CN109706552A - Carbon nanometer fabric and preparation method thereof - Google Patents
Carbon nanometer fabric and preparation method thereof Download PDFInfo
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- CN109706552A CN109706552A CN201811505066.0A CN201811505066A CN109706552A CN 109706552 A CN109706552 A CN 109706552A CN 201811505066 A CN201811505066 A CN 201811505066A CN 109706552 A CN109706552 A CN 109706552A
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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, styrene and methyl methacrylate progress polymerization reaction obtaining modifier；Under the first protective gas atmosphere, graft reaction is carried out to modifier 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 polyacrylic resin and polyurethane resin；Modified fibre is weaved to obtain modified cloth, modified cloth is placed in immersion in lytic agent and obtains carbon nanometer fabric.The wetability of modified fibre in above-mentioned preparation method is higher, is easy to weave, and obtained carbon nanometer fabric wearability with higher.
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
Carbon nanotube is as monodimension nanometer material, and light-weight, hexagonal structure connection is perfect, has many abnormal power
, electricity and chemical property are widely used in middle life and every field, such as cosmetics, coating and the energy of production etc..Especially
It is in textile industry, carbon nanotube can spinning carbon nano-fiber is made, and be used to make carbon nano-fiber cloth.However,
During making cloth, the wetability of traditional carbon nano-fiber is poor, is unfavorable for the weaving of carbon nano-fiber, and makes
The wearability of standby cloth is poor, is not able to satisfy actual demand.
Summary of the invention
Based on this, it is necessary to provide a kind of preparation method of carbon nanometer fabric, the profit of the modified fibre in the preparation method
Carbon nanometer fabric wearability with higher that is moist higher, being easy to weave, and obtain.
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, styrene and methyl methacrylate progress polymerization reaction are obtained into modifier, the insatiable hunger
At least one of maleic acid, dichloromaleic acid, phenyl maleic acid and diphenyl maleic acid are selected from dicarboxylic acids；
Under the first protective gas atmosphere, graft reaction is carried out to the modifier 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 polyacrylic resin and polyurethane resin；
The modified fibre is weaved, modified cloth is obtained；
In third protective gas atmosphere, heating pressurized treatments are carried out to the modified cloth；And
The modified cloth after heating pressurized treatments is placed in lytic agent and is impregnated, carbon nanometer fabric is obtained, it is described molten
Contain methyl ethyl ketone in solution agent.
The preparation method of above-mentioned carbon nanometer fabric, unsaturated dicarboxylic, styrene and methyl methacrylate are gathered
It closes reaction and obtains modifier, unsaturated dicarboxylic is in maleic acid, dichloromaleic acid, phenyl maleic acid and diphenyl maleic acid
At least one, then modifier is grafted to using ultraviolet light by the surface of carbon nano pipe array, by by the modified carbon nano tube
Presoma is sprayed on carbon nano-fiber made of managing, is selected from polyacrylic resin and polyurethane resin selected from presoma
At least one of, so that presoma is reacted with-the COOR- (ester group) of modifier, the preferable modified fibre of wetability is obtained, easily
In being woven into cloth, heating pressurized treatments, the molding of advantageous cloth are carried out by the way that cloth will be modified, so that carbon nano-fiber arranges
Wearability that is finer and close and increasing cloth, then modified cloth is impregnated by lytic agent containing methyl ethyl ketone, so that changing
Property the conjugate that is formed with presoma of object removed from modified cloth, guarantee carbon nanometer fabric to restore the structure of carbon nanotube
Wearability.Experiment proves that the water infiltration contact angle for the modified fibre that above-mentioned preparation method obtains is 11.7 °~20.8 °, system
At carbon nanometer fabric effective abrasion index be 20000 times~30000 times, amount of thickness reduction be 0.07mm~0.16mm, tool
There is higher wear-resisting property.
