CN109972387A - Graphene graft modification conductive fiber and its preparation method and application - Google Patents
Graphene graft modification conductive fiber and its preparation method and application Download PDFInfo
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M10/00—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements
- D06M10/04—Physical treatment combined with treatment with chemical compounds or elements
- D06M10/06—Inorganic compounds or elements
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/73—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof
- D06M11/74—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof with carbon or graphite; with carbides; with graphitic acids or their salts
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
- D06M13/12—Aldehydes; Ketones
- D06M13/127—Mono-aldehydes, e.g. formaldehyde; Monoketones
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/02—Natural fibres, other than mineral fibres
- D06M2101/04—Vegetal fibres
- D06M2101/06—Vegetal fibres cellulosic
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- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/35—Abrasion, pilling or fibrillation resistance
Abstract
The present invention provides a kind of graphene graft modification conductive fibers, it includes matrix fiber parts, the graphene part with the assistant activator part of described matrix fiber part chemical bonding and with assistant activator part chemical bonding, wherein the graphene graft modification conductive fiber is after washing 20 times, resistivity increases by 0.1% to 2%, and after being rubbed 600 times to 800 times on YG522 type abrasiometer according to ISO 5470-1-1999, resistivity increases by 0.1% to 5%, therefore with excellent water-fastness, rub resistance and resistance stability.The present invention also provides the methods for preparing the graphene graft modification conductive fiber.In addition, the purposes the present invention also provides the graphene graft modification conductive fiber in intelligent textile, flexible sensor, electronic device or electric heating health textile.
Description
Technical field
The present invention relates to a kind of conductive fiber, preparation method and use more particularly to a kind of graphene graft modifications to lead
Electric fiber, preparation method and use.
Background technique
In recent years, intelligent fiber and textile were increasingly becoming the research hotspot of people, and conductive fiber is in intelligent textile
Important component as signal transmission, sensing response and energy storage is increasingly becoming the forward position material of research.Graphene is that one kind has
The carbon nanomaterial of two-dimensional nanostructure has the performances such as conductivity outstanding, thermal conductivity, mechanics enhancing, leads in functional fibre
Domain has broad application prospects.
Graphene conductive fiber is mainly prepared by the modified two methods of composite and surface, wherein composite side
Method mainly graphene is blended with polymer raw material, then spinning, but its graphene for usually requiring high level and
The resistance of gained fiber is larger, fiber mechanical property is undesirable.Surface modification is in general fibre surface grafting graphite oxide
Then alkene prepares graphene conductive composite fibre and restoring graphene oxide again.
Locate in advance for example, a kind of preparation method (CN103966844A) of graphene conductive composite fibre chooses silane coupling agent
Fiber is managed, solution reduction is carried out after grafted graphene oxide.A kind of system of graphene coated polyacrylonitrile fibre composite material
Preparation Method (CN102619080A) then coats polyacrylonitrile fibre by multilayer graphene oxide, then passes through hydrazine hydrate reduction again
To prepare graphene conductive fiber.However, in above-mentioned surface modifying method, however it remains the grafting rate of graphene modified fibre
Low, the problems such as interface binding power is poor, water-wash resistance is poor and rub resistance is poor.
Therefore, there is still a need for the graphene graft modifications with improved grafting rate, water-wash resistance and rub resistance for this field
Conductive fiber and corresponding preparation method.
Summary of the invention
The present invention is intended to provide the stone that a kind of grafting rate and water-wash resistance, rub resistance and resistance stability are improved
Black alkene graft modification conductive fiber and preparation method thereof, to overcome the above deficiencies in the existing technologies.
According to an aspect of the invention, there is provided a kind of graphene graft modification conductive fiber, the graphene grafting
Denatured conductive fiber includes: matrix fiber part, has on the surface one or more selected from hydroxyl, carboxyl, amino, isocyanide
The functional group of perester radical, acid halide group；Assistant activator part is chemically bound on described matrix fiber part, and contains
The group of functional group reactions on multiple surfaces with described matrix fiber part；And graphene part, via with it is described
Assistant activator part is chemically bonded and is grafted on described matrix fiber, wherein the graphene graft modification conductive fiber is in water
After washing 20 times, resistivity increases by 0.1% to 2%, and is rubbed on YG522 type abrasiometer according to ISO 5470-1-1999
After wiping 600 times to 800 times, resistivity increases by 0.1% to 5%.
In one embodiment, described matrix fiber part is selected from one of group consisting of or a variety of: polysaccharide
Fiber, for example, cotton fiber, degreasing cotton fiber, hemp, flax fiber, ramee, tossa, apocynum fibre,
Oil flax fibre, viscose rayon, copper ammonia fiber, acetate fiber, alginate fibre, chitin fiber, sodium alginate fiber, tencel, not
Dai Er, nandina；And the chemical fibre containing the functional group, for example, vinal, acrylic fiber, polyurethane fiber,
Acid fiber by polylactic, polyacrylonitrile fibre.
In one embodiment, the assistant activator part is derived from comprising being selected from hydroxyl, carboxyl, amino, isocyanic acid
The assistant activator of one of ester group, acid halide group or a variety of functional groups, it is preferable that the assistant activator is selected from consisting of
One of group is a variety of: dopamine, poly-dopamine, chitosan, sodium alginate, polylactic acid, polyacrylic acid, glutamic acid tetrem
Acid, ascorbic acid, ethylenediamine tetra-acetic acid, polyvinyl alcohol, polyethylene glycol, polypropylene glycol, hydroxypropyl methyl cellulose, Ji Wusi
Alcohol, trien, tetren, melamine, spermine, pyromellitic trimethylsilyl chloride.
In one embodiment, the graphene graft modification conductive fiber has 1 × 101Ω m to 1 × 105Ω·
The resistivity of m and 80% to 95% far infrared transmissivity；And/or wherein the graphene graft modification conductive fiber is being washed
After 20 times, resistivity increase by 0.2% to 1.8%, 0.3% to 1.6%, 0.4% to 1.4%, 0.6% to 1.2% or 0.8% to
1.0%；And/or the graphene graft modification conductive fiber according to ISO 5470-1-1999 on YG522 type abrasiometer
Friction 600 times, 700 times or 800 times after, resistivity increase by 0.2% to 4.5%, 0.3% to 4.0%, 0.4% to 3.5%,
0.6% to 3.0%, 0.8% to 2.5% or 1.0% to 2.0%.
According to another aspect of the present invention, it provides and prepares graphene graft modification conductive fiber described in claim 1
Method, which comprises matrix fiber is placed in polar organic solvent or its aqueous solution ultrasonic vibration and is handled, then
Drying is taken out, to obtain pretreatment of fiber；It is chemically bound in assistant activator on the surface of the pretreatment of fiber, to obtain work
Chemical fibre dimension；Graphene oxide is configured to solution and it is made to graft on the activation via being chemically bonded with the assistant activator
On fiber, to obtain graphene oxide graft modification fiber；And make the graphene oxide graft modification fiber reduction, to obtain
Obtain the graphene graft modification conductive fiber.
In one embodiment, the polar organic solvent is selected from one of group consisting of or a variety of: ethyl alcohol,
Isopropanol, methyl ethyl ketone, acetone, 1,4- butanediol, butyl glycol ether；Wherein described matrix fiber and the polar organic solvent or
The weight ratio of its aqueous solution is selected from any one of group consisting of: 1:20 to 1:110,1:30 to 1:100,1:40 is extremely
1:90,1:50 are to 1:80,1:60 to 1:70.
