CN107151323A - A kind of preparation method of polypyrrole/nano antimony tin oxide/attapulgite conductive composite material - Google Patents
A kind of preparation method of polypyrrole/nano antimony tin oxide/attapulgite conductive composite material Download PDFInfo
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- CN107151323A CN107151323A CN201710274452.2A CN201710274452A CN107151323A CN 107151323 A CN107151323 A CN 107151323A CN 201710274452 A CN201710274452 A CN 201710274452A CN 107151323 A CN107151323 A CN 107151323A
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/0605—Polycondensates containing five-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
- C08G73/0611—Polycondensates containing five-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with only one nitrogen atom in the ring, e.g. polypyrroles
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
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- C08K3/346—Clay
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- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Abstract
The invention discloses a kind of preparation method of polypyrrole/nano antimony tin oxide/attapulgite conductive composite material, it includes the preparation of nano antimony tin oxide aqueous precursor gel, the preparation of nano antimony tin oxide/attapulgite composite material, the preparation of polypyrrole/nano antimony tin oxide/attapulgite conductive composite material.It is of the invention first with SnCl4·5H2O and SbCl3For raw material, the inner conducting layer of nano antimony tin oxide formation has been coated in attapulgite's surface using sol-gal process, again using dodecyl sodium sulfate as dopant, ammonium persulfate is oxidant, the chemical oxidising polymerisation of pyrroles is carried out in the suspension system of nano antimony tin oxide/attapulgite composite material, the outer conducting layer of polypyrrole formation in nano antimony tin oxide/attapulgite composite material Surface coating, make obtained conducing composite material that not only there is higher electrical conductivity and mechanical strength, also there is excellent heat endurance, inoxidizability, weatherability, mechanical ductility and processability.
Description
Technical field
The present invention relates to a kind of preparation method of conductive material, and in particular to a kind of polypyrrole/nano antimony tin oxide/bumps
The preparation method of rod soil conducing composite material.
Background technology
Attapulgite is the clay mineral of zeopan containing Shuifu County of a kind of layer of chain structure, and its crystal is in needle-like, fiber
Shape aggregate, the brilliant diameter of single fiber is in 20nm or so, and length, up to several μm, is a kind of natural 1-dimention nano material
Material.In coating industry, attapulgite can be used to make up the deficiency of some thickeners and dispersant, preferable effect has been obtained
Really.Attapulgite can be used as the thickener, stop-off gent and levelling agent of coating, the exterior coating that is particularly suitable for use in, roof paint, structure
Coating and gelling coating.Wherein conductive attapulgite is also used as a kind of functional material, has in antistatic coating extensive
Application.
Nano antimony tin oxide is as a kind of novel and multifunctional powder, with visible light transmissivity is high, electrical conductivity is high, can reflect
The features such as infrared ray.With traditional anti-static material, such as carbon black, surfactant, metal-powder are compared, nano tin dioxide
Antimony has obvious advantage, is mainly manifested in good electric conductivity, light-coloured transparent, good weatherability and stability and low
Infrared emittance in terms of, be a kind of extremely potential novel and multifunctional conductive material.For reduction nano antimony tin oxide
Use cost or improve the colourity of original nano antimony tin oxide（Navy blue such as tin-antiomony oxide weakens as light gray）, Ke Yitong
Chemical method is crossed on some white powder surfaces（Such as white attapulgite）Coat nano antimony tin oxide formation composite conductive powder
Body, so as to reduce production cost.
Polypyrrole is one kind in conducting polymer, and its conductance is up to 220scm-1Left and right, with good electrochemistry and
Chemistry redox stability, its electrical conductivity can keep stable in the 2-3, be the best conducting polymer of conductive stability it
One.But pure polypyrrole also has very important defect simultaneously, such as mechanical ductility is poor, processing difficulties, comprehensive mechanical property
Energy difference etc., modified must be applied, and composite modified be particularly with the compound of inorganic matter of wherein polypyrrole is to solve its processing
The most effective approach of performance and mechanical property.Resulting polypyrrole/inorganic conductive composite is combined with inorganic matter, was both had
The excellent electric conductivity of polypyrrole, has the unique physical and chemical performance of inorganic matter again.Therefore, the present invention have studied a kind of polypyrrole/
The preparation method of nano antimony tin oxide/attapulgite conductive composite material, by by attapulgite, nano antimony tin oxide, poly- pyrrole
Cough up three kinds of materials be mutually combined it is mutually modified, not only with higher electrical conductivity and mechanical strength, also with excellent thermally-stabilised
Property, inoxidizability, weatherability, mechanical ductility and processability.
