CN107475818A - Compound carbon fiber of graphene polyacrylonitrile-radical and preparation method thereof - Google Patents
Compound carbon fiber of graphene polyacrylonitrile-radical and preparation method thereof Download PDFInfo
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- CN107475818A CN107475818A CN201710712537.4A CN201710712537A CN107475818A CN 107475818 A CN107475818 A CN 107475818A CN 201710712537 A CN201710712537 A CN 201710712537A CN 107475818 A CN107475818 A CN 107475818A
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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
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
- D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
- D01F9/20—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products
- D01F9/21—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D01F9/22—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyacrylonitriles
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F292/00—Macromolecular compounds obtained by polymerising monomers on to inorganic materials
-
- 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
-
- 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
Abstract
The invention discloses compound carbon fiber of graphene polyacrylonitrile-radical and preparation method thereof, realize in accordance with the following steps：(1) graphene of surface modification is provided；(2) graphene of the surface modification is reacted in the first organic solvent with acrylonitrile monemer, to obtain graphene polyacrylonitrile compound；(3) the graphene polyacrylonitrile compound is subjected to spinning, to obtain graphene polyacrylonitrile composite fiber；(4) the graphene polyacrylonitrile composite fiber is pre-oxidized and carbonization treatment, to obtain the compound carbon fiber of graphene polyacrylonitrile-radical.There is higher mechanical property using the compound carbon fiber of graphene polyacrylonitrile-radical obtained by this method, specifically, compared with plain polypropylene itrile group carbon fiber, the filament strength of the compound carbon fiber of graphene polyacrylonitrile-radical of present invention gained can improve at least 8%, and modulus can improve at least 10%.
Description
Technical field
The invention belongs to technical field of polymer materials, and specifically, the present invention relates to graphene-polyacrylonitrile-radical is compound
Carbon fiber and preparation method thereof.
Background technology
Graphene has excellent mechanics, electricity and magnetic performance, turns into graphene/polymer composites and works as this life
The focus of boundary's research.But graphene is dispersed because the Van der Waals force of itself interlayer makes it be difficult in the polymer.Poly- third
Alkene nitrile is the important presoma for preparing carbon fiber, is had a wide range of applications in fields such as Aero-Space, industry.Into polyacrylonitrile
Graphene is added in precursor can increase sawtooth conformation, and crystallinity and crystal grain orientation lift the mechanical property of final carbon fiber.
Graphene is typically added by the method for blending, due to graphenic surface inertia with polymer interface active force is weak causes final fibre
The performance boost unobvious of dimension.Therefore, the existing technology for preparing the compound carbon fiber of graphene-polyacrylonitrile-radical is urgently improved.
The content of the invention
The technical problems to be solved by the invention are to provide a kind of compound carbon fiber of graphene-polyacrylonitrile-radical and its preparation
Method, there is higher mechanical property using the compound carbon fiber of graphene-polyacrylonitrile-radical obtained by this method, specifically, with it is general
Logical polyacrylonitrile-based carbon fibre is compared, and the filament strength of the compound carbon fiber of graphene-polyacrylonitrile-radical of present invention gained can carry
Height at least 8%, modulus can improve at least 10%.
In one aspect of the invention, the present invention proposes a kind of graphene-polyacrylonitrile-radical compound carbon fiber of preparing
Method.According to an embodiment of the invention, methods described includes：(1) graphene of surface modification is provided；(2) surface is repaiied
The graphene of decorations reacts with acrylonitrile monemer in the first organic solvent, to obtain graphene-polyacrylonitrile compound；(3)
The graphene-polyacrylonitrile compound is subjected to spinning, to obtain graphene-polyacrylonitrile composite fiber；(4) by described in
Graphene-polyacrylonitrile composite fiber is pre-oxidized and carbonization treatment, fine to obtain graphene-polyacrylonitrile-radical composite carbon
Dimension.
Preferably, in step (1), the graphene of the surface modification is selected from carboxylated graphene, acyl chlorides graphite
At least one of alkene and amination graphene.Thus, it is possible to ensure that the gained compound carbon fiber of graphene-polyacrylonitrile-radical has
Excellent mechanical property.
