CN109735964A - Carbon nano-tube fibre and its preparation method and application - Google Patents
Carbon nano-tube fibre and its preparation method and application Download PDFInfo
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- CN109735964A CN109735964A CN201811458196.3A CN201811458196A CN109735964A CN 109735964 A CN109735964 A CN 109735964A CN 201811458196 A CN201811458196 A CN 201811458196A CN 109735964 A CN109735964 A CN 109735964A
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Abstract
The present invention relates to a kind of carbon nano-tube fibres and its preparation method and application.The preparation method includes the following steps: under protective gas atmosphere; ultraviolet light processing is carried out to carry out graft reaction to polymer and carbon nano pipe array; obtain modified carbon nano tube array; polymer is selected from least one of ethylenecarbon monoxide block copolymer and carbon monoxide-Ethylene-Propylene Block Copolymer; ultraviolet light is the monochromatic narrow band light that illumination wavelength is 218nm~289nm, and irradiation power is 20mW~30mW；Modified carbon nano tube array is subjected to spinning, obtains modified fibre；And reinforcement is set on modified fibre, and reacts at 80 DEG C~100 DEG C under protective gas atmosphere, carbon nano-tube fibre is obtained, reinforcement is selected from least one of phenolic resin and carbamide resin.The carbon nano-tube fibre that above-mentioned preparation method obtains can be used in preparing the higher cloth of more docile and tensile strength.
Description
Technical field
The present invention relates to field of material technology, more particularly to a kind of carbon nano-tube fibre and its preparation method and application.
Background technique
Carbon nano-tube fibre has many advantages, such as high temperature resistant, corrosion-resistant, wear-resistant, is widely used in aerial model airplane, lamp
With in the fields such as bracket, medical instrument.In recent years, carbon nano-tube fibre is gradually applied in textile industry.Wherein, carbon nanometer
Pipe fibre weight is light, and mechanical property is preferable, and application prospect is extensive in preparing various protective garments and functional cloth.However, passing
Cloth made of the carbon nano-tube fibre of system is not docile enough, and tensile strength is poor, is not able to satisfy actual demand.
Summary of the invention
Based on this, it is necessary to provide a kind of preparation method of carbon nano-tube fibre, the carbon nanotube which obtains
Fiber can be used in preparing the higher cloth of more docile and tensile strength.
In addition, also providing a kind of carbon nano-tube fibre and its application.
A kind of preparation method of carbon nano-tube fibre, includes the following steps:
Under the first protective gas atmosphere, ultraviolet light processing is carried out to carry out to polymer and carbon nano pipe array
Graft reaction, obtains modified carbon nano tube array, and the polymer is selected from ethylenecarbon monoxide block copolymer and carbon monoxide-
At least one of Ethylene-Propylene Block Copolymer, the ultraviolet light are the monochromatic narrowband that illumination wavelength is 218nm~289nm
Light, irradiation power are 20mW~30mW；
The modified carbon nano tube array is subjected to spinning, obtains modified fibre；And
Reinforcement is set on the modified fibre, and anti-at 80 DEG C~100 DEG C under the second protective gas atmosphere
It answers, obtains carbon nano-tube fibre, the reinforcement is selected from least one of phenolic resin and carbamide resin.
The preparation method of above-mentioned carbon nano-tube fibre uses illumination wavelength for the monochromatic narrow band light of 218nm~289nm, and
Irradiation power is 20mW~30mW, carries out ultraviolet light to polymer and carbon nano pipe array and handles to carry out graft reaction,
Polymer is grafted on the upper of carbon nano pipe array, polymer is selected from ethylenecarbon monoxide block copolymer and carbon monoxide-
At least one of Ethylene-Propylene Block Copolymer, the carbon nano pipe array being easily dispersed, to improve carbon nano-tube fibre
Adhesive force and can be used in preparing more docile cloth；By the way that reinforcement is arranged on modified fibre, reinforcement is selected from phenol
At least one of urea formaldehyde and carbamide resin, so that reinforcement is reacted with polymer in 80 DEG C~100 DEG C, reinforcement and polymer
Carbonyl formed hydrogen bond improve the tensile strength of carbon nano-tube fibre to form protective film on modified fibre and can be used in
Prepare the higher cloth of tensile strength.Experiment proves that cloth made of the carbon nano-tube fibre obtained using above-mentioned preparation method
The adhesive force of material is 214MPa~281MPa, and tensile strength is 7.70GPa~8.42GPa.Above-mentioned cloth is more docile, and has
Preferably mechanical property.
It is described in one of the embodiments, that the modified carbon nano tube array is subjected to spinning, obtain the step of modified fibre
Suddenly specifically: the modified carbon nano tube array is clamped from the edge of the modified carbon nano tube array, along perpendicular to the modification
The direction of carbon nano-array growth is pulled and is rotated, and the modified fibre is obtained.
When being pulled in one of the embodiments, along the direction perpendicular to the modified carbon nano tube array growth
Rate is 0.05m/s~0.5mm/s, revolving speed when being rotated along the direction perpendicular to the modified carbon nano tube array growth
For 1000rpm~3000rpm.
