CN109267199A - A kind of electrically conductive polyaniline/carbon nano-tube fibre composite material and preparation method and purposes - Google Patents
A kind of electrically conductive polyaniline/carbon nano-tube fibre composite material and preparation method and purposes Download PDFInfo
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- CN109267199A CN109267199A CN201810936717.5A CN201810936717A CN109267199A CN 109267199 A CN109267199 A CN 109267199A CN 201810936717 A CN201810936717 A CN 201810936717A CN 109267199 A CN109267199 A CN 109267199A
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- D—TEXTILES; PAPER
- D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
- D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
- D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
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- D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
- D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
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Abstract
The present invention provides a kind of electrically conductive polyaniline/carbon nano-tube fibre composite material and preparation method and purposes.The electrically conductive polyaniline/carbon nano-tube fibre composite material is by first by more carbon nano-tube fibre boundlings, acidification is impregnated in concentrated acid, removes impurity, form acidification carbon nano-tube fibre beam, then it is reacted in acid solution with aniline, in-situ deposition polyaniline, electrically conductive polyaniline enveloped carbon nanometer tube fibre bundle is formed, the method finally twisted is prepared.Electrically conductive polyaniline provided by the invention/carbon nano-tube fibre composite material conductivity with higher and tensile strength, can be used for the fields such as electromagnetic shielding material, conducting wire, heating wire or weaving.
Description
Technical field
The invention belongs to technical field of composite materials, are related to a kind of conducing composite material more particularly to a kind of conducting polyaniline
Amine/carbon nano-tube fibre composite material and preparation method and purposes.
Background technique
Carbon nanotube is as monodimension nanometer material, and light-weight, hexagonal structure connection is perfect, has many excellent power
, electricity and chemical property.Polyaniline because of pi-electron conjugated structure present in strand, with pi-electron system in strand
Expand, and gradually form valence band and conduction band, this non-localized pi-electron conjugated structure is doped to make polyaniline become conductive
State.Pi bond in the six-membered ring structure and polyaniline of carbon nanotube can act synergistically, and after the two is compound, can obtain excellent
Electric property and mechanical property.
Polyaniline and the complex method of carbon nanotube have physical blending and in-situ polymerization etc..The prior art is using object mostly
Blending method is managed, using carbon nanotube powder as in doping body incorporation polyaniline, then fiber is made in bunchy.But this method
The conductivity of fiber obtained is generally 100-1000S/m, and conductivity is lower.
CN 101235199A discloses a kind of preparation method of carbon nano-tube modified polyaniline nano fiber composite material,
By first handling carbon nanotube acidification, is then reacted in high chloro acid solution with aniline, in-situ polymerization, obtain doped carbon
Nanotube modified polyaniline nanofiber conducing composite material, but its conductivity is still lower, is no more than 20S/cm." CTAB exists
The preparation and representation of lower sulfosalisylic acid doped polyaniline/carbon nano tube compound material " (is appointed beautiful etc., " fine chemistry industry ", 2010
2 months, the 2nd phase of volume 27) carbon nanotube is surface-treated using cetyl trimethylammonium bromide (CTAB), in aniline
In hydrochloric acid solution, using ammonium persulfate as oxidant, sulfosalicylic acid is dopant, using chemical oxidization method be prepared for polyaniline/
Carbon nano tube compound material, but its conductivity is only 4.613S/cm.
If it is possible to further increase the conductivity of the composite material of polyaniline and carbon nanotube, it will help promote
Into its application and development.
Summary of the invention
It is fine in view of the deficiencies of the prior art, the present invention intends to provide a kind of electrically conductive polyaniline/carbon nanotube
Tie up composite material and preparation method and purposes.Composite material conductivity with higher and tensile strength, can be used for electromagnetism
The fields such as shielding material, conducting wire, heating wire or weaving.
