CN109763208A - Modified carbon nano-tube fiber and its preparation method and application - Google Patents
Modified carbon nano-tube fiber and its preparation method and application Download PDFInfo
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- CN109763208A CN109763208A CN201811503930.3A CN201811503930A CN109763208A CN 109763208 A CN109763208 A CN 109763208A CN 201811503930 A CN201811503930 A CN 201811503930A CN 109763208 A CN109763208 A CN 109763208A
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Abstract
The present invention relates to a kind of modified carbon nano-tube fibers and its preparation method and application.The preparation method includes the following steps: that unsaturated dicarboxylic, styrene and methyl methacrylate are carried out to polymerization reaction obtains copolymer, and unsaturated dicarboxylic 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 copolymer and carbon nano pipe array, obtains modified carbon nano-tube array；Modified carbon nano-tube array is subjected to spinning, obtains carbon nano-tube fibre；Presoma is sprayed on carbon nano-tube fibre, and is reacted at 140 DEG C~160 DEG C under the second protective gas atmosphere, modified carbon nano-tube fiber is obtained, and presoma is selected from least one of polyacrylic resin and polyurethane resin.The wellability for the modified carbon nano-tube fiber that above-mentioned preparation method obtains is preferable.
Description
Technical field
The present invention relates to field of material technology, more particularly to a kind of modified carbon nano-tube fiber and preparation method thereof and answer
With.
Background technique
Nano material is widely used in the every field of middle life and production, example because of the uniqueness in its structure and performance
Such as cosmetics, coating and the energy.Especially in textile industry, nanomaterials and nanotechnology has boundless prospect of the application.
Wherein, carbon nanotube is as monodimension nanometer material, and light-weight, hexagonal structure connection is perfect, has many abnormal mechanics, electricity
And chemical property, are increasingly used for preparing fabric fibre.However, traditional carbon nanotube is fine during making cloth
The wellability of dimension is poor, is unfavorable for the weaving of carbon nano-tube fibre.
Summary of the invention
Based on this, it is necessary to provide a kind of preparation method of modified carbon nano-tube fiber, the modification which obtains
The wellability of carbon nano-tube fibre is preferable.
In addition, also providing a kind of modified carbon nano-tube fiber and its preparation method and application.
A kind of preparation method of modified carbon nano-tube fiber, includes the following steps:
Unsaturated dicarboxylic, styrene and methyl methacrylate progress polymerization reaction are obtained into copolymer, 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 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-tube fibre；
Presoma is sprayed on the carbon nano-tube fibre, and in 140 DEG C~160 DEG C under the second protective gas atmosphere
Lower reaction obtains modified carbon nano-tube fiber, and the presoma is in polyacrylic resin and polyurethane resin
At least one.
The preparation method of above-mentioned modified carbon nano-tube fiber, by unsaturated dicarboxylic, styrene and methyl methacrylate
It carries out polymerization reaction and obtains copolymer, unsaturated dicarboxylic is selected from maleic acid, dichloromaleic acid, phenyl maleic acid and diphenyl horse
It is at least one of sour, then using ultraviolet light by the surface of copolymer grafted to carbon nano pipe array, by by the modification
Presoma is sprayed on carbon nano-tube fibre made of carbon nanotube, in polyacrylic resin and polyurethane resin
At least one obtain the preferable modified carbon nano-tube of wellability so that presoma is reacted with-the COOR- (ester group) of copolymer
Fiber.Experiment proves that the wetting contact angle for the modified carbon nano-tube fiber that above-mentioned preparation method obtains is 8 °~15 °, more hold
Easily it is made into cloth.
The presoma includes polyacrylic resin and polyurethane resin in one of the embodiments, and
The molar ratio of the polyacrylic resin and the polyurethane resin is 0.8:1~3.5:1.
It is described in one of the embodiments, to polymerize unsaturated dicarboxylic, styrene and methyl methacrylate
The step of reaction obtains copolymer specifically: by the unsaturated dicarboxylic, the styrene and the methyl methacrylate
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, instead
It is 30min~40min between seasonable.
