CN109736087A - Carbon nanometer fabric and preparation method thereof - Google Patents
Carbon nanometer fabric and preparation method thereof Download PDFInfo
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- CN109736087A CN109736087A CN201811505041.0A CN201811505041A CN109736087A CN 109736087 A CN109736087 A CN 109736087A CN 201811505041 A CN201811505041 A CN 201811505041A CN 109736087 A CN109736087 A CN 109736087A
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Abstract
The present invention relates to a kind of carbon nanometer fabrics and preparation method thereof.The preparation method includes the following steps: unsaturated dicarboxylic, brominated styrene and methyl methacrylate progress polymerization reaction obtaining copolymer；Under the first protective gas atmosphere, graft reaction is carried out to copolymer and carbon nano pipe array, obtains modified carbon nano-tube array；Modified carbon nano-tube array is subjected to spinning, obtains carbon nano-fiber；Presoma is formed on carbon nano-fiber, and is reacted at 140 DEG C~160 DEG C under the second protective gas atmosphere, modified fibre is obtained, and presoma is selected from least one of polystyrene resin and epoxy resin；Modified fibre is weaved to obtain modified cloth, modified cloth is placed in immersion in lytic agent and obtains carbon nanometer fabric.The carbon nanometer fabric that above-mentioned preparation method obtains has both electric conductivity and flexibility.
Description
Technical field
The present invention relates to field of material technology, more particularly to a kind of carbon nanometer fabric and preparation method thereof.
Background technique
Fiber cloth is also known as carbon fiber sheet.Because of composite material intensity with higher and lighter in weight made of it, in state
" black gold " is known as on border, it is referred to as " third generation material " after the metals such as stone implement and steel in the world.However,
The conductivity of the cloth of traditional carbon nano-fiber production is lower, causes manufactured clothing antistatic performance poor, and cloth is soft
Toughness is poor.
Summary of the invention
Based on this, it is necessary to provide a kind of preparation method of carbon nanometer fabric, the carbon nanometer fabric which obtains
Have both flexibility and static electricity resistance.
Further it is provided that a kind of carbon nanometer fabric.
A kind of preparation method of carbon nanometer fabric, includes the following steps:
Unsaturated dicarboxylic, brominated styrene and methyl methacrylate progress polymerization reaction are obtained into copolymer, it is described
Unsaturated dicarboxylic is selected from least one of citraconic acid and dimethyl maleic acid；
Under the first protective gas atmosphere, graft reaction is carried out to the copolymer and carbon nano pipe array, is changed
Property carbon nano pipe array；
The modified carbon nano-tube array is subjected to spinning, obtains carbon nano-fiber；
Presoma is formed on the carbon nano-fiber, and under the second protective gas atmosphere at 140 DEG C~160 DEG C
Reaction, obtains modified fibre, and the presoma is selected from least one of polystyrene resin and epoxy resin；
The modified fibre is weaved, modified cloth is obtained；And
The modified cloth is placed in lytic agent and is impregnated, carbon nanometer fabric is obtained, contains acetone in the lytic agent.
The preparation method of above-mentioned carbon nanometer fabric, by unsaturated dicarboxylic, brominated styrene and methyl methacrylate into
Row polymerization reaction obtains copolymer, and unsaturated dicarboxylic is selected from least one of citraconic acid and dimethyl maleic acid, then uses
Ultraviolet light is by the surface of copolymer grafted to carbon nano pipe array, in the carbon nano-fiber made of the modified carbon nano-tube
Upper formation presoma is selected from least one of polystyrene resin and epoxy resin, so that presoma and copolymer-
COOR- (ester group) reaction, obtains the preferable modified fibre of flexibility, so that the cloth being made from it has preferable flexibility,
By impregnating modified cloth in the lytic agent containing acetone, so that the conjugate that copolymer and presoma are formed is from modified cloth
Removing, guarantees the electric conductivity of carbon nanometer fabric to restore the structure of carbon nanotube.Experiment proves that above-mentioned preparation method obtains
The flexibility of the carbon nanometer fabric arrived is 5.75 × 10-3mm2/ kN~7.19 × 10-3mm2/ kN, resistivity are 5.17 × 10-5
M~6.90 × 10 Ω-5Ω m, has both flexibility and antistatic performance.
It is described in one of the embodiments, to carry out unsaturated dicarboxylic, brominated styrene and methyl methacrylate
Polymerization reaction obtains the step of copolymer specifically: by the unsaturated dicarboxylic, the brominated styrene, the metering system
Sour methyl esters and initiator mixing, and Raolical polymerizable is carried out at 60 DEG C~65 DEG C, the reaction time is 6h~8h, described to draw
Hair agent is azodiisobutyronitrile.
The molar ratio of the initiator and the unsaturated dicarboxylic is 1:18~1:24 in one of the embodiments,.
Further include before the described the step of modified cloth is placed in immersion in lytic agent in one of the embodiments,
Following steps: in third protective gas atmosphere, heating pressurized treatments are carried out to the modified cloth.
In one of the embodiments, in described the step of carrying out heating pressurized treatments to the modified cloth, heating temperature
Degree is 110 DEG C~115 DEG C, and pressure is 45kPa~98kPa, and the processing time is 5min~60min.
It is described in one of the embodiments, that the modified cloth was placed in the step of impregnating in lytic agent, it is described molten
The aqueous solution that agent is the acetone for being 90%~100% containing mass percentage is solved, the time of immersion is 70min~100min.
It is described in one of the embodiments, that presoma is formed on the carbon nano-fiber, and in 140 DEG C~160 DEG C
In the step of lower reaction, the reaction time is 1h~2h.
The weight average molecular weight of the copolymer is 3500~30000 in one of the embodiments,；And/or
The mass ratio of the unsaturated dicarboxylic, the brominated styrene and the methyl methacrylate is (2~7):
(9~14): (4~7).
The presoma is made of polystyrene resin and epoxy resin in one of the embodiments, and the polyphenyl
The molar ratio of vinyl and the epoxy resin is 1:99~1:92.
The preparation method of a kind of carbon nanometer fabric, above-mentioned carbon nanometer fabric is prepared.
