CN109183392A - Graphene denatured conductive cellulose fibre and its preparation method and application - Google Patents
Graphene denatured conductive cellulose fibre and its preparation method and application Download PDFInfo
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- CN109183392A CN109183392A CN201810901953.3A CN201810901953A CN109183392A CN 109183392 A CN109183392 A CN 109183392A CN 201810901953 A CN201810901953 A CN 201810901953A CN 109183392 A CN109183392 A CN 109183392A
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- D—TEXTILES; PAPER
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- 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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- 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
- D06M13/244—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 sulfur or phosphorus
- D06M13/248—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 sulfur or phosphorus with compounds containing sulfur
- D06M13/256—Sulfonated compounds esters thereof, e.g. sultones
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Abstract
The present invention provides a kind of methods for preparing graphene denatured conductive cellulose fibre comprising makes graphene oxide in conjunction with cellulose fibre to obtain graphene oxide modified cellulose fibre by surface modification mode in graphene oxide solution；And in sulfinic acid compound aqueous solution, in 50 DEG C to 100 DEG C at a temperature of restore the graphene oxide modified cellulose fibre, to obtain graphene denatured conductive cellulose fibre.The resistance of graphene denatured conductive cellulose fibre obtained is 1 × 101Ω to 1 × 105Ω, after water-fastness experiment, the absolute value of the change rate of resistance is 5% to 50%, therefore has excellent water-fastness and electric conductivity.The present invention also provides the graphene denatured conductive cellulose fibres obtained by the method.In addition, the purposes the present invention also provides the graphene denatured conductive cellulose fibre in intelligence sensor, electromagnetic shielding, electric heating medical supplies, conductive spinning product or antistatic textile.
Description
Technical field
The present invention relates to denatured conductive fibers, preparation method and use, and in particular, to graphene denatured conductive fiber
Cellulose fiber, preparation method and use.
Background technique
Graphene is the two-dimentional monoatomic layer formed by the carbon atom of sp2 hydridization with honeycomb hexagonal structure close-packed arrays
Flat crystal material.Special nanostructure makes it have the characteristics such as excellent intensity, conduction, thermally conductive, thus composite material,
The fields such as intellectual material, electronic device, energy storage and pharmaceutical carrier show huge application potential.Simultaneously because graphene
With ultrathin flexible structure and excellent performance characteristics, the application in textile fiber material field is also increasingly extensive, such as
Pure graphene fiber, graphene composite fibre, graphene coated fiber and textile etc..
Currently, by graphene be applied to conductive fiber method there are mainly two types of: one kind be conventional fibre surface apply
Cover graphene conductive material；Another kind is that conductive fiber is made in graphene and fibrous raw material co-blended spinning.Cladding process preparation
Filamentary conductive can be excellent, but water-wash resistance and durability are not ideal enough, and co-blended spinning rule deposit reunite during the spinning process,
The problems such as spinning is not smooth.
In recent years, the pass that conductive fiber also increasingly obtains people is prepared by redox graphene modified fibre
Note.The restoring method of graphene oxide mainly has chemical reduction method, thermal reduction and electrochemical reducing, wherein chemical reduction method
It is at low cost, yield is big, favor by researcher.Currently, more effective reducing agent has hydrazine, NaBH4With HI etc., this is utilized
Redox graphene (rGO) C/O made from a little reducing agents can reach 10 or so, even 12 or more.However, these reagents are often
With stronger toxicity or corrosivity, health and ambient enviroment to staff, which exist, to be seriously threatened.For this purpose, people once attempt
Graphene oxide is restored as reducing agent using ascorbic acid, chitosan, but finds these reducing agents longer anti-
It is also difficult to obtain preferable reduction effect under between seasonable.
Therefore, there is an urgent need in the art to a kind of nontoxic, efficient, energy-efficient restoring method, to obtain water-wash resistance and to lead
The good graphene denatured conductive fiber of electrical property.
Summary of the invention
The present invention is intended to provide a kind of method for preparing nontoxic, efficient and energy-efficient graphene denatured conductive cellulose fibre
To obtain electric conductivity height and the good graphene denatured conductive cellulose fibre of water-wash resistance, deposited in the prior art to overcome
Above-mentioned deficiency.
