CN105906842A - Modified graphene oxide and epoxy resin composite material and method for preparing same - Google Patents
Modified graphene oxide and epoxy resin composite material and method for preparing same Download PDFInfo
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- CN105906842A CN105906842A CN201610280462.2A CN201610280462A CN105906842A CN 105906842 A CN105906842 A CN 105906842A CN 201610280462 A CN201610280462 A CN 201610280462A CN 105906842 A CN105906842 A CN 105906842A
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/08—Ingredients agglomerated by treatment with a binding agent
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
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Abstract
The invention discloses a modified graphene oxide and epoxy resin composite material and a method for preparing the same. The modified graphene oxide and epoxy resin composite material and the method have the advantages that graphene oxide is modified by the aid of polyether amine to obtain novel polyether amine modified graphene oxide materials, and accordingly the problems in the aspect of dispersibility of graphene in polymer matrixes can be effectively solved; as proved by test results, the tensile mechanical strength, the toughness and the bending strength of epoxy resin materials can be simultaneously greatly improved by the added polyether amine modified graphene oxide while the glass transition temperatures of the epoxy resin materials is increased by the added polyether amine modified graphene oxide, enhancement effects of the epoxy resin materials are superior to enhancement effects of epoxy resin materials with unmodified graphene oxide, and accordingly the modified graphene oxide and epoxy resin composite material and the method have broad market application prospects.
Description
Technical field
The present invention relates to a kind of modified graphene oxide and the epoxy resin composite material comprising this modified graphene oxide, and
Their preparation method.
Background technology
Graphene, due to its outstanding mechanics, electricity and thermal property, is that one preferably prepares polymer nanocomposites
Inorganic filler.But, graphenic surface is inert, without any active group, so and work between polymeric matrix
The least, working process be also result in certain difficulty.Owing to surface of graphene oxide contains abundant carboxyl, hydroxyl
The group such as base and epoxy, can be modified for reflecting point Graphene with these active groups by multiple chemical reaction,
It is that to prepare covalent modified Graphene be a kind of the most the most frequently used method to presoma hence with graphene oxide.
But, owing to surface of graphene oxide is due to substantial amounts of hydrophilic radical, therefore with most of non-water-soluble polymer meetings
There is incompatible situation.Therefore, it is necessary to by graphene oxide is carried out surface modification, prepare functional graphite oxide
Alkene, and then obtain functional graphene oxide, improve the compatibility of graphene oxide and polymer.
Summary of the invention
For solving the problems referred to above, the invention provides the polyethex amine modification graphene oxide shown in formula (I):
Cn-A-B (Ⅰ)
Wherein, CnRepresent Graphene；A represents and is bonded to the carbonyl of carbon atom, carboxyl, hydroxyl or epoxy radicals in Graphene；
B represents and the polyethers amido of any one group bonding in carbonyl, carboxyl, hydroxyl or epoxy radicals.In the reality that the present invention is concrete
Execute in mode, it is generally the case that amino is easier to and graphite oxide as a strong nucleophilic group, the amino on polyetheramine
Carboxyl generation condensation reaction in alkene, simultaneously the most easily with carbonyl formation imine structure and there is the epoxy radicals of high tension take
Generation reaction forms open-loop products.
Instantiation as this formula, it may include one or more of following form, but other forms can be included, do not limit
Form in following concrete example；Wherein, m is natural number:
Further, described polyethex amine modification graphene oxide is at 3442cm-1、2972cm-1、2848cm-1、1638cm-1、
1454cm-1、1100cm-1There is infrared absorption peak at place.
There is infrared absorption peak at place.
Further, the interlamellar spacing of described polyethex amine modification graphene oxide is 1.28～1.82nm.
Present invention also offers a kind of method preparing described polyethex amine modification graphene oxide, it is characterised in that: include following
Step:
(1) graphene oxide is disperseed in organic solvent；
(2) being added thereto to polyetheramine, at 80 DEG C～120 DEG C, reaction obtains polyethex amine modification graphene oxide.In the present invention
In specific embodiment, it is generally the case that the main reaction occurred is the amino on polyetheramine and the carboxylic on graphene oxide
The condensation reaction that base occurs.