It is described in third protective gas atmosphere in one of the embodiments, the modified cloth is heated
In the step of pressurized treatments, heating temperature be 110 DEG C~115 DEG C, pressure be 45kPa~98kPa, the processing time for 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
Solve the aqueous solution that agent is the methyl ethyl ketone for being 95%~100% containing mass percentage, time of immersion be 50min~
85min。
It is described in one of the embodiments, to polymerize unsaturated dicarboxylic, styrene and methyl methacrylate
The step of reaction obtains modifier specifically: the unsaturated dicarboxylic, the styrene and the polymethylacrylic acid exist
Polymerization reaction is carried out under ultraviolet light, and controlling reaction temperature is 20 DEG C~45 DEG C, ultraviolet ray intensity is 45W~55W, reaction
Time is 30min~40min.
The presoma is made of polyacrylic resin and polyurethane resin in one of the embodiments,
And the molar ratio of polyacrylic resin and polyurethane resin is 0.7:1~1.43:1.
The irradiation power of the ultraviolet light is 15mW~35mW in one of the embodiments, and the ultraviolet light is irradiation
Wavelength is the monochromatic narrow band light of 196nm~350nm, and the time of the ultraviolet light processing is 10min~35min.
It is described in one of the embodiments, that presoma is formed on the carbon nano-fiber, and in the second protectiveness gas
In the step of reacting at 140 DEG C~160 DEG C under body atmosphere, the reaction time is 1h~2h.
The weight average molecular weight of the modifier is 4000~27000 in one of the embodiments,.
The unsaturated dicarboxylic, the styrene and the methyl methacrylate in one of the embodiments,
Mass ratio is (2~7): (9~14): (4~7).
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.The present invention can be with many not
With form realize, however it is not limited to embodiment described herein.On the contrary, purpose of providing these embodiments is makes to this
The understanding of the disclosure of invention is more thorough and comprehensive.
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 wetability of the modified fibre which obtains compared with
Height is easy to weave, obtained carbon nanometer fabric wearability with higher.The preparation method of the carbon nanometer fabric includes following step
Rapid S110~S170:
S110, unsaturated dicarboxylic, styrene and methyl methacrylate progress polymerization reaction are obtained into modifier.Insatiable hunger
At least one of maleic acid, dichloromaleic acid, phenyl maleic acid and diphenyl maleic acid are selected from dicarboxylic acids.
The weight average molecular weight of modifier is 4000~27000 in one of the embodiments,.Further, modifier
Weight average molecular weight is 6000~20000.
In one of the embodiments, the mass ratio of unsaturated dicarboxylic, styrene and methyl methacrylate be (2~
7): (9~14): (4~7).The modifier of this setting grafts on the surface of carbon nano pipe array, can increase modified carbon nano-tube
The hardness of array, to obtain the higher carbon nanometer fabric of wearability, this setting can also increase the distance between carbon nanotube, with
The reunion due to caused by the Van der Waals force between carbon nanotube is reduced, with the modified carbon nano-tube array being easily dispersed, with
Obtain the preferable modified fibre of wetability.
The mass ratio of styrene and methyl methacrylate is 1.5~2.5 in one of the embodiments,.Such setting
So that the hardness of modified carbon nano-tube array is higher, wearability is more preferable.Further, the matter of styrene and methyl methacrylate
Amount is than being 2.It is such that the wearability for further increasing modified carbon nano-tube array is set.
Unsaturated dicarboxylic includes maleic acid and phenyl maleic acid in one of the embodiments, and maleic acid and phenyl
The molar ratio of maleic acid is 0.8:1~1.3:1.Such setting can further increase the wearability of modified fibre.Further,
The molar ratio of maleic acid and phenyl maleic acid is 1:1.
Unsaturated dicarboxylic, styrene and methyl methacrylate are subjected to polymerization reaction in one of the embodiments,
The step of specifically: unsaturated dicarboxylic, styrene and polymethylacrylic acid are subjected to free radical polymerization under ultraviolet light
Reaction, and controlling reaction temperature is 20 DEG C~45 DEG C, ultraviolet ray intensity is 45W~55W, and the reaction time is 30min~40min.