According to an aspect of the invention, there is provided the method for preparing graphene denatured conductive cellulose fibre, the side
Method includes: to make graphene oxide in conjunction with cellulose fibre to obtain oxygen by surface modification mode in graphene oxide solution
Graphite alkene modified cellulose fibre；And in sulfinic acid compound aqueous solution, in 50 DEG C to 100 DEG C at a temperature of restore institute
Graphene oxide modified cellulose fibre is stated, to obtain graphene denatured conductive cellulose fibre.
In one embodiment, the partial size of the graphene oxide is selected from any one of group consisting of: 0.1
μm to 7.0 μm, 0.2 μm to 6.5 μm, 0.3 μm to 6.0 μm, 0.4 μm to 5.5 μm, 0.5 μm to 5.0 μm, 0.6 μm to 4.5 μm,
0.8 μm to 4.0 μm, 1.0 μm to 3.5 μm, 1.2 μm to 3.0 μm, 1.5 μm to 2.5 μm, 1.8 μm to 2.0 μm.
In one embodiment, the cellulose fibre is selected from one of group consisting of or a variety of: cotton is fine
Dimension, flaxen fiber, viscose rayon, bamboo fibre, acetate fiber, copper ammonia fiber or combinations thereof.
In one embodiment, the sulfinic acid compound is selected from one of group consisting of or a variety of: alkane
Base sulfinic acid, for example, methylol sulfinic acid, 3- methyl sulfinic acid, 2- hydroxyl -2- sulfinatoacetic acid, trifluoromethanesulpacidc acidc,
1- hydroxyethylsulfinic acid, 1- hydroxypropylsulfinic acid, 1- hydroxyl butyl sulfinic acid, 1- hydroxyl -1- methylethylsulfinic acid, 1- hydroxyl -
1- ethylpropylsulfinic acid, 1- hydroxyl -1- methylpropylsulfinic acid or 1- hydroxyl -1- methylpentylsulfinic acid or its salt；Aryl
Sulfinic acid, for example, 3- nitro benzenesulfinic acid, 4- chlorobenzene sulfinic acid, 4- cyano benzenesulfinic acid, 4- ethoxy carbonyl benzenesulfinic acid,
4- trifluoromethyl benzenesulfinic acid, 3- trifluoromethyl benzenesulfinic acid, 1- anthraquinone sulfinic acid, 1- naphthalene sulfinic acid, 2- naphthalene sulfinic acid, phenyl
Sulfinic acid, p-methoxyphenyl sulfinic acid, p-methylphenyl sulfinic acid, rubigan sulfinic acid, p-bromophenyl sulfinic acid, to iodine
Phenyl sulfinic acid, p-nitrophenyl sulfinic acid, Chloro-O-Phenyl sulfinic acid, O-Nitrophenylfluorone sulfinic acid or naphthalene sulfinic acid or its
Salt；Or combinations thereof, wherein the sulfinic acid compound is preferably methylol sulfinic acid, 3- methyl sulfinic acid or its salt, more preferably
For sodium hydroxymethanesulfinate or 3- methyl sulfinic acid ammonium.
In one embodiment, the graphene oxide in the graphene oxide solution and the cellulose fibre
Weight ratio be 1.0:10 to 3.0:10,1.5:10 to 2.5:10 or 1.8:10 to 2.0:10.
In one embodiment, the sulfinic acid compound in the sulfinic acid compound aqueous solution and the oxidation
The weight ratio of graphene modified cellulose fibre is 1.0:10 to 3.0:10,1.5:10 to 2.5:10 or 1.8:10 to 2.0:10.
According to another aspect of the present invention, the graphene denatured conductive cellulose prepared by method as described above is provided
Fiber, wherein the graphene denatured conductive cellulose fibre, after water-fastness experiment, the absolute value of the change rate of resistance is 5%
To 50%.
In one embodiment, the graphene denatured conductive cellulose fibre is after water-fastness experiment, the change of resistance
The absolute value of rate is 10% to 45%, 15% to 40%, 20% to 35% or 25% to 30%.