To achieve this purpose, the present invention adopts the following technical scheme:
In a first aspect, the present invention provides a kind of preparation method of electrically conductive polyaniline/carbon nano-tube fibre composite material, including
Following steps:
(1) it by more carbon nano-tube fibre boundlings, is impregnated in concentrated acid, is acidified the carbon nano-tube fibre and removes impurity elimination
Matter obtains carbon nano-tube fibre beam；
(2) the carbon nano-tube fibre beam and aniline obtained step (1) in acid solution, under the conditions of existing for the oxidant into
Row reaction, obtains electrically conductive polyaniline enveloped carbon nanometer tube fibre bundle；
(3) the electrically conductive polyaniline enveloped carbon nanometer tube fibre bundle for obtaining step (2) is twisted, and obtains the conducting polyaniline
Amine/carbon nano-tube fibre composite material.
The present invention is improved by the complex method to polyaniline and carbon nanotube, and carbon nano-tube fibre is first integrated one
Then stock deposits polyaniline in its surface in situ, forms the carbon nano-tube fibre beam of electrically conductive polyaniline cladding, will finally obtain
Fibre bundle twisting, thus the composite material made conductivity with higher and tensile strength.
As the preferred technical solution of the present invention, the diameter of carbon nano-tube fibre described in step (1) is 60-70 μm；Example
It such as can be 60 μm, 61 μm, 62 μm, 63 μm, 64 μm, 65 μm, 66 μm, 67 μm, 68 μm, 69 μm or 70 μm.
Preferably, the diameter of the carbon nano-tube fibre beam is 300-500 μm；Such as it can be 300 μm, 310 μm, 320 μ
m、330μm、340μm、350μm、360μm、370μm、380μm、390μm、400μm、410μm、420μm、430μm、440μm、450
μm, 460 μm, 470 μm, 480 μm, 490 μm or 500 μm etc..
As the preferred technical solution of the present invention, concentrated acid described in step (1) is the concentrated sulfuric acid and/or concentrated nitric acid.
Preferably, the time of immersion described in step (1) is 30-60s；Such as can be 30s, 32s, 35s, 38s, 40s,
42s, 45s, 48s, 50s, 52s, 55s, 58s or 60s etc..
Preferably, after impregnating described in step (1), cleaning and drying process are also carried out.
The present invention is not particularly limited the reagent of cleaning, illustratively can be using water, acetone, ethyl alcohol etc..By clear
It washes and dries, can make between more carbon nano-tube fibres because of the Van der Waals force between the convergent force and carbon nanotube of solvent evaporation
And one is synthesized, the concentration of carbon nano-tube fibre beam is helped to improve, the conductivity of composite material and strong is further increased
Degree.
As the preferred technical solution of the present invention, the quality of carbon nano-tube fibre beam and the aniline described in step (2)
Than for 3-6:1；Such as can be 3:1,3.2:1,3.3:1,3.5:1,3.6:1,3.8:1,4:1,4.2:1,4.3:1,4.5:1,
4.6:1,4.8:1,5:1,5.2:1,5.3:1,5.5:1,5.6:1,5.8:1 or 6:1 etc..
Cooperated under above-mentioned specific ratio by carbon nano-tube fibre beam and aniline, composite material can be further increased
Conductivity and tensile strength.When carbon nano-tube fibre beam is excessive or aniline is excessive, under the performance that will lead to composite material
Drop.
Preferably, acid solution described in step (2) is the mix acid liquor of sulfosalicylic acid and sulfuric acid.
Preferably, the concentration of acid solution described in step (2) is 0.8-1.5mol/L；Such as can be 0.8mol/L,
0.9mol/L, 1mol/L, 1.1mol/L, 1.2mol/L, 1.3mol/L, 1.4mol/L or 1.5mol/L etc..
Preferably, the mass ratio of the sulfuric acid and the sulfosalicylic acid is 3-5:1；Such as can be 3:1,3.2:1,
3.3:1,3.5:1,3.6:1,3.8:1,4:1,4.2:1,4.3:1,4.5:1,4.6:1,4.8:1 or 5:1 etc..
As the preferred technical solution of the present invention, oxidant described in step (2) is the mixed of ammonium persulfate and potassium bichromate
Close object.