It is described under the first protective gas atmosphere in one of the embodiments, to polymer and carbon nano pipe array
It further include preparing the ethylenecarbon monoxide block to be total to before carrying out the step of ultraviolet light processing is to carry out graft reaction
The step of polymers: ethylene, carbon monoxide are reacted at 50 DEG C~120 DEG C, 4MPa~15MPa with catalyst, obtain the second
Alkene-carbon monoxide block copolymer, the catalyst are 1,3- pairs of 2-phenyl-phosphine oxide palladium chloride；
And/or it is described under the first protective gas atmosphere, ultraviolet light is carried out to polymer and carbon nano pipe array
It further include the step for preparing the carbon monoxide-Ethylene-Propylene Block Copolymer before the step of processing is to carry out graft reaction
It is rapid: ethylene, carbon monoxide, propylene being reacted at 60 DEG C~180 DEG C, 6MPa~12MPa with catalyst, obtain an oxidation
Carbon-Ethylene-Propylene Block Copolymer, the catalyst are 1,3- pairs of 2-phenyl-phosphine oxide palladium chloride.
The reinforcement is made of phenolic resin and carbamide resin in one of the embodiments, and the phenolic resin with
The molar ratio of the carbamide resin is 0.8:1~1.13:1.
In one of the embodiments, in the ethylenecarbon monoxide block copolymer, the ethylene segment and described one
The molar ratio of carbonoxide segment is 0.8:1~1.13:1；And/or
In the carbon monoxide-Ethylene-Propylene Block Copolymer, the carbon monoxide segment, the ethylene segment and institute
The molar ratio for stating polypropylene segments is 1:3:3~1:1:1.
The polymer is by ethylenecarbon monoxide block copolymer and carbon monoxide-second in one of the embodiments,
Alkene-propylene-based block copolymer composition, the carbon monoxide-Ethylene-Propylene Block Copolymer and ethylenecarbon monoxide block
The molar ratio of copolymer is 1:1.13~1:0.8.
The weight average molecular weight of the polymer is 20000~30000 in one of the embodiments,.
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
It to facilitate the understanding of the present invention, below will be to invention is more fully described.The present invention can be with many not
With form realize, however it is not limited to embodiment described herein.On the contrary, purpose of providing these embodiments is makes to this
The understanding of the disclosure of invention is more thorough and comprehensive.
Unless otherwise defined, all technical and scientific terms used herein and belong to technical field of the invention
The normally understood meaning of technical staff is identical.Term as used herein in the specification of the present invention is intended merely to description tool
The purpose of the embodiment of body, it is not intended that in the limitation present invention.
The preparation method of the carbon nano-tube fibre of one embodiment, obtained carbon nano-tube fibre can be used in production attachment
Power is higher and the higher cloth of tensile strength.
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 be spun using single-root carbon nano-tube fiber
It knits, more carbon nano-tube fibres can also be twisted into one in parallel and weaved again.
Specifically, the preparation method of the carbon nano-tube fibre includes the following steps S110~S130:
S110, under the first protective gas atmosphere, ultraviolet light processing is carried out to polymer and carbon nano pipe array
To carry out graft reaction, modified carbon nano tube array is obtained.Polymer is selected from ethylenecarbon monoxide block copolymer and an oxidation
At least one of carbon-Ethylene-Propylene Block Copolymer.Ultraviolet light is the monochromatic narrowband that illumination wavelength is 218nm~289nm
Light, irradiation power are 20mW~30mW.
Use illumination wavelength for the monochromatic narrow band light of 218nm~289nm, and irradiation power is 20mW~30mW, to polymerization
Object and carbon nano pipe array carry out ultraviolet light processing to carry out graft reaction, and polymer is grafted on carbon nano pipe array
It is upper, polymer in ethylenecarbon monoxide block copolymer and carbon monoxide-Ethylene-Propylene Block Copolymer at least
One kind obtaining the higher carbon nano pipe array of mechanical property, can be used in preparing to improve the adhesive force of carbon nano-tube fibre
More docile cloth.
The weight average molecular weight of polymer is 20000~30000 in one of the embodiments,.Further, polymer
Weight average molecular weight is 22000~27000.
In one of the embodiments, in ethylenecarbon monoxide block copolymer, ethylene segment and carbon monoxide segment
Molar ratio is 0.8:1~1.13:1.The setting can guarantee carbon nano-tube fibre tensile strength with higher and preferable attached
Property.
In one of the embodiments, under the first protective gas atmosphere, polymer and carbon nano pipe array are carried out
It further include the step for preparing ethylenecarbon monoxide block copolymer before the step of ultraviolet light processing is to carry out graft reaction
It is rapid: ethylene, carbon monoxide being reacted at 50 DEG C~120 DEG C, 4MPa~15MPa with catalyst, it is embedding to obtain ethylenecarbon monoxide
Section copolymer.Catalyst is 1,3- pairs of 2-phenyl-phosphine oxide palladium chloride.Reaction time is 10min~30min.
Further, the step of preparing ethylenecarbon monoxide block copolymer are as follows: by ethylene, carbon monoxide and catalyst
It is reacted at 65 DEG C~85 DEG C, 7MPa~12MPa, obtains ethylenecarbon monoxide block copolymer.Reaction time be 15min~
25min。
In one of the embodiments, in carbon monoxide-Ethylene-Propylene Block Copolymer, carbon monoxide segment, ethylene chain
Section and the molar ratio of polypropylene segments are 1:3:3~1:1:1.The setting can guarantee that carbon nano-tube fibre is with higher and stretch by force
Degree and preferable adhesion.
