CN109704311A - Modified carbon nano-tube array, carbon nano-tube fibre and its preparation method and application - Google Patents
Modified carbon nano-tube array, carbon nano-tube fibre and its preparation method and application Download PDFInfo
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Abstract
The present invention relates to a kind of modified carbon nano-tube arrays, carbon nano-tube fibre and its preparation method and application.The preparation method of the modified carbon nano-tube array includes the following steps: unsaturated dicarboxylic, brominated styrene and methyl methacrylate progress polymerization reaction obtaining copolymer, unsaturated dicarboxylic is selected from least one of citraconic acid and dimethyl maleic acid；And under protective gas atmosphere, copolymer and carbon nano pipe array are subjected to ultraviolet light processing to carry out graft reaction, obtain modified carbon nano-tube array.The modified carbon nano-tube array that above-mentioned preparation method obtains can be used in preparation with the carbon nano-tube fibre compared with high adhesion force.
Description
Technical field
The present invention relates to field of material technology, more particularly to a kind of modified carbon nano-tube array, carbon nano-tube fibre and
Preparation method and application.
Background technique
Carbon nanotube is with a wide range of applications because of its excellent mechanical property and electric property.In recent years, with
Further investigation to carbon nanotube, carbon nanotube have progressed into textile industry.By the way that carbon nano-tube fibre is carried out spinning, energy
A kind of carbon nano-tube fibre is accessed, to replace traditional carbon fiber and glass fibre.However, using traditional carbon nanotube system
The adhesive force of standby carbon nano-tube fibre is poor, and then influences the quality of the cloth made by the 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 array, the modification which obtains
Carbon nano pipe array can be used in preparation with the carbon nano-tube fibre compared with high adhesion force.
In addition, also providing a kind of modified carbon nano-tube array and carbon nano-tube fibre and its preparation method and application.
A kind of preparation method of modified carbon nano-tube array, includes the following steps:
Unsaturated dicarboxylic, brominated styrene and methyl methacrylate are subjected to polymerization reaction, obtain copolymer, it is described
Unsaturated dicarboxylic is selected from least one of citraconic acid and dimethyl maleic acid；And
Under protective gas atmosphere, the copolymer and carbon nano pipe array are subjected to ultraviolet light processing to carry out
Graft reaction obtains modified carbon nano-tube array.
Copolymer grafted is arrived carbon nano pipe array using ultraviolet light by the preparation method of above-mentioned modified carbon nano-tube array
Surface, and copolymer is mainly formed by unsaturated dicarboxylic, brominated styrene and methyl methacrylate polymerization, unsaturation two
Carboxylic acid is selected from least one of citraconic acid and dimethyl maleic acid, and obtained modified carbon nano-tube array is easily dispersed, can
Prepare the carbon nano-tube fibre having compared with high adhesion force.Experiment proves that the carbon prepared using above-mentioned modified carbon nano-tube array
The adhesive force of nanotube fibers is 30MPa~51MPa, can be used in preparing more docile, the higher cloth of quality.
It is described in one of the embodiments, to carry out unsaturated dicarboxylic, brominated styrene and methyl methacrylate
The step of polymerization reaction specifically: by the unsaturated dicarboxylic, the brominated styrene, the polymethylacrylic acid and initiation
Agent mixing, and Raolical polymerizable is carried out at 60 DEG C~65 DEG C, the reaction time is 6h~8h, and the initiator is azo two
Isobutyronitrile.
The molar ratio of the initiator and the unsaturated dicarboxylic is 1:18~1:24 in one of the embodiments,.
It is described under protective gas atmosphere in one of the embodiments, by the copolymer and carbon nano pipe array
Before carrying out the step of ultraviolet light processing is to carry out graft reaction, further include the steps that preparing the carbon nano pipe array:
The deposit catalyst layers in first substrate；And
Under protective gas atmosphere, first substrate for being deposited with the 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 ethylene and hexane, the second
The partial pressure ratio of alkene and the hexane is 1.25:1~8:1, 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.
The unsaturated dicarboxylic, the brominated styrene and the methyl methacrylate in one of the embodiments,
The mass ratio of ester is (2~7): (9~14): (4~7).
The weight average molecular weight of the copolymer is 3000~20000 in one of the embodiments,.
