CN107938009A - A kind of graphene oxide modified fibre and its preparation method and application - Google Patents
A kind of graphene oxide modified fibre and its preparation method and application Download PDFInfo
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- CN107938009A CN107938009A CN201711244394.5A CN201711244394A CN107938009A CN 107938009 A CN107938009 A CN 107938009A CN 201711244394 A CN201711244394 A CN 201711244394A CN 107938009 A CN107938009 A CN 107938009A
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/09—Addition of substances to the spinning solution or to the melt for making electroconductive or anti-static filaments
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
- D01F6/46—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polyolefins
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
- D01F6/54—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polymers of unsaturated nitriles
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
- D01F6/94—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of other polycondensation products
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Abstract
The present invention provides a kind of graphene oxide modified fibre and its preparation method and application.A kind of preparation method of graphene oxide modified fibre, comprises the following steps：The monomer of graphene oxide, free radical scavenger, water and fibre-forming polymer is mixed, mixed liquor is made；The mixed liquor is irradiated in an inert atmosphere, obtains spinning solution；By the spinning solution spinning, graphene oxide modified fibre is made.Electric conductivity is low after the present invention solves the problems, such as graphene oxide modified fibre and its product, have the advantages that conductivity is high, light, antistatic, applied widely using graphene oxide modified fibre made from this method, and preparation method need not introduce reducing agent, initiator, the pollution to environment is reduced.
Description
Technical field
The present invention relates to chemical field, more particularly, to a kind of graphene oxide modified fibre and preparation method thereof and answers
With.
Background technology
Conductive fiber has good electric conductivity and durability, particularly still there is well durable to resist under the low humidity quiet
Electrically, after conductive layer reaches certain thickness or conductive compositions reach certain proportion, just there is excellent electro-magnetic screen function, because
This has very big purposes, such as the conductive mesh of electronics, power industry, conductive work clothes, medical row in the field such as industrial, civilian
The electric heating clothes of industry, electric heating bandage, Aeronautics and Astronautics, the electro-magnetic shielding cover etc. of precise electronic industry.Conductive fiber it is antistatic
Mechanism is to make to produce corona discharge between conductive fiber.Corona discharge is a kind of discharge type relaxed very much, when electrostatic pressure reaches
After certain numerical value, that is, producing nonarcing corona discharge makes static elimination.This phenomenon is commonly referred to be the conduction in fabric
Fiber, under the action of electrostatic field, makes the air of surrounding produce ionization and form negative ions, one kind in negative ions
Mutually neutralized on the contrary with fabric institute static electrification lotus, it is another then with environment or the earth neutralization, so as to eliminate electrostatic.
At present, the problems such as conductive fiber generally existing processing cost is higher, and technique is also more complicated, this is limited to a certain extent
The production of conductive fiber has been made, also limit and used and popularize, therefore conductive fiber is mainly used in high-tech area at present, and
It is also less applied to civilian kind.With the improvement of people ' s living standards and the enhancing to own health protective awareness, it is civilian
Promoting the use of for conductive fiber necessarily becomes trend, therefore the processing of conductive fiber should be sent out in the simple, direction of low cost to technique
Exhibition, and it is one of approach for solving problem above to assign general fibre electric conductivity.
Graphene be one kind by carbon atom by SP2The stratiform similar to honeycomb structure that hybrid form close-packed arrays are formed
Structure, because getting more and more people's extensive concerning with excellent heat conduction, electric conductivity, it is considered to be the choosing of modified fibre electric conductivity
One of select.But it is weak with the interaction of other media since inert condition is presented in graphene surface, and between graphene film and piece
There are stronger Van der Waals force, easily reunite, it is difficult to dispersed in fibrous inside or surface, it is impossible to the excellent of graphene
It is benign to be sufficiently reserved in the composite.Graphene oxide is product of the powdered graphite after chemical oxidation and stripping, oxidation
Graphene is single atomic layer, can expand to some tens of pm on lateral dimension at any time, and graphene oxide has in water
Superior dispersiveness, can substitute graphene uniform and disperse in the fibre, but since the electric conductivity of graphene oxide is than common
Graphite is also poor, therefore graphene oxide is directly appended to be unable to reach in fiber to the requirement of conductive material.