In one of the embodiments, under the first protective gas atmosphere, polymer and carbon nano pipe array are carried out
It further include preparing carbon monoxide-Ethylene-Propylene Block Copolymer before the step of ultraviolet light processing is to carry out graft reaction
The step of: ethylene, carbon monoxide, propylene are reacted at 60 DEG C~180 DEG C, 6MPa~12MPa with catalyst, obtain an oxidation
Carbon-Ethylene-Propylene Block Copolymer.Catalyst is 1,3- pairs of 2-phenyl-phosphine oxide palladium chloride.Reaction time be 10min~
30min。
Further, the step of preparing carbon monoxide-Ethylene-Propylene Block Copolymer are as follows: by ethylene, carbon monoxide, third
Alkene is reacted at 110 DEG C~130 DEG C, 8MPa~10MPa with catalyst, obtains carbon monoxide-Ethylene-Propylene Block Copolymer.
Reaction time is 15min~25min.
Polymer is by ethylenecarbon monoxide block copolymer and carbon monoxide-ethylene-the third in one of the embodiments,
Alkene block copolymer composition.Mole of carbon monoxide-Ethylene-Propylene Block Copolymer and ethylenecarbon monoxide block copolymer
Than for 1:1.13~1:0.8.The polymer of this setting grafts on the surface of carbon nano pipe array, can further increase carbon nanometer
The dispersibility of pipe array, additionally it is possible to improve the mechanical property of carbon nano pipe array, be received with obtaining the carbon with more excellent mechanical property
Mitron fiber.
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.
When carrying out ultraviolet light processing in one of the embodiments, the irradiation power of ultraviolet light is 23mW~26mW.
Under this irradiation power, be conducive to the fuel factor for improving reaction system, so that system temperature is increased to polymer and forms gaseous state shape
State, and be moved under the action of protective gas air-flow the surface of carbon nano pipe array and carbon nano pipe array that grafting occurs is poly-
Close reaction.
Ultraviolet light is the monochrome that illumination wavelength is 256nm~289nm in one of the embodiments,
(monochromatic) narrow band light.Further, monochromatic narrow band light is the monochromatic light that bandwidth is 218nm~298nm.
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 20min.
When carrying out ultraviolet light processing in one of the embodiments, the irradiation power of ultraviolet light is 25mW, ultraviolet light
The monochromatic narrow band light for being 256nm for illumination wavelength, the time for carrying out ultraviolet light processing is 20min.With this condition, favorably
In guarantee polymer can be grafted to carbon nano pipe array in the case where reduce ultraviolet light to polymer and carbon nano pipe array
Structural damage, to guarantee the mechanical property of carbon nano pipe array.
The step of S110 in one of the embodiments, specifically: carbon nano pipe array is formed in the first substrate,
Polymer is formed in two substrates；Under the first protective gas atmosphere, to the first substrate and shape for being formed with carbon nano pipe array
Ultraviolet light processing is carried out at the second substrate for having polymer, so that polymer and carbon nano pipe array carry out graft reaction,
Obtain modified carbon nano tube array.
Further, ultraviolet source distance is at the first substrate for having carbon nano pipe array and the second base for being formed with polymer
The distance at bottom is 2mm~20mm.
The first substrate is alumina plate in one of the embodiments,.The size of first substrate is 5 feet.Certainly, at it
In his embodiment, the size of the first substrate is also possible to any other size.Further, the first substrate has the first work
Face to form carbon nano pipe array layer in the first working face
The second substrate is silicon wafer, nickel sheet or copper sheet in one of the embodiments,.The main function of second substrate is pair
Carrier polymer, and the stability of silicon wafer, nickel sheet and copper sheet is good, will not react with polymer.Further, the second substrate
Size be 50mm*50mm, certainly, in other embodiments, the size of the second substrate is also possible to any other size.
Polymer is set in the form of a film in the second substrate in one of the embodiments, certainly, in other realities
It applies in mode, it can also be in such a way that shear polymer solution material be placed in again in the second substrate.Further, the second substrate has
Second working face.Thin polymer film is formed on the second working face.The second working face is completely covered in thin polymer film.Further
Ground, the thin polymer film formed in the second substrate with a thickness of 1mm~5mm.
By the first substrate for being formed with carbon nano pipe array and it is formed with the second of polymer 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 polymer and discharges
It is placed in reaction chamber.Further, the first substrate of carbon nano pipe array will be formed with and be formed with the second base of polymer
Bottom is placed side by side, so that carbon nano pipe array and polymer are in same level.Specifically, the edge of carbon nano pipe array
With the EDGE CONTACT of thin polymer film.
To the first substrate for being formed with carbon nano pipe array and it is formed with the second of polymer in one of the embodiments,
Substrate is formed with the first substrate of carbon nano pipe array and is formed with the second substrate progress ultraviolet light processing of polymer
In the process, firstly, the air inlet of capping chamber and gas outlet, and vacuumize process is carried out to reaction chamber, made in reaction chamber
Air pressure is down to 10-2Torr or less.Optionally, make air pressure drop in reaction chamber down to 10-6Torr or less.Secondly, passing through air inlet again
Mouth is passed through protective gas into reaction chamber until reaching normal atmosphere (An), opens gas outlet, it is not open close enter protective gas
The pressure of holding system.
To the first substrate for being formed with carbon nano pipe array and it is formed with the second of polymer in one of the embodiments,
Substrate be formed with the first substrate of carbon nano pipe array and be formed with polymer the second substrate carry out ultraviolet light handle it
It afterwards, further include the operation that the first substrate is placed in natural cooling under protective gas atmosphere.It should be noted that in other realities
It applies in mode, the operation that the first substrate is placed in natural cooling under protective gas atmosphere also 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.This operation can prevent carbon nano pipe array to be exposed to sky
It is oxidized in gas.
