CN109401167A - Conductive plastics and preparation method thereof and shell - Google Patents
Conductive plastics and preparation method thereof and shell Download PDFInfo
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- CN109401167A CN109401167A CN201811261439.4A CN201811261439A CN109401167A CN 109401167 A CN109401167 A CN 109401167A CN 201811261439 A CN201811261439 A CN 201811261439A CN 109401167 A CN109401167 A CN 109401167A
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/041—Carbon nanotubes
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/001—Conductive additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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Abstract
The present invention provides conductive plastics and preparation method thereof and shells.Wherein, conductive plastics includes: resin matrix；Nitrogen-doped carbon nanometer pipe, the nitrogen-doped carbon nanometer pipe are dispersed in the resin matrix.Inventor's discovery, the conductive plastics structure is simple, is easily achieved, nitrogen-doped carbon nanometer pipe is uniformly dispersed in resin matrix, it forms good conductive network in conductive plastics, so that the conductive capability of conductive plastics is good, and the binding force of nitrogen-doped carbon nanometer pipe and resin matrix is strong, so that the stable structure of conductive plastics, long service life.
Description
Technical field
The present invention relates to conductive material technical fields, and in particular, to conductive plastics and preparation method thereof and shell.
Background technique
Conductive plastics is ideal shielding material, can be used as the shell of electronic device and equipment to realize shielding.It and tradition
Conductive material is compared, and more lightly, easily molded processing is corrosion-resistant, and resistance is easy to adjust and totle drilling cost is lower.Due to carbon nanotube
With good electric conductivity, but carbon nanotube is because of its biggish draw ratio and crimpness, it is easy to reunite together, it is difficult to point
It dissipates, and is difficult to good compatible with resin matrix.Thus, current conductive plastics still in research among.
Summary of the invention
The present invention is directed to solve at least some of the technical problems in related technologies.For this purpose, of the invention
One purpose is to propose a kind of conductive plastics, and the conductive plastics structure is simple, is easily achieved, and nitrogen-doped carbon nanometer pipe uniformly divides
It is dispersed in resin matrix or conductive effect is good.
In one aspect of the invention, the present invention provides a kind of conductive plastics.According to an embodiment of the invention, the conduction
Plastics include: resin matrix；Nitrogen-doped carbon nanometer pipe, the nitrogen-doped carbon nanometer pipe are dispersed in the resin matrix.Invention
People's discovery, the conductive plastics structure is simple, is easily achieved, and nitrogen-doped carbon nanometer pipe is uniformly dispersed in resin matrix, is leading
Good conductive network is formed in electric plastics, so that the conductive capability of conductive plastics is good, and nitrogen-doped carbon nanometer pipe and resin
The binding force of matrix is strong, so that the stable structure of conductive plastics, long service life.
According to an embodiment of the invention, the gross mass based on the conductive plastics, the content of the nitrogen-doped carbon nanometer pipe
For 0.1wt%-20wt%.
According to an embodiment of the invention, the gross mass based on the nitrogen-doped carbon nanometer pipe, the doping of nitrogen are
0.1wt%-20wt%.
According to an embodiment of the invention, the draw ratio of the nitrogen-doped carbon nanometer pipe is 10-100000, crimpness is
0.1%-50%.
According to an embodiment of the invention, the material for forming the resin matrix include polypropylene, polyethylene, polycarbonate,
Polystyrene, acrylonitrile-butadiene-styrene copolymer, polybutylene terephthalate (PBT), polyethylene terephthalate
Ester, polyphenylene sulfide, polyvinyl chloride, polyamide, polymethyl methacrylate, epoxy resin, styrene analog thermoplastic elastomer, alkene
At least one of hydrocarbon thermoplastic's elastomer and polyurethane-type thermoplastic elastomer.
According to an embodiment of the invention, the gross mass based on the conductive plastics, the conductive plastics includes: 0.1wt%-
The nitrogen-doped carbon nanometer pipe of 20wt%；The auxiliary agent of 0.1wt%-50wt%；And the resin matrix of surplus.
According to an embodiment of the invention, the auxiliary agent includes dispersing agent.
According to an embodiment of the invention, the dispersing agent include polyethylene wax, calcium stearate, vinyl bis-stearamides and
At least one of ethylene-vinyl acetate copolymer.
In another aspect of this invention, the present invention provides a kind of methods for preparing mentioned-above conductive plastics.According to
The embodiment of the present invention, this method comprises: N doping is entered in carbon nanotube, to obtain nitrogen-doped carbon nanometer pipe；By institute
It states and carries out extruding pelletization processing after nitrogen-doped carbon nanometer pipe is mixed with resin matrix, obtain the conductive plastics.Invention human hair
Existing, this method is easy to operate, convenient, it is easy to accomplish, production cost is low, and can obtain with mentioned-above feature and advantage
Conductive plastics.
According to an embodiment of the invention, it is described N doping is entered in carbon nanotube include: by nitrogen source dispersion in a solvent,
To obtain the first mixed liquor；The first ball-milling treatment is carried out after carbon nanotube is mixed with first mixed liquor, so as to
To the second mixed liquor；It will be calcined under an inert atmosphere after second mixed liquor drying, to obtain the N doping
Carbon nanotube.
According to an embodiment of the invention, the nitrogen source is selected from melamine, urea, polyacrylonitrile, polyvinylpyridine, pyrrole
It coughs up, at least one of quinoline.
According to an embodiment of the invention, the solvent is selected from least one of formaldehyde, ethyl alcohol, acetone.
According to an embodiment of the invention, the revolving speed of first ball-milling treatment is 200-800 revs/min, time 2-24h.