It is described in one of the embodiments, that presoma is sprayed on the carbon nano-tube fibre, and in the second protectiveness
In the step of reacting at 140 DEG C~160 DEG C under atmosphere, the reaction time is 1h~2h.
The unsaturated dicarboxylic, the styrene and the methyl methacrylate in one of the embodiments,
Mass ratio is (2~7): (9~14): (4~7).
The weight average molecular weight of the copolymer is 3000~30000 in one of the embodiments,.
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 under the first protective gas atmosphere in one of the embodiments, to the copolymer and carbon nanotube
Before array carries out the step of graft reaction, further include the steps that preparing the carbon nano pipe array:
The deposit catalyst layers in first substrate；And
Under third protective gas atmosphere, first substrate for being formed with catalyst layer is warming up to 550 DEG C~900
Carbon-source gas reaction is passed through after DEG C again, obtains the carbon nano pipe array；The carbon-source gas includes hexane and ethylene, it is described oneself
The partial pressure of alkane and ethylene ratio is 1:8~1:1.25, and the flow velocity of the carbon-source gas is 5mL/min~15mL/min,
Being passed through the time that the carbon-source gas is reacted is 10min~25min.
A kind of modified carbon nano-tube fiber is prepared by the preparation method of above-mentioned modified carbon nano-tube fiber.
Above-mentioned modified carbon nano-tube fiber is preparing the application in cloth.
Specific embodiment
To facilitate the understanding of the present invention, below to invention is more fully described.The present invention can be with many differences
Form realize, however it is not limited to embodiment described herein.On the contrary, purpose of providing these embodiments is makes to this hair
The understanding of bright disclosure 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 modified carbon nano-tube fiber of one embodiment can obtain the preferable modified carbon nano tube of wellability
Pipe fiber is easy to weave, and can be applied to the preparation better cloth of quality.The preparation method of the modified carbon nano-tube fiber includes
Following steps S110~S140:
S110, unsaturated dicarboxylic, styrene and methyl methacrylate progress polymerization reaction are obtained into copolymer.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 copolymer is 3000~30000 in one of the embodiments,.Further, copolymer
Weight average molecular weight is 8000~10000.
In one of the embodiments, the mass ratio of unsaturated dicarboxylic, styrene and methyl methacrylate be (2~
7): (9~14): (4~7).The copolymer grafted of this setting can either increase modified carbon nano tube in the surface of carbon nano pipe array
The hardness of pipe array, additionally it is possible to increase the distance between carbon nanotube, to reduce by the Van der Waals force institute between carbon nanotube
The reunion of cause is obtained with the modified carbon nano-tube array being easily dispersed with can more preferably play the mechanical property of carbon nanotube
To the higher modified carbon nano-tube array of wearability.
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, wear-resisting property is more preferable.Further, styrene and methyl methacrylate
Mass ratio is 2.Such setting further increases modified carbon nano-tube array so that the hardness of modified carbon nano-tube array is moderate
Wear-resisting property.
Unsaturated dicarboxylic is made of maleic acid and phenyl maleic acid in one of the embodiments, and maleic acid and benzene
The molar ratio of base maleic acid is 3:1~5:1.Such setting can further increase the wear-resisting property of modified carbon nano-tube fiber.
Further, the molar ratio of maleic acid and phenyl maleic acid is 4:1.
Unsaturated dicarboxylic, styrene and methyl methacrylate are subjected to polymerization reaction in one of the embodiments,
The step of specifically: unsaturated dicarboxylic, styrene and methyl methacrylate are subjected to radical polymerization under ultraviolet light
Close 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, 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 copolymer.
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 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.
S120 specifically includes S121~S123 in one of the embodiments:
S121, carbon nano pipe array is prepared.
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.
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.
S121 includes S1211~S1212 in one of the embodiments:
S1211, 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.The size of the first substrate is 8 feet in one of the embodiments,.Certainly, in other embodiments,
The size of one substrate is also possible to any other size.
The first substrate has the first working face in one of the embodiments,.It deposits to form catalyst in the first working face
Layer.