Specific embodiment
It to facilitate the understanding of the present invention, below will be to invention is more fully described.But the present invention can be to be permitted
Mostly different form is realized, however it is not limited to embodiment described herein.On the contrary, purpose of providing these embodiments is makes
It is more thorough and comprehensive to the understanding of the disclosure.
Unless otherwise defined, all technical and scientific terms used herein and belong to technical field of the invention
The normally understood meaning of technical staff is identical.Term as used herein in the specification of the present invention is intended merely to description tool
The purpose of the embodiment of body, it is not intended that in the limitation present invention.
The preparation method of the carbon nanometer fabric of one embodiment, the carbon nanometer fabric of preparation have both static electricity resistance and flexible
Property.The preparation method of the carbon nanometer fabric includes the following steps S110~S160:
S110, unsaturated dicarboxylic, brominated styrene and methyl methacrylate progress polymerization reaction are obtained into copolymer.
Unsaturated dicarboxylic is selected from least one of citraconic acid and dimethyl maleic acid.
The weight average molecular weight of copolymer is 5000~26000 in one of the embodiments,.Further, copolymer
Weight average molecular weight is 7500~17500.
The mass ratio of unsaturated dicarboxylic, brominated styrene and methyl methacrylate is in one of the embodiments,
(2~7): (9~14): (4~7).The copolymer grafted of this setting can either increase carbon modified in the surface of carbon nano pipe array
The hardness of nano-tube array, additionally it is possible to increase the distance between carbon nanotube, to reduce due to the Van der Waals between carbon nanotube
Reunion caused by power is obtained with the modified carbon nano-tube array being easily dispersed with can more preferably play the performance of carbon nanotube
To the better modified carbon nano-tube array of antistatic performance.
The mass ratio of styrene and methyl methacrylate is 1.5~2.5 in one of the embodiments,.Such setting
So that the adhesive force of modified carbon nano-tube array is more preferable.Further, the mass ratio of styrene and methyl methacrylate is 2.
It is such that the adhesive force for further increasing modified carbon nano-tube array is set.
Unsaturated dicarboxylic is made of citraconic acid and dimethyl maleic acid in one of the embodiments, and citraconic acid and
The molar ratio of dimethyl maleic acid is 0.8:1~1.13:1.Such setting can further increase the flexibility of modified fibre.Into
One step, the molar ratio of citraconic acid and dimethyl maleic acid is 1:1.
Unsaturated dicarboxylic, brominated styrene and methyl methacrylate are polymerize in one of the embodiments,
The step of reaction specifically: carry out unsaturated dicarboxylic, styrene and methyl methacrylate under ultraviolet light freely
Base polymerization reaction, and control reaction temperature be 20 DEG C~45 DEG C, ultraviolet ray intensity be 45W~55W, the reaction time be 30min~
40min。
Unsaturated dicarboxylic, brominated styrene and methyl methacrylate are polymerize in one of the embodiments,
Further include that solvent is added into the reactant of polymerization reaction after the step of reaction, precipitating is collected after separation of solid and liquid, is copolymerized
Object.Further, solvent is selected from least one of carbon tetrachloride, tetrahydrofuran and methylene chloride.The mode of separation of solid and liquid is
Centrifugation.It should be noted that the mode being separated by solid-liquid separation be not limited to it is above-mentioned point out method, can be other modes, such as can be
Filtering.
It further include being done to precipitating after the step of collecting precipitating after separation of solid and liquid in one of the embodiments,
Dry step, to obtain dry copolymer.It should be noted that being carried out if precipitating can satisfy demand to precipitating
Dry step can be omitted.
S120, under the first protective gas atmosphere, graft reaction is carried out to copolymer and carbon nano pipe array, is changed
Property carbon nano pipe array.
Carbon nano-pipe array is classified as single-wall carbon nanotube array in one of the embodiments,.It should be noted that carbon nanometer
Pipe array is also possible to array of multi-walled carbon nanotubes.It should be noted that using the preparation side of above-mentioned modified carbon nano-tube array
When method, the surface of single-wall carbon nanotube array is bigger compared with the surface modification difficulty of array of multi-walled carbon nanotubes.
The length of carbon nano pipe array is 650 μm~1200 μm in one of the embodiments,.Carbon in carbon nano pipe array
The diameter of nanotube is 10nm~15nm.
S120 specifically includes S121~S124 in one of the embodiments:
S121, the deposit catalyst layers in the first substrate.
Catalyst layer is formed on the surface of the first substrate using electron beam evaporation method in one of the embodiments,.Into one
The material on step ground, catalyst layer is selected from least one of iron, cobalt and nickel.Catalyst layer with a thickness of 20nm~23nm.
The first substrate is alumina plate in one of the embodiments,.The main function of first substrate is to carrying carbon
Nano-tube array.Further, the size of the first substrate is 8 feet.Certainly, in other embodiments, the size of the first substrate
It is also possible to any other size.Further, the first substrate has the first working face.It deposits to be formed in the first working face and urge
Agent layer.
S122, under protective gas atmosphere, after the first substrate for being formed with catalyst is warming up to 550 DEG C~900 DEG C,
It is passed through carbon-source gas reaction again, obtains carbon nano pipe array.
In one of the embodiments, by the first substrate for being deposited with catalyst layer be placed in chemical gas phase reaction furnace into
Row reaction.Further, it is first passed through protective gas into chemical gas phase reaction furnace, then increases the temperature of chemical gas phase reaction furnace
To 550 DEG C~900 DEG C, so that catalyst layer homogeneous nucleation in the first substrate；Carbon-source gas is passed through thereto again to be reacted.
Further, carbon-source gas includes ethylene and hexane, and the partial pressure ratio of ethylene and hexane is 1.25:1~8:
1.The flow velocity of carbon-source gas is 5mL/min~15mL/min, and being passed through the time that carbon-source gas is reacted is 10min~25min.
It is arranged by this, the mechanical property of obtained carbon nano pipe array is preferable, to obtain the preferable modified fibre of flexibility.
Protective gas is selected from least one of nitrogen, hydrogen, argon gas and helium in one of the embodiments,.
S123, copolymer is formed in the second substrate.