Preferably, the molar ratio of the ammonium persulfate and the potassium bichromate is 2-15:1；Such as can be 2:1,3:1,
4:1,5:1,6:1,7:1,8:1,9:1,10:1,11:1,12:1,13:1,14:1 or 15:1 etc..
Preferably, the mass ratio of the ammonium persulfate and the aniline is 1.25-1.5:1, for example, can be 1.25:1,
1.28:1,1.3:1,1.32:1,1.35:1,1.38:1,1.4:1,1.42:1,1.45:1,1.48:1 or 1.5:1 etc..
As the preferred technical solution of the present invention, oxidant described in step (2) is that institute is added to by way of dropwise addition
It states in acid solution.
Preferably, the oxidant 10-20min (such as 10min, 11min, 12min, 13min, 14min, 15min,
16min, 17min, 18min, 19min or 20min etc.) in be added dropwise.
Preferably, the temperature of reaction described in step (2) is 0-5 DEG C；Such as it can be 0 DEG C, 0.5 DEG C, 1 DEG C, 1.5 DEG C, 2
DEG C, 2.5 DEG C, 3 DEG C, 3.5 DEG C, 4 DEG C, 4.5 DEG C or 5 DEG C etc..
Preferably, the time of reaction described in step (2) is 6-8h；Such as can be 6h, 6.2h, 6.5h, 6.8h, 7h,
7.2h, 7.5h, 7.8h or 8h etc..
As the preferred technical solution of the present invention, the twist of twisting described in step (3) is 200-300 twirl/m；Such as it can
Be 200 twirls/m, 210 twirls/m, 220 twirls/m, 230 twirls/m, 240 twirls/m, 250 twirls/m, 260 twirls/m, 270 twirls/m, 280 twirls/m,
290 twirls/m or 300 twirls/m etc..
As the preferred technical solution of the present invention, the preparation method includes the following steps:
(1) by more 60-70 μm of diameter of carbon nano-tube fibre boundling, 30- is impregnated in the concentrated sulfuric acid and/or concentrated nitric acid
60s is acidified the carbon nano-tube fibre and removes impurity, then cleaned and dried, obtains 300-500 μm of diameter of carbon
Nanotube fibers beam is wound in winding tube；
(2) mix acid liquor for being 3-5:1 preparation 0.8-1.5mol/L by sulfuric acid and sulfosalicylic acid mass ratio, with described mixed
Conjunction acid solution is solvent, prepares aniline solution and oxidizing agent solution respectively, the carbon nano-tube fibre beam that step (1) obtains is put into institute
It states in aniline solution, the oxidizing agent solution is added dropwise under conditions of 0-5 DEG C, is added dropwise in 10-20min, keep temperature
6-8h is reacted, electrically conductive polyaniline enveloped carbon nanometer tube fibre bundle is obtained；
Wherein, the mass ratio of the carbon nano-tube fibre beam and aniline is 3-6:1, and the oxidant is by ammonium persulfate and again
15-2:1 is formed potassium chromate in molar ratio, and the mass ratio of the ammonium persulfate and aniline is 1.25-1.5:1；
(3) the electrically conductive polyaniline enveloped carbon nanometer tube fibre bundle that step (2) obtains is placed in water and is unreeled, after unreeling
Fibre bundle drying, winds again, twists through twisting mill, and the twist is 200-300 twirl/m, obtains the electrically conductive polyaniline/carbon nanometer
Pipe fibrous composite.
Second aspect, the present invention provide a kind of electrically conductive polyaniline/carbon nano-tube fibre composite material, the conducting polyaniline
Amine/carbon nano-tube fibre composite material is prepared by the method that first aspect present invention provides.
The third aspect, the present invention provides a kind of purposes of above-mentioned electrically conductive polyaniline/carbon nano-tube fibre composite material, described
Electrically conductive polyaniline/carbon nano-tube fibre composite material is for fields such as electromagnetic shielding material, conducting wire, heating wire or weavings.