S1212, under third protective gas atmosphere, by the first substrate for being formed with catalyst layer be warming up to 550 DEG C~
Carbon-source gas is passed through after 900 DEG C again to react to obtain 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 hexane and ethylene, and the partial pressure ratio of hexane and ethylene is 1:8~1:
1.25.The flow velocity of carbon-source gas is 5mL/min~15mL/min, be passed through time that carbon-source gas is reacted be 10min~
25min.It is arranged by this, the mechanical property of obtained carbon nano pipe array is preferable, is received with obtaining the preferable carbon modified of wearability
Mitron fiber.
Protective gas is selected from least one of nitrogen, hydrogen, argon gas and helium in one of the embodiments,.
S122, copolymer is set 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.
The size of the second substrate is 50mm*50mm in one of the embodiments, certainly, in other embodiments, the
The size of two substrates 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, copolymerization 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 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 the modified carbon nano-tube fiber with preferable wellability, and can make
Modified carbon nano-tube array wearability with higher can be used in preparing the higher cloth of wearability.
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, it will be formed with the first substrate and shape of carbon nano pipe array in one of the embodiments,
At there is the second substrate of copolymer 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,
The irradiation power that substrate carries out ultraviolet light when ultraviolet light processing 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 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-tube fibre.
The operation that spinning obtains carbon nano-tube fibre is carried out to modified carbon nano-tube array in one of the embodiments, to have
Body are as follows: modified carbon nano-tube array is clamped from the edge of modified carbon nano-tube array using clamping tool, and along perpendicular to changing
The direction of growth of property carbon nano pipe array is pulled and is rotated, and carbon nano-tube fibre is obtained.
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 and makes modified carbon nano-tube battle array in filiform, then by rotating modified carbon nano-tube array
Every modified carbon nano-tube in column is threaded together, as carbon nano-tube fibre.
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 rotated and dragged along the extending direction of silky nano pipe array
It drags, so that silky nano pipe array is stretched, and is threaded together every silky nano pipe in silky nano pipe array, obtains
Carbon nano-tube fibre.
It is wide when clamping modified carbon nano-tube array from the edge of modified carbon nano-tube array in one of the embodiments,
Degree is 50 μm~200 μm.Further, when clamping modified carbon nano-tube array from the edge of modified carbon nano-tube array, width
It is 100 μm~150 μm.
Speed when being pulled in one of the embodiments, along the direction of growth perpendicular to modified carbon nano-tube array
Rate is 0.05m/s~0.5mm/s.Further, when being pulled along the direction of growth perpendicular to modified carbon nano-tube array
Rate be 0.1m/s~0.4mm/s.Further, it is dragged along the direction of growth perpendicular to modified carbon nano-tube array
Rate when dragging is 0.2m/s~0.3mm/s.
Turn when being rotated in one of the embodiments, along the direction of growth perpendicular to modified carbon nano-tube array
Speed is 1000rpm~3000rpm.Further, when being rotated along the direction of growth perpendicular to modified carbon nano-tube array
Revolving speed be 2000rpm.
The diameter of carbon nano-tube fibre is 10 μm~200 μm in one of the embodiments,.
The length of carbon nano-tube fibre is 100m~6000m in one of the embodiments,.It should be noted that carbon is received
The length of mitron fiber is not limited to above-mentioned length, can be configured according to actual needs.
S140, presoma is sprayed in carbon nano-tube fibre, and in 140 DEG C~160 DEG C under the second protective gas atmosphere
Lower reaction, obtains modified carbon nano-tube fiber, presoma in polyacrylic resin and polyurethane resin extremely
Few one kind.
By spraying presoma on the surface of carbon nano-tube fibre, and specific presoma is selected, so that presoma is together
- the COOR- of polymers reacts, and obtains the preferable modified carbon nano-tube fiber of wellability.It should be noted that in carbon nano-tube fibre
The presoma of surface spraying can come into full contact with copolymer.Further, in the presoma of carbon nano-tube fibre surface spraying
The surface of carbon nano-tube fibre is completely covered, to guarantee that presoma comes into full contact with copolymer.
