CN109251461A - A kind of functionalization graphene/Polymethacrylimide composite wave-suction material and preparation method - Google Patents
A kind of functionalization graphene/Polymethacrylimide composite wave-suction material and preparation method Download PDFInfo
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Abstract
The present invention relates to a kind of functionalization graphene/Polymethacrylimide composite wave-suction materials and preparation method thereof.Preparation method includes the following steps: that graphene, resin, dressing agent, coupling agent, dispersing agent, wetting agent and organic solvent are uniformly mixed by (1), obtains functionalization graphene slurry；Wherein, the dressing agent is any one or more of selected from KH550, KH560, KH570, and quality is the 1%~5% of graphene quality；The coupling agent is any one or more of selected from TMC-101, TMC-102, TMC-201, and quality is the 0.5%~2% of graphene quality；(2) mixing of functionalization graphene slurry and expanding foam solution；(3) prepolymerization；(4) it polymerize.Properties of product made from this method are reliable, and quality is stablized, and can not only play the effect of electromagnetic wave absorption, and be also equipped with lightweight, wideband, advantage easy to process.
Description
Technical field
The present invention relates to absorbing material technical field more particularly to a kind of functionalization graphene/Polymethacrylimides
Composite wave-suction material and preparation method.
Background technique
Traditional absorbing material mainly includes ferrite, magnetic metal micro mist, ceramic-like materials etc., such as carbonyl iron dust
Saturation induction density is higher, and magnetic conductivity is high within the scope of microwave frequency band, high-selenium corn, low reflection is advantageously implemented, using carbonyl
Iron powder can satisfy the requirement of high band microwave absorption and anti-interference device.But due to the impedance of carbonyl iron dust and air
It is bad with property, and Absorber Bandwidth is also narrow, and density is larger, this limits its application to a certain extent.It is used alone
There are some problems for these materials, for example density is big, stability is poor, absorption band is narrow etc., thus it is not able to satisfy absorbing material
The requirement of " thin, light, wide, strong ".The appearance of these problems just promotes people to explore novel absorbing material, and material is existed
There are preferable matching properties in broadband, has stronger electromagnetic wave attenuation ability under lower thickness, in addition to this also have both
There is the requirement such as lesser surface density and good heat-resisting weather resistance.
Design, exploitation, the manufacture preferable lightweight absorbing material of absorbent properties, are always the side that professional skill field is made great efforts
To.It by the way that wave absorbing agent is added to hard polyurethane foam system, is re-introduced into mold and reacts foaming, or by soft poly- ammonia
Ester foam is cut into predetermined shape, impregnates wave absorbing agent solution to prepare polyurethane foam composite wave-suction material, these materials have been answered
Built for microwave dark room etc..But the temperature tolerance of polyurethane foam absorbing material, specific strength, specific modulus be also in it is lower
Level lead to easily occur what absorbent picking fell off when in use simultaneously because absorbent components and the binding force of matrix be not high
Situation, to affect service performance.Compared to the foam of other types, PMI foam anti-fatigue performance is best, suitable for height
Load application field such as locomotive, high-speed ship, space flight and aviation and wind electricity blade etc..Therefore it selects PMI as basis material, passes through
Theory analysis design, compound or specific low-density absorbent components such as carbon dust, carbon nanotube, graphene, mesoporous carbon of addition etc., can
To obtain the efficient absorbing material of light weight type.
Carbon atom of the graphene by is arranged in two-dimensional surface space so that hexagonal honeycomb structure type is regular, all
Carbon atom shares delocalization π orbital electron, has relaxation response with the resonance characteristics that polarize, the form that electromagnetic energy can be converted
Decay.Therefore, Polymethacrylimide (PMI) foam of graphene and high temperature resistant, high specific strength, high ratio modulus is multiple
Close the composite wave-suction material that can obtain high-strength light.
During graphene and PMI foam is compound, inventors have found that the compound presence of graphene and foam base plate
The composite effect of technology barrier, graphene and PMI foam base plate has direct shadow to the absorbing property of the composite wave-suction material of formation
It rings.Based on this research, present patent application is inventors herein proposed.