In one embodiment, the resistance of the graphene denatured conductive cellulose fibre is 1.0 × 101Ω to 1.0
×105Ω or 2.0 × 101Ω to 5.0 × 104Ω or 4.0 × 101Ω to 2.0 × 104Ω or 8.0 × 101Ω to 1.0 ×
104Ω or 1.0 × 102Ω to 5 × 103Ω or 2 × 102Ω to 2 × 103Ω or 4.0 × 102Ω to 1.0 × 103Ω。
Method of the invention is with easy to operate, process flow is short, be easy to large-scale production, low energy consumption, waste water is easy to handle
And the advantages that graphene modified cellulose fibre electric conductivity height obtained and good water-wash resistance.In addition, the method has
Have the advantages that nontoxic, nonirritant, at low cost.
According to another aspect of the present invention, the graphene denatured conductive cellulose fibre prepared by the method is provided
Purposes in intelligence sensor, electromagnetic shielding, electric heating medical supplies, conductive spinning product or antistatic textile.
Detailed description of the invention
Fig. 1 shows the electron microscopic picture of (a) viscose rayon before modified；(b) electron microscope of graphene oxide modified viscose fiber
Piece；(c) electron microscopic picture of graphene modified viscose fiber；And (d) office of the graphene modified viscose fiber in (c) in box
Portion's enlarged drawing.
Fig. 2 shows the electronic photos of (a) graphene denatured conductive cellulose fibre；And (b) graphene denatured conductive is fine
Cellulose fiber is for conductive performance.
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.
The present invention provides the methods for preparing graphene denatured conductive cellulose fibre, which comprises uses improvement
Hummer ' s method prepare graphene oxide；The graphene oxide is configured to solution, then in graphene oxide solution
In make graphene oxide in conjunction with cellulose fibre by surface modifying method, it is fine to obtain graphene oxide modified cellulose
Dimension；And in sulfinic acid compound aqueous solution, in 50 DEG C to 100 DEG C at a temperature of restore the graphene oxide modified fibre
Cellulose fiber, to obtain graphene denatured conductive cellulose fibre.
In one embodiment, the graphene denatured conductive cellulose fibre can also include additive, such as resistance to
Grinding agent, colorant, pigment, delustering agent, fire retardant, wetting agent, softening agent, levelling agent, finishing agent, color fixing agent, smooth agent etc., with
Just desired additional performance is assigned to the conductive cellulose fiber.
In one embodiment, graphene oxide can also by brodie method and Staudenmaier method, with
And other methods known in the art obtain.
In another embodiment, the partial size of the graphene oxide can be any in group consisting of
: 0.1 μm to 7.0 μm, 0.2 μm to 6.5 μm, 0.3 μm to 6.0 μm, 0.4 μm to 5.5 μm, 0.5 μm to 5.0 μm, 0.6 μm extremely
4.5 μm, 0.8 μm to 4.0 μm, 1.0 μm to 3.5 μm, 1.2 μm to 3.0 μm, 1.5 μm to 2.5 μm, 1.8 μm to 2.0 μm.It is preferred that
Ground, in specific embodiments, the partial size of the graphene oxide can for 0.1 μm, 0.2 μm, 0.3 μm, 0.4 μm, 0.5 μm,
0.6 μm, 0.7 μm, 0.8 μm, 0.9 μm or 1.0 μm.In further specific embodiment, the partial size of the graphene oxide
It can be 0.1 μm, 0.2 μm, 0.3 μm, 0.4 μm or 0.5 μm, so that graphene oxide particle is evenly dispersed in solution.
In one embodiment, the weight ratio of the graphene oxide in the graphene oxide solution and cellulose fibre
For 1:10 to 3:10.In specific embodiments, the graphene oxide in the graphene oxide solution and cellulose fibre
Weight ratio is 1.5:10 to 2.5:10 or 1.8:10 to 2.0:10.In another particular embodiment, the graphene oxide is molten
The weight ratio of graphene oxide and cellulose fibre in liquid can for 1.2:10,1.4:10,1.6:10,1.8:10,2.0:10,
2.2:10,2.6:10 or 2.8:10.