In one of the embodiments, the second protective gas in nitrogen, helium, neon and argon gas at least one
Kind.
Presoma is sprayed on the surface of carbon nano-tube fibre in one of the embodiments, and in the second protective gas
In the step of reacting at 140 DEG C~160 DEG C under atmosphere, the reaction time is 1h~2h.Under this reaction time, forerunner can be made
Body is sufficiently reacted with carbon nano-tube fibre, to guarantee the wellability of modified carbon nano-tube fiber.
Presoma is misty or film-form in one of the embodiments,.Such setting enables presoma more equal
The even surface coated on carbon nano-tube fibre.
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 0.8:1~3.5:1.Such setting can obtain wellability
The more preferable and better modified carbon nano-tube fiber of wearability.
The preparation method of above-mentioned modified carbon nano-tube fiber, by unsaturated dicarboxylic, styrene and methyl methacrylate
It carries out polymerization reaction and obtains copolymer, unsaturated dicarboxylic is selected from maleic acid, dichloromaleic acid, phenyl maleic acid and diphenyl horse
It is at least one of sour, then using ultraviolet light by the surface of copolymer grafted to carbon nano pipe array, by by the modification
Presoma is sprayed on carbon nano-tube fibre made of carbon nanotube, in polyacrylic resin and polyurethane resin
At least one obtain the preferable modified carbon nano-tube of wellability so that presoma is reacted with-the COOR- (ester group) of copolymer
Fiber.Experiment proves that the wetting contact angle for the modified carbon nano-tube fiber that above-mentioned preparation method obtains is 8 °~15 °, more hold
Easily it is made into cloth.
Furthermore the preparation method of above-mentioned modified carbon nano-tube fiber, by carbon nano pipe array surface grafting characteristic
Copolymer is capable of increasing the distance between carbon nanotube, reduces the reunion due to caused by the Van der Waals force between carbon nanotube, makes
Obtained modified carbon nano-tube array is easily dispersed, and makes it possible to preferably play the mechanical property of carbon nanotube, resistance to obtain
The better modified carbon nano-tube fiber of mill property can be applied to the preparation higher cloth of quality.
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 ensure that modified carbon nano-tube array and modified carbon nano tube
The mechanical property of pipe fiber, solvent-free equal residual, the purity of obtained modified carbon nano-tube fiber are higher.
The cloth of one embodiment, the modified carbon nano-tube fiber including above embodiment.
It should be noted that can use traditional Weaving method by modified carbon nano-tube fibrous woven at cloth.Tradition
Weaving method for example can be flat weaving method or twill.
It should be noted that can be weaved using single modified carbon nano-tube fiber, it can also be by more carbon modifieds
Nanotube fibers twist into one in parallel and weave again.
Above-mentioned cloth includes the modified carbon nano-tube fiber of above embodiment, since the modified carbon nano-tube fiber has
Higher wellability and wearability, so that cloth quality with higher.
It is below the part of specific embodiment.
Unless otherwise instructed, following embodiment is without containing other groups not yet explicitly pointed out in addition to inevitable impurity
Point.
Unless otherwise instructed, in following embodiment, the first substrate is alumina plate.Second substrate is copper sheet.Presoma is complete
The surface of all standing carbon nano-tube fibre.
Embodiment 1
The preparation process of the cloth 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 hexane and second
The partial pressure ratio of alkene, hexane and ethylene is 1:1.25), 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, 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 copolymer.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 copolymer is 3000.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 are evacuated to air pressure and are 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 narrowband that illumination wavelength is 196nm and bandwidth is 218nm
Light, irradiation time 35min；Ultraviolet light module is closed, the first substrate is exposed to nitrogen atmosphere down toward natural cooling, is changed
Property carbon nano 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
Directly the direction of growth in modified carbon nano-tube array is pulled and is rotated, and obtains carbon nano-tube fibre.From modified carbon nano-tube
When the edge of array clamps modified carbon nano-tube array, width is 200 μm.The speed of dragging is 0.5mm/s, and revolving speed is
3000rpm.The diameter of obtained carbon nano-tube fibre is 10 μm.