According to an embodiment of the invention, the temperature of the calcining is 400-1000 degrees Celsius, time 0.5-10h.
According to an embodiment of the invention, further include before the carbon nanotube is mixed with first mixed liquor will be described
Carbon nanotube carries out the step of the second ball-milling treatment.
According to an embodiment of the invention, the revolving speed of second ball-milling treatment is 200-600 revs/min, time 1-10h.
In another aspect of this invention, the present invention provides a kind of shells.According to an embodiment of the invention, the shell is extremely
Few a part is prepared using mentioned-above conductive plastics.Inventors have found that the shell it is light and handy, be easily processed into
Type, corrosion-resistant, at low cost, conductive effect is good, and the effect for shielding electromagnetic signal is good, and service performance is good.
The present invention can at least obtain following technical effect:
1) present invention mainly carries out nitrogen-doped carbon nanometer pipe by nitrogen source of materials such as low-cost melamine and urea,
This method is low in cost, succinct efficient, easy to industrialized production.
2) carbon nanotube is mixed with nitrogen source using high-energy ball milling wet grinding, is had and is substantially reduced reaction activity, refinement
Crystal grain is greatly improved powder activity and improves particle distribution uniformity and enhance the combination at interface between matrix and matrix, is one
Kind energy conservation, efficient material preparation technology.
3) by changing carbon pipe and nitrogen source type and adjusting the temperature and time of ball milling and high-temperature calcination, different nitrogen are obtained
The N doping of structure (such as amino structure nitrogen, graphite structure nitrogen, pyridine structure nitrogen and pyrrole structure nitrogen etc.) and conductivity
Carbon nanotube product, preparation method are easily controllable.
4) this method preparation nitrogen-doped carbon nanometer pipe be used to prepare conductive plastics, in resin matrix dispersibility and
Electric conductivity is significantly improved, and enhances its application effect in the industry.
Detailed description of the invention
Fig. 1 is the method flow schematic diagram that conductive plastics is prepared in one embodiment of the invention.
Fig. 2 is the method flow schematic diagram entered N doping in one embodiment of the invention in carbon nanotube.
Fig. 3 is the low power scanning electron microscope (SEM) photograph (SEM) of the conductive plastics in embodiment 1.
Fig. 4 is the high power scanning electron microscope (SEM) photograph of the conductive plastics in embodiment 1.
Specific embodiment
The embodiment of the present invention is described below in detail.The embodiments described below is exemplary, and is only used for explaining this hair
It is bright, and be not considered as limiting the invention.Particular technique or condition are not specified in embodiment, according to text in the art
It offers described technology or conditions or is carried out according to product description.Reagents or instruments used without specified manufacturer,
For can be with conventional products that are commercially available.
Carbon nanotube is because of its biggish draw ratio and crimpness, it is easy to reunite together, it is difficult to divide in resin matrix
It scatters and, and be difficult to good compatible with resin matrix.In view of the above technical problems, inventor conducts in-depth research, and grinds
It is found after studying carefully, after carbon doping has been carried out in carbon nanotube, it is made to take functional group in end and tube wall position, thus
Carbon nano tube surface is activated, plays electric conductivity of the carbon nanotube in resin matrix to the greatest extent.
In view of this, in one aspect of the invention, the present invention provides a kind of conductive plastics.Implementation according to the present invention
Example, which includes: resin matrix；Nitrogen-doped carbon nanometer pipe, the nitrogen-doped carbon nanometer pipe are dispersed in the resin base
In body.Inventors have found that the conductive plastics structure is simple, is easily achieved, the knot between nitrogen-doped carbon nanometer pipe and resin matrix
It is high to close intensity, is easy to be uniformly dispersed in resin matrix, forms good conductive network in conductive plastics, so that conductive modeling
The conductive capability of material is good, and the binding force of nitrogen-doped carbon nanometer pipe and resin matrix is strong, so that the stable structure of conductive plastics,
Long service life.
According to an embodiment of the invention, in carbon nanotube carry out N doping after, introduced in carbon nanotube amino,
Pyridine, pyrroles, graphite mould Dan Deng functional group, since the functional groups such as these functional groups and the hydroxyl on resin matrix surface and carboxyl have
Interaction force, the oxygen atom in nitrogen-atoms and hydroxy or carboxy in amino, pyridine, pyrroles or graphite mould Dan Deng functional group
There are Hyarogen-bonding and intermolecular force etc., so that the carbon nanotube of N doping and the binding force of resin matrix greatly enhance,
Therefore the carbon nanotube of N doping is more easily dispersed in resin matrix, so that the conductive network formed is good, so that leading
The electric conductivity of electric plastics is relatively good.
According to an embodiment of the invention, the gross mass based on the nitrogen-doped carbon nanometer pipe, the doping of nitrogen are
0.1wt%-20wt% (such as 0.1wt%, 0.5wt%, 1wt%, 1.5wt%, 2wt%, 2.5wt%, 3wt%, 3.5wt%,
4wt%, 4.5wt%, 5wt%, 5.5wt%, 6wt%, 6.5wt%, 7wt%, 7.8wt%, 8wt%, 8.5wt%, 9wt%,
9.5wt%, 10wt%, 10.5wt%, 11wt%, 11.5wt%, 12wt%, 12.5wt%, 13wt%, 13.5wt%,
14wt%, 14.5wt%, 15wt%, 15.5wt%, 16wt%, 16.5wt%, 17wt%, 17.5wt%, 18wt%,
18.5wt%, 19wt%, 19.5wt%, 20wt% etc.).As a result, the content of the amido functional group in nitrogen-doped carbon nanometer pipe compared with
To be suitable, so that the excellent electric conductivity of nitrogen-doped carbon nanometer pipe, and be easier in conjunction with resin matrix and then be more easily dispersed in
In resin matrix, so that the electric conductivity of conductive plastics is more preferably.Relative to above-mentioned doping, when the doping of nitrogen is very few,
Binding force then between nitrogen-doped carbon nanometer pipe and resin matrix is inadequate, will affect nitrogen-doped carbon nanometer pipe in resin matrix
Dispersion effect can then destroy the structure of carbon nanotube itself when the doping of nitrogen is excessive, cause under carbon nano-tube conductive energy
Drop.