The second substrate is nickel sheet or copper sheet in one of the embodiments,.The main function of second substrate is to carrying
Copolymer, and nickel sheet and the chemical stability of copper sheet are good, will not react with copolymer.Further, the ruler of the second substrate
Very little is 50mm*50mm, and certainly, in other embodiments, the size of the second substrate is also possible to any other size.
Copolymer is set in the second substrate in a manner of film in one of the embodiments,.Further, second
The copolymer film formed in substrate with a thickness of 1mm~5mm.Certainly, in other embodiments, copolymer can also first be sheared
Material is placed in the mode in the second substrate again.Further, the second substrate has the second working face.The shape on the second working face
At copolymer film.The second working face is completely covered in copolymer film.
S123, under the first protective gas atmosphere, to the first substrate for being formed with carbon nano pipe array and be formed with altogether
Second substrate of polymers carries out ultraviolet light processing, so that copolymer and carbon nano pipe array carry out graft reaction, is changed
Property carbon nano pipe array.
Using ultraviolet light by the surface of copolymer grafted to carbon nano pipe array, and specific copolymer is selected, so that
Modified carbon nano-tube array is easily dispersed, and can prepare has preferable flexible modified fibre, and carbon modified can be made to receive
Mitron array adhesive force with higher can be used in preparing the higher cloth of adhesive force.
By the first substrate for being formed with carbon nano pipe array and it is formed with the second of copolymer in one of the embodiments,
Substrate is placed in same reaction chamber.Reaction chamber can be closed, and reaction chamber has an air inlet and a gas outlet.It is set in reaction chamber
There is ultraviolet light module, ultraviolet light processing can be carried out to reaction chamber.
Further, it by the first substrate for being formed with carbon nano pipe array and the second substrate for being formed with copolymer and discharges
It is placed in reaction chamber.Further, the first substrate of carbon nano pipe array will be formed with and be formed with the second base of copolymer
Bottom is placed side by side, so that carbon nano pipe array is contacted with copolymer.
To the first substrate for being formed with carbon nano pipe array and it is formed with the second of copolymer in one of the embodiments,
During substrate carries out ultraviolet light processing, the air inlet of capping chamber and gas outlet first, and reaction chamber is carried out
Vacuumize process makes the air pressure in reaction chamber be down to 10-2Torr or less.Preferably, make air pressure drop in reaction chamber down to 10- 6Torr or less.Secondly, being passed through protective gas into reaction chamber until reaching normal atmosphere (An) by air inlet again, open out
Port, it is not open close enter protective gas keep system pressure.
The flow velocity of the first protective gas is 2L/min~3L/min in one of the embodiments,.First protectiveness gas
Body is selected from least one of nitrogen, helium, neon and argon gas.
To the first substrate for being formed with carbon nano pipe array and it is formed with the second of copolymer in one of the embodiments,
When substrate carries out ultraviolet light processing, the irradiation power of ultraviolet light is 15mW~35mW.Under this irradiation power, be conducive to mention
The fuel factor of high reaction system, so that system temperature is increased to copolymer and forms gaseous state, and in protective gas air-flow
Graft polymerization reaction occurs for the surface and carbon nano pipe array that carbon nano pipe array is moved under effect.
Ultraviolet light is the monochrome that illumination wavelength is 196nm~350nm in one of the embodiments,
(monochromatic) narrow band light.Further, monochromatic narrow band light is the monochromatic light that bandwidth is 218nm~298nm.
Ultraviolet source distance is formed with the first substrate of carbon nano pipe array and is formed with altogether in one of the embodiments,
The distance of second substrate of polymers is 2mm~20mm.
The time for carrying out ultraviolet light processing in one of the embodiments, is 10min~35min.One wherein
In embodiment, the time for carrying out ultraviolet light processing is 15min~30min.Ultraviolet light is carried out in one of the embodiments,
The time for the treatment of with irradiation is 23min.
To the first substrate for being formed with carbon nano pipe array and it is formed with the second of copolymer in one of the embodiments,
When substrate carries out ultraviolet light processing, the irradiation power of ultraviolet light is 15mW~35mW, and ultraviolet light is 196nm~350nm's
Monochromatic narrow band light, the time for carrying out ultraviolet light processing is 15min~30min.With this condition, be conducive to guaranteeing to be copolymerized
Object reduces destruction of the ultraviolet light to copolymer and carbon nano tube array structure in the case where capable of being grafted to carbon nano pipe array, with
Guarantee the mechanical property of carbon nano pipe array.
To the first substrate for being formed with carbon nano pipe array and it is formed with the second of copolymer in one of the embodiments,
It further include the behaviour that the first substrate is placed in natural cooling under protective gas atmosphere after substrate carries out ultraviolet light processing
Make.It should be noted that in other embodiments, the first substrate to be placed in the operation of natural cooling under protective gas atmosphere
Also it can be omitted.
The first substrate is placed under protective gas atmosphere in the operation of natural cooling in one of the embodiments,
Protective gas is selected from least one of nitrogen, argon gas and helium.By the first substrate be placed under protective gas atmosphere into
Row natural cooling can prevent carbon nano pipe array exposure to be oxidized in air.
S130, spinning is carried out to modified carbon nano-tube array, obtains carbon nano-fiber.
The step of S130 in one of the embodiments, specifically: using clamping tool from modified carbon nano-tube array
Edge clamps modified carbon nano-tube array, and is pulled and revolved along the direction perpendicular to modified carbon nano-tube array growth
Turn, so that modified carbon nano-tube array is stretched, and every modified carbon nano-tube in modified carbon nano-tube array is made to be screwed in one
It rises, obtains carbon nano-fiber.
In clamping tool drawing and modifying carbon nano pipe array, modified carbon nano-tube is by Van der Waals force and modification in modification
Non-covalent interaction power between the copolymer on carbon nano pipe array surface or the decomposition product of copolymer drives carbon modified to receive
Mitron array is continuously drawn out in filiform, makes modified carbon nano-tube array by rotating modified carbon nano-tube array
In every modified carbon nano-tube be threaded together, as carbon nano-fiber.