A kind of modified carbon nano-tube array is prepared by the preparation method of above-mentioned modified carbon nano-tube array.
Above-mentioned modified Nano pipe array is carried out spinning, obtains carbon nanotube by a kind of preparation method of carbon nano-tube fibre
Fiber.
A kind of carbon nano-tube fibre is prepared by the preparation method of above-mentioned carbon nano-tube fibre.
Above-mentioned carbon nano-tube fibre 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 adhesive force of the preparation method of the carbon nano-tube fibre of one embodiment, obtained carbon nano-tube fibre is higher, energy
It is enough in and prepares more docile, the higher cloth of quality.
It should be noted that carbon nano-tube fibre can be woven into cloth using traditional Weaving method.Traditional spinning
Organization method for example can be flat weaving method or twill.It should be noted that can using single modified carbon nano-tube fiber into
More modified carbon nano-tube fibers parallels can also be made one and weaved again by row weaving.
Specifically, the preparation method of the carbon nano-tube fibre includes the following steps S110~S120:
S110, modified carbon nano-tube array is prepared.
Specifically, the step of S110 includes S111~S113:
S111, unsaturated dicarboxylic, brominated styrene and methyl methacrylate are subjected to polymerization reaction, are copolymerized
Object.Unsaturated dicarboxylic is selected from least one of citraconic acid and dimethyl maleic acid.
The weight average molecular weight of copolymer is 3000~20000 in one of the embodiments,.Further, copolymer
Weight average molecular weight is 5000~15000.
The mass ratio of unsaturated dicarboxylic, brominated styrene and methyl methacrylate is in one of the embodiments,
(2~7): (9~14): (4~7).The copolymer grafted that this setting obtains can not only increase in the surface of carbon nano pipe array
The adhesive force of modified carbon nano-tube array, additionally it is possible to increase the distance between carbon nanotube, to reduce due between carbon nanotube
Van der Waals force caused by reunion, with the modified carbon nano-tube array being easily dispersed, can more preferably play carbon nanotube
Mechanical property, obtain the higher modified carbon nano-tube array of flexibility.
The mass ratio of brominated styrene and methyl methacrylate is 1.5~2.5 in one of the embodiments,.It is such
It is arranged so that the adhesive force of modified carbon nano-tube array is higher, the flexibility of obtained carbon nano-tube fibre is preferable.Further,
The mass ratio of brominated styrene and methyl methacrylate is 2.Such setting can further provide for modified carbon nano-tube array
Adhesive force, obtain the better carbon nano-tube fibre of flexibility.
Unsaturated dicarboxylic is made of citraconic acid and dimethyl maleic acid in one of the embodiments, and citraconic acid and
The molar ratio of dimethyl maleic acid is 0.8:1~1.5:1.Such setting can further increase the attached of modified carbon nano-tube fiber
Put forth effort.Further, the molar ratio of citraconic acid and dimethyl maleic acid is 1.1:1.
Unsaturated dicarboxylic, brominated styrene and methyl methacrylate are polymerize in one of the embodiments,
The step of reaction specifically: mix unsaturated dicarboxylic, brominated styrene, methyl methacrylate and initiator, and in 60
DEG C~65 DEG C at carry out Raolical polymerizable, the reaction time is 6h~8h, and initiator is AIBN (i.e. azodiisobutyronitrile).More
Further, the molar ratio of initiator and unsaturated dicarboxylic is 1:18~1:24.
Unsaturated dicarboxylic, brominated styrene and methyl methacrylate are polymerize in one of the embodiments,
Further include that solvent is added in the reactant obtained after polymerization reaction after the step of reaction, precipitating is collected after separation of solid and liquid, is obtained
To copolymer.Further, solvent is selected from least one of carbon tetrachloride, tetrahydrofuran and methylene chloride.Further,
The mode of separation of solid and liquid is centrifugation.It should be noted that the mode being separated by solid-liquid separation is not limited to be centrifuged, or other solid-liquids
Separate mode, such as 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.
S112, under protective gas atmosphere, by copolymer and carbon nano pipe array carry out ultraviolet light processing with into
Row graft reaction obtains modified carbon nano-tube array.
Specifically, S112 includes S1121~1123:
S1121, carbon nano pipe array is prepared.