In view of this, it is special to propose the present invention.
The content of the invention
It is a primary object of the present invention to provide a kind of preparation method of graphene oxide modified fibre, the preparation side
Electric conductivity is low after method solves the problems, such as graphene oxide modified fibre and its product, utilizes graphite oxide made from this method
Alkene modified fibre has the advantages that conductivity is high, light, antistatic, applied widely.
In order to solve the above technical problems, the present invention provides following technical scheme：
A kind of preparation method of graphene oxide modified fibre, comprises the following steps：
The monomer of graphene oxide, free radical scavenger, water and fibre-forming polymer is mixed, mixed liquor is made；
The mixed liquor is irradiated in an inert atmosphere, obtains spinning solution；
By the spinning solution spinning, graphene oxide modified fibre is made.
The present invention is mainly by mixing, irradiating and graphene oxide and fibre-forming polymer are bonded in one by spinning three-procedure
Rise, while reduced graphene oxide by radiating, equivalent to coating one layer of reduction-oxidation graphite in fibrous inside continuity
Alkene, so as to assign filamentary conductive energy.
But modification of the present invention to fiber surface is different from physics cladding of the prior art, is needed in the technique of the present invention
Overcome following difficult point：
First, the problem of overcoming graphene oxide poorly conductive：The present invention passes through free radical scavenger and irradiation Duplex treatment
Solves the problems, such as this, irradiation can make water power separate out H free radicals, aqueous electron e- aqWith OH free radicals, H free radicals and water
Closing electronics has very strong reduction, and graphene oxide is reduced to graphene, then profit using H free radicals and aqueous electron
OH free radicals are removed with free radical scavenger.
2nd, it must assure that graphene oxide is distributed in the continuity of fibrous inside, so that electric current continues through, it is really real
Existing conduction.For this point, the present invention makes surface of graphene oxide generate multiple free radicals, multiple free radical increases by irradiation
Crosslinking points between graphene oxide and fibre-forming polymer and monomer, make graphene oxide in fibre-forming polymer molecular level
Upper continuous, uniformly bonding, i.e. graphene oxide are distributed in fibrous inside continuity.
3rd, the present invention adds graphene oxide during monomer polymerization so that graphene oxide can be crosslinked or be coated on
In multiple dimensions such as intramolecular, intermolecular, so as to improve the comprehensive performance of fiber on organic whole.
In addition, irradiation also provides heat for polymerisation and cross-linking reaction, promote between graphene oxide and polymer
Cross-linking reaction and monomer between polymerisation quickly carry out.
The present invention introduces grapheme material before being also different from existing spinning, of the invention by polymerization process and graphite oxide
The cross-linking process of alkene is completed at the same time, i.e., there occurs the friendship of the polymerisation of monomer, monomer and graphene oxide at the same time under irradiation
The crosslinking of connection and polymer and graphene oxide.The present invention has reached following purpose using process above：It is first, two steps are anti-
A step should be merged into, saves the time, improves production efficiency；Second, graphene oxide in multiple dimensions to fibre modification, bag
Include the crosslinking on monomer, the crosslinking on oligomer, crosslinking on high polymer etc..
Raw material used in the present invention --- graphene oxide refers to graphene oxide made from any means, and (name definition is joined
See graphene alliance standard T/CGIA001-2017).
Fibre-forming polymer of the present invention refers to the synthesising macromolecule copolymer that fiber can be made, and should not only have and be formed
The ability of fiber, it is necessary to be completely dissolved in a suitable solvent, form sticky concentrated solution；Or melting is converted at an elevated temperature
Viscous state is without decomposing, to carry out solution-polymerized SBR or melt spinning.For example, polypropylene, polyacrylonitrile, polyamide, poly-
Vinyl formal, polyethylene terephthalate, polyurethanes, polyvinyl chloride or makrolon etc., manufactured fibre
Dimension has polypropylene fibre, acrylic fibers, polyvinyl, spandex, terylene, polyvinyl chloride fibre etc..
