CN109736086A - Modified fibre and its preparation method and application - Google Patents
Modified fibre and its preparation method and application Download PDFInfo
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- CN109736086A CN109736086A CN201811503929.0A CN201811503929A CN109736086A CN 109736086 A CN109736086 A CN 109736086A CN 201811503929 A CN201811503929 A CN 201811503929A CN 109736086 A CN109736086 A CN 109736086A
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Abstract
The present invention relates to a kind of modified fibres and its preparation method and application.The preparation method includes the following steps: that unsaturated dicarboxylic, brominated styrene and methyl methacrylate are carried out to polymerization reaction obtains copolymer, and unsaturated dicarboxylic is selected from least one of citraconic acid and dimethyl maleic acid;Under the first protective gas atmosphere, graft reaction is carried out to copolymer and carbon nano pipe array, obtains modified carbon nano-tube array;Modified carbon nano-tube array is subjected to spinning, obtains carbon nano-tube fibre;Presoma is sprayed on carbon nano-tube fibre, and is reacted at 140 DEG C~160 DEG C under the second protective gas atmosphere, modified fibre is obtained, and presoma is selected from least one of polystyrene resin and epoxy resin.The flexibility for the modified fibre that above-mentioned preparation method obtains is preferable.
Description
Technical field
The present invention relates to field of material technology, more particularly to a kind of modified fibre and its preparation method and application.
Background technique
Fiber is a kind of common material, is often used as cloth.Fiber cloth is also known as carbon fiber sheet, is praised in the world
For " black gold ", it is referred to as " third generation material ", made of carbon fiber after the metals such as stone implement and steel in the world
Composite material intensity with higher, and lighter in weight.However, the flexibility of traditional carbon nano-tube fibre is poor, influence by
The quality of cloth is made in the carbon nano-tube fibre.
Summary of the invention
Based on this, it is necessary to a kind of preparation method of modified fibre is provided, the modified fibre which obtains it is soft
Toughness is preferable.
In addition, also providing a kind of modified fibre and its preparation method and application.
A kind of preparation method of modified fibre, 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;
Under the first protective gas atmosphere, graft reaction is carried out to the copolymer and carbon nano pipe array, is changed
Property carbon nano pipe array;
The modified carbon nano-tube array is subjected to spinning, obtains carbon nano-tube fibre;
Presoma is sprayed on the carbon nano-tube fibre, and in 140 DEG C~160 DEG C under the second protective gas atmosphere
Lower reaction, obtains modified fibre, and the presoma is selected from least one of polystyrene resin and epoxy resin.
The preparation method of above-mentioned modified fibre carries out unsaturated dicarboxylic, brominated styrene and methyl methacrylate
Polymerization reaction obtains copolymer, and unsaturated dicarboxylic is selected from least one of citraconic acid and dimethyl maleic acid, then using purple
Outer light irradiation is by the surface of copolymer grafted to carbon nano pipe array, in the carbon nanotube made of the modified carbon nano-tube
Presoma is sprayed on fiber, presoma is selected from least one of polystyrene resin and epoxy resin, so that presoma is together
- the COOR- (ester group) of polymers reacts, and obtains the preferable modified fibre of flexibility.Experiment proves that above-mentioned preparation method obtained
The flexibility of modified fibre is 6.85 × 10-3mm2/ kN~9.78 × 10-3mm2/ kN, so that the flexibility for the cloth being made into is
3.47×10-3mm2/ kN~5.16 × 10-3mm2/ kN, quality are higher.
The presoma is made of polystyrene resin and epoxy resin in one of the embodiments, and the polyphenyl
The molar ratio of vinyl and the epoxy resin is 1:99~1:95.
It is described in one of the embodiments, to carry out unsaturated dicarboxylic, brominated styrene and methyl methacrylate
Polymerization reaction obtains the step of copolymer specifically: by the unsaturated dicarboxylic, the brominated styrene, the poly- methyl-prop
Olefin(e) acid and initiator mixing, and Raolical polymerizable is carried out at 60 DEG C~65 DEG C, the reaction time is 6h~8h, the initiation
Agent is azodiisobutyronitrile.
The molar ratio of the initiator and the unsaturated dicarboxylic is 1:18~1:24 in one of the embodiments,.
It is described in one of the embodiments, that presoma is sprayed on the carbon nano-tube fibre, and in the second protectiveness
In the step of reacting at 140 DEG C~160 DEG C under atmosphere, the reaction time is 1h~2h.
The unsaturated dicarboxylic, the styrene and the methyl methacrylate in one of the embodiments,
Mass ratio is (2~7): (9~14): (4~7).