Further, the step of S130 specifically: clamp modified carbon nano-tube battle array from the edge of modified carbon nano-tube array
Column, and pulled along the direction perpendicular to modified carbon nano-tube array growth, obtain silky nano pipe array；It is received from filiform
The edge of mitron array clamps silky nano pipe array, and is rotated along the extending direction perpendicular to silky nano pipe array
And pull, so that silky nano pipe array is stretched, and is threaded together every silky nano pipe in silky nano pipe array,
Obtain carbon nano-fiber.
When clamping modified carbon nano-tube array from the edge of modified carbon nano-tube array in one of the embodiments, folder
The width taken is 50 μm~200 μm.Further, modified carbon nano-tube array is clamped from the edge of modified carbon nano-tube array
When, the width of clamping is 100 μm~150 μm.
Speed when being pulled in one of the embodiments, along the direction perpendicular to modified carbon nano-tube array growth
Rate is 0.05m/s~0.5mm/s.Further, when being pulled along the direction perpendicular to modified carbon nano-tube array growth
Rate be 0.1m/s~0.4mm/s.Further, it is dragged along the direction perpendicular to modified carbon nano-tube array growth
Rate when dragging is 0.2m/s~0.3mm/s.
Turn when being rotated in one of the embodiments, along the direction perpendicular to modified carbon nano-tube array growth
Speed is 1000rpm~3000rpm.Further, when being rotated along the direction perpendicular to modified carbon nano-tube array growth
Revolving speed be 2000rpm.
The diameter of carbon nano-fiber is 10 μm~200 μm in one of the embodiments,.
The length of carbon nano-fiber is 100m~6000m in one of the embodiments,.It should be noted that carbon nanometer
The length of fiber is not limited to above-mentioned length, can be configured according to actual needs.
S140, presoma is formed on carbon nano-fiber, and in 140 DEG C~160 DEG C under the second protective gas atmosphere
Lower reaction, obtains modified fibre, and presoma is selected from least one of polystyrene resin and epoxy resin.
By forming presoma on carbon nano-fiber, and specific presoma is selected, so that presoma and copolymer-
COOR- reaction, obtains the preferable modified fibre of flexibility.
It should be noted that the presoma formed on carbon nano-fiber can come into full contact with copolymer.Further,
The surface of carbon nano-fiber can be completely covered in the presoma formed on carbon nano-fiber, to guarantee that presoma is filled with copolymer
Tap touching.
In one of the embodiments, the second protective gas in nitrogen, helium, neon and argon gas at least one
Kind.
Presoma is formed on carbon nano-fiber in one of the embodiments, and under the second protective gas atmosphere
In the step of reacting at 140 DEG C~160 DEG C, the reaction time is 1h~2h.Under this reaction time, presoma and carbon can be made
Nanofiber sufficiently reacts, to guarantee the wetability of modified fibre.
In one of the embodiments, by spraying presoma on carbon nano-fiber, so as to be formed on carbon nano-fiber
Presoma.Such setting, enables the surface coated on carbon nano-fiber that presoma is more uniform.Further, forerunner
Body is misty or film-form.It should be noted that the mode for forming presoma on carbon nano-fiber is not limited to the above-mentioned side of pointing out
Method can be other modes, such as coat.
Presoma is made of polystyrene resin and epoxy resin in one of the embodiments, and polystyrene resin
And the molar ratio of epoxy resin is 1:99~1:92.Such setting, can obtain that wetability is more preferable and flexibility is preferably modified
Fiber.
S150, modified fibre is weaved, obtains modified cloth.
Modified fibre is woven by cloth using traditional Weaving method in one of the embodiments,.Traditional weaving
Method for example can be flat weaving method or twill.It should be noted that can be weaved using single modified fibre, it can also
It is weaved again so that more modified fibres are made one in parallel.
S160, modified cloth is placed in lytic agent and is impregnated, obtained carbon nanometer fabric, contain acetone in lytic agent.
By impregnating modified cloth in the lytic agent containing acetone, so that the conjugate that is formed with presoma of copolymer is from changing
It is removed on property cloth, guarantees the electric conductivity of carbon nanometer fabric to restore the structure of carbon nanotube.
Modified cloth was placed in the step of impregnating in lytic agent in one of the embodiments, lytic agent is to contain matter
The aqueous solution for the acetone that percentage composition is 90%~100% is measured, the time of immersion is 70min~100min.Further, it dissolves
Agent is the aqueous solution for the acetone for being 98%~100% containing mass percentage, and the time of immersion is 75min~85min.
It further includes walking as follows that modified cloth, which was placed in front of the step of impregnating in lytic agent, in one of the embodiments,
It is rapid: in third protective gas atmosphere, heating pressurized treatments being carried out to modified cloth.Wherein, third protective gas is selected from
At least one of nitrogen, helium, neon and argon gas.By carrying out heating pressurized treatments to modified cloth, advantageous cloth at
Type, so that carbon nano-fiber arrangement is finer and close, to guarantee the mechanical property of modified cloth.
In the step of carrying out heating pressurized treatments to modified cloth in one of the embodiments, heating temperature is 110 DEG C
~115 DEG C, pressure is 45kPa~98kPa, and the processing time is 5min~60min.Further, pressure is 60kPa~80kPa,
The processing time is 10min~30min.
The preparation method of above-mentioned carbon nanometer fabric, by unsaturated dicarboxylic, brominated styrene and methyl methacrylate into
Row polymerization reaction obtains copolymer, and unsaturated dicarboxylic is selected from least one of citraconic acid and dimethyl maleic acid, then uses
Ultraviolet light is by the surface of copolymer grafted to carbon nano pipe array, in the carbon nano-fiber made of the modified carbon nano-tube
Upper formation presoma is selected from least one of polystyrene resin and epoxy resin, so that presoma and copolymer-
COOR- (ester group) reaction, obtains the preferable modified fibre of flexibility, so that the cloth being made from it has preferable flexibility,
By impregnating modified cloth in the lytic agent containing acetone, so that the conjugate that copolymer and presoma are formed is from modified cloth
Removing, guarantees the electric conductivity of carbon nanometer fabric to restore the structure of carbon nanotube.Experiment proves that above-mentioned preparation method obtains
The flexibility of the carbon nanometer fabric arrived is 5.75 × 10-3mm2/ kN~7.19 × 10-3mm2/ kN, resistivity are 5.17 × 10-5
M~6.90 × 10 Ω-5Ω m, has both flexibility and antistatic performance.
