CN110227396A - Graphene with nearly zero dielectric constant/polyolefin elastomer method for preparing microsphere - Google Patents
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- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
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Abstract
The present invention relates to the graphene with nearly zero dielectric constant/polyolefin elastomer method for preparing microsphere, potassium permanganate is uniformly added in the concentrated sulfuric acid, graphite, sodium nitrate low-temperature mixed afterwards, then hydrogen peroxide is added dropwise and filters, dispersed after cleaning to neutrality, obtained powder is added to the water and carries out twice dispersing, dispersion liquid is obtained, heat treatment obtains grapheme foam after acid solution is added, and is ground into graphene powder after freeze-drying；It is stirred after toluene to polyolefin elastomer granules swell is added dropwise, graphene powder is added and is uniformly mixed, stands and is dried to obtain graphene/polyolefin elastomer microballoon.Compared with prior art, graphene prepared by the present invention/polyolefin elastomer microballoon composite material dielectric constant is under special frequency channel close to zero, the research category of current Meta Materials experience is widened, the special dielectric constant in natural material system can be pushed further into the development of chemical controllable preparation electromagnetic performance material.
Description
Technical field
The present invention relates to the preparation method of nearly zero material of dielectric constant, more particularly, to a kind of with nearly zero dielectric constant
Graphene/polyolefin elastomer method for preparing microsphere.
Background technique
Nearly zero material of dielectric constant is a kind of more popular artificial special electromagnetic material of current research.1998,
Pendry et al., which is proposed, may be implemented lower equivalent plasma frequency using the wire array of periodic arrangement, be based on
This, 2002, the researcher of French Fresnel Institute changed structure size and working frequency by selection, by gold
Belong to copper sheet structure and obtain the effective dielectric constant close to 0, assembles, realize so that electromagnetic wave be made to generate wave beam by this structure
The high directionality of dipole.But the synthetic material for rarely having researcher's research that there is dielectric constant nearly zero.Graphene has
Excellent electronic transmission performance, the characteristics such as biggish specific surface area, excellent electric conductivity, good mechanical performance, especially has
There are good translucency and unique quantum hall effect, the way of electron-transport can be provided for polyolefin elastomer matrix
Diameter.Effective dielectric constant nearly zero may be implemented by positive dielectric constant appropriate, negative permittivity in studies have shown that, to obtain
Zero refraction materials.However, being currently also difficult to realize the dielectric constant material close to zero by synthesizing mean.
Therefore nearly zero dielectric constant of graphene/polyolefin elastomer microballoon is realized using effective ways, for it in people
The application in work electromagnetic material field is of great significance.Chinese patent CN105504453A discloses a kind of high thermo-oxidative stability
Polyolefin composite insulating material and preparation method thereof.Polyolefin composite insulating material in terms of mass fraction 100%, including 98~
99.5% polyolefin polymer matrix and 0.5~2% modified graphene oxide filler.Wherein modified graphene oxide is poly-
The graphene oxide of the antioxidant functionalization of dopamine cladding, the thermal oxidation stability of composite material can be improved by the antioxidant of grafting
Property, and graphene oxide can play the role of inhibiting antioxidant migration.The modified graphene oxide of use can both enhance polymer
Interface binding power between matrix and filler, can also prevent graphene oxide in composite insulating material preparation process by depth also
Original makes composite material keep good insulation performance.
Poly-dopamine is coated on the surface grafting two dimensional oxidation graphene surface of antioxidant by above-mentioned patent, then will
It is hot-forming with polyolefin substrate that the two dimensional oxidation graphene nanometer sheet of this functionalization does filler, graphene oxide and base therein
The mass difference of body is larger, filler in the base dispersibility be relatively difficult to guarantee it is uniform, and the two-dimensional slice of functionalization it is flexible, folding
It is folded, thus interstitital texture is easy to reunite, stacked form be difficult it is identical.The dielectric constant of above-mentioned patent is all just in low frequency.
Summary of the invention
It is an object of the present invention to overcome the above-mentioned drawbacks of the prior art and provide one kind to have nearly zero dielectric
The graphene of constant/polyolefin elastomer microballoon preparation method.