Preferably, graphene and the concentrated sulfuric acid and concentrated nitric acid will be reacted to obtain by the carboxylated graphene.
Preferably, the chloride graphene is to react the carboxylated graphene in a second organic solvent with acyl chlorides
Obtain.
Preferably, the amination graphene obtains the chloride graphene with reacting ethylenediamine.
Preferably, in step (2), the mass ratio of the graphene of the surface modification and the acrylonitrile monemer for 1~
5:1000.Thus, it is possible to further improve the mechanical property of the gained compound carbon fiber of graphene-polyacrylonitrile-radical.
Preferably, in step (2), the reaction temperature is 50~70 DEG C, and the time is 6~50 hours.Thus, it is possible to enter
One step improves the mechanical property of the gained compound carbon fiber of graphene-polyacrylonitrile-radical.
Preferably, in step (2), the graphene of the surface modification and the acrylonitrile monemer are organic described first
Solid content summation in solvent is 5~30wt%.Thus, it is possible to further improve gained graphene-polyacrylonitrile-radical composite carbon
The mechanical property of fiber.
Compared with the heart has technology, the method for preparing the compound carbon fiber of graphene-polyacrylonitrile-radical of the invention by using
The graphene of surface modification carries out reactive polymeric with propylene monomer, and polyacrylonitrile can be generated on graphene original position, and
There is higher interface cohesion, so as to obtain homogeneous graphite between the graphene and resulting polymers of the surface modification
Alkene-polyacrylonitrile compound, spinning, pre-oxidation and carbonization then are carried out to the graphene-polyacrylonitrile compound, due to graphite
Alkene can strengthen the mechanical property of gained carbon fiber as phase is strengthened, and not only intensity is high, good toughness for graphene, and compare
Surface area is big, heat conduction is good, big with the contact area of polymeric matrix so that and fiber is heated evenly, and reduces core-skin difference, so as to
To obtain the compound carbon fiber of graphene-polyacrylonitrile-radical of excellent in mechanical performance.Test result indicates that with plain polypropylene itrile group
Carbon fiber is compared, and the filament strength of the compound carbon fiber of graphene-polyacrylonitrile-radical of present invention gained can improve at least 8%, mould
Amount can improve at least 10%.
In another aspect of the invention, the present invention proposes a kind of compound carbon fiber of graphene-polyacrylonitrile-radical.According to
Embodiments of the invention, the compound carbon fiber of graphene-polyacrylonitrile-radical are prepared using method described above.By
This, the compound carbon fiber of graphene-polyacrylonitrile-radical has excellent mechanical property, test result indicates that, with plain polypropylene
Itrile group carbon fiber is compared, and the filament strength of the compound carbon fiber of graphene-polyacrylonitrile-radical of the invention can improve at least 8%, mould
Amount can improve at least 10%.It is it should be noted that above-mentioned for preparing described by the compound carbon fiber of graphene-polyacrylonitrile-radical
Feature and advantage are equally applicable to the compound carbon fiber of graphene-polyacrylonitrile-radical, and here is omitted.
Brief description of the drawings
Fig. 1 is the method flow according to an embodiment of the invention for preparing the compound carbon fiber of graphene-polyacrylonitrile-radical
Schematic diagram.
Embodiment
Below by conjunction with the embodiments and its Fig. 1 the invention will be further described, following examples be it is descriptive,
It is not limited, it is impossible to which protection scope of the present invention is limited with this.
In one aspect of the invention, the present invention proposes a kind of graphene-polyacrylonitrile-radical compound carbon fiber of preparing
Method.According to an embodiment of the invention, with reference to figure 1, this method includes：
S100：The graphene of surface modification is provided
In the step, the graphene of surface modification can be selected from carboxylated graphene, chloride graphene and amination
At least one of graphene.
