℃; Suction filtration takes off assortedly with 2.0mol/L ammoniacal liquor, be washed till filtrate with deionized water again and be colourless neutrality; The 3.6g Witco 1298 Soft Acid is dissolved in the 100mL deionized water, managing slurry with bluish voilet polyaniline in eigenstate/attapulgite composite material joins in the three-necked flask, stir under 20 ℃ and mix, doping time is 4 hours again, obtains the blackish green slurry of sticky starchiness; Suction filtration is used deionized water wash, and is dry in 80 ℃ of baking ovens, obtains blackish green powder through grinding.The volume specific resistance of prepared polyaniline/attapulgite nano-electric conducting composite material is 18 Ω cm.
Embodiment 12: among the embodiment 11, removing oxygenant is 4.2g iron(ic) chloride, adulterated again organic acid is the 5.5g p-methyl benzenesulfonic acid, taking off assorted agent is outside the NaOH aqueous solution of 1.0mol/L, other operations are identical with embodiment 11, and the volume specific resistance of prepared polyaniline/attapulgite nano-electric conducting composite material is 357 Ω cm.
Embodiment 13: among the embodiment 11, removing oxygenant is the 7.6g potassium bichromate, mineral acid is the phosphate aqueous solution of 100mL1.0mol/L, adulterated again organic acid is the 2.6g camphorsulfonic acid, taking off assorted agent is outside the KOH aqueous solution of 3.0mol/L, other operations are identical with embodiment 11, and the volume specific resistance of prepared polyaniline/attapulgite nano-electric conducting composite material is 255 Ω cm.
Embodiment 14: among the embodiment 11, removing mineral acid is the sulphuric acid soln of 100mL1.0mol/L, oxygenant is the 5.5g Potassium Iodate, adulterated again organic acid is outside the 2.3g naphthene sulfonic acid, other operations are identical with embodiment 11, and the volume specific resistance of prepared polyaniline/attapulgite nano-electric conducting composite material is 160 Ω cm.
Embodiment 15: among the embodiment 11, removing mineral acid is the salpeter solution of 100mL3.0mol/L, oxygenant is the 4.3g potassium bromate, adulterated again organic acid is outside the 5.1g dinonylnaphthalene sulfonic acid, other operations are identical with embodiment 11, and the volume specific resistance of prepared polyaniline/attapulgite nano-electric conducting composite material is 180 Ω cm.
Embodiment 16: among the embodiment 11, removing oxygenant is the 2.8g sodium chlorate, adulterated again organic acid is outside the 2.9g dibutyl naphthene sulfonic acid, and other operations are identical with embodiment 11, and the volume specific resistance of prepared polyaniline/attapulgite nano-electric conducting composite material is 200 Ω cm.
Embodiment 17: among the embodiment 11, removing oxygenant is the 2.4g Textone, adulterated again organic acid is outside 2.0g Witco 1298 Soft Acid and the 1.3g sulphosalicylic acid, other operations are identical with embodiment 11, and the volume specific resistance of prepared polyaniline/attapulgite nano-electric conducting composite material is 120 Ω cm.
Embodiment 18: embodiment 11 prepared polyaniline/attapulgite nano-electric conducting composite materials are put into 80 ℃ of bakings 5 hours, record its volume specific resistance after the taking-up and remain unchanged; Conductive nano composites is put into 150 ℃ of bakings 2 hours, recording its volume specific resistance after the taking-up is 140 Ω cm again.
Comparative example 1 a: doping process that embodiment 11 is changed into Witco 1298 Soft Acid: the slurry that 8g attapulgite and 50g deionized water is made, the aqueous solution and the 2.4g aniline that the 3.6g Witco 1298 Soft Acid is dissolved in the 100mL deionized water join in the there-necked flask, stir; The 5.9g ammonium persulphate is dissolved in the 30mL deionized water, and dropwise splashes into initiated polymerization in the slurry with dropping funnel; Stir oxypolymerization 12 hours down at 20 ℃; Suction filtration is used deionized water wash, and is dry in 80 ℃ of baking ovens, obtains yellow blackish green powder through grinding.Prepared polyaniline/attapulgite nano-electric conducting composite material volume specific resistance is 140 Ω cm.
Comparative example 2 a: doping process that embodiment 12 is changed into p-methyl benzenesulfonic acid: the slurry that 8g attapulgite and 50g deionized water is made, the aqueous solution and the 2.4g aniline that the 5.5g p-methyl benzenesulfonic acid is dissolved in the 100mL deionized water join in the there-necked flask, stir; 4.2g iron(ic) chloride is dissolved in the 30mL deionized water, and dropwise splashes into initiated polymerization in the slurry with dropping funnel; Stir oxypolymerization 12 hours down at 20 ℃; Suction filtration is used deionized water wash, and is dry in 80 ℃ of baking ovens, obtains blackish green powder through grinding.Prepared polyaniline/attapulgite nano-electric conducting composite material volume specific resistance is 250 Ω cm.
