CN109897189A - A kind of preparation method of situ-formed graft graphene oxide modified, high temperature resistant epoxy resin composite material - Google Patents
A kind of preparation method of situ-formed graft graphene oxide modified, high temperature resistant epoxy resin composite material Download PDFInfo
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Abstract
A kind of preparation method of situ-formed graft graphene oxide modified, high temperature resistant epoxy resin composite material, it is related to a kind of preparation method of high-temperature-resistant epoxy resin composite material.The invention aims to solve the preparation process of existing graphene/epoxy resin composite material complexity, glass transition temperature improves the low problem of degree.Method: one, wet mixing method prepares situ-formed graft graphene oxide/epoxy resin blend；Two, grinding, desolventizing plus curing agent, obtain situ-formed graft graphene oxide modified, high temperature resistant epoxy resin composite material.The present invention can get situ-formed graft graphene oxide modified, high temperature resistant epoxy resin composite material.
Description
Technical field
The present invention relates to a kind of preparation methods of high-temperature-resistant epoxy resin composite material.
Background technique
Epoxy resin bulk strength with higher and excellent adhesive property, be commonly used in industrial circle adhesive,
Matrix resin, Embedding Material etc..Raising with every profession and trade to application material requirements, researcher improve ring by a variety of methods
The performances such as the intensity of oxygen resin, heat-resisting, toughness, fire-retardant.It improves epoxy resin mechanical strength and there are many durothermic approach, including
The enhancing and heatproof to epoxy resin are realized using polyfunctional epoxy resin, aromatic amine curing agent, fiber and nano material
It is modified.
Graphene oxide (GO) is a kind of important Graphene derivative, be connected on lamella edge hydroxyl abundant,
The oxygen-containing functional groups such as carboxyl and epoxy group, the presence of these polar groups keep GO well compatible with epoxy resin, are mentioning
It can play a positive role in terms of the mechanical property for rising material.Chinese patent CN105906842B disperses graphene oxide
In organic solvent, polyetheramine is added later and is modified.It will be redispersed in after modified graphene washing drying dissolved with epoxy
In the organic solvent of resin, curing agent is added after solvent removal and solidifies obtained composite material.Significantly improve the drawing of polymer
Stretch intensity, toughness, bending strength and glass transition temperature.Chinese patent CN102153835B is first by graphene oxide
Ultrasonic disperse is modified it in tetrahydrofuran, and using isocyanates and amine curing agent, and it is solid to add epoxy resin
Change, the toughness that graphene/epoxy resin composite material is made improves significantly.
Although composite material of good performance can be accessed by addressing in similar research, be generally required to oxidation stone
Black alkene (GO) or modified graphene oxide (GO) are dried, and the methods of ultrasound is recycled to be scattered in organic solvent
It carries out chemical modification and prepares composite material, operated in preparation process relatively complicated.Oxidation stone after drying used in research
Black alkene due to stacking again, be extremely difficult to it is dry before dispersity, cause its dispersibility in the epoxy poor, also limit
The performance of graphene effect is made.In addition to this, the temperature tolerance for the composite material that Many researchers are prepared is compared to pure resin
It decreases or slightly improves, the report that glass transition temperature significantly improves is seldom.
Summary of the invention
The invention aims to solve the preparation process of existing graphene/epoxy resin composite material complexity, vitrifying
Transition temperature improves the low problem of degree, and provides a kind of situ-formed graft graphene oxide modified, high temperature resistant epoxy resin composite wood
The preparation method of material.