Summary of the invention
(1) technical problems to be solved
The invention solves following one or more technical problems:
Absorbing material density is big in the prior art, impedance matching is poor, absorption band width, structure are asked using inflexible
Topic.
(2) technical solution
In order to solve the above-mentioned technical problems, the present invention provides following technical solutions:
A kind of preparation method of functionalization graphene/Polymethacrylimide composite wave-suction material, the method includes
Following steps:
(1) graphene, resin, dressing agent, coupling agent, dispersing agent, wetting agent and organic solvent are uniformly mixed, obtain function
It can graphite alkene slurry；Wherein, the dressing agent is any one or more of selected from KH550, KH560, KH570, and quality is
The 1%~5% of graphene quality；The coupling agent is any one or more of selected from TMC-101, TMC-102, TMC-201,
Quality is the 0.5%~2% of graphene quality；
(2) expanding foam solution comprising the first monomer, second comonomer, initiator, foaming agent and crosslinking agent is uniformly mixed, then plus
Enter functionalization graphene slurry, be uniformly dispersed, obtains foaming mixed liquor；
(3) foaming mixed liquor is injected in mold, polymerization, obtains the raw plate of FGO/PMI copolymer；
(4) first the raw plate of FGO/PMI copolymer is heat-treated, then carries out gradient heat treatment, obtain function graphite
Alkene/Polymethacrylimide composite wave-suction material.
Preferably, the graphene is the graphene that the number of plies is 2~13 layers.
Preferably, first monomer is selected from methacrylic acid and/or methyl methacrylate；
The second comonomer is selected from acrylonitrile and/or methacrylonitrile；
The initiator is selected from one of azodiisobutyronitrile, dibenzoyl peroxide, peroxidized t-butyl perbenzoate；
The foaming agent is selected from n-butanol and/or the tert-butyl alcohol；And/or
The crosslinking agent is selected from one of acrylamide, Methacrylamide, n,N-Dimethylformamide.
Preferably, first monomer, the second comonomer, the initiator, the foaming agent and the crosslinking agent
Mass ratio is (50~100): (50~100): (0.5~1.5): (4~16): (2~10).
Preferably, the expanding foam solution quality is the 30%~45% of the functionalization graphene slurry.
Preferably, the dispersing agent is any one or more of selected from BYK-W903, BYK-W9012, BYK-P104S, matter
Amount is the 1%~3% of graphene quality；And/or
The wetting agent is any one or more of selected from BYK-103, BYK-104, BYK-105, and quality is graphene matter
The 1%~2.5% of amount.
Preferably, the resin is selected from epoxy resin or silicone resin, and quality is 1~3 times of graphene quality；With/
Or
The organic solvent is selected from dehydrated alcohol, butanol, N-Methyl pyrrolidone, n,N-Dimethylformamide, dimethyl
Acetamide is any one or more of, and quality is 1~5 times of graphene quality.
Preferably, in step (3), described be aggregated at 40 DEG C~60 DEG C is carried out, and the time is no more than 2 hours.
Preferably, in step (4), the process of thermal treatment condition are as follows: 100 DEG C~140 DEG C of temperature, time 15min
~45min.
Preferably, in step (4), the process conditions of the gradient heat treatment are as follows:
120 DEG C~150 DEG C heat preservation 2h~4h,
160 DEG C~180 DEG C heat preservation 2h~4h, and
200 DEG C~260 DEG C heat preservation 2h~4h.
The present invention also provides a kind of functionalization graphene/Polymethacrylimide composite wave-suction material, the suction wave materials
Material is made using preparation method described in any of the above embodiments.
(3) beneficial effect
Above-mentioned technical proposal of the invention has the advantages that
The present invention carries out graphene using particular kind of silane coupling agent and particular kind of titante coupling agent
Functionalization makes graphene be uniformly dispersed in PMI matrix, while can also optimize the electromagnetic performance of graphene, realizes graphite
The designing impedance matching of alkene and PMI matrix.
Using functionalization graphene as the composite wave-suction material of absorbent, can keep preferably inhaling under conditions of lightweight
Wave effect, effective Absorber Bandwidth cover 2~18GHz.
