CN105776190A - Method for preparing graphene micro-sheets through foaming expansion and stretching of screw machine - Google Patents
Method for preparing graphene micro-sheets through foaming expansion and stretching of screw machine Download PDFInfo
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- CN105776190A CN105776190A CN201610078250.6A CN201610078250A CN105776190A CN 105776190 A CN105776190 A CN 105776190A CN 201610078250 A CN201610078250 A CN 201610078250A CN 105776190 A CN105776190 A CN 105776190A
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- C01B2204/00—Structure or properties of graphene
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- C—CHEMISTRY; METALLURGY
- 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
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- C01B2204/32—Size or surface area
Abstract
The invention provides a method for preparing graphene micro-sheets through a shear force produced by a screw machine in high-speed rotation in cooperation with foaming expansion and stretching.The method uses natural flake graphite as a main raw material and utilizes the polymer melt stretching effect of air bubbles during polymer foaming to make the flake graphite subjected to the expansion and stretching of a melt, and accordingly the graphene micro-sheets are obtained through stripping.The defect that a graphene layer crystal structure is excessively extruded and damaged by adopting a single mechanical stripping method during graphene micro-sheet preparation is overcome, the crystal lattice integrity of the graphene is better kept, accordingly the graphene micro-sheets with the lateral dimension greater than 10 microns are obtained, the layer number of the graphene micro-sheets is smaller, and a crystal structure is more complete and orderly.High-efficiency, low-cost, clean and large-scale production of high-quality graphene micro-sheets under the high shear condition is achieved.
Description
Technical field
The present invention relates to grapheme material field, be specifically related to a kind of method that screw machine foaming and intumescing stretches preparation graphene microchip.
Background technology
Graphene is the two dimensional crystal with monoatomic layer thickness being made up of carbon atom, is bonded mutually formation honeycomb crystal lattice network between carbon atom with sp2 hybrid form, and its basic structural unit is benzene hexatomic ring, is considered as one layer of graphite flake being stripped.Graphene is two-dimensional material the thinnest in the world, and its thickness is only 0.35nm.Carbon atom within Graphene is connected with each other by the big conjugatedπbond of significantly high bond energy, and its carbon-carbon bond length is about 0.142nm.Connection between each carbon atom of Graphene is very pliable and tough, and when applying external mechanical force, carbon atom face is with regard to flexural deformation.So, carbon atom avoids the need for being rearranged to adapt to external force, and this also ensures that stablizing of graphene-structured so that Graphene is also harder than diamond, can stretch as drawing rubber simultaneously.This stable lattice structure also makes Graphene have outstanding electric conductivity.When electronics in Graphene moves in track, scattering will not be there is because of lattice defect or introducing foreign atom.Owing to its interatomic force is very strong, at normal temperatures, even if around carbon atom telescopes, the electronics experienced interference in Graphene is also very little.Accordingly, because the two-dimentional conjugated structure of its uniqueness, Graphene shows many prominent physicochemical properties, including excellent electricity, calorifics, optics and mechanical property and huge specific surface area.At present existing include mechanical stripping method, oxidation-reduction method, chemical vapour deposition technique, substrate grow nonparasitically upon another plant the technology of preparing of the Graphene such as method, chemistry cleavage method.
Chinese invention patent application number 201310411516.0 discloses the ball-milling preparation method of a kind of grapheme material, the mass volume ratio of hexa-atomic to graphitic carbon and alkyl aromatic ring or condensed ring polyether nonionic surfactant is 1:2～1:15 by this invention and deionized water mixes and is loaded on ball grinder, is fixed on ball mill rotating speed ball milling 5-30 hour with 200-500rpm；Proceed to again in deionized water, with the centrifugal 10-30min of the rotating speed of 3000-8000rpm, obtain black upper strata soliquid, prepare variable concentrations graphene aqueous solution.But owing to medium ball is very big to the impulsive force of graphite linings, makes Graphene produce 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 and shears the method peeling off two-dimensional layer material, the shearing force that the method is produced by the cold and hot gas circulative convection of high pressure peels off two-dimensional layer material, by the cold and hot gas shear action of iterative cycles, it is possible to generate the two-dimensional material such as Graphene of monolayer and minority layer.The method reduce the production technology destruction to two-dimensional layer inorganic material crystal structure.But owing to shearing force relies on convection gas to produce, shearing force is more weak, it is necessary to the long-time iterative cycles collision of 2 hours, therefore yield poorly.