In one embodiment, the assistant activator carries out chemical bond with the pretreatment of fiber as a solution
It closes, and the concentration of the solution of the assistant activator is selected from any one of group consisting of: 0.05 weight % to 12 weights
Measure %, 0.1 weight % to 10 weight %, 0.2 weight % to 9 weight %, 0.3 weight % to 8 weight %, 0.4 weight % to 7 weights
Measure %, 0.5 weight % to 6 weight %, 0.6 weight % to 5 weight %, 0.7 weight % to 4 weight %, 0.8 weight % to 3 weights
Measure %, 0.9 weight % to 2 weight %, 1 weight % to 1.8 weight %.
In one embodiment, the concentration of the solution of the graphene oxide is any in group consisting of
: 0.05mg/mL to 110mg/mL, 0.1mg/mL to 100mg/mL, 0.2mg/mL to 90mg/mL, 0.4mg/mL to 80mg/
ML, 0.8mg/mL to 70mg/mL, 1.0mg/mL to 60mg/mL, 2.0mg/mL to 50mg/mL, 4.0mg/mL to 40mg/mL,
8.0mg/mL is to 30mg/mL, 10.0mg/mL to 20mg/mL.
In one embodiment, make the graphene oxide graft modification fiber reduction technique include solution reduction,
High pressure thermal reduction, microwave irradiation reduction or combinations thereof, wherein the solution reduction includes being restored using the solution of reducing agent,
And the reducing agent is selected from one of group consisting of or a variety of: hydrazine class compound, such as hydrazine hydrate, dimethyl
Hydrazine, phenylhydrazine or to sulfonyloxy methyl hydrazine；Metal hydride, such as sodium borohydride, lithium aluminium hydride reduction；Active metal, such as aluminium, zinc, iron；
Reproducibility acid, such as ascorbic acid, pyrogallic acid；Reproducibility phenol, for example, to biphenol, tea polyphenols；Reducing sugar, example
Such as, glucose, fructose, sucrose；Alkali compounds, for example, sodium hydroxide, potassium hydroxide, sodium bicarbonate, ammonium hydroxide；Iodide, example
Such as potassium iodide, ammonium iodide, sodium iodide, iron iodide.
According to another aspect of the present invention, the graphene graft modification conductive fiber is provided in intelligent textile, soft
Purposes in property sensor, electronic device or electric heating health textile
Detailed description of the invention
Fig. 1 shows the electron microscopic picture before matrix fiber graft modification.
Fig. 2 shows the electron microscopic pictures after matrix fiber graft modification.
Specific embodiment
For purpose following detailed description of, it should be appreciated that embodiment provided by the invention can take various substitutions to become
Body and sequence of steps, other than these alternative variations and sequence of steps clearly not apply to embodiments herein.In addition, removing
Other than specific operational instances, or in the case where otherwise indicated, institute in all expression specification and claims
Be interpreted as modifying by term " about " with the number of composition quantity, " about " refer to each occurrence that it is modified ±
10%, ± 5% or ± 3% variable.Therefore, unless otherwise specified, the number stated in specification and appended book
Value parameter is approximation, can according to the present invention the desired performance obtained and change.Each numerical parameter should be according at least to institute
The quantity of the significant digit of report and by explaining using common rounding-off technology.
Furthermore, it is to be understood that any numberical range as described herein is intended to be included in all subranges wherein included.Example
Such as, " 1 to 10 " be intended to include between the minimum value 1 and the maximum value 10 all subranges (and including 1 and 10 this two
A end value), such as 1 to 5,2 to 8 or 4 to 6 etc..
The term as used herein is only used for the purpose of description specific embodiment, limits without being intended for."or" means
"and/or".As used herein, term "and/or" includes the relevant any combination for listing one or more items in item and institute
There is combination.
According to the first aspect of the invention, a kind of graphene graft modification conductive fiber, the graphene grafting are provided
Denatured conductive fiber may include: matrix fiber part, can have on the surface it is one or more selected from hydroxyl, carboxyl,
The functional group of amino, isocyanate group, acid halide group；Assistant activator part is chemically bound on described matrix fiber part,
And the group of the functional group reactions on multiple surfaces with described matrix fiber part can be contained；And graphene part,
It can be grafted on described matrix fiber via being chemically bonded with the assistant activator, wherein the graphene graft modification
For conductive fiber after washing 20 times, resistivity increases by 0.1% to 2%, and is ground according to ISO 5470-1-1999 in YG522 type
After rubbing 600 times to 800 times on consumption testing machine, resistivity increases by 0.1% to 5%.
In one embodiment, the graphene graft modification conductive fiber can also include other additive parts,
Such as anti-wear agent, colorant, pigment, delustering agent, fire retardant, wetting agent etc..
In one embodiment, described matrix fiber part can be polysaccharide fiber, the chemistry containing the functional group
Fiber or combinations thereof.In specific embodiments, described matrix fiber part can be polysaccharide fiber, for example, cotton fiber, de-
Rouge cotton fiber, hemp, flax fiber, ramee, tossa, apocynum fibre, oil flax fibre, viscose rayon, copper
Ammonia fiber, acetate fiber, alginate fibre, chitin fiber, sodium alginate fiber, tencel, Modal, nandina.Another specific
In embodiment, described matrix fiber part can be the chemical fibre containing the functional group, for example, vinal, third
Olefin(e) acid fiber, polyurethane fiber, acid fiber by polylactic, polyacrylonitrile fibre.In further specific embodiment, described matrix
Fiber can be one of cotton fiber, viscose rayon, hemp, acid fiber by polylactic, chitin fiber, sodium alginate fiber
Or it is a variety of, it is modified with will pass through chemical modification to described matrix fiber.
In one embodiment, the assistant activator can be derived from comprising being selected from hydroxyl, carboxyl, amino, isocyanic acid
The assistant activator of one of ester group, acid halide group or a variety of functional groups.In another embodiment, the assistant activator can be with
Selected from one of group consisting of or a variety of: dopamine, poly-dopamine, chitosan, sodium alginate, polylactic acid, polypropylene
Acid, glutamic acid tetraacethyl, ascorbic acid, ethylenediamine tetra-acetic acid, polyvinyl alcohol, polyethylene glycol, polypropylene glycol, hydroxypropyl methyl are fine
Tie up element, pentaerythrite, trien, tetren, melamine, spermine, pyromellitic trimethylsilyl chloride.Preferably, specific
In embodiment, the assistant activator can be selected from one of group consisting of or a variety of: dopamine, poly-dopamine, shell
Glycan, sodium alginate, polylactic acid.In further specific embodiment, the assistant activator can be poly-dopamine, thus
There are multiple binding sites with the functional group on described matrix fiber part to increase the fastness being bonded.
In one embodiment, the resistivity of the graphene graft modification conductive fiber can be 1 × 101Ω·m
To 1 × 105Ω·m、2×101Ω m to 8 × 104Ω·m、4×101Ω m to 6 × 104Ω·m、6×101Ω m to 4
×104Ω·m、8×101Ω m to 2 × 104Ω·m、1×102Ω m to 8 × 103Ω·m、2×102Ω m to 6 ×
103Ω·m、4×102Ω m to 4 × 103Ω·m、8×102Ω m to 2 × 103Ω·m.In specific embodiments, institute
The resistivity for stating graphene graft modification conductive fiber can be 1 × 101Ω m to 1 × 104Ω m or 1 × 102Ω m to 1
×103Ω·m.In further specific embodiment, the resistivity of the graphene graft modification conductive fiber can be 1
×101Ω m to 1 × 102Ω m, the graphene graft modification conductive fiber shows good electric conductivity as a result,.