The carbon nano-pipe array prepared in one of the embodiments, is classified as single-wall carbon nanotube array.It should be noted that
Carbon nano pipe array is also possible to array of multi-walled carbon nanotubes.It should be noted that using above-mentioned modified carbon nano-tube array
When preparation 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.
The step of preparing carbon nano pipe array in one of the embodiments, specifically: deposit carbon in the first substrate and receive
Mitron array.
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, deposits to form carbon nanometer in the first working face
Pipe array layer.
In one of the embodiments, the step of deposition of carbon nanotubes array in the first substrate include S1121a~
S1122b:
S1121a, 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.
S1122b, under protective gas atmosphere, the first substrate for being formed with catalyst layer is warming up to 550 DEG C~900
After DEG C, 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 enhance the adhesive force of carbon nano-tube fibre.
Protective gas is selected from least one of nitrogen, hydrogen, argon gas and helium in one of the embodiments,.
S1122, copolymer 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
Copolymer is carried, and the stability of silicon wafer, nickel sheet and copper sheet is 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, it is copolymerized
Object film with a thickness of 1mm~5mm.Certainly, in other embodiments, it can also be placed in the again using shearing copolymer material
Mode in two substrates.
The second substrate has the second working face in one of the embodiments,.Copolymer is set on the second working face.Altogether
The second working face is completely covered in polymers layer.
S1123, under protective gas atmosphere, to the first substrate for being formed with carbon nano pipe array and be formed with copolymer
The second substrate carry out ultraviolet light processing so that copolymer and carbon nano pipe array carry out graft reaction, obtain carbon modified
Nano-tube array.
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, the of carbon nano pipe array will be formed with
One substrate and the second substrate for being formed with copolymer are placed side by side in reaction chamber.Further, carbon nanotube will be formed with
First substrate of array and the second substrate for being formed with copolymer are placed side by side, and carbon nano-pipe array tubulation connects in copolymer edge
Touching.
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 protective gas is 2L/min~3L/min in one of the embodiments,.Protective gas is selected from nitrogen
At least one of gas, 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~10mm.
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,
The irradiation power that substrate carries out ultraviolet light when ultraviolet light processing is 15mW~35mW, and ultraviolet light is that illumination wavelength is 196nm
The monochromatic narrow band light of~350nm, the time for carrying out ultraviolet light processing is 15min~30min.With this condition, be conducive to
Ultraviolet light is reduced in the case where guaranteeing that copolymer can be grafted to carbon nano pipe array to copolymer and carbon nano pipe array knot
The destruction of structure to guarantee the mechanical property of carbon nano pipe array, and obtains the better carbon nano-tube fibre of flexibility.
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.
S120, spinning is carried out to modified Nano pipe array, obtains carbon nano-tube fibre.
In a wherein embodiment, the step of S120 in one of the embodiments, specifically: use clamping tool
Modified carbon nano-tube array is clamped from the edge of modified carbon nano-tube array, and along perpendicular to modified carbon nano-tube array growth
Direction pulled and rotated so that modified carbon nano-tube array is stretched, and make every in modified carbon nano-tube array
Modified carbon nano-tube is threaded together, and obtains modified fibre.
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 modified fibre.
Further, the step of S120 specifically: clamp modified carbon nano-tube battle array from the edge of modified carbon nano-tube array
Column, and pulled along the direction perpendicular to modified carbon nano-tube array growth, obtain silky nano pipe array；It is received from filiform
The edge of mitron array clamps silky nano pipe array, and is rotated along the extending direction perpendicular to silky nano pipe array
And pull, so that silky nano pipe array is stretched, and is threaded together every silky nano pipe in silky nano pipe array,
Obtain modified fibre.
In a wherein embodiment, when clamping modified carbon nano-tube array from the edge of modified carbon nano-tube array,
The width of clamping 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.
In a wherein embodiment, when being pulled along the direction of growth perpendicular to modified carbon nano-tube array
Rate is 0.05m/s~0.5mm/s.Further, it is pulled along the direction of growth perpendicular to modified carbon nano-tube array
When rate be 0.1m/s~0.4mm/s.Further, along the direction of growth progress perpendicular to modified carbon nano-tube array
Rate when dragging is 0.2m/s~0.3mm/s.