According to one embodiment of present invention, carboxylated graphene is to be reacted graphene and the concentrated sulfuric acid and concentrated nitric acid
Obtain, specifically, graphene is added in the mixed solution of the concentrated sulfuric acid and concentrated nitric acid, ultrasonic disperse, be then stirred for bar
Oxidation reaction is carried out under part, obtains carboxylated graphene.Wherein, the mass concentration of the concentrated sulfuric acid and concentrated nitric acid of the present invention does not have
It is specifically limited, it can be used using the mass concentration of concentrated nitric acid well known to those skilled in the art and the concentrated sulfuric acid, such as concentrated sulfuric acid
Commercially available mass concentration be 98% the concentrated sulfuric acid, concentrated nitric acid can use commercially available mass concentration for 65% concentrated nitric acid.At this
In invention, the concentrated sulfuric acid and the concentrated nitric acid volume ratio is (1-9)：1, more preferably (2-6)：1；The quality of the graphene and institute
The cumulative volume ratio for stating the concentrated sulfuric acid and concentrated nitric acid is preferably (1-5) g：(60-120) ml, more preferably (1.5-4) g:(70-110)
ml.The present invention to it is described ultrasound and stirring method there is no special limitation, using it is well known to those skilled in the art ultrasound and
Stirring technique scheme；In this step, the temperature of the oxidation reaction is preferably 60-80 DEG C, more preferably 65-75 DEG C；
The time of the oxidation reaction is preferably 8-12h, more preferably 9-10h.After the oxidation reaction for completing the graphene, the present invention
The reaction product preferably obtained is filtered and dried, obtains carboxylated graphene.Filtering of the present invention and the side dried
Method does not have special limitation, using filtering well known to those skilled in the art and the technical scheme dried.
According to still a further embodiment, chloride graphene carboxylated graphene obtained above and acyl chlorides are the
Reaction obtains in two organic solvents.The present invention preferably by the carboxylated graphene dispersion organic solvent and acyl chlorides mixing
In solution, heating reflux reaction is carried out after well mixed, obtains chloride graphene.In the present invention, the acyl chlorides is preferred
Chloroacetic chloride, chlorobenzoyl chloride, the one or more of oxalyl chloride, more preferably nitrosyl chloride, chlorosulfuric acid, phosphoryl chloride phosphorus oxychloride and thionyl chloride
In one or more, be preferably thionyl chloride：The mass ratio of the carboxylated graphene and the acyl chlorides is (1-3)：
(60-110), more preferably (1.5-2.5)：(65-105).The present invention does not have special limitation to the species of the organic solvent,
Good reaction medium can be provided for carboxylated graphene and acyl chlorides, such as described organic solvent can be dimethyl sulfoxide (DMSO)
(DMSO)；The present invention to the dosage for having solvent also without special limitation, can be by the carboxylated graphene and acyl chlorides
Dissolving, in the present invention, the quality and the organic solvent and volume ratio of the added shield graphene are preferably (1-4) g：
(10-30) ml, more preferably (1.5-2.5) g:(15-25)ml.It is preferably in the temperature of heating reflux reaction of the present invention
60-80 DEG C, more preferably 65-75 DEG C；The time of the heating reflux reaction is preferably 4-8h, more preferably 5-7h；Complete institute
State carboxylated graphene and after the reaction of the acyl chlorides, obtained reaction solution is preferably evaporated under reduced pressure by the present invention, is distillated
Organic solvent and unnecessary acyl chlorides, then obtained solid is dried again, obtains the graphene of chloride.The present invention is to institute
Stating the method for vacuum distillation does not have special limitation, and those skilled in the art can select according to the species of the organic solvent of selection
Select the parameters such as the temperature and time of distillation.The present invention does not have special limitation to the method for the drying, using art technology
The technical scheme dried known to personnel.