The purpose of the present invention can be achieved through the following technical solutions:
A kind of preparation method of the graphene having nearly zero dielectric constant/polyolefin elastomer microballoon, the specific steps are as follows:
(1) it prepares dispersion liquid A: measuring the 10-150ml concentrated sulfuric acid, 0.5-1.5g graphite and 0.2-0.75g sodium nitrate, be placed in
In ice bath environment, magnetic agitation is slowly added to 1.0-4.5g potassium permanganate to after being uniformly dispersed.Then by mixture at 25-55 DEG C
Water-bath continues to keep magnetic agitation, while being slow added into 1.0-4.5g potassium permanganate, and control reaction temperature is 25-35 DEG C；It will
Reaction mixture pours into the beaker equipped with 20-200 milliliters of ice water, and 30% hydrogen peroxide is added dropwise while stirring, filters while hot, first
It is cleaned afterwards with dilute hydrochloric acid solution and deionized water to neutrality, after being centrifuged 10-50min under 8000r/min revolving speed, in 10-70KHz
Ultrasonic disperse 10-30min under frequency；Weigh the above-mentioned solution of 0.1-1g it is dry it is finely ground after powder be added in beaker and be added
100-500ml deionized water, under 10-70KHz frequency twice ultrasonic handle 0.5-2h, with 3000-8000r/min revolving speed from
The heart takes supernatant liquor after half an hour；
(2) prepare graphene powder: measure 10-100ml it is configured at dispersion liquid A under 10-70KHz frequency at ultrasound
After managing 1-8h, it is slowly added to acid solution when being kept stirring, mixed liquor is poured into reaction kettle and is placed in baking oven 100-180 DEG C
Three-dimensional column grapheme foam can be obtained in lower reaction 8-16h.By grind into powder after foam freeze-drying 24-36h；
(3) the polyolefin elastic granule for weighing 1-5g is placed in surface plate, and toluene is added dropwise to polyolefin elastomer
Magnetic agitation 0.5-2.5h after grain swelling；Graphene powder is added, is ground to uniformly mixed, standing 24-36h.
(4) it dries: the material after standing being dried to 5-24 hours in 50-100 DEG C of air dry oven to get graphite is arrived
Alkene/polyolefin elastomer microballoon.
Acid solution described in step (2) be it is any in ascorbic acid or hydroiodic acid, dispersion liquid A and acid solution rub
You are than being 1:1 to 5:1.
The additive amount of graphene described in step (3) is the 10%-80% of composite material quality.
Graphene prepared by the present invention/polyolefin elastomer microballoon composite material dielectric constant approaches under special frequency channel
Zero has widened the research category of current Meta Materials experience, and the special dielectric constant in natural material system can be further
Promote the development of chemical controllable preparation electromagnetic performance material.What preparation process of the invention was different from current main-stream passes through periodicity
The method of the split ring resonator array of arrangement, but nearly zero material, the phase having are prepared by the method for materials synthesis
Become the characteristics such as cancellation, super coupling effect and electromagnetism tunnelling, in building waveguide coupler, enhances directionality and wave that day wire spoke is penetrated
Preceding integer etc. is widely used.Graphene prepared by the present invention/polyolefin elastomer microballoon is in powdered, uniform particle sizes.This
Invention can be used for preparing zero refractive index metamaterial material.
The application is obtained by modified hummer legal system after the graphene oxide water solution of various concentration in a manner of hydro-thermal, one
It is shaped to three-dimensional foam, lamella interweaves uniformly, and freeze-dried and after grinding redox graphene three-dimensional structure is not easy to roll into a ball
It is poly-, in the polyolefin elastomer external sheath of swelling, inherent matrix is protected, shock resistance and heat resistance are improved；Separately
On the one hand since the electric conductivity of the graphene of hydrothermal reduction is excellent, dielectric constant is also further promoted in 1M-1GHz frequency
Positive and negative transformation in range makes it have a characteristic of nearly zero material, while the further expansion frequency of dielectric constant nearly zero
Range.
Compared with prior art, the invention has the following advantages that
One, the present invention uses improved Hummers method, prepares graphene oxide solution, this process relative ease and green
Color, efficiently, passing through control reaction temperature during this and the oxidants such as the concentrated sulfuric acid, potassium permanganate, hydrogen peroxide are added makes day
Right graphite is sufficiently removed；Ultrasonic disperse is used during the reaction, ensure that the homogeneity of reaction system and the dispersion of graphene
Property.