The weight average molecular weight of the copolymer is 4000~27000 in one of the embodiments,.
The irradiation power of the ultraviolet light is 15mW~35mW in one of the embodiments, and the ultraviolet light is irradiation
Wavelength is the monochromatic narrow band light of 196nm~350nm, and the time of the ultraviolet light processing is 10min~35min.
A kind of modified fibre is prepared by the preparation method of above-mentioned modified fibre.
Above-mentioned modified 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.But the present invention can be to be permitted
Mostly different form is realized, however it is not limited to embodiment described herein.On the contrary, purpose of providing these embodiments is makes
It is more thorough and comprehensive to the understanding of the disclosure.
Unless otherwise defined, all technical and scientific terms used herein and belong to technical field of the invention
The normally understood meaning of technical staff is identical.Term as used herein in the specification of the present invention is intended merely to description tool
The purpose of the embodiment of body, it is not intended that in the limitation present invention.
The preparation method of the modified fibre of one embodiment can obtain the preferable modified fibre of flexibility, be easy to weave,
It can be applied to the preparation preferable cloth of quality.The preparation method of the modified fibre includes the following steps S110~S140:
S110, unsaturated dicarboxylic, brominated styrene and methyl methacrylate progress polymerization reaction are obtained into copolymer.
Unsaturated dicarboxylic is selected from least one of citraconic acid and dimethyl maleic acid.
The weight average molecular weight of copolymer is 4000~27000 in one of the embodiments,.Further, copolymer
Weight average molecular weight is 6000~20000.
The mass ratio of unsaturated dicarboxylic, brominated styrene and methyl methacrylate is in one of the embodiments,
(2~7): (9~14): (4~7).The copolymer grafted of this setting can either increase carbon modified in the surface of carbon nano pipe array
The hardness of nano-tube array, additionally it is possible to increase the distance between carbon nanotube, to reduce due to the Van der Waals between carbon nanotube
Reunion caused by power is obtained with the modified carbon nano-tube array being easily dispersed with can more preferably play the performance of carbon nanotube
To the higher modified carbon nano-tube array of adhesive force.
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 modified carbon nano-tube array has both adhesive force and flexibility.Further, brominated styrene and methyl methacrylate
The mass ratio of ester is 2.Such setting further increases the adhesive force and flexibility of modified carbon nano-tube array.
Unsaturated dicarboxylic is made of citraconic acid and dimethyl maleic acid in one of the embodiments, and citraconic acid and
The molar ratio of dimethyl maleic acid is 0.8:1~1.13:1.Such setting can further increase the adhesive force of modified fibre.Into
One step, the molar ratio of citraconic acid and dimethyl maleic acid is 1:1.
Unsaturated dicarboxylic, brominated styrene and methyl methacrylate are polymerize in one of the embodiments,
The step of reaction specifically: mix unsaturated dicarboxylic, brominated styrene, polymethylacrylic acid and initiator, and in 60 DEG C
Raolical polymerizable is carried out at~65 DEG C, the reaction time is 6h~8h, and initiator is AIBN (i.e. azodiisobutyronitrile).
The molar ratio of initiator and the unsaturated dicarboxylic is 1:18~1:24 in one of the embodiments,.
Unsaturated dicarboxylic, styrene and methyl methacrylate are subjected to polymerization reaction in one of the embodiments,
The step of after, further include that solvent is added into the reactant of polymerization reaction, after separation of solid and liquid collect precipitating, obtain copolymer.
Further, solvent is selected from least one of carbon tetrachloride, tetrahydrofuran and methylene chloride.The mode of separation of solid and liquid be from
The heart.It should be noted that the mode being separated by solid-liquid separation be not limited to it is above-mentioned point out method, can be other modes, such as can be
Filter.
It further include being done to precipitating after the step of collecting precipitating after separation of solid and liquid in one of the embodiments,
Dry step, to obtain dry copolymer.It should be noted that being carried out if precipitating can satisfy demand to precipitating
Dry step can be omitted.
S120, under the first protective gas atmosphere, graft reaction is carried out to copolymer and carbon nano pipe array, is changed
Property carbon nano pipe array.
Carbon nano-pipe array is classified as single-wall carbon nanotube array in one of the embodiments,.It should be noted that carbon nanometer
Pipe array is also possible to array of multi-walled carbon nanotubes.
The length of carbon nano pipe array is 650 μm~1200 μm in one of the embodiments,.Carbon in carbon nano pipe array
The diameter of nanotube is 10nm~15nm.