Volume production in order to realize Graphene is peeled off, and generally adopts graphite oxide reducing process at present.The method is simple to operate, preparation cost is low, it is possible to prepare Graphene on a large scale, it has also become effective way prepared by Graphene.Its specific operation process is first with strong oxidizer concentrated sulphuric acid, concentrated nitric acid, potassium permanganate etc., graphite oxidation to become graphite oxide, namely oxidizing process interts some oxygen-containing functional groups in graphite layers, thus increase graphite layers from, then after sonicated a period of time, just can form monolayer or several layers of graphene oxide, then with strong reductant hydrazine hydrate, sodium borohydride etc., graphene oxide is reduced into Graphene.But, easily caused by the crystal structure defects of Graphene in oxidation-reduction process, destroy the electric property of Graphene, have impact on its application at electronic information field.It addition, substantial amounts of waste water can be produced, environment is caused severe contamination, limit the industrialized development of Graphene.
Chinese invention patent application number 201110048734.3 discloses a kind of method that chemically based sedimentation prepares grapheme material; by the soluble-salt of graphitization catalyst and polymer and organic solvent Homogeneous phase mixing; and under inert atmosphere protection, temperature of reactor is risen to 450～1000 DEG C; under inert gas shielding, pass into reactor carry out chemical deposition, prepare grapheme material.Can meeting scale and prepare the requirement of high-quality, large-area graphene, although can obtain the graphene sheet layer of quality energy, it is also possible to control the size of thin film, preparation process is polluted few.But the condition of control requires harshness, and it is with high costs, it is not suitable for producing in enormous quantities, present stage is because of its higher cost, complicated technique and is accurately controlled processing conditions and constrains this method and prepare the development of Graphene, and, owing to its product is generally lamelliform, and need to be transferred on various matrix, and it is bigger to shift difficulty.
By contrast, mechanical stripping is more easy to the Graphene obtaining low cost.The method of mechanical stripping carries out from the surface of graphite flake successively peeling off obtaining graphene film.And existing machinery is peeled off acquisition Graphene and not only yielded poorly, and the energy consumption height time is long.Particularly constantly refinement is relied on to reach the purpose peeled off at powerful process of lapping, it is difficult to the performance of Graphene intactly to be retained.
On the other hand, the performance that Graphene is excellent 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 prepare the number of plies on a large scale and become the key breakthrough mouth of Graphene application the graphene microchip of 100 layers.
Graphene microchip refers to the ultra-thin Graphene stratiform accumulation body that carbon-coating number is more than 10 layers, thickness is in 5-100 nanometer range.Owing to graphene microchip maintains graphite original planar carbon hexatomic ring conjugation crystal structure, thickness is within the scope of nanoscale, its radial width can reach several to dozens of micron, there is the mechanical strength of excellence, conduction, heat conductivility, and good lubrication, high temperature resistant and anticorrosion properties, have a wide range of applications in field of compound material.
Summary of the invention
It is contemplated that obtain graphene microchip by manufacture method efficient, low cost, cleaning, in order to retain Graphene excellent properties to greatest extent while improving graphene microchip yield, thus proposing a kind of shearing force produced by screw machine high speed rotating, the method that collaborative foaming and intumescing stretches preparation graphene microchip.By the method that the collaborative foaming and intumescing of screw rod shearing stretches preparation graphene microchip.The method is with natural flake graphite for primary raw material; while being peeled off by screw rod high shear; when utilizing polymer foaming, the stretching action of polymer melt is made the expansion that crystalline flake graphite therein is subject to melt stretch by bubble; graphene microchip is obtained thus peeling off; overcome the defect to the damage of graphene layer crystal structure excessive compression when single mechanical stripping method prepares graphene microchip, it is achieved that under high shear conditions. efficiently, low cost, cleaning, large-scale production high-quality graphene microplate.