Unsaturated dicarboxylic, styrene and methyl methacrylate are subjected to polymerization reaction in one of the embodiments,
The step of after, further include that solvent is added into the reactant of polymerization reaction, after separation of solid and liquid collect precipitating, obtain modifier.
Further, solvent is selected from least one of carbon tetrachloride, tetrahydrofuran and methylene chloride.The mode of separation of solid and liquid be from
The heart.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
Filter.
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 modifier.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 modifier 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 ruler of the first substrate
It is very little to be 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
Catalyst layer.
S122, under protective gas atmosphere, the first substrate for being formed with catalyst layer is warming up to 550 DEG C~900 DEG C
Afterwards, then it is passed through carbon-source gas reaction, 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 wearability.
Protective gas is selected from least one of nitrogen, hydrogen, argon gas and helium in one of the embodiments,.
S123, modifier is set in the second substrate.
The second substrate is silicon wafer, nickel sheet or copper sheet in one of the embodiments,.The main function of second substrate is pair
Modifier is carried, and the stability of silicon wafer, nickel sheet and copper sheet is good, will not react with modifier.Further, the second substrate
Size be 50mm*50mm, certainly, in other embodiments, the size of the second substrate is also possible to any other size.
Modifier is set in the second substrate in a manner of film in one of the embodiments,.Further, second
The modifier film formed in substrate with a thickness of 1mm~5mm.Certainly, in other embodiments, modification can also first be sheared
Object material is placed in the mode in the second substrate again.Further, the second substrate has the second working face.On the second working face
Form modifier film.The second working face is completely covered in modifier film.
S124, under the first protective gas atmosphere, the first substrate for being formed with carbon nano pipe array and being formed with is changed
Property object the second substrate carry out ultraviolet light processing so that modifier and carbon nano pipe array carry out graft reaction, changed
Property carbon nano pipe array.
Modifier is grafted to the surface of carbon nano pipe array using ultraviolet light, and selects specific modifier, so that
Modified carbon nano-tube array is easily dispersed, and can prepare the modified fibre with preferable wetability.
By the first substrate for being formed with carbon nano pipe array and it is formed with the second of modifier 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 modifier 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 modifier
Bottom is placed side by side, so that carbon nano pipe array is contacted with modifier.
To the first substrate for being formed with carbon nano pipe array and it is formed with the second of modifier 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 modifier 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 modifier 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 and changes in one of the embodiments,
Property object the second substrate distance be 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 modifier 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 modified
Object reduces destruction of the ultraviolet light to modifier 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 modifier 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 behaviour 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 array is existed by Van der Waals force and modification
Non-covalent interaction power between the copolymer of modified carbon nano-tube array surface or the decomposition product of copolymer, which drives, to be modified
Carbon nano pipe array is continuously drawn out and makes modified carbon nano tube in filiform, then by rotating modified carbon nano-tube array
Every modified carbon nano-tube in pipe array is 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 silky nano pipe array of the edge clamping of mitron array, and revolved along the direction extended perpendicular to silky nano pipe array
Turn and pull, so that silky nano pipe array is stretched, and every silky nano pipe in silky nano pipe array is made to be screwed in one
It rises, obtains 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 polyacrylic resin and polyurethane resin.
By forming presoma on carbon nano-fiber, and specific presoma is selected, so that presoma and modifier-
COOR- reaction, obtains the preferable modified fibre of wetability.It should be noted that the presoma formed on carbon nano-fiber surface
It can be come into full contact with modifier.Further, carbon nanometer can be completely covered in the presoma that carbon nano-fiber surface is formed
The surface of fiber, to guarantee that presoma comes into full contact with modifier.
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 polyacrylic resin and polyurethane resin in one of the embodiments, and poly-
The molar ratio of acrylic resin and polyurethane resin is 0.7:1~1.43:1.Such setting can obtain wetability
The more preferable and better modified fibre of wearability.
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, in third protective gas atmosphere, heating pressurized treatments are carried out to modified cloth.