The present invention prepares the from a wealth of sources, low in cost of the raw material of functionalization graphene liquid slurry, is guaranteeing to inhale wave effect
While fruit, moreover it is possible to which significant decrease prepares the cost of absorbing material.Meanwhile raw material sources abundant are also conducive to properties of product and matter
The stabilization of amount improves functionalization graphene/Polymethacrylimide absorbing material reliability.
Preparation method provided by the invention is at low cost, preparation side's simple process and it is easy to operate, be easily industrialized life
It produces, properties of product obtained are reliable, and quality is stablized, and can not only play the effect of electromagnetic wave absorption, and be also equipped with lightweight, width
Frequently, advantage easy to process.
Detailed description of the invention
Fig. 1 is the flow diagram of preparation method provided by the invention；
Fig. 2 is functionalization graphene made from embodiment 1/Polymethacrylimide composite wave-suction material reflectance test
Curve；
Fig. 3 is functionalization graphene made from embodiment 2/Polymethacrylimide composite wave-suction material reflectance test
Curve.
Specific embodiment
To make the object, technical solutions and advantages of the present invention clearer, below in conjunction with the embodiment of the present invention, to this hair
Bright technical solution is clearly and completely described.Obviously, described embodiment is a part of the embodiments of the present invention, and
The embodiment being not all of.Based on the embodiments of the present invention, those of ordinary skill in the art are not making creative work
Under the premise of every other embodiment obtained, shall fall within the protection scope of the present invention.
The present invention provides a kind of functionalization graphene/Polymethacrylimide composite wave-suction material in first aspect
Preparation method, as shown in Figure 1, described method includes following steps:
(1) preparation of functionalization graphene slurry
Graphene, resin, dressing agent, coupling agent, dispersing agent, wetting agent and organic solvent are uniformly mixed, function is obtained
Graphite alkene slurry；Wherein, the dressing agent is any one or more of selected from KH550, KH560, KH570, and quality is stone
The 1%~5% of black alkene quality；The coupling agent is any one or more of selected from TMC-101, TMC-102, TMC-201, matter
Amount is the 0.5%~2% of graphene quality.
The surface of graphene is inert, and chemical stability is high and is easy aggregation, so that graphene is in solvent (such as water, organic
Solvent) in be not easy to be uniformly dispersed.Graphene is added in PMI (Chinese name: Polymethacrylimide) matrix, and there is also be not easy
The problem of being uniformly dispersed directly affects the wave-absorbing effect of absorbing material.Inventor is in the research for carrying out functionalization to graphene
The certain components for belonging to silane coupling agent and the certain components belonged in titante coupling agent are applied in combination to stone for middle discovery
When black alkene is modified processing, preferable dispersion effect can be obtained, while the electromagnetic performance of graphene can also be optimized, realize stone
The designing impedance matching of black alkene and PMI matrix.Wherein, selected from KH550, (Chinese chemical name is known as 3- aminopropyl to silane coupling agent
Triethoxysilane), KH560 (Chinese chemical name is known as γ-(2,3- the third oxygen of epoxy) propyl trimethoxy silicane), KH570 (in
Entitled γ-the methacryloxypropyl trimethoxy silane of science of culture) any one or more of, titante coupling agent
Selected from from TMC-101 (Chinese chemical name is known as two oleic acid acyloxy of isopropyl (dioctyl phosphoric acid acyloxy) titanate esters), TMC-
102 (Chinese chemical name is known as isopropyl three (dioctyl phosphoric acid acyloxy) titanate esters), (Chinese chemical name is referred to as different by TMC-201
Propyl three (dioctylphyrophosphoric acid acyloxy) titanate esters) it is any one or more of, as described in foregoing teachings, these components association
Graphene can be better dispersed in PMI matrix with use, while also achieve the impedance matching of graphene and PMI matrix
Design, makes absorbing material show preferable absorbing property.