According to an embodiment of the invention, the draw ratio of the nitrogen-doped carbon nanometer pipe be 10-100000 (such as 10,100,
500,1000,5000,10000,50000,100000 etc.), crimpness be 0.1%-50% (such as 0.1%, 1%, 5%,
10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50% etc.).As a result, the draw ratio of nitrogen-doped carbon nanometer pipe and
Crimpness is more appropriate, it is not easy to reunite together, what can be dispersed in resin matrix is relatively uniform, so that conductive modeling
The electric conductivity of material is excellent.Relative to above-mentioned draw ratio and crimpness, when the draw ratio of nitrogen-doped carbon nanometer pipe is too small, then by
Bridge can not be overlapped to form in carbon nanotube is too short, thus conductive network can not be formed in resin matrix, work as nitrogen-doped carbon nanometer pipe
Draw ratio it is excessive when, then due to carbon nanotube is too long thus mutually wound in resin matrix and reunite it is more serious, can not
It is good to be dispersed in resin matrix；When the crimpness of nitrogen-doped carbon nanometer pipe is too small, then carbon nanotube shape is excessively single
And be difficult to be overlapped to form bridge, thus good conductive network can not be formed in resin matrix, when the curling of nitrogen-doped carbon nanometer pipe
When spending big, then good it can not be dispersed in resin matrix since carbon nanotube is wound and it is more serious to reunite.
According to an embodiment of the invention, in order to enable the electric conductivity of conductive plastics more preferably, based on the conductive plastics
Gross mass, the content of the nitrogen-doped carbon nanometer pipe be 0.1wt%-20wt% (such as 0.1wt%, 0.5wt%, 1wt%,
2wt%, 4wt%, 6wt%, 8wt%, 10wt%, 12wt%, 14wt%, 16wt%, 18wt%, 20wt% etc.).Nitrogen as a result,
The content of doped carbon nanometer pipe within the above range can be more uniform be dispersed in resin matrix, the conductive network of formation
Effect is more preferable, so that the electric conductivity of conductive plastics is stronger, the effect for shielding electromagnetic signal is preferable, is particularly suitable for electronics, integrates
The fields such as circuit packaging and electromagnetic shielding.Relative to above-mentioned content, when the content of nitrogen-doped carbon nanometer pipe is very few, then carbon is received
Mitron spacing is excessive to be difficult to be overlapped to form bridge, thus good conductive network can not be formed in resin matrix, when nitrogen-doped carbon is received
When the content of mitron is excessive, the electric conductivity for improving conductive plastics is not promoted further, and greatly improve conductive plastics
Difficulty of processing so that extrusion molding is difficult, while the mechanical property of conductive plastics can also be greatly reduced.Of the invention some
In preferred embodiment, based on the gross mass of the conductive plastics, the content of the nitrogen-doped carbon nanometer pipe is 12wt%-
20wt%.The electric conductivity ratio of the conductive plastics of the content of nitrogen-doped carbon nanometer pipe within the above range contains pure carbon and receives as a result,
The conductive plastics of mitron conducts electricity very well that (wherein, the content of pure nano-carbon tube may be up to 20wt%, resistivity in conductive plastics
Can be down to 124.6 Ω), and the resistivity of conductive plastics can down to 45.8 Ω, be particularly suitable for electronics, integrated circuit packaging and
The fields such as electromagnetic shielding.
According to an embodiment of the invention, it (may include horse that the material for forming the resin matrix, which includes polypropylene, polyethylene,
Maleic anhydride grafted polyethylene etc.), polycarbonate, polystyrene, acrylonitrile-butadiene-styrene copolymer, poly terephthalic acid
Butanediol ester, polyethylene terephthalate, polyphenylene sulfide, polyvinyl chloride, polyamide, polymethyl methacrylate, epoxy
Resin, styrene analog thermoplastic elastomer (can be used interchangeably with phenylethylene TPE thermoplastic elastomer (TPE)), olefin hydrocarbons thermoplasticity bullet
Property body (can be used interchangeably with olefines TPE thermoplastic elastomer (TPE)) and polyurethane-type thermoplastic elastomer (can be with polyurethanes TPE
At least one of thermoplastic elastomer (TPE) is used interchangeably).Material source is extensive as a result, and price is lower, environmentally friendly, and nitrogen
Doped carbon nanometer pipe can be uniformly dispersed in above-mentioned resin matrix, so that the conductive effect of the conductive plastics obtained is good.