S120 specifically includes S121~S124 in one of the embodiments:
S121, the deposit catalyst layers in the first substrate.
Catalyst layer is formed on the surface of the first substrate using electron beam evaporation method in one of the embodiments,.Into one
The material on step ground, catalyst layer is selected from least one of iron, cobalt and nickel.Catalyst layer with a thickness of 20nm~23nm.
The first substrate is alumina plate in one of the embodiments,.The main function of first substrate is to carrying carbon
Nano-tube array.Further, the size of the first substrate is 8 feet.Certainly, in other embodiments, the size of the first substrate
It is also possible to any other size.Further, the first substrate has the first working face.It deposits to be formed in the first working face and urge
Agent layer.
S122, under protective gas atmosphere, the first substrate for being formed with catalyst layer is warming up to 550 DEG C~900 DEG C
Afterwards, then it is passed through carbon-source gas reaction, obtains carbon nano pipe array.
In one of the embodiments, by the first substrate for being deposited with catalyst layer be placed in chemical gas phase reaction furnace into
Row reaction.Further, it is first passed through protective gas into chemical gas phase reaction furnace, then increases the temperature of chemical gas phase reaction furnace
To 550 DEG C~900 DEG C, so that catalyst layer homogeneous nucleation in the first substrate;Carbon-source gas is passed through thereto again to be reacted.
Further, carbon-source gas includes ethylene and hexane, and the partial pressure ratio of ethylene and hexane is 1.25:1~8:
1.The flow velocity of carbon-source gas is 5mL/min~15mL/min, and being passed through the time that carbon-source gas is reacted is 10min~25min.
It is arranged by this, the mechanical property of obtained carbon nano pipe array is preferable, to obtain the preferable modified fibre of adhesive force.
Protective gas is selected from least one of nitrogen, hydrogen, argon gas and helium in one of the embodiments,.
It is prepared it should be noted that carbon nano pipe array is not limited to the above method, commercially available purchase etc. can also be passed through
Other modes obtain.
S123, 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.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.
Copolymer is set in the second substrate in a manner of film in one of the embodiments,.Further, second
The copolymer film formed in substrate with a thickness of 1mm~5mm.Certainly, in other embodiments, copolymer can also first be sheared
Material is placed in the mode in the second substrate again.Further, the second substrate has the second working face.Copolymer film is formed in
On second working face.The second working face is completely covered in copolymer film.
S124, under the first protective gas atmosphere, to the first substrate for being formed with carbon nano pipe array and be formed with altogether
Second substrate of polymers carries out ultraviolet light processing, so that copolymer and carbon nano pipe array carry out graft reaction, is changed
Property carbon nano pipe array.
Using ultraviolet light by the surface of copolymer grafted to carbon nano pipe array, and specific copolymer is selected, so that
Modified carbon nano-tube array is easily dispersed, and can prepare has preferable flexible modified fibre, and carbon modified can be made to receive
Mitron array adhesive force with higher can be used in preparing the higher cloth of adhesive force.
By the first substrate for being formed with carbon nano pipe array and it is formed with the second of copolymer in one of the embodiments,
Substrate is placed in same reaction chamber.Reaction chamber can be closed, and reaction chamber has an air inlet and a gas outlet.It is set in reaction chamber
There is ultraviolet light module, ultraviolet light processing can be carried out to reaction chamber.
Further, it by the first substrate for being formed with carbon nano pipe array and the second substrate for being formed with copolymer and discharges
It is placed in reaction chamber.Further, the first substrate of carbon nano pipe array will be formed with and be formed with the second base of copolymer
Bottom is placed side by side, so that carbon nano pipe array is contacted with copolymer.
To the first substrate for being formed with carbon nano pipe array and it is formed with the second of copolymer in one of the embodiments,
During substrate carries out ultraviolet light processing, the air inlet of capping chamber and gas outlet first, and reaction chamber is carried out
Vacuumize process makes the air pressure in reaction chamber be down to 10-2Torr or less.Preferably, make air pressure drop in reaction chamber down to 10- 6Torr or less.Secondly, being passed through protective gas into reaction chamber until reaching normal atmosphere (An) by air inlet again, open out
Port, it is not open close enter protective gas keep system pressure.
The flow velocity of 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,
When substrate carries out ultraviolet light processing, the irradiation power of ultraviolet light is 15mW~35mW.Under this irradiation power, be conducive to mention
The fuel factor of high reaction system, so that system temperature is increased to copolymer and forms gaseous state, and in protective gas air-flow
Graft polymerization reaction occurs for the surface and carbon nano pipe array that carbon nano pipe array is moved under effect.