The content of the invention
It is an object of the invention to provide a kind of system of polypyrrole/nano antimony tin oxide/attapulgite conductive composite material
Attapulgite, nano antimony tin oxide, three kinds of materials of polypyrrole are mutually combined and are mutually modified by Preparation Method, the present invention, not only have
Higher electrical conductivity and mechanical strength, also with excellent heat endurance, inoxidizability, weatherability, mechanical ductility and processing
Property.
To achieve the above object, the present invention is adopted the following technical scheme that：
A kind of preparation method of polypyrrole/nano antimony tin oxide/attapulgite conductive composite material, comprises the following steps：
（1）According to mass ratio 1:0.05-0.15 is by SnCl4·5H2O and SbCl3It is well mixed, then according to solid-to-liquid ratio 1:20-30
Add mixture in absolute ethyl alcohol, the Macrogol 600 equivalent to mixture quality 3-5% is added after stirring, and
Solution PH=2-3 is adjusted for 25% ammonia spirit with mass fraction, 30- is stirred with 1500-2500r/min rotating speed at room temperature
50min, still aging 5-10h, centrifuge jello, remove after supernatant liquor, are washed, then centrifuged again with ethanol,
Repeated washing is centrifuged 3-4 times, obtains nano antimony tin oxide aqueous precursor gel；
（2）According to mass ratio 1:0.3-0.4 brightens nano antimony tin oxide aqueous precursor gel and purification the attapulgite after processing
Mixing, 20-40min is stirred under 2000-3000r/min rotating speed, supercritical CO is then carried out2Dry, dry after the completion of with
2-3 DEG C/min speed is warming up to 380-440 DEG C, is incubated 1-2h, then be warming up to 550-600 DEG C, guarantor with 1-2 DEG C/min speed
Warm 2-3h, is cooled to room temperature, obtains nano antimony tin oxide/attapulgite composite material；
（3）Mass fraction is made it is according to nano antimony tin oxide/attapulgite composite material obtained above ultrasonic agitation that adds water
8-12% slurries；Then add pyrroles equivalent to nano antimony tin oxide/attapulgite composite material quality 30-40% and
20-30% dodecyl sodium sulfate, 10-15min is stirred under 800-1200r/min rotating speed；Finally dissolve ammonium persulfate into
In the water of 25-30 times of quality, the mol ratio of ammonium persulfate and pyrroles are 1-1.5:1, then be quickly adding into above-mentioned slurries in 15-
Stirring reaction 2-4h under 20 DEG C of temperature and 1000-1500r/min rotating speed, suction filtration, and be washed with deionized to filtrate and be
It is colourless, by filter cake in drying 4-7h at 60-70 DEG C, grind, sieving produces required polypyrrole/nano antimony tin oxide/concave convex rod
Native conducing composite material.
Step（1）Described in centrifugation rotating speed be 4000-6000r/min, the time is 20-40min.
Step（2）Described in supercritical CO2Drying condition is：Supercritical CO2Flow be 15-25ml/min, temperature is
40-45 DEG C, pressure is 10-15MPa, and drying time is 4-6h.