In a wherein embodiment, when being rotated along the direction of growth perpendicular to modified carbon nano-tube array
Revolving speed is 1000rpm~3000rpm.Further, it is rotated along the direction of growth perpendicular to modified carbon nano-tube array
When revolving speed be 2000rpm.
In a wherein embodiment, the diameter of carbon nano-tube fibre is 10 μm~200 μm.
In a wherein embodiment, the length of carbon nano-tube fibre is 100m~6000m.It should be noted that carbon
The length of nanotube fibers is not limited to above-mentioned length, can be configured according to actual needs.
The preparation method of above-mentioned carbon nano-tube fibre, using ultraviolet light by the table of copolymer grafted to carbon nano pipe array
Face, and copolymer is mainly formed by unsaturated dicarboxylic, brominated styrene and methyl methacrylate polymerization, unsaturated dicarboxyl
Acid is selected from least one of citraconic acid and dimethyl maleic acid, and obtained modified carbon nano-tube array is easily dispersed, can make
The standby carbon nano-tube fibre having compared with high adhesion force.Experiment proves that being received using carbon prepared by above-mentioned modified carbon nano-tube array
The adhesive force of mitron fiber is 30MPa~51MPa, can be used in preparing more docile, the higher cloth of quality.
Furthermore above-mentioned preparation method by by specific copolymer introduce carbon nano-tube fibre surface so that being changed by this
Property carbon nano pipe array made of carbon nano-tube fibre have preferable flexibility；Also, above-mentioned preparation method is not needed carbon
Nano-tube array dispersion carries out subsequent processing again in a solvent, will not destroy the array structure of carbon nano pipe array, be conducive to protect
The mechanical property for demonstrate,proving modified carbon nano-tube array and carbon nano-tube fibre, also avoids causing human body and ring using toxic reagent
The injury in border.
Finally, above-mentioned preparation method, prepares modified carbon nano-tube array by raw material of copolymer, convenient for what is operated and react
Control, and can directly modify copolymer to the surface of carbon nano pipe array, multi-time modification and processing are not needed, is reduced anti-
Process is answered, be conducive to improve reaction efficiency and reduces synthesis cost, simultaneously as not needing to receive in carbon in above-mentioned preparation method
The dispersion of mitron array carries out subsequent processing again in a solvent, i.e., without the operation for removing solvent, technique simplifies, meanwhile, it is solvent-free
Deng residual, the purity of modified carbon nano-tube array is 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.First substrate is alumina plate.Second substrate is copper sheet.Ultraviolet light is the monochromatic light that bandwidth is 218nm.
Embodiment 1
The preparation process of the carbon nano-tube fibre 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 1.25:1), and the flow control of carbon-source gas reacts 25min at 15L/min,
So that the first substrate surface is completely covered with carbon nano pipe array, carbon nano-pipe array is classified as single-wall carbon nanotube array, carbon nanometer
The length of pipe array is 650 μm, and the diameter of carbon nanotube is 15nm in carbon nano pipe array.
(2) one piece of second substrate is taken, forms the copolymer film with a thickness of 1mm in the second substrate.The preparation of copolymer
Process are as follows: unsaturated dicarboxylic, brominated styrene, methyl methacrylate and initiator are mixed, and carried out certainly at 65 DEG C
By base polymerization reaction 6h, reactant is obtained；Solvent is added into reactant, collects precipitating after separation of solid and liquid, precipitating is done
It is dry, obtain copolymer.Initiator is AIBN.The molar ratio of initiator and unsaturated dicarboxylic is 1:18.Unsaturated dicarboxylic is
Citraconic acid.The mass ratio of unsaturated dicarboxylic, brominated styrene and methyl methacrylate is 2:9:7.Copolymer is divided equally again
Son amount is 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 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 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, the width of clamping is 200 μm.The speed of dragging is 0.5mm/s, and revolving speed is
3000rpm。
Embodiment 2
The preparation process of the carbon nano-tube fibre 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 8:1), and the flow control of carbon-source gas reacts 10min at 5L/min, so that
First substrate surface is completely covered with carbon nano pipe array, and carbon nano-pipe array is classified as single-wall carbon nanotube array, carbon nano-pipe array
The length of column is 1180 μm, and the diameter of carbon nanotube is 15nm 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, brominated styrene, methyl methacrylate and initiator mixing, and carried out freely at 60 DEG C
Base polymerization reaction 8h, obtains reactant；Solvent is added into reactant, collects precipitating after separation of solid and liquid, precipitating is dried,
Obtain copolymer.Wherein, the molar ratio of initiator AIBN, initiator and unsaturated dicarboxylic is 1:24.Unsaturated dicarboxylic
For dimethyl maleic acid.The mass ratio of unsaturated dicarboxylic, brominated styrene and methyl methacrylate is 7:14:4.Copolymer
Weight average molecular weight be 20000.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
From for 10mm, 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 Nano Guan Zhen
Column.