A kind of preparation method of situ-formed graft graphene oxide modified, high temperature resistant epoxy resin composite material, is by following step
Suddenly it completes:
One, wet mixing method prepares situ-formed graft graphene oxide/epoxy resin blend:
1., weigh 100 parts of liquid-state epoxy resins, 50 parts~500 parts organic solvents and 10 parts~200 parts matter in parts by weight
Measure the graphene oxide aqueous dispersions that score is 0.001%~10%；
2., 100 parts of liquid-state epoxy resins are dissolved into 50 parts~500 parts organic solvents, obtain mixed solution A；
3., using acid solution by 10 parts~200 parts mass fractions be 0.001%~2% graphene oxide aqueous dispersions
PH value be adjusted to 3~5, then be added drop-wise to obtain in the mixed solution A of the mixing speed of 50r/min~500r/min stirring
Mixed solution B；
4., mixed solution B is placed in wide mouth beaker, then with 50r/ in the constant temperature oil bath that temperature is 80 DEG C~150 DEG C
Mixing speed heating stirring 4h~12h of min~600r/min, obtain the situ-formed graft graphene oxide containing residual solvent/
Epoxy resin blend；
Two, situ-formed graft graphene oxide modified, high temperature resistant epoxy resin composite material is prepared:
1., contain using three-roll grinder or ball mill grinding situ-formed graft graphene oxide/asphalt mixtures modified by epoxy resin of residual solvent
Resin blends, then residual solvent is removed under conditions of temperature is for 80 DEG C~120 DEG C and less than 1000Pa, until situ-formed graft oxygen
Graphite alkene/epoxy resin blend quality is no longer changed, and obtains situ-formed graft graphene oxide/ring of removing solvent
Oxygen resin blend；
2., to removing solvent situ-formed graft graphene oxide/epoxy resin blend in curing agent is added, be stirred for
It is even, then solidification 3h~6h is carried out at being 60 DEG C~180 DEG C in temperature, obtain situ-formed graft graphene oxide modified, high temperature resistant epoxy
Resin composite materials；
Step 2 2. described in removing solvent situ-formed graft graphene oxide/epoxy resin blend and curing agent
Mass ratio is 100:(10~100).
The principle of the present invention:
The present invention adjusts the pH value for the graphene oxide aqueous dispersions that mass fraction is 0.001%~2% using acid solution
3~5 are adjusted to, then the mixed liquor by acid graphene oxide aqueous dispersions directly with liquid-state epoxy resin and organic solvent mixes
Close, liquid-state epoxy resin is cycloaliphatic epoxy resin, the epoxy group in cycloaliphatic epoxy resin under hydrionic catalysis with
Carboxyl reaction on graphene oxide, epoxy molecular are grafted in graphene oxide layer that (reaction principle is shown in Figure of description
Fig. 1), three-roll grinder or ball mill grinding are reused, then carries out the processing of the conventional methods such as vacuum desolvation agent, is added later solid
Situ-formed graft graphene oxide modified, high temperature resistant epoxy resin composite material is made in agent.Due to avoiding drying process, aoxidize
Stacking will not occur for the lamella of graphene, still there is larger interlamellar spacing between each other, mixed with liquid-state epoxy resin and organic solvent
It is easy to occur interting between epoxy molecule chain and graphene oxide layer after closing liquid mixing, and in the effect of catalyst
Lower generation graft reaction.It is participated in admittedly since graphene oxide layer is sufficiently removed and dispersed, and by the epoxy molecular of grafting
Change reaction and generates good action power, final situ-formed graft graphene oxide modified, high temperature resistant asphalt mixtures modified by epoxy resin obtained with matrix resin
The mechanical strength and glass transition temperature of resin composite material are significantly improved.