In another embodiment, the resistivity of the graphene graft modification conductive fiber can increase after washing 20 times
Add 0.1% to 2%, 0.2% to 1.8%, 0.3% to 1.6%, 0.4% to 1.4%, 0.6% to 1.2% or 0.8% to
1.0%.In specific embodiments, the resistivity of the graphene graft modification conductive fiber can increase after washing 20 times
1% to 2% or 0.5% to 1.5%, the graphene graft modification conductive fiber shows excellent water-wash resistance as a result,.?
In another embodiment, the resistivity of the graphene graft modification conductive fiber can exist according to ISO 5470-1-1999
Increase by 0.1% to 5%, 0.2% to 4.5%, 0.3% after rubbing 600 times, 700 times or 800 times on YG522 type abrasiometer
To 4.0%, 0.4% to 3.5%, 0.6% to 3.0%, 0.8% to 2.5% or 1.0% to 2.0%.In specific embodiment
In, the resistivity of the graphene graft modification conductive fiber can be according to ISO 5470-1-1999 in YG522 type abrasion test
Increase by 2% to 4.5%, 2.5% to 4.0% or 3.0% to 3.5% after rubbing 600 times on machine, as a result, the graphene grafting
Denatured conductive fiber shows excellent rub resistance.In another particular embodiment, the graphene graft modification is conductive
The resistivity of fiber increases by 1.5% after can rubbing 700 times on YG522 type abrasiometer according to ISO 5470-1-1999
To 4.5%, 2.0% to 4.0% or 3.0% to 3.5%.In another particular embodiment, the graphene graft modification is led
The resistivity of electric fiber increases after being rubbed 800 times on YG522 type abrasiometer according to ISO 5470-1-1999
2.5% to 5.0%, 3.0% to 4.5% or 3.5% to 4.0%.
In one embodiment, the far infrared transmissivity of the graphene graft modification conductive fiber can for 80% to
95%, 81% to 94%, 82% to 93%, 83% to 92%, 84% to 91%, 85% to 90%, 86% to 89%, 87% to
88%.In specific embodiments, the far infrared transmissivity of the graphene graft modification conductive fiber can for 85% to
93%, 87% to 92% or 88% to 90%, thus graphene graft modification conductive fiber shows good insulation effect.
According to the second aspect of the invention, a kind of method for preparing graphene graft modification conductive fiber is provided, it is described
Method includes: that matrix fiber is placed in ultrasonic vibration in polar organic solvent or its aqueous solution to handle, and then takes out drying, with
Obtain pretreatment of fiber；It is chemically bound in assistant activator on the surface of the pretreatment of fiber, to obtain activated fiber；By oxygen
Graphite alkene is configured to solution and grafts on it on the activated fiber via being chemically bonded with the assistant activator, to obtain
Obtain graphene oxide graft modification fiber；And make the graphene oxide graft modification fiber reduction, to obtain the graphite
Alkene graft modification conductive fiber.
In one embodiment, described matrix fiber can use the matrix fiber part according to first aspect；
And/or the assistant activator can use the assistant activator according to first aspect.
In one embodiment, the polar organic solvent can be selected from one of group consisting of or a variety of:
Ethyl alcohol, isopropanol, methyl ethyl ketone, acetone, 1,4-butanediol, butyl glycol ether etc., wherein the polar organic solvent removes matrix
The grease of fiber surface or slurry agent, and fibrous inside is penetrated into reduce the regularity and crystallinity of strand, so that from fibre
Dimension is internal to release more functional groups, to be conducive to further activate.In specific embodiments, the polarity is organic molten
Agent can be selected from isopropanol or acetone.In further specific embodiment, the polar organic solvent can be acetone.
In one embodiment, can by described matrix fiber with certain weight ratio be placed on polar organic solvent or
In its aqueous solution, wherein described matrix fiber can be for selected from following with the weight ratio of polar organic solvent or its aqueous solution
Any one of group of composition: 1:20 to 1:110,1:30 to 1:100,1:40 to 1:90,1:50 to 1:80,1:60 to 1:70.
In another embodiment, the weight ratio of described matrix fiber and polar organic solvent or its aqueous solution can be 1:30 to 1:
50 or 1:60 to 1:100.In specific embodiments, the weight of described matrix fiber and polar organic solvent or its aqueous solution
Than that can be 1:30 to 1:50,1:35 to 1:45 or 1:38 to 1:40, effectively so as to polar organic solvent or its aqueous solution
Matrix fiber is pre-processed.
In one embodiment, described matrix fiber can persistently be surpassed in polar organic solvent or its aqueous solution
Acoustic shock is swung 5 minutes to 110 minutes, 10 minutes to 100 minutes, 20 minutes to 90 minutes, 30 minutes to 80 minutes, 40 minutes to 70
Minute or 50 minutes to 60 minutes.In specific embodiments, the time of the ultrasonic vibration can for 10 minutes to 60 minutes,
20 minutes to 50 minutes or 30 minutes to 40 minutes, rapidly and sufficiently to promote polar organic solvent or its aqueous solution to base
The Effect of Pretreatment of body fiber.
It in one embodiment, can be by the matrix fiber by ultrasonic treatment at 40 DEG C to 110 DEG C, 50 DEG C to 100
DEG C, 60 DEG C to 90 DEG C, it is dry at a temperature of 70 DEG C to 80 DEG C.In specific embodiments, the temperature of the drying can be 50
DEG C to 100 DEG C or 60 DEG C to 80 DEG C.In further specific embodiment, the temperature of the drying can be 50 DEG C to 80 DEG C
Or 60 DEG C to 100 DEG C, polar organic solvent or its aqueous solution are more, quickly enter fibrous inside to promote, so that fiber
Internal functional group is released.
In one embodiment, the assistant activator in the form of a solution with the surface chemistry key of the pretreatment of fiber
It closes, wherein the concentration of the solution of the assistant activator can be for selected from any one of group consisting of: 0.05 weight % is extremely
12 weight %, 0.1 weight % are to 10 weight %, 0.2 weight % to 9 weight %, 0.3 weight % to 8 weight %, 0.4 weight %
To 7 weight %, 0.5 weight % to 6 weight %, 0.6 weight % to 5 weight %, 0.7 weight % to 4 weight %, 0.8 weight %
To 3 weight %, 0.9 weight % to 2 weight %, 1 weight % to 1.8 weight %.In specific embodiments, the assistant activator
The concentration of solution can be 0.1 weight % to 2.0 weight %, 0.15 weight % to 1.5 weight % or 0.2 weight % to 1.0
Weight % or 0.3 weight % to 0.5 weight %.In further particular implementation originating party case, the solution of the assistant activator
Concentration can for 0.1 weight % to 1.0 weight %, 0.15 weight % to 0.8 weight %, 0.2 weight % to 0.6 weight % or
0.3 weight % to 0.5 weight %, so that the assistant activator fills the functional group of fiber surface
Ground is divided to be chemically bonded with assistant activator, to be firmly attached assistant activator.
In one embodiment, pretreatment of fiber can activated by infiltration technique with certain weight ratio infiltration
It is activated in compounding agent solution, the weight ratio of the pretreatment of fiber and assistant activator solution can be for selected from group consisting of
Any one of: 1:20 to 1:110,1:30 to 1:100,1:40 to 1:90,1:50 to 1:80,1:60 to 1:70.In specific reality
It applies in scheme, the weight ratio of the pretreatment of fiber and assistant activator solution can be 1:30 to 1:80,1:40 to 1:60.Another
In one specific embodiment, the weight ratio of the pretreatment of fiber and assistant activator solution can be 1:30 to 1:50.Into one
In the specific embodiment of step, the weight ratio of the pretreatment of fiber and assistant activator solution can be 1:30 so that assistant activator
In group be sufficiently bonded with the chemical functional groups on pretreatment of fiber surface and the remaining group not being bonded is for further
Processing.