(5) presoma is sprayed on the surface of carbon nano-tube fibre, and reacts 1h at 140 DEG C under a nitrogen, be modified
Carbon nano-tube fibre, presoma are polyacrylic resin.
(6) modified carbon nano-tube fiber is weaved, obtains cloth.
Embodiment 2
The preparation process of the cloth 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 hexane and second
The partial pressure ratio of alkene, hexane and ethylene is 1:8), 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 are as follows: unsaturated dicarboxylic, styrene and methyl methacrylate in the ultraviolet light that intensity is 45W and are controlled into reaction
Temperature is polymerization reaction 30min at 45 DEG C, obtains reactant；Solvent is added into reactant, collects precipitating after separation of solid and liquid, it will
Precipitating is dried, and obtains copolymer.Unsaturated dicarboxylic is dichloromaleic acid.Unsaturated dicarboxylic, styrene and methyl-prop
The mass ratio of e pioic acid methyl ester is 7:14:4.The weight average molecular weight of copolymer is 30000.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 are evacuated to air pressure and are 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
It is 15mW from the irradiation power for 10mm, ultraviolet light, ultraviolet light is that the monochrome that illumination wavelength is 350nm and bandwidth is 298nm is narrow
Band light, irradiation time 10min；Ultraviolet light module is closed, the first substrate is exposed to nitrogen atmosphere down toward natural cooling, is obtained
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 the direction of growth in modified carbon nano-tube array is pulled and rotates to obtain carbon nano-tube fibre.From modified carbon nano-tube battle array
When the edge of column clamps modified carbon nano-tube array, width is 50 μm.The speed of dragging is 0.05mm/s, revolving speed 1000rpm.
The diameter of obtained carbon nano-tube fibre is 200 μm.
(5) presoma is sprayed on the surface of carbon nano-tube fibre, and reacts 2h at 160 DEG C under a nitrogen, be modified
Carbon nano-tube fibre, presoma are polyurethane resin.
(6) modified carbon nano-tube fiber is weaved, obtains cloth.
Embodiment 3
The preparation process of the cloth 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 hexane and second
The partial pressure ratio of alkene, hexane and ethylene is 1:4), 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 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 copolymer.Unsaturated dicarboxylic is made of maleic acid and phenyl maleic acid, and maleic acid and phenyl horse
Carrying out sour molar ratio is 4:1.The mass ratio of unsaturated dicarboxylic, styrene and methyl methacrylate is 4.5:12:6.Copolymerization
The weight average molecular weight of object is 15000.Solvent is carbon dichloride.
(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 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 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 5mm, and the irradiation power of ultraviolet light is 25mW, and ultraviolet light is that the monochrome that illumination wavelength is 218nm and bandwidth is 256nm is narrow
Band light, irradiation time 23min；Ultraviolet light module is closed, the first substrate is exposed to nitrogen atmosphere down toward natural cooling, is obtained
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 the direction of growth in modified carbon nano-tube array is pulled and rotates to obtain carbon nano-tube fibre.From modified carbon nano-tube battle array
When the edge of column clamps modified carbon nano-tube array, width is 130 μm.The speed of dragging is 0.3mm/s, revolving speed 2000rpm.
The diameter of obtained carbon nano-tube fibre is 100 μm.
(5) presoma is sprayed on the surface of carbon nano-tube fibre, and reacts 1.5h at 150 DEG C under a nitrogen, changed
Property carbon nano-tube fibre, presoma are made of polyacrylic resin and polyurethane resin, and polyacrylic resin and
Polyurethane resin is that mass ratio is 2.15:1.
(6) modified carbon nano-tube fiber is weaved, obtains cloth.
Embodiment 4
The preparation process of the cloth of the present embodiment is roughly the same with embodiment 1, the difference is that: unsaturated dicarboxyl
The mass ratio of acid, styrene and methyl methacrylate is 2:9:6.