The present invention compared with prior art the advantage is that:
1, the aqueous dispersions of graphene oxide used in the present invention are that the graphene oxide of chemical oxidization method preparation is initial
State can be used after adjusting pH value by acid solution, not need to be dried or modification；
2, the present invention is graphene oxide aqueous dispersions used in the dispersion process, not because doing between graphene oxide layer
Dry and generate stacking again, wet mixing method, chemical graft and mechanical lapping both contribute to graphene oxide layer and sufficiently remove and equal
It is even to be scattered in epoxy resin；
3, preparation process of the invention is simple, it is only necessary to pass through stirring, mixing, the heating conventional means such as desolventizing and grinding
Can be obtained situ-formed graft graphene oxide modified, high temperature resistant epoxy resin composite material, preparation process it is suitable for scale production and
Using；
4, joined due to graphene oxide degree of scatter height, graphene oxide by the epoxy molecule of situ-formed graft in the present invention
Good interaction force is generated with curing reaction and matrix resin, composite property obtained is excellent, intensity, modulus and glass
The more unmodified epoxy resin of glass transition temperature has been greatly improved；
5, the tensile strength of situ-formed graft graphene oxide modified, high temperature resistant epoxy resin composite material prepared by the present invention
For 52.5MPa~87.5MPa, Young's modulus is 2.84GPa~4.21GPa, and glass transition temperature is 62 DEG C~213 DEG C.
The present invention can get situ-formed graft graphene oxide modified, high temperature resistant epoxy resin composite material.
Detailed description of the invention
Fig. 1 is the schematic diagram of epoxy resin grafted graphene oxide in specific embodiment one；
Fig. 2 is infrared spectrogram, and 1 is 3,4- epoxycyclohexyl-methyl 3, the infrared light of 4- epoxycyclohexyl formic acid esters in figure
Spectral curve, 2 have 3, a 4- epoxycyclohexyl-methyl 3 for situ-formed graft, the graphene oxide of 4- epoxycyclohexyl formic acid esters it is infrared
The curve of spectrum, 3 be the infrared spectrum curve of graphene oxide；
Fig. 3 is 2. situ-formed graft graphene oxide modified, high temperature resistant epoxy resin composite wood that one step 2 of embodiment obtains
The TEM of material schemes；
Fig. 4 is Tan δ figure, the 1 situ-formed graft graphene oxide modified, high temperature resistant 2. obtained for one step 2 of embodiment in figure
The Tan δ curve of epoxy resin composite material, 2 be the Tan δ curve of unmodified epoxy resin.
Specific embodiment
Specific embodiment 1: embodiment is described with reference to Fig. 1, a kind of situ-formed graft graphene oxide of present embodiment
The preparation method of modified, high temperature resistant epoxy resin composite material is completed by the following steps:
One, wet mixing method prepares situ-formed graft graphene oxide/epoxy resin blend:
1., weigh 100 parts of liquid-state epoxy resins, 50 parts~500 parts organic solvents and 10 parts~200 parts matter in parts by weight
Measure the graphene oxide aqueous dispersions that score is 0.001%~10%；
2., 100 parts of liquid-state epoxy resins are dissolved into 50 parts~500 parts organic solvents, obtain mixed solution A；
3., using acid solution by 10 parts~200 parts mass fractions be 0.001%~2% graphene oxide aqueous dispersions
PH value be adjusted to 3~5, then be added drop-wise to obtain in the mixed solution A of the mixing speed of 50r/min~500r/min stirring
Mixed solution B；
4., mixed solution B is placed in wide mouth beaker, then with 50r/ in the constant temperature oil bath that temperature is 80 DEG C~150 DEG C
Mixing speed heating stirring 4h~12h of min~600r/min, obtain the situ-formed graft graphene oxide containing residual solvent/
Epoxy resin blend；
Two, situ-formed graft graphene oxide modified, high temperature resistant epoxy resin composite material is prepared:
1., contain using three-roll grinder or ball mill grinding situ-formed graft graphene oxide/asphalt mixtures modified by epoxy resin of residual solvent
Resin blends, then residual solvent is removed under conditions of temperature is for 80 DEG C~120 DEG C and less than 1000Pa, until situ-formed graft oxygen
Graphite alkene/epoxy resin blend quality is no longer changed, and obtains situ-formed graft graphene oxide/ring of removing solvent
Oxygen resin blend；
2., to removing solvent situ-formed graft graphene oxide/epoxy resin blend in curing agent is added, be stirred for
It is even, then solidification 3h~6h is carried out at being 60 DEG C~180 DEG C in temperature, obtain situ-formed graft graphene oxide modified, high temperature resistant epoxy
Resin composite materials；
Step 2 2. described in removing solvent situ-formed graft graphene oxide/epoxy resin blend and curing agent
Mass ratio is 100:(10~100).