According to still another embodiment of the invention, amination graphene is to obtain chloride graphene with reacting ethylenediamine
's.Present invention preferably employs the technical scheme of above-mentioned preparation chloride graphene, chloride graphene is prepared, then by institute
Chloride graphene and reacting ethylenediamine are stated, obtains amination graphene.In the present invention, the quality of the chloride graphene
Volume ratio with ethylenediamine is preferably (1-3) g：(40-30) ml, more preferably (1.5-3.5) g:(45-55)ml；The acyl chlorides
The temperature of graphite alkene and the reacting ethylenediamine is preferably 90-130 DEG C, more preferably 95-105 DEG C；The acyl chlorides graphite
Alkene and the reacting ethylenediamine time are preferably 12-50h, more preferably 24-48h；Complete chloride graphene and the second two
After the reaction of amine, obtained reaction solution is preferably filtered and washed with ethanol by the present invention, removes excessive ethylenediamine, then will
Obtained solid is dried, and obtains amination graphene.The present invention is not special to the method being filtered, washed and dried
Limitation, using the technical scheme well known to those skilled in the art being filtered, washed and dried.
S200：The graphene of surface modification is reacted in the first organic solvent with acrylonitrile monemer
In the step, the present invention preferably disperses the graphene of the surface modification in the first organic solvent, obtains stone
Black alkene suspension；Then under nitrogen protection, it is (even that acrylonitrile monemer, itaconic acid and initiator are added into graphene suspension
The isobutyl cyanogen of nitrogen two), reacted, obtain graphene-polyacrylonitrile compound.In the present invention, the graphite of the surface modification
Alkene and the reaction temperature of acrylonitrile monemer reaction are 50~70 DEG C, and the time is preferably 4-50h, and more preferably temperature is 60 DEG C, when
Between be 6-48h.The present invention does not have special limitation to the species of first organic solvent, using known to those skilled in the art
The graphene that can dissolve surface modification, acrylonitrile monemer, itaconic acid and initiator, such as can be dimethyl sulfoxide (DMSO)
And one or both of N, N '-dimethyl acetamide (DMAC) (DMSO).
In the present invention, the mass ratio of the graphene of the surface modification and the acrylonitrile monemer is 1~5：1000.Invention
People's discovery, the too low appearance phenomenon pockety of graphene content, and raising unobvious of the too high levels to mechanical property, by
This can significantly improve the mechanical property of final gained carbon fiber using the mixing ratio of the application.
Also, in the step, the graphene of the surface modification and the acrylonitrile monemer are in first organic solvent
In solid content summation be 5~30wt%.Inventor has found that the too low fibre forming property of solid content is poor, and solid content too high viscosity is very much not
Easily obtain uniform solution.
S300：Graphene-polyacrylonitrile compound is subjected to spinning
In the step, graphene-polyacrylonitrile compound is filtered and deaeration is obtained by above-mentioned, obtains graphene-poly-
Acrylonitrile spinning solution, the graphene-polyacrylonitrile spinning solution is subjected to spinning, it is compound to obtain graphene-polyacrylonitrile
Fiber.The present invention does not have special limitation to the method for the filtering and deaeration, using preparation well known to those skilled in the art
The filtering of spinning solution and deaeration technical scheme.And the present invention does not have special limitation to the method for the spinning, adopts
With spining technology scheme well known to those skilled in the art, in the present invention, the spinning is preferably dry-jet wet-spinning or wet
Spin.
S400：Graphene-polyacrylonitrile composite fiber is pre-oxidized and carbonization treatment
In the step, the graphene-polyacrylonitrile composite fiber is pre-oxidized and is carbonized, obtain graphene-poly-
The compound carbon fiber of acrylonitrile group.In the present invention, there is no special limitation to the pre-oxidation and carbonization method, using this area skill
The technical scheme for pre-oxidizing and being carbonized in the Preparation of PAN-based Carbon Fibers known to art personnel.Through what is be dried to obtain
Graphene-polyacrylonitrile composite fiber is successively by pre-oxidation and carbonization, the obtained compound carbon fiber of graphene-polyacrylonitrile-radical
It is collected on winder, completes the preparation process of whole fiber.