According to an embodiment of the invention, can also include auxiliary agent in conductive plastics, in order to enable nitrogen-doped carbon nanometer pipe exists
More evenly, the auxiliary agent may include dispersing agent for dispersion in resin matrix.Dispersing agent facilitates nitrogen-doped carbon nanometer pipe as a result,
Dispersion so that the electric conductivity of conductive plastics is more preferable.In some embodiments of the invention, the dispersing agent includes poly- second
At least one of alkene wax, calcium stearate, vinyl bis-stearamides, ethylene-vinyl acetate copolymer, as a result, above-mentioned dispersion
The addition of agent is more advantageous to that nitrogen-doped carbon nanometer pipe is evenly dispersed in resin matrix, is more advantageous to and improves leading for conductive plastics
Electrically.According to an embodiment of the invention, in order to further increase the service performance of conductive plastics, auxiliary agent can also include plasticizer
(for example including but be not limited to phthalate compound etc.), antioxidant (for example including but be not limited to phenol type antioxidant, Asia
Phosphate antioxidant etc.), wetting agent (for example including but be not limited to paraffin oil, polyethers, polyethylene glycol, polypropylene glycol, polyethylene glycol
Single (double) ester, sapn, tween, alcohol ether phosphate, polyol ester etc.), fire retardant (for example including but be not limited to magnesium hydroxide, hydrogen
At least one of aluminium oxide, aluminum diethylphosphinate, polyphosphoric acid melamine, melamine cyanurate etc.).It is conductive as a result,
The service life is longer for plastics, and processing performance and mechanical performance are more excellent.
According to an embodiment of the invention, the gross mass based on the conductive plastics, the conductive plastics includes: 0.1wt%-
20wt% (such as 0.1wt%, 0.5wt%, 1wt%, 2wt%, 4wt%, 6wt%, 8wt%, 10wt%, 12wt%,
14wt%, 16wt%, 18wt%, 20wt% etc.) the nitrogen-doped carbon nanometer pipe；0.1wt%-50wt% (such as
0.1wt%, 1wt%, 5wt%, 10wt%, 15wt%, 20wt%, 25wt%, 30wt%, 35wt%, 40wt%, 45wt%,
50wt% etc.) auxiliary agent；And the resin matrix of surplus.In the conductive plastics obtained as a result, nitrogen-doped carbon nanometer pipe
More evenly, the conductive effect of conductive plastics is more preferably for dispersion.In some currently preferred embodiments of the present invention, it is based on the conductive plastics
Gross mass, the additional amount of the dispersing agent in auxiliary agent be 0.1wt%-10wt% (such as 0.1wt%, 0.5wt%, 1wt%,
2wt%, 4wt%, 6wt%, 8wt%, 10wt% etc.), nitrogen-doped carbon nanometer pipe disperses more evenly in conductive plastics as a result,
The electric conductivity of conductive plastics is more preferably.
In another aspect of this invention, the present invention provides a kind of methods for preparing mentioned-above conductive plastics.According to
The embodiment of the present invention, referring to Fig.1, this method comprises:
S100: N doping is entered in carbon nanotube, to obtain nitrogen-doped carbon nanometer pipe.
According to an embodiment of the invention, nitrogen-doped carbon nanometer pipe is consistent with the description of front, no longer excessively repeat herein.
According to an embodiment of the invention, referring to Fig. 2, it is described N doping is entered in carbon nanotube include:
S110: in a solvent by nitrogen source dispersion, to obtain the first mixed liquor.
According to an embodiment of the invention, the nitrogen source is selected from melamine, urea, polyacrylonitrile, polyvinylpyridine, pyrrole
It coughs up, at least one of quinoline.According to an embodiment of the invention, the solvent is selected from least one of formaldehyde, ethyl alcohol, acetone.
Material source is extensive as a result, and price is lower, and above-mentioned nitrogen source is soluble in above-mentioned solvent, be conducive to subsequent step into
Row.In some currently preferred embodiments of the present invention, nitrogen source is at least two in above-mentioned nitrogen source.Two kinds or more of nitrogen as a result,
It can produce synergistic effect between source, specifically, a variety of nitrogen sources can be carbon nano tube-doped a variety of N structures, promote doping effect
Fruit such as selects melamine and polyvinylpyridine as nitrogen source simultaneously, available while having amino, pyridine and graphene
The nitrogen-doped carbon nanometer pipe of the various structures such as type nitrogen.
According to an embodiment of the invention, the gross mass based on the first mixed liquor, the content of above-mentioned nitrogen source is 0.1wt%-
50wt% (such as 0.1wt%, 0.5wt%, 1wt%, 2wt%, 4wt%, 6wt%, 8wt%, 10wt%, 12wt%,
14wt%, 16wt%, 18wt%, 20wt%, 25wt%, 30wt%, 35wt%, 40wt%, 45wt%, 50wt% etc.), by
This, nitrogen source is dispersed relatively uniform, and the mixing of subsequent first mixed liquor and carbon nanotube is conducive to.
S120: the first ball-milling treatment is carried out after carbon nanotube is mixed with first mixed liquor, to obtain second
Mixed liquor.
According to an embodiment of the invention, the revolving speed of first ball-milling treatment be 200-800 revs/min (such as 200 revs/min,
400 revs/min, 600 revs/min, 800 revs/min etc.), the time be 2-24h (such as 2h, 64h, 8h, 10h, 12h, 14h, 16h, 18h,
20h, 22h, for 24 hours etc.).The first ball-milling treatment can be significantly reduced reaction activity, refine crystal grain, carbon is greatly improved receive as a result,
The activity of mitron and nitrogen source, the uniformity for improving carbon nanotube particle diameter distribution, advantageously allow the knot between nitrogen and carbon nanotube
Resultant force is stronger, and then can be easier to be entrained in carbon nanotube to obtain nitrogen-doped carbon nanometer pipe.Relative to above-mentioned ball milling
The revolving speed of processing and time then make carbon nanotube partial size ball when the revolving speed of the first ball-milling treatment is excessive or overlong time
It is honed short, the draw ratio and crimpness of carbon nanotube are greatly reduced, makes it that can not be overlapped to form bridge in resin matrix, and then influence
The formation of conductive network is then unable to improve carbon nanotube partial size when the revolving speed of the first ball-milling treatment is too small or the time is too short
The uniformity of distribution, be unfavorable between nitrogen source and carbon nanotube it is effective mix, and then influence the doping of subsequent nitrogen.