Monomer of the present invention can be liquid or solid.Liquid monomer refers to the list being in a liquid state at normal temperatures
Body, can be in direct polymerization under irradiation.Solid monomer forms the liquid of flowing after being dissolved in coordinative solvent, can also irradiate
Lower generation polymerisation.I.e., it is preferable that when the monomer is solid monomer not soluble in water, be additionally added in the mixed liquor
Solvent, dissolves the monomer.
Present invention method made above can also be improved further, such as：
Preferably, the concentration of graphene oxide is more excellent in below 30mg/mL, preferably below 20mg/mL in the mixed liquor
Select 10-20mg/mL.
The concentration of graphene oxide can use the arbitrary value of below 30mg/mL, such as 30mg/mL, 29mg/mL, 28mg/
mL、27mg/mL、26mg/mL、25mg/mL、24mg/mL、23mg/mL、20mg/mL、18mg/mL、15mg/mL、10mg/mL、
8mg/mL, 5mg/mL, 1mg/mL, 0.5mg/mL, 0.1mg/mL etc., wherein preferable scope has below 20mg/mL, more preferably
10-20mg/mL or 15-20mg/mL etc..
Preferably, the weight content of water described in the mixed liquor is 30~100mg/mL, such as 30mg/mL, 40mg/
mL、50mg/mL、60mg/mL、70mg/mL、80mg/mL、90mg/mL、100mg/mL。
Preferably, the concentration of free radical scavenger described in the mixed liquor is 5-50mg/mL.
Preferably, the free radical scavenger is the one or more in alcohol, amine and ketone, such as alcohol, amine, ketone, alcohol and amine
Mixing, the mixing of alcohol and ketone, or the mixing of amine and ketone, or the mixing of alcohol, amine and ketone three.
Wherein, the alcohol is preferably selected from the one or more in methanol, ethanol and isopropanol；Such as methanol, ethanol, isopropyl
The mixing of the mixing of the mixing of alcohol, methanol and ethanol, methanol and isopropanol, ethanol and isopropanol, or methanol, ethanol and isopropanol
The mixing of three.
The amine is preferably selected from the one or more in monoethanolamine, diethanol amine and triethanolamine, such as monoethanolamine, diethyl
The mixing of the mixing of hydramine, triethanolamine, monoethanolamine and diethanol amine, monoethanolamine and triethanolamine, monoethanolamine, diethanol amine and
The mixing of triethanolamine three；In above scheme, preferred triethanolamine.
The ketone is the mixing of acetone or butanone or both.
Preferably, the monomer of the fibre-forming polymer and the weight ratio of the graphene oxide are 90-100:3-10.
Before spinning, it is not that the graphene oxide that is added in monomer mixture solution is more, electric conductivity is better, passes through
Investigate, find when the monomer of fibre-forming polymer and the weight ratio of the graphene oxide are 90-100:During 3-10, it could obtain more
Good synergy, such as 90:3、100:3、90:5、95:3、97:3、90:5、100:4、100:6、100:8、100:9、100:
10、90:10 etc..
Preferably, the weight ratio of the free radical scavenger and graphene oxide is 0.1~3:3, more preferably 0.1~2:3,
0.5~2:3,1~2:3,1.5~2:3 etc..
Preferably, the weight ratio of the water and graphene oxide is 5-10:3, more preferably 5-8:3,5-7:3,5-6:3 etc..
Preferably, the dosage rate of the irradiation is：1-500KGy/h.
Irradiation dose has a major impact the bonding strength between graphene oxide and cellulosic, through screening, convenient
Irradiation dose is 1-500KGy/h, more preferably 100-200KGy/h, for example, 1KGy/h, 10KGy/h, 20KGy/h, 50KGy/h,
100KGy/h, 150KGy/h, 200KGy/h, 250KGy/h, 300KGy/h, 350KGy/h, 400KGy/h, 450KGy/h or
500KGy/h.In practical operation, possibly constant irradiation dose can not be realized, it is allowed to have a certain range of fluctuation.
The radiation source usually irradiated does not limit, such as common -60 (60Co) gamma-ray radiation source or electron accelerator,
Or the αsource of caesium -137, Iridium-192 source, gamma ray radiator etc., preferably -60 (60Co) gamma-ray radiation source or electron accelerator.