Inventors have found that the dosage of above-mentioned silane coupling agent and titante coupling agent has certain shadow to the performance of material
It rings.In collaborative processes, the quality of the silane coupling agent of mentioned kind is preferably the 1%~5% of graphene quality, for example, can
Think 1%, 2%, 3%, 4% or 5%；The quality of the titante coupling agent of mentioned kind is preferably graphene quality
0.5%~2%, for example, can be 0.5%, 1%, 1.5% or 2%.It has been confirmed by experiments that when the dosage of silane coupling agent and
When the dosage of titante coupling agent exceeds above range, the absorbing property of final absorbing material obtained is showed not as good as this hair
It is bright.
In addition, the number of plies of graphene used also has certain influence to the absorbing property of absorbing material, it is preferred to use use layer
The graphene that number is 2~13 layers.It should be noted that graphene used in the present invention can select existing commercial product,
It can use existing method to be prepared, such as mechanical stripping method, chemical vapour deposition technique, epitaxial growth method, solvent stripping method, change
Method etc..
Dispersing agent can select BYK-W903, BYK-W9012, BYK-P104S any one or more of, and dosage (refers to matter
Amount) it is the 1%~3% of graphene quality, for example, can be 1%, 1.5%, 2%, 2.5% or 3%.
Wetting agent can select BYK-103, BYK-104, BYK-105 any one or more of, and dosage (referring to quality) is
The 1%~2.5% of graphene quality, for example, can be 1%, 1.5%, 2% or 2.5%.
Resin can select conventional fire resistant resin, such as epoxy resin or silicone resin, and dosage (referring to quality) is
1~3 times of graphene quality, for example, can be 1 times, 1.5 times, 2 times, 2.5 times or 3 times.
Organic solvent can select the existing organic solvent for capableing of dissolving resin, such as dehydrated alcohol, butanol, N- methyl
Pyrrolidones, n,N-Dimethylformamide, dimethyl acetamide are any one or more of, and dosage (referring to quality) is graphene
1~5 times of quality, for example, can be 1 times, 2 times, 3 times, 4 times or 5 times.
In preparation process, in order to obtain finely dispersed functionalization graphene slurry, can using homogenizer by graphene,
The mixture that resin, dressing agent, coupling agent, dispersing agent, wetting agent and organic solvent form is mixed.
(2) mixing of functionalization graphene slurry and expanding foam solution
Expanding foam solution comprising the first monomer, second comonomer, initiator, foaming agent and crosslinking agent is uniformly mixed, is added
Functionalization graphene slurry, is uniformly dispersed, and obtains foaming mixed liquor.
First monomer can select methacrylic acid and/or methyl methacrylate；The second comonomer can select
With acrylonitrile and/or methacrylonitrile；The initiator can select azodiisobutyronitrile, dibenzoyl peroxide, peroxidating
One of t-butyl perbenzoate；The foaming agent can select n-butanol and/or the tert-butyl alcohol；The crosslinking agent can select third
One of acrylamide, Methacrylamide, n,N-Dimethylformamide.Preferably, first monomer, second list
Body, the initiator, the foaming agent and the crosslinking agent mass ratio be (50~100): (50~100): (0.5~1.5):
(4~16): (2~10) can obtain lightweight while also with the PMI matrix of preferable mechanical strength.
In this step, the expanding foam solution quality is the 30%~45% of the functionalization graphene slurry, for example, can be with
It is 30%, 35%, 40% or 45%.
(3) prepolymerization
Foaming mixed liquor is injected in mold, mold can select two pieces of glass plates being placed in parallel, and have between the two
Cavity, the cavity form die cavity, and the mixed liquor that foams is by injection die cavity.Then foaming mixed liquor polymerize, and polymerization preferably exists
It is carried out under 40 DEG C~60 DEG C (for example, can be 40 DEG C, 45 DEG C, 50 DEG C, 55 DEG C or 60 DEG C), mold can be put into 40 DEG C~60
DEG C water-bath in polymerize, the time of polymerization will not be too long, does not exceed 2 hours, when the mixed liquor in die cavity no longer occurs
Expansion can be considered polymerization terminal, generally require 1~2 hour.It can get the raw plate of FGO/PMI copolymer after polymerization.