Step（2）Described in the purification of attapulgite brighten processing and comprise the following steps：
（1）Attapulgite is crushed, is crossed after 80-120 mesh sieves, is calcined 1-2h at 680-740 DEG C, is cooled to room temperature；Then press
According to solid-to-liquid ratio 1:Attapulgite after roasting is added in the hydrochloric acid solution that molar concentration is 1mol/L by 10-15, then carries out height
Impulse electric field processing is pressed, electric-field intensity is 20-30kV/cm, and impulse electric field frequency is 200-300Hz, and processing time is 8-12s,
Heating water bath stirs 30-40min to 65-75 DEG C under 1000-1500r/min rotating speeds after being disposed, and filtering, filter residue steams
Distilled water is washed to neutrality, is dried, and is crushed, finely ground, crosses 100-150 mesh sieves；
（2）According to solid-to-liquid ratio 1:20-30 is by step（1）Obtained attapulgite is added to the water, 2000-3000r/min's
Stirring pulping under rotating speed and under 70-80 DEG C of bath temperature, obtains attapulgite suspension, then into attapulgite suspension
The acrylamide-sodium acrylate copolymer of the calgon and 5-10% equivalent to attapulgite quality 8-12% is added,
40-50min is stirred under 800-1200r/min rotating speed, then 20-30min is centrifuged under 5000-6000r/min rotating speed,
1-2h is stood, supernatant liquor is sucked with siphonage, same location is added water, repeats settle, stand, sucking supernatant liquor above
Operation 3-4 times, 6-8h is dried by solid product at 70-80 DEG C；
（3）According to solid-to-liquid ratio 1:20-25 is by step（2）It is molten that obtained attapulgite is added to the oxalic acid that molar concentration is 1mol/L
In liquid, the titanium trichloride equivalent to attapulgite quality 3-5% is added, microwave is heated to 70-80 DEG C, and microwave power is 600-
800W, stirs 10-15min under 1500-2500r/min rotating speed, filtering, filter residue distilled water washes clean, Ran Hou
3-5h is dried at 100-110 DEG C, then 2-3h is calcined at 560-620 DEG C, room temperature is cooled to, it is finely ground, 150-200 mesh sieves are crossed, i.e.,
Obtain required attapulgite.
Step（3）Described in ultrasonic power be 200-400W.
Beneficial effects of the present invention：
It is of the invention first with SnCl4·5H2O and SbCl3For raw material, nanometer has been coated in attapulgite's surface using sol-gel process
Tin-antiomony oxide formation inner conducting layer, then by dopant of dodecyl sodium sulfate, ammonium persulfate be oxidant, nano oxidized
The chemical oxidising polymerisation of pyrroles is carried out in the suspension system of tin antimony/attapulgite composite material, in nano antimony tin oxide/concave convex rod
The outer conducting layer of soil composite material Surface coating polypyrrole formation, makes obtained polypyrrole/nano antimony tin oxide/attapulgite
Conducing composite material not only has higher electrical conductivity and mechanical strength, also with excellent heat endurance, inoxidizability, weather-proof
Property, mechanical ductility and processability.
Embodiment
Embodiment 1
A kind of preparation method of polypyrrole/nano antimony tin oxide/attapulgite conductive composite material, comprises the following steps：
（1）According to mass ratio 1:0.05 by SnCl4·5H2O and SbCl3It is well mixed, then according to solid-to-liquid ratio 1:20 by mixture
It is added in absolute ethyl alcohol, the Macrogol 600 equivalent to mixture quality 3% is added after stirring, and use mass fraction
Solution PH=2 are adjusted for 25% ammonia spirit, 50min, still aging 5h are stirred with 1500r/min rotating speed at room temperature, from
Heart separating gel thing, is removed after supernatant liquor, is washed, then centrifuged again with ethanol, and repeated washing is centrifuged 3 times, is received
Rice tin-antiomony oxide aqueous precursor gel；
（2）According to mass ratio 1:0.3, which brightens nano antimony tin oxide aqueous precursor gel and purification the attapulgite after processing, mixes,
40min is stirred under 2000r/min rotating speed, supercritical CO is then carried out2Dry, with 2 DEG C/min speed after the completion of drying
380 DEG C are warming up to, 2h is incubated, then 550 DEG C are warming up to 1 DEG C/min speed, 3h is incubated, is cooled to room temperature, obtains nano oxygen
Change tin antimony/attapulgite composite material；
（3）Mass fraction is made it is according to nano antimony tin oxide/attapulgite composite material obtained above ultrasonic agitation that adds water
8% slurries；Then the pyrroles equivalent to nano antimony tin oxide/attapulgite composite material quality 30% and the ten of 20% are added
Dialkyl sulfonates, 15min is stirred under 800r/min rotating speed；In the water for finally dissolving ammonium persulfate into 25 times of quality, mistake
The mol ratio of ammonium sulfate and pyrroles are 1:1, then the rotating speed in 15 DEG C of temperature and 1000r/min is quickly adding into above-mentioned slurries
Lower stirring reaction 4h, suction filtration, and it is colourless to be washed with deionized to filtrate, by filter cake in drying 7h at 60 DEG C, is ground, mistake
Sieve, produces required polypyrrole/nano antimony tin oxide/attapulgite conductive composite material.