Further, described organic solvent is selected from dimethylformamide or dimethyl sulfoxide (DMSO).
Further, the weight average molecular weight of described polyetheramine is 230-2000, and degree of functionality is 2.
Further, in the reaction of described step (2), polyetheramine is excessive；In specific embodiment of the present invention,
Described graphene oxide is no more than 1:10g/mmol with the quality mol ratio of polyetheramine.Such proportioning ensures polyetheramine mistake
Amount is so that it is with graphite oxide alkene reaction.Inventor in experiments it is found that, at 1:10g/mmol, 1:15g/mmol and 1:
Under conditions of 30g/mmol, the characterization result no significant difference of product, it was demonstrated that under 1:10g/mmol, graphene oxide
The most react completely with polyetheramine.
Further, the reaction of described step (2) is carried out in the presence of condensing agent, and described condensing agent is selected from 4-bis-
Methylamino pyridine, 1-hydroxy benzo triazole, dicyclohexylcarbodiimide, DIC or 1-(3-dimethylamine
Base propyl group)-3-ethyl carbodiimide.Wherein, polyetheramine and condensing agent are 4-dimethylamino in a particular embodiment
The mol ratio of pyridine can be 1:0.5～1:1.
Further, described graphene oxide is 0.5～2mg/mL with the w/v of organic solvent.Concrete in the present invention
Embodiment in, this ratio specifically 1mg/mL.
Further, the reaction of described step (2) is carried out at 90 DEG C.
The time of previous reaction can be 12h～72h, makes polyetheramine modified completely to graphene oxide.In the reality that the present invention is concrete
Execute in mode, be 24h.
After reacting, can take following method that polyethex amine modification graphene oxide is purified, by obtain after reaction
Liquid is transferred in the mixed solution of dichloromethane and petroleum ether, the membrane filtration of 0.2 micron, after taking solid freeze-drying is
Can.The volume ratio relation of dichloromethane (DCM) and petroleum ether can be 1:5-1:10；Two kinds of solvents are low boiling
Point solvent, it is simple to remove in product drying course；Dichloromethane can be miscible with reaction dissolvent DMF simultaneously, and petroleum ether can
Dissolve the polyetheramine not reacted, reach the purpose of purified product with this.In a particular embodiment, the 1:6 of selection
Proportionate relationship is that layering is very fast, and solvent consumption is relatively fewer.
Owing to epoxy resin (EP) is the most widely used matrix resin of polymer matrix composite, there is the cementability of excellence
Energy, resistance to abrasion, mechanical property, chemical stability, electrical apparatus insulation, and shrinkage factor machine-shaping low, easy, preferably
Stress transmission and the advantage such as with low cost, be widely used in coating, adhesive, light industry, building, machinery, space flight and aviation,
The every field such as electric insulating materials, advanced composite material matrix.But after solidifying due to EP, crosslink density is high, in three
, there is the deficiencies such as internal stress is big, matter is crisp, fatigue durability, heat resistance, poor impact resistance in dimension network structure, causes peeling off by force
Degree, shear strength are poor, cracking answers the shortcomings such as step-down, it is difficult to meet the requirement of engineering so that it is application is by certain
Limit.
For solving the problems referred to above, the modified graphene oxide obtained is used for the modification of epoxy resin, is greatly improved by the present invention
The toughness of epoxy resin and intensity.
Present invention also offers described polyethex amine modification graphene oxide and prepare epoxy resin composite wood as addO-on therapy
Application in material.
Present invention also offers a kind of epoxy resin composite material, it includes following component: epoxy resin, curing agent and front
State polyethex amine modification graphene oxide.The range of choice of epoxy resin is very wide, concrete, it may include thermosetting resin, such as ring
Epoxy resins E44, E51, phenolic resin etc.；Thermoplastic resin, such as polyimides, Merlon etc..
Further, described epoxy resin is 1:0.001～1:0.003 with the weight ratio of polyethex amine modification graphene oxide,
Preferably 1:0.003.
Further, described polyethex amine modification graphene oxide is the oxidation stone that polyetheramine D2000 or polyetheramine D230 is modified
Ink alkene.
Further, described epoxy resin is the epoxy resin of epoxide number 0.49～0.54.