(4) it polymerize
First the raw plate of FGO/PMI copolymer is heat-treated, the raw plate of FGO/PMI copolymer can be put into baking oven and be carried out
Heat treatment, the temperature condition of heat treatment is preferably 100 DEG C~140 DEG C, for example, can be 100 DEG C, 110 DEG C, 120 DEG C, 130 DEG C
Or 140 DEG C, heat treatment time can control in 15min~45min, for example, can for 15min, 20min, 25min, 30min,
35min, 40min or 45min.After heat treatment, raw plate is subjected to gradient heat treatment, obtains functionalization graphene/poly- first
Base acrylimide composite wave-suction material.The condition of gradient heat treatment is preferred are as follows:
120 DEG C~150 DEG C heat preservation 2h~4h,
160 DEG C~180 DEG C heat preservation 2h~4h, and
200 DEG C~260 DEG C heat preservation 2h~4h.
The present invention provides a kind of functionalization graphene/Polymethacrylimide composite wave-suction material in second aspect,
It is prepared using the above method.The absorbing material performance is reliable, and quality is stablized, and can not only play the effect of electromagnetic wave absorption
Fruit, and it is also equipped with lightweight, wideband, advantage easy to process.
It is the embodiment that the present invention enumerates below.
Embodiment 1
(1) preparation of functionalization graphene slurry
Weigh 90 mass parts of graphene, 1.2 mass parts of dressing agent KH550, double groups of 210 mass parts of mass parts epoxy resin,
120 mass parts of dehydrated alcohol, 1.3 mass parts of dispersant B YK-W903,1.2 mass parts of wetting agent BYK-103, coupling agent TMC-
101 0.8 mass parts are handled through homogenizer high speed dispersion, obtain uniformly mixed functionalization graphene slurry.
(2) mixing of functionalization graphene slurry and expanding foam solution
It weighs 80 mass parts of methacrylic acid, 80 mass parts of methacrylonitrile, 0.7 mass parts of azodiisobutyronitrile, just
Mixture (mass ratio of the two is 1: 1) 8 mass parts of butanol and the tert-butyl alcohol, 3 mass parts of acrylamide after mixing, are added
Functionalization graphene liquid slurry made from step (1) keeps system uniform by high shear agitation and high-power ultrasonic processing
Dispersion obtains functionalization graphene/PMI foaming mixed liquor.
(3) prepolymerization
It will foam to be put into 40 DEG C of water-baths after mixed liquor injects in the die cavity that two pieces of parallel plates are formed and carry out prepolymerization,
Obtain the raw plate of FGO/PMI copolymer.
(4) it polymerize
The raw plate of FGO/PMI copolymer is heat-treated in high temperature oven, temperature is 100 DEG C, time 45min, it
Raw plate is placed in progress gradient heat treatment, actual conditions between mold afterwards are as follows: 120 DEG C (heat preservation 2h) → 160 DEG C (heat preservation 2h)
It → 200 DEG C (heat preservation 2h), finally obtains based on functionalization graphene/Polymethacrylimide composite wave-suction material.
Embodiment 2
(1) preparation of functionalization graphene slurry
Weigh 120 mass parts of graphene, 1.2 mass parts of dressing agent KH550, double groups of 210 mass of mass parts epoxy resin
Part, 120 mass parts of dehydrated alcohol, 1.3 mass parts of dispersant B YK-W903,1.2 mass parts of wetting agent BYK-103, coupling agent
0.8 mass parts of TMC-101, are handled through homogenizer high speed dispersion, obtain uniformly mixed functionalization graphene slurry.
(2) mixing of functionalization graphene slurry and expanding foam solution
It weighs 80 mass parts of methacrylic acid, 80 mass parts of methacrylonitrile, 0.7 mass parts of azodiisobutyronitrile, just
Mixture (mass ratio of the two is 1: 1) 8 mass parts of butanol and the tert-butyl alcohol, 3 mass parts of acrylamide after mixing, are added
Functionalization graphene liquid slurry made from step (1) keeps system uniform by high shear agitation and high-power ultrasonic processing
Dispersion obtains functionalization graphene/PMI foaming mixed liquor.