Step（1）Described in centrifugation rotating speed be 4000r/min, the time is 40min.
Step（2）Described in supercritical CO2Drying condition is：Supercritical CO2Flow be 15ml/min, temperature is 40
DEG C, pressure is 10MPa, and drying time is 6h.
Step（2）Described in the purification of attapulgite brighten processing and comprise the following steps：
（1）Attapulgite is crushed, is crossed after 80 mesh sieves, is calcined 2h at 680 DEG C, is cooled to room temperature；Then according to solid-to-liquid ratio 1:
10 are added to the attapulgite after roasting in the hydrochloric acid solution that molar concentration is 1mol/L, then carry out at high-pressure pulse electric
Reason, electric-field intensity is 20kV/cm, and impulse electric field frequency is 200Hz, and processing time is 12s, and heating water bath is to 65 after being disposed
DEG C, 40min is stirred under 1000r/min rotating speeds, is filtered, filter residue is washed with distilled water to neutrality, is dried, is crushed, finely ground, mistake
100 mesh sieves；
（2）According to solid-to-liquid ratio 1:20 by step（1）Obtained attapulgite is added to the water, under 2000r/min rotating speed with
And stirring pulping under 70 DEG C of bath temperatures, obtain attapulgite suspension, then added into attapulgite suspension equivalent to
The calgon of attapulgite quality 8% and 5% acrylamide-sodium acrylate copolymer, are stirred under 800r/min rotating speed
50min is mixed, then 30min is centrifuged under 5000r/min rotating speed, 1h is stood, sucks supernatant liquor with siphonage, add water
To same location, repeat settle, stand above, suck supernatant liquor operation 3 times, solid product is dried into 8h at 70 DEG C；
（3）According to solid-to-liquid ratio 1:20 by step（2）Obtained attapulgite is added to the oxalic acid solution that molar concentration is 1mol/L
In, the titanium trichloride equivalent to attapulgite quality 3% is added, microwave is heated to 70 DEG C, and microwave power is 600W,
15min is stirred under 1500r/min rotating speed, is filtered, filter residue distilled water washes clean, then the dry 5h at 100 DEG C, then
3h is calcined at 560 DEG C, room temperature is cooled to, it is finely ground, 150 mesh sieves are crossed, required attapulgite is produced.
Step（3）Described in ultrasonic power be 200W.
Embodiment 2
A kind of preparation method of polypyrrole/nano antimony tin oxide/attapulgite conductive composite material, comprises the following steps：
（1）According to mass ratio 1:0.1 by SnCl4·5H2O and SbCl3It is well mixed, then according to solid-to-liquid ratio 1:25 by mixture
It is added in absolute ethyl alcohol, the Macrogol 600 equivalent to mixture quality 4% is added after stirring, and use mass fraction
Solution PH=2.5 are adjusted for 25% ammonia spirit, 40min, still aging 8h are stirred with 2000r/min rotating speed at room temperature,
Jello is centrifuged, is removed after supernatant liquor, is washed, then centrifuged again with ethanol, repeated washing is centrifuged 3 times, is obtained
Nano antimony tin oxide aqueous precursor gel；
（2）According to mass ratio 1:0.35 attapulgite for brightening nano antimony tin oxide aqueous precursor gel and purification after processing is mixed
Close, 30min is stirred under 2500r/min rotating speed, supercritical CO is then carried out2Dry, with 2.5 DEG C/min's after the completion of drying
Speed is warming up to 410 DEG C, is incubated 1.5h, then is warming up to 580 DEG C with 1.5 DEG C/min speed, is incubated 2.5h, is cooled to room temperature,
Obtain nano antimony tin oxide/attapulgite composite material；
（3）Mass fraction is made it is according to nano antimony tin oxide/attapulgite composite material obtained above ultrasonic agitation that adds water
10% slurries；Then the pyrroles equivalent to nano antimony tin oxide/attapulgite composite material quality 35% and the ten of 25% are added
Dialkyl sulfonates, 12min is stirred under 1000r/min rotating speed；In the water for finally dissolving ammonium persulfate into 27 times of quality, mistake
The mol ratio of ammonium sulfate and pyrroles are 1.2:1, then turn in 18 DEG C of temperature and 1200r/min is quickly adding into above-mentioned slurries
The lower stirring reaction 3h of speed, suction filtration, and it is colourless to be washed with deionized to filtrate, by filter cake in drying 6h at 65 DEG C, is ground, mistake
Sieve, produces required polypyrrole/nano antimony tin oxide/attapulgite conductive composite material.