The method for preparing the compound carbon fiber of graphene-polyacrylonitrile-radical according to embodiments of the present invention is repaiied by using surface
The graphene of decorations carries out reactive polymeric with propylene monomer, and polyacrylonitrile, and the surface can be generated on graphene original position
There is higher interface cohesion, so as to obtain homogeneous graphene-poly- third between the graphene and resulting polymers of modification
Alkene nitrile compound, spinning, pre-oxidation and carbonization then are carried out to the graphene-polyacrylonitrile compound, due to graphene conduct
Strengthen phase, the mechanical property of gained carbon fiber can be strengthened, and not only intensity is high, good toughness for graphene, and specific surface area
Greatly, heat conduction is good, big with the contact area of polymeric matrix so that fiber is heated evenly, and reduces core-skin difference, so as to obtain
The compound carbon fiber of graphene-polyacrylonitrile-radical of excellent in mechanical performance.Test result indicates that with plain polypropylene itrile group carbon fiber
Compare, the filament strength of the compound carbon fiber of graphene-polyacrylonitrile-radical of present invention gained can improve at least 8%, and modulus can carry
Height at least 10%.
Below with reference to specific embodiment, present invention is described, it is necessary to which explanation, these embodiments are only to describe
Property, without limiting the invention in any way.
Embodiment 1
Addition 6.00g graphenes, the 150ml concentrated sulfuric acids and 60ml concentrated nitric acids in flask, the thermostatic ultrasonic 3h at 25 DEG C, then
Constant temperature stirs 24h at 70 DEG C；Room temperature is cooled to, adds deionized water dilution, stands until graphene precipitation, topples over upper strata
The stillness of night of brown color, the filtering of lower black suspension, washing is until filtrate into neutrality, obtains the black filter cake containing graphene；
Obtained black filter cake is dried into 48h under 100 DEG C of vacuum, carboxylated graphene is obtained, stores for future use；
At room temperature, the carboxylated graphene that 0.5g is obtained is added to ultrasonic disperse in 60ml dimethyl sulfoxide (DMSO)s (DMSO)
3h, obtain the DMSO suspension of the graphene of black even；Under nitrogen protection, once (1mol) is added into the suspension
Acrylonitrile, then add 2000mlDMSO thereto, it is after obtained mixed solution is reacted into 50h at 60 DEG C, obtained reaction is molten
Liquid is filtered, deaeration, obtains spinning solution：
Through 1000 holes, aperture 0.15mm, air layer height is 120mm；It is dried to obtain after as-spun fibre washing through hot-rolling
Carboxylated graphene-polyacrylonitrile composite fiber, then after drying, pre-oxidation and carbonization, obtain carboxylated graphene-polypropylene
The compound carbon fiber of itrile group.
Embodiment 2
Above-described embodiment 1 is added in flask and reacts obtained 6g carboxylated graphene, 11ml chloroacetic chlorides, 60ml dimethyl
Sulfoxide.The thermostatic ultrasonic 3h at 25 DEG C, then the constant temperature back flow reaction 6h at 70 DEG C；After cooling is well mixed be heated to reflux instead
Should, obtain chloride graphene.Obtained reaction solution is evaporated under reduced pressure, distillates organic solvent and unnecessary acyl chlorides, so
Obtained solid is dried in vacuo 48h at 100 DEG C again afterwards, the graphene for obtaining chloride stores for future use.
At room temperature, the chloride graphene that 0.5g is obtained is added to ultrasonic disperse in 60ml dimethyl sulfoxide (DMSO)s (DMSO)
3h, obtain the DMSO suspension of the chloride graphene of black even；Under nitrogen protection, once added into the suspension
(1mol) acrylonitrile, then add 2000mlDMSO thereto, after obtained mixed solution is reacted into 50h at 60 DEG C, by what is obtained
Reaction solution is filtered, deaeration, obtains spinning solution：
Through 1000 holes, aperture 0.15mm, air layer height is 120mm；It is dried to obtain after as-spun fibre washing through hot-rolling
Chloride graphene-polyacrylonitrile composite fiber, then after drying, pre-oxidation and carbonization, obtain chloride graphene-polypropylene
The compound carbon fiber of itrile group.
Embodiment 3
Above-described embodiment 2 is added in flask and reacts obtained 6g chlorides graphene, 240ml ethylenediamines.At 25 DEG C
Thermostatic ultrasonic 3h, then the isothermal reaction 30h at 100 DEG C；Room temperature is cooled to, filters and add the second two that ethanol washing removes excess
Amine, the black filter cake containing graphene is obtained, obtained black filter cake is dried into 48h under 100 DEG C of vacuum, obtains amino fossil
Black alkene, is stored for future use；
At room temperature, amination graphene 0.5g obtained is added to ultrasonic disperse in 60ml dimethyl sulfoxide (DMSO)s (DMSO)
3h, obtain the DMSO suspension of the amination graphene of black even；Under nitrogen protection, once added into the suspension
(1mol) acrylonitrile, then add 2000mlDMSO thereto, after obtained mixed solution is reacted into 50h at 60 DEG C, by what is obtained
Reaction solution is filtered, deaeration, obtains spinning solution：
Through 1000 holes, aperture 0.15mm, air layer height is 120mm；It is dried to obtain after as-spun fibre washing through hot-rolling
Amination graphene-polyacrylonitrile composite fiber, then after drying, pre-oxidation and carbonization, obtain amination graphene-polypropylene
The compound carbon fiber of itrile group.
Comparative example
Polyacrylonitrile-based carbon fibre is prepared using the technical scheme of embodiment, repaiied the difference is that not adding surface in comparative example
The graphene of decorations.
Conclusion：The polypropylene obtained to embodiment 1-3 gained graphene-compound carbon fiber of polyacrylonitrile-radical and comparative example
Itrile group carbon fiber carries out performance test, the results showed that, carboxylated graphene-polyacrylonitrile based composite fibre that embodiment 1 obtains
Filament strength be 3.78Gpa, modulus 260GPa, the monofilament of the gained graphene of embodiment 2-polyacrylonitrile based composite fibre is strong
Spend for 3.85Gpa, modulus 255GPa, the filament strength of the gained amination graphene of embodiment 3-polyacrylonitrile based composite fibre
For 3.88Gpa, modulus 263GPa, the filament strength of polyacrylonitrile-based carbon fibre is 3.5GPa obtained by comparative example, and its modulus is
230GPa, compared with the polyacrylonitrile-based carbon fibre that comparative example obtains, the gained carboxylated graphene of embodiment 1-polyacrylonitrile-radical
Compound carbon fiber strength improves 8%, and modulus improves 13%, and the gained chloride graphene of embodiment 2-polyacrylonitrile-radical is compound
Carbon fiber strength improves 10%, and modulus improves 11%, the gained amination graphene of embodiment 3-polyacrylonitrile-radical composite carbon
Fibre strength improves 11%, and modulus improves 14%.
Described above is only the preferred embodiments of the present invention, it is noted that for the ordinary skill people of the art
For member, without departing from the technical principles of the invention, some improvements and modifications can also be made, these improvements and modifications
Also it should be regarded as the protection domain do not invented.
Claims (9)
- A kind of 1. method for preparing the compound carbon fiber of graphene-polyacrylonitrile-radical, it is characterised in that including：(1) graphene of surface modification is provided；(2) graphene of the surface modification is reacted in the first organic solvent with acrylonitrile monemer, so as to obtain graphene- Polyacrylonitrile compound；(3) graphene-polyacrylonitrile compound is subjected to spinning, to obtain graphene-polyacrylonitrile composite fiber；(4) graphene-polyacrylonitrile composite fiber is pre-oxidized and carbonization treatment, to obtain graphene-poly- third The compound carbon fiber of alkene itrile group.
- 2. the method as described in claim 1, it is characterised in that in step (1), the graphene of the surface modification be selected from At least one of carboxylated graphene, chloride graphene and amination graphene.
- 3. method as claimed in claim 2, it is characterised in that the carboxylated graphene be by by graphene and the concentrated sulfuric acid and Concentrated nitric acid is reacted what is obtained.
- 4. method as claimed in claim 3, it is characterised in that the chloride graphene be by the carboxylated graphene with Acyl chlorides reacts what is obtained in a second organic solvent.
- 5. method as claimed in claim 4, it is characterised in that the amination graphene be by the chloride graphene with What reacting ethylenediamine obtained.
- 6. the method as described in claim 1, it is characterised in that in step (2), the graphene of the surface modification with it is described The mass ratio of acrylonitrile monemer is 1~5：1000.
- 7. method as claimed in claim 6, it is characterised in that in step (2), the reaction temperature is 50~70 DEG C, when Between be 6~50 hours.
- 8. the method as described in claim 1, it is characterised in that in step (2), the graphene of the surface modification and described Solid content summation of the acrylonitrile monemer in first organic solvent is 5~30wt%.
- A kind of 9. compound carbon fiber of graphene-polyacrylonitrile-radical, it is characterised in that the graphene-polyacrylonitrile-radical composite carbon Fiber is prepared using method any one of claim 1-8.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108166092A (en) * | 2017-12-30 | 2018-06-15 | 杭州高烯科技有限公司 | A kind of preparation method of polyacrylonitrile-graphene oxide composite fibre |
| CN111411412A (en) * | 2020-04-01 | 2020-07-14 | 华北水利水电大学 | Graphene-polyacrylonitrile-based nano composite material and preparation method and application thereof |
| CN113430680A (en) * | 2021-05-28 | 2021-09-24 | 南通强生石墨烯科技有限公司 | Graphene-carbon composite fiber prepared from graphene-itaconic acid monomer and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102560746A (en) * | 2011-12-29 | 2012-07-11 | 中国科学院宁波材料技术与工程研究所 | Preparation method of polyacrylonitrile/graphene composite-based carbon fiber |
| CN102586951A (en) * | 2012-01-18 | 2012-07-18 | 浙江大学 | Preparation method for composite carbon fiber based on graphene/ polyacrylonitrile |
| CN102586922A (en) * | 2012-01-18 | 2012-07-18 | 浙江大学 | Preparation method for macroscopic fiber of polyacrylonitrile grafted graphene |
| CN102704027A (en) * | 2012-06-14 | 2012-10-03 | 东华大学 | Preparation method for graphene oxide-modified PAN carbon fiber precursor |
| CN104846466A (en) * | 2015-04-09 | 2015-08-19 | 浙江泰索科技有限公司 | High thermal conductivity polyacrylonitrile fiber and preparation method thereof |
-
2017
- 2017-08-18 CN CN201710712537.4A patent/CN107475818A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102560746A (en) * | 2011-12-29 | 2012-07-11 | 中国科学院宁波材料技术与工程研究所 | Preparation method of polyacrylonitrile/graphene composite-based carbon fiber |
| CN102586951A (en) * | 2012-01-18 | 2012-07-18 | 浙江大学 | Preparation method for composite carbon fiber based on graphene/ polyacrylonitrile |
| CN102586922A (en) * | 2012-01-18 | 2012-07-18 | 浙江大学 | Preparation method for macroscopic fiber of polyacrylonitrile grafted graphene |
| CN102704027A (en) * | 2012-06-14 | 2012-10-03 | 东华大学 | Preparation method for graphene oxide-modified PAN carbon fiber precursor |
| CN104846466A (en) * | 2015-04-09 | 2015-08-19 | 浙江泰索科技有限公司 | High thermal conductivity polyacrylonitrile fiber and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 王国建: "《高分子现代合成方法与技术》", 31 July 2013, 同济大学出版社 * |
| 胡桢等: "《新型高分子合成与制备工艺》", 31 May 2014, 哈尔滨工业大学出版社 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108166092A (en) * | 2017-12-30 | 2018-06-15 | 杭州高烯科技有限公司 | A kind of preparation method of polyacrylonitrile-graphene oxide composite fibre |
| CN111411412A (en) * | 2020-04-01 | 2020-07-14 | 华北水利水电大学 | Graphene-polyacrylonitrile-based nano composite material and preparation method and application thereof |
| CN111411412B (en) * | 2020-04-01 | 2022-07-26 | 华北水利水电大学 | Graphene-polyacrylonitrile-based nano composite material and preparation method and application thereof |
| CN113430680A (en) * | 2021-05-28 | 2021-09-24 | 南通强生石墨烯科技有限公司 | Graphene-carbon composite fiber prepared from graphene-itaconic acid monomer and preparation method thereof |
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