In one embodiment, the cellulose fibre can be cotton fiber, flaxen fiber, viscose rayon, bamboo fibre, vinegar
Sour fiber, copper ammonia fiber or combinations thereof.In specific embodiments, the cellulose fibre can for cotton fiber, viscose rayon,
Acetate fiber fiber or combinations thereof.In preferred embodiments, the cellulose fibre can for cotton fiber, viscose rayon or
A combination thereof.
In one embodiment, the sulfinic acid compound in the sulfinic acid compound aqueous solution changes with graphene oxide
Property cellulose fibre weight ratio be 1:10 to 3:10.In specific embodiments, in the sulfinic acid compound aqueous solution
The weight ratio of sulfinic acid compound and graphene oxide modified cellulose fibre is 1.5:10 to 2.5:10 or 1.8:10 to 2.0:
10.In another particular embodiment, the sulfinic acid compound in the sulfinic acid compound aqueous solution changes with graphene oxide
Property cellulose fibre weight ratio be 1.2:10,1.4:10,1.6:10,1.8:10,2.0:10,2.2:10,2.6:10 or 2.8:
10。
In one embodiment, the recovery time of the graphene oxide modified cellulose fibre can be for selected from following
Any one of group of composition: 0.15 hour to 3.0 hours, 0.2 hour to 2.8 hours, 0.3 hour to 2.5 hours, it is 0.4 small
Up to 2.2 hours, 0.5 hour to 2.0 hours, 0.6 hour to 1.8 hours, 0.8 hour to 1.5 hours, it is 1.0 hours to 1.2 small
When.Preferably, in specific embodiments, the recovery time of the graphene oxide modified cellulose fibre can be small for 0.15
When, 0.2 hour, 0.3 hour, 0.4 hour, 0.5 hour, 0.6 hour, 0.7 hour, 0.8 hour, 0.9 hour or 1.0 hours.
In further specific embodiment, the recovery time of the graphene oxide modified cellulose fibre can be small for 0.15
When, 0.2 hour, 0.3 hour, 0.4 hour or 0.5 hour.
In one embodiment, the reduction temperature of the graphene oxide modified cellulose fibre is selected from consisting of
Any one of group: 50 DEG C to 100 DEG C, 55 DEG C to 95 DEG C, 60 DEG C to 90 DEG C, 65 DEG C to 85 DEG C, 70 DEG C to 80 DEG C, 75 DEG C extremely
78℃.Preferably, in specific embodiments, the reduction temperature of the graphene oxide modified cellulose fibre is 60 DEG C, 70
DEG C, 80 DEG C, 90 DEG C or 100 DEG C.In further specific embodiment, the graphene oxide modified cellulose fibre is gone back
Former temperature is 80 DEG C, 90 DEG C or 100 DEG C, to promote sulfinic acid compound to go back graphene oxide modified cellulose fibre
It is former.
In one embodiment, the sulfinic acid compound can be alkyl sulfinic acid, aryl sulfinic acid or its salt；Or
A combination thereof, wherein alkyl or aryl can be substituted or unsubstituted.In another particular embodiment, the sulfinic acid chemical combination
Object can be alkyl sulfinic acid or sylvite, sodium salt or the ammonium salt of aryl sulfinic acid etc..
Specifically, in one embodiment, the sulfinic acid compound can be alkyl sulfinic acid, such as methylol Asia
Sulfonic acid, 3- methyl sulfinic acid, 2- hydroxyl -2- sulfinatoacetic acid, trifluoromethanesulpacidc acidc, 1- hydroxyethylsulfinic acid, 1- hydroxypropyl
Base sulfinic acid, 1- hydroxyl butyl sulfinic acid, 1- hydroxyl -1- methylethylsulfinic acid, 1- hydroxyl -1- ethylpropylsulfinic acid, 1- hydroxyl
Base -1- methylpropylsulfinic acid or 1- hydroxyl -1- methylpentylsulfinic acid or its salt.In another embodiment, the sub- sulphur
Acid compound can be aryl sulfinic acid, for example, 3- nitro benzenesulfinic acid, 4- chlorobenzene sulfinic acid, 4- cyano benzenesulfinic acid, 4- second
Epoxide carbonyl benzenesulfinic acid, 4- trifluoromethyl benzenesulfinic acid, 3- trifluoromethyl benzenesulfinic acid, 1- anthraquinone sulfinic acid, 1- naphthalene Asia sulphur
Acid, 2- naphthalene sulfinic acid, phenyl sulfinic acid, p-methoxyphenyl sulfinic acid, p-methylphenyl sulfinic acid, rubigan sulfinic acid,
P-bromophenyl sulfinic acid, to iodophenyl sulfinic acid, p-nitrophenyl sulfinic acid, Chloro-O-Phenyl sulfinic acid, O-Nitrophenylfluorone Asia sulphur
Acid or naphthalene sulfinic acid or its salt.