Step（1）Described in centrifugation rotating speed be 5000r/min, the time is 30min.
Step（2）Described in supercritical CO2Drying condition is：Supercritical CO2Flow be 20ml/min, temperature is 42
DEG C, pressure is 12MPa, and drying time is 5h.
Step（2）Described in the purification of attapulgite brighten processing and comprise the following steps：
（1）Attapulgite is crushed, is crossed after 100 mesh sieves, is calcined 1.5h at 710 DEG C, is cooled to room temperature；Then according to solid-to-liquid ratio
1:12 are added to the attapulgite after roasting in the hydrochloric acid solution that molar concentration is 1mol/L, then carry out at high-pressure pulse electric
Reason, electric-field intensity is 25kV/cm, and impulse electric field frequency is 250Hz, and processing time is 10s, and heating water bath is to 70 after being disposed
DEG C, 35min is stirred under 1200r/min rotating speeds, is filtered, filter residue is washed with distilled water to neutrality, is dried, is crushed, finely ground, mistake
120 mesh sieves；
（2）According to solid-to-liquid ratio 1:25 by step（1）Obtained attapulgite is added to the water, under 2500r/min rotating speed with
And stirring pulping under 75 DEG C of bath temperatures, obtain attapulgite suspension, then added into attapulgite suspension equivalent to
The calgon of attapulgite quality 10% and 8% acrylamide-sodium acrylate copolymer, under 1000r/min rotating speed
45min is stirred, then 25min is centrifuged under 5500r/min rotating speed, 1.5h is stood, supernatant liquor is sucked with siphonage, then
Add water to same location, repeat settle, stand above, suck supernatant liquor operation 3 times, solid product is dried at 75 DEG C
7h；
（3）According to solid-to-liquid ratio 1:22 by step（2）Obtained attapulgite is added to the oxalic acid solution that molar concentration is 1mol/L
In, the titanium trichloride equivalent to attapulgite quality 4% is added, microwave is heated to 75 DEG C, and microwave power is 700W,
12min is stirred under 2000r/min rotating speed, is filtered, filter residue distilled water washes clean, then the dry 4h at 105 DEG C, then
2.5h is calcined at 590 DEG C, room temperature is cooled to, it is finely ground, 180 mesh sieves are crossed, required attapulgite is produced.
Step（3）Described in ultrasonic power be 300W.