Carbon nano-pipe array is classified as single-wall carbon nanotube array in one of the embodiments,.It should be noted that carbon nanometer
Pipe array is also possible to array of multi-walled carbon nanotubes.It should be noted that using the preparation method of above-mentioned modified carbon nano tube array
When, 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 800 μm~1000 μm in one of the embodiments,.Carbon in carbon nano pipe array
The diameter of nanotube is 10nm~15nm.
Ultraviolet light processing is carried out to be grafted to polymer and carbon nano pipe array in one of the embodiments,
Before the step of reaction, further include the steps that preparing carbon nano pipe array.The step of preparing carbon nano pipe array include S111~
S112:
S111, catalyst layer is formed in the first substrate.
Use electron beam evaporation method in the surface deposit catalyst layers of the first substrate in one of the embodiments,.Into one
The material on step ground, catalyst layer is selected from least one of cobalt and nickel.Further, the material of catalyst layer is by nickel and cobalt group
At the mass ratio of nickel and cobalt is 0.8:1~1.2:1.
In one of the embodiments, catalyst layer with a thickness of 20nm~23nm.
S112, under third protective gas atmosphere, by the first substrate for being formed with catalyst layer be warming up to 700 DEG C~
After 900 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 formed with catalyst layer be placed in chemical gas phase reaction furnace into
Row reaction.Further, it is first passed through third protective gas into chemical gas phase reaction furnace, then increases chemical gas phase reaction furnace
Temperature is to 700 DEG C~900 DEG C, so that catalyst layer homogeneous nucleation in the first substrate；It is passed through carbon-source gas progress thereto again
Reaction.
Further, carbon-source gas includes ethylene and hexane, and the partial pressure ratio of ethylene and hexane is 3:2~4:1.Carbon
The flow velocity of source gas is 8mL/min~12mL/min, and being passed through the time that carbon-source gas is reacted is 10min~25min.Pass through
This setting can obtain the better carbon nano pipe array of dispersibility, can obtain having the carbon nanotube of preferable mechanical property
Fiber.
In one of the embodiments, third protective gas in nitrogen, hydrogen, argon gas and helium at least one
Kind.
S120, spinning is carried out to modified carbon nano tube array, obtains modified fibre.
The step of S120 in one of the embodiments, specifically: using clamping tool from the side of modified carbon nano tube array
Edge clamps modified carbon nano tube array, and is pulled and rotated along the direction perpendicular to modified carbon nano tube array growth, so that
Modified carbon nano tube array is stretched, and is threaded together every modified carbon nano-tube in modified carbon nano tube array, is modified
Fiber.
In clamping tool drawing and modifying carbon nano-array, modified carbon nano-tube is by Van der Waals force and modification in carbon modified
Non-covalent interaction power between nano-array surface polymer or the decomposition product of polymer drives modified carbon nano tube array
It is continuously drawn out and makes every in modified carbon nano tube array to change in filiform, then by rotating modified carbon nano tube array
Property carbon nanotube is threaded together, as modified fibre.
Further, the step of S120 specifically: modified carbon nano tube array is clamped from the edge of modified carbon nano tube array, and
It is pulled along the direction perpendicular to modified carbon nano tube array growth, obtains silky nano pipe array；From silky nano Guan Zhen
The silky nano pipe array of the edge clamping of column, and rotated and dragged along the extending direction perpendicular to 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
Modified fibre.
When clamping modified carbon nano tube array from modified carbon nano tube array edges in one of the embodiments, the width of clamping
Degree is 50 μm~150 μm.When further, from from modified carbon nano tube array edges clamping modified carbon nano tube array, the width of clamping
Degree is 100 μm~150 μm.
It is along rate when being pulled perpendicular to the direction that modified carbon nano-tube is grown in one of the embodiments,
0.05m/s~0.5mm/s.Further, it is along rate when being pulled perpendicular to the direction that modified carbon nano-tube is grown
0.1m/s~0.4mm/s.Further, it is along rate when being pulled perpendicular to the direction that modified carbon nano-tube is grown
0.2m/s~0.3mm/s.
In one of the embodiments, along when being pulled and rotated perpendicular to the direction that modified carbon nano-tube is grown
Revolving speed is 1000rpm~3000rpm.Further, it is pulled and is revolved along perpendicular to the direction that modified carbon nano-tube is grown
Revolving speed when turning is 2000rpm.
The diameter of modified fibre is 10 μm~200 μm in one of the embodiments,.
The length of modified fibre is 100m~500m in one of the embodiments,.It should be noted that modified fibre
Length is not limited to above-mentioned length, can be configured according to actual needs.
S130, reinforcement is set on modified fibre, and anti-at 80 DEG C~100 DEG C under the second protective gas atmosphere
It answers, obtains carbon nano-tube fibre, reinforcement is selected from least one of phenolic resin and carbamide resin.
By the way that reinforcement is arranged on modified fibre, reinforcement is selected from least one of phenolic resin and carbamide resin, makes
It obtains reinforcement to react with polymer in 80 DEG C~100 DEG C, the carbonyl of reinforcement and polymer forms hydrogen bond, on modified fibre
Protective film is formed, the tensile strength of carbon nano-tube fibre is improved and can be used in preparing the higher cloth of tensile strength.