According to an embodiment of the invention, further include before the carbon nanotube is mixed with first mixed liquor will be described
Carbon nanotube carries out the step of the second ball-milling treatment.Thus, it is possible to obtain, major diameter is smaller, the lesser carbon nanotube of crimpness,
Increase its specific surface area, is conducive to the doping of subsequent nitrogen.
According to an embodiment of the invention, carbon nanotube can be in single-walled carbon nanotube and multi-walled carbon nanotube extremely
It is one of few, and above-mentioned carbon nanotube can be array carbon nano tube, be also possible to wind carbon nanotube.Material source is extensive, easily
Enter wherein in by N doping, so that dispersing type of the nitrogen-doped carbon nanometer pipe obtained in resin matrix is good, acquisition is led
Electric Plastic conductive is good.
According to an embodiment of the invention, the revolving speed of second ball-milling treatment be 200-600 revs/min (such as 200 revs/min,
400 revs/min, 600 revs/min etc.), the time is 1-10h (such as 1h, 3h, 5h, 7h, 9h, 10h etc.).The length of carbon nanotube as a result,
Diameter is than smaller, crimpness is smaller.
S130: it will be calcined under an inert atmosphere after second mixed liquor drying, to obtain the N doping
Carbon nanotube.
According to an embodiment of the invention, the temperature of the calcining be 400-1000 degrees Celsius (such as 400 degrees Celsius, 600 take the photograph
Family name's degree, 800 degrees Celsius, 1000 degrees Celsius etc.), the time is 0.5-10h (such as 0.5h, 1h, 3h, 5h, 7h, 9h, 10h etc.).By
This, N doping enters the better effect in carbon nanometer, can obtain the more appropriate nitrogen-doped carbon of excellent electric conductivity, nitrogen content and receive
Mitron.Relative to above-mentioned calcination condition, when the excessively high acquisition overlong time of the temperature of calcining, then do not have to the doping content for improving nitrogen
Have and be further obviously improved, while increasing experimental cost, when calcination temperature is too low or too short, is then unable to get compared with high nitrogen
The carbon nanotube of doping content.
According to an embodiment of the invention, above-mentioned inert atmosphere can be argon atmosphere or nitrogen atmosphere etc..
According to an embodiment of the invention, the hydrochloric acid that can be about after calcining 2mol/L with concentration washes away residue, so
It can be obtained required nitrogen-doped carbon nanometer pipe after being washed with deionized 2-3 times again afterwards.
According to an embodiment of the invention, the nitrogen source difference of selection can obtain different types of N structure.Of the invention one
In a little specific embodiments, by selecting melamine as nitrogen source, 600 DEG C of calcining 1h is selected, amino structure N doping can be obtained.
In other specific embodiments of the invention, by selecting urea as nitrogen source, 800 DEG C of calcining 1h is selected, graphite can be obtained
Type N structure N doping.In other specific embodiments of the invention, by selecting polyvinylpyridine as nitrogen source, selection
500 DEG C of calcining 1h, can be obtained pyridine structure N doping.In other specific embodiments of the invention, made by selection pyrroles
For nitrogen source, 500 DEG C of calcining 1h are selected, pyrrole structure N doping can be obtained.Thus, it is possible to be realized by the adjusting to nitrogen source different
The N doping of structure, and then meet the actual needs.
S200: carrying out extruding pelletization processing after the nitrogen-doped carbon nanometer pipe is mixed with resin matrix, obtains described
Conductive plastics.
According to an embodiment of the invention, resin matrix is consistent with the description of front, no longer excessively repeat herein.
According to an embodiment of the invention, the method that above-mentioned resin matrix is mixed with nitrogen-doped carbon nanometer pipe are as follows: in valve bag
A certain amount of white oil is added to resin matrix in middle elder generation, it is made uniformly to be wrapped in resin particle surfaces, and nitrogen-doped carbon nanometer is then added
It mixes well after pipe, so that resin matrix surface coats the carbon nanotube of one layer of N doping, is eventually adding after auxiliary agent again manually
It mixes well manually, so that coat one layer of auxiliary agent again in carbon nanotube outer layer, nitrogen-doped carbon nanometer pipe and auxiliary agent can be with as a result,
Sufficiently, it is uniformly dispersed in resin matrix, and then help to obtain the excellent conductive plastics of electric conductivity.
According to an embodiment of the invention, can be using parallel double-screw extruder to nitrogen-doped carbon nanometer pipe and resin matrix
Mixture carries out extruding pelletization processing, the revolving speed of parallel double-screw extruder can for 40-120rpm (rev/min) (such as
40rpm, 60rpm, 80rpm, 100rpm, 120rpm etc.), rate of feeding can for 300-1000rpm (such as 300rpm,
500rpm, 700rpm, 900rpm, 1000rpm), extrusion temperature can be 150-250 DEG C (such as 150 DEG C, 200 DEG C, 250 DEG C
Deng).It is simple, convenient as a result, it is easy to accomplish, and the above-mentioned parameter setting of parallel double-screw extruder can make nitrogen mix
Miscellaneous carbon nanotube is sufficiently mixed with resin matrix, obtains the preferable conductive plastics of electric conductivity.
According to an embodiment of the invention, the above-mentioned method for preparing conductive plastics is easy to operate, and it is convenient, it is easy to accomplish, it is easy to
Control, production cost is low, is a kind of technology that is energy saving, efficiently preparing conductive plastics.