Compared with prior art, the invention has the following advantages:
Electrically conductive polyaniline provided by the invention/carbon nano-tube fibre composite material conductivity with higher and stretching are strong
Degree, conductivity reach (1-2) × 105S/m, tensile strength reach 140-200MPa, can be used for electromagnetic shielding material, conducting wire,
The fields such as heating wire or weaving.
Specific embodiment
Below by specific embodiment to further illustrate the technical scheme of the present invention.Those skilled in the art should be bright
, the described embodiments are merely helpful in understanding the present invention, should not be regarded as a specific limitation of the invention.
In the embodiment of the present invention, the method for preparing carbon nano-tube fibre with FCCVD (floating catalytic chemical vapor deposition) method
It is as follows:
Ferrocene is weighed, ethyl alcohol, deionized water and thiophene that a certain amount of concentration is 99.8% are poured into, stirring, filters ultrasound
After obtain growth carbon nanotube reaction mixture (wherein mass ratio mEthyl alcohol:mFerrocene=50:1, volume ratio VEthyl alcohol:VDeionized water=50:
1, VEthyl alcohol:VThiophene=100:1).Above-mentioned reaction solution is injected in the high-temperature corundum boiler tube that temperature is 1310 DEG C with the rate of 60mL/h,
It is passed through argon gas (1.7L/min), hydrogen (5L/min) and nitrogen (30L/min).Carbon is grown in argon gas and hydrogen mixed gas stream
Carbon nanotube is at the uniform velocity pulled out from boiler tube with 4.5m/min, obtains carbon nano-tube fibre by nanotube.
The preparation method of the solution used in the embodiment of the present invention is as follows:
Mix acid liquor: it weighs sulfosalicylic acid (SSA) and is added in beaker, a certain amount of water is added and stirs evenly, uses liquid relief
Pipe takes 98% concentrated sulfuric acid (SA) to be slowly added in SSA solution, pours into container after solution is cooling, constant volume stirs evenly, and obtains
To SA-SSA mix acid liquor (the mass ratio m of 1.0mol/LSA:mSSA=4:1).Acid needed for mix acid liquor provides reaction for aniline
Property environment.
Aniline solution: aniline (AN) being added in a certain amount of above-mentioned mix acid liquor and is uniformly mixed, and is stirred by ultrasonic complete to AN
Dissolution, is configured to the aniline solution of 0.5mol/L.
Oxidizing agent solution: a certain amount of ammonium persulfate (APS) and potassium bichromate (PDS) and above-mentioned mix acid liquor are taken, by APS
It is dissolved in the mix acid liquor with PDS, the molar ratio n of APS and PDSAPS:nPDS=7.4:1, the oxidant for being configured to 0.8mol/L are molten
Liquid.
The test method of conductivity and tensile strength is as follows in the embodiment of the present invention:
Conductivity: it is tested according to the method for GBT 32993-2016；
Tensile strength: it is tested according to the method for BS ISO 11566-1996.
Embodiment 1
The present embodiment provides a kind of electrically conductive polyaniline/carbon nano-tube fibre composite material, preparation method is as follows:
(1) FCCVD method is used to prepare carbon nano-tube fibre (diameter of single-root carbon nano-tube fiber is 60-70 μm) union
30s is drawn into the concentrated sulfuric acid and impregnated to bulk by beam, is acidified carbon nano-tube fibre and removes impurity, then uses flowing water
Carbon nano-tube fibre is cleaned up, is dried carbon nano-tube fibre using continuous tunnel furnace, more carbon nano-tube fibres is shunk and closes
It at one, is formed carbon nano-tube fibre beam (330 μm of diameter), is wound in winding tube；
(2) carbon nano-tube fibre Shu Liantong winding tube is put into aniline solution together, is slowly dripped under ice-water bath (0 DEG C)
Oxidizer solution, is added dropwise with 10min, then keeps ice-water bath, is reacted 8h, is obtained electrically conductive polyaniline enveloped carbon nanometer tube
Fibre bundle；
Wherein, the mass ratio of carbon nano-tube fibre beam and aniline is 6:1, the ammonium persulfate and aniline in oxidizing agent solution
Mass ratio is 1.25:1；
(3) the electrically conductive polyaniline enveloped carbon nanometer tube fibre bundle that step (2) obtains is placed in clear water and is unreeled, then passed through
Continuous tunnel furnace drying, then winds, the fibre bundle wound is twisted with twisting mill, and the twist is 200 twirls/m, obtain electrically conductive polyaniline/
Carbon nano-tube fibre composite material.