Furthermore above-mentioned preparation method does not need to disperse carbon nano pipe array to carry out subsequent processing, work in a solvent
Skill simplifies, and will not destroy the array structure of carbon nano pipe array, advantageously ensures that modified carbon nano-tube array and modified fibre
Mechanical property, solvent-free equal residual, the purity of obtained modified fibre are higher.
It is below the part of specific embodiment.
Unless otherwise instructed, following embodiment is not known without containing other in addition to the inevitable impurity and points out
Component.First substrate is alumina plate.Second substrate is copper sheet.The surface of carbon nano-fiber is completely covered in presoma.Asphalt mixtures modified by epoxy resin
Rouge is bisphenol A type epoxy resin.Ultraviolet light is the monochromatic light that bandwidth is 256nm.
Embodiment 1
The preparation process of the carbon nanometer fabric of the present embodiment is as follows:
(1) take one piece of first substrate, deposition forms the catalyst layer of 20nm thickness in the first substrate, catalyst layer be nickel with
The mixing material (mass ratio of nickel and cobalt is 1:1) of cobalt, then the first substrate is placed in chemical vapour deposition reactor furnace and is passed through
Nitrogen, then be warming up to 900 DEG C, then into chemical vapour deposition reactor furnace be passed through carbon-source gas (carbon-source gas includes ethylene and oneself
The partial pressure ratio of alkane, ethylene and hexane is 1.25:1), and the flow control of carbon-source gas reacts 25min at 15L/min,
So that the first substrate surface is completely covered with carbon nano pipe array, carbon nano-pipe array is classified as single-wall carbon nanotube array, carbon nanometer
The length of pipe array is 650 μm, and the diameter of carbon nanotube is 15nm in carbon nano pipe array.
(2) one piece of second substrate is taken, forms the copolymer film with a thickness of 1mm in the second substrate.The preparation of copolymer
Process are as follows: unsaturated dicarboxylic, brominated styrene, methyl methacrylate and initiator are mixed, and carried out certainly at 65 DEG C
By base polymerization reaction 6h, reactant is obtained；Solvent is added into reactant, collects precipitating after separation of solid and liquid, precipitating is done
It is dry, obtain copolymer.Initiator is AIBN.The molar ratio of initiator and unsaturated dicarboxylic is 1:18.Unsaturated dicarboxylic is
Citraconic acid.The mass ratio of unsaturated dicarboxylic, brominated styrene and methyl methacrylate is 2:9:7.Copolymer is divided equally again
Son amount is 5000.Solvent is carbon tetrachloride.
(3) the first substrate for being formed with carbon nano pipe array and the second substrate for being formed with copolymer is placed side by side in anti-
It answers in chamber, is formed with the first substrate of carbon nano pipe array and is formed with the second substrate of copolymer and be in same level, and
Carbon nano pipe array and copolymer contact；Reaction chamber is evacuated to air pressure and is down to 10-2It is being passed through nitrogen after Torr, is keeping nitrogen
Flow velocity is 2L/min, carries out ultraviolet light to the first substrate for being formed with carbon nano pipe array and the second substrate for being formed with copolymer
Treatment with irradiation, ultraviolet source distance be formed with the first substrate of carbon nano pipe array and be formed with the second substrate of copolymer away from
From for 2mm, the irradiation power of ultraviolet light is 35mW, and ultraviolet light is the monochromatic narrow band light that illumination wavelength is 196nm, and irradiation time is
35min；Ultraviolet light module is closed, the first substrate is exposed to nitrogen atmosphere down toward natural cooling, obtains modified carbon nano-tube battle array
Column.
(4) modified carbon nano-tube array is clamped from the edge of modified carbon nano-tube array using clamping tool, and along vertical
It is directly pulled and is rotated in the direction of modified carbon nano-tube array growth, obtain carbon nano-fiber.From modified carbon nano-tube battle array
When the edge of column clamps modified carbon nano-tube array, the width of clamping is 200 μm.The speed of dragging is 0.05mm/s, and revolving speed is
3000rpm.The diameter of obtained carbon nano-fiber is 10 μm.
(5) presoma is formed on carbon nano-fiber, and reacts 1h at 140 DEG C in nitrogen atmosphere, obtains modified fibre
Dimension, presoma is polystyrene resin.
(6) modified fibre is weaved, obtains modified cloth.Modified cloth is placed in lytic agent and impregnates 85min, is obtained
To carbon nanometer fabric, lytic agent is the aqueous solution for the acetone for being 90% containing mass percentage.
Embodiment 2
The preparation process of the carbon nanometer fabric of the present embodiment is as follows:
(1) take one piece of first substrate, deposition forms the catalyst layer of 23nm thickness in the first substrate, catalyst layer be nickel with
The mixing material (mass ratio of nickel and cobalt is 1:1) of cobalt, then the first substrate is placed in chemical vapour deposition reactor furnace and is passed through
Nitrogen, then be warming up to 550 DEG C, then into chemical vapour deposition reactor furnace be passed through carbon-source gas (carbon-source gas includes ethylene and oneself
The partial pressure ratio of alkane, ethylene and hexane is 8:1), and the flow control of carbon-source gas reacts 10min at 5L/min, so that
First substrate surface is completely covered with carbon nano pipe array, and carbon nano-pipe array is classified as single-wall carbon nanotube array, carbon nano-pipe array
The length of column is 1180 μm, and the diameter of carbon nanotube is 10nm in carbon nano pipe array.
(2) one piece of second substrate is taken, forms the copolymer film with a thickness of 5mm in the second substrate.The preparation of copolymer
Process is as follows: unsaturated dicarboxylic, brominated styrene, methyl methacrylate and initiator being mixed, and carried out at 60 DEG C
Raolical polymerizable 8h, obtains reactant；Solvent is added into reactant, collects precipitating after separation of solid and liquid, precipitating is carried out
It is dry, obtain copolymer.Wherein, the molar ratio of initiator AIBN, initiator and unsaturated dicarboxylic is 1:24.Unsaturation two
Carboxylic acid is dimethyl maleic acid.The mass ratio of unsaturated dicarboxylic, brominated styrene and methyl methacrylate is 7:14:4.Altogether
The weight average molecular weight of polymers is 26000.Solvent is tetrahydrofuran.