Embodiment 3
A kind of preparation method of polypyrrole/nano antimony tin oxide/attapulgite conductive composite material, comprises the following steps：
（1）According to mass ratio 1:0.15 by SnCl4·5H2O and SbCl3It is well mixed, then according to solid-to-liquid ratio 1:30 by mixture
It is added in absolute ethyl alcohol, the Macrogol 600 equivalent to mixture quality 5% is added after stirring, and use mass fraction
Solution PH=3 are adjusted for 25% ammonia spirit, 30min, still aging 10h are stirred with 2500r/min rotating speed at room temperature, from
Heart separating gel thing, is removed after supernatant liquor, is washed, then centrifuged again with ethanol, and repeated washing is centrifuged 4 times, is received
Rice tin-antiomony oxide aqueous precursor gel；
（2）According to mass ratio 1:0.4, which brightens nano antimony tin oxide aqueous precursor gel and purification the attapulgite after processing, mixes,
20min is stirred under 3000r/min rotating speed, supercritical CO is then carried out2Dry, with 3 DEG C/min speed after the completion of drying
440 DEG C are warming up to, 1h is incubated, then 600 DEG C are warming up to 2 DEG C/min speed, 2h is incubated, is cooled to room temperature, obtains nano oxygen
Change tin antimony/attapulgite composite material；
（3）Mass fraction is made it is according to nano antimony tin oxide/attapulgite composite material obtained above ultrasonic agitation that adds water
12% slurries；Then the pyrroles equivalent to nano antimony tin oxide/attapulgite composite material quality 40% and the ten of 30% are added
Dialkyl sulfonates, 10min is stirred under 1200r/min rotating speed；In the water for finally dissolving ammonium persulfate into 30 times of quality, mistake
The mol ratio of ammonium sulfate and pyrroles are 1.5:1, then turn in 20 DEG C of temperature and 1500r/min is quickly adding into above-mentioned slurries
The lower stirring reaction 2h of speed, suction filtration, and it is colourless to be washed with deionized to filtrate, by filter cake in drying 4h at 70 DEG C, is ground, mistake
Sieve, produces required polypyrrole/nano antimony tin oxide/attapulgite conductive composite material.
Step（1）Described in centrifugation rotating speed be 6000r/min, the time is 20min.
Step（2）Described in supercritical CO2Drying condition is：Supercritical CO2Flow be 25ml/min, temperature is 45
DEG C, pressure is 15MPa, and drying time is 4h.
Step（2）Described in the purification of attapulgite brighten processing and comprise the following steps：
（1）Attapulgite is crushed, is crossed after 120 mesh sieves, is calcined 1h at 740 DEG C, is cooled to room temperature；Then according to solid-to-liquid ratio 1:
15 are added to the attapulgite after roasting in the hydrochloric acid solution that molar concentration is 1mol/L, then carry out at high-pressure pulse electric
Reason, electric-field intensity is 30kV/cm, and impulse electric field frequency is 300Hz, and processing time is 8s, and heating water bath is to 75 after being disposed
DEG C, 30min is stirred under 1500r/min rotating speeds, is filtered, filter residue is washed with distilled water to neutrality, is dried, is crushed, finely ground, mistake
150 mesh sieves；
（2）According to solid-to-liquid ratio 1:30 by step（1）Obtained attapulgite is added to the water, under 3000r/min rotating speed with
And stirring pulping under 80 DEG C of bath temperatures, obtain attapulgite suspension, then added into attapulgite suspension equivalent to
The calgon of attapulgite quality 12% and 10% acrylamide-sodium acrylate copolymer, under 1200r/min rotating speed
40min is stirred, then 20min is centrifuged under 6000r/min rotating speed, 2h is stood, supernatant liquor is sucked with siphonage, then add
Water repeats settle, stand above, sucks supernatant liquor operation 4 times, solid product is dried into 6h at 80 DEG C to same location；
（3）According to solid-to-liquid ratio 1:25 by step（2）Obtained attapulgite is added to the oxalic acid solution that molar concentration is 1mol/L
In, the titanium trichloride equivalent to attapulgite quality 5% is added, microwave is heated to 80 DEG C, and microwave power is 800W,
10min is stirred under 2500r/min rotating speed, is filtered, filter residue distilled water washes clean, then the dry 3h at 110 DEG C, then
2h is calcined at 620 DEG C, room temperature is cooled to, it is finely ground, 200 mesh sieves are crossed, required attapulgite is produced.
Step（3）Described in ultrasonic power be 400W.