(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, the width of clamping is 50 μm.The speed of dragging is 0.05mm/s, and revolving speed is
1000rpm。
Embodiment 3
The preparation process of the carbon nano-tube fibre 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 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 copolymer film with a thickness of 3mm in the second substrate.The preparation of copolymer
Process are as follows: unsaturated dicarboxylic, brominated styrene, methyl methacrylate and initiator are mixed, and carried out certainly at 63 DEG C
By base polymerization reaction 7h, reactant is obtained；Solvent is added into reactant, collects precipitating after separation of solid and liquid, precipitating is done
It is dry, obtain copolymer；Initiator is AIBN, and the molar ratio of initiator and unsaturated dicarboxylic is 1:20.Unsaturated dicarboxylic by
Citraconic acid and dimethyl maleic acid composition, and the molar ratio of citraconic acid and dimethyl maleic acid is 1.1:1.Unsaturated dicarboxylic,
The mass ratio of brominated styrene and methyl methacrylate is 4.5:12:6.The weight average molecular weight of copolymer is 10000.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 the monochromatic narrow band light that illumination wavelength is 218nm, irradiation time
For 23min；Ultraviolet light module is closed, the first substrate is exposed to nitrogen atmosphere down toward natural cooling, obtains modified Nano Guan Zhen
Column.
(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, the width of clamping is 130 μm.The speed of dragging is 0.3mm/s, and revolving speed is
2000rpm。
Embodiment 4
The preparation process of the carbon nano-tube fibre of the present embodiment is roughly the same with embodiment 1, the difference is that: insatiable hunger
Mass ratio with dicarboxylic acids, brominated styrene and methyl methacrylate is 2:9:6.
Embodiment 5
The preparation process of the carbon nano-tube fibre of the present embodiment is roughly the same with embodiment 2, the difference is that: insatiable hunger
Mass ratio with dicarboxylic acids, brominated styrene and methyl methacrylate is 7:12.5:5.
Embodiment 6
The preparation process of the carbon nano-tube fibre of the present embodiment is roughly the same with embodiment 3, the difference is that: citraconic acid
And the molar ratio of dimethyl maleic acid is 0.8:1.
Embodiment 7
The preparation process of the carbon nano-tube fibre of the present embodiment is roughly the same with embodiment 3, the difference is that: citraconic acid
And the molar ratio of dimethyl maleic acid is 1.5:1.
Embodiment 8
The preparation process of the carbon nano-tube fibre of the present embodiment is roughly the same with embodiment 3, the difference is that: by insatiable hunger
With dicarboxylic acids by Raolical polymerizable, reactant is obtained；Solvent is added into reactant, collects precipitating after separation of solid and liquid,
Precipitating is dried, copolymer is obtained.
Embodiment 9
The preparation process of the carbon nano-tube fibre of the present embodiment is roughly the same with embodiment 3, the difference is that: by bromination
Styrene obtains reactant by Raolical polymerizable；Solvent is added into reactant, collects precipitating after separation of solid and liquid, it will
Precipitating is dried, and obtains copolymer.
Embodiment 10
The preparation process of the carbon nano-tube fibre of the present embodiment is roughly the same with embodiment 3, the difference is that: by methyl
Methyl acrylate obtains reactant by Raolical polymerizable；Solvent is added into reactant, it is heavy to collect after separation of solid and liquid
It forms sediment, precipitating is dried, copolymer is obtained.
Embodiment 11
The preparation process of the carbon nano-tube fibre 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 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 copolymer film with a thickness of 3mm in the second substrate.Copolymer is polyphenyl
Ethylene.The weight average molecular weight of copolymer is 10000.