In another aspect of this invention, the present invention provides a kind of shells.According to an embodiment of the invention, the shell is extremely
Few a part is prepared using mentioned-above conductive plastics.Inventors have found that the shell it is light and handy, be easily processed into
Type, corrosion-resistant, at low cost, conductive effect is good, and the effect for shielding electromagnetic signal is good, and service performance is good.
According to an embodiment of the invention, above-mentioned shell can be applied to electronics, integrated circuit packaging and electromagnetic shielding etc.
Field, use scope is wider, and service performance is good.
Embodiments herein is described below in detail.
Embodiment
Embodiment 1
The melamine and 100g formaldehyde of 2.6g are added in beaker, ultrasonic disperse 30min adds 6.0g preparatory ball
The multi wall winding-type carbon nanotube for grinding (ball milling speed 400rpm, time 4h), pours into high energy ball mill continue after mixing evenly
High-energy ball milling (ball milling speed 400rpm) for 24 hours, is then dried.Mixture after drying is placed in tube furnace, in N2Atmosphere
600 DEG C of calcining 1h of lower progress, the product after Temperature fall washed once with the hydrochloric acid solution of 2mol/L, deionized water washing 2
It is filtered after secondary and can be obtained nitrogen-doped carbon nanometer pipe after dry.Nitrogen-doped carbon nanometer pipe and high-impact polystyrene resin particle
Configured and mixed (wherein, the gross mass based on nitrogen-doped carbon nanometer pipe Yu high-impact polystyrene resin particle, N doping
The content of carbon nanotube is 3wt%), mixture is then sent into parallel double-screw extruding granulator and carries out extruding pelletization, 20 types
Extruder revolving speed 120rpm, rate of feeding 1000rpm, 220 DEG C of extrusion temperature, obtained conductive plastics particle multitester measuring
Its resistivity.The nitrogen-doped carbon nanometer pipe of the present embodiment is 5.29% by its N element doping content of determination of elemental analysis, preparation
Conductive plastics particle surface resistivity be 5.95*104Ω, the scanning electron microscope (SEM) photograph of the conductive plastics of acquisition can refer to Fig. 3 and
Fig. 4.
Embodiment 2
The urea and 160g formaldehyde of 3.72g are added in beaker, ultrasonic disperse 40min adds 8.6g preparatory ball milling
(ball milling speed 400rpm, time 4h) multi wall winding-type carbon nanotube, poured into high energy ball mill after mixing evenly continue it is high
Energy ball milling is dried afterwards for 24 hours (ball milling speed 400rpm).Mixture after drying is placed in tube furnace, in N2It is carried out under atmosphere
700 DEG C of calcining 2h washed once the product after Temperature fall with the hydrochloric acid solution of 2mol/L, and deionized water filters after washing 2 times
And it can be obtained nitrogen-doped carbon nanometer pipe after drying.Nitrogen-doped carbon nanometer pipe is configured with high-impact polystyrene resin particle
With mixing (wherein, the gross mass based on nitrogen-doped carbon nanometer pipe Yu high-impact polystyrene resin particle, nitrogen-doped carbon nanometer pipe
Content be 3wt%), then by mixture be sent into parallel double-screw extruding granulator carry out extruding pelletization, 20 type extruders turn
Fast 120rpm, rate of feeding 1000rpm, 220 DEG C of extrusion temperature, obtained conductive plastics particle multitester measuring its resistance
Rate.The nitrogen-doped carbon nanometer pipe of the present embodiment is 5.82% by its N element doping content of determination of elemental analysis, the conduction of preparation
The surface resistivity of plastic grain is 4.63*104Ω。
Embodiment 3
The urea and 160g formaldehyde of 3.72g are added in beaker, ultrasonic disperse 40min adds 8.6g preparatory ball milling
(ball milling speed 400rpm, time 4h) multi wall winding-type carbon nanotube, poured into high energy ball mill after mixing evenly continue it is high
Energy ball milling is dried afterwards for 24 hours (ball milling speed 400rpm).Mixture after drying is placed in tube furnace, in N2It is carried out under atmosphere
700 DEG C of calcining 2h, the product after Temperature fall washed once with the hydrochloric acid solution of 2mol/L, and deionized water is taken out after washing 2 times
It can be obtained nitrogen-doped carbon nanometer pipe after filter and drying.Nitrogen-doped carbon nanometer pipe and MAPE (maleic anhydride grafted polyethylene) resin
Particle is mixed, and (wherein, the gross mass based on nitrogen-doped carbon nanometer pipe Yu MAPE resin particle, nitrogen-doped carbon nanometer pipe contain
Amount is 5wt%), mixture is then sent into parallel double-screw extruding granulator and carries out extruding pelletization, 20 type extruder revolving speeds
40rpm, rate of feeding 300rpm, 150 DEG C of extrusion temperature, obtained conductive plastics particle multitester measuring its resistivity.This
The nitrogen-doped carbon nanometer pipe of embodiment is 4.82% by its N element doping content of determination of elemental analysis, the conductive plastics of preparation
The surface resistivity of particle is 8.89*103Ω。
Embodiment 4:
The melamine and 7.30g polyacrylonitrile of 1.56g, 400g formaldehyde are added in beaker, ultrasonic disperse 2h is added
(ball milling speed 600rpm, time 6h) multi wall array type carbon nanotube of 25.5g preparatory ball milling, pours into high energy after mixing evenly
Continue high-energy ball milling in ball mill to dry afterwards for 24 hours (ball milling speed 600rpm).Mixture after drying is placed in tube furnace,
In N2800 DEG C of calcining 4h are carried out under atmosphere, the product after Temperature fall washed once with the hydrochloric acid solution of 2mol/L, deionization
It is filtered after water washing 2 times and can be obtained nitrogen-doped carbon nanometer pipe after dry.Nitrogen-doped carbon nanometer pipe and PC and PBT resin particle
It is nitrogen-doped carbon nanometer pipe: PC (polycarbonate): PBT (polybutylene terephthalate (PBT))=3:20:80 according to mass ratio
It is configured and is mixed, mixture is then sent into parallel double-screw extruding granulator and carries out extruding pelletization, 20 type extruders turn
Fast 120rpm, rate of feeding 500rpm, 250 DEG C of extrusion temperature, obtained conductive plastics particle multitester measuring its resistivity.