Further, described curing agent is polyamine curing agent.
Further, described curing agent is selected from 4,4-MDA, 4,4-MDA (DDS), two
ADP base sulfone, IPD (IPDA) or 3,3 '-two chloro-4,4 '-MDAs (MOCA).
Further, described curing agent is polyamine curing agent.
Further, described epoxy resin is 4:1 with the weight ratio of curing agent.
The present invention has gone back a kind of method preparing described epoxy resin composite material, it is characterised in that: comprise the following steps:
A, by polyethex amine modification graphene oxide disperse in organic solvent；
B, addition epoxy resin, dissolve, mix；
After c, removing solvent, adding curing agent, solidification obtains epoxy resin composite material.
Further, described modified graphene oxide is 0.3-1.5mg/mL with the w/v of organic solvent.
Further, described modified graphene oxide is 1mg/mL with the w/v of organic solvent.
Further, described organic solvent is selected from acetone, oxolane or dichloromethane.
It is demonstrated experimentally that the addition of the graphene oxide that the present invention is after polyethex amine modification can be greatly improved epoxy resin material simultaneously
Stretching mechanical intensity, toughness, bending strength and the glass transition temperature of material, promotes effect and is superior to add unmodified oxygen
The epoxide resin material of functionalized graphene.
To sum up compare it can be seen that the new modified graphene oxide of present invention offer, effectively overcome graphene oxide with poly-
The consistency problem of compound, significantly improves stretching mechanical intensity, toughness, bending strength and the glass transition temperature of polymer
Degree.Especially when in existing epoxy resin/graphene oxide composite material the addition of graphene oxide reach 0.3phr, it draws
Stretch intensity, elongation at break, toughness, bending modulus and glass transition temperature when being greatly reduced rapidly, and ring of the present invention
Epoxy resins/modified graphene oxide composite wood the most still can continue to improve it along with the increase of modified graphene oxide addition
Performance, effectively overcomes the defect that existing composite property is relatively low.
Obviously, according to the foregoing of the present invention, according to ordinary technical knowledge and the customary means of this area, without departing from this
Invent under above-mentioned basic fundamental thought premise, it is also possible to make the amendment of other various ways, replace or change.
The detailed description of the invention of form by the following examples, is described in further detail the foregoing of the present invention again.
But this should not being interpreted as, the scope of the above-mentioned theme of the present invention is only limitted to Examples below.All real based on foregoing of the present invention institute
Existing technology belongs to the scope of the present invention.
Accompanying drawing explanation
Fig. 1 is the infrared spectrum of unmodified graphene oxide GO.
Fig. 2 is the infrared spectrum of graphene oxide GO modified for polyetheramine D230.
Fig. 3 is the infrared spectrum of graphene oxide GO modified for polyetheramine D2000.
Fig. 4 is the XRD phenogram of unmodified graphene oxide GO and modified graphene oxide DGO, dGO
Spectrum.
Fig. 5 is the thermogravimetic analysis (TGA) figure of unmodified graphene oxide GO and modified graphene oxide DGO, dGO.
Fig. 6 is the DMA test result of epoxy resin/graphene oxide composite material.
Fig. 7 is the DMA test result of the epoxy resin/polyetheramine D2000 modified graphene oxide composite of the present invention.
Fig. 8 is the DMA test result of the epoxy resin/polyetheramine D230 modified graphene oxide composite of the present invention.
Detailed description of the invention
In the embodiment of the present invention raw materials used as follows:
The preparation of embodiment 1 polyethex amine modification of the present invention graphene oxide
1, prepared by graphene oxide solution (powder)
Employing natural graphite powder is raw material, prepares graphene oxide according to Hummers method, specific as follows: 2g graphite powder
Join in the beaker of 250mL, add 1gNaNO3, it is slowly added to the 46mL concentrated sulfuric acid and stirs, beaker is placed in
In ice-water bath, under stirring state, it is slowly added to 6gKMnO4, this process temperature is no more than 20 DEG C.5 minutes recession deicings
Water-bath, is warmed up to 35 DEG C and maintains 30min.Add 92mL deionized water, stir 15 minutes, be subsequently adding 80mL temperature
Spend the 3%H at 60 DEG C2O2Solution reduces unnecessary KMnO4, until without obvious bubble.Last 7200rpm turns
Lower centrifugal 30 minutes of speed, topples over supernatant, is centrifuged after washing with water again, be repeated several times until the pH value of supernatant liquor is
4-6, it is thus achieved that brown solid be dispersed back in water, weak ultrasonic 15min obtains uniform solution, filters or centrifugal removes
Go not oxidized black residue, it is thus achieved that uniform graphene oxide (GO) solution, and GO powder can be from this solution
Freeze-drying obtains.