In another embodiment, the pretreatment of fiber can be placed in assistant activator solution and is infiltrated 2 minutes to 110
Minute, 5 minutes to 100 minutes, 10 minutes to 90 minutes, 20 minutes to 80 minutes, 30 minutes to 70 minutes or 40 minutes to 60
Minute.In specific embodiments, infiltrating time of the pretreatment of fiber in assistant activator solution can be for 10 minutes extremely
60 minutes, 20 minutes to 50 minutes, 30 minutes to 40 minutes.In further specific embodiment, the pretreatment of fiber
Infiltrating time in assistant activator solution can be 10 minutes to 40 minutes, so that the group in assistant activator is fully and in advance
Handle the chemical functional groups bonding of fiber surface.
In one embodiment, assistant activator solution can be uniformly coated on pretreatment of fiber by coating processes
To be activated, the coating processes may include high pressure painting, aerial spraying, thermal spraying or atomizing spraying on surface.Preferably,
The coating processes can be high pressure painting technique.In another embodiment, the spray pressure of the high pressure painting technique can
Think selected from any one of group consisting of: 0.1bar to 10bar, 0.2bar to 8bar, 0.3bar to 8bar, 0.4bar
To 7bar, 0.5bar to 6bar, 0.6bar to 5bar, 0.8bar to 4bar, 0.9bar to 3bar, 1bar to 2bar.Specific
In embodiment, the spray pressure of the high pressure painting technique can be 1bar to 5bar or 2bar to 4bar.Further
In specific embodiment, the spray pressure of the high pressure painting technique can be 1bar to 3bar.
In yet another embodiment, the quantity for spray of the high pressure painting technique can be appointing in group consisting of
One: 5mL/min to 600mL/min, 10mL/min to 550mL/min, 20mL/min to 500mL/min, 30mL/min extremely
450mL/min, 40mL/min are to 400mL/min, 50mL/min to 350mL/min, 60mL/min to 300mL/min, 70mL/
Min is to 250mL/min, 80mL/min to 200mL/min, 90mL/min to 150mL/min, 100mL/min to 120mL/min.
In specific embodiments, the quantity for spray of the high pressure painting technique can be 200mL/min to 600mL/min, 250mL/min
To 550mL/min, 300mL/min to 500mL/min, 350mL/min to 450mL/min.In further specific embodiment
In, the quantity for spray of the high pressure painting technique can be 300mL/min to 600mL/min, 350mL/min to 400mL/min, with
Ensure that the amount of assistant activator is enough to activate pretreatment of fiber.
In one embodiment, hummer ' s oxidizing process can be passed through and obtain graphene oxide, thickness can be 1 layer
To 5 layers, 2 layers to 4 layers or 3 layers to 5 layers, planar dimension can be for selected from any one of group consisting of: 1 μm to 200 μm,
2 μm to 190 μm, 3 μm to 180 μm, 4 μm to 170 μm, 5 μm to 160 μm, 6 μm to 150 μm, 7 μm to 140 μm, 8 μm to 130 μm,
9 μm to 120 μm, 10 μm to 110 μm, 20 μm to 100 μm, 30 μm to 90 μm, 40 μm to 80 μm, 50 μm to 70 μm.In specific reality
It applies in scheme, the thickness of the graphene oxide can be 1 layer to 3 layers.In further particular implementation side, the oxidation stone
The thickness of black alkene can be 1 layer.In yet another embodiment, the planar dimension of the graphene oxide can be 20 μm to 120 μ
M, 40 μm to 100 μm or 50 μm to 80 μm, so that the graphene oxide is evenly dispersed in the medium for being grafted.
In one embodiment, graphene oxide can be configured to solution in the medium, then pass through infiltration technique
It is grafted on activated fiber surface, so that graphene oxide is quickly and evenly grafted on fiber surface, the infiltration technique is will
Activated fiber is infiltrated in graphene oxide solution, wherein the weight ratio of activated fiber and graphene oxide solution can for selected from
Any one of group consisting of: 1:20 to 110,1:30 to 1:100,1:40 to 1:90,1:50 to 1:80,1:60 to 1:
70.In specific embodiments, the weight ratio of the activated fiber and graphene oxide solution can be 1:30 to 1:80,1:40
To 1:70 or 1:50 to 1:60.In further specific embodiment, the weight of the activated fiber and graphene oxide solution
Amount is than that can be 1:30 to 1:60 or 1:40 to 1:50, to ensure that graphene oxide is fully grafted on activated fiber surface.
In another embodiment, the medium can be for selected from one of group consisting of or a variety of: ethyl alcohol,
Water, methanol, tetrahydrofuran, dimethyl sulfoxide, N-Methyl pyrrolidone, ethylene glycol, so that graphene oxide is better dispersed in
Wherein.In specific embodiments, the medium can be ethyl alcohol, water, methanol, tetrahydrofuran.In further particular implementation
Fang Zhong, the medium can be water.
In another embodiment, the graphene oxide solution ultrasonic vibration for being impregnated with activated fiber can be handled 1 point
Clock was to 60 minutes, 5 minutes to 55 minutes, 10 minutes to 50 minutes, 15 minutes to 45 minutes, 20 minutes to 40 minutes, 25 minutes
To 35 minutes or 28 minutes to 30 minutes.It in specific embodiments, can be molten by the graphene oxide for being impregnated with activated fiber
Liquid ultrasonic vibration is handled 10 minutes to 40 minutes or 20 minutes to 30 minutes.In another particular embodiment, work will be impregnated with
The graphene oxide solution ultrasonic vibration of chemical fibre dimension is handled 10 minutes to 40 minutes, to ensure that graphene oxide is uniform in the medium
Disperse and to the abundant graft modification of activated fiber.
In one embodiment, the graphene oxide solution for being impregnated with activated fiber can be stirred 0.5 minute to 65
Minute, 1 minute to 60 minutes, 2 minutes to 55 minutes, 4 minutes to 50 minutes, 6 minutes to 45 minutes, 8 minutes to 40 minutes, 10
Minute was to 35 minutes, 12 minutes to 30 minutes, 14 minutes to 25 minutes or 16 minutes to 20 minutes.In specific embodiments,
Be impregnated with the graphene oxide solution of activated fiber mixing time can for 10 minutes to 40 minutes or 20 minutes to 30 minutes,
So that fiber is in grafting treatment process always in movement and dispersity.
In one embodiment, the temperature control that can will be impregnated with the graphene oxide solution of activated fiber is 30 DEG C
To 110 DEG C, 40 DEG C to 100 DEG C, 45 DEG C to 95 DEG C, 50 DEG C to 90 DEG C, 55 DEG C to 85 DEG C, 60 DEG C to 80 DEG C or 65 DEG C to 75 DEG C.
In specific embodiments, the temperature can be 50 DEG C to 80 DEG C or 60 DEG C to 70 DEG C.In further specific embodiment
In, the temperature can be 50 DEG C to 60 DEG C, rapidly be grafted with activated fiber to advantageously facilitate graphene oxide.
In one embodiment, graphene oxide solution can be coated uniformly on activated fiber table by coating processes
On face, so that graphene oxide is grafted on fiber surface, the coating processes may include high pressure painting, aerial spraying, thermal jet
Painting or atomizing spraying.In another embodiment, the spray pressure of high pressure painting technique is spray pressure described in first aspect；
And/or the quantity for spray of the high pressure painting technique is quantity for spray described in first aspect.