For solve the problems referred to above, the present invention by the following technical solutions:
A kind of screw machine foaming and intumescing stretches the method for preparation graphene microchip, it is characterized in that: with natural flake graphite for primary raw material, the collaborative foaming and intumescing stretch release of shearing force produced by screw extruder high speed rotating prepares graphene microchip, and concrete grammar is as follows:
1) water of the natural flake graphite of weight portion 85-90, the soluble-salt of weight portion 3-5, the activating agent of weight portion 1-3, weight portion 10-15 is added reactor, temperature of reaction kettle maintains 80-100 DEG C, adjusting reactor speed of agitator is 50-100rpm, stirring reaction 5-30 minute, make soluble-salt permeate in the Rotating fields of natural flake graphite, then temperature of reaction kettle is risen to more than 120 DEG C, dry obtain modified natural crystalline flake graphite；
2) step 1) obtains modified natural crystalline flake graphite to be mixed homogeneously by high-speed mixer with the foaming agent of the water-soluble thermoplastic polymer of weight portion 5-10, weight portion 1-5, being then fed into screw extruder, wherein said foaming agent is at least one in ammonium carbonate, sodium bicarbonate, carbamide；
3) engine speed 100 ~ 400 revs/min of screw extruder is set, each district extrusion temperature controls respectively: one to three 120 DEG C of district ~ 140 DEG C, four to six 160 DEG C of districts ~ 180 DEG C, seven to nine 180 DEG C of districts ~ 200 DEG C, 180 DEG C ~ 160 DEG C, ten to No.12 District, head discharge opening quantity is adjustable, adjustment by discharge opening quantity, keep head pressure at 2 ~ 3Mpa, in screw extruder extrusion, foaming agent produces microbubble rapid expanding, water-soluble thermoplastic polymer is made to be subject to the stretching action of high rate of extension, crystalline flake graphite therein is by the effective stretch release of polymer, dispersion, injection is occurred to form the foaming body of puffy through screw extruder discharge opening；
3) foaming body that step 3) obtains is immersed in the water, carries out dissolution, cleaning, filtration, dry obtain graphene microchip.
Described natural flake graphite fixed carbon > 99.5%, sheet footpath is sized to 20-50 μm.
Described soluble-salt is at least one in sodium chloride, potassium chloride, calcium chloride, sodium sulfate, potassium sulfate, sodium silicate, potassium silicate.
Described activating agent is at least one in zincic acid ester, phosphate ester, titanate esters, Aluminate, stearate.
Described water-soluble thermoplastic polymer is at least one in thermoplastic starch, polyvinyl alcohol, polyoxyethylene.
Described screw extruder is the one in equidirectional parallel double-screw extruder, cocurrent and parallel three-screw extruder, incorgruous part engagement conical double screw extruder.
Screw extruder is a kind of High shear device continuously, including drive motor, shaft coupling, reduction box, distributor box, feed system, screw rod, machine barrel, aerofluxus etc., screw rod is modular construction, combined by high shear type kneading block, pass through high speed rotating, the region of engagement making screw rod produces the shearing of motion continuously, and this efficient continuous shear stress effect, makes crystalline flake graphite be stripped just.But due to excessive extruding, the efficiency of stripping is not high, and owing to extruding easily causes the densification of graphite layers or the damage of Rotating fields.The feature that the present invention highlights is that crystalline flake graphite is screw extruder carries out high shear stripping while, when utilizing polymer foaming, the stretching action of polymer melt is made the foaming and intumescing that crystalline flake graphite therein is subject to melt stretch by bubble, obtains graphene microchip thus peeling off.This foaming and intumescing stretches and occurs in screw extruder, and when air bubble expansion, polymer melt around is subject to the order of magnitude of the rate of extension of bubble up to 106s-1, owing to polymer melt obtains 106s-1High rate of extension about the order of magnitude, thus the ultrahigh in efficiency of this stretch release, namely enter screw rod at material and peel off to can complete in 10 minutes of discharging, it is achieved that the manufacture graphene microchip of efficient, low cost, cleaning.
Further, utilize the pressure that Screw Extrusion head sets, occurring injection to form the foaming body of puffy by screw extruder discharge opening, being conducive to graphene microchip dissolution in subsequent treatment, thus efficiently separating with the auxiliary material such as water-soluble thermoplastic polymer, soluble-salt.
