CN105776190B - A kind of method that screw machine foaming and intumescing stretching prepares graphene microchip - Google Patents
A kind of method that screw machine foaming and intumescing stretching prepares graphene microchip Download PDFInfo
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- CN105776190B CN105776190B CN201610078250.6A CN201610078250A CN105776190B CN 105776190 B CN105776190 B CN 105776190B CN 201610078250 A CN201610078250 A CN 201610078250A CN 105776190 B CN105776190 B CN 105776190B
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- C01B2204/00—Structure or properties of graphene
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
- C01B2204/32—Size or surface area
Abstract
The present invention provides a kind of shearing force for rotating generation at a high speed by screw machine, the method that collaboration foaming and intumescing stretching prepares graphene microchip.This method is using natural flake graphite as primary raw material, while stripping by screw rod high shear, crystalline flake graphite therein is set to be stretched by the expansion of melt to the stretching action of polymer melt using bubble during polymer foaming, graphene microchip is obtained so as to peel off, overcome single mechanical stripping method and prepare the defect damaged during graphene microchip to graphene layer crystal structure excessive compression, preferably save the perfection of lattice of graphene, so as to obtain the graphene microchip that lateral dimension is more than 10 microns, make the number of plies of graphene microchip less, crystal structure is more complete and orderly.Realize efficient, low cost, cleaning, large-scale production high-quality graphene microplate under high shear conditions..
Description
Technical field
The present invention relates to grapheme material field, and in particular to a kind of screw machine foaming and intumescing stretching prepares graphene microchip
Method.
Background technology
Graphene is with sp2 hydridization between the two dimensional crystal with monoatomic layer thickness being made up of carbon atom, carbon atom
Mode bonds together to form mutually honeycomb crystal lattice network, its basic structural unit is benzene hexatomic ring, is considered as one layer and is stripped
Graphite flake.Graphene is most thin two-dimensional material in the world, and its thickness is only 0.35 nm.Carbon atom inside graphene is by very
The big conjugatedπbond of high bond energy is connected with each other, and its carbon-carbon bond length is about 0.142 nm.Connection between each carbon atom of graphene is non-
Often flexible, when applying external mechanical force, carbon atom face is with regard to flexural deformation.So, carbon atom avoids the need for being rearranged to fit
External force is answered, this also ensures that the stabilization of graphene-structured so that graphene is also harder than diamond, while can be as drawing rubber
Equally stretched.The lattice structure of this stabilization also makes graphene have outstanding electric conductivity.Electronics in graphene is in-orbit
When being moved in road, it will not be scattered because of lattice defect or introducing foreign atom.Because its interatomic force is very strong,
Under normal temperature, even if surrounding carbon atom is telescoped, the interference that the electronics in graphene is subject to is also very small.Therefore, because its is only
Special two-dimentional conjugated structure, graphene shows the physicochemical properties of many protrusions, including excellent electricity, calorifics, optics
With mechanical property and huge specific surface area.Include mechanical stripping method, oxidation-reduction method, chemical vapor deposition at present
Method, substrate are grown nonparasitically upon another plant the technologies of preparing of the graphenes such as method, chemical cleavage method.
Chinese invention patent application number 201310411516.0 discloses a kind of ball-milling preparation method of grapheme material, should
The mass volume ratio of graphitic carbon and the hexa-atomic aromatic ring of alkyl or condensed ring polyether nonionic surfactant is 1 by invention：2~1：15
Ball grinder is loaded on deionized water mixing, ball mill is fixed on 200-500rpm rotating speed ball milling 5-30 hours；It is transferred to again
In ionized water, 10-30min is centrifuged with 3000-8000rpm rotating speed, black upper strata soliquid is obtained, various concentrations are made
Graphene aqueous solution.But it is due to that medium ball is very big to the impulsive force of graphite linings, graphene is produced fault of construction, and production
Efficiency is low, it is difficult to volume production.
Chinese invention patent application number 201310238984.2 discloses a kind of convection gas shearing and peels off two-dimensional layer material
The method of material, this method peels off two-dimensional layer material by the shearing force of the cold and hot gas circulation convection current generation of high pressure, by anti-
The cold and hot gas shear action circulated again, can generate the two-dimensional material such as graphene of individual layer and a small number of layers.It the method reduce
Destruction of the production technology to two-dimensional layer inorganic material crystal structure.But because shearing force is produced by convection gas, shearing force
It is weaker, it is necessary to which the long-time iterative cycles collision of 2 hours or so, therefore yields poorly.
In order to realize that the volume production of graphene is peeled off, graphite oxide reducing process is generally used at present.This method is simple to operate, system
Standby cost is low, and graphene can be prepared on a large scale, it has also become effective way prepared by graphene.Its specific operation process is
First use the strong oxidizer concentrated sulfuric acid, concentrated nitric acid, potassium permanganate etc. by graphite oxidation into graphite oxide, oxidizing process is i.e. in graphite layers
Intert some oxygen-containing functional groups, so as to increase graphite layers away from then after sonicated a period of time, so that it may form single
Layer or several layers of graphene oxide, then graphene oxide is reduced into graphene with strong reductant hydrazine hydrate, sodium borohydride etc..But
It is easily to cause the crystal structure defects of graphene in oxidation-reduction process, destroy the electric property of graphene, have impact on it
In the application of electronic information field.In addition, substantial amounts of waste water can be produced, severe contamination is caused to environment, graphene is limited
Industrialized development.
Chinese invention patent application number 201110048734.3 discloses one kind and prepares graphene material based on chemical deposition
The method of material, the soluble-salt of graphitization catalyst is uniformly mixed with polymer and organic solvent, and is protected in inert atmosphere
Temperature of reactor is risen to 450~1000 DEG C under shield, reactor is passed through under inert gas shielding and carries out chemical deposition, stone is made
Black alkene material.Can meet that prepare with scale is high-quality, large-area graphene requirement, although can obtain quality can graphite
Alkene lamella, can also control the size of film, and preparation process pollution is few.But control condition requires harsh and with high costs, no
It is suitable to produce in enormous quantities, because of its higher cost, complicated technique and it is accurately controlled processing conditions at this stage and constrains this
The method of kind prepares the development of graphene, is additionally, since its product generally lamelliform, and need to be transferred into various matrixes
On, and it is larger to shift difficulty.
By contrast, mechanical stripping is more easy to obtain the graphene of low cost.The method of mechanical stripping is from the surface of graphite flake
Successively peel off and obtain graphene film.And existing machinery is peeled off acquisition graphene and not only yielded poorly, and the high energy consumption time is long.
The purpose for particularly reaching stripping by constantly refining in the process of lapping of strength, it is difficult to intactly protect the performance of graphene
Stay.
On the other hand, the excellent performance of graphene is badly in need of widely applying in fields such as composite, lubriation material, coating.
And existing machinery lift-off technology is difficult to meet this large-scale demand.Therefore graphene of the number of plies at 100 layers is prepared on a large scale
Microplate turns into the key breakthrough mouthful that graphene is applied.
Graphene microchip refers to that carbon-coating number is more than 10 layers, ultra-thin graphene stratiform of the thickness in 5-100 nanometer ranges
Accumulation body.Because graphene microchip maintains the original planar carbon hexatomic ring conjugation crystal structure of graphite, thickness is in nanometer
In range scale, its radial width can reach it is several to dozens of micron, with excellent mechanical strength, conduction, thermal conductivity
Can, and good lubrication, high temperature resistant and anticorrosion properties, had a wide range of applications in field of compound material.
The content of the invention
It is contemplated that graphene microchip is obtained by efficient, inexpensive, cleaning manufacture method, in order to improve graphite
Retain graphene excellent properties to greatest extent while alkene microplate yield, so as to propose a kind of by screw machine rotation production at a high speed
Raw shearing force, the method that collaboration foaming and intumescing stretching prepares graphene microchip.Foaming and intumescing is cooperateed with to stretch by screw rod shearing
The method for preparing graphene microchip.This method is using natural flake graphite as primary raw material, while stripping by screw rod high shear,
Crystalline flake graphite therein is set to be stretched by the expansion of melt to the stretching action of polymer melt using bubble during polymer foaming,
Graphene microchip is obtained so as to peeling off, is overcome when single mechanical stripping method prepares graphene microchip to graphene layer crystal structure
The defect of excessive compression damage, realizes efficient, low cost, cleaning, the high-quality graphite of large-scale production under high shear conditions.
Alkene microplate.
To solve the above problems, the present invention uses following technical scheme：
A kind of method that screw machine foaming and intumescing stretching prepares graphene microchip, it is characterised in that:With natural flake graphite
For primary raw material, foaming and intumescing stretch release is cooperateed with to prepare graphene by the screw extruder shearing force that rotation is produced at a high speed micro-
Piece, specific method is as follows：
1) by parts by weight 85-90 natural flake graphite, parts by weight 3-5 soluble-salt, parts by weight 1-3 activating agent,
Parts by weight 10-15 water adds reactor, and temperature of reaction kettle maintains 80-100 DEG C, and adjustment reactor speed of agitator is 50-
100rpm, stirring reaction 5-30 minutes makes soluble-salt infiltration in the Rotating fields of natural flake graphite, then by reactor
Temperature rises to more than 120 DEG C, is dried to obtain modified natural crystalline flake graphite；
2）By step 1）Obtain water-soluble thermoplastic polymer, the parts by weight of modified natural crystalline flake graphite and parts by weight 5-10
1-5 foaming agent is well mixed by high-speed mixer, is then fed into screw extruder, wherein described foaming agent is carbonic acid
At least one of ammonium, sodium acid carbonate, urea；
3）100 ~ 400 revs/min of the engine speed of screw extruder is set, and each area's extrusion temperature is controlled respectively：One to
Three 120 DEG C of areas ~ 140 DEG C, four to six 160 DEG C of areas ~ 180 DEG C, seven to nine 180 DEG C of areas ~ 200 DEG C, ten to No.12 District 180 DEG C ~ 160
DEG C, head discharging hole number is adjustable, by the regulation for the hole number that discharges, and head pressure is kept in 2 ~ 3 Mpa, in screw extruder
In extrusion, foaming agent produces microbubble rapid expanding, water-soluble thermoplastic polymer is stretched by high rate of extension
Effect, crystalline flake graphite therein is occurred injection through screw extruder discharge opening and formed by the effective stretch release of polymer, scattered
The foaming body of puffy；
3）By step 3）Obtained foaming body is immersed in the water, and is carried out dissolution, is cleaned, filters, being dried to obtain graphene microchip.
Described natural flake graphite fixed carbon ＞ 99.5%, piece footpath size is 20-50 μm.
Described soluble-salt is in sodium chloride, potassium chloride, calcium chloride, sodium sulphate, potassium sulfate, sodium metasilicate, potassium silicate
It is at least one.
Described activating agent is at least one of zincic acid ester, phosphate, titanate esters, Aluminate, stearate.
Described water-soluble thermoplastic polymer is at least one of thermoplastic starch, polyvinyl alcohol, polyoxyethylene.
Described screw extruder is equidirectional parallel double-screw extruder, cocurrent and parallel three-screw extruder, incorgruous part
Engage one kind in conical double screw extruder.
Screw extruder is a kind of continuous High shear device, including motor, shaft coupling, reduction box, distributor box, feeding
System, screw rod, machine barrel, exhaust etc., screw rod are modular construction, are combined by high shear type kneading block, are rotated by high speed,
The region of engagement of screw rod is set to produce the shearing continuously moved, exactly this efficient continuous shear stress effect is stripped crystalline flake graphite.
But due to excessive extruding, the efficiency of stripping is not high, and because extruding easily causes densification or the Rotating fields of graphite layers
Damage.The characteristics of present invention is prominent be crystalline flake graphite while screw extruder carries out high shear stripping, utilize polymer
Bubble makes crystalline flake graphite therein be stretched by the foaming and intumescing of melt to the stretching action of polymer melt during foaming, so as to shell
From obtaining graphene microchip.This foaming and intumescing stretching occurs in screw extruder, when air bubble expansion, the polymer of surrounding
Melt by the rate of extension of bubble the order of magnitude up to 106s-1, because polymer melt obtains 106s-1The height of the order of magnitude or so
Rate of extension, thus the ultrahigh in efficiency of this stretch release, i.e., in material is into screw rod to 10 minutes of discharging
Complete to peel off, realize the manufacture graphene microchip of efficient, inexpensive cleaning.
Further, the pressure set using Screw Extrusion head, is occurred injection by screw extruder discharge opening and forms fluffy
The foaming body of loose shape, is conducive to graphene microchip dissolution in subsequent treatment, thus with water-soluble thermoplastic polymer, solubility
The auxiliary materials such as salt are efficiently separated.
The method that a kind of screw machine foaming and intumescing stretching of the present invention prepares graphene microchip, passes through screw extruder high shear
While stripping, producing instantaneous bubble using foaming agent makes the crystalline flake graphite for adhering to water-soluble thermoplastic polymer produce quickly
Stretching action, it is micro- under screw rod shearing and the effect of water-soluble thermoplastic polymer melt drawn crystalline flake graphite to be peeled off into graphene
Piece.This stretch release is overcome at the damage that Strong shear extruding is caused to graphite Rotating fields, the graphene microchip thickness of acquisition
In the range of nanoscale, its radial width reach it is several to dozens of micron, with excellent mechanical strength, conduction, heat conduction
Performance, and good lubrication, high temperature resistant and anticorrosion properties, have a wide range of applications in field of compound material.
At present using mechanical stripping prepare graphene microchip be one kind can simply, efficiently, inexpensive, large-scale production stone
The method of black alkene microplate.But damage is caused to the Rotating fields of graphene by the way of grinding, and stirred using liquid phase intercalation
Mix stripping then poor due to peeling off directionality, therefore shearing force is not enough.A kind of screw machine foaming and intumescing stretching of the present invention prepares graphite
The method of alkene microplate, both ensure that high-strength shearing force, while having carried out quick stretching again, it is to avoid graphene layer structure
Damage, preferably saves the perfection of lattice of graphene, so that obtain lateral dimension is less than 15 nanometers more than 10 microns, thickness
Graphene microchip.This method that graphene microchip is prepared by shearing collaboration expansion stretching has industrial prospect and is adapted to
Large-scale production, with significant market application value.
The present invention cooperates with graphene microchip prepared by foaming and intumescing stretching using by screw rod shearing, with using ball milling at present
The graphene microchip that directly grinding, oxidization abrasive are restored is compared, and the lateral dimension of graphene microchip of the present invention is bigger, and the number of plies is more
Few, crystal structure is more complete and orderly, and production efficiency is significantly improved.Main performance contrast is as shown in table 1 below.
Table 1：
The method that a kind of screw machine foaming and intumescing stretching of the present invention prepares graphene microchip, stone is prepared with existing machinery stripping
Black alkene microchip technology is compared, and the characteristics of it is protruded and excellent effect are：
1st, bubble pair during polymer foaming is utilized while screw extruder carries out high shear stripping by crystalline flake graphite
The stretching action of polymer melt makes crystalline flake graphite therein be stretched by the expansion of melt, so as to peel off, to obtain graphene micro-
Piece.
2nd, pass through high shear and foaming and intumescing to stretch, it is to avoid the damage of graphene layer structure, preferably save graphite
The perfection of lattice of alkene, so as to obtain the graphene microchip that lateral dimension is more than 10 microns.Graphene microchip, the number of plies is less,
Crystal structure is more complete and orderly.
3rd, by shearing the method that collaboration expansion stretching prepares graphene microchip, the system of efficient, inexpensive cleaning is realized
Graphene microchip is made, with industrial prospect and suitable large-scale production, with significant market application value.
Embodiment
Below by way of embodiment, the present invention is described in further detail, but this should not be interpreted as to the present invention
Scope be only limitted to following example.In the case where not departing from above method thought of the present invention, according to ordinary skill
Various replacements or change that knowledge and customary means are made, should be included in the scope of the present invention.
Embodiment 1
The method that a kind of stretching of screw machine foaming and intumescing prepares graphene microchip, it is characterised in that using natural flake graphite as
Primary raw material, shearing stripping and foaming and intumescing stretching by screw extruder prepare graphene microchip, and specific method is as follows：
1) by the natural flake graphite of parts by weight 85, the sodium chloride of parts by weight 3, the odium stearate of parts by weight 1, parts by weight
10 water adds reactor, and temperature of reaction kettle maintains 80-100 DEG C, and adjustment reactor speed of agitator is 50-100rpm, stirring
Reaction 30 minutes, make soluble-salt infiltration in the Rotating fields of natural flake graphite, then by temperature of reaction kettle rise to 120 DEG C with
Above, it is dried to obtain modified natural crystalline flake graphite；
2）By step 1）Modified natural crystalline flake graphite is obtained with the thermoplastic starch of parts by weight 5, the ammonium carbonate of parts by weight 3 to lead to
Cross high-speed mixer to be well mixed, be then fed into equidirectional parallel double-screw extruder；
3）100 revs/min of the engine speed of equidirectional parallel double-screw extruder is set, and each area's extrusion temperature is controlled respectively
：One to three 120 DEG C of area ~ 140 DEG C, four to six 160 DEG C of areas ~ 180 DEG C, seven to nine 180 DEG C of areas ~ 200 DEG C, ten to No.12 District 180
DEG C ~ 160 DEG C, by the regulation for the hole number that discharges, head pressure is kept in 2 ~ 3 Mpa, in screw extruder extrusion, carbon
Sour ammonium produces microbubble rapid expanding, water-soluble thermoplastic polymer is stretched the order of magnitude of speed up to 106s-1Stretching
Effect, crystalline flake graphite therein is occurred injection through screw extruder discharge opening and formed by the effective stretch release of polymer, scattered
The foaming body of puffy；
3）By step 3）Obtained foaming body is immersed in the water, and is carried out dissolution, is cleaned, filters, being dried to obtain graphene microchip.
By test, obtained graphene microchip lateral dimension 85% is more than 10 μm；Thickness is less than 15nm.Added in rubber
2% graphene microchip, tensile strength improves more than 100%.
Embodiment 2
The method that a kind of stretching of screw machine foaming and intumescing prepares graphene microchip, it is characterised in that using natural flake graphite as
Primary raw material, shearing stripping and foaming and intumescing stretching by screw extruder prepare graphene microchip, and specific method is as follows：
1) by the fixed carbon ＞ 99.5% of parts by weight 90, piece footpath size is 20-50 μm of natural flake graphite, parts by weight 5
Potassium sulfate, the zincic acid ester of parts by weight 3, the water of parts by weight 10 add reactor, and temperature of reaction kettle maintains 80-100 DEG C, and adjustment is anti-
It is 100rpm to answer kettle speed of agitator, and stirring reaction 25 minutes makes potassium sulfate infiltration in the Rotating fields of natural flake graphite, so
Temperature of reaction kettle is risen to more than 120 DEG C afterwards, modified natural crystalline flake graphite is dried to obtain；
2）By step 1）Modified natural crystalline flake graphite is obtained to urinate with the polyoxyethylene of parts by weight 10, the foaming agent of parts by weight 4
Element is well mixed by high-speed mixer, is then fed into cocurrent and parallel three-screw extruder；
3）250 revs/min of the engine speed of cocurrent and parallel three-screw extruder is set, and each area's extrusion temperature is controlled respectively
：One to three 120 DEG C of area ~ 140 DEG C, four to six 160 DEG C of areas ~ 180 DEG C, seven to nine 180 DEG C of areas ~ 200 DEG C, ten to No.12 District 180
DEG C ~ 160 DEG C, head discharging hole number is adjustable, by the regulation for the hole number that discharges, and head pressure is kept in 2 ~ 3 Mpa, in screw rod
In extruder extrusion, foaming agent produces microbubble rapid expanding, makes water-soluble thermoplastic polymer by high rate of extension
Stretching action, crystalline flake graphite therein sprayed by the effective stretch release of polymer, scattered through screw extruder discharge opening
Penetrate the foaming body to form puffy；
3）By step 3）Obtained foaming body is immersed in the water, and is carried out dissolution, is cleaned, filters, being dried to obtain graphene microchip.
10wt% graphene microchip is added in PA66 nylon, its thermal conductivity brings up to 2.0W/mK by 0.4W/mK.
Embodiment 3
The method that a kind of stretching of screw machine foaming and intumescing prepares graphene microchip, it is characterised in that using natural flake graphite as
Primary raw material, shearing stripping and foaming and intumescing stretching by screw extruder prepare graphene microchip, and specific method is as follows：
1) by the natural flake graphite of parts by weight 85, the sodium metasilicate of parts by weight 5, the activating agent phosphate of parts by weight 2, again
The water for measuring part 15 adds reactor, and temperature of reaction kettle maintains 80-100 DEG C, and adjustment reactor speed of agitator is 50-100rpm,
Stirring reaction 5-30 minutes, makes sodium metasilicate infiltration in the Rotating fields of natural flake graphite, temperature of reaction kettle then is risen into 120
More than DEG C, it is dried to obtain modified natural crystalline flake graphite；
2）By step 1）Obtain modified natural crystalline flake graphite and parts by weight 10 water-soluble thermoplastic polymer polyvinyl alcohol,
The foaming agent sodium acid of parts by weight 5 is well mixed by high-speed mixer, is then fed into incorgruous part engagement conical double-screw
In extruder；
3）Incorgruous part is set to engage 100 revs/min of the engine speed of conical double screw extruder, each area's extrusion temperature point
Do not control：One to three 120 DEG C of area ~ 140 DEG C, four to six 160 DEG C of areas ~ 180 DEG C, seven to nine 180 DEG C of areas ~ 200 DEG C, ten to 12
180 DEG C ~ 160 DEG C of area, head discharging hole number is adjustable, by the regulation for the hole number that discharges, and keeps head pressure in 2 ~ 3 Mpa,
In screw extruder extrusion, foaming agent produces microbubble rapid expanding, water-soluble thermoplastic polymer is drawn by height
Stretch the stretching action of speed, crystalline flake graphite therein is by the effective stretch release of polymer, scattered, through screw extruder discharge opening
Occurs the foaming body that injection forms puffy；
3）By step 3）Obtained foaming body is immersed in the water, and is carried out dissolution, is cleaned, filters, being dried to obtain graphene microchip.
3wt% graphene microchip is added in makrolon, its conductance reaches 1.2*10-4S/CM。
Embodiment 4
The method that a kind of stretching of screw machine foaming and intumescing prepares graphene microchip, it is characterised in that using natural flake graphite as
Primary raw material, shearing stripping and foaming and intumescing stretching by screw extruder prepare graphene microchip, and specific method is as follows：
1) by the natural flake graphite of parts by weight 85, the soluble-salt calcium chloride of parts by weight 3, parts by weight 3 activating agent aluminium
Acid esters, the water of parts by weight 12 add reactor, and temperature of reaction kettle maintains 80-100 DEG C, and adjustment reactor speed of agitator is 50-
100rpm, stirring reaction 5-30 minutes makes soluble-salt infiltration in the Rotating fields of natural flake graphite, then by reactor
Temperature rises to more than 120 DEG C, is dried to obtain modified natural crystalline flake graphite；
2）By step 1）Obtain modified natural crystalline flake graphite and parts by weight 8 water-soluble thermoplastic polymer polyoxyethylene,
The foaming agent ammonium carbonate of parts by weight 1 is well mixed by high-speed mixer, screw extruder is then fed into, wherein described foaming
Agent is at least one of ammonium carbonate, sodium acid carbonate, urea；
3）300 revs/min of the engine speed of screw extruder is set, and each area's extrusion temperature is controlled respectively：One to three area
120 DEG C ~ 140 DEG C, four to six 160 DEG C of areas ~ 180 DEG C, seven to nine 180 DEG C of areas ~ 200 DEG C, ten to 180 DEG C of No.12 District ~ 160 DEG C, machine
Head discharging hole number is adjustable, by the regulation for the hole number that discharges, and head pressure is kept in 2 ~ 3 Mpa, in screw extruder extrusion
During, foaming agent produces microbubble rapid expanding, makes water-soluble thermoplastic polymer by the stretching action of high rate of extension,
Crystalline flake graphite therein is occurred injection through screw extruder discharge opening and is formed fluffy by the effective stretch release of polymer, scattered
The foaming body of shape；
3）By step 3）Obtained foaming body is immersed in the water, and is carried out dissolution, is cleaned, filters, being dried to obtain graphene microchip.
1wt% graphene microchip is added in corrosion-resistant epoxy paint, its salt fog resistance was improved to 4200 small by 600 hours
When, performance equivalent to add 20% zinc, thus than use zinc cost it is lower.
Claims (7)
1. a kind of method that screw machine foaming and intumescing stretching prepares graphene microchip, it is characterised in that:Using natural flake graphite as
Primary raw material, cooperates with foaming and intumescing stretch release to prepare graphene micro- by the screw extruder shearing force that rotation is produced at a high speed
Piece, specific method is as follows：
1) by parts by weight 85-90 natural flake graphite, parts by weight 3-5 soluble-salt, parts by weight 1-3 activating agent, weight
Part 10-15 water adds reactor, and temperature of reaction kettle maintains 80-100 DEG C, and adjustment reactor speed of agitator is 50-100rpm,
Stirring reaction 5-30 minutes, makes soluble-salt infiltration in the Rotating fields of natural flake graphite, then rises to temperature of reaction kettle
More than 120 DEG C, be dried to obtain modified natural crystalline flake graphite；
2）By step 1）Obtain modified natural crystalline flake graphite and parts by weight 5-10 water-soluble thermoplastic polymer, parts by weight 1-5
Foaming agent it is well mixed by high-speed mixer, screw extruder is then fed into, wherein described foaming agent is ammonium carbonate, carbon
At least one of sour hydrogen sodium, urea；
3）100 ~ 400 revs/min of the engine speed of screw extruder is set, and each area's extrusion temperature is controlled respectively：One to three area
120 DEG C ~ 140 DEG C, four to six 160 DEG C of areas ~ 180 DEG C, seven to nine 180 DEG C of areas ~ 200 DEG C, ten to 180 DEG C of No.12 District ~ 160 DEG C, machine
Head discharging hole number is adjustable, by the regulation for the hole number that discharges, and head pressure is kept in 2 ~ 3 MPa, in screw extruder extrusion
During, foaming agent produces microbubble rapid expanding, makes water-soluble thermoplastic polymer by the stretching action of high rate of extension,
Crystalline flake graphite therein is occurred injection through screw extruder discharge opening and is formed fluffy by the effective stretch release of polymer, scattered
The foaming body of shape；
4）By step 3）Obtained foaming body is immersed in the water, and is carried out dissolution, is cleaned, filters, being dried to obtain graphene microchip.
2. a kind of method that screw machine foaming and intumescing stretching prepares graphene microchip according to claim 1, it is characterised in that：
The described .5% of natural flake graphite fixed carbon ＞ 99, piece footpath size is 20-50 μm.
3. a kind of method that screw machine foaming and intumescing stretching prepares graphene microchip according to claim 1, it is characterised in that：
Described soluble-salt is at least one of sodium chloride, potassium chloride, calcium chloride, sodium sulphate, potassium sulfate, sodium metasilicate, potassium silicate.
4. a kind of method that screw machine foaming and intumescing stretching prepares graphene microchip according to claim 1, it is characterised in that：
Described activating agent is at least one of zincic acid ester, phosphate, titanate esters, Aluminate, stearate.
5. a kind of method that screw machine foaming and intumescing stretching prepares graphene microchip according to claim 1, it is characterised in that：
Described water-soluble thermoplastic polymer is at least one of thermoplastic starch, polyvinyl alcohol, polyoxyethylene.
6. a kind of method that screw machine foaming and intumescing stretching prepares graphene microchip according to claim 1, it is characterised in that：
Described screw extruder is equidirectional parallel double-screw extruder, cocurrent and parallel three-screw extruder, the engagement taper of incorgruous part
One kind in double screw extruder.
7. a kind of method that screw machine foaming and intumescing stretching prepares graphene microchip according to claim 1, it is characterised in that：
The shearing force produced that rotated at a high speed by screw extruder cooperates with foaming and intumescing stretching to refer to crystalline flake graphite in Screw Extrusion
While machine carries out high shear stripping, scale therein is made to the stretching action of polymer melt using bubble during foaming agent foam
Graphite is stretched by the foaming and intumescing of melt, and graphene microchip is obtained so as to peel off.
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| CN109608891B (en) * | 2018-11-26 | 2021-03-23 | 国宏中晶集团有限公司 | Graphene-containing high-elastic modulus composite material and preparation method thereof |
| CN110240154A (en) * | 2019-06-27 | 2019-09-17 | 中素新科技有限公司 | The preparation method of multi-layer graphene |
| EP4046961A4 (en) * | 2019-12-27 | 2023-02-15 | Tongxiang Small Boss Special Plastic Products Co., Ltd. | Cured product containing single-layer graphene, single-layer graphene, preparation method therefor, and article containing single-layer graphene |
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| US7662321B2 (en) * | 2005-10-26 | 2010-02-16 | Nanotek Instruments, Inc. | Nano-scaled graphene plate-reinforced composite materials and method of producing same |
| CN101817516A (en) * | 2010-05-21 | 2010-09-01 | 哈尔滨工业大学 | Method for preparing graphene or graphene oxide by using high-efficiency and low-cost mechanical stripping |
| CN104609413B (en) * | 2015-02-11 | 2016-08-24 | 合肥微晶材料科技有限公司 | A kind of tonne of class mechanical stripping device producing Graphene and production method thereof |
| CN105271206B (en) * | 2015-11-23 | 2017-05-10 | 成都新柯力化工科技有限公司 | Method for continuously preparing graphene material in cut mode through screw machine |
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