(3) the first substrate for being formed with carbon nano pipe array and the second substrate for being formed with copolymer is placed side by side in anti-
It answers in chamber, is formed with the first substrate of carbon nano pipe array and is formed with the second substrate of copolymer and be in same level, and
Carbon nano pipe array and copolymer contact；Reaction chamber is evacuated to air pressure and is down to 10-2It is being passed through nitrogen after Torr, is keeping nitrogen
Flow velocity is 3L/min, carries out ultraviolet light to the first substrate for being formed with carbon nano pipe array and the second substrate for being formed with copolymer
Treatment with irradiation, ultraviolet source distance be formed with the first substrate of carbon nano pipe array and be formed with the second substrate of copolymer away from
From for 20mm, the irradiation power of ultraviolet light is 15mW, and ultraviolet light is the monochromatic narrow band light that illumination wavelength is 350nm, irradiation time
For 10min；Ultraviolet light module is closed, the first substrate is exposed to nitrogen atmosphere down toward natural cooling, obtains modified carbon nano-tube
Array.
(4) modified carbon nano-tube array is clamped from the edge of modified carbon nano-tube array using clamping tool, and along vertical
Directly is pulled and rotated in the direction of modified carbon nano-tube array growth；Obtain carbon nano-fiber.From modified carbon nano-tube battle array
When the edge of column clamps modified carbon nano-tube array, the width of clamping is 50 μm.The speed of dragging is 0.5mm/s, and revolving speed is
1000rpm.The diameter of obtained carbon nano-fiber is 200 μm.
(5) presoma is formed on carbon nano-fiber, and reacts 2h at 160 DEG C in nitrogen atmosphere, obtains modified fibre
Dimension, presoma is epoxy resin.
(6) modified fibre is weaved, obtains modified cloth.Modified cloth is placed in lytic agent and impregnates 75min, is obtained
To carbon nanometer fabric, lytic agent is pure acetone.
Embodiment 3
The preparation process of the carbon nanometer fabric of the present embodiment is as follows:
(1) take one piece of first substrate, deposition forms the catalyst layer of 21nm thickness in the first substrate, catalyst layer be nickel with
The mixing material (mass ratio of nickel and cobalt is 1:1) of cobalt, then the first substrate is placed in chemical vapour deposition reactor furnace and is passed through
Nitrogen, then be warming up to 700 DEG C, then into chemical vapour deposition reactor furnace be passed through carbon-source gas (carbon-source gas includes ethylene and oneself
The partial pressure ratio of alkane, ethylene and hexane is 5:1), and the flow control of carbon-source gas reacts 20min at 10L/min, so that
First substrate surface is completely covered with carbon nano pipe array, and carbon nano-pipe array is classified as single-wall carbon nanotube array, carbon nano-pipe array
The length of column is 800 μm, and the diameter of carbon nanotube is 12nm in carbon nano pipe array.
(2) one piece of second substrate is taken, forms the copolymer film with a thickness of 3mm in the second substrate.The preparation of copolymer
Process is as follows: unsaturated dicarboxylic, brominated styrene, methyl methacrylate and initiator being mixed, and carried out at 63 DEG C
Raolical polymerizable 7h, obtains reactant；Solvent is added into reactant, collects precipitating after separation of solid and liquid, precipitating is carried out
It is dry, obtain copolymer；Initiator is AIBN, and the molar ratio of initiator and unsaturated dicarboxylic is 1:20.Unsaturated dicarboxylic
Including citraconic acid and dimethyl maleic acid, and the molar ratio of citraconic acid and dimethyl maleic acid is 1:1.Unsaturated dicarboxylic, bromine
The mass ratio for changing styrene and methyl methacrylate is 4.5:12:6.The weight average molecular weight of copolymer is 15500.Solvent is two
Chlorination carbon.
(3) the first substrate for being formed with carbon nano pipe array and the second substrate for being formed with copolymer is placed side by side in anti-
It answers in chamber, is formed with the first substrate of carbon nano pipe array and is formed with the second substrate of copolymer and be in same level, and
Carbon nano pipe array and copolymer contact；Reaction chamber is evacuated to air pressure and is down to 10-2It is being passed through nitrogen after Torr, is keeping nitrogen
Flow velocity is 2.5L/min, is carried out to the first substrate for being formed with carbon nano pipe array and the second substrate for being formed with copolymer ultraviolet
Photo-irradiation treatment, ultraviolet source distance are formed with the first substrate of carbon nano pipe array and are formed with the second substrate of copolymer
Distance is 10mm, and the irradiation power of ultraviolet light is 25mW, and ultraviolet light is the monochromatic narrow band light that illumination wavelength is 256nm, when irradiation
Between be 23min；Ultraviolet light module is closed, the first substrate is exposed to nitrogen atmosphere down toward natural cooling, obtains modified carbon nano tube
Pipe array.
(4) modified carbon nano-tube array is clamped from the edge of modified carbon nano-tube array using clamping tool, and along vertical
It is directly pulled and is rotated in the direction of modified carbon nano-tube array growth, obtain carbon nano-fiber.From modified carbon nano-tube battle array
When the edge of column clamps modified carbon nano-tube array, the width of clamping is 130 μm.The speed of dragging is 0.3mm/s, and revolving speed is
2000rpm.The diameter of obtained carbon nano-fiber is 100 μm.
(5) presoma is sprayed on carbon nano-fiber, and reacts 1.5h at 150 DEG C in nitrogen atmosphere, is modified
Fiber, presoma are made of epoxy resin and polystyrene resin, and the molar ratio of polystyrene resin and epoxy resin is
1.1。
(6) modified fibre is weaved, obtains modified cloth.Modified cloth is placed in lytic agent and impregnates 80min, is obtained
To carbon nanometer fabric, lytic agent is the aqueous solution for the acetone for being 96% containing mass percentage.