Ultraviolet light is the monochrome that illumination wavelength is 196nm~350nm in one of the embodiments,
(monochromatic) narrow band light.Further, monochromatic narrow band light is the monochromatic light that bandwidth is 218nm~298nm.
Ultraviolet source distance is formed with the first substrate of carbon nano pipe array and is formed with altogether in one of the embodiments,
The distance of second substrate of polymers is 2mm~20mm.
The time for carrying out ultraviolet light processing in one of the embodiments, is 10min~35min.One wherein
In embodiment, the time for carrying out ultraviolet light processing is 15min~30min.Ultraviolet light is carried out in one of the embodiments,
The time for the treatment of with irradiation is 23min.
To the first substrate for being formed with carbon nano pipe array and it is formed with the second of copolymer in one of the embodiments,
When substrate carries out ultraviolet light processing, the irradiation power of ultraviolet light is 15mW~35mW, and ultraviolet light is 196nm~350nm's
Monochromatic narrow band light, the time for carrying out ultraviolet light processing is 15min~30min.With this condition, be conducive to guaranteeing to be copolymerized
Object reduces destruction of the ultraviolet light to copolymer and carbon nano tube array structure in the case where capable of being grafted to carbon nano pipe array, with
Guarantee the mechanical property of carbon nano pipe array.
To the first substrate for being formed with carbon nano pipe array and it is formed with the second of copolymer in one of the embodiments,
It further include the behaviour that the first substrate is placed in natural cooling under protective gas atmosphere after substrate carries out ultraviolet light processing
Make.It should be noted that in other embodiments, the first substrate to be placed in the behaviour of natural cooling under protective gas atmosphere
Also it can be omitted.
The first substrate is placed under protective gas atmosphere in the operation of natural cooling in one of the embodiments,
Protective gas is selected from least one of nitrogen, argon gas and helium.By the first substrate be placed under protective gas atmosphere into
Row natural cooling can prevent carbon nano pipe array exposure to be oxidized in air.
S130, spinning is carried out to modified carbon nano-tube array, obtains carbon nano-tube fibre.
The step of S130 in one of the embodiments, specifically: using clamping tool from modified carbon nano-tube array
Edge clamps modified carbon nano-tube array, and is pulled and revolved along the direction perpendicular to modified carbon nano-tube array growth
Turn, so that modified carbon nano-tube array is stretched, and every modified carbon nano-tube in modified carbon nano-tube array is made to be screwed in one
It rises, obtains carbon nano-tube 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 carbon nano-tube fibre.
Further, the step of S130 specifically: clamp modified carbon nano-tube battle array from the edge of modified carbon nano-tube array
Column, and pulled along the direction perpendicular to modified carbon nano-tube array growth, obtain silky nano pipe array;It is received from filiform
The edge of mitron array clamps silky nano pipe array, and is rotated along the extending direction perpendicular to silky nano pipe array
And pull, so that silky nano pipe array is stretched, and is threaded together every silky nano pipe in silky nano pipe array,
Obtain carbon nano-tube fibre.
When clamping modified carbon nano-tube array from the edge of modified carbon nano-tube array in one of the embodiments, folder
The width taken is 50 μm~200 μm.Further, modified carbon nano-tube array is clamped from the edge of modified carbon nano-tube array
When, the width of clamping is 100 μm~150 μm.
Speed when being pulled in one of the embodiments, along the direction of growth perpendicular to modified carbon nano-tube array
Rate is 0.05m/s~0.5mm/s.Further, when being pulled along the direction of growth perpendicular to modified carbon nano-tube array
Rate be 0.1m/s~0.4mm/s.Further, it is dragged along the direction of growth perpendicular to modified carbon nano-tube array
Rate when dragging is 0.2m/s~0.3mm/s.
Turn when being rotated in one of the embodiments, along the direction of growth perpendicular to modified carbon nano-tube array
Speed is 1000rpm~3000rpm.Further, when being rotated along the direction of growth perpendicular to modified carbon nano-tube array
Revolving speed be 2000rpm.
The diameter of carbon nano-tube fibre is 10 μm~200 μm in one of the embodiments,.
The length of carbon nano-tube fibre is 100m~6000m in one of the embodiments,.It should be noted that carbon is received
The length of mitron fiber is not limited to above-mentioned length, can be configured according to actual needs.
S140, presoma is sprayed on carbon nano-tube fibre, and in 140 DEG C~160 under the second protective gas atmosphere
It is reacted at DEG C, obtains modified fibre, presoma is selected from least one of polystyrene resin and epoxy resin.