Two, dielectric constant of the graphene prepared by the present invention/polyolefin elastomer microballoon under 365-491MHz frequency
Between 2 to -2, compared with graphene/polyolefin elastomer dielectric constant of existing method synthesis, have apparent close
Characteristic in 0 the characteristics of.The electric conductivity of polyolefin elastomer itself is not strong enough, and dielectric constant is in 1M-1GHz frequency range
It is positive, the cladding of three-dimensional graphene foam piece makes it have conductive network, certain metallicity is showed, in 365-491MHz
Plasma resonance is excited, makes dielectric constant that 2 to -2 transformation occur.It can root by the joint product that this method is prepared
The range that dielectric constant is efficiently controlled according to the filler and matrix of addition, makes it have nearly zero material property of positive and negative transformation；And
Soft, controllable, efficient preparation method also makes dielectric constant that stable variation tendency be presented in higher frequency range.
Three, graphene polyolefin elastic composite material prepared by the present invention can be used for preparing zero refractive index metamaterial material
Material.
Detailed description of the invention
Fig. 1 is graphene/polyolefin elastomer microballoon dielectric properties figure that embodiment 6,7 is prepared.
Specific embodiment
The present invention is described in detail combined with specific embodiments below.Following embodiment will be helpful to the technology of this field
Personnel further understand the present invention, but the invention is not limited in any way.It should be pointed out that the ordinary skill of this field
For personnel, without departing from the inventive concept of the premise, various modifications and improvements can be made.These belong to the present invention
Protection scope.
A kind of preparation method of the graphene having nearly zero dielectric constant/polyolefin elastomer microballoon, the specific steps are as follows:
(1) it prepares dispersion liquid A: measuring the 10-150ml concentrated sulfuric acid, 0.5-1.5g graphite and 0.2-0.75g sodium nitrate, be placed in
In ice bath environment, magnetic agitation is slowly added to 1.0-4.5g potassium permanganate to after being uniformly dispersed.Then by mixture at 25-55 DEG C
Water-bath continues to keep magnetic agitation, while being slow added into 1.0-4.5g potassium permanganate, and control reaction temperature is 25-35 DEG C；It will
Reaction mixture pours into the beaker equipped with 20-200 milliliters of ice water, and 30% hydrogen peroxide is added dropwise while stirring, filters while hot, first
It is cleaned afterwards with dilute hydrochloric acid solution and deionized water to neutrality, after being centrifuged 10-50min under 8000r/min revolving speed, in 10-70KHz
Ultrasonic disperse 10-30min under frequency；Weigh the above-mentioned solution of 0.1-1g it is dry it is finely ground after powder be added in beaker and be added
100-500ml deionized water, under 10-70KHz frequency twice ultrasonic handle 0.5-2h, with 3000-8000r/min revolving speed from
The heart takes supernatant liquor after half an hour；
(2) prepare graphene powder: measure 10-100ml it is configured at dispersion liquid A under 10-70KHz frequency at ultrasound
After managing 1-8h, it is slowly added to acid solution when being kept stirring, can be any in ascorbic acid or hydroiodic acid, dispersion liquid A
Molar ratio with acid solution is 1:1 to 5:1；Mixed liquor is poured into reaction kettle and is placed in baking oven at 100-180 DEG C and reacts 8-
Three-dimensional column grapheme foam can be obtained in 16h.By grind into powder after foam freeze-drying 24-36h；
(3) the polyolefin elastic granule for weighing 1-5g is placed in surface plate, and toluene is added dropwise to polyolefin elastomer
Magnetic agitation 0.5-2.5h after grain swelling；Graphene powder is added, graphene is made to account for the mass fraction 10- of composite material
80%, it is ground to uniformly mixed, standing 24-36h.
(4) it dries: the material after standing being dried to 5-24 hours in 50-100 DEG C of air dry oven to get graphite is arrived
Alkene/polyolefin elastomer microballoon.
More detailed case study on implementation below, by following case study on implementation further illustrate technical solution of the present invention with
And the technical effect that can be obtained.