Claims (5)
1. a kind of preparation method of polypyrrole/nano antimony tin oxide/attapulgite conductive composite material, it is characterised in that including
Following steps：
(1) according to mass ratio 1:0.05-0.15 is by SnCl4·5H2O and SbCl3It is well mixed, then according to solid-to-liquid ratio 1:20-30
Add mixture in absolute ethyl alcohol, the Macrogol 600 equivalent to mixture quality 3-5% is added after stirring, and
Solution PH=2-3 is adjusted for 25% ammonia spirit with mass fraction, 30- is stirred with 1500-2500r/min rotating speed at room temperature
50min, still aging 5-10h, centrifuge jello, remove after supernatant liquor, are washed, then centrifuged again with ethanol,
Repeated washing is centrifuged 3-4 times, obtains nano antimony tin oxide aqueous precursor gel；
(2) according to mass ratio 1:0.3-0.4 brightens nano antimony tin oxide aqueous precursor gel and purification the attapulgite after processing
Mixing, 20-40min is stirred under 2000-3000r/min rotating speed, supercritical CO is then carried out2Dry, dry after the completion of with
2-3 DEG C/min speed is warming up to 380-440 DEG C, is incubated 1-2h, then be warming up to 550-600 DEG C, guarantor with 1-2 DEG C/min speed
Warm 2-3h, is cooled to room temperature, obtains nano antimony tin oxide/attapulgite composite material；
(3) mass fraction is made it is according to nano antimony tin oxide/attapulgite composite material obtained above ultrasonic agitation that adds water
8-12% slurries；Then add pyrroles equivalent to nano antimony tin oxide/attapulgite composite material quality 30-40% and
20-30% dodecyl sodium sulfate, 10-15min is stirred under 800-1200r/min rotating speed；Finally dissolve ammonium persulfate into
In the water of 25-30 times of quality, the mol ratio of ammonium persulfate and pyrroles are 1-1.5:1, then be quickly adding into above-mentioned slurries in 15-
Stirring reaction 2-4h under 20 DEG C of temperature and 1000-1500r/min rotating speed, suction filtration, and be washed with deionized to filtrate and be
It is colourless, by filter cake in drying 4-7h at 60-70 DEG C, grind, sieving produces required polypyrrole/nano antimony tin oxide/concave convex rod
Native conducing composite material.
2. a kind of preparation side of polypyrrole/nano antimony tin oxide/attapulgite conductive composite material according to claim 1
Method, it is characterised in that step（1）Described in centrifugation rotating speed be 4000-6000r/min, the time is 20-40min.
3. a kind of preparation side of polypyrrole/nano antimony tin oxide/attapulgite conductive composite material according to claim 1
Method, it is characterised in that step（2）Described in supercritical CO2Drying condition is：Supercritical CO2Flow be 15-25ml/min,
Temperature is 40-45 DEG C, and pressure is 10-15MPa, and drying time is 4-6h.
4. a kind of preparation side of polypyrrole/nano antimony tin oxide/attapulgite conductive composite material according to claim 1
Method, it is characterised in that step（2）Described in the purification of attapulgite brighten processing and comprise the following steps：
（1）Attapulgite is crushed, is crossed after 80-120 mesh sieves, is calcined 1-2h at 680-740 DEG C, is cooled to room temperature；Then press
According to solid-to-liquid ratio 1:Attapulgite after roasting is added in the hydrochloric acid solution that molar concentration is 1mol/L by 10-15, then carries out height
Impulse electric field processing is pressed, electric-field intensity is 20-30kV/cm, and impulse electric field frequency is 200-300Hz, and processing time is 8-12s,
Heating water bath stirs 30-40min to 65-75 DEG C under 1000-1500r/min rotating speeds after being disposed, and filtering, filter residue steams
Distilled water is washed to neutrality, is dried, and is crushed, finely ground, crosses 100-150 mesh sieves；
（2）According to solid-to-liquid ratio 1:20-30 is by step（1）Obtained attapulgite is added to the water, 2000-3000r/min's
Stirring pulping under rotating speed and under 70-80 DEG C of bath temperature, obtains attapulgite suspension, then into attapulgite suspension
The acrylamide-sodium acrylate copolymer of the calgon and 5-10% equivalent to attapulgite quality 8-12% is added,
40-50min is stirred under 800-1200r/min rotating speed, then 20-30min is centrifuged under 5000-6000r/min rotating speed,
1-2h is stood, supernatant liquor is sucked with siphonage, same location is added water, repeats settle, stand, sucking supernatant liquor above
Operation 3-4 times, 6-8h is dried by solid product at 70-80 DEG C；
（3）According to solid-to-liquid ratio 1:20-25 is by step（2）It is molten that obtained attapulgite is added to the oxalic acid that molar concentration is 1mol/L
In liquid, the titanium trichloride equivalent to attapulgite quality 3-5% is added, microwave is heated to 70-80 DEG C, and microwave power is 600-
800W, stirs 10-15min under 1500-2500r/min rotating speed, filtering, filter residue distilled water washes clean, Ran Hou
3-5h is dried at 100-110 DEG C, then 2-3h is calcined at 560-620 DEG C, room temperature is cooled to, it is finely ground, 150-200 mesh sieves are crossed, i.e.,
Obtain required attapulgite.