2, the preparation of polyethex amine modification graphene oxide and sign
0.2g graphene oxide powder adds in 500mL round-bottomed flask, adds 200mL dimethylformamide (DMF), protects
Demonstrate,proving its concentration is 1mg/mL, and ultrasonic 30min obtains homogeneous solution.The solution of GO is slowly added to polyetheramine the most successively
D2000 and dimethylamino naphthyridine (DMAP), it is ensured that m (GO): n (polyetheramine): n (DMAP)=0.2g:6mmol:6mmol.
This mixed liquor reacts 24h at 90 DEG C, and after reaction terminates, solution is transferred in the mixed solvent of dichloromethane and petroleum ether,
Use 0.2um tetrafluoroethene filtering with microporous membrane to wash away unnecessary polyetheramine, solid will be obtained and carry out freeze-drying and changed
Graphene oxide DGO after property.
According to method same as before, prepare the graphene oxide dGO modified with polyetheramine D230.
The IR Characterization of unmodified graphene oxide GO and modified graphene oxide DGO, dGO as it is shown in figure 1,
XRD characterizes as shown in Figure 4, and thermogravimetic analysis (TGA) figure is as shown in Figure 5.
XRD result shows: the interlamellar spacing of modified graphene oxide is all significantly improved relative to GO, and polyethers is described
Amine molecule is successfully grafted on graphene sheet layer.Simultaneously, it can be seen that molecular weight is the biggest, strand is the longest, modified
GO interlamellar spacing is the biggest.
Thermal weight loss result shows: analyzed by the thermal weight loss (TGA curve) of three kinds of materials, it can be seen that through polyethex amine modification
After the thermogravimetric curve of graphite oxide difference substantially occurs.The residual heavy of graphite oxide is 38.57%, and through polyethex amine modification
After the residual heavy obvious reduction of graphite oxide, and the raising of molecular weight of the polyetheramine used along with modification, residual heavy the lowest.This is main
If being due to the different reason of the length of strand of the polyetheramine in grafting.Modified polyether amine molecule amount is the biggest, modified
Graphite oxide interlayer organic content the highest.Meanwhile, by the contrast of the weight loss rate curve to three kinds of nano particles, it is known that
The heat endurance of the graphite oxide surface group after polyethex amine modification is greatly improved, and improves to more than 370 DEG C from 206 DEG C.
This proves the most simultaneously, really happens is that graft reaction in modifying process in oxidized graphite flake layer.The polyetheramine of long-chain successfully connects
Branch, on the oxy radical of graphite oxide, greatly increases its heat endurance.
From Fig. 1-3 it can be seen that compared with unmodified graphene oxide, polyethex amine modification graphene oxide of the present invention exists
3442cm-1、2972cm-1、2848cm-1、1638cm-1、1454cm-1There is new infrared absorption peak at place.3442cm-1Place
It is the N-H stretching vibration peak of-CONH-, 2972cm-1、2848cm-1Place is-CH2-C-H stretching vibration peak, 1638cm-1
Place is the stretching vibration peak of C=O bond, 1454cm in-CONH--1Place is-CH2-the flexural vibrations peak of C-H, 1100cm-1
Place is C-N.
Meanwhile, 1075cm-1、1250cm-1-C-O-C-the peak at place, 1635cm-1The C-O peak of place COOH, 1733cm-1
The C=O peak of place COOH, 3420cm-1-OH the peak of place COOH almost disappears, it was demonstrated that the active group of graphene oxide
Group carboxyl, epoxy radicals are reacted with polyetheramine.