Present embodiment compared with prior art the advantage is that:
1, the aqueous dispersions of graphene oxide used in present embodiment are the graphene oxide of chemical oxidization method preparation
Initial conditions can be used after adjusting pH value by acid solution, not need to be dried or modification；
2, present embodiment is graphene oxide aqueous dispersions used in the dispersion process, between graphene oxide layer not
Stacking again is generated because dry, wet mixing method, chemical graft and mechanical lapping both contribute to graphene oxide layer and sufficiently removes
And it is dispersed in epoxy resin；
3, the preparation process of present embodiment is simple, it is only necessary to conventional by stirring, mixing, heating desolventizing and grinding etc.
Means can be obtained situ-formed graft graphene oxide modified, high temperature resistant epoxy resin composite material, preparation process proper scale metaplasia
It produces and applies；
4, divided due to graphene oxide degree of scatter height, graphene oxide by the epoxy of situ-formed graft in present embodiment
Son participates in curing reaction and matrix resin generates good interaction force, and composite property obtained is excellent, intensity, modulus
It is had been greatly improved with the more unmodified epoxy resin of glass transition temperature；
5, the stretching of the situ-formed graft graphene oxide modified, high temperature resistant epoxy resin composite material of present embodiment preparation
Intensity is 52.5MPa~87.5MPa, and Young's modulus is 2.84GPa~4.21GPa, and glass transition temperature is 62 DEG C~213
℃。
Present embodiment can get situ-formed graft graphene oxide modified, high temperature resistant epoxy resin composite material.
Specific embodiment 2: the differences between this implementation mode and the specific implementation mode are that: step 1 1. described in liquid
State epoxy resin is cycloaliphatic epoxy resin.Other steps are same as the specific embodiment one.
Specific embodiment 3: one of present embodiment and specific embodiment one or two difference are: the alicyclic ring
Race's epoxy resin be 3,4- epoxycyclohexyl-methyl 3,4- epoxycyclohexyl formic acid esters, bis- ((3,4- epoxycyclohexyl) methyl) oneself
Two acid esters, 4,5- 7-oxa-bicyclo[4.1.0-1,2- dicarboxylic acid diglycidyl ester, 4- vinyl-1- cyclohexene dicyclic oxide and 1,
One of bis- (3,4- 7-oxa-bicyclo[4.1.0 formic acid) esters of 4- cyclohexanedimethanol or in which several mixtures.Other steps and tool
Body embodiment one or two is identical.
Specific embodiment 4: one of present embodiment and specific embodiment one to three difference are: step 1 1. in
The organic solvent is dimethyl sulfoxide, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide and N-Methyl pyrrolidone
One of or in which several mixtures.Other steps are identical as specific embodiment one to three.