Embodiment 5
The preparation process of the cloth of the present embodiment is roughly the same with embodiment 2, the difference is that: unsaturated dicarboxyl
The mass ratio of acid, styrene and methyl methacrylate is 7:12.5:5.
Embodiment 6
The preparation process of the cloth of the present embodiment is roughly the same with embodiment 3, the difference is that: maleic acid and phenyl horse
Carrying out sour molar ratio is 3:1.
Embodiment 7
The preparation process of the cloth of the present embodiment is roughly the same with embodiment 3, the difference is that: saturated dicarboxylic acid is by horse
Carry out sour and phenyl maleic acid composition, and the molar ratio of maleic acid and phenyl maleic acid is 5:1.
Embodiment 8
The preparation process of the cloth of the present embodiment is roughly the same with embodiment 3, the difference is that: polyacrylic resin and
Polyurethane resin is that mass ratio is 0.8:1.
Embodiment 9
The preparation process of the cloth of the present embodiment is roughly the same with embodiment 3, the difference is that: polyacrylic resin and
Polyurethane resin is that mass ratio is 3.5:1.
Embodiment 10
The preparation process of the cloth of the present embodiment is roughly the same with embodiment 3, the difference is that: by unsaturated dicarboxylic
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 copolymer.
Embodiment 11
The preparation process of the cloth of the present embodiment is roughly the same with embodiment 3, the difference is that: styrene is passed through certainly
By base polymerization reaction, reactant is obtained；Solvent is added into reactant, collects precipitating after separation of solid and liquid, precipitating is dried,
Obtain copolymer.
Embodiment 12
The preparation process of the cloth of the present embodiment is roughly the same with embodiment 3, the difference is that: by methyl methacrylate
Ester obtains reactant by Raolical polymerizable；Solvent is added into reactant, collects precipitating after separation of solid and liquid, will precipitate
It is dried, obtains copolymer.
Embodiment 13
The preparation process of the cloth of the present embodiment is as follows:
(1) carbon nano-tube fibre is obtained according to the operation of (1) the step of embodiment 3~(4).
(2) carbon nano-tube fibre is weaved, obtains cloth.
Embodiment 14
The preparation process of the cloth 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 rotates to obtain carbon nano-tube fibre.From the edge of carbon nano pipe array, clamping carbon is received
When mitron array, the width of clamping is 130 μm.The speed of dragging is 0.3mm/s, revolving speed 2000rpm.Obtained carbon nanotube
The diameter of fiber is 100 μm.
(3) carbon nano-tube fibre is weaved, obtains cloth.
Test:
The carbon nano-tube fibre of embodiment 1~14 and the wellability of cloth are measured, the carbon modified of measurement embodiment 1~12 is received
The wellability of mitron fiber, see Table 1 for details for measurement result.What table 1 indicated is the carbon nano-tube fibre and cloth of embodiment 1~14
The wellability of the modified carbon nano-tube fiber of wellability, embodiment 1~12.
Specifically, using the wetting contact angle of measuring method the measurement fiber and cloth of JIS R 3257:1999 defined
(sessile drop method)；
The wear-resisting property of carbon nano-tube fibre and cloth is tested using the experimental method of 1454 prescribed by standard of JIS A,
In, effective abrasion index, which refers to, wears up to abrasion number needed for obvious silk thread breaking state occurs in material for test material, examination
Test the carbon nano-tube fibre and cloth that material is embodiment 1~13.
Table 1
As it can be seen from table 1 the wetting contact angle of the carbon nano-tube fibre of Examples 1 to 9 is 13.2 °~28.5 °, it is lower than
Embodiment 13 and 14；And the wetting contact angle of the modified carbon nano-tube fiber of Examples 1 to 9 is 8 °~15 °, Examples 1 to 9
The wetting contact angle of cloth is 6.3 °~13.3 °, is lower than embodiment 13 and 14, and the carbon modified for illustrating that above embodiment obtains is received
The wellability of mitron fiber is preferable, is easy to be woven into cloth.Meanwhile effective abrasion index of the cloth of Examples 1 to 9 is 2.21
×104Secondary~2.85 × 104It is secondary, it is better than embodiment 13 and 14, illustrates the modified carbon nano-tube fiber energy that above embodiment obtains
It is enough in the cloth that preparation has high wear resistance, there is preferably quality.