Modified fibre is weaved to obtain modified cloth, carries out heating pressurized treatments, advantageous cloth by the way that cloth will be modified
The molding of material, so that the wearability that is finer and close and increasing cloth of carbon nano-fiber arrangement.
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.Wherein, third protective gas in nitrogen, helium, neon and argon gas at least one
Kind.
S170, the modification cloth after heating pressurized treatments is placed in lytic agent and is impregnated, obtain carbon nanometer fabric, lytic agent
In contain methyl ethyl ketone.
Modified cloth is impregnated by the lytic agent containing methyl ethyl ketone, so that the conjugate that modifier and presoma are formed
It is removed from modified cloth, guarantees the wearability 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 methyl ethyl ketone that percentage composition is 95%~100% is measured, the time of immersion is 50min~85min.Further
Ground, lytic agent are the aqueous solution for the methyl ethyl ketone for being 98%~100% containing mass percentage, and the time of immersion is
60min~75min.
The preparation method of above-mentioned carbon nanometer fabric, unsaturated dicarboxylic, styrene and methyl methacrylate are gathered
It closes reaction and obtains modifier, unsaturated dicarboxylic is in maleic acid, dichloromaleic acid, phenyl maleic acid and diphenyl maleic acid
At least one, then modifier is grafted to using ultraviolet light by the surface of carbon nano pipe array, by by the modified carbon nano tube
Presoma is sprayed on carbon nano-fiber made of managing, is selected from polyacrylic resin and polyurethane resin selected from presoma
At least one of, so that presoma is reacted with-the COOR- (ester group) of modifier, the preferable modified fibre of wetability is obtained, easily
In being woven into cloth, heating pressurized treatments, the molding of advantageous cloth are carried out by the way that cloth will be modified, so that carbon nano-fiber arranges
Wearability that is finer and close and increasing cloth, then modified cloth is impregnated by lytic agent containing methyl ethyl ketone, so that changing
Property the conjugate that is formed with presoma of object removed from modified cloth, guarantee carbon nanometer fabric to restore the structure of carbon nanotube
Wearability.Experiment proves that the water infiltration contact angle for the modified fibre that above-mentioned preparation method obtains is 11.7 °~20.8 °, system
At carbon nanometer fabric effective abrasion index be 20000 times~30000 times, amount of thickness reduction be 0.07mm~0.16mm, tool
There is higher wear-resisting property.
Furthermore above-mentioned preparation method impregnates modified cloth by lytic agent containing methyl ethyl ketone so that modifier with
The conjugate that presoma is formed is removed from modified cloth, and the conduction of carbon nanometer fabric is improved to restore the structure of carbon nanotube
Performance.It is measured through test, the resistivity of the carbon nanometer fabric is 0.91 × 10-5M~2.15 × 10 Ω-5Ω m, have compared with
Good antistatic performance.
Finally, 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.To formation
When having the first substrate of carbon nano pipe array and being formed with the second substrate progress ultraviolet light processing of modifier, ultraviolet light is
Bandwidth is the monochromatic light of 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 10min at 5L/min, makes
It obtains the first substrate surface and is completely covered with carbon nano pipe array, carbon nano-pipe array is classified as single-wall carbon nanotube array, carbon nanotube
The length of 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 modifier film with a thickness of 1mm in the second substrate.The preparation of modifier
Process are as follows: unsaturated dicarboxylic, styrene and methyl methacrylate in the ultraviolet light that intensity is 55W and are controlled into reaction
Temperature is polymerization reaction 50min at 20 DEG C, obtains reactant；Solvent is added into reactant, collects precipitating after separation of solid and liquid, it will
Precipitating is dried, and obtains modifier.Unsaturated dicarboxylic is maleic acid.Unsaturated dicarboxylic, styrene and methacrylic acid
The mass ratio of methyl esters is 2:9:7.The weight average molecular weight of modifier is 4000.Solvent is carbon tetrachloride.