Specific embodiment 5: one of present embodiment and specific embodiment one to four difference are: step 1 1. in
The mass fraction be 0.001%~2% graphene oxide aqueous dispersions the preparation method is as follows:
1., graphite powder is added in reaction vessel, add the concentrated sulfuric acid that mass fraction is 98% and mass fraction be
85% phosphoric acid, ice-water bath and stirring under conditions of potassium permanganate is added, be stirred to react under conditions of ice-water bath 20min~
System is heated to 45 DEG C~50 DEG C using heating device later by 60min, and 8h~20h is kept the temperature under conditions of 45 DEG C~50 DEG C,
Cooled to room temperature, is added distilled water under conditions of ice-water bath and is diluted, and hydrogen peroxide to color is added dropwise at normal temperature and becomes
Until generating for golden yellow and without bubble, 10min~30min is centrifuged under conditions of revolving speed is 2000rpm~4000rpm,
Supernatant is poured out, the removal of bottom black substance obtains graphene dispersing solution；
Step 1. described in graphite powder and mass fraction be 98% the mass ratio of the concentrated sulfuric acid be 1:(30~150)；
Step 1. described in graphite powder and mass fraction be 85% the mass ratio of phosphoric acid be 1:(3~15)；
Step 1. described in graphite powder and potassium permanganate mass ratio be 1:(5~15)；
Step 1. described in graphite powder quality and distilled water volume ratio be 1g:(500mL~1000mL)；
2., using distilled water graphene dispersing solution is washed, then in the item that revolving speed is 8000rpm~10000rpm
Supernatant is outwelled after being centrifuged 20min~60min under part；
3., until the supernatant pH after the step of repeating step 2. to centrifugation is greater than 6, last time outwells supernatant after being centrifuged
Liquid adds distilled water, obtains the graphene oxide aqueous dispersions that mass fraction is 0.001%~2%.Other steps and specific
Embodiment one to four is identical.
Specific embodiment 6: one of present embodiment and specific embodiment one to five difference are: step 1 3. in
The acid solution is the hydrochloric acid solution that mass fraction is 1%~10%.Other steps are identical as specific embodiment one to five.
Specific embodiment 7: one of present embodiment and specific embodiment one to six difference are: step 1 3. in
The speed of the dropwise addition is 5 drops/min~30 drops/min.Other steps are identical as specific embodiment one to six.
Specific embodiment 8: one of present embodiment and specific embodiment one to seven difference are: step 2 1. in
It is 1:3:9 that the parameter of the three-roll grinder grinding, which is the ratio between three roller rates, and the gap between three rollers is 0.1 μm~10 μm,
Milling time is 0.5h~2h.Other steps are identical as specific embodiment one to seven.
Specific embodiment 9: one of present embodiment and specific embodiment one to eight difference are: step 2 1. in
The parameter of the ball mill grinding is ratio of grinding media to material (1~4): 1, ball milling speed is 100r/min~600r/min, Ball-milling Time
For 2h~4h.Other steps are identical as specific embodiment one to eight.
Specific embodiment 10: one of present embodiment and specific embodiment one to nine difference are: step 2 2. in
The curing agent is polyamide, fatty amine, polyetheramine, aliphatic cyclic amine, anhydride compound, glyoxaline compound and piperazines
Close one of object or in which several mixtures.Other steps are identical as specific embodiment one to nine.
Anhydride compound described in present embodiment is methyl tetrahydro phthalic anhydride；
Glyoxaline compound described in present embodiment is 2-ethyl-4-methylimidazole；
Piperazine compounds described in present embodiment are N- aminoethyl piperazine；
Beneficial effects of the present invention are verified using following embodiment:
Embodiment one: a kind of preparation method of situ-formed graft graphene oxide modified, high temperature resistant epoxy resin composite material is
It completes according to the following steps:
One, wet mixing method prepares situ-formed graft graphene oxide/epoxy resin blend:
1., to weigh 100 parts of liquid-state epoxy resins, 250 parts of organic solvents and 100 parts of mass fractions in parts by weight be 1%
Graphene oxide aqueous dispersions；
Step 1 1. described in liquid-state epoxy resin be cycloaliphatic epoxy resin, the cycloaliphatic epoxy resin be 3,
4- epoxycyclohexyl-methyl 3,4- epoxycyclohexyl formic acid esters；
Step 1 1. described in organic solvent be DMAC N,N' dimethyl acetamide；
Step 1 1. described in mass fraction be 1% graphene oxide aqueous dispersions the preparation method is as follows:
(1), graphite powder is added in reaction vessel, adds the concentrated sulfuric acid that mass fraction is 98% and mass fraction is
85% phosphoric acid, ice-water bath and stirring under conditions of potassium permanganate is added, be stirred to react under conditions of ice-water bath 20min~
System is heated to 48 DEG C using heating device later by 60min, keeps the temperature 14h under conditions of 48 DEG C, cooled to room temperature,
Distilled water is added under conditions of ice-water bath to be diluted, hydrogen peroxide to color is added dropwise at normal temperature becomes golden yellow and without gas
Until bubble generates, it is centrifuged 20min under conditions of revolving speed is 3000rpm, supernatant is poured out, the removal of bottom black substance obtains
To graphene dispersing solution；The mass ratio for the concentrated sulfuric acid that the graphite powder and mass fraction is 98% is 1:30；The graphite
The mass ratio for the phosphoric acid that powder and mass fraction are 85% is 1:6；The mass ratio of the graphite powder and potassium permanganate is 1:5；Institute
The quality for the graphite powder stated and the volume ratio of distilled water are 1g:1000mL；
(2), graphene dispersing solution is washed using distilled water, is then centrifuged under conditions of revolving speed is 10000rpm
Supernatant is outwelled after 30min；
(3), the step of repeating step (2) until the supernatant pH after centrifugation is greater than 6, outwell after being centrifuged by last time
Clear liquid adds distilled water, obtains the graphene oxide aqueous dispersions that mass fraction is 1%；
2., 100 parts of liquid-state epoxy resins are dissolved into 250 parts of organic solvents, obtain mixed solution A；
3., using acid solution the pH value of graphene oxide aqueous dispersions that 100 parts of mass fractions are 1% is adjusted to 5, then
It is added drop-wise to obtain mixed solution B in the mixed solution A of the mixing speed stirring of 300r/min；
Step 1 3. described in acid solution be hydrochloric acid solution that mass fraction is 10%；
Step 1 3. described in dropwise addition speed be 10 drops/min；
4., mixed solution B is placed in wide mouth beaker, then with 300r/min's in the constant temperature oil bath that temperature is 100 DEG C
Mixing speed heating stirring 5h obtains situ-formed graft graphene oxide/epoxy resin blend containing residual solvent；
Two, situ-formed graft graphene oxide modified, high temperature resistant epoxy resin composite material is prepared:
1., using three-roll grinder grind situ-formed graft graphene oxide/epoxy resin blend containing residual solvent,
Residual solvent is removed under conditions of temperature is 80 DEG C and 100Pa again, until situ-formed graft graphene oxide/epoxy blend
The quality of object is no longer changed, and obtains situ-formed graft graphene oxide/epoxy resin blend of removing solvent；
Step 2 1. described in the abrasive parameters of three-roll grinder be the ratio between three roller rates be 1:3:9, between three rollers
Gap is 10 μm, milling time 1h；
2., to removing solvent situ-formed graft graphene oxide/epoxy resin blend in curing agent is added, be stirred for
It is even, then solidification 3h is carried out at being 160 DEG C in temperature, obtain situ-formed graft graphene oxide modified, high temperature resistant epoxy resin composite wood
Material；
Step 2 2. described in curing agent be aliphatic cyclic amine, the aliphatic cyclic amine be 3,3- dimethyl -4,4- diamino two
Cyclohexyl-methane；
Step 2 2. described in removing solvent situ-formed graft graphene oxide/epoxy resin blend and curing agent
Mass ratio is 100:90.