Wherein, the wetting contact angle of the modified carbon nano-tube fiber of embodiment 3 is less than embodiment 10~12, and illustrates insatiable hunger
The infiltration for improving modified carbon nano-tube fiber is more advantageous to copolymer made of dicarboxylic acids, styrene and methyl methacrylate
Property.
In conclusion the preparation method of above embodiment can prepare the modified carbon nano-tube fibre with higher wellability
Dimension, to be easy to weave, to improve the wear-resisting property of cloth, obtains the higher cloth of quality.
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 modified carbon nano-tube fiber, which comprises the steps of:
Unsaturated dicarboxylic, styrene and methyl methacrylate progress polymerization reaction are obtained into copolymer, 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 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-tube fibre；
Presoma is sprayed on the carbon nano-tube fibre, and anti-at 140 DEG C~160 DEG C under the second protective gas atmosphere
Answer, obtain modified carbon nano-tube fiber, the presoma in polyacrylic resin and polyurethane resin extremely
Few one kind.
2. the preparation method of modified carbon nano-tube fiber according to claim 1, which is characterized in that the presoma includes
Polyacrylic resin and polyurethane resin, and the polyacrylic resin and the polyurethane resin
Molar ratio is 0.8:1~3.5:1.
3. the preparation method of modified carbon nano-tube fiber according to claim 1, which is characterized in that described by unsaturation two
Carboxylic acid, styrene and methyl methacrylate carry out the step of polymerization reaction obtains copolymer specifically: by described unsaturated two
Carboxylic acid, the styrene and the methyl methacrylate carry out polymerization reaction under ultraviolet light, and control reaction temperature
It is 20 DEG C~45 DEG C, ultraviolet ray intensity is 45W~55W, and the reaction time is 30min~40min.
4. the preparation method of modified carbon nano-tube fiber according to claim 1, which is characterized in that described to be received in the carbon
Presoma is sprayed on mitron fiber, and in the step of reacting at 140 DEG C~160 DEG C under the second protective gas atmosphere, instead
It is 1h~2h between seasonable.
5. the preparation method of modified carbon nano-tube fiber according to claim 1, which is characterized in that the unsaturation dicarboxyl
The mass ratio of sour, the described styrene and the methyl methacrylate is (2~7): (9~14): (4~7).
6. the preparation method of modified carbon nano-tube fiber according to claim 1, which is characterized in that the weight of the copolymer
Average molecular weight is 3000~30000.
7. the preparation method of modified carbon nano-tube fiber according to claim 1, which is characterized in that the photograph of the ultraviolet light
Penetrating power is 15mW~35mW, and the ultraviolet light is the monochromatic narrow band light that illumination wavelength is 196nm~350nm, the ultraviolet light
The time for the treatment of with irradiation is 10min~35min.
8. the preparation method of modified carbon nano-tube fiber according to claim 1, which is characterized in that described in the first protection
Property atmosphere under, further include described in preparation before the step of carrying out graft reaction to the copolymer and carbon nano pipe array
The step of carbon nano pipe array:
The deposit catalyst layers in first substrate；And
Under third protective gas atmosphere, after first substrate for being formed with catalyst layer is warming up to 550 DEG C~900 DEG C
It is passed through carbon-source gas reaction again, obtains the carbon nano pipe array；The carbon-source gas includes hexane and ethylene, the hexane and
The partial pressure ratio of the ethylene is 1:8~1:1.25, and the flow velocity of the carbon-source gas is 5mL/min~15mL/min, is passed through
The time that the carbon-source gas is reacted is 10min~25min.
9. a kind of modified carbon nano-tube fiber, which is characterized in that by modified carbon nano-tube according to any one of claims 1 to 8
The preparation method of fiber is prepared.
10. modified carbon nano-tube fiber as claimed in claim 9 is preparing the application in cloth.
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| 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 |
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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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