Embodiment 1:
The present embodiment is a kind of preparation method of the graphene with nearly zero dielectric constant/polyolefin elastomer microballoon, is pressed
Following steps carry out.
(1) it prepares dispersion liquid A: measuring the 138ml concentrated sulfuric acid, 1.5g graphite and 0.75g sodium nitrate, be placed in ice bath environment,
Magnetic agitation is slowly added to 4.5g potassium permanganate to after being uniformly dispersed.Then mixture is continued that magnetic force is kept to stir in 35 DEG C of water-baths
It mixes, while being slow added into 4.5g potassium permanganate, control reaction temperature is 35 DEG C；Reaction mixture is poured into equipped with 200 milliliters
In the beaker of ice water, 30% hydrogen peroxide is added dropwise while stirring, filters, is successively cleaned with dilute hydrochloric acid solution and deionized water while hot
To neutrality, after being centrifuged 10min under 8000r/min revolving speed, the ultrasound 30min under 10KHz frequency；It is dry to weigh the above-mentioned solution of 0.2g
It is dry it is finely ground after powder be added in beaker and be added 100ml deionized water, be ultrasonically treated 2h under 10KHz frequency, with
8000r/min revolving speed takes supernatant liquor after centrifugation half an hour；
(2) prepare graphene powder: measure 100ml it is configured at dispersion liquid A be ultrasonically treated 8h under 10KHz frequency
Afterwards, it is slowly added to ascorbic acid when being kept stirring, the molar ratio of dispersion liquid A and acid solution is 1:1；Mixed liquor is poured into reaction kettle
It is placed in baking oven, at 180 DEG C, three-dimensional column grapheme foam is can be obtained in reaction 16h.Foam freeze-drying is ground afterwards for 24 hours
It clays into power；
(3) the polyolefin elastic granule for weighing 1g is placed in surface plate, and toluene is added dropwise to polyolefin elastomer particle
Magnetic agitation 0.5h after swelling；Graphene powder is added, so that graphene is accounted for the mass fraction 40% of composite material, is ground to
It is uniformly mixed, stands for 24 hours.
(4) it dries: the material after standing being dried to 12 hours in 50 DEG C of air dry ovens to get graphene/polyene is arrived
Olefin elastomer microballoon.
Embodiment 2:
The present embodiment is a kind of preparation method of the graphene with nearly zero dielectric constant/polyolefin elastomer microballoon, is pressed
Following steps carry out.
(1) it prepares dispersion liquid A: measuring the 138ml concentrated sulfuric acid, 1.5g graphite and 0.75g sodium nitrate, be placed in ice bath environment,
Magnetic agitation is slowly added to 4.5g potassium permanganate to after being uniformly dispersed.Then mixture is continued that magnetic force is kept to stir in 35 DEG C of water-baths
It mixes, while being slow added into 4.5g potassium permanganate, control reaction temperature is 35 DEG C；Reaction mixture is poured into equipped with 200 milliliters
In the beaker of ice water, 30% hydrogen peroxide is added dropwise while stirring, filters, is successively cleaned with dilute hydrochloric acid solution and deionized water while hot
To neutrality, after being centrifuged 10min under 8000r/min revolving speed, the ultrasound 30min under 20KHz frequency；It is dry to weigh the above-mentioned solution of 0.2g
It is dry it is finely ground after powder be added in beaker and be added 100ml deionized water, be ultrasonically treated 2h under 20KHz frequency, with
8000r/min revolving speed takes supernatant liquor after centrifugation half an hour；
(2) prepare graphene powder: measure 100ml it is configured at dispersion liquid A be ultrasonically treated 8h under 20KHz frequency
Afterwards, it is slowly added to ascorbic acid when being kept stirring, the molar ratio of dispersion liquid A and acid solution is 1:2；Mixed liquor is poured into reaction kettle
It is placed in baking oven, at 180 DEG C, three-dimensional column grapheme foam is can be obtained in reaction 16h.Foam freeze-drying is ground afterwards for 24 hours
It clays into power；
(3) the polyolefin elastic granule for weighing 1g is placed in surface plate, and toluene is added dropwise to polyolefin elastomer particle
Magnetic agitation 0.5h after swelling；Graphene powder is added, so that graphene is accounted for the mass fraction 50% of composite material, is ground to
It is uniformly mixed, stands for 24 hours.