After tested, electrically conductive polyaniline provided in this embodiment/carbon nano-tube fibre composite material conductivity be 1.5 ×
105S/m, tensile strength 160MPa.
Comparative example 1
The difference from embodiment 1 is that the carbon nano-tube fibre beam that step (1) is obtained is directly with 200 twirls/m twist
Twisting.The performance of obtained material is tested, conductivity is 6 × 104S/m, tensile strength 100MPa.
Embodiment 2
The present embodiment provides a kind of electrically conductive polyaniline/carbon nano-tube fibre composite material, preparation method is as follows:
(1) FCCVD method is used to prepare carbon nano-tube fibre (diameter of single-root carbon nano-tube fiber is 60-70 μm) union
60s is drawn into concentrated nitric acid and impregnated to bulk by beam, is acidified carbon nano-tube fibre and removes impurity, then uses flowing water
Carbon nano-tube fibre is cleaned up, is dried carbon nano-tube fibre using continuous tunnel furnace, more carbon nano-tube fibres is shunk and closes
It at one, is formed carbon nano-tube fibre beam (450 μm of diameter), is wound in winding tube；
(2) carbon nano-tube fibre Shu Liantong winding tube is put into aniline solution together, oxidant is slowly added dropwise at 5 DEG C
Solution is added dropwise with 20min, and then keeping temperature is 5 DEG C, is reacted 6h, is obtained electrically conductive polyaniline enveloped carbon nanometer tube fiber
Beam；
Wherein, the mass ratio of carbon nano-tube fibre beam and aniline is 3:1, the ammonium persulfate and aniline in oxidizing agent solution
Mass ratio is 1.5:1；
(3) the electrically conductive polyaniline enveloped carbon nanometer tube fibre bundle that step (2) obtains is placed in clear water and is unreeled, then passed through
Continuous tunnel furnace drying, then winds, the fibre bundle wound is twisted with twisting mill, and the twist is 300 twirls/m, obtain electrically conductive polyaniline/
Carbon nano-tube fibre composite material.
After tested, electrically conductive polyaniline provided in this embodiment/carbon nano-tube fibre composite material conductivity be 1.2 ×
105S/m, tensile strength 143MPa.
Comparative example 2
The difference from example 2 is that the carbon nano-tube fibre beam that step (1) is obtained is directly with 300 twirls/m twist
Twisting.The performance of obtained material is tested, conductivity is 6.3 × 104S/m, tensile strength 91MPa.
Embodiment 3
The present embodiment provides a kind of electrically conductive polyaniline/carbon nano-tube fibre composite material, preparation method is as follows:
(1) FCCVD method is used to prepare carbon nano-tube fibre (diameter of single-root carbon nano-tube fiber is 60-70 μm) union
45s is drawn into the concentrated sulfuric acid and impregnated to bulk by beam, is acidified carbon nano-tube fibre and removes impurity, then uses flowing water
Carbon nano-tube fibre is cleaned up, is dried carbon nano-tube fibre using continuous tunnel furnace, more carbon nano-tube fibres is shunk and closes
It at one, is formed carbon nano-tube fibre beam (415 μm of diameter), is wound in winding tube；
(2) carbon nano-tube fibre Shu Liantong winding tube is put into aniline solution together, oxidant is slowly added dropwise at 3 DEG C
Solution is added dropwise with 15min, and then keeping temperature is 3 DEG C, reacts 6.5h, and it is fine to obtain electrically conductive polyaniline enveloped carbon nanometer tube
Tie up beam；
Wherein, the mass ratio of carbon nano-tube fibre beam and aniline is 4:1, the ammonium persulfate and aniline in oxidizing agent solution
Mass ratio is 1.3:1；
(3) the electrically conductive polyaniline enveloped carbon nanometer tube fibre bundle that step (2) obtains is placed in clear water and is unreeled, then passed through
Continuous tunnel furnace drying, then winds, the fibre bundle wound is twisted with twisting mill, and the twist is 220 twirls/m, obtain electrically conductive polyaniline/
Carbon nano-tube fibre composite material.