In one embodiment, the concentration for infiltrating the graphene oxide solution of technique or coating processes can be choosing
From any one of group consisting of: 0.05mg/mL to 110mg/mL, 0.1mg/mL to 100mg/mL, 0.2mg/mL is extremely
90mg/mL, 0.4mg/mL are to 80mg/mL, 0.8mg/mL to 70mg/mL, 1.0mg/mL to 60mg/mL, 2.0mg/mL to 50mg/
ML, 4.0mg/mL are to 40mg/mL, 8.0mg/mL to 30mg/mL, 10.0mg/mL to 20mg/mL.In specific embodiments, institute
The concentration for stating graphene oxide solution can be 0.1mg/mL to 0.5mg/mL or 0.2mg/mL to 0.3mg/mL.Further
In specific embodiment, the concentration of the graphene oxide solution can be 0.1mg/mL to 0.3mg/mL, to be conducive to aoxidize
Graphene is evenly dispersed in the solution.
It in one embodiment, can be by the graphene oxide solution of preparation in 10W to 1000W, 20W to 900W, 40W
It is ultrasonic under power to 800W, 80W to 700W, 100W to 600W, 200W to 500W or 300W to 400W, and extremely with 10rpm
1000rpm, 20rpm to 900rpm, 40rpm to 800rpm, 80rpm to 700rpm, 100rpm to 600rpm, 200rpm extremely
The speed of 500rpm or 300rpm to 400rpm stirs.In specific embodiments, the power of the ultrasound can be for 400W extremely
1000W, 500W are to 900W or 600W to 800W.In further specific embodiment, the power of the ultrasound can be
600W to 800W.In yet another embodiment, the speed of the stirring can be 500rpm to 800rpm.
In one embodiment, wherein the technique of the graphene oxide graft modification fiber reduction is made to may include molten
Liquid reduction, high pressure thermal reduction, microwave irradiation reduction or combinations thereof.In specific embodiments, the technique of the reduction can be
High pressure thermal reduction, microwave irradiation reduction or combinations thereof.It in another embodiment, can be using solution reduction to graphene oxide
Graft modification fiber carries out reduction treatment, and the solution reduction is that graphene oxide graft modification fiber is dipped in reducing agent solution
In, to obtain graphene graft modification conductive fiber, the weight of the solution of the graphene oxide graft modification fiber and reducing agent
Amount is than that can be selected from any one of group consisting of: 1:5 to 1:110,1:10 to 1:100,1:20 to 1:90,1:30 is extremely
1:80,1:40 are to 1:70,1:50 to 1:60, sufficiently to restore the graphene oxide on graft modification fiber.In particular implementation side
In case, the weight ratio of the solution of the graphene oxide graft modification fiber and reducing agent can for 1:20 to 1:60,1:30 extremely
1:50 or 1:40 to 1:45.
In yet another embodiment, the concentration of the solution of reducing agent can be for selected from any one of group consisting of:
0.05 weight % to 6 weight %, 0.1 weight % to 5 weight %, 0.2 weight % to 4 weight %, 0.4 weight % to 3 weight %,
0.6 weight % to 2 weight %, 0.8 weight % are to 1 weight %.In specific embodiments, the concentration of the solution of the reducing agent
It can be 1 weight % to 10 weight %, 2 weight % to 8 weight % or 4 weight % to 6 weight %.In yet another embodiment,
By the graphene oxide graft modification fiber being dipped in reducing agent solution at 60 DEG C to 140 DEG C, 70 DEG C to 130 DEG C, 80 DEG C to 120
DEG C, 85 DEG C to 115 DEG C, 90 DEG C to 110 DEG C, restore at a temperature of 95 DEG C to 100 DEG C, the recovery time is 1 hour to 10 hours, 2
Hour was to 8 hours, 3 hours to 6 hours.In specific embodiments, the temperature of the reduction be 60 DEG C to 120 DEG C or 80 DEG C extremely
100℃.In another embodiment, the recovery time is 2 hours to 6 hours or 3 hours to 4 hours.
In yet another embodiment, the reducing agent can be for selected from one of group consisting of or a variety of: hydrazine
Compound, such as hydrazine hydrate, dimethylhydrazine, phenylhydrazine or to sulfonyloxy methyl hydrazine etc.；Metal hydride, such as sodium borohydride, hydrogenation
Aluminium lithium etc.；Active metal, such as aluminium, zinc, iron etc.；Reproducibility acid, such as ascorbic acid, pyrogallic acid etc.；Reproducibility phenol,
For example, to biphenol, tea polyphenols etc.；Reducing sugar, for example, glucose, fructose, sucrose etc.；Alkali compounds, for example, hydrogen-oxygen
Change sodium, potassium hydroxide, sodium bicarbonate, ammonium hydroxide etc.；Iodide, such as potassium iodide, ammonium iodide, sodium iodide, iron iodide etc.；Or it
Combination.In another embodiment, the reducing agent can be hydrazine class compound, reproducibility acid or combinations thereof.Specific
In embodiment, the reducing agent preferably can be one of hydrazine hydrate, ascorbic acid, glucose, sodium bicarbonate, tea polyphenols
Or it is a variety of, so that the reducing degree of graphene oxide is high and does not destroy the structure of graphene film.In further particular implementation side
In case, the reducing agent can be hydrazine hydrate.
In one embodiment, high pressure thermal reduction can be used, also original place is carried out to graphene oxide graft modification fiber
Reason, high pressure thermal reduction be graphene oxide graft modification fiber is placed between two flat plate heats in certain temperature and
Heating reduction is carried out under pressure, to obtain graphene graft modification conductive fiber.In another embodiment, reduction temperature can be with
It is 80 DEG C to 220 DEG C, 90 DEG C to 210 DEG C, 100 DEG C to 200 DEG C, 110 DEG C to 190 DEG C, 120 DEG C to 180 DEG C, 130 DEG C to 170 DEG C
Or 140 DEG C to 160 DEG C, pressure can for 0.1Mpa to 10Mpa, 0.2Mpa to 9.0Mpa, 0.4Mpa to 8.0Mpa, 0.6Mpa extremely
7.0Mpa, 0.8Mpa are to 6.0Mpa, 1.0Mpa to 5.0Mpa or 2.0Mpa to 4.0Mpa, in the case where not needing reducing agent
Rapidly redox graphene.In specific embodiments, the reduction temperature can for 120 DEG C to 160 DEG C, 130 DEG C extremely
150 DEG C, 140 DEG C to 145 DEG C, sufficiently redox graphene and the structure of fiber and graphene oxide can not destroyed.?
Further specific is in embodiment, and the reduction temperature can be 120 DEG C to 140 DEG C.In another embodiment, described
Pressure can be 1.0Mpa to 4.0Mpa or 2.0Mpa to 3.0Mpa.In specific embodiments, the pressure can be
3.0Mpa。
In yet another embodiment, the heating time of high pressure thermal reduction can be 5 minutes to 10 minutes, 10 minutes to 100
Minute, 20 minutes to 90 minutes, 30 minutes to 80 minutes, 40 minutes to 70 minutes or 50 minutes to 60 minutes, to ensure to be grafted
Graphene oxide on modified fibre is reduced sufficiently.In specific embodiments, the heating time of the high pressure thermal reduction can
Think 10 minutes to 40 minutes or 20 minutes to 30 minutes.In further specific embodiment, the high pressure thermal reduction
Heating time can be 10 minutes to 20 minutes.
In one embodiment, microwave irradiation reduction can be used to restore graphene oxide graft modification fiber
Processing, the microwave irradiation reduction is that graphene oxide graft modification fiber is placed in microwave irradiation device with certain spoke
It is restored according to power and irradiation time, to obtain graphene graft modification conductive fiber.In another embodiment, the spoke
It can be 10W to 1000W, 20W to 900W, 30W to 800W, 40W to 700W, 50W to 600W, 60W to 500W, 70W according to power
To 400W, 80W to 300W, 90W to 200W.In specific embodiments, the irradiation power can for 500W to 1000W or
600W to 800W.In further specific embodiment, the irradiation power can be 500W to 600W, not need also
Rapidly redox graphene in the case where former agent.