(4) it dries: the material after standing being dried to 12 hours in 50 DEG C of air dry ovens to get graphene/polyene is arrived
Olefin elastomer microballoon.
Dielectric constant of the graphene prepared by the present invention/polyolefin elastomer microballoon under 970MHz frequency is 0.05,
Compared with graphene/polyolefin elastomer dielectric constant of existing method synthesis, have the characteristics that significantly close to 0
Characteristic.
Embodiment 3:
The present embodiment is a kind of preparation method of the graphene with nearly zero dielectric constant/polyolefin elastomer microballoon, is pressed
Following steps carry out.
(1) it prepares dispersion liquid A: measuring the 138ml concentrated sulfuric acid, 1.5g graphite and 0.75g sodium nitrate, be placed in ice bath environment,
Magnetic agitation is slowly added to 4.5g potassium permanganate to after being uniformly dispersed.Then mixture is continued that magnetic force is kept to stir in 35 DEG C of water-baths
It mixes, while being slow added into 4.5g potassium permanganate, control reaction temperature is 35 DEG C；Reaction mixture is poured into equipped with 200 milliliters
In the beaker of ice water, 30% hydrogen peroxide is added dropwise while stirring, filters, is successively cleaned with dilute hydrochloric acid solution and deionized water while hot
To neutrality, after being centrifuged 10min under 8000r/min revolving speed, the ultrasound 30min under 50KHz frequency；It is dry to weigh the above-mentioned solution of 0.2g
It is dry it is finely ground after powder be added in beaker and be added 100ml deionized water, be ultrasonically treated 2h under 50KHz frequency, with
8000r/min revolving speed takes supernatant liquor after centrifugation half an hour；
(2) prepare graphene powder: measure 100ml it is configured at dispersion liquid A be ultrasonically treated 8h under 50KHz frequency
Afterwards, it is slowly added to hydroiodic acid when being kept stirring, the molar ratio of dispersion liquid A and acid solution is 1:1；After mixed liquor is poured into reaction kettle
It is placed in baking oven, at 180 DEG C, three-dimensional column grapheme foam is can be obtained in reaction 16h.Foam freeze-drying is ground afterwards for 24 hours
At powder；
(3) the polyolefin elastic granule for weighing 1g is placed in surface plate, and toluene is added dropwise to polyolefin elastomer particle
Magnetic agitation 0.5h after swelling；Graphene powder is added, so that graphene is accounted for the mass fraction 40% of composite material, is ground to
It is uniformly mixed, stands for 24 hours.
(4) it dries: the material after standing being dried to 12 hours in 50 DEG C of air dry ovens to get graphene/polyene is arrived
Olefin elastomer microballoon.
Graphene prepared by the present invention/dielectric constant of the polyolefin elastomer microballoon under 369MHz frequency is 0.42, with
Graphene/polyolefin elastomer dielectric constant of existing method synthesis is compared, and has the characteristics that the spy significantly close to 0
Property.
Embodiment 4:
The present embodiment is a kind of preparation method of graphene polyolefin elastic composite material with nearly zero dielectric constant,
The present embodiment is as different from Example 2: using acid solution being hydroiodic acid in step (2), other steps are identical.
Embodiment 5:
The present embodiment is a kind of preparation method of the graphene with negative permittivity/polypyrrole nanoparticle, this implementation
Example as different from Example 3: in step (3) additive amount of graphene be 60%, other steps are identical.