Preferably, in specific embodiments, the sulfinic acid compound can be methylol sulfinic acid, 3- methyl Asia sulphur
Acid, trifluoromethanesulpacidc acidc, 1- hydroxyethylsulfinic acid, p-methylphenyl sulfinic acid, phenyl sulfinic acid or its salt, or combinations thereof.
It is highly preferred that in specific embodiments, the sulfinic acid compound can be methylol sulfinic acid, 3- methyl sulfinic acid, benzene
Base sulfinic acid or its salt, or combinations thereof.Most preferably, in specific embodiments, the sulfinic acid compound can be hydroxyl first
Base sulfinic acid, sodium hydroxymethanesulfinate, 3- methyl sulfinic acid ammonium or combinations thereof.
The present invention also provides the graphene denatured conductive cellulose fibre prepared by method as described above, such stones
The absolute value of black alkene denatured conductive cellulose fibre change rate of resistance after water-fastness experiment can be 5% to 50%.
In one embodiment, the graphene denatured conductive cellulose fibre is after water-fastness experiment, the change of resistance
The absolute value of rate can be 10% to 45%, 15% to 40%, 20% to 35% or 25% to 30%.
In one embodiment, the graphene denatured conductive cellulose fibre is after water-fastness experiment, the change of resistance
The absolute value of rate can be 8%, 16%, 18%, 22%, 28%, 32%, 38%, 42% or 48%.In specific embodiment
In, the graphene denatured conductive cellulose fibre after water-fastness experiment, the absolute value of the change rate of resistance can for 5%,
10%, 15% or 18%.
In one embodiment, the resistance of the graphene denatured conductive cellulose fibre can be 1.0 × 101Ω is extremely
1.0×105Ω、2.0×101Ω to 5.0 × 104Ω、4.0×101Ω to 2.0 × 104Ω、8.0×101Ω to 1.0 × 104
Ω、1.0×102Ω to 5 × 103Ω or 2 × 102Ω to 2 × 103Ω or 4.0 × 102Ω to 1.0 × 103Ω。
In one embodiment, the resistance of the graphene denatured conductive cellulose fibre can be 1.5 × 101Ω、
3.0×101Ω、6.0×101Ω、1.5×102Ω、3.0×102Ω、6.0×102Ω、1.5×103Ω、3.0×103Ω、
6.0×103Ω、1.5×104Ω、3.0×104Ω or 6.0 × 104Ω。
The present invention also provides the graphene denatured conductive cellulose fibres in intelligence sensor, electromagnetic shielding, electric heating
Purposes in medical supplies, conductive spinning product or antistatic textile.
In one embodiment, the intelligence sensor can be PH perspiration sensor, blood pressure pulse sensor, breathing
Rate sensor, arthrogryposis sensor, human motion detection sensor, electronic skin etc..
In another embodiment, the conductive spinning product can spin for wearable device, temperature-regulation fabric, electrochromism
Fabric, shape memory textile or luminescent textile product etc..
In yet another embodiment, the electric heating medical supplies can be electric heating medical pad, electrothermal pulse treatment band, operation
Warming blanket, medical heating sheet or electric heating Magnetotherapeutic apparatus etc..