By spraying presoma on the surface of carbon nano-tube fibre, and specific presoma is selected, so that presoma is together
- the COOR- of polymers reacts, and obtains the preferable modified fibre of flexibility.
It should be noted that the presoma in the spraying of carbon nano-tube fibre surface can come into full contact with copolymer.Into one
Step ground, on carbon nano-tube fibre surface, the surface of carbon nano-tube fibre can be completely covered in the presoma of spraying, to guarantee forerunner
Body comes into full contact with copolymer.
In one of the embodiments, the second protective gas in nitrogen, helium, neon and argon gas at least one
Kind.
Presoma is sprayed on carbon nano-tube fibre in one of the embodiments, and in the second protective gas atmosphere
Under at 140 DEG C~160 DEG C react the step of in, the reaction time be 1h~2h.Under this reaction time, can make presoma with
Carbon nano-tube fibre sufficiently reacts, to guarantee the flexibility of modified fibre.
Presoma is misty or film-form in one of the embodiments,.Such setting enables presoma more equal
The even surface coated on carbon nano-tube fibre.
Presoma is made of polystyrene resin and epoxy resin in one of the embodiments, and polystyrene resin
And the molar ratio of epoxy resin is 1:99~1:95.Such setting, can obtain that flexibility is more preferable and adhesive force is preferably modified
Fiber.Further, epoxy resin is bisphenol A type epoxy resin.
The preparation method of above-mentioned modified fibre carries out unsaturated dicarboxylic, brominated styrene and methyl methacrylate
Polymerization reaction obtains copolymer, and unsaturated dicarboxylic is selected from least one of citraconic acid and dimethyl maleic acid, then using purple
Outer light irradiation is by the surface of copolymer grafted to carbon nano pipe array, in the carbon nanotube made of the modified carbon nano-tube
Presoma is sprayed on fiber, presoma is selected from least one of polystyrene resin and epoxy resin, so that presoma is together
- the COOR- (ester group) of polymers reacts, and obtains the preferable modified fibre of flexibility.Experiment proves that above-mentioned preparation method obtained
The flexibility of modified fibre is 6.85 × 10-3mm2/ kN~9.78 × 10-3mm2/ kN, so that the flexibility for the cloth being made into is
3.47×10-3mm2/ kN~5.16 × 10-3mm2/ kN, quality are higher.
Furthermore the preparation method of above-mentioned modified fibre passes through the copolymer in carbon nano pipe array surface grafting characteristic, energy
Enough increase the distance between carbon nanotube, reduces the reunion due to caused by the Van der Waals force between carbon nanotube, what is made changes
Property carbon nano pipe array be easily dispersed, make it possible to preferably play carbon nanotube mechanical property, it is more preferable to obtain adhesive force
Modified fibre, can be applied to preparation the higher cloth of quality.
Finally, above-mentioned preparation method does not need to disperse carbon nano pipe array to carry out subsequent processing, work in a solvent
Skill simplifies, and will not destroy the array structure of carbon nano pipe array, advantageously ensures that modified carbon nano-tube array and modified fibre
Mechanical property, solvent-free equal residual, the purity of obtained modified fibre are higher.
The cloth of one embodiment, the modified fibre including above embodiment.
It should be noted that modified fibre can be woven into cloth using traditional Weaving method.Traditional weaving side
Method for example can be flat weaving method or twill.
It should be noted that can be weaved using single modified fibre, more modified fibres can also be made in parallel
Cheng Yigen weaves again.
Above-mentioned cloth includes the modified fibre of above embodiment, due to modified fibre flexibility with higher and attached
Put forth effort, so that cloth quality with higher.
It is below the part of specific embodiment.
Unless otherwise instructed, following embodiment is without containing other groups not yet explicitly pointed out in addition to inevitable impurity
Point.And in following embodiment, the first substrate is alumina plate.Second substrate is copper sheet.Carbon nanotube fibre is completely covered in presoma
The surface of dimension.Epoxy resin is bisphenol A type epoxy resin.Ultraviolet light is the monochromatic light that bandwidth is 256nm.