Embodiment 6:
One, it prepares dispersion liquid A: measuring the 138ml concentrated sulfuric acid, 1.5g graphite and 0.75g sodium nitrate, be placed in ice bath environment,
Magnetic agitation is slowly added to 4.5g potassium permanganate to after being uniformly dispersed.Then mixture is continued that magnetic force is kept to stir in 35 DEG C of water-baths
It mixes, while being slow added into 4.5g potassium permanganate, control reaction temperature is 35 DEG C；Reaction mixture is poured into equipped with 200 milliliters
In the beaker of ice water, 30% hydrogen peroxide is added dropwise while stirring, filters, is successively cleaned with dilute hydrochloric acid solution and deionized water while hot
To neutrality, after being centrifuged 10min under 8000r/min revolving speed, the ultrasound 30min under 70KHz frequency；It is dry to weigh the above-mentioned solution of 0.2g
Powder after finely ground is added in beaker and is added 100ml deionized water, 2h is ultrasonically treated under 70KHz frequency, with 8000r/
Min revolving speed takes supernatant liquor after centrifugation half an hour；
Two, prepare graphene powder: measure 100ml it is configured at dispersion liquid A be ultrasonically treated 8h under 70KHz frequency
Afterwards, it is slowly added to ascorbic acid when being kept stirring, the molar ratio of dispersion liquid A and acid solution is 1:1；Mixed liquor is poured into reaction kettle
It is placed in baking oven, at 180 DEG C, three-dimensional column grapheme foam is can be obtained in reaction 16h.Foam freeze-drying is ground afterwards for 24 hours
It clays into power；
Three, the polyolefin elastic granule for weighing 1g is placed in surface plate, and toluene is added dropwise to polyolefin elastomer particle
Magnetic agitation 0.5h after swelling；Graphene powder is added, so that graphene is accounted for the mass fraction 40% of composite material, is ground to
It is uniformly mixed, stands for 24 hours.
Four, it dries: the material after standing being dried to 12 hours in 50 DEG C of air dry ovens to get graphene/polyene is arrived
Olefin elastomer microballoon.
A kind of graphene polyolefin elastic composite material with nearly zero dielectric constant of this experiment preparation is named as
40% graphene/poly- polyolefin elastomer microballoon composite material.
Graphene/polyolefin elastomer with nearly zero dielectric constant of this experiment preparation is tested using Agilent E4991A
The dielectric properties of microballoon (40%wt graphene/polyolefin elastomer), dielectric constant is when 970MHz frequency as shown in Figure 1
0.05。
Embodiment 7:
One, it prepares dispersion liquid A: measuring the 138ml concentrated sulfuric acid, 1.5g graphite and 0.75g sodium nitrate, be placed in ice bath environment,
Magnetic agitation is slowly added to 4.5g potassium permanganate to after being uniformly dispersed.Then mixture is continued that magnetic force is kept to stir in 35 DEG C of water-baths
It mixes, while being slow added into 4.5g potassium permanganate, control reaction temperature is 35 DEG C；Reaction mixture is poured into equipped with 200 milliliters
In the beaker of ice water, 30% hydrogen peroxide is added dropwise while stirring, filters, is successively cleaned with dilute hydrochloric acid solution and deionized water while hot
To neutrality, after being centrifuged 10min under 8000r/min revolving speed, the ultrasound 30min under 40KHz frequency；It is dry to weigh the above-mentioned solution of 0.2g
Powder after finely ground is added in beaker and is added 100ml deionized water, 2h is ultrasonically treated under 40KHz frequency, with 8000r/
Min revolving speed takes supernatant liquor after centrifugation half an hour；
Two, prepare graphene powder: measure 100ml it is configured at dispersion liquid A be ultrasonically treated 8h under 40KHz frequency
Afterwards, it is slowly added to hydroiodic acid when being kept stirring, the molar ratio of dispersion liquid A and acid solution is 1:2；After mixed liquor is poured into reaction kettle
It is placed in baking oven, at 180 DEG C, three-dimensional column grapheme foam is can be obtained in reaction 16h.Foam freeze-drying is ground afterwards for 24 hours
At powder；
Three, the polyolefin elastic granule for weighing 1g is placed in surface plate, and toluene is added dropwise to polyolefin elastomer particle
Magnetic agitation 0.5h after swelling；Graphene powder is added, so that graphene is accounted for the mass fraction 50% of composite material, is ground to
It is uniformly mixed, stands for 24 hours.
Four, it dries: the material after standing being dried to 12 hours in 50 DEG C of air dry ovens to get graphene/polyene is arrived
Olefin elastomer microballoon.
A kind of graphene polyolefin elastic composite material with nearly zero dielectric constant of this experiment preparation is named as
50% graphene/poly- polyolefin elastomer microballoon composite material.
Graphene/polyolefin elastomer with nearly zero dielectric constant of this experiment preparation is tested using Agilent E4991A
The dielectric properties of microballoon (40% graphene/polyolefin elastomer), in 985MHz, its dielectric constant is -1.13 as shown in Figure 1,
Nearly zero.