(3) prepolymerization
It will foam to be put into 40 DEG C of water-baths after mixed liquor injects in the die cavity that two pieces of parallel plates are formed and carry out prepolymerization,
Obtain the raw plate of FGO/PMI copolymer.
(4) it polymerize
The raw plate of FGO/PMI copolymer is heat-treated in high temperature oven, temperature is 100 DEG C, time 45min, it
Raw plate is placed in progress gradient heat treatment, actual conditions between mold afterwards are as follows: 120 DEG C (heat preservation 2h) → 160 DEG C (heat preservation 2h)
It → 200 DEG C (heat preservation 2h), finally obtains based on functionalization graphene/Polymethacrylimide composite wave-suction material.
Fig. 2 is that functionalization graphene/Polymethacrylimide composite wave-suction material reflectivity that embodiment 1 provides is surveyed
Curve is tried, Fig. 3 is that functionalization graphene/Polymethacrylimide composite wave-suction material reflectivity that embodiment 2 provides is surveyed
Curve is tried, in figure, abscissa is frequency (unit GHz), and ordinate is reflectivity (unit dB).According to fig. 2, Fig. 3 it is found that
Reflectivity≤- 5dB (68% absorb) of the material in most of frequency range of 2~18GHz, high-frequency band≤- 10dB (90%
Absorb), have extraordinary absorbing property.
Comparative example 1
That the preparation method is the same as that of Example 1 is essentially identical for comparative example 1, the difference is that: comparative example 1 makes in step (1)
What is used is dodecyltrimethoxysilane as dressing agent, uses TMC-311W (bis- (two octyloxy pyrophosphoric acid ester groups) ethylenes
The chelate of titanate esters and triethanolamine) it is used as coupling agent.
Comparative example 2
That the preparation method is the same as that of Example 1 is substantially the same for comparative example 2, the difference is that: in step (1), it is not used
Silane coupling agent KH550.
Comparative example 3
That the preparation method is the same as that of Example 1 is substantially the same for comparative example 3, the difference is that: in step (1), it is not used
Titante coupling agent TMC-101.
Comparative example 4
That the preparation method is the same as that of Example 1 is substantially the same for comparative example 4, the difference is that: in step (1), dressing agent
The dosage of KH550 is 9 mass parts, is the 10% of graphene quality；The dosage of coupling agent TMC-101 is 4.5 mass parts, is graphite
The 5% of alkene quality.
Comparative example 5
That the preparation method is the same as that of Example 1 is substantially the same for comparative example 5, the difference is that:
In step (2), weigh 100 mass parts of methacrylic acid, 100 mass parts of methacrylonitrile, two isobutyl of azo
Mixture (mass ratio of the two is 1: 1) 16 mass parts, 10 mass of acrylamide of 1.5 mass parts of nitrile, n-butanol and the tert-butyl alcohol
Part.
Table 1 is the dosage situation of each embodiment and comparative example and the performance test results of absorbing material.It can be with from table 1
Find out, absorbing material made from each embodiment and comparative example is without significant difference in density, but absorbing property performance is different.Comparison
Example 1 has used the silane coupling agent and titante coupling agent of other types when preparing absorbing material, obtained to inhale wave material
The absorbing property of material is not as good as the present invention.Comparative example 2 is not used silane coupling agent and is modified, and the absorbing property of absorbing material is not
Such as the present invention, inventor speculates the reason is that graphene can not be uniformly dispersed in the base.Titanate ester idol is not used in comparative example 3
Join agent, the electromagnetic parameter of graphene can not be adjusted, so that the absorbing property of absorbing material is far away from the present invention.Comparative example 4 is being made
Excessive silane coupling agent and titante coupling agent are used when standby, absorbing material develops to low frequency band, in high-frequency band
Suction wave perform poor.The foaming liquid measure that comparative example 5 uses in the preparation is big, so that the content of graphene drops in absorbing material
Low, the absorbing property of absorbing material is not as good as the present invention.Finally, it should be noted that above embodiments are only to illustrate skill of the invention
Art scheme, rather than its limitations；Although the present invention is described in detail referring to the foregoing embodiments, the common skill of this field
Art personnel are it is understood that it is still possible to modify the technical solutions described in the foregoing embodiments, or to its middle part
Technical characteristic is divided to be equivalently replaced；And these are modified or replaceed, the present invention that it does not separate the essence of the corresponding technical solution
The spirit and scope of each embodiment technical solution.