Comparative example 3: with the comparison of the dopant acid consumption of conductive nano composites among the embodiment 11: the slurry that 8g attapulgite and 50g deionized water is made, the aqueous solution and the 2.4g aniline that the 7.2g Witco 1298 Soft Acid is dissolved in the 100mL deionized water join in the there-necked flask, stir; The 5.9g ammonium persulphate is dissolved in the 30mL deionized water, and dropwise splashes into initiated polymerization in the slurry with dropping funnel; Stir oxypolymerization 12 hours down at 20 ℃; Suction filtration is used deionized water wash, and is dry in 80 ℃ of baking ovens, obtains yellow blackish green powder through grinding.Prepared polyaniline/attapulgite nano-electric conducting composite material volume specific resistance is 18 Ω cm.
Comparative example 4: with the comparison of the thermostability of conductive nano composites among the embodiment 18: slurry, 200mL2.0mol/L hydrochloric acid and 3.2g aniline that 8g attapulgite and 50g deionized water is made join in the there-necked flask, stir; The 7.8g ammonium persulphate is dissolved in the 100mL deionized water, and dropwise splashes into initiated polymerization in the slurry with dropping funnel; Stir oxypolymerization 12 hours down at 20 ℃; Suction filtration is used deionized water wash, and drying is 2.5 hours in 80 ℃ of baking ovens, obtains blackish green powder through grinding.Prepared polyaniline/attapulgite nano-electric conducting composite material volume specific resistance is 20 Ω cm.This conductive nano composites is continued to dry by the fire 5 hours down at 80 ℃, and recording the conductive nano composites volume specific resistance after the taking-up is 200 Ω cm; And this conductive nano composites was directly dried by the fire 2 hours down at 150 ℃, it is non-conductive to record matrix material after the taking-up.
Claims (5)
1. the preparation method of a polyaniline/attapulgite nano-electric conducting composite material is characterized in that processing step is as follows:
1) preparation of attapulgite slurry: in deionized water, add the attapulgite raw material, make the account for slurry of ionized water quality 3%～25% of attapulgite quality;
2) preparation of mineral acid doped polyaniline/attapulgite clay nano conductive composite material: under continuous stirring condition, in slurry, add aniline, the aniline quality accounts for 20%～80% of attapulgite quality, in slurry, add mineral acid again, the mol ratio of mineral acid and aniline is 3.8～15.5: 1, in above-mentioned slurry, slowly splash into the oxidizing agent solution that concentration is 0.42～1.72mol/L then, the mol ratio of oxygenant and aniline is 0.5～2.0: 1, oxypolymerization 2～24 hours, polymerization temperature are 10～60 ℃;
3) mineral acid doped polyaniline/attapulgite clay nano conductive composite material take off assorted: take off assorted with taking off assorted agent to the adulterated polyaniline/attapulgite nano-electric conducting composite material of mineral acid, suction filtration then, and be washed till filtrate with deionized water and be colourless neutrality, obtain polyaniline in eigenstate/attapulgite clay nano composite material;
4) preparation of organic acid doped polyaniline/attapulgite clay nano conductive composite material: polyaniline in eigenstate/attapulgite clay nano composite material is dispersed in again forms slurry in the water, adding organic acid then in slurry mixes again, the mol ratio of organic acid and aniline is 0.24～1.20: 1, doping time is 2～24 hours again, the temperature of mixing again is 10～60 ℃, during constantly stir;
5) aftertreatment: with the polyaniline/attapulgite nano-electric conducting composite material slurries suction filtration of organic acid doped gained, and with deionized water with free organic acid flush away, place then 40～80 ℃ down dry, obtain blackish green powder through pulverizing.
2. the preparation method of polyaniline/attapulgite nano-electric conducting composite material according to claim 1 is characterized in that: described oxygenant is a kind of in persulfuric acid salt, dichromic acid salt, iodates, bromic acid salt, chloric acid salt, chlorous acid salt, hydrogen peroxide and the iron(ic) chloride.
3. the preparation method of polyaniline/attapulgite nano-electric conducting composite material according to claim 1 is characterized in that: the described the 2nd) mineral acid of step is a kind of in hydrochloric acid, sulfuric acid, nitric acid and the phosphoric acid.
4. the preparation method of polyaniline/attapulgite nano-electric conducting composite material according to claim 1 is characterized in that: the described the 3rd) the assorted agent of taking off of step is a kind of in ammoniacal liquor, sodium hydroxide and the potassium hydroxide.
5. the preparation method of polyaniline/attapulgite nano-electric conducting composite material according to claim 1 and 2, it is characterized in that: the described the 4th) organic acid of step is one or more in p-methyl benzenesulfonic acid, camphorsulfonic acid, sulphosalicylic acid, Witco 1298 Soft Acid, naphthene sulfonic acid, dinonylnaphthalene sulfonic acid and the dibutyl naphthene sulfonic acid.
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