(3) the first substrate for being formed with carbon nano pipe array and the second substrate for being formed with modifier 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 modifier and be in same level, and
Carbon nano pipe array and modifier 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 modifier
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 modifier 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 sprayed on carbon nano-fiber, and reacts 1h at 140 DEG C in nitrogen atmosphere, obtains modified fibre
Dimension, presoma is polyacrylic resin.
(6) 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
50min is impregnated, obtains carbon nanometer fabric, lytic agent is methyl ethyl ketone.
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 1.25:1~8:1), and the flow control of carbon-source gas is reacted at 15L/min
25min, 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,
The length of carbon nano pipe array 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 modifier film with a thickness of 5mm in the second substrate.The preparation of modifier
Process is as follows: unsaturated dicarboxylic, styrene and methyl methacrylate in the ultraviolet light that intensity is 45W and are controlled anti-
Answering temperature is polymerization reaction 30min at 45 DEG C, obtains reactant；Solvent is added into reactant, collects precipitating after separation of solid and liquid,
Precipitating is dried, modifier is obtained.Unsaturated dicarboxylic is dichloromaleic acid.Unsaturated dicarboxylic, styrene and methyl
The mass ratio of methyl acrylate is 7:14:4.The weight average molecular weight of modifier is 26800.Solvent is tetrahydrofuran.
(3) the first substrate for being formed with carbon nano pipe array and the second substrate for being formed with modifier 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 modifier and be in same level, and
Carbon nano pipe array and modifier 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 modifier
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 modifier 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
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 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 sprayed on carbon nano-fiber, and reacts 2h at 160 DEG C in nitrogen atmosphere, obtains modified fibre
Dimension, presoma is polyurethane resin.
(6) 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
85min is steeped, carbon nanometer fabric is obtained, lytic agent is the aqueous solution for the methyl ethyl ketone for being 95% containing mass percentage.
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 4:1), 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 modifier film with a thickness of 3mm in the second substrate.The preparation of modifier
Process are as follows: unsaturated dicarboxylic, styrene and methyl methacrylate in the ultraviolet light that intensity is 50W and are controlled into reaction
Temperature is polymerization reaction 40min at 30 DEG C, obtains reactant；Solvent is added into reactant, collects precipitating after separation of solid and liquid, it will
Precipitating is dried, and obtains modifier.Unsaturated dicarboxylic is made of maleic acid and phenyl maleic acid, and maleic acid and phenyl horse
Carrying out sour molar ratio is 1:1.The mass ratio of unsaturated dicarboxylic, styrene and methyl methacrylate is 4.5:12:6.It is modified
The weight average molecular weight of object is 16500.Solvent is carbon dichloride.
(3) the first substrate for being formed with carbon nano pipe array and the second substrate for being formed with modifier 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 modifier and be in same level, and
Carbon nano pipe array and modifier contact, reaction chamber are evacuated to air pressure and are 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 modifier 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 modifier
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, obtains modified fibre,
Presoma includes polyurethane resin and polyacrylic resin, and polyacrylic resin and polyurethane resin
Molar ratio be 1.1.
(6) 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
68min is impregnated, carbon nanometer fabric is obtained, lytic agent is the aqueous solution for the methyl ethyl ketone for being 98% containing mass percentage.
Embodiment 4
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, styrene and methyl methacrylate is 2:9:6.
Embodiment 5
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, styrene and methyl methacrylate is 7:12.5:5.
Embodiment 6
The preparation process of the carbon nanometer fabric of the present embodiment is roughly the same with embodiment 3, the difference is that: unsaturation two
Carboxylic acid is made of maleic acid and phenyl maleic acid, and the molar ratio of maleic acid and phenyl maleic acid is 0.8:1.
Embodiment 7
The preparation process of the carbon nanometer fabric of the present embodiment is roughly the same with embodiment 3, the difference is that: unsaturation two
Carboxylic acid is made of maleic acid and phenyl maleic acid, and the molar ratio of maleic acid and phenyl maleic acid is 1.3:1.