The means of spinning are not particularly limited in the present invention, for example, the spinning is electrostatic spinning or solution-polymerized SBR, can root
Spinning solution is made according to spinning technique to adapt to adjustment.
Preferably, crosslinking agent is additionally added when preparing the mixed liquor；Crosslinking agent can increase graphene oxide and gather with into fine
Cross-linking amount and crosslinked stability between compound.
The crosslinking agent is one kind in alkenes crosslinking agent, organic silicon crosslinking agent and epichlorohydrin resin class crosslinking agent
It is or several.
On the one hand crosslinking agent is inserted into the piece of graphene oxide as the bridge formation between graphene oxide and fibre-forming polymer
In Rotating fields, graphene oxide is kept good characteristic while being inserted into fibre-forming polymer intramolecular, on the one hand make oxidation
Graphene is cross-linked into net structure with fibre-forming polymer, has not only retained the good characteristic of fibre-forming polymer, but also improve graphene oxide
Bond strength between fibre-forming polymer.Based on object above, preferably alkenes crosslinking agent, organic silicon crosslinking agent and epoxy chlorine
One or more in propane resinae crosslinking agent, these crosslinking agents can realize object above, and obtain preferable effect.
These crosslinking agents can be used alone, and can also be used in any combination, such as alkenes crosslinking agent and organic silicon crosslinker combination,
Either organic silicon crosslinking agent and epichlorohydrin resin class crosslinker combination or alkenes crosslinking agent and epichlorohydrin resin
Class crosslinker combination, or alkenes crosslinking agent, organic silicon crosslinking agent and epichlorohydrin resin class crosslinking agent three combination, group
Preferable resultant effect can be obtained when using by closing.
Preferably, the alkenes crosslinking agent is selected from polyethyleneglycol diacrylate, polyethylene polyamine, three allyl of melamine
One or more in ester, triallyl cyanurate, trimethylolpropane tris-(3- aziridinyls)-propionic ester.
Polyethyleneglycol diacrylate, polyethylene polyamine, melamine triallyl, triallyl cyanurate, three hydroxyls
Methylpropane three-(3- aziridinyls)-propionic ester has stronger conjugation, and the cross-linking system formed is more stable.
Preferably, the organic silicon crosslinking agent is silane coupling agent.
Silane coupling agent can not only strengthen the stability that fibre-forming polymer and graphene oxide combine, and can improve fibre
The electric conductivity and ageing resistance of dimension.In principle, arbitrary silane coupling agent YSiX3It is all feasible, n=0~3；X is hydrolyzable base
Group, is typically chloro, methoxyl group, ethyoxyl, methoxy ethoxy, acetoxyl group etc., silanol is generated when these groups hydrolyze
(Si(OH)3), and combined with inorganic substances, form siloxanes；Y is organo-functional group, can be reacted with resin, be vinyl,
Amino, epoxy group, methacryloxy, sulfydryl or urea groups.In above type, can be selected vinyl silanes, amino silane,
Epoxy radicals silicone hydride, hydrosulphonyl silane and methacryloxypropyl silane etc., these crosslinking agents can be used alone, and also can be combined makes
With wherein preferred vinyl.
Preferably, the epichlorohydrin resin class crosslinking agent is crosslinking agent DE, crosslinking agent EH, crosslinking agent FH etc..
The advantages of epichlorohydrin resin class crosslinking agent is that dissolubility is good, and use condition is gentle, and DE, EH and FH can individually make
With can also be applied in combination, preferably individually use crosslinking agent DE.
Preferably, the weight ratio of crosslinking agent and graphene oxide described in the mixed liquor is 1-3:1.
The weight ratio of crosslinking agent and graphene oxide can be 1:1、1.5:1、2:1、2.5:1、3:1 etc..
It is widely used by the graphene oxide modified fibre made of method made above of the present invention, available for making electronics
Conductive devices in multiple industries such as industry, power industry and aerospace industry, the conductive devices include electric heating fabrics, electricity
Magnetic screen fabric or circuit board, specifically there is conductive mesh, conductive work clothes, electric heating clothes, electric heating bandage, electro-magnetic shielding cover and circuit
Printing plate etc..