It should be noted that the reinforcement in the setting of modified fibre surface can come into full contact with copolymer.Further,
On modified fibre surface, the surface of carbon nano-tube fibre can be completely covered in the reinforcement of setting, to guarantee reinforcement and copolymer
It comes into full contact with.
In one of the embodiments, the second protective gas in nitrogen, helium, neon and argon gas at least one
Kind.
Reinforcement is set on modified fibre in one of the embodiments, and under the second protective gas atmosphere in
The step of being reacted at 80 DEG C~100 DEG C specifically: spray reinforcement on the surface of modified fibre, and in the second protective gas atmosphere
Reaction is 10min~15min at 80 DEG C~100 DEG C under enclosing.Under this setting, reinforcement can be made sufficiently anti-with modified fibre
It answers, to guarantee the tensile strength of carbon nano-tube fibre.It should be noted that the mode of setting reinforcement is not limited to spray, may be used also
Think other modes, such as can be coating.
Reinforcement is misty or film-form in one of the embodiments,.Such setting enables reinforcement more equal
Even is set on modified fibre.
Carbamide resin is melamine formaldehyde resin or benzoguanamine resin in one of the embodiments,.
Reinforcement is made of phenolic resin and carbamide resin in one of the embodiments, and phenolic resin and carbamide resin
Molar ratio is 0.8:1~1.13:1.Such setting can obtain the better carbon nano-tube fibre of tensile strength.
The preparation method of above-mentioned carbon nano-tube fibre uses illumination wavelength for the monochromatic narrow band light of 218nm~289nm, and
Irradiation power is 20mW~30mW, carries out ultraviolet light to polymer and carbon nano pipe array and handles to carry out graft reaction,
Polymer is grafted on the upper of carbon nano pipe array, polymer is selected from ethylenecarbon monoxide block copolymer and carbon monoxide-
At least one of Ethylene-Propylene Block Copolymer, the carbon nano pipe array being easily dispersed, to improve carbon nano-tube fibre
Adhesive force and can be used in preparing more docile cloth；By the way that reinforcement is arranged on modified fibre, reinforcement is selected from phenol
At least one of urea formaldehyde and carbamide resin, so that reinforcement is reacted with polymer in 80 DEG C~100 DEG C, reinforcement and polymer
Carbonyl formed hydrogen bond improve the tensile strength of carbon nano-tube fibre to form protective film on modified fibre and can be used in
Prepare the higher cloth of tensile strength.Experiment proves that cloth made of the carbon nano-tube fibre obtained using above-mentioned preparation method
The adhesive force of material is 214MPa~281MPa, and tensile strength is 7.70GPa~8.42GPa.Above-mentioned cloth is more docile, and has
Preferably mechanical property.
Above-mentioned preparation method does not need that carbon nano pipe array is dispersed to carry out in a solvent subsequent processing, technique letter
Change, the array structure of carbon nano pipe array will not be destroyed, advantageously ensure that the power of modified carbon nano tube array and carbon nano-tube fibre
Performance is learned, solvent-free to wait residual, the purity of obtained carbon nano-tube fibre 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.
Unless otherwise instructed, in following embodiment, the first substrate is alumina plate.Second substrate is copper sheet.Reinforcement is complete
The surface of all standing modified fibre.Ultraviolet light is the monochromatic light that bandwidth is 298nm.Carbamide resin is benzoguanamine resin.
If not otherwise specified, in following embodiment, the preparation process of ethylenecarbon monoxide block copolymer are as follows: by ethylene,
Carbon monoxide is reacted at 75 DEG C, 10MPa with catalyst, obtains ethylenecarbon monoxide block copolymer.Ethylene segment and an oxygen
The molar ratio for changing carbochain section is 1:1.Catalyst is 1,3- pairs of 2-phenyl-phosphine oxide palladium chloride.Reaction time is 20min.Catalysis
The additive amount of agent is to be excessively added, so that sufficiently reaction.
If not otherwise specified, in following embodiment, carbon monoxide-Ethylene-Propylene Block Copolymer preparation process is as follows:
Ethylene, carbon monoxide, propylene are reacted at 120 DEG C, 9MPa with catalyst, obtain carbon monoxide-ethylene-propylene blocks copolymerization
Object.The molar ratio of carbon monoxide segment, ethylene segment and polypropylene segments is 1:2:2.Catalyst is 1,3- pairs of 2-phenyl-phosphine oxide
Palladium chloride.Reaction time is 20min.The additive amount of catalyst is to be excessively added, so that sufficiently reaction.
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 0.8:1) of cobalt, then the first substrate is placed in chemical vapour deposition reactor furnace and is led to
Nitrogen is crossed, then is warming up to 900 DEG C, then into chemical vapour deposition reactor furnace is passed through carbon-source gas (carbon-source gas is by ethylene and oneself
The partial pressure ratio of alkane composition, ethylene and hexane is 4:1), and the flow control of carbon-source gas reacts 25min at 12L/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 15nm in carbon nano pipe array.
(2) one piece of second substrate is taken, forms the thin polymer film with a thickness of 1mm in the second substrate.Polymer is ethylene-
Carbon monoxide block copolymer.The weight average molecular weight of polymer is 20000.