After tested, electrically conductive polyaniline provided in this embodiment/carbon nano-tube fibre composite material conductivity be 1.6 ×
105S/m, tensile strength 155MPa.
Comparative example 3
Difference with embodiment 3 is that the carbon nano-tube fibre beam for obtaining step (1) is directly with 220 twirls/m twist
Twisting.The performance of obtained material is tested, conductivity is 7.4 × 104S/m, tensile strength 95MPa.
Embodiment 4
The present embodiment provides a kind of electrically conductive polyaniline/carbon nano-tube fibre composite material, preparation method is as follows:
(1) FCCVD method is used to prepare carbon nano-tube fibre (diameter of single-root carbon nano-tube fiber is 60-70 μm) union
30s is drawn into concentrated nitric acid and impregnated to bulk by beam, is acidified carbon nano-tube fibre and removes impurity, then uses flowing water
Carbon nano-tube fibre is cleaned up, is dried carbon nano-tube fibre using continuous tunnel furnace, more carbon nano-tube fibres is shunk and closes
It at one, is formed carbon nano-tube fibre beam (486 μm of diameter), is wound in winding tube；
(2) carbon nano-tube fibre Shu Liantong winding tube is put into aniline solution together, oxidant is slowly added dropwise at 2 DEG C
Solution is added dropwise with 12min, and then keeping temperature is 2 DEG C, is reacted 7h, is obtained electrically conductive polyaniline enveloped carbon nanometer tube fiber
Beam；
Wherein, the mass ratio of carbon nano-tube fibre beam and aniline is 5:1, the ammonium persulfate and aniline in oxidizing agent solution
Mass ratio is 1.25:1；
(3) the electrically conductive polyaniline enveloped carbon nanometer tube fibre bundle that step (2) obtains is placed in clear water and is unreeled, then passed through
Continuous tunnel furnace drying, then winds, the fibre bundle wound is twisted with twisting mill, and the twist is 250 twirls/m, obtain electrically conductive polyaniline/
Carbon nano-tube fibre composite material.
After tested, electrically conductive polyaniline provided in this embodiment/carbon nano-tube fibre composite material conductivity be 1.9 ×
105S/m, tensile strength 182MPa.
Comparative example 4
Difference with embodiment 4 is that the carbon nano-tube fibre beam for obtaining step (1) is directly with 250 twirls/m twist
Twisting.The performance of obtained material is tested, conductivity is 7.6 × 104S/m, tensile strength 107MPa.
Embodiment 5
The present embodiment provides a kind of electrically conductive polyaniline/carbon nano-tube fibre composite material, preparation method is as follows:
(1) FCCVD method is used to prepare carbon nano-tube fibre (diameter of single-root carbon nano-tube fiber is 60-70 μm) union
50s is drawn into the concentrated sulfuric acid and impregnated to bulk by beam, is acidified carbon nano-tube fibre and removes impurity, then uses flowing water
Carbon nano-tube fibre is cleaned up, is dried carbon nano-tube fibre using continuous tunnel furnace, more carbon nano-tube fibres is shunk and closes
It at one, is formed carbon nano-tube fibre beam (364 μm of diameter), is wound in winding tube；
(2) carbon nano-tube fibre Shu Liantong winding tube is put into aniline solution together, oxidant is slowly added dropwise at 4 DEG C
Solution is added dropwise with 18min, and then keeping temperature is 4 DEG C, reacts 7.5h, and it is fine to obtain electrically conductive polyaniline enveloped carbon nanometer tube
Tie up beam；
Wherein, the mass ratio of carbon nano-tube fibre beam and aniline is 4.5:1, ammonium persulfate and aniline in oxidizing agent solution
Mass ratio be 1.25:1；
(3) the electrically conductive polyaniline enveloped carbon nanometer tube fibre bundle that step (2) obtains is placed in clear water and is unreeled, then passed through
Continuous tunnel furnace drying, then winds, the fibre bundle wound is twisted with twisting mill, and the twist is 280 twirls/m, obtain electrically conductive polyaniline/
Carbon nano-tube fibre composite material.