(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
It is formed with the first substrate of carbon nano pipe array and is formed with the second substrate contact of copolymer, reaction chamber is evacuated to air pressure drop
To 10-2It is being passed through nitrogen after Torr, keeping the flow velocity of nitrogen is 2.5L/min, is carried out to carbon nano pipe array and 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 the monochromatic narrow band light of 218nm, irradiation time 35min；It closes
Ultraviolet light module is closed, the first substrate is exposed to nitrogen atmosphere down toward natural cooling, obtains modified 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, the width of clamping is 130 μm.The speed of dragging is 0.3mm/s, and revolving speed is
2000rpm。
Embodiment 12
The preparation process of the carbon nano-tube fibre 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 iron,
The mixing material (mass ratio of nickel and cobalt is 1:1) of nickel and cobalt, then the first substrate is placed in chemical vapour deposition reactor furnace simultaneously
By nitrogen, then 700 DEG C are warming up to, then into chemical vapour deposition reactor furnace are passed through carbon-source gas (carbon-source gas includes hexane
And ethylene, the partial pressure ratio of hexane and ethylene are 4:1), and the flow control of carbon-source gas reacts 20min at 10L/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 800 μm, and the diameter of carbon nanotube is 12nm in carbon nano pipe array.
(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 primary filament is obtained, and primary filament is placed in the first substrate.From carbon
When the edge of nano-tube array clamps carbon nano pipe array, the width of clamping is 130 μm.The speed of dragging is 0.3mm/s, revolving speed
For 2000rpm.
(3) one piece of second substrate is taken, forms the copolymer film with a thickness of 3mm in the second substrate.The preparation of copolymer
Process is as follows: unsaturated dicarboxylic, brominated styrene, methyl methacrylate and initiator being mixed, and carried out at 63 DEG C
Raolical polymerizable 7h, obtains reactant, and solvent is added into reactant, collects precipitating after separation of solid and liquid, precipitating is carried out
It is dry, obtain copolymer；Initiator is AIBN, and the molar ratio of initiator and unsaturated dicarboxylic is 1:20.Unsaturated dicarboxylic
It is made of citraconic acid and dimethyl maleic acid, and the molar ratio of citraconic acid and dimethyl maleic acid is 1.1:1.Unsaturated dicarboxyl
The mass ratio of acid, brominated styrene and methyl methacrylate is 4.5:12:6.The weight average molecular weight of copolymer is 10000.It is molten
Agent is carbon dichloride.
(4) the first substrate for being formed with primary filament and the second substrate for being formed with copolymer is placed side by side in reaction chamber
In, it is formed with the first substrate of primary filament and is formed with the second substrate of copolymer and be in same level, and primary filament
And copolymer contact, reaction chamber are evacuated to air pressure and are down to 10-2It is being passed through nitrogen after Torr, keeping the flow velocity of nitrogen is 2.5L/
Min carries out ultraviolet light processing to the first substrate for being formed with primary filament and the second substrate for being formed with copolymer, ultraviolet
It is 5mm that light source distance, which is formed with the first substrate of primary filament and is formed with the distance of the second substrate of copolymer, ultraviolet light
Irradiation power is 25mW, and ultraviolet light is the monochromatic narrow band light of 218nm, irradiation time 23min；Ultraviolet light module is closed, by the
One substrate is exposed to nitrogen atmosphere down toward natural cooling, obtains carbon nano-tube fibre.
Embodiment 13
The preparation process of the carbon nano-tube fibre 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-tube fibre is obtained.Carbon nanotube is clamped from carbon nano pipe array
When array, the width of clamping is 130 μm.The speed of dragging is 0.3mm/s, revolving speed 2000rpm.
Test:
Measure the attachment of the modified carbon nano-tube array of embodiment 1~11 and the carbon nano pipe array of embodiment 12~13
Property, and the adhesion of the carbon nano-tube fibre of embodiment 1~12 is measured, and measure the carbon nano-tube fibre of embodiment 1~12
Flexibility.See Table 1 for details for measurement result.Table 1 indicate be embodiment 1~11 modified carbon nano-tube array and embodiment 12~
Adhesion, the adhesion and flexibility of the carbon nano-tube fibre of embodiment 1~12 of 13 carbon nano pipe array.