(3) the first substrate for being formed with carbon nano pipe array and the second substrate for being formed with polymer 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 polymer and be in same level, and
Carbon nano pipe array and thin polymer film contact, reaction chamber are evacuated to air pressure and are down to 10-2It is being passed through nitrogen after Torr, is keeping nitrogen
The flow velocity of gas is 2L/min, is carried out to the first substrate for being formed with carbon nano pipe array and the second substrate for being formed with polymer purple
Outer 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 polymer
Distance be 2mm, the irradiation power of ultraviolet light is 30mW, and ultraviolet light is the monochromatic narrow band light that illumination wavelength is 218nm, when irradiation
Between be 35min；Ultraviolet light module is closed, the first substrate is exposed to nitrogen atmosphere down toward natural cooling, obtains modified carbon nano tube
Array.
(4) using clamping tool from the edge of modified carbon nano tube array clamp modified carbon nano tube array, and along perpendicular to
The direction of modified carbon nano-tube growth is pulled and is rotated, and carbon nano-tube fibre is obtained.It is pressed from both sides from modified carbon nano tube array edges
When taking modified carbon nano tube array, the width of clamping is 150 μm.The speed of dragging is 0.5mm/s, and the revolving speed of rotation is 3000rpm.
(5) reinforcement is sprayed on the surface of modified fibre, and reacts 15min at 100 DEG C under a nitrogen, obtain carbon nanometer
Pipe fiber, reinforcement are phenolic resin.
(6) carbon nano-tube fibre 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 1.2:1) of cobalt, then the first substrate is placed in chemical vapour deposition reactor furnace and is led to
Nitrogen is crossed, then is warming up to 700 DEG C, then into chemical vapour deposition reactor furnace is passed through carbon-source gas (carbon-source gas is by ethylene and oneself
Alkane composition, ethylene and the partial pressure of hexane ratio are 3:2) and the flow control of carbon-source gas react 10min at 8L/min, make
It obtains the first substrate surface and is completely covered with carbon nano pipe array, carbon nano-pipe array is classified as single-wall carbon nanotube array, carbon nanotube
The length of array is 1000 μm, and the diameter of carbon nanotube is 10nm in carbon nano pipe array.
(2) one piece of second substrate is taken, forms the thin polymer film with a thickness of 5mm in the second substrate.Polymer is an oxygen
Change carbon-Ethylene-Propylene Block Copolymer.The weight average molecular weight of polymer is 30000.
(3) the first substrate for being formed with carbon nano pipe array and the second substrate for being formed with polymer 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 polymer and be in same level, and
Carbon nano pipe array and thin polymer film contact, reaction chamber are evacuated to air pressure and are down to 10-2It is being passed through nitrogen after Torr, is keeping nitrogen
The flow velocity of gas is 3L/min, is carried out to the first substrate for being formed with carbon nano pipe array and the second substrate for being formed with polymer purple
Outer 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 polymer
Distance be 20mm, the irradiation power of ultraviolet light is 20mW, and ultraviolet light is the monochromatic narrow band light that illumination wavelength is 289nm, irradiation
Time is 10min；Ultraviolet light module is closed, the first substrate is exposed to nitrogen atmosphere down toward natural cooling, carbon modified is obtained and receives
Rice array.
(4) using clamping tool from the edge of modified carbon nano tube array clamp modified carbon nano tube array, and along perpendicular to
The direction of modified carbon nano-tube growth is pulled and is rotated, and modified fibre is obtained.Change from the clamping of modified carbon nano tube array edges
Property carbon nano-array when, the width of clamping is 50 μm.The speed of dragging is 0.05mm/s, and the revolving speed of rotation is 1000rpm.
(5) reinforcement is sprayed on the surface of modified fibre, and reacts 10min at 80 DEG C under a nitrogen, obtain carbon nanometer
Pipe fiber, reinforcement are carbamide resin.
(6) carbon nano-tube fibre 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 800 DEG C, then into chemical vapour deposition reactor furnace be passed through carbon-source gas (carbon-source gas is by ethylene and hexane
The partial pressure ratio of composition, ethylene and hexane is 2:1), and the flow control of carbon-source gas reacts 20min at 10L/min, makes
It obtains the first substrate surface and is completely covered with carbon nano pipe array, carbon nano-pipe array is classified as single-wall carbon nanotube array, carbon nanotube
The length of array is 900 μm, and the diameter of carbon nanotube is 12nm in carbon nano pipe array.
(2) one piece of second substrate is taken, forms the thin polymer film with a thickness of 3mm in the second substrate.Polymer is by ethylene-
Carbon monoxide block copolymer and carbon monoxide-Ethylene-Propylene Block Copolymer form.Ethylenecarbon monoxide block copolymer
And carbon monoxide-Ethylene-Propylene Block Copolymer molar ratio is 1:1.The Weight-average molecular of ethylenecarbon monoxide block copolymer
Amount is 22100.Carbon monoxide-Ethylene-Propylene Block Copolymer weight average molecular weight is 23500.
(3) the first substrate for being formed with carbon nano pipe array and the second substrate for being formed with polymer 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 polymer and be in same level, and
Carbon nano pipe array and thin polymer film contact, reaction chamber are evacuated to air pressure and are down to 10-2It is being passed through nitrogen after Torr, is keeping nitrogen
The flow velocity of gas 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 polymer
Ultraviolet light processing, ultraviolet source distance are formed with the first substrate of carbon nano pipe array and are formed with the second base of polymer
The distance at bottom is 5mm, and the irradiation power of ultraviolet light is 25mW, and ultraviolet light is the monochromatic narrow band light that illumination wavelength is 256nm, irradiation
Time is 20min；Ultraviolet light module is closed, the first substrate is exposed to nitrogen atmosphere down toward natural cooling, carbon modified is obtained and receives
Rice array.