Embodiment 8
The preparation process of the carbon nanometer fabric of the present embodiment is roughly the same with embodiment 3, the difference is that: presoma by
Polyacrylic resin and polyurethane resin composition, and polyacrylic resin and polyurethane resin are quality
Than for 0.7:1.
Embodiment 9
The preparation process of the carbon nanometer fabric of the present embodiment is roughly the same with embodiment 3, the difference is that: presoma by
Polyacrylic resin and polyurethane resin composition, and polyacrylic resin and polyurethane resin are quality
Than for 1.43:1.
Embodiment 10
The preparation process of the carbon nanometer fabric of the present embodiment is roughly the same with embodiment 3, 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 modifier.
Embodiment 11
The preparation process of the carbon nanometer fabric of the present embodiment is roughly the same with embodiment 3, the difference is that: by styrene
By Raolical polymerizable, reactant is obtained；Be added solvent into reactant, precipitating collected after separation of solid and liquid, will precipitate into
Row drying, obtains modifier.
Embodiment 12
The preparation process of the carbon nanometer fabric of the present embodiment is roughly the same with embodiment 3, 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, modifier is obtained.
Embodiment 13
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.Modified cloth is placed in lytic agent and impregnates 68min, is obtained
To carbon nanometer fabric, lytic agent is the aqueous solution for the methyl ethyl ketone for being 98% containing mass percentage.
Embodiment 14
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.Heating pressurized treatments are carried out to modified cloth, are heated
Temperature is 112 DEG C, pressure 70kPa, and the processing time is 20min.Modification cloth after heating pressurized treatments is placed in lytic agent
Middle immersion 68min, obtains carbon nanometer fabric, lytic agent be 98% containing mass percentage methyl ethyl ketone it is water-soluble
Liquid.
Embodiment 15
The preparation process of the carbon nanometer fabric of the present embodiment is as follows:
(1) carbon nano pipe array is prepared according to (1) the step of embodiment 3.
(2) carbon nano pipe array is clamped from the edge of carbon nano pipe array using clamping tool, and is received along perpendicular to carbon
The direction of growth of mitron array is pulled and is rotated, and carbon nano-fiber is obtained.Carbon nano-pipe array is clamped from carbon nano pipe array
When column, the width of clamping is 130 μm.The speed of dragging is 0.3mm/s, revolving speed 2000rpm.Obtained carbon nano-fiber it is straight
Diameter is 100 μm.
(3) carbon nano-fiber is weaved, obtains carbon nanometer fabric.
Test:
The wetability of the modified fibre of embodiment 1~13 and the carbon nano-fiber of embodiment 14~15 is measured, measurement is implemented
The wearability and conductivity of the carbon nanometer fabric of example 1~15.See Table 1 for details for measurement result.What table 1 indicated is embodiment 1~13
The wetability of modified fibre and the carbon nano-fiber of embodiment 14~15, the wearability of the carbon nanometer fabric of embodiment 1~15 and
Conductivity.
Specifically, using the wetting contact angle (intravenous infusion of the measuring method measurement fiber of IS R 3257:1999 defined
Method)；
Using the wear-resisting property of the experimental method test carbon nanometer fabric of 1454 prescribed by standard of JIS A, wherein effectively
Abrasion index, which refers to, wears up to abrasion number needed for obvious silk thread breaking state occurs in material for test material, and test material is
The cloth of embodiment 1~15；Amount of thickness reduction refers to the preceding amount of thickness reduction with material after abrasion of abrasion；
Using the conductivity of four-point method measurement carbon nanometer fabric.