The method that a kind of screw machine foaming and intumescing of the present invention stretches preparation graphene microchip, while being peeled off by screw extruder high shear, utilize foaming agent to produce instantaneous bubble and make to adhere to the crystalline flake graphite generation Rapid stretching effect of water-soluble thermoplastic polymer, under screw rod shearing with water-soluble thermoplastic polymer melt drawn effect, crystalline flake graphite is peeled off into graphene microchip.This stretch release overcomes Strong shear and extrudes the damage that graphite linings structure is caused, the graphene microchip thickness obtained is within the scope of nanoscale, its radial width reaches several to dozens of micron, there is the mechanical strength of excellence, conduction, heat conductivility, and good lubrication, high temperature resistant and anticorrosion properties, have a wide range of applications in field of compound material.
Adopt at present mechanical stripping prepare graphene microchip be a kind of can simply, the method for efficient, low cost, large-scale production graphene microchip.But adopt the mode ground that the Rotating fields of Graphene is caused damage, and adopt liquid phase intercalation stirring to peel off then poor owing to peeling off directionality, therefore shearing force is not enough.The method that a kind of screw machine foaming and intumescing of the present invention stretches preparation graphene microchip, both ensure that high-strength shearing force, carried out again quick stretching simultaneously, avoid the damage of graphene layer structure, save the perfection of lattice of Graphene preferably, thus obtain lateral dimension more than 10 microns, the thickness graphene microchip less than 15 nanometers.This method stretching preparation graphene microchip by shearing collaborative expansion has industrial prospect and applicable large-scale production, has significant market using value.
The present invention adopts the graphene microchip being stretched preparation by the collaborative foaming and intumescing of screw rod shearing, compared with adopting the graphene microchip that ball milling directly grinds, oxidization abrasive restores at present, the lateral dimension of graphene microchip of the present invention is bigger, the number of plies is less, crystal structure is more complete and orderly, and production efficiency significantly improves.Main performance contrast is as shown in table 1 below.
Table 1:
The method that a kind of screw machine foaming and intumescing of the present invention stretches preparation graphene microchip, peels off compared with preparation graphene microchip technology with existing machinery, and its prominent feature and excellent effect are in that:
1, by crystalline flake graphite while screw extruder carries out high shear stripping, when utilizing polymer foaming, the stretching action of polymer melt is made the expansion that crystalline flake graphite therein is subject to melt stretch by bubble, obtains graphene microchip thus peeling off.
2, being stretched by high shear and foaming and intumescing, it is to avoid the damage of graphene layer structure, saving the perfection of lattice of Graphene preferably, thus obtaining the lateral dimension graphene microchip more than 10 microns.Graphene microchip, the number of plies is less, and crystal structure is more complete and orderly.
3, by shearing the collaborative method expanding and stretching preparation graphene microchip, it is achieved that efficiently, the manufacture graphene microchip of low cost, cleaning, there is industrial prospect and applicable large-scale production, there is significant market using value.
Detailed description of the invention
Below by way of detailed description of the invention, the present invention is described in further detail, but this should not being interpreted as, the scope of the present invention is only limitted to Examples below.When without departing from said method thought of the present invention, the various replacements made according to ordinary skill knowledge and customary means or change, should be included in the scope of the present invention.
Embodiment 1
A kind of screw machine foaming and intumescing stretches the method for preparation graphene microchip, it is characterised in that with natural flake graphite for primary raw material, stretches preparation graphene microchip by the shearing stripping of screw extruder and foaming and intumescing, and concrete grammar is as follows:
1) water of the natural flake graphite of weight portion 85, the sodium chloride of weight portion 3, the sodium stearate of weight portion 1, weight portion 10 is added reactor, temperature of reaction kettle maintains 80-100 DEG C, adjusting reactor speed of agitator is 50-100rpm, stirring reaction 30 minutes, make soluble-salt permeate in the Rotating fields of natural flake graphite, then temperature of reaction kettle is risen to more than 120 DEG C, dry obtain modified natural crystalline flake graphite；
2) step 1) obtains modified natural crystalline flake graphite to be mixed homogeneously by high-speed mixer with the ammonium carbonate of the thermoplastic starch of weight portion 5, weight portion 3, be then fed into equidirectional parallel double-screw extruder；
3) engine speed 100 revs/min of equidirectional parallel double-screw extruder is set, each district extrusion temperature controls respectively: one to three 120 DEG C of district ~ 140 DEG C, four to six 160 DEG C of districts ~ 180 DEG C, seven to nine 180 DEG C of districts ~ 200 DEG C, 180 DEG C ~ 160 DEG C, ten to No.12 District, by the adjustment of discharge opening quantity, keep head pressure at 2 ~ 3Mpa, in screw extruder extrusion, ammonium carbonate produces microbubble rapid expanding, makes the order of magnitude that water-soluble thermoplastic polymer is stretched speed reach 106s-1Stretching action, crystalline flake graphite therein by the effective stretch release of polymer, dispersion, occurs injection to form the foaming body of puffy through screw extruder discharge opening；
3) foaming body that step 3) obtains is immersed in the water, carries out dissolution, cleaning, filtration, dry obtain graphene microchip.