(4) using clamping tool from the edge of modified carbon nano tube array clamp modified carbon nano tube array, and along perpendicular to
The direction of modified carbon nano-tube growth is pulled and is rotated, and modified fibre is obtained.Change from the clamping of modified carbon nano tube array edges
Property carbon nano-array when, the width of clamping is 100 μm.The speed of dragging is 0.3mm/s, and the revolving speed of rotation is 2000rpm.
(5) reinforcement is sprayed on the surface of modified fibre, and reacts 13min at 90 DEG C under a nitrogen, obtain carbon nanometer
Pipe fiber, reinforcement are made of phenolic resin and carbamide resin, and it is 1:1 that phenolic resin and carbamide resin, which are molar ratio,.
(6) carbon nano-tube fibre is weaved, obtains cloth.
Embodiment 4
The preparation process of the cloth of the present embodiment is roughly the same with embodiment 3 as follows, the difference is that: an oxidation
Carbon-Ethylene-Propylene Block Copolymer and the molar ratio of ethylenecarbon monoxide block copolymer are 1:0.8.
Embodiment 5
The preparation process of the cloth of the present embodiment is roughly the same with embodiment 3 as follows, the difference is that: an oxidation
Carbon-Ethylene-Propylene Block Copolymer and the molar ratio of ethylenecarbon monoxide block copolymer are 1:1.13.
Embodiment 6
The preparation process of the cloth of the present embodiment is roughly the same with embodiment 3 as follows, the difference is that: phenolic resin and
Carbamide resin is that molar ratio is 0.8:1.
Embodiment 7
The preparation process of the cloth of the present embodiment is roughly the same with embodiment 3 as follows, the difference is that: phenolic resin and
Carbamide resin is that molar ratio is 1.13:1.
Embodiment 8
The preparation process of the cloth of the present embodiment is roughly the same with embodiment 1, the difference is that: polymer is poly- second
Alkene.The weight average molecular weight of polymer is 20000.
Embodiment 9
The preparation process of the cloth of the present embodiment is roughly the same with embodiment 2, the difference is that: polymer is poly- third
Alkene.The weight average molecular weight of polymer is 30000.
Embodiment 10
The preparation process of the cloth of the present embodiment is as follows:
(1) carbon nano pipe array is made 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 nanotube growth is pulled and is rotated, and modified fibre is obtained.Modified carbon nano tube battle array is clamped from carbon nano-pipe array column border
When column, the width of clamping is 100 μm.The speed of dragging is 0.3mm/s, and the revolving speed of rotation is 2000rpm.
(3) cloth is made according to (5) the step of embodiment 3~(6).
Embodiment 11
The preparation process of the cloth of the present embodiment is as follows:
(1) carbon nano pipe array is set in the first substrate.Carbon nano pipe array is purchased from Cnano company and article No. is
The carbon nano pipe array of Flotube 9110.
(2) according to the operation of (2) the step of embodiment 3~(6), cloth is obtained.
Embodiment 12
The preparation process of the cloth of the present embodiment is as follows:
(1) modified fibre is obtained according to the operation of (1) the step of embodiment 3~(4).
(2) modified fibre is weaved, obtains cloth.
Test:
The adhesive force and tensile strength of the cloth of embodiment 1~12 are measured, see Table 1 for details for measurement result.What table 1 indicated is real
Apply the adhesive force and tensile strength of the cloth of example 1~12.
Specifically, using the adhesive force of the method measurement cloth of 6854 defined of JIS K；
Using the tensile strength of extension test method measurement cloth.
Table 1
| Adhesive force (MPa) | Tensile strength (GPa) | |
| Embodiment 1 | 214 | 7.81 |
| Embodiment 2 | 225 | 7.70 |
| Embodiment 3 | 281 | 8.42 |
| Embodiment 4 | 271 | 7.95 |
| Embodiment 5 | 269 | 7.99 |
| Embodiment 6 | 256 | 8.35 |
| Embodiment 7 | 253 | 8.38 |
| Embodiment 8 | 198 | 7.61 |
| Embodiment 9 | 210 | 7.52 |
| Embodiment 10 | 151 | 5.36 |
| Embodiment 11 | 263 | 7.85 |
| Embodiment 12 | 193 | 6.88 |
As it can be seen from table 1 the adhesive force of the cloth of Examples 1 to 7 is 214MPa~281MPa, tensile strength is
7.70GPa~8.42GPa is better than embodiment 10 and embodiment 12, illustrates fine using carbon nanotube made of above embodiment
Dimension, which can be used in preparation, has the cloth for having both adhesive force and tensile strength, to obtain the preferable cloth of more docile and retractility
Material.
Wherein, the adhesive force of the cloth of embodiment 8 and tensile strength are below embodiment 1, illustrate that ethylenecarbon monoxide is embedding
Section copolymer is more advantageous to the mechanical property for improving cloth than polyethylene.The adhesive force and tensile strength of the cloth of embodiment 9 are equal
Lower than embodiment 2 is lower than, illustrate that carbon monoxide-Ethylene-Propylene Block Copolymer is more advantageous to raising than polypropylene and changes cloth
Mechanical property.The adhesive force and tensile strength of the cloth of embodiment 12 are slightly below embodiment 3, illustrate using above embodiment
The carbon nano-tube fibre of preparation is more advantageous to the mechanical property for improving cloth.