Table 1
As it can be seen from table 1 the water infiltration contact angle of the modified fibre of Examples 1 to 9 is 11.7 °~20.8 °, it is below
Embodiment 15 illustrates that the wetability of modified fibre made of above embodiment is higher, it is easier to which it is higher that weaving obtains quality
Cloth；Also, effective abrasion index of the carbon nanometer fabric of Examples 1 to 9 is 20000 times~30000 times, obviously higher than
Embodiment 15；The amount of thickness reduction of the carbon nanometer fabric of Examples 1 to 9 is 0.07mm~0.16mm, is below embodiment 15, says
The bright modified fibre wear-resisting property with higher obtained using above embodiment, and can prepare with high wear resistance
Cloth.In addition, the resistivity of the carbon nanometer fabric of Examples 1 to 9 is 0.91 × 10-5M~2.15 × 10 Ω-5Ω m,
It is below embodiment 15, illustrates that can be used in preparation using the modified fibre that above embodiment obtains has high conductance
Cloth, to obtain the preferable cloth of antistatic performance.
Wherein, effective abrasion index of the carbon nano-fiber and cloth of embodiment 10~13 is below embodiment 3, and implements
The amount of thickness reduction of the cloth of example 10~12 is above embodiment 3, illustrates using unsaturated dicarboxylic, styrene and metering system
Copolymer made of sour methyl esters is more advantageous to the wetability for improving modified fibre, it is easier to be made into the cloth with high wear resistance
Material.
In conclusion the preparation method of above embodiment can be prepared with the modified fibre compared with high wettability, it is easy to
Weaving, the carbon nanometer fabric with high wear resistance and high conductance can be prepared, with can be used in making it is wear-resistant and
The protective garment of antistatic.
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, styrene and methyl methacrylate progress polymerization reaction are obtained into modifier, described unsaturated two
Carboxylic acid is selected from least one of maleic acid, dichloromaleic acid, phenyl maleic acid and diphenyl maleic acid；
Under the first protective gas atmosphere, graft reaction is carried out to the modifier 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 polyacrylic resin and polyurethane resin；
The modified fibre is weaved, modified cloth is obtained；
In third protective gas atmosphere, heating pressurized treatments are carried out to the modified cloth；And
The modified cloth after heating pressurized treatments is placed in lytic agent and is impregnated, carbon nanometer fabric, the lytic agent are obtained
In contain methyl ethyl ketone.
2. the preparation method of carbon nanometer fabric according to claim 1, which is characterized in that described in third protective gas
In atmosphere, in the step of carrying out heating pressurized treatments to the modified cloth, heating temperature is 110 DEG C~115 DEG C, and pressure is
45kPa~98kPa, processing time are 5min~60min.
3. the preparation method of carbon nanometer fabric according to claim 1, which is characterized in that described to set the modified cloth
In the step of impregnating in lytic agent, the lytic agent is the methyl ethyl ketone for being 95%~100% containing mass percentage
Aqueous solution, time of immersion is 50min~85min.
4. the preparation method of carbon nanometer fabric according to claim 1, which is characterized in that it is described by unsaturated dicarboxylic,
Styrene and methyl methacrylate carry out the step of polymerization reaction obtains modifier specifically: by the unsaturated dicarboxylic,
The styrene and the polymethylacrylic acid carry out polymerization reaction under ultraviolet light, and control reaction temperature be 20 DEG C~
45 DEG C, ultraviolet ray intensity is 45W~55W, and the reaction time is 30min~40min.
5. the preparation method of carbon nanometer fabric according to claim 1, which is characterized in that the presoma is by polyacrylic acid
Resin and polyurethane resin composition, and the molar ratio of polyacrylic resin and polyurethane resin is 0.7:
1~1.43:1.
6. the preparation method of carbon nanometer fabric according to claim 1, which is characterized in that the irradiation power of the ultraviolet light
For 15mW~35mW, the ultraviolet light is the monochromatic narrow band light that illumination wavelength is 196nm~350nm, at the ultraviolet light
The time of reason is 10min~35min.
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 under the second protective gas atmosphere, 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 modifier
Amount is 4000~27000.
9. the preparation method of carbon nanometer fabric according to claim 1, which is characterized in that the unsaturated dicarboxylic, institute
The mass ratio for stating styrene and the methyl methacrylate is (2~7): (9~14): (4~7).
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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| 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 |
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| 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 |
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