To sum up, compared with prior art, invention achieves following technique effect：
(1) graphene oxide is crosslinked in fibrous inside, while redox graphene using the mode of irradiation, added
The electric conductivity of fiber, and can at least reach the conductivity level equal with conventional conductive fiber, provided for conventional conductive fiber
Preferable substitute, so as to avoid conventional conductive fibre technology it is complicated, of high cost the problems such as.
(2) stability of graphene oxide modified fibre is improved by increasing crosslinking agent；
(3) present invention before spinning and polymerization before add graphene oxide into fibre-forming polymer, from intramolecule to
The comprehensive performance of fiber is improved on the various dimensions such as outside.
Embodiment
Technical scheme is clearly and completely described below in conjunction with embodiment, but ability
Field technique personnel will be understood that following described embodiment is part of the embodiment of the present invention, instead of all the embodiments,
The present invention is merely to illustrate, and is not construed as limiting the scope of the invention.Based on the embodiments of the present invention, the common skill in this area
Art personnel all other embodiments obtained without making creative work, belong to the model that the present invention protects
Enclose.The person that is not specified actual conditions in embodiment, the condition suggested according to normal condition or manufacturer carry out.Agents useful for same or instrument
Production firm person is not specified, is the conventional products that can be obtained by commercially available purchase.
The type for the graphene oxide composite material that following embodiments of the present invention are provided has：
Graphene oxide A：The graphene oxide prepared by Hummers methods.
Graphene oxide B：The graphene oxide prepared by Brodie methods.
Embodiment 1
Prepare modified acrylic fibre
(1)：The mixed liquor of the A containing graphene oxide, including acrylonitrile are prepared, free radical scavenger (isopropanol), aoxidizes stone
Black alkene A and deionized water, take above raw material, stir and evenly mix, and the weight ratio of acrylonitrile and graphene oxide A are 90:3, obtain with
Lower concentration mixed liquor：
The concentration of free radical scavenger is 10mg/mL,
The concentration of graphene oxide A is 30mg/mL,
The concentration of water is 30mg/mL.
(2)：Above-mentioned mixed liquor is placed in closed container, air is excluded, is passed through inert gas, utilizes electron accelerator pair
Mixed liquor is irradiated.
The radiation dose rate uses 100KGy/h, exposure time 1h.
(3)：Using the solution after irradiation as spinning solution, electrostatic spinning, is made polyacrylonitrile fibre.
Polyacrylonitrile fibre after irradiation is tested for the property.
Embodiment 2 to 6
Embodiment 2 to 6 and embodiment 1 differ only in that radiation dose rate is different, remaining step and parameter are identical, implement
The radiation dose rate of example 2 to 6 is respectively：1KGy/h、10KGy/h、50KGy/h、200KGy/h、500KGy/h.
Embodiment 7 to 8
Embodiment 7 to 8 and embodiment 1 differ only in that monomeric species are different, remaining step and parameter are identical, embodiment
7 to 8 kinds of fibers is respectively：Propylene (embodiment 7), toluene di-isocyanate(TDI) and ethylene glycol 3:2 mixed in molar ratio (is implemented
Example 8).
Embodiment 9 to 12
Embodiment 9 to 12 and embodiment 1 to differ only in polymer monomer different with the weight ratio of graphene oxide, but
The proportioning of graphene oxide and free radical scavenger and water is constant, and the weight ratio of polymer monomer and graphene oxide is respectively
95:3 (embodiments 9), 100:3 (embodiments 10), 10:1 (embodiment 11), 9:1 (embodiment 12).
Embodiment 13 and 14
Embodiment 13 and 14 is different from the concentration for differing only in graphene oxide A in mixed liquor of embodiment 1, respectively
For：20mg/mL, 10mg/mL, and in the case of graphene oxide A and free radical scavenger, water proportioning inconvenience, Qi Tayuan
The concentration of material also respective change.
Embodiment 15,16
Embodiment 15,16 and embodiment 1 are difference lies in the type of free radical scavenger is different, by the isopropyl of embodiment 1
Alcohol replaces with respectively：Triethanolamine (embodiment 15), acetone (embodiment 16).