To sum up, the carbon nano-tube fibre made of above embodiment, which can be used in preparing having, has both adhesive force and stretching
The cloth of intensity, to obtain the preferable cloth of more docile and retractility.
Each technical characteristic of embodiment described above can be combined arbitrarily, for simplicity of description, not to above-mentioned reality
It applies all possible combination of each technical characteristic in example to be all described, as long as however, the combination of these technical characteristics is not deposited
In contradiction, all should be considered as described in this specification.
The embodiments described above only express several embodiments of the present invention, and the description thereof is more specific and detailed, but simultaneously
It cannot therefore be construed as limiting the scope of the patent.It should be pointed out that coming for those of ordinary skill in the art
It says, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to protection of the invention
Range.Therefore, the scope of protection of the patent of the invention shall be subject to the appended claims.
Claims (10)
1. a kind of preparation method of carbon nano-tube fibre, which comprises the steps of:
Under the first protective gas atmosphere, ultraviolet light processing is carried out to be grafted to polymer and carbon nano pipe array
Reaction, obtains modified carbon nano tube array, and the polymer is selected from ethylenecarbon monoxide block copolymer and carbon monoxide-ethylene-
At least one of propylene-based block copolymer, the ultraviolet light are the monochromatic narrow band light that illumination wavelength is 218nm~289nm, are shone
Penetrating power is 20mW~30mW；
The modified carbon nano tube array is subjected to spinning, obtains modified fibre；And
Reinforcement is set on the modified fibre, and is reacted at 80 DEG C~100 DEG C under the second protective gas atmosphere, is obtained
To carbon nano-tube fibre, the reinforcement is selected from least one of phenolic resin and carbamide resin.
2. the preparation method of carbon nano-tube fibre according to claim 1, which is characterized in that described to receive the carbon modified
The step of rice array carries out spinning, obtains modified fibre specifically: change described in being clamped from the edge of the modified carbon nano tube array
Property carbon nano-array, pulled and rotated along the direction perpendicular to the modified carbon nano tube array growth, obtain described change
Property fiber.
3. the preparation method of carbon nano-tube fibre according to claim 2, which is characterized in that along perpendicular to the modification
The rate when direction of carbon nano-array growth is pulled is 0.05m/s~0.5mm/s, is received along perpendicular to the carbon modified
The revolving speed when direction of rice array growth is rotated is 1000rpm~3000rpm.
4. the preparation method of carbon nano-tube fibre according to claim 1, which is characterized in that described in the first protectiveness gas
Under body atmosphere, before carrying out the step of ultraviolet light processing is to carry out graft reaction to polymer and carbon nano pipe array, also
Include the steps that preparing the ethylenecarbon monoxide block copolymer: by ethylene, carbon monoxide and catalyst 50 DEG C~120
DEG C, react under 4MPa~15MPa, obtain the ethylenecarbon monoxide block copolymer, the catalyst is the bis- diphenyl of 1,3-
Phosphine propane palladium chloride；
And/or it is described under the first protective gas atmosphere, ultraviolet light processing is carried out to polymer and carbon nano pipe array
Before the step of carrying out graft reaction, further include the steps that preparing the carbon monoxide-Ethylene-Propylene Block Copolymer: will
Ethylene, carbon monoxide, propylene are reacted at 60 DEG C~180 DEG C, 6MPa~12MPa with catalyst, obtain the carbon monoxide-second
Alkene-propylene-based block copolymer, the catalyst are 1,3- pairs of 2-phenyl-phosphine oxide palladium chloride.
5. the preparation method of carbon nano-tube fibre according to claim 1, which is characterized in that the reinforcement is by phenolic aldehyde tree
Rouge and carbamide resin composition, and the molar ratio of the phenolic resin and the carbamide resin is 0.8:1~1.13:1.
6. the preparation method of carbon nano-tube fibre according to claim 1, which is characterized in that the ethylenecarbon monoxide
In block copolymer, the molar ratio of the ethylene segment and the carbon monoxide segment is 0.8:1~1.13:1；And/or
In the carbon monoxide-Ethylene-Propylene Block Copolymer, the carbon monoxide segment, the ethylene segment and described third
The molar ratio of alkene segment is 1:3:3~1:1:1.
7. the preparation method of carbon nano-tube fibre according to claim 1, which is characterized in that the polymer is by ethylene-
Carbon monoxide block copolymer and carbon monoxide-Ethylene-Propylene Block Copolymer composition, the carbon monoxide-ethylene-propylene are embedding
The molar ratio of section copolymer and the ethylenecarbon monoxide block copolymer is 1:1.13~1:0.8.
8. the preparation method of carbon nano-tube fibre according to claim 1 again, which is characterized in that the polymer is divided equally
Son amount is 20000~30000.
9. a kind of carbon nano-tube fibre, which is characterized in that by the system of carbon nano-tube fibre according to any one of claims 1 to 8
Preparation Method is prepared.
10. carbon nano-tube fibre as claimed in claim 9 is preparing the application in cloth.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108314009A (en) * | 2018-03-30 | 2018-07-24 | 深圳烯湾科技有限公司 | The surface modification method of carbon nano pipe array |
| CN108532287A (en) * | 2018-03-30 | 2018-09-14 | 深圳烯湾科技有限公司 | The surface modification method of carbon nano-tube fibre |
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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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| FEI DENG 等: "Grafting polymer coatings onto the surfaces of carbon nanotube forests and yarns via a photon irradiation process", 《APPLIED PHYSICS LETTERS》 * |
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