Embodiment 4
The preparation process of the carbon nanometer fabric of the present embodiment is as follows:
(1) modified fibre is prepared according to (1) the step of embodiment 1~(5).
(2) modified fibre is weaved, obtains modified cloth.Heating pressurized treatments, heating temperature are carried out to modified cloth
Degree is 110 DEG C, pressure 98kPa, and the processing time is 60min.Modification cloth after heating pressurized treatments is placed in lytic agent
85min is impregnated, carbon nanometer fabric is obtained, lytic agent is the aqueous solution for the acetone for being 90% containing mass percentage.
Embodiment 5
The preparation process of the carbon nanometer fabric of the present embodiment is as follows:
(1) modified fibre is prepared according to (1) the step of embodiment 2~(5).
(2) modified fibre is weaved, obtains modified cloth.Heating pressurized treatments, heating temperature are carried out to modified cloth
Degree is 115 DEG C, pressure 45kPa, and the processing time is 5min.Modification cloth after heating pressurized treatments is placed in lytic agent and is soaked
75min is steeped, obtains carbon nanometer fabric, lytic agent is pure acetone.
Embodiment 6
The preparation process of the carbon nanometer fabric of the present embodiment is as follows:
(1) modified fibre is prepared according to (1) the step of embodiment 3~(5).
(2) modified fibre is weaved, obtains modified cloth.Heating pressurized treatments, heating temperature are carried out to modified cloth
Degree is 112 DEG C, pressure 70kPa, and the processing time is 20min.Modification cloth after heating pressurized treatments is placed in lytic agent
80min is impregnated, carbon nanometer fabric is obtained, lytic agent is the aqueous solution for the acetone for being 96% containing mass percentage.
Embodiment 7
The preparation process of the carbon nanometer fabric of the present embodiment is roughly the same with embodiment 1, the difference is that: it is unsaturated
The mass ratio of dicarboxylic acids, brominated styrene and methyl methacrylate is 2:9:6.
Embodiment 8
The preparation process of the carbon nanometer fabric of the present embodiment is roughly the same with embodiment 2, the difference is that: it is unsaturated
The mass ratio of dicarboxylic acids, brominated styrene and methyl methacrylate is 7:12.5:5.
Embodiment 9
The preparation process of the carbon nanometer fabric of the present embodiment is roughly the same with embodiment 6, the difference is that: presoma by
Polystyrene resin and epoxy resin composition, and it is 1:99 that polystyrene resin and epoxy resin, which are mass ratio,.
Embodiment 10
The preparation process of the carbon nanometer fabric of the present embodiment is roughly the same with embodiment 6, the difference is that: presoma by
Polystyrene resin and epoxy resin composition, and it is 1:92 that polystyrene resin and epoxy resin, which are mass ratio,.
Embodiment 11
The preparation process of the carbon nanometer fabric of the present embodiment is roughly the same with embodiment 6, the difference is that: citraconic acid and
The molar ratio of dimethyl maleic acid is 0.8:1.
Embodiment 12
The preparation process of the carbon nanometer fabric of the present embodiment is roughly the same with embodiment 6, the difference is that: citraconic acid and
The molar ratio of dimethyl maleic acid is 1.13:1.
Embodiment 13
The preparation process of the carbon nanometer fabric of the present embodiment is roughly the same with embodiment 6, the difference is that: it will be unsaturated
Dicarboxylic acids obtains reactant by Raolical polymerizable；Solvent is added into reactant, collects precipitating after separation of solid and liquid, it will
Precipitating is dried, and obtains copolymer.
Embodiment 14
The preparation process of the carbon nanometer fabric of the present embodiment is roughly the same with embodiment 6, the difference is that: by bromination benzene
Ethylene obtains reactant by Raolical polymerizable；Solvent is added into reactant, collects precipitating after separation of solid and liquid, will sink
Shallow lake is dried, and obtains copolymer.
Embodiment 15
The preparation process of the carbon nanometer fabric of the present embodiment is roughly the same with embodiment 6, the difference is that: by methyl-prop
E pioic acid methyl ester obtains reactant by Raolical polymerizable；Solvent is added into reactant, collects precipitating after separation of solid and liquid,
Precipitating is dried, copolymer is obtained.
Embodiment 16
The preparation process of the carbon nanometer fabric of the present embodiment is as follows:
(1) carbon nano-fiber is prepared according to (1) the step of embodiment 3~(4).
(2) carbon nano-fiber is weaved, obtains modified cloth.Modified cloth is placed in lytic agent and impregnates 80min,
Carbon nanometer fabric is obtained, lytic agent is the aqueous solution for the acetone for being 96% containing mass percentage.
Test:
Measure the modification cloth of embodiment 1~16 and flexibility, adhesive force and the conductivity of carbon nanometer fabric.Measurement result
See Table 1 for details.What table 1 indicated is the modification cloth of embodiment 1~16 and flexibility, adhesive force and the conductivity of carbon nanometer fabric.
Specifically, using the flexibility of extension test method measurement cloth；
Using the adhesive force of the method measurement cloth of 6854 defined of JIS K；
Using the resistivity of four-point method measurement cloth.
Table 1
As it can be seen from table 1 the flexibility of the carbon nanometer fabric of embodiment 1~13 is 7.77 × 10-3mm2/ kN~8.15
×10-3mm2/ kN is higher than embodiment 16, and the resistivity of the carbon nanometer fabric of Examples 1 to 3 is 5.17 × 10-5Ω m~
6.90×10-5Ω m is lower than embodiment 16, illustrates that the flexibility for the carbon nanometer fabric that above embodiment obtains is preferable, more
Comfortable cloth, quality is higher, can be used in the protective garment that production has preferable anti-static function.Meanwhile embodiment 1~13
The adhesive force of carbon nanometer fabric is 178MPa~193MPa, is higher than embodiment 16, illustrates the carbon nanometer that above embodiment obtains
Cloth is more docile.