In the description of this specification, the description of reference term " one embodiment ", " example ", " specific example " etc. means
Particular features, structures, materials, or characteristics described in conjunction with this embodiment or example are contained at least one implementation of the invention
In example or example.In the present specification, schematic expression of the above terms may not refer to the same embodiment or example.
Moreover, particular features, structures, materials, or characteristics described can be in any one or more of the embodiments or examples to close
Suitable mode combines.
The above description of the embodiments is intended to facilitate ordinary skill in the art to understand and use the invention.
Person skilled in the art obviously easily can make various modifications to these embodiments, and described herein general
Principle is applied in other embodiments without having to go through creative labor.Therefore, the present invention is not limited to the above embodiments, ability
Field technique personnel announcement according to the present invention, improvement and modification made without departing from the scope of the present invention all should be of the invention
Within protection scope.
Claims (10)
1. graphene/polyolefin elastomer method for preparing microsphere with nearly zero dielectric constant, which is characterized in that this method packet
It includes:
Potassium permanganate is uniformly added in the concentrated sulfuric acid, graphite, sodium nitrate low-temperature mixed afterwards, hydrogen peroxide is then added dropwise and is filtered, is cleaned
Dispersed after to neutrality, obtained powder is added to the water and carries out twice dispersing, obtains dispersion liquid；
Acid solution is added in obtained dispersion liquid under dispersity, then heat treatment obtains grapheme foam, and freezing is dry
Graphene powder is ground into after dry；
It is stirred after toluene to polyolefin elastomer granules swell is added dropwise, graphene powder is added and is uniformly mixed, stands；
Material after standing is obtained into graphene/polyolefin elastomer microballoon through being dried.
2. graphene/polyolefin elastomer method for preparing microsphere according to claim 1 with nearly zero dielectric constant,
Be characterized in that, the concentrated sulfuric acid, graphite, sodium nitrate additional proportion be 10-150ml:0.5-1.5g:0.2-0.75g.
3. graphene/polyolefin elastomer method for preparing microsphere according to claim 1 with nearly zero dielectric constant,
It is characterized in that, the potassium permanganate is added in two portions by 1:1, and the mass ratio of the potassium permanganate and graphite that are added every time is 1.0-
4.5:0.5-1.5。
4. graphene/polyolefin elastomer method for preparing microsphere according to claim 3 with nearly zero dielectric constant,
It is characterized in that, the concentrated sulfuric acid, graphite, sodium nitrate are dispersed with stirring addition potassium permanganate in ice bath environment, then controlled at 25-
It 55 DEG C, is kept stirring and is slow added into potassium permanganate.
5. graphene/polyolefin elastomer method for preparing microsphere according to claim 1 with nearly zero dielectric constant,
It is characterized in that, is cleaned with dilute hydrochloric acid solution and deionized water to neutrality, it is ultrasonic under 10-70KHz frequency after centrifugal treating
Dispersion.
6. graphene/polyolefin elastomer method for preparing microsphere according to claim 1 with nearly zero dielectric constant,
It is characterized in that, twice dispersing ultrasonic disperse under 10-70KHz frequency.
7. graphene/polyolefin elastomer method for preparing microsphere according to claim 1 with nearly zero dielectric constant,
It being characterized in that, the acid solution is ascorbic acid or hydroiodic acid, and the molar ratio of dispersion liquid and acid solution is 1:1 to 5:1, point
Dispersion liquid is slowly added to acid solution after being ultrasonically treated under 10-70KHz frequency.
8. the graphene with nearly zero dielectric constant/polyolefin elastomer microballoon preparation side according to claim 1 or 6
Method, which is characterized in that dispersion liquid reacts 8-16h at 100-180 DEG C with acid solution and three-dimensional column graphene bubble is prepared
Foam.
9. graphene/polyolefin elastomer method for preparing microsphere according to claim 1 with nearly zero dielectric constant,
It is characterized in that, the graphene powder of addition is the 10%-80% of material gross mass.
10. graphene/polyolefin elastomer method for preparing microsphere according to claim 1 with nearly zero dielectric constant,
It is characterized in that, the dry 5-24h at 50-100 DEG C of the material after standing.
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