The preparation of embodiment 2 composite of the present invention and performance
1, the preparation of composite
The preparation of nano composite material EP/DGO: weigh the modified graphene oxide DGO of a certain amount of (0.1phr) with
The ratio of 1mg/mL is dispersed in acetone soln, ultrasonically treated 30min, and 50g epoxy resin is added modified graphite oxide
In the acetone soln of alkene, regulation oil bath temperature is 60 DEG C, continues electric stirring 30min.Graphene to be oxidized and asphalt mixtures modified by epoxy resin
After fat is sufficiently mixed uniformly, puts into vacuum drying oven, temperature 80 DEG C, place 24h, remove solvent.Again by 12.5g curing agent
DDM (4,4-MDA) joins in beaker, stops after continuously stirred 2-3min, takes out beaker.Again by beaker
It is placed in vacuum drying chamber, vacuumizes removing bubble.Finally gained mixing liquid is cast in the polytetrafluoroethylene (PTFE) of standard batten
In mould, putting into curing molding in baking oven, condition of cure is 135 DEG C × 2h+175 DEG C × 2h.
The preparation method of EP/GO, EP/dGO is identical with the preparation method of EP/DGO.
2, the performance test of composite
Stretching mechanical property testing: use Instron universal testing machine, test according to GB/T 1040-92, draw
Stretching speed is 10mm/min.
Sliding and bending deformation is tested: uses Instron universal testing machine, tests according to ISO 178-2010 standard,
Applying stress rate is 2mm/min.
Dynamic mechanical analysis (DMA): use the Q800 type dynamic thermomechanical analysis apparatus that TA company of the U.S. produces, selects
Three-point bending chuck is tested, and test frequency is 1Hz, and heating rate is 3 DEG C/min, and Range of measuring temp is
100-220℃。
(1) stretching mechanical strength break, elongation at break and toughness test
Table 1. stretching mechanical intensity, elongation at break and toughness test result
EP: epoxy resin；
EP/GO: epoxy resin/graphene oxide composite material；
The epoxy resin of EP/DGO: the present invention/polyetheramine D2000 modified graphene oxide composite
The epoxy resin of EP/dGO: the present invention/polyetheramine D230 modified graphene oxide composite
Tensile Strength: stretching mechanical intensity；
Elongation at break: elongation at break；
Toughness: toughness.
Table 1 result shows, compared with epoxy resin/graphene oxide composite material, and the epoxy resin of the present invention/modified oxidized
Graphene composite material is all significantly enhanced at aspects such as stretching mechanical intensity, elongation at break and toughness.This illustrates warp
Graphene after polyethex amine modification can be good be dispersed among epoxy resin-base material, give full play to it as two wieners
The interface interaction of rice material, intensity is obviously improved.
In addition, table 1 result it is also shown that in the case of addition is higher (0.3phr), epoxy resin/graphite oxide
The hot strength of alkene composite, elongation at break, toughness are greatly reduced, this may with nano material intrinsic silicon point
Bulk condition is relevant, illustrates that the graphene oxide hydrophily of non-modified is obvious, and the compatibility between polymer is bad.
And the composite of the present invention still can continue to lift up the stretching mechanical intensity of composite, elongation at break and tough
Property, it was demonstrated that the modified graphene oxide of the present invention can be effectively improved the interface cohesion between nano particle and matrix material, gram
Take the defect that graphene oxide is poor with polymer compatibility, still can improve symbol composite along with the increase of addition
Performance.
(2) bending mechanical performance test
Table 2 bending mechanical performance test result
Table 2 result shows, the graphene oxide after polyethex amine modification can also improve the bending modulus of material significantly, from
And reach material is strengthened and toughness reinforcing effect simultaneously.Modified graphene oxide/epoxy-resin systems bending modulus is bright
Show and be better than unmodified graphene oxide/epoxy-resin systems.
(3) dynamic mechanical properties
The dynamic mechanical analysis result of composite is as shown in Fig. 6-8 and table 3:
Table 3 dynamic mechanical analysis result
It can be seen that the modified graphene oxide/epoxy-resin systems glass transition temperature of the present invention is substantially better than and does not changes
Property graphene oxide/epoxy-resin systems, improve composite use temperature the upper limit, there is broader practice prospect.