Claims (10)
1. a kind of functionalization graphene/Polymethacrylimide composite wave-suction material preparation method, which is characterized in that described
Method includes the following steps:
(1) graphene, resin, dressing agent, coupling agent, dispersing agent, wetting agent and organic solvent are uniformly mixed, obtain functionalization
Graphene slurry；Wherein, the dressing agent is any one or more of selected from KH550, KH560, KH570, and quality is graphite
The 1%~5% of alkene quality；The coupling agent is any one or more of selected from TMC-101, TMC-102, TMC-201, quality
It is the 0.5%~2% of graphene quality；
(2) expanding foam solution comprising the first monomer, second comonomer, initiator, foaming agent and crosslinking agent is uniformly mixed, adds function
Energy graphite alkene slurry, is uniformly dispersed, and obtains foaming mixed liquor；
(3) foaming mixed liquor is injected in mold, polymerization, obtains the raw plate of FGO/PMI copolymer；
(4) first the raw plate of FGO/PMI copolymer is heat-treated, then carries out gradient heat treatment, obtain functionalization graphene/poly-
Methacrylimide composite wave-suction material.
2. preparation method according to claim 1, which is characterized in that the graphene is the graphite that the number of plies is 2~13 layers
Alkene.
3. preparation method according to claim 1, which is characterized in that first monomer be selected from methacrylic acid and/or
Methyl methacrylate；
The second comonomer is selected from acrylonitrile and/or methacrylonitrile；
The initiator be selected from any one of azodiisobutyronitrile, dibenzoyl peroxide, peroxidized t-butyl perbenzoate or
It is a variety of；
The foaming agent is selected from n-butanol and/or the tert-butyl alcohol；And/or
It is any one or more of that the crosslinking agent is selected from acrylamide, Methacrylamide, N,N-dimethylformamide.
4. preparation method according to claim 3, which is characterized in that first monomer, described draws the second comonomer
The mass ratio for sending out agent, the foaming agent and the crosslinking agent is (50~100): (50~100): (0.5~1.5): (4~16):
(2~10).
5. preparation method according to claim 1, which is characterized in that the expanding foam solution quality is the functionalization graphene
The 30%~45% of slurry.
6. preparation method according to claim 1, which is characterized in that the dispersing agent is selected from BYK-W903, BYK-
W9012, BYK-P104S are any one or more of, and quality is the 1%~3% of graphene quality；And/or
The wetting agent is any one or more of selected from BYK-103, BYK-104, BYK-105, and quality is graphene quality
1%~2.5%.
7. preparation method according to claim 1, which is characterized in that the resin is selected from epoxy resin or organosilicon tree
Rouge, quality are 1~3 times of graphene quality；And/or
The organic solvent is selected from dehydrated alcohol, butanol, N-Methyl pyrrolidone, n,N-Dimethylformamide, dimethylacetamide
Amine is any one or more of, and quality is 1~5 times of graphene quality.
8. preparation method according to claim 1, which is characterized in that described to be aggregated in 40 DEG C~60 DEG C in step (3)
Lower progress, time are no more than 2 hours；And/or
In step (4), the process of thermal treatment condition are as follows: 100 DEG C~140 DEG C of temperature, time 15min~45min.
9. preparation method according to claim 1, which is characterized in that in step (4), the work of the gradient heat treatment
Skill condition are as follows:
120 DEG C~150 DEG C heat preservation 2h~4h,
160 DEG C~180 DEG C heat preservation 2h~4h, and
200 DEG C~260 DEG C heat preservation 2h~4h.
10. a kind of functionalization graphene/Polymethacrylimide composite wave-suction material, which is characterized in that use claim
The described in any item preparation methods of 1-9 are made.
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