After tested, electrically conductive polyaniline provided in this embodiment/carbon nano-tube fibre composite material conductivity be 1.7 ×
105S/m, tensile strength 192MPa.
Comparative example 5
Difference with embodiment 5 is that the carbon nano-tube fibre beam for obtaining step (1) is directly with 280 twirls/m twist
Twisting.The performance of obtained material is tested, conductivity is 6.6 × 104S/m, tensile strength 103MPa.
Comparative example 6
The difference from embodiment 1 is that the mass ratio of carbon nano-tube fibre beam and aniline is 2.5:1 in step (2), other
Raw material, dosage and preparation step are same as Example 1.
The performance of obtained composite material is tested, conductivity is 9.3 × 104S/m, tensile strength are
125MPa。
Comparative example 7
The difference from embodiment 1 is that the mass ratio of carbon nano-tube fibre beam and aniline is 6.5:1 in step (2), other
Raw material, dosage and preparation step are same as Example 1.
The performance of obtained composite material is tested, conductivity is 7.8 × 104S/m, tensile strength are
132MPa。
In summary, the present invention has obtained a kind of tool in conjunction with specific preparation method by the proportion between controlling each raw material
There is the electrically conductive polyaniline of high conductance and tensile strength/carbon nano-tube fibre composite material.When carbon nano-tube fibre beam and benzene
When the mass ratio of amine is too high or too low, the conductivity and tensile strength decline of composite material will lead to.
The Applicant declares that the foregoing is merely a specific embodiment of the invention, but protection scope of the present invention not office
It is limited to this, it should be clear to those skilled in the art, any to belong to those skilled in the art and take off in the present invention
In the technical scope of dew, any changes or substitutions that can be easily thought of, and all of which fall within the scope of protection and disclosure of the present invention.
Claims (10)
1. a kind of electrically conductive polyaniline/carbon nano-tube fibre composite material preparation method, which is characterized in that the preparation method packet
Include following steps:
(1) it by more carbon nano-tube fibre boundlings, is impregnated in concentrated acid, be acidified the carbon nano-tube fibre and remove impurity,
Obtain carbon nano-tube fibre beam；
(2) the carbon nano-tube fibre beam and aniline obtained step (1) carries out anti-in acid solution, under the conditions of existing for the oxidant
It answers, obtains electrically conductive polyaniline enveloped carbon nanometer tube fibre bundle；
(3) the electrically conductive polyaniline enveloped carbon nanometer tube fibre bundle for obtaining step (2) is twisted, and obtains the electrically conductive polyaniline/carbon
Nanotube fibers composite material.
2. preparation method according to claim 1, which is characterized in that the diameter of carbon nano-tube fibre described in step (1)
It is 60-70 μm；
Preferably, the diameter of the carbon nano-tube fibre beam is 300-500 μm.
3. preparation method according to claim 1 or 2, which is characterized in that concentrated acid described in step (1) be the concentrated sulfuric acid and/
Or concentrated nitric acid；
Preferably, the time of immersion described in step (1) is 30-60s；
Preferably, after impregnating described in step (1), cleaning and drying process are also carried out.
4. preparation method according to claim 1-3, which is characterized in that carbon nanotube described in step (2) is fine
The mass ratio for tieing up beam and the aniline is 3-6:1；
Preferably, acid solution described in step (2) is the mix acid liquor of sulfosalicylic acid and sulfuric acid；
Preferably, the concentration of acid solution described in step (2) is 0.8-1.5mol/L；
Preferably, the mass ratio of the sulfuric acid and the sulfosalicylic acid is 3-5:1.