Specifically, using the adhesion of method the measurement array and carbon nano-tube fibre of 6854 defined of jis k, wherein
Array is carbon nano pipe array or modified carbon nano-tube array；
Using the flexibility of extension test method measurement carbon nano-tube fibre.
Table 1
As it can be seen from table 1 the adhesive force of the modified carbon nano-tube array of Examples 1 to 7 is 150MPa~250MPa, it is real
The adhesive force for applying the carbon nano-tube fibre of example 1~7 is 30MPa~51MPa, and flexibility is 4.35 × 10-3mm2/ kN~7.69 ×
10-3mm2/ kN is significantly better than that embodiment 13, illustrate the modified carbon nano-tube array obtained using above embodiment have compared with
High adhesive force, can make has compared with high adhesion force and compared with the carbon nano-tube fibre of high-flexibility.
Wherein, the adhesive force of the carbon nano-tube fibre of embodiment 8~10 is lower than embodiment 3, illustrates using unsaturated dicarboxyl
Copolymer made of acid, brominated styrene and methyl methacrylate is more advantageous to the adhesive force for improving carbon nano-tube fibre.It is real
The adhesive force of the carbon nano-tube fibre of example 9 is applied better than embodiment 11, illustrates to compare polyphenyl using copolymer made of brominated styrene
Ethylene is more advantageous to the adhesive force for improving carbon nano-tube fibre.The adhesive force and embodiment 12 of the carbon nano-tube fibre of embodiment 3
Quite, illustrate first to be modified carbon nano pipe array and carry out spinning again also and can prepare with the carbon nanotube compared with high adhesion force
Fiber.
In conclusion the preparation method of above embodiment, which can be prepared, to be had compared with high adhesion force and compared with the carbon of high-flexibility
Nanotube fibers.
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 array, which comprises the steps of:
Unsaturated dicarboxylic, brominated styrene and methyl methacrylate are subjected to polymerization reaction, obtain copolymer, the insatiable hunger
At least one of citraconic acid and dimethyl maleic acid are selected from dicarboxylic acids；And
Under protective gas atmosphere, the copolymer and carbon nano pipe array are subjected to ultraviolet light processing to be grafted
Reaction, obtains modified carbon nano-tube array.
2. the preparation method of modified carbon nano-tube array according to claim 1, which is characterized in that described by unsaturation two
Carboxylic acid, brominated styrene and methyl methacrylate carry out the step of polymerization reaction specifically: by the unsaturated dicarboxylic, institute
Brominated styrene, the polymethylacrylic acid and initiator mixing are stated, and carries out Raolical polymerizable at 60 DEG C~65 DEG C,
Reaction time is 6h~8h, and the initiator is azodiisobutyronitrile.
3. the preparation method of modified carbon nano-tube array according to claim 2, which is characterized in that the initiator and institute
The molar ratio for stating unsaturated dicarboxylic is 1:18~1:24.
4. the preparation method of modified carbon nano-tube array according to claim 1, which is characterized in that described in protectiveness gas
Under body atmosphere, by the copolymer and carbon nano pipe array carry out the step of ultraviolet light processing is to carry out graft reaction it
Before, further include the steps that preparing the carbon nano pipe array:
The deposit catalyst layers in first substrate；And
Under protective gas atmosphere, after first substrate for being deposited with the 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 ethylene and hexane, the ethylene with
The partial pressure ratio of the hexane is 1.25:1~8:1, 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.
5. the preparation method of modified carbon nano-tube array according to claim 1, which is characterized in that the unsaturation dicarboxyl
The mass ratio of sour, the described brominated styrene and the methyl methacrylate is (2~7): (9~14): (4~7).
6. the preparation method of modified carbon nano-tube array according to claim 1, which is characterized in that the weight of the copolymer
Average molecular weight is 3000~20000.
7. a kind of modified carbon nano-tube array, which is characterized in that by the described in any item modified carbon nano-tubes of claim 1~6
The preparation method of array is prepared.
8. a kind of preparation method of carbon nano-tube fibre, which is characterized in that by modified Nano pipe array as claimed in claim 7 into
Row spinning, obtains carbon nano-tube fibre.
9. a kind of carbon nano-tube fibre, which is characterized in that prepared by the preparation method of carbon nano-tube fibre according to any one of claims 8
It obtains.
10. carbon nano-tube fibre as claimed in claim 9 is preparing the application in cloth.
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