Embodiment 1
The preparation process of the cloth of the present embodiment is as follows:
(1) take one piece of first substrate, deposition forms the catalyst layer of 20nm thickness in the first substrate, catalyst layer be nickel with
The mixing material (mass ratio of nickel and cobalt is 1:1) of cobalt, then the first substrate is placed in chemical vapour deposition reactor furnace and is passed through
Nitrogen, then be warming up to 900 DEG C, then into chemical vapour deposition reactor furnace be passed through carbon-source gas (carbon-source gas includes ethylene and oneself
The partial pressure ratio of alkane, ethylene and hexane is 1.25:1), and the flow control of carbon-source gas reacts 25min at 15L/min,
So that the first substrate surface is completely covered with carbon nano pipe array, carbon nano-pipe array is classified as single-wall carbon nanotube array, carbon nanometer
The length of pipe array is 650 μm, and the diameter of carbon nanotube is 15nm in carbon nano pipe array.
(2) one piece of second substrate is taken, forms the copolymer film with a thickness of 1mm in the second substrate.The preparation of copolymer
Process are as follows: unsaturated dicarboxylic, brominated styrene, methyl methacrylate and initiator are mixed, and carried out certainly at 65 DEG C
By base polymerization reaction 6h, reactant is obtained;Solvent is added into reactant, collects precipitating after separation of solid and liquid, precipitating is done
It is dry, obtain copolymer.Initiator is AIBN.The molar ratio of initiator and unsaturated dicarboxylic is 1:18.Unsaturated dicarboxylic is
Citraconic acid.The mass ratio of unsaturated dicarboxylic, brominated styrene and methyl methacrylate is 2:9:7.Copolymer is divided equally again
Son amount is 4000.Solvent is carbon tetrachloride.
(3) the first substrate for being formed with carbon nano pipe array and the second substrate for being formed with 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 carbon nano-tube battle array
Column.
(4) modified carbon nano-tube array is clamped from the edge of modified carbon nano-tube array using clamping tool, and along vertical
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.The diameter of obtained carbon nano-tube fibre is 10 μm.
(5) presoma is sprayed on the surface of carbon nano-tube fibre, and reacts 1h at 140 DEG C under a nitrogen, be modified
Fiber, presoma are polystyrene resin.
(6) modified 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 1:1) of cobalt, then the first substrate is placed in chemical vapour deposition reactor furnace and is passed through
Nitrogen, then be warming up to 550 DEG C, then into chemical vapour deposition reactor furnace be passed through carbon-source gas (carbon-source gas includes ethylene and oneself
The partial pressure ratio of alkane, ethylene and hexane is 8:1), and the flow control of carbon-source gas reacts 10min at 5L/min, so that
First substrate surface is completely covered with carbon nano pipe array, and carbon nano-pipe array is classified as single-wall carbon nanotube array, carbon nano-pipe array
The length of column is 1180 μm, and the diameter of carbon nanotube is 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 are mixed, and carried out certainly at 60 DEG C
By base polymerization reaction 8h, reactant is obtained;Solvent is added into reactant, collects precipitating after separation of solid and liquid, precipitating is done
It is dry, obtain copolymer.Wherein, the molar ratio of initiator AIBN, initiator and unsaturated dicarboxylic is 1:24.Unsaturated dicarboxyl
Acid is dimethyl maleic acid.The mass ratio of unsaturated dicarboxylic, brominated styrene and methyl methacrylate is 7:14:4.Copolymerization
The weight average molecular weight of object is 27000.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 carbon nano-tube
Array.
(4) modified carbon nano-tube array is clamped from the edge of modified carbon nano-tube array using clamping tool, and along vertical
Directly the direction of growth in modified carbon nano-tube array is pulled and 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.The diameter of obtained carbon nano-tube fibre is 200 μm.
(5) presoma is sprayed on the surface of carbon nano-tube fibre, and reacts 2h at 160 DEG C under a nitrogen, be modified
Fiber, presoma are epoxy resin.
(6) modified 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 700 DEG C, then into chemical vapour deposition reactor furnace be passed through carbon-source gas (carbon-source gas includes ethylene and oneself
The partial pressure ratio of alkane, ethylene and hexane is 4:1), and the flow control of carbon-source gas reacts 20min at 10L/min, 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 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.Unsaturated dicarboxylic, bromine
The mass ratio for changing styrene and methyl methacrylate is 4.5:12:6.The weight average molecular weight of copolymer is 15000.Solvent is two
Chlorination carbon.
(3) the first substrate for being formed with carbon nano pipe array and the second substrate for being formed with copolymer is placed side by side in anti-
It answers in chamber, is formed with the first substrate of carbon nano pipe array and is formed with the second substrate of copolymer and be in same level, and
Carbon nano pipe array and copolymer contact, reaction chamber 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 carbon nano-tube
Array.
(4) modified carbon nano-tube array is clamped from the edge of modified carbon nano-tube array using clamping tool, and along vertical
Directly the direction of growth in modified carbon nano-tube array is pulled and 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.The diameter of obtained carbon nano-tube fibre is 100 μm.