Embodiment 17
Graphene oxide A is replaced with oxygen difference lies in the type of graphene oxide is different by embodiment 17 and embodiment 1
Graphite alkene B.
Embodiment 18 to 20
Embodiment 18 to 20 is also added into crosslinking agent with differing only in for embodiment 1 in (1) step, crosslinking agent difference
For：Polyethyleneglycol diacrylate (embodiment 18), crosslinking agent DE (embodiment 19), crosslinking agent DE and silane coupling agent monomer etc.
Recombination (embodiment 20), and the concentration of crosslinking agent is 30mg/mL in the mixed liquor of embodiment 18 to 20.
Embodiment 21
Embodiment 21 is different from the concentration for differing only in crosslinking agent in mixed liquor of embodiment 18, is：90mg/mL.
Embodiment 22
Embodiment 22 is different with the proportioning of graphene oxide A difference lies in free radical scavenger, water from embodiment 1, the
In the mixing that one step is prepared, the concentration of free radical scavenger is 30mg/mL, and the concentration of graphene oxide A is 30mg/mL, water
Concentration is 50mg/mL.
Embodiment 23
Embodiment 23 is different with the proportioning of graphene oxide A difference lies in free radical scavenger, water from embodiment 1, the
In the mixing that one step is prepared, the concentration of free radical scavenger is 1mg/mL, and the concentration of graphene oxide A is 30mg/mL, water it is dense
Spend for 100mg/mL.
Comparative example 1
Comparative example 1 adds water, remaining step and parameter phase with embodiment 1 difference lies in no in the mixed liquor of the first step
Together.
Comparative example 2
Difference lies in, without free radical scavenger is added, remaining is walked in the mixed liquor of the first step with embodiment 1 for comparative example 1
Rapid and parameter is identical.
Comparative example 3
It is specific as follows with embodiment 1 difference lies in having completed to polymerize before irradiation：
(1)：Prepare the mixed liquor of the A containing graphene oxide, including polyacrylonitrile, free radical scavenger (isopropanol), oxidation
Graphene A, deionized water and and dimethylformamide, take above raw material, stirred and evenly mixed in dimethylformamide, polyacrylonitrile
Weight ratio with graphene oxide A is 90:3, obtain following concentration mixed liquor：
The concentration of free radical scavenger is 10mg/mL,
The concentration of graphene oxide A is 30mg/mL,
The concentration of water is 30mg/mL.
(2)：Above-mentioned mixed liquor is placed in closed container, air is excluded, is passed through inert gas, utilizes electron accelerator pair
Mixed liquor is irradiated.
The radiation dose rate uses 100KGy/h, exposure time 1h.
(3)：Using the solution after irradiation as spinning solution, electrostatic spinning, is made polyacrylonitrile fibre.
Polyacrylonitrile fibre after irradiation is tested for the property.
The performance of fiber is as shown in table 1 obtained by all of above embodiment and comparative example.
The performance of 1 graphene oxide modified fibre of table
Finally it should be noted that：The above embodiments are only used to illustrate the technical solution of the present invention., rather than its limitations；To the greatest extent
Pipe is described in detail the present invention with reference to foregoing embodiments, it will be understood by those of ordinary skill in the art that：Its according to
Can so modify to the technical solution described in foregoing embodiments, either to which part or all technical characteristic into
Row equivalent substitution；And these modifications or replacement, the essence of appropriate technical solution is departed from various embodiments of the present invention technology
The scope of scheme.
Claims (10)
1. a kind of preparation method of graphene oxide modified fibre, it is characterised in that comprise the following steps：
The monomer of graphene oxide, free radical scavenger, water and fibre-forming polymer is mixed, mixed liquor is made；
The mixed liquor is irradiated in an inert atmosphere, obtains spinning solution；
By the spinning solution spinning, graphene oxide modified fibre is made.
2. preparation method according to claim 1, it is characterised in that the fibre-forming polymer for polypropylene, polyacrylonitrile,
Polyamide, polyvinyl formal, polyurethanes, polyethylene terephthalate, polyvinyl chloride or makrolon；
Preferably, when the monomer is solid monomer not soluble in water, solvent is additionally added in the mixed liquor, dissolves the list
Body.