The graphene denatured conductive cellulose fibre obtained by means of the present invention has lower resistance and good
Water-wash resistance, therefore the preparation method of graphene denatured conductive cellulose fibre is industrially obviously 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 denatured conductive viscose rayon
Graphene oxide is prepared using improved Hummer ' s method, obtains the solution for the graphene oxide that partial size is 1 μm,
The solution of resulting graphene oxide is diluted with water, to obtain the graphene oxide solution of 2mg/ml.Then by viscose rayon
It is that 1:10 is immersed in the graphene oxide solution with the weight ratio of graphene oxide and viscose rayon, so that graphene oxide
Surface is carried out to viscose rayon to be modified, and continues 2 hours, to obtain graphene oxide modified viscose fiber.
By graphene oxide modified viscose fiber obtained with sodium hydroxymethanesulfinate and the modified viscose glue of graphene oxide
The weight ratio of fiber is that 1:10 is placed in sodium hydroxymethanesulfinate aqueous solution, and mixture is heated 1.5 hours at 80 DEG C, is made
It obtains graphene oxide modified viscose fiber and carries out reduction reaction, to obtain graphene denatured conductive viscose rayon.
The resistance of graphene denatured conductive viscose rayon obtained is 7.0 × 103Ω, after water-fastness experiment, resistance
It is 9.0 × 103Ω。
Embodiment 2
The preparation of graphene denatured conductive flaxen fiber
Graphene oxide is prepared using improved Hummer ' s method, obtains the solution for the graphene oxide that partial size is 1 μm.
The solution of resulting graphene oxide is diluted with water, to obtain the graphene oxide solution of 2mg/ml.Then by flaxen fiber with
The weight ratio of graphene oxide and flaxen fiber is that 3:10 is immersed in the graphene oxide solution, so that graphene oxide is to fiber crops
Fiber carries out surface and is modified, and continues 2 hours, to obtain the modified flaxen fiber of graphene oxide.
The modified flaxen fiber of graphene oxide obtained is modified flaxen fiber with methylol sulfinic acid and graphene oxide
Weight ratio is that 3:10 is placed in methylol sulfinic acid aqueous solution, and mixture is heated 1 hour at 100 DEG C, so that oxidation stone
The modified flaxen fiber of black alkene carries out reduction reaction, to obtain graphene denatured conductive flaxen fiber.
The resistance of graphene denatured conductive flaxen fiber obtained is 6.0 × 104Ω, after water-fastness experiment, resistance is
8.0×104Ω。
Embodiment 3
The preparation of graphene denatured conductive bamboo fibre
Graphene oxide is prepared using improved Hummer ' s method, obtains the solution for the graphene oxide that partial size is 5 μm.
The solution of resulting graphene oxide is diluted with water, to obtain the graphene oxide solution of 5mg/ml.Then by bamboo fibre with
The weight ratio of graphene oxide and bamboo fibre is that 2:10 is immersed in the graphene oxide solution, so that graphene oxide is to bamboo
Fiber carries out surface and is modified, and continues 2 hours, to obtain graphene oxide modified bamboo fiber.
By graphene oxide modified bamboo fiber obtained with 3- methyl sulfinic acid ammonium and graphene oxide modified bamboo fiber
Weight ratio be 2:10 be placed in 3- methyl sulfinic acid aqueous ammonium, and by mixture 85 DEG C heat 0.5 hour so that oxygen
Graphite alkene modified bamboo fiber carries out reduction reaction, to obtain graphene denatured conductive bamboo fibre.
The resistance of graphene denatured conductive bamboo fibre obtained is 8.0 × 103Ω, after washing experiment, resistance 9.0
×103Ω。
Embodiment 4
The preparation of graphene denatured conductive cotton fiber
Graphene oxide is prepared using improved Hummer ' s method, obtains the solution for the graphene oxide that partial size is 3 μm.
The solution of resulting graphene oxide is diluted with water to obtain the graphene oxide solution of 2mg/ml.Then by cotton fiber with oxygen
The weight ratio of graphite alkene and cotton fiber is that 2:10 is immersed in the graphene oxide solution, so that graphene oxide is to cotton fibre
Dimension carries out surface and is modified, and continues 2 hours, to obtain graphene oxide modified cotton fiber.