The nitrogen-doped carbon nanometer pipe of the present embodiment is 7.56% by its N element doping content of determination of elemental analysis, the conductive modeling of preparation
The surface resistivity for expecting particle is 3.75*104Ω。
Embodiment 5
The method of conductive plastics is prepared in the present embodiment with embodiment 1, the difference is that: total matter based on conductive plastics
Amount, the content of nitrogen-doped carbon nanometer pipe are 0.1wt%.
The nitrogen-doped carbon nanometer pipe of the present embodiment is 5.29% by its N element doping content of determination of elemental analysis, preparation
Conductive plastics particle surface resistivity be 8.75*108Ω。
Embodiment 6
The method of conductive plastics is prepared in the present embodiment with embodiment 1, the difference is that: total matter based on conductive plastics
Amount, the content of nitrogen-doped carbon nanometer pipe are 20wt%.
The nitrogen-doped carbon nanometer pipe of the present embodiment is 5.29% by its N element doping content of determination of elemental analysis, preparation
Conductive plastics particle surface resistivity be 45.8 Ω.
Comparative example 1:
Multi wall winding-type carbon nanotube is configured and mixed with high-impact polystyrene resin particle and (wherein, is received based on carbon
The gross mass of mitron and high-impact polystyrene resin particle, the content of carbon nanotube are 3wt%), then carry out parallel double spiral shells
Bar extruding pelletization, 20 type extruder revolving speed 120rpm, rate of feeding 1000rpm, 220 DEG C of extrusion temperature, obtained conductive plastics
Particle its resistivity of multitester measuring.The surface resistivity of the conductive plastics particle of this comparative example preparation is 6.35*105Ω。
Comparative example 2:
Multi wall winding-type carbon nanotube is configured and is mixed with MAPE resin particle (wherein, based on carbon nanotube with
The gross mass of MAPE resin particle, the content of carbon nanotube are 5wt%), parallel double-screw extruding pelletization is then carried out, 20 types squeeze
Machine revolving speed 40rpm out, rate of feeding 300rpm, 150 DEG C of extrusion temperature, its electricity of obtained conductive plastics particle multitester measuring
Resistance rate.The surface resistivity of the conductive plastics particle of this comparative example preparation is 4.36*104Ω。
Comparative example 3:
It according to mass ratio is carbon nanotube: PC:PBT=by multi wall array type carbon nanotube and PC and PBT resin particle
3:20:80 is configured and is mixed, and parallel double-screw extruding pelletization, 20 type extruder revolving speed 120rpm, feeding speed are then carried out
Spend 500rpm, 250 DEG C of extrusion temperature, obtained conductive plastics particle multitester measuring its resistivity.The preparation of this comparative example
The surface resistivity of conductive plastics particle is 2.94*105Ω。
Comparative example 4:
Multi wall winding-type carbon nanotube is configured and mixed with high-impact polystyrene resin particle and (wherein, is based on
The gross mass of carbon nanotube and high-impact polystyrene resin particle, the content of carbon nanotube are 0.1wt%), it then carries out flat
Row double-screw extruding pelletizing, 20 type extruder revolving speed 120rpm, rate of feeding 1000rpm, 220 DEG C of extrusion temperature, what is obtained leads
Electric plastic grain its resistivity of multitester measuring.The surface resistivity of the conductive plastics particle of this comparative example preparation is 4.21*
1012Ω。
Comparative example 5
The method of conductive plastics is prepared in the present embodiment with embodiment 1, the difference is that: total matter based on conductive plastics
Amount, the content of nitrogen-doped carbon nanometer pipe are 0.05wt%.
The nitrogen-doped carbon nanometer pipe of the present embodiment is 5.29% by its N element doping content of determination of elemental analysis, preparation
Conductive plastics particle surface resistivity be 3.36*1015Ω。
Comparative example 6
The method of conductive plastics is prepared in the present embodiment with embodiment 1, the difference is that: total matter based on conductive plastics
Amount, the content of nitrogen-doped carbon nanometer pipe are 25wt%.
The nitrogen-doped carbon nanometer pipe of the present embodiment is 5.29% by its N element doping content of determination of elemental analysis, preparation
Conductive plastics particle be difficult to form.
In addition, term " first ", " second " are used for descriptive purposes only and cannot be understood as indicating or suggesting relative importance
Or implicitly indicate the quantity of indicated technical characteristic.Define " first " as a result, the feature of " second " can be expressed or
Implicitly include one or more of the features.In the description of the present invention, the meaning of " plurality " is two or more,
Unless otherwise specifically defined.