By testing, the graphene microchip lateral dimension 85% obtained is more than 10 μm；Thick in 15nm.Adding the graphene microchip of 2% in rubber, hot strength improves more than 100%.
Embodiment 2
A kind of screw machine foaming and intumescing stretches the method for preparation graphene microchip, it is characterised in that with natural flake graphite for primary raw material, stretches preparation graphene microchip by the shearing stripping of screw extruder and foaming and intumescing, and concrete grammar is as follows:
1) by weight portion 90 fixed carbon > 99.5%, sheet footpath be sized to 20-50 μm natural flake graphite, the potassium sulfate of weight portion 5, the zincic acid ester of weight portion 3, weight portion 10 water add reactor, temperature of reaction kettle maintains 80-100 DEG C, adjusting reactor speed of agitator is 100rpm, stirring reaction 25 minutes, make potassium sulfate permeate in the Rotating fields of natural flake graphite, then temperature of reaction kettle is risen to more than 120 DEG C, dry obtain modified natural crystalline flake graphite；
2) step 1) obtains modified natural crystalline flake graphite mixed homogeneously by high-speed mixer with the foaming agent carbamide of the polyoxyethylene of weight portion 10, weight portion 4, be then fed into cocurrent and parallel three-screw extruder；
3) engine speed 250 revs/min of cocurrent and parallel three-screw extruder is set, each district extrusion temperature controls respectively: one to three 120 DEG C of district ~ 140 DEG C, four to six 160 DEG C of districts ~ 180 DEG C, seven to nine 180 DEG C of districts ~ 200 DEG C, 180 DEG C ~ 160 DEG C, ten to No.12 District, head discharge opening quantity is adjustable, adjustment by discharge opening quantity, keep head pressure at 2 ~ 3Mpa, in screw extruder extrusion, foaming agent produces microbubble rapid expanding, water-soluble thermoplastic polymer is made to be subject to the stretching action of high rate of extension, crystalline flake graphite therein is by the effective stretch release of polymer, dispersion, injection is occurred to form the foaming body of puffy through screw extruder discharge opening；
3) foaming body that step 3) obtains is immersed in the water, carries out dissolution, cleaning, filtration, dry obtain graphene microchip.
Adding the graphene microchip of 10wt% in PA66 nylon, its thermal conductivity is brought up to 2.0W/mK by 0.4W/mK.