By graphene oxide modified cotton fiber obtained with 3- methyl sulfinic acid ammonium and graphene oxide modified cotton fiber
Weight ratio be 2:10 be placed in 3- methyl sulfinic acid aqueous ammonium, and by mixture 85 DEG C heat 0.5 hour so that oxygen
Graphite alkene modified cotton fiber carries out reduction reaction, to obtain graphene denatured conductive cotton fiber.
The resistance of graphene denatured conductive cotton fiber obtained is 4.0 × 104Ω, after washing experiment, resistance 6.0
×104Ω。
Comparative example 1
The preparation of graphene denatured conductive viscose rayon
Prepare contrast sample graphene denatured conductive viscose rayon in the same manner as in Example 1, but reduction used
Agent is hydrazine hydrate, and heating time is 2 hours.
The resistance of graphene denatured conductive viscose rayon obtained is 6.0 × 104Ω, after water-fastness experiment, resistance liter
Up to 5.0 × 105Ω。
Comparative example 2
The preparation of graphene denatured conductive flaxen fiber
Contrast sample graphene denatured conductive flaxen fiber is prepared in method same as Example 2, but reducing agent used
For hydrazine hydrate, heating time is 1.5 hours.
The resistance of graphene denatured conductive flaxen fiber obtained is 5.0 × 105Ω m, after washable experiment, resistance is increased
To 4.0 × 106Ω·m。
Comparative example 3
The preparation of graphene denatured conductive bamboo fibre
Contrast sample graphene denatured conductive bamboo fibre is prepared in method same as Example 3, but reducing agent used
For hydrazine hydrate, heating time is 1 hour.
The resistance of graphene denatured conductive bamboo fibre obtained is 1.0 × 104Ω, after washable experiment, resistance is increased to
1.0×105Ω。
Comparative example 4
The preparation of graphene denatured conductive cotton fiber
Contrast sample graphene denatured conductive cotton fiber is prepared in method same as Example 4, but reducing agent used
For hydrazine hydrate, heating time is 1 hour.
The resistance of graphene denatured conductive cotton fiber obtained is 4.0 × 104Ω, after washing experiment, resistance is increased to
4.0×105Ω。
By graphene denatured conductive cellulose obtained in embodiment 1 to embodiment 4 and comparative example 1 to comparative example 4
Fiber carries out conducting performance test and is compared, as a result shown in table 1.As it can be seen from table 1 before washing and after washing,
The electric conductivity and water-wash resistance for graphene denatured conductive cellulose fibre sulfinic acid compound is used as reducing agent prepared are all excellent
In the electric conductivity and water-wash resistance of the graphene denatured conductive cellulose fibre prepared with hydrazine hydrate reduction.
Table 1
The test of water-wash resistance
It is molten to prepare test to contain 5 grams of soap powder and 2 grams of sodium carbonate in every liter of solution according to GB/T 3921-2008
Liquid.Then the graphene denatured conductive cellulose fibre of preparation is placed in the test solution with the weight ratio of 1:50, and
It is stirred 30 minutes at 60 DEG C, then cleaned and dry.It tests before the washing of graphene denatured conductive cellulose fibre and after washing
Resistance, with the absolute value representation water-wash resistance of the change rate of conductive fiber resistance.
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. the method for preparing graphene denatured conductive cellulose fibre, comprising:
Make graphene oxide in conjunction with cellulose fibre to be aoxidized by surface modification mode in graphene oxide solution
Graphene modified cellulose fibre；And
In sulfinic acid compound aqueous solution, in 50 DEG C to 100 DEG C at a temperature of restore the graphene oxide modified cellulose
Fiber, to obtain graphene denatured conductive cellulose fibre.
2. the method as described in claim 1, wherein the partial size of the graphene oxide is appointing in group consisting of
One: 0.1 μm to 7.0 μm, 0.2 μm to 6.5 μm, 0.3 μm to 6.0 μm, 0.4 μm to 5.5 μm, 0.5 μm to 5.0 μm, 0.6 μm extremely
4.5 μm, 0.8 μm to 4.0 μm, 1.0 μm to 3.5 μm, 1.2 μm to 3.0 μm, 1.5 μm to 2.5 μm, 1.8 μm to 2.0 μm.