5. preparation method according to claim 1-4, which is characterized in that oxidant described in step (2) was
The mixture of ammonium sulfate and potassium bichromate；
Preferably, the molar ratio of the ammonium persulfate and the potassium bichromate is 2-15:1；
Preferably, the mass ratio of the ammonium persulfate and the aniline is 1.25-1.5:1.
6. preparation method according to claim 1-5, which is characterized in that oxidant described in step (2) is logical
The mode being added dropwise is crossed to be added in the acid solution；
Preferably, the oxidant is added dropwise in 10-20min；
Preferably, the temperature of reaction described in step (2) is 0-5 DEG C；
Preferably, the time of reaction described in step (2) is 6-8h.
7. preparation method according to claim 1-6, which is characterized in that the twist of twisting described in step (3)
For 200-300 twirl/m.
8. preparation method according to claim 1-7, which is characterized in that the preparation method includes following step
It is rapid:
(1) by more 60-70 μm of diameter of carbon nano-tube fibre boundling, 30-60s is impregnated in the concentrated sulfuric acid and/or concentrated nitric acid, is made
The carbon nano-tube fibre is acidified and removes impurity, is then cleaned and is dried, and 300-500 μm of diameter of carbon nanotube is obtained
Fibre bundle is wound on devices for taking-up；
(2) mix acid liquor for being 3-5:1 preparation 0.8-1.5mol/L by sulfuric acid and sulfosalicylic acid mass ratio, with the mixed acid
Liquid is solvent, prepares aniline solution and oxidizing agent solution respectively, the carbon nano-tube fibre beam that step (1) obtains is put into the benzene
In amine aqueous solution, the oxidizing agent solution is added dropwise under conditions of 0-5 DEG C, is added dropwise in 10-20min, keeps thermotonus
6-8h obtains electrically conductive polyaniline enveloped carbon nanometer tube fibre bundle；
Wherein, the mass ratio of the carbon nano-tube fibre beam and aniline is 3-6:1, and the oxidant is by ammonium persulfate and dichromic acid
2-15:1 is formed potassium in molar ratio, and the mass ratio of the ammonium persulfate and aniline is 1.25-1.5:1；
(3) the electrically conductive polyaniline enveloped carbon nanometer tube fibre bundle that step (2) obtains is placed in water and is unreeled, by the fiber after unreeling
Beam drying, winds again, twists through twisting mill, and the twist is 200-300 twirl/m, and it is fine to obtain the electrically conductive polyaniline/carbon nanotube
Tie up composite material.
9. a kind of electrically conductive polyaniline/carbon nano-tube fibre composite material, which is characterized in that the electrically conductive polyaniline/carbon nanotube
Fibrous composite is prepared by the described in any item methods of claim 1-8.
10. a kind of purposes of electrically conductive polyaniline as claimed in claim 9/carbon nano-tube fibre composite material, which is characterized in that
The electrically conductive polyaniline/carbon nano-tube fibre composite material is used for electromagnetic shielding material, conducting wire, heating wire or field of textiles.
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| CN110183731A (en) * | 2019-06-07 | 2019-08-30 | 青岛泰歌新材料科技有限公司 | A kind of preparation method of polyaniline-modified nano-carbon material |
| CN111472165A (en) * | 2020-04-24 | 2020-07-31 | 安徽工程大学 | Polyaniline-coated carbon nanotube coating flexible electromagnetic shielding fabric and preparation method thereof |
| CN113143258A (en) * | 2021-02-24 | 2021-07-23 | 浙江理工大学 | Stretchable sensor preparation method |
| CN114420343A (en) * | 2022-01-20 | 2022-04-29 | 广东腐蚀科学与技术创新研究院 | Conductive material and grounding material |
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| CN113143258A (en) * | 2021-02-24 | 2021-07-23 | 浙江理工大学 | Stretchable sensor preparation method |
| CN114420343A (en) * | 2022-01-20 | 2022-04-29 | 广东腐蚀科学与技术创新研究院 | Conductive material and grounding material |
| CN114420343B (en) * | 2022-01-20 | 2024-06-25 | 广东腐蚀科学与技术创新研究院 | Conductive material and grounding material |
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