In yet another embodiment, the irradiation time can be 5 minutes to 70 minutes, 10 minutes to 60 minutes, 20 points
Clock was to 50 minutes or 30 minutes to 40 minutes.In specific embodiments, the irradiation time can be 10 minutes to 50 points
Clock or 20 minutes to 40 minutes.In further specific embodiment, the irradiation time can be 10 minutes to 20 minutes,
To ensure that the graphene oxide on graft modification fiber sufficiently and is efficiently restored.
According to the third aspect of the invention we, graphene graft modification conductive fiber is provided in intelligent textile, flexible biography
Purposes in sensor, electronic device or electric heating health textile.
In one embodiment, the intelligent textile can be wearable device, temperature-regulation fabric, discoloration weaving
Product, shape memory textile, flame retardant textiles, Far-Infrared Health Textiles, corrosion-resistant function textile or luminescent textile product etc..
In another embodiment, the sensor can be PH perspiration sensor, blood pressure pulse sensor, respiratory rate
Sensor, arthrogryposis sensor, human motion detection sensor, electronic skin etc..
In yet another embodiment, the electronic device can be music electronic device, communication electronic device, liquid crystal
Show device, active display, flexible lighting clothes, fibrous solid-state super capacitor etc..
In yet another embodiment, the electric heating health textile can for electric heating health neck guard, waist support, knee-pad, eyeshade,
Facial mask and Far-infrared Heating carpet textile etc..
About these features, graphene graft modification conductive fiber of the invention ensures to have lower resistivity, higher
Water-wash resistance and rub resistance and far infrared transmissivity.Therefore graphene graft modification conductive fiber and preparation method thereof is bright
Aobvious is industrially valuable.
Embodiment
Below with reference to embodiment, the present invention will be described in more detail.However, the present invention is not limited to following embodiments.
Embodiment 1
The preparation of graphene graft modification conduction cotton fiber
Cotton fiber is placed in aqueous acetone solution with the weight ratio of 1:30, ultrasonic vibration is handled 10 minutes, 80 after taking-up
It is dry at DEG C, to obtain by pretreatment cotton fiber.
Then pretreatment cotton fiber is immersed in the poly-dopamine solution of 1 weight % and continues 10 minutes, wherein pre-processing
The weight ratio of cotton fiber and solution is 1:30, to obtain the activation cotton fiber for being coated with poly-dopamine.
Pass through Hummer ' s oxidizing process and prepare graphene oxide, obtained in graphene oxide layer with a thickness of 1 layer, put down
Face is having a size of 20 μm.Resulting graphene oxide is prepared into concentration under 600W ultrasonic power and 500rpm magnetic agitation rotating speed
For the aqueous solution of 0.1mg/mL.Activation cotton fiber is soaked in graphene oxide by solution impregnation technique with the weight ratio of 1:30
In aqueous solution, the graphene oxide water solution for being soaked with activation cotton fiber is handled using probe-type large power supersonic, continues 10 minutes；
Meanwhile being stirred 10 minutes in aqueous solution bottom by magnetic rotor using magnetic stirring apparatus, so that fiber is in grafting treatment process
In always in movement and dispersity；Use external water bath with thermostatic control system control graphene oxide graft modification reaction temperature for
About 60 DEG C, to obtain graphene oxide graft modification cotton fiber.
Above-mentioned graphene oxide graft modification cotton fiber is placed between two flat plate heats, with the pressure of 1MPa 160
Heating reduction 10 minutes at DEG C, to obtain graphene graft modification conduction cotton fiber.
The resistivity of the graphene graft modification conduction cotton fiber is 1.0 × 103Ω m, the resistance after washing 20 times
Rate increases by 2%, and resistivity increases by 3% after being rubbed 600 times on YG522 type abrasiometer according to ISO 5470-1-1999；Far
Infrared emittance is 85%.
Embodiment 2
The preparation of graphene graft modification conduction viscose fiber
Viscose fiber is placed in aqueous acetone solution with the weight ratio of 1:30, ultrasonic vibration handle 20 minutes, after taking-up
It is dry at 80 DEG C, to obtain by pretreatment viscose fiber.
Then 1 weight % poly-dopamine solution is coated uniformly on pretreatment viscose fiber table by high pressure painting technique
Face, to obtain activation viscose rayon, wherein the pressure sprayed is 1bar, quantity for spray 300mL/min.
Pass through Hummer ' s oxidizing process and prepare graphene oxide, obtained in graphene oxide layer with a thickness of 1 layer, put down
Face is having a size of 50 μm.Resulting graphene oxide is prepared into concentration under 800W ultrasonic power and 800rpm magnetic agitation rotating speed
For the aqueous solution of 0.5mg/mL.Activation viscose fiber is soaked in graphite oxide by solution impregnation technique with the weight ratio of 1:30
In aqueous solution, the graphene oxide water solution for being soaked with activation cotton fiber, ultrasonic vibration are handled using probe-type large power supersonic
40 minutes；Meanwhile being stirred 40 minutes in aqueous solution bottom by magnetic rotor using magnetic stirring apparatus, so that fiber is at grafting
Always in movement and dispersity during reason；Using the control graphene oxide graft modification reaction of external water bath with thermostatic control system
Temperature is about 80 DEG C, to obtain graphene oxide graft modification viscose fiber.
Above-mentioned graphene oxide graft modification viscose fiber is placed between two flat plate heats, is existed with the pressure of 2MPa
Heating reduction 10 minutes at 160 DEG C；Then fiber is placed in microwave irradiation device with the power irradiance of 600W 10 minutes again,
To obtain graphene graft modification conduction viscose fiber.
The resistivity of the graphene graft modification conduction viscose fiber is 1.0 × 104Ω m, the electricity after washing 20 times
Resistance rate increases by 1%, and resistivity increases by 2% after being rubbed 600 times on YG522 type abrasiometer according to ISO 5470-1-1999；
Far infrared transmissivity is 90%.
Embodiment 3
The preparation of graphene graft modification conduction hemp
Hemp is placed in aqueous acetone solution with the weight ratio of 1:50, ultrasonic vibration handle 50 minutes, after taking-up
It is dry at 100 DEG C, to obtain by pretreatment hemp.
Then 0.1 weight % poly-dopamine solution is coated uniformly on pretreatment hemp table by high pressure painting technique
On face, to obtain activation hemp, wherein the pressure sprayed is 1bar, quantity for spray 300mL/min.
Pass through Hummer ' s oxidizing process and prepare graphene oxide, obtained in graphene oxide layer with a thickness of 1 layer, put down
Face is having a size of 100 μm.Resulting graphene oxide is prepared under 800W ultrasonic power and 800rpm magnetic agitation rotating speed dense
Degree is the aqueous solution of 0.1mg/mL.The graphene oxide water solution of 0.1mg/mL is coated uniformly on work by high pressure painting technique
Change hemp surface, to obtain graphene oxide graft modification hemp, wherein the pressure sprayed is 1bar, quantity for spray is
600mL/min。
Above-mentioned graphene oxide graft modification hemp is placed between two flat plate heats, is existed with the pressure of 3MPa
Heating reduction 10 minutes at 120 DEG C, to obtain graphene graft modification conduction hemp.