(5) presoma is sprayed on the surface of carbon nano-tube fibre, and reacts 1.5h at 150 DEG C under a nitrogen, changed
Property fiber.Presoma is made of polystyrene resin and epoxy resin, and the molar ratio of polystyrene resin and epoxy resin is
1:97。
(6) modified fibre is weaved, obtains cloth.
Embodiment 4
The preparation process of the cloth of the present embodiment is roughly the same with embodiment 1, the difference is that: unsaturated dicarboxyl
The molar ratio of acid, brominated styrene and methyl methacrylate is 2:9:6.
Embodiment 5
The preparation process of the cloth of the present embodiment is roughly the same with embodiment 2, the difference is that: unsaturated dicarboxyl
The molar ratio of acid, brominated styrene and methyl methacrylate is 7:12.5:5.
Embodiment 6
The preparation process of the cloth of the present embodiment is roughly the same with embodiment 3, the difference is that: unsaturated dicarboxylic by
Citraconic acid and dimethyl maleic acid composition, and the molar ratio of citraconic acid and dimethyl maleic acid is 0.8:1.
Embodiment 7
The preparation process of the cloth of the present embodiment is roughly the same with embodiment 3, the difference is that: unsaturated dicarboxylic by
Citraconic acid and dimethyl maleic acid composition, and the molar ratio of citraconic acid and dimethyl maleic acid is 1.13:1.
Embodiment 8
The preparation process of the cloth of the present embodiment is roughly the same with embodiment 3, the difference is that: presoma is by polyphenyl second
Olefine resin and epoxy resin composition, and the molar ratio of polystyrene resin and epoxy resin is 1:99.
Embodiment 9
The preparation process of the cloth of the present embodiment is roughly the same with embodiment 3, the difference is that: presoma is by polyphenyl second
Olefine resin and epoxy resin composition, and the molar ratio of polystyrene resin and epoxy resin is 1:95.
Embodiment 10
The preparation process of the cloth of the present embodiment is roughly the same with embodiment 3, the difference is that: by unsaturated dicarboxylic
By Raolical polymerizable, reactant is obtained;Be added solvent into reactant, precipitating collected after separation of solid and liquid, will precipitate into
Row drying, obtains copolymer.
Embodiment 11
The preparation process of the cloth of the present embodiment is roughly the same with embodiment 3, the difference is that: brominated styrene is led to
Raolical polymerizable is crossed, reactant is obtained;Solvent is added into reactant, collects precipitating after separation of solid and liquid, precipitating is carried out
It is dry, obtain copolymer.
Embodiment 12
The preparation process of the cloth of the present embodiment is roughly the same with embodiment 3, the difference is that: by methyl methacrylate
Ester obtains reactant by Raolical polymerizable;Solvent is added into reactant, collects precipitating after separation of solid and liquid, will precipitate
It is dried, obtains copolymer.
Embodiment 13
The preparation process of the cloth of the present embodiment is as follows:
(1) carbon nano 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.Obtained carbon nano-tube fibre
Diameter be 100 μm.
(3) presoma is sprayed on the surface of carbon nano-tube fibre, and reacts 1.5h at 150 DEG C under a nitrogen, changed
Property fiber, presoma is made of polystyrene resin and epoxy resin, and the molar ratio of polystyrene resin and epoxy resin is
1:97。
(4) modified fibre is weaved, obtains cloth.
Embodiment 14
The preparation process of the cloth of the present embodiment is as follows:
(1) carbon nano-tube fibre is obtained according to the operation of (1) the step of embodiment 3~(4).
(2) carbon nano-tube fibre is weaved, obtains cloth.
Embodiment 15
The preparation process of the cloth of the present embodiment is as follows:
(1) carbon nano pipe array is prepared according to (1) the step of embodiment 3.
(2) carbon nano pipe array is clamped from the edge of carbon nano pipe array using clamping tool, and is received along perpendicular to carbon
The direction of growth of mitron array is pulled and 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.Obtained carbon nano-tube fibre
Diameter be 100 μm.
(3) carbon nano-tube fibre is weaved, obtains cloth.
Test:
The modified fibre of embodiment 1~13 and the flexibility and adhesive force of cloth are measured, the carbon of embodiment 14~15 is measured
The flexibility and adhesive force of nanotube fibers and cloth, see Table 1 for details for measurement result.What table 1 indicated is the modification of embodiment 1~13
The flexibility and adhesive force of fiber and cloth, the carbon nano-tube fibre of embodiment 14~15 and the flexibility of cloth and adhesive force.