Embodiment 3
A kind of screw machine foaming and intumescing stretches the method for preparation graphene microchip, it is characterised in that with natural flake graphite for primary raw material, stretches preparation graphene microchip by the shearing stripping of screw extruder and foaming and intumescing, and concrete grammar is as follows:
1) water of the natural flake graphite of weight portion 85, the sodium silicate of weight portion 5, the activating agent phosphate ester of weight portion 2, weight portion 15 is added reactor, temperature of reaction kettle maintains 80-100 DEG C, adjusting reactor speed of agitator is 50-100rpm, stirring reaction 5-30 minute, make sodium silicate permeate in the Rotating fields of natural flake graphite, then temperature of reaction kettle is risen to more than 120 DEG C, dry obtain modified natural crystalline flake graphite；
2) step 1) obtains modified natural crystalline flake graphite mixed homogeneously by high-speed mixer with the foaming agent sodium bicarbonate of the water-soluble thermoplastic polymer polyvinyl alcohol of weight portion 10, weight portion 5, be then fed in incorgruous part engagement conical double screw extruder；
3) engine speed 100 revs/min of incorgruous part engagement conical double screw extruder is set, each district extrusion temperature controls respectively: one to three 120 DEG C of district ~ 140 DEG C, four to six 160 DEG C of districts ~ 180 DEG C, seven to nine 180 DEG C of districts ~ 200 DEG C, 180 DEG C ~ 160 DEG C, ten to No.12 District, head discharge opening quantity is adjustable, adjustment by discharge opening quantity, keep head pressure at 2 ~ 3Mpa, in screw extruder extrusion, foaming agent produces microbubble rapid expanding, water-soluble thermoplastic polymer is made to be subject to the stretching action of high rate of extension, crystalline flake graphite therein is by the effective stretch release of polymer, dispersion, injection is occurred to form the foaming body of puffy through screw extruder discharge opening；
3) foaming body that step 3) obtains is immersed in the water, carries out dissolution, cleaning, filtration, dry obtain graphene microchip.
Adding the graphene microchip of 3wt% in Merlon, its conductivity reaches 1.2*10-4S/CM。
Embodiment 4
A kind of screw machine foaming and intumescing stretches the method for preparation graphene microchip, it is characterised in that with natural flake graphite for primary raw material, stretches preparation graphene microchip by the shearing stripping of screw extruder and foaming and intumescing, and concrete grammar is as follows:
1) water of the natural flake graphite of weight portion 85, the soluble-salt calcium chloride of weight portion 3, the activating agent Aluminate of weight portion 3, weight portion 12 is added reactor, temperature of reaction kettle maintains 80-100 DEG C, adjusting reactor speed of agitator is 50-100rpm, stirring reaction 5-30 minute, make soluble-salt permeate in the Rotating fields of natural flake graphite, then temperature of reaction kettle is risen to more than 120 DEG C, dry obtain modified natural crystalline flake graphite；
2) step 1) obtains modified natural crystalline flake graphite mixed homogeneously by high-speed mixer with the foaming agent ammonium carbonate of the water-soluble thermoplastic polymer polyoxyethylene of weight portion 8, weight portion 1, being then fed into screw extruder, wherein said foaming agent is at least one in ammonium carbonate, sodium bicarbonate, carbamide；
3) engine speed 300 revs/min of screw extruder is set, each district extrusion temperature controls respectively: one to three 120 DEG C of district ~ 140 DEG C, four to six 160 DEG C of districts ~ 180 DEG C, seven to nine 180 DEG C of districts ~ 200 DEG C, 180 DEG C ~ 160 DEG C, ten to No.12 District, head discharge opening quantity is adjustable, adjustment by discharge opening quantity, keep head pressure at 2 ~ 3Mpa, in screw extruder extrusion, foaming agent produces microbubble rapid expanding, water-soluble thermoplastic polymer is made to be subject to the stretching action of high rate of extension, crystalline flake graphite therein is by the effective stretch release of polymer, dispersion, injection is occurred to form the foaming body of puffy through screw extruder discharge opening；
3) foaming body that step 3) obtains is immersed in the water, carries out dissolution, cleaning, filtration, dry obtain graphene microchip.
Adding the graphene microchip of 1wt% in corrosion-resistant epoxy paint, its salt fog resistance was increased to 4200 hours by 600 hours, and performance is equivalent to add the zinc of 20%, thus more lower in cost than using zinc.