3. preparation method according to claim 1, it is characterised in that the concentration of graphene oxide exists in the mixed liquor
Below 30mg/mL, preferably below 20mg/mL, more preferably 10-20mg/mL.
4. according to claim 1-3 any one of them preparation methods, it is characterised in that the free radical scavenger is alcohol, amine
With the one or more in ketone；The alcohol is preferably selected from the one or more in methanol, ethanol and isopropanol；The amine preferably selects
One or more from monoethanolamine, diethanol amine and triethanolamine, preferably triethanolamine；The ketone is preferably acetone or butanone
Or both mixing.
5. according to claim 1-3 any one of them preparation methods, it is characterised in that the monomer of the fibre-forming polymer and institute
The weight ratio for stating graphene oxide is 90-100:3-10；
Preferably, the weight ratio of the free radical scavenger and graphene oxide is 0.1~3:3；
Preferably, the weight ratio of the water and graphene oxide is 5-10:3.
6. preparation method according to claim 1, it is characterised in that the dosage rate of the irradiation is 1-500KGy/h.
7. preparation method according to claim 1, it is characterised in that the spinning is electrostatic spinning or solution-polymerized SBR.
8. preparation method according to claim 1, it is characterised in that be additionally added crosslinking agent when preparing the mixed liquor；
Preferably, the crosslinking agent is in alkenes crosslinking agent, organic silicon crosslinking agent and epichlorohydrin resin class crosslinking agent
It is one or more of；
Preferably, the alkenes crosslinking agent be selected from polyethyleneglycol diacrylate, polyethylene polyamine, melamine triallyl,
One or more in triallyl cyanurate, trimethylolpropane tris-(3- aziridinyls)-propionic ester；
Preferably, the organic silicon crosslinking agent is silane coupling agent；
Preferably, the epichlorohydrin resin class crosslinking agent is crosslinking agent DE；
Preferably, the weight ratio of crosslinking agent described in the mixed liquor and the graphene oxide is 1-3:1.
9. a kind of graphene oxide modified fibre, it is characterised in that using claim 1-8 any one of them preparation method systems
.
10. the application of the graphene oxide modified fibre described in claim 9, it is characterised in that the graphene oxide is modified
Fiber is used to make conductive devices in electronics industry, power industry and aerospace industry, and the preferred electric heating of conductive devices is knitted
Thing, Electromagnetically shielding fabrics or circuit board.
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| CN108824760A (en) * | 2018-08-01 | 2018-11-16 | 北京启顺京腾科技有限责任公司 | A kind of foamed cement composite floor board and preparation method thereof of modified fibre enhancing |
| CN108823808A (en) * | 2018-06-28 | 2018-11-16 | 中原工学院 | A kind of preparation method of haze polylactic acid nano fiber film |
| CN109082727A (en) * | 2018-07-12 | 2018-12-25 | 山东佳星环保科技有限公司 | A kind of preparation method for the polyester blended fabric that graphene is modified |
| CN112090169A (en) * | 2020-08-12 | 2020-12-18 | 柳州紫荆技术转移中心有限公司 | Preparation method of graphene composite filtering material for efficient integrated water purification equipment for sewage treatment |
| CN113151911A (en) * | 2021-04-20 | 2021-07-23 | 东华大学 | Preparation method of antistatic wool fabric |
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| CN109082727A (en) * | 2018-07-12 | 2018-12-25 | 山东佳星环保科技有限公司 | A kind of preparation method for the polyester blended fabric that graphene is modified |
| CN108824760A (en) * | 2018-08-01 | 2018-11-16 | 北京启顺京腾科技有限责任公司 | A kind of foamed cement composite floor board and preparation method thereof of modified fibre enhancing |
| CN112090169A (en) * | 2020-08-12 | 2020-12-18 | 柳州紫荆技术转移中心有限公司 | Preparation method of graphene composite filtering material for efficient integrated water purification equipment for sewage treatment |
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| CN113151911B (en) * | 2021-04-20 | 2022-11-04 | 东华大学 | Preparation method of antistatic wool fabric |
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