Wherein, the flexibility of 1~13 carbon nanometer fabric of embodiment is respectively higher than the flexible of the modification cloth of embodiment 1~13
Property, illustrate that the immersion by lytic agent can be improved the flexibility of carbon nanometer fabric, so that carbon nanometer fabric is more docile and easypro
It is suitable.Meanwhile the resistivity of 1~13 carbon nanometer fabric of embodiment is respectively higher than the resistivity of the modification cloth of embodiment 1~13, says
The bright conductivity that can be improved carbon nanometer fabric by the immersion of lytic agent, to improve the antistatic performance of carbon nanometer fabric.
The flexibility and adhesive force of the carbon nanometer fabric of embodiment 3 are above embodiment 13~15, and illustrate unsaturation two
Copolymer made of carboxylic acid, brominated styrene and methyl methacrylate, which is more advantageous to, improves the flexibility of carbon nanometer fabric and attached
Put forth effort, obtains the higher cloth of quality.
In conclusion the preparation method of above embodiment, which can be prepared, has both flexibility, adhesive force and antistatic performance
Carbon nanometer fabric, can be used in preparing protective garment.
Each technical characteristic of embodiment described above can be combined arbitrarily, for simplicity of description, not to above-mentioned reality
It applies all possible combination of each technical characteristic in example to be all described, as long as however, the combination of these technical characteristics is not deposited
In contradiction, all should be considered as described in this specification.
The embodiments described above only express several embodiments of the present invention, and the description thereof is more specific and detailed, but simultaneously
It cannot therefore be construed as limiting the scope of the patent.It should be pointed out that coming for those of ordinary skill in the art
It says, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to protection of the invention
Range.Therefore, the scope of protection of the patent of the invention shall be subject to the appended claims.
Claims (10)
1. a kind of preparation method of carbon nanometer fabric, which comprises the steps of:
Unsaturated dicarboxylic, brominated styrene and methyl methacrylate progress polymerization reaction are obtained into copolymer, the insatiable hunger
At least one of citraconic acid and dimethyl maleic acid are selected from dicarboxylic acids；
Under the first protective gas atmosphere, graft reaction is carried out to the copolymer and carbon nano pipe array, obtains carbon modified
Nano-tube array；
The modified carbon nano-tube array is subjected to spinning, obtains carbon nano-fiber；
Presoma is formed on the carbon nano-fiber, and anti-at 140 DEG C~160 DEG C under the second protective gas atmosphere
It answers, obtains modified fibre, the presoma is selected from least one of polystyrene resin and epoxy resin；
The modified fibre is weaved, modified cloth is obtained；And
The modified cloth is placed in lytic agent and is impregnated, carbon nanometer fabric is obtained, contains acetone in the lytic agent.
2. the preparation method of carbon nanometer fabric according to claim 1, which is characterized in that it is described by unsaturated dicarboxylic,
Brominated styrene and methyl methacrylate carry out the step of polymerization reaction obtains copolymer specifically: by the unsaturated dicarboxyl
Sour, the described brominated styrene, the methyl methacrylate and initiator mixing, and radical polymerization is carried out at 60 DEG C~65 DEG C
Reaction is closed, the reaction time is 6h~8h, and the initiator is azodiisobutyronitrile.
3. the preparation method of carbon nanometer fabric according to claim 2, which is characterized in that the initiator and the insatiable hunger
Molar ratio with dicarboxylic acids is 1:18~1:24.
4. the preparation method of carbon nanometer fabric according to claim 1, which is characterized in that described to set the modified cloth
It further include following steps before the step of being impregnated in lytic agent: in third protective gas atmosphere, to the modified cloth
Carry out heating pressurized treatments.
5. the preparation method of carbon nanometer fabric according to claim 4, which is characterized in that it is described to the modified cloth into
Row heating pressurized treatments the step of in, heating temperature be 110 DEG C~115 DEG C, pressure be 45kPa~98kPa, processing the time be
5min~60min.
6. the preparation method of carbon nanometer fabric according to claim 1, which is characterized in that described to set the modified cloth
In lytic agent impregnate the step of in, the lytic agent be containing mass percentage be 90%~100% acetone it is water-soluble
Liquid, the time of immersion are 70min~100min.
7. the preparation method of carbon nanometer fabric according to claim 1, which is characterized in that described in the carbon nano-fiber
Upper formation presoma, and in the step of being reacted at 140 DEG C~160 DEG C, the reaction time is 1h~2h.
8. the preparation method of carbon nanometer fabric according to claim 1, which is characterized in that the Weight-average molecular of the copolymer
Amount is 3500~30000；And/or
The mass ratio of the unsaturated dicarboxylic, the brominated styrene and the methyl methacrylate is (2~7): (9~
14): (4~7).
9. the preparation method of modified fibre according to claim 1, which is characterized in that the presoma is by polystyrene tree
Rouge and epoxy resin composition, and the molar ratio of the polystyrene resin and the epoxy resin is 1:99~1:92.
10. a kind of carbon nanometer fabric, which is characterized in that by the preparation side of carbon nanometer fabric according to any one of claims 1 to 9
Method is prepared.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108314009A (en) * | 2018-03-30 | 2018-07-24 | 深圳烯湾科技有限公司 | The surface modification method of carbon nano pipe array |
| CN108532287A (en) * | 2018-03-30 | 2018-09-14 | 深圳烯湾科技有限公司 | The surface modification method of carbon nano-tube fibre |
-
2018
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108314009A (en) * | 2018-03-30 | 2018-07-24 | 深圳烯湾科技有限公司 | The surface modification method of carbon nano pipe array |
| CN108532287A (en) * | 2018-03-30 | 2018-09-14 | 深圳烯湾科技有限公司 | The surface modification method of carbon nano-tube fibre |
Non-Patent Citations (5)
| Title |
|---|
| FEI DENG 等: "Grafting polymer coatings onto the surfaces of carbon nanotube forests and yarns via a photon irradiation process", 《APPLIED PHYSICS LETTERS》 * |
| 娄春华等: "《聚合物结构与性能》", 31 May 2016, 哈尔滨工程大学出版社 * |
| 潘才元: "《高分子化学》", 31 July 2012, 中国科学技术大学出版社 * |
| 王善琦: "《高分子化学原理》", 31 January 1993, 北京航空航天大学出版社 * |
| 王国建等: "《功能高分子材料》", 31 January 2010, 同济大学出版社 * |
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