3. the method as described in claim 1, wherein the cellulose fibre is selected from one of group consisting of or more
Kind: cotton fiber, flaxen fiber, viscose rayon, bamboo fibre, acetate fiber, copper ammonia fiber or combinations thereof.
4. the method as described in claim 1, wherein the sulfinic acid compound be selected from one of group consisting of or
It is a variety of: alkyl sulfinic acid, such as methylol sulfinic acid, 3- methyl sulfinic acid, 2- hydroxyl -2- sulfinatoacetic acid, trifluoromethyl
Sulfinic acid, 1- hydroxyethylsulfinic acid, 1- hydroxypropylsulfinic acid, 1- hydroxyl butyl sulfinic acid, 1- hydroxyl -1- methylethylsulfinic acid,
1- hydroxyl -1- ethylpropylsulfinic acid, 1- hydroxyl -1- methylpropylsulfinic acid or 1- hydroxyl -1- methylpentylsulfinic acid or its
Salt；Aryl sulfinic acid, for example, 3- nitro benzenesulfinic acid, 4- chlorobenzene sulfinic acid, 4- cyano benzenesulfinic acid, 4- ethoxy carbonyl benzene
Sulfinic acid, 4- trifluoromethyl benzenesulfinic acid, 3- trifluoromethyl benzenesulfinic acid, 1- anthraquinone sulfinic acid, 1- naphthalene sulfinic acid, 2- naphthalene Asia sulphur
Acid, phenyl sulfinic acid, p-methoxyphenyl sulfinic acid, p-methylphenyl sulfinic acid, rubigan sulfinic acid, p-bromophenyl Asia sulphur
Acid, to iodophenyl sulfinic acid, p-nitrophenyl sulfinic acid, Chloro-O-Phenyl sulfinic acid, O-Nitrophenylfluorone sulfinic acid or naphthalene Asia sulphur
Acid or its salt；Or combinations thereof,
Wherein the sulfinic acid compound is preferably methylol sulfinic acid, 3- methyl sulfinic acid or its salt, more preferably methylol
Sulfinic acid sodium or 3- methyl sulfinic acid ammonium.
5. the method as described in claim 1, wherein the graphene oxide and the fibre in the graphene oxide solution
The weight ratio of cellulose fiber is 1.0:10 to 3.0:10,1.5:10 to 2.5:10 or 1.8:10 to 2.0:10.
6. the method as described in claim 1, wherein the sulfinic acid compound in the sulfinic acid compound aqueous solution with
The weight ratio of the graphene oxide modified cellulose fibre be 1.0:10 to 3.0:10,1.5:10 to 2.5:10 or 1.8:10 extremely
2.0:10。
7. such as the graphene denatured conductive cellulose fibre of method described in any one of claims 1 to 6 preparation, wherein described
For graphene denatured conductive cellulose fibre after water-fastness experiment, the absolute value of the change rate of resistance is 5% to 50%.
8. graphene denatured conductive cellulose fibre as claimed in claim 7, wherein the graphene denatured conductive cellulose
Fiber after water-fastness experiment, the absolute value of the change rate of resistance be 10% to 45%, 15% to 40%, 20% to 35% or
25% to 30%.
9. graphene denatured conductive cellulose fibre as claimed in claim 7 or 8, wherein the graphene denatured conductive fiber
The resistance of cellulose fiber is 1.0 × 101Ω to 1.0 × 105Ω or 2.0 × 101Ω to 5.0 × 104Ω or 4.0 × 101Ω to 2.0
×104Ω or 8.0 × 101Ω to 1.0 × 104Ω or 1.0 × 102Ω to 5 × 103Ω or 2 × 102Ω to 2 × 103Ω or
4.0×102Ω to 1.0 × 103Ω。
10. the graphene denatured conductive cellulose fibre or power that are obtained by method described in any one of claims 1 to 6
Benefit require any one of 7 to 9 described in graphene denatured conductive cellulose fibre intelligence sensor, electromagnetic shielding, electric heating doctor
Treat the purposes in articles, conductive spinning product or antistatic textile.
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