To sum up compare it can be seen that the new modified graphene oxide of present invention offer, effectively overcome graphene oxide with poly-
The consistency problem of compound, significantly improves stretching mechanical intensity, toughness, bending strength and the glass transition temperature of polymer
Degree.Especially when in existing epoxy resin/graphene oxide composite material the addition of graphene oxide reach 0.3phr, it draws
Stretch intensity, elongation at break, toughness, bending modulus and glass transition temperature when being greatly reduced rapidly, and ring of the present invention
Epoxy resins/modified graphene oxide composite wood the most still can continue to improve it along with the increase of modified graphene oxide addition
Performance, effectively overcomes the defect that existing composite property is relatively low.
Claims (10)
1. the polyethex amine modification graphene oxide shown in formula (I):
Cn-A-B (Ⅰ)
Wherein, CnRepresent Graphene；A represents and is bonded to the carbonyl of carbon atom, carboxyl, hydroxyl or epoxy radicals in Graphene；
B represents and the polyethers amido of any one group bonding in carbonyl, carboxyl, hydroxyl or epoxy radicals.
Polyethex amine modification graphene oxide the most according to claim 1, it is characterised in that: described polyethex amine modification oxygen
Functionalized graphene is at 3442cm-1、2972cm-1、2848cm-1、1638cm-1、1454cm-1、1100cm-1There is infrared suction at place
Receive peak.
Polyethex amine modification graphene oxide the most according to claim 1 and 2, it is characterised in that: described polyetheramine changes
The interlamellar spacing of property graphene oxide is 1.28～1.82nm.
4. prepare the method for polyethex amine modification graphene oxide described in any one of claim 1-3 for one kind, it is characterised in that:
Comprise the following steps:
(1) graphene oxide is disperseed in organic solvent；Preferably organic solvent is dimethylformamide or dimethyl Asia
Sulfone；
(2) being added thereto to polyetheramine, at 80 DEG C～120 DEG C, reaction obtains polyethex amine modification graphene oxide；The most anti-
Answering temperature is 90 DEG C；
The reaction of described step (2) is carried out in the presence of condensing agent, described condensing agent selected from DMAP,
1-hydroxy benzo triazole, dicyclohexylcarbodiimide, DIC or 1-(3-dimethylamino-propyl)-3-ethyl
Carbodiimide.
Method the most according to claim 4, it is characterised in that: in step (2), the Weight-average molecular of described polyetheramine
Amount is 230-2000, and degree of functionality is 2；
In this reaction, polyetheramine is excessive；Preferably, graphene oxide is no more than 1 with the quality mol ratio of polyetheramine:
10g/mmol。
6. the polyethex amine modification graphene oxide described in any one of claim 1-3 is preparing epoxy resin as addO-on therapy
Application in composite.
7. an epoxy resin composite material, it is characterised in that: it includes following component:
Epoxy resin, curing agent and the polyethex amine modification graphene oxide described in any one of claim 1-3.
Epoxy resin composite material the most according to claim 7, it is characterised in that: described epoxy resin and polyetheramine
The weight ratio of modified graphene oxide is 1:0.001～1:0.003, preferably 1:0.003.
Epoxy resin composite material the most according to claim 8, it is characterised in that:
Described polyethex amine modification graphene oxide is the graphene oxide that polyetheramine D2000 or polyetheramine D230 is modified；
Described epoxy resin is the epoxy resin of epoxide number 0.49～0.54；
Described curing agent is polyamine curing agent；Preferably, described curing agent is selected from 4,4-MDA, diaminourea
The chloro-4,4 '-MDA in diphenyl sulfone, IPD or 3,3 '-two.
10. the method preparing epoxy resin composite material described in claim 8 or 9, it is characterised in that: include following
Step:
A, by polyethex amine modification graphene oxide disperse in organic solvent；Preferably organic solvent is acetone, oxolane
Or dichloromethane；
B, addition epoxy resin, dissolve, mix；
After c, removing solvent, adding curing agent, solidification obtains epoxy resin composite material；
Preferably, described modified graphene oxide is 0.3-1.5mg/mL with the w/v of organic solvent, the heaviest
Amount volume ratio is 1mg/mL.
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