Situ-formed graft has the acquisition side of the graphene oxide of 3,4- epoxycyclohexyl-methyl 3,4- epoxycyclohexyl formic acid esters
Method:
One, the situ-formed graft graphite oxide containing residual solvent 4. obtained using one step 1 of acetone solution embodiment
Then alkene/epoxy resin blend is centrifuged 5min in the case where revolving speed is 3000rpm again, then outwells supernatant；Add acetone point
It dissipates；
Two, step 1 is repeated, until not having epoxy resin in the supernatant after centrifugation, obtaining situ-formed graft has 3,4- epoxy
Cyclohexyl methyl 3, the graphene oxide of 4- epoxycyclohexyl formic acid esters, infrared spectrum curve are shown in curve 2 in Fig. 2；
Fig. 2 is infrared spectrogram, and 1 is 3,4- epoxycyclohexyl-methyl 3, the infrared light of 4- epoxycyclohexyl formic acid esters in figure
Spectral curve, 2 have 3, a 4- epoxycyclohexyl-methyl 3 for situ-formed graft, the graphene oxide of 4- epoxycyclohexyl formic acid esters it is infrared
The curve of spectrum, 3 be the infrared spectrum curve of graphene oxide；
Figure it is seen that 3358cm in situ-formed graft graphene oxide/epoxy resin blend of removing solvent-1It is right
That answer is-OH stretching vibration characteristic peak, 2920 and 2850cm-1Corresponding is C-H stretching vibration characteristic peak, 1456cm-1It is corresponding
It is C-H bending vibration characteristic peak, 912cm-1Corresponding is epoxy group characteristic peak, and features above peak illustrates that epoxy resin successfully connects
Branch is in graphene oxide layer；In addition, in situ-formed graft graphene oxide/epoxy resin blend of removing solvent
1730cm-1Locating corresponding C=O stretching vibration characteristic peak is enhanced and 1230 and 1117cm-1The aromatic ester characteristic peak of appearance
It can further illustrate that graft reaction has occurred in epoxy resin and graphene oxide.
Fig. 3 is 2. situ-formed graft graphene oxide modified, high temperature resistant epoxy resin composite wood that one step 2 of embodiment obtains
The TEM of material schemes；
It is answered from figure 3, it can be seen that the graphene oxide by graft modification is sufficiently removed and is highly dispersed in epoxy resin
In condensation material, and with epoxy resin-base good combination, the excellent properties of graphene oxide and it is good dispersion so that composite wood
Material has higher intensity and modulus, while glass transition temperature also greatly improves, it may thus be appreciated that availability of the present invention
The excellent situ-formed graft graphene oxide modified, high temperature resistant epoxy resin composite material of energy.
The situ-formed graft graphene oxide modified, high temperature resistant prepared according to GB/T 2567-2008 standard testing embodiment one
The tensile bars and DMA test bars of epoxy resin composite material.Test structure shows: situ-formed graft oxygen prepared by embodiment one
The tensile strength and Young's modulus of graphite alkene modified, high temperature resistant epoxy resin composite material are respectively 72.5MPa and 3.84GPa,
34.0% and 25.9% has been respectively increased in more unmodified epoxy resin.
Fig. 4 is Tan δ figure, the 1 situ-formed graft graphene oxide modified, high temperature resistant 2. obtained for one step 2 of embodiment in figure
The Tan δ curve of epoxy resin composite material, 2 be the Tan δ curve of unmodified epoxy resin.
Figure 4, it is seen that 2. situ-formed graft graphene oxide modified, high temperature resistant ring that one step 2 of embodiment obtains
The glass transition temperature of epoxy resin composite material is 189 DEG C, and more unmodified epoxy resin improves 39 DEG C.
Claims (10)
1. a kind of preparation method of situ-formed graft graphene oxide modified, high temperature resistant epoxy resin composite material, it is characterised in that one
The preparation method of kind situ-formed graft graphene oxide modified, high temperature resistant epoxy resin composite material is completed by the following steps:
One, wet mixing method prepares situ-formed graft graphene oxide/epoxy resin blend:
1., weigh 100 parts of liquid-state epoxy resins, 50 parts~500 parts organic solvents and 10 parts~200 parts quality point in parts by weight
The graphene oxide aqueous dispersions that number is 0.001%~10%；
2., 100 parts of liquid-state epoxy resins are dissolved into 50 parts~500 parts organic solvents, obtain mixed solution A；
3., using acid solution by 10 parts~200 parts mass fractions be 0.001%~2% graphene oxide aqueous dispersions pH
Value is adjusted to 3~5, then is added drop-wise to be mixed in the mixed solution A of the mixing speed stirring