In the description of this specification, reference term " one embodiment ", " some embodiments ", " example ", " specifically show
The description of example " or " some examples " etc. means specific features, structure, material or spy described in conjunction with this embodiment or example
Point is included at least one embodiment or example of the invention.In the present specification, schematic expression of the above terms are not
It must be directed to identical embodiment or example.Moreover, particular features, structures, materials, or characteristics described can be in office
It can be combined in any suitable manner in one or more embodiment or examples.In addition, without conflicting with each other, the skill of this field
Art personnel can tie the feature of different embodiments or examples described in this specification and different embodiments or examples
It closes and combines.
Although the embodiments of the present invention has been shown and described above, it is to be understood that above-described embodiment is example
Property, it is not considered as limiting the invention, those skilled in the art within the scope of the invention can be to above-mentioned
Embodiment is changed, modifies, replacement and variant.
Claims (10)
1. a kind of conductive plastics characterized by comprising
Resin matrix；
Nitrogen-doped carbon nanometer pipe, the nitrogen-doped carbon nanometer pipe are dispersed in the resin matrix.
2. conductive plastics according to claim 1, which is characterized in that the gross mass based on the conductive plastics, the nitrogen
The content of doped carbon nanometer pipe is 0.1wt%-20wt%.
3. conductive plastics according to claim 1, which is characterized in that the gross mass based on the nitrogen-doped carbon nanometer pipe,
The doping of nitrogen is 0.1wt%-20wt%.
4. conductive plastics according to claim 1, which is characterized in that the draw ratio of the nitrogen-doped carbon nanometer pipe is 10-
100000, crimpness 0.1%-50%.
5. conductive plastics according to claim 1, which is characterized in that the material for forming the resin matrix includes poly- third
Alkene, polyethylene, polycarbonate, polystyrene, acrylonitrile-butadiene-styrene copolymer, polybutylene terephthalate (PBT),
Polyethylene terephthalate, polyphenylene sulfide, polyvinyl chloride, polyamide, polymethyl methacrylate, epoxy resin, benzene second
At least one of ethylenic thermoplastic elastomer, olefin hydrocarbons thermoplasticity elastic body and polyurethane-type thermoplastic elastomer.
6. conductive plastics according to claim 1, which is characterized in that the gross mass based on the conductive plastics, it is described to lead
Electric plastics include:
The nitrogen-doped carbon nanometer pipe of 0.1wt%-20wt%；
The auxiliary agent of 0.1wt%-50wt%；And
The resin matrix of surplus,
Optionally, the auxiliary agent includes dispersing agent；
Optionally, the dispersing agent includes that polyethylene wax, calcium stearate, vinyl bis-stearamides and ethene-vinyl acetate are total
At least one of polymers.
7. a method of prepare conductive plastics described in any one of claims 1-6 characterized by comprising
N doping is entered in carbon nanotube, to obtain nitrogen-doped carbon nanometer pipe；
Extruding pelletization processing is carried out after the nitrogen-doped carbon nanometer pipe is mixed with resin matrix, obtains the conductive plastics.
8. the method according to the description of claim 7 is characterized in that it is described N doping is entered in carbon nanotube include:
In a solvent by nitrogen source dispersion, to obtain the first mixed liquor；
The first ball-milling treatment is carried out after carbon nanotube is mixed with first mixed liquor, to obtain the second mixed liquor；
It will be calcined under an inert atmosphere after second mixed liquor drying, to obtain the nitrogen-doped carbon nanometer pipe,
Optionally, the nitrogen source in melamine, urea, polyacrylonitrile, polyvinylpyridine, pyrroles, quinoline at least
One of；
Optionally, the solvent is selected from least one of formaldehyde, ethyl alcohol, acetone；
Optionally, the revolving speed of first ball-milling treatment is 200-800 revs/min, time 2-24h；
Optionally, the temperature of the calcining is 400-1000 degrees Celsius, time 0.5-10h.
9. according to the method described in claim 8, it is characterized in that, the carbon nanotube is mixed it with first mixed liquor
Before further include the steps that by the carbon nanotube carry out the second ball-milling treatment；
Optionally, the revolving speed of second ball-milling treatment is 200-600 revs/min, time 1-10h.
10. a kind of shell, which is characterized in that at least part of the shell is using described in any one of claims 1-6
What conductive plastics was prepared.
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| CN114454568A (en) * | 2020-10-22 | 2022-05-10 | 中国石油化工股份有限公司 | High-impact PVC (polyvinyl chloride) pipe for gas drainage of coal mine and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103985884A (en) * | 2014-05-21 | 2014-08-13 | 华中科技大学 | Nitrogen-doped carbon nano-material as well as preparation method and application thereof |
| CN108017840A (en) * | 2017-12-27 | 2018-05-11 | 新奥石墨烯技术有限公司 | Conductive plastics and preparation method thereof |
| CN108102183A (en) * | 2017-12-27 | 2018-06-01 | 新奥石墨烯技术有限公司 | Conductive rubber and preparation method thereof |
-
2018
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103985884A (en) * | 2014-05-21 | 2014-08-13 | 华中科技大学 | Nitrogen-doped carbon nano-material as well as preparation method and application thereof |
| CN108017840A (en) * | 2017-12-27 | 2018-05-11 | 新奥石墨烯技术有限公司 | Conductive plastics and preparation method thereof |
| CN108102183A (en) * | 2017-12-27 | 2018-06-01 | 新奥石墨烯技术有限公司 | Conductive rubber and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114454568A (en) * | 2020-10-22 | 2022-05-10 | 中国石油化工股份有限公司 | High-impact PVC (polyvinyl chloride) pipe for gas drainage of coal mine and preparation method thereof |
| CN114454568B (en) * | 2020-10-22 | 2023-06-16 | 中国石油化工股份有限公司 | High-impact PVC (polyvinyl chloride) pipe for extracting and discharging gas for coal mine and preparation method thereof |
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