5. a kind of preparation side of polypyrrole/nano antimony tin oxide/attapulgite conductive composite material according to claim 1
Method, it is characterised in that step（3）Described in ultrasonic power be 200-400W.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114921096A (en) * | 2022-06-15 | 2022-08-19 | 瓮福（集团）有限责任公司 | Method for preparing attapulgite/polypyrrole composite material based on iron-containing wastewater |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101559348A (en) * | 2009-06-03 | 2009-10-21 | 南京工业大学 | Adsorbent for separating CO2 from gas containing CH4 and/or N2, preparation method and application thereof |
| CN101818000A (en) * | 2009-03-14 | 2010-09-01 | 兰州理工大学 | Method for removing iron and whitening for iron-containing attapulgite clay |
| CN101898765A (en) * | 2010-07-30 | 2010-12-01 | 淮阴工学院 | Method for effectively dispersing depolymerization and preventing secondary agglomeration of attapulgite clay crystal bundle |
| CN101935489A (en) * | 2010-08-24 | 2011-01-05 | 中国科学院宁波材料技术与工程研究所 | Concave-convex rod conductive coating and preparation method thereof |
| CN102010197A (en) * | 2010-09-29 | 2011-04-13 | 大连交通大学 | Method for preparing antimony-doped tin oxide (ATO) nano powder |
| CN102311703A (en) * | 2011-09-28 | 2012-01-11 | 常州大学 | Aqueous polypyrrole/attapulgite electrically-conducting paint and its preparation method |
| CN104593890A (en) * | 2015-02-06 | 2015-05-06 | 江苏盛虹科技股份有限公司 | Attapulgite hybrid conductive fibers and preparation method thereof |
| CN105036355A (en) * | 2015-07-31 | 2015-11-11 | 邵素英 | Biological purification carrier for wastewater treatment |
| CN105331054A (en) * | 2015-11-19 | 2016-02-17 | 福州顺升科技有限公司 | Composite conductive film |
-
2017
- 2017-04-25 CN CN201710274452.2A patent/CN107151323A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101818000A (en) * | 2009-03-14 | 2010-09-01 | 兰州理工大学 | Method for removing iron and whitening for iron-containing attapulgite clay |
| CN101559348A (en) * | 2009-06-03 | 2009-10-21 | 南京工业大学 | Adsorbent for separating CO2 from gas containing CH4 and/or N2, preparation method and application thereof |
| CN101898765A (en) * | 2010-07-30 | 2010-12-01 | 淮阴工学院 | Method for effectively dispersing depolymerization and preventing secondary agglomeration of attapulgite clay crystal bundle |
| CN101935489A (en) * | 2010-08-24 | 2011-01-05 | 中国科学院宁波材料技术与工程研究所 | Concave-convex rod conductive coating and preparation method thereof |
| CN102010197A (en) * | 2010-09-29 | 2011-04-13 | 大连交通大学 | Method for preparing antimony-doped tin oxide (ATO) nano powder |
| CN102311703A (en) * | 2011-09-28 | 2012-01-11 | 常州大学 | Aqueous polypyrrole/attapulgite electrically-conducting paint and its preparation method |
| CN104593890A (en) * | 2015-02-06 | 2015-05-06 | 江苏盛虹科技股份有限公司 | Attapulgite hybrid conductive fibers and preparation method thereof |
| CN105036355A (en) * | 2015-07-31 | 2015-11-11 | 邵素英 | Biological purification carrier for wastewater treatment |
| CN105331054A (en) * | 2015-11-19 | 2016-02-17 | 福州顺升科技有限公司 | Composite conductive film |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114921096A (en) * | 2022-06-15 | 2022-08-19 | 瓮福（集团）有限责任公司 | Method for preparing attapulgite/polypyrrole composite material based on iron-containing wastewater |
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