Specifically, using the adhesive force of method the measurement fiber and cloth of 6854 defined of jis k;
Using the flexibility of extension test method measurement fiber and cloth.
Table 1
As it can be seen from table 1 the flexibility of the modified fibre of Examples 1 to 9 is 6.85 × 10-3mm2/ kN~9.78 ×
10-3mm2/ kN, adhesive force are 180MPa~207MPa, are higher than embodiment 15;Also, the flexibility of the cloth of Examples 1 to 9 is
3.47×10-3mm2/ kN~5.16 × 10-3mm2/ kN, adhesive force are 70MPa~95MPa, hence it is evident that are higher than embodiment 15, in explanation
The flexibility for stating the modified fibre that embodiment obtains is preferable, and adhesive force is higher, and it is more docile and comfortable to can be used in production
Cloth, obtain the higher cloth of quality.
Wherein, the flexibility of the modified fibre of embodiment 3 and adhesive force are above embodiment 10~12, and illustrate unsaturation
Copolymer made of dicarboxylic acids, brominated styrene and methyl methacrylate, which is more advantageous to, improves the flexibility of modified fibre and attached
Put forth effort, obtains the higher cloth of quality.
In conclusion the preparation method of above embodiment can prepare the modified fibre for having both flexibility and adhesive force,
Can be used in the more docile and comfortable cloth of production, the higher cloth of quality is obtained.
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 fibre, 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;
Under the first protective gas atmosphere, graft reaction is carried out to the copolymer and carbon nano pipe array, obtains carbon modified
Nano-tube array;
The modified carbon nano-tube array is subjected to spinning, obtains carbon nano-tube fibre;And
Presoma is sprayed on the carbon nano-tube fibre, and anti-at 140 DEG C~160 DEG C under the second protective gas atmosphere
It answers, obtains modified fibre, the presoma is selected from least one of polystyrene resin and epoxy resin.
2. the preparation method of modified fibre according to claim 1, which is characterized in that the presoma is by polystyrene tree
Rouge and epoxy resin composition, and the molar ratio of the polystyrene resin and the epoxy resin is 1:99~1:95.
3. the preparation method of modified fibre according to claim 1, which is characterized in that described by unsaturated dicarboxylic, bromine
Change styrene and methyl methacrylate carries out the step of polymerization reaction obtains copolymer specifically: by the unsaturated dicarboxyl
Sour, the described brominated styrene, the polymethylacrylic acid and initiator mixing, and free radical polymerization is carried out at 60 DEG C~65 DEG C
Reaction, reaction time are 6h~8h, and the initiator is azodiisobutyronitrile.
4. the preparation method of modified fibre according to claim 3, which is characterized in that the initiator and the unsaturation
The molar ratio of dicarboxylic acids is 1:18~1:24.
5. the preparation method of modified fibre according to claim 1, which is characterized in that described in the carbon nano-tube fibre
Upper spraying presoma, and in the step of being reacted at 140 DEG C~160 DEG C under the second protective gas atmosphere, the reaction time is
1h~2h.
6. the preparation method of modified fibre according to claim 1, which is characterized in that the unsaturated dicarboxylic, described
The mass ratio of styrene and the methyl methacrylate is (2~7): (9~14): (4~7).
7. the preparation method of modified fibre according to claim 1, which is characterized in that the weight average molecular weight of the copolymer
It is 4000~27000.
8. the preparation method of modified fibre according to claim 1, which is characterized in that the irradiation power of the ultraviolet light is
15mW~35mW, the ultraviolet light are the monochromatic narrow band light that illumination wavelength is 196nm~350nm, the ultraviolet light processing
Time be 10min~35min.
9. a kind of modified fibre, which is characterized in that by the preparation method system of modified fibre according to any one of claims 1 to 8
It is standby to obtain.
10. modified fibre as claimed in claim 9 is preparing the application in cloth.
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CN108314009A (en) * | 2018-03-30 | 2018-07-24 | 深圳烯湾科技有限公司 | The surface modification method of carbon nano pipe array |
CN108532287A (en) * | 2018-03-30 | 2018-09-14 | 深圳烯湾科技有限公司 | The surface modification method of carbon nano-tube fibre |
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CN108314009A (en) * | 2018-03-30 | 2018-07-24 | 深圳烯湾科技有限公司 | The surface modification method of carbon nano pipe array |
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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娄春华等: "《聚合物结构与性能》", 31 May 2016, 哈尔滨工程大学出版社 * |
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