The resistivity of the graphene graft modification conduction hemp is 1.0 × 103Ω m, the electricity after washing 20 times
Resistance rate increases by 1.5%, and resistivity increases after being rubbed 600 times on YG522 type abrasiometer according to ISO 5470-1-1999
5%；Far infrared transmissivity is 91%.
Embodiment 4
The preparation of graphene graft modification conductive polylactic acid fiber
Acid fiber by polylactic is placed in aqueous acetone solution with the weight ratio of 1:40, ultrasonic vibration is handled 60 minutes, after taking-up
It is dry at 100 DEG C, to obtain by pretreatment acid fiber by polylactic.
Then 0.2 weight % poly-dopamine solution is coated uniformly on pretreatment acid fiber by polylactic by high pressure painting technique
On surface, to obtain activated poly-lactic acid fiber, wherein the pressure sprayed is 1bar, quantity for spray 350mL/min.
Pass through Hummer ' s oxidizing process and prepare graphene oxide, obtained in graphene oxide layer with a thickness of 1 layer, put down
Face is having a size of 120 μm.Resulting graphene oxide is prepared under 800W ultrasonic power and 800rpm magnetic agitation rotating speed dense
Degree is the aqueous solution of 0.3mg/mL.The graphene oxide water solution of 0.3mg/mL is coated uniformly on work by high pressure painting technique
Change polylactic acid fiber surface, to obtain graphene oxide graft modification acid fiber by polylactic, wherein the pressure sprayed is 1bar, spraying
Amount is 600mL/min.
Above-mentioned graphene oxide graft modification acid fiber by polylactic is placed between two flat plate heats, is existed with the pressure of 3MPa
Heating reduction 10 minutes at 120 DEG C, to obtain graphene graft modification conductive polylactic acid fiber.
The resistivity of the graphene graft modification conductive polylactic acid fiber is 1.0 × 102Ω m, after washing 20 times
Resistivity increases by 2%, and resistivity increases after being rubbed 600 times on YG522 type abrasiometer according to ISO 5470-1-1999
4%；Far infrared transmissivity is 90%.
Embodiment 5
The preparation of graphene graft modification conduction chitin fiber
Chitin fiber is placed in acetone soln with the weight ratio of 1:45, ultrasonic vibration handle 40 minutes, after taking-up
It is dry at 100 DEG C, to obtain by pretreatment chitin fiber.
Then it is fine 0.15 weight % poly-dopamine solution to be coated uniformly on pretreatment chitosan by high pressure painting technique
On dimension table face, to obtain activation chitin fiber, wherein the pressure sprayed is 1bar, quantity for spray 400mL/min.
Pass through Hummer ' s oxidizing process and prepare graphene oxide, obtained in graphene oxide layer with a thickness of 1 layer, put down
Face is having a size of 120 μm.Resulting graphene oxide is prepared under 800W ultrasonic power and 800rpm magnetic agitation rotating speed dense
Degree is the aqueous solution of 0.3mg/mL.The graphene oxide water solution of 0.3mg/mL is coated uniformly on work by high pressure painting technique
Change chitin fiber surface, to obtain graphene oxide graft modification chitin fiber, wherein the pressure sprayed is 1bar, spraying
Amount is 600mL/min.
Above-mentioned graphene oxide graft modification chitin fiber is placed between two flat plate heats, is existed with the pressure of 3MPa
Heating reduction 10 minutes at 120 DEG C, to obtain graphene graft modification conduction chitin fiber.
The resistivity of the graphene graft modification conduction chitin fiber is 1 × 101Ω m, the electricity after washing 20 times
Resistance rate increases by 2%, and resistivity increases after being rubbed 600 times on YG522 type abrasiometer according to ISO 5470-1-1999
4.5%；Far infrared transmissivity is 92%.
Embodiment 6
The preparation of graphene graft modification conduction sodium alginate fiber
Sodium alginate fiber is placed in acetone soln with the weight ratio of 1:50, ultrasonic vibration is handled 40 minutes, after taking-up
It is dry at 50 DEG C, to obtain by pretreatment sodium alginate fiber.
Then it is fine 0.2 weight % poly-dopamine solution to be coated uniformly on pretreatment sodium alginate by high pressure painting technique
On dimension table face, sodium alginate fiber is activated to obtain, wherein the pressure sprayed is 1bar, quantity for spray 350mL/min.
Pass through Hummer ' s oxidizing process and prepare graphene oxide, obtained in graphene oxide layer with a thickness of 1 layer, put down
Face is having a size of 120 μm.Resulting graphene oxide is prepared under 800W ultrasonic power and 800rpm magnetic agitation rotating speed dense
Degree is the aqueous solution of 0.3mg/mL.The graphene oxide water solution of 0.3mg/mL is coated uniformly on work by high pressure painting technique
Change sodium alginate fiber surface, to obtain graphene oxide graft modification sodium alginate fiber, wherein the pressure sprayed is 1bar,
Quantity for spray is 600mL/min.
Above-mentioned graphene oxide graft modification sodium alginate fiber is placed between two flat plate heats, with the pressure of 3MPa
Heating reduction 10 minutes at 120 DEG C, to obtain graphene graft modification conduction sodium alginate fiber.
The resistivity of the graphene graft modification conduction sodium alginate fiber is 1 × 103Ω m, after washing 20 times
Resistivity increases by 1%, and resistivity increases after being rubbed 600 times on YG522 type abrasiometer according to ISO 5470-1-1999
4%；Far infrared transmissivity is 93%.
Embodiment 7
Graphene graft modification conduction cotton fiber is prepared by solution reduction
Graphene oxide graft modification cotton fiber is prepared in the same manner as example 1, then by oxidation obtained
Graphene graft modification cotton fiber is placed in the hydrazine hydrate aqueous solution that concentration is 0.1% with the weight ratio of 1:50, and 100
DEG C water bath under heating reduction 60 minutes, to obtain graphene graft modification conduction cotton fiber.
The resistivity of the graphene graft modification conduction cotton fiber is 1.0 × 102Ω m, the resistance after washing 20 times
Rate increases by 1%, and resistivity increases by 2.5% after being rubbed 800 times on YG522 type abrasiometer according to ISO 5470-1-1999；
Far infrared transmissivity is 88%.
Embodiment 8
Graphene graft modification conduction viscose fiber is prepared by solution reduction
Graphene oxide graft modification viscose fiber is prepared in the same way as in example 2, then by oxygen obtained
Graphite alkene graft modification viscose fiber is placed in the hydrazine hydrate aqueous solution that concentration is 0.2% with the weight ratio of 1:60, and
Heating reduction 80 minutes under 90 DEG C of water bath, to obtain graphene graft modification conduction viscose fiber.
The resistivity of the graphene graft modification conduction viscose fiber is 5.0 × 103Ω m, the electricity after washing 20 times
Resistance rate increases by 0.5%, and resistivity increases after being rubbed 700 times on YG522 type abrasiometer according to ISO 5470-1-1999
1.5%；Far infrared transmissivity is 91%.
Embodiment 9
Graphene graft modification conduction hemp is prepared by solution reduction
Graphene oxide graft modification hemp is prepared in mode same as Example 3, then by oxygen obtained
Graphite alkene graft modification hemp is placed in the hydrazine hydrate aqueous solution that concentration is 0.15% with the weight ratio of 1:40, and
Heating reduction 120 minutes under 90 DEG C of water bath, to obtain graphene graft modification conduction hemp.
The resistivity of the graphene graft modification conduction viscose fiber is 5.0 × 102Ω m, the electricity after washing 20 times
Resistance rate increases by 2%, and resistivity increases by 4% after being rubbed 600 times on YG522 type abrasiometer according to ISO 5470-1-1999；
Far infrared transmissivity is 90%.
Fig. 1 to Fig. 2 respectively illustrates the electron microscopic picture before and after matrix fiber graft modification, shows that graphene is effectively grafted on
On fiber surface.
The embodiment above and embodiment only exemplify the specific embodiment of the disclosure, but the embodiment of the disclosure
It is not limited by the foregoing content.It is made in the case where the purport and principle of the not substantive inventive concept for deviating from the disclosure
Any changes, modifications, substitutions, combinations, simplifications, should be equivalent substitute mode, and be included in and determined by claim
Protection scope within.
Claims (10)
1. graphene graft modification conductive fiber, includes:
Matrix fiber part has one or more selected from hydroxyl, carboxyl, amino, isocyanate group, acid halide group on the surface
Functional group；
Assistant activator part is chemically bound on described matrix fiber part, and contains multiple and described matrix fiber
The group of functional group reactions on partial surface；And
Graphene part is grafted on described matrix fiber via being chemically bonded with the assistant activator part,
Wherein the graphene graft modification conductive fiber is after washing 20 times, resistivity increase by 0.1% to 2%, and according to
After ISO 5470-1-1999 rubs 600 times to 800 times on YG522 type abrasiometer, resistivity increases by 0.1% to 5%.
2. graphene graft modification conductive fiber as described in claim 1, wherein described matrix fiber part is selected from the following group
At one of group or a variety of: polysaccharide fiber, for example, cotton fiber, degreasing cotton fiber, hemp, flax fiber, ramie
Fiber, tossa, apocynum fibre, oil flax fibre, viscose rayon, copper ammonia fiber, acetate fiber, alginate fibre, chitosan
Fiber, sodium alginate fiber, tencel, Modal, nandina；And the chemical fibre containing the functional group, for example, polyvinyl alcohol is fine
Dimension, acrylic fiber, polyurethane fiber, acid fiber by polylactic, polyacrylonitrile fibre.
3. graphene graft modification conductive fiber as described in claim 1, wherein the assistant activator part be derived from comprising
Assistant activator selected from one of hydroxyl, carboxyl, amino, isocyanate group, acid halide group or a variety of functional groups, it is preferable that
The assistant activator is selected from one of group consisting of or a variety of: dopamine, chitosan, sodium alginate, gathers at poly-dopamine
Lactic acid, polyacrylic acid, glutamic acid tetraacethyl, ascorbic acid, ethylenediamine tetra-acetic acid, polyvinyl alcohol, polyethylene glycol, polypropylene glycol,
Hydroxypropyl methyl cellulose, pentaerythrite, trien, tetren, melamine, spermine, pyromellitic trimethylsilyl chloride.
4. graphene graft modification conductive fiber as described in claim 1, wherein the graphene graft modification conductive fiber
With 1 × 101Ω m to 1 × 105The resistivity of Ω m and 80% to 95% far infrared transmissivity, and/or
Wherein the graphene graft modification conductive fiber washing 20 times after, resistivity increase by 0.2% to 1.8%, 0.3% to
1.6%, 0.4% to 1.4%, 0.6% to 1.2% or 0.8% to 1.0%, and/or
The graphene graft modification conductive fiber rubs 600 according to ISO 5470-1-1999 on YG522 type abrasiometer
After secondary, 700 times or 800 times, resistivity increase by 0.2% to 4.5%, 0.3% to 4.0%, 0.4% to 3.5%, 0.6% to
3.0%, 0.8% to 2.5% or 1.0% to 2.0%.
5. the method for preparing graphene graft modification conductive fiber described in claim 1, comprising:
Matrix fiber is placed in ultrasonic vibration in polar organic solvent or its aqueous solution to handle, then takes out drying, to obtain
Pretreatment of fiber；
It is chemically bound in assistant activator on the surface of the pretreatment of fiber, to obtain activated fiber；
Graphene oxide is configured to solution and it is made to graft on the activation fibre via being chemically bonded with the assistant activator
In dimension, to obtain graphene oxide graft modification fiber；And
Make the graphene oxide graft modification fiber reduction, to obtain the graphene graft modification conductive fiber.
6. method as claimed in claim 5, wherein the polar organic solvent is selected from one of group consisting of or more
Kind: ethyl alcohol, isopropanol, methyl ethyl ketone, acetone, 1,4- butanediol, butyl glycol ether；Wherein described matrix fiber has with the polarity
Solvent or the weight ratio of its aqueous solution are selected from any one of group consisting of: 1:20 to 1:110,1:30 to 1:
100,1:40 is to 1:90,1:50 to 1:80,1:60 to 1:70.
7. method as claimed in claim 5, wherein the assistant activator is carried out with the pretreatment of fiber as a solution
Chemical bonding, and the concentration of the solution of the assistant activator is selected from any one of group consisting of: 0.05 weight %
To 12 weight %, 0.1 weight % to 10 weight %, 0.2 weight % to 9 weight %, 0.3 weight % to 8 weight %, 0.4 weight
Measure % to 7 weight %, 0.5 weight % to 6 weight %, 0.6 weight % to 5 weight %, 0.7 weight % to 4 weight %, 0.8 weight
Measure % to 3 weight %, 0.9 weight % to 2 weight %, 1 weight % to 1.8 weight %.
8. method as claimed in claim 5, wherein the concentration of the solution of the graphene oxide is selected from group consisting of
Any one of: 0.05mg/mL to 110mg/mL, 0.1mg/mL to 100mg/mL, 0.2mg/mL to 90mg/mL, 0.4mg/mL
Extremely to 80mg/mL, 0.8mg/mL to 70mg/mL, 1.0mg/mL to 60mg/mL, 2.0mg/mL to 50mg/mL, 4.0mg/mL
40mg/mL, 8.0mg/mL are to 30mg/mL, 10.0mg/mL to 20mg/mL.
9. method as claimed in claim 5, wherein the technique of the graphene oxide graft modification fiber reduction is made to include molten
Liquid reduction, high pressure thermal reduction, microwave irradiation reduction or combinations thereof, wherein the solution reduction include using reducing agent solution into
Row reduction, and
The reducing agent is selected from one of group consisting of or a variety of: hydrazine class compound, such as hydrazine hydrate, dimethyl
Hydrazine, phenylhydrazine or to sulfonyloxy methyl hydrazine；Metal hydride, such as sodium borohydride, lithium aluminium hydride reduction；Active metal, such as aluminium, zinc, iron；
Reproducibility acid, such as ascorbic acid, pyrogallic acid；Reproducibility phenol, for example, to biphenol, tea polyphenols；Reducing sugar, example
Such as, glucose, fructose, sucrose；Alkali compounds, for example, sodium hydroxide, potassium hydroxide, sodium bicarbonate, ammonium hydroxide；Iodide, example
Such as potassium iodide, ammonium iodide, sodium iodide, iron iodide.
10. graphene graft modification conductive fiber according to any one of claims 1 to 4 or according to claim 5 to 9
Any one of described in method preparation graphene graft modification conductive fiber in intelligent textile, flexible sensor, electronics device
Purposes in part or electric heating health textile.
Priority Applications (1)
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| CN114351277B (en) * | 2021-12-15 | 2023-11-28 | 徐州丽君工艺品有限公司 | Graphene-quaternary ammonium salt antibacterial bed fabric and preparation method thereof |
| CN116716726A (en) * | 2023-08-03 | 2023-09-08 | 武汉理工大学三亚科教创新园 | Polylactic acid/reduced graphene oxide coaxial coated conductive fiber and application thereof |
| CN116716726B (en) * | 2023-08-03 | 2023-10-24 | 武汉理工大学三亚科教创新园 | Polylactic acid/reduced graphene oxide coaxial coated conductive fiber and application thereof |
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