Claims (7)
1. the method that a screw machine foaming and intumescing stretches preparation graphene microchip, it is characterized in that: with natural flake graphite for primary raw material, the collaborative foaming and intumescing stretch release of shearing force produced by screw extruder high speed rotating prepares graphene microchip, and concrete grammar is as follows:
1) water of the natural flake graphite of weight portion 85-90, the soluble-salt of weight portion 3-5, the activating agent of weight portion 1-3, weight portion 10-15 is added reactor, temperature of reaction kettle maintains 80-100 DEG C, adjusting reactor speed of agitator is 50-100rpm, stirring reaction 5-30 minute, make soluble-salt permeate in the Rotating fields of natural flake graphite, then temperature of reaction kettle is risen to more than 120 DEG C, dry obtain modified natural crystalline flake graphite；
2) step 1) obtains modified natural crystalline flake graphite to be mixed homogeneously by high-speed mixer with the foaming agent of the water-soluble thermoplastic polymer of weight portion 5-10, weight portion 1-5, being then fed into screw extruder, wherein said foaming agent is at least one in ammonium carbonate, sodium bicarbonate, carbamide；
3) engine speed 100 ~ 400 revs/min of screw extruder is set, each district extrusion temperature controls respectively: one to three 120 DEG C of district ~ 140 DEG C, four to six 160 DEG C of districts ~ 180 DEG C, seven to nine 180 DEG C of districts ~ 200 DEG C, 180 DEG C ~ 160 DEG C, ten to No.12 District, head discharge opening quantity is adjustable, adjustment by discharge opening quantity, keep head pressure at 2 ~ 3Mpa, in screw extruder extrusion, foaming agent produces microbubble rapid expanding, water-soluble thermoplastic polymer is made to be subject to the stretching action of high rate of extension, crystalline flake graphite therein is by the effective stretch release of polymer, dispersion, injection is occurred to form the foaming body of puffy through screw extruder discharge opening；
3) foaming body that step 3) obtains is immersed in the water, carries out dissolution, cleaning, filtration, dry obtain graphene microchip.
2. a kind of method that screw machine foaming and intumescing stretches preparation graphene microchip according to claim 1, it is characterised in that: described natural flake graphite fixed carbon > 99.5%, sheet footpath is sized to 20-50 μm.
3. a kind of method that screw machine foaming and intumescing stretches preparation graphene microchip according to claim 1, it is characterised in that: described soluble-salt is at least one in sodium chloride, potassium chloride, calcium chloride, sodium sulfate, potassium sulfate, sodium silicate, potassium silicate.
4. a kind of method that screw machine foaming and intumescing stretches preparation graphene microchip according to claim 1, it is characterised in that: described activating agent is at least one in zincic acid ester, phosphate ester, titanate esters, Aluminate, stearate.
5. a kind of method that screw machine foaming and intumescing stretches preparation graphene microchip according to claim 1, it is characterised in that: described water-soluble thermoplastic polymer is at least one in thermoplastic starch, polyvinyl alcohol, polyoxyethylene.
6. a kind of method that screw machine foaming and intumescing stretches preparation graphene microchip according to claim 1, it is characterised in that: described screw extruder is the one in equidirectional parallel double-screw extruder, cocurrent and parallel three-screw extruder, incorgruous part engagement conical double screw extruder.
7. a kind of method that screw machine foaming and intumescing stretches preparation graphene microchip according to claim 1, it is characterized in that: described in go out by screw rod shearing work in coordination with expansion stretch be that crystalline flake graphite is screw extruder carries out high shear stripping while, when utilizing polymer foaming, the stretching action of polymer melt is made the foaming and intumescing that crystalline flake graphite therein is subject to melt stretch by bubble, obtains graphene microchip 2 thus peeling off.
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| CN109608891A (en) * | 2018-11-26 | 2019-04-12 | 国宏中晶集团有限公司 | A kind of plateau modulus composite material and preparation method containing graphene |
| CN110240154A (en) * | 2019-06-27 | 2019-09-17 | 中素新科技有限公司 | The preparation method of multi-layer graphene |
| WO2021128257A1 (en) * | 2019-12-27 | 2021-07-01 | 桐乡市小老板特种塑料制品有限公司 | Cured product containing single-layer graphene, single-layer graphene, preparation method therefor, and article containing single-layer graphene |
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| TWI625299B (en) * | 2017-01-24 | 2018-06-01 | Apparatus for producing graphene and method thereof | |
| CN109608891A (en) * | 2018-11-26 | 2019-04-12 | 国宏中晶集团有限公司 | A kind of plateau modulus composite material and preparation method containing graphene |
| 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 |
| WO2021128257A1 (en) * | 2019-12-27 | 2021-07-01 | 桐乡市小老板特种塑料制品有限公司 | Cured product containing single-layer graphene, single-layer graphene, preparation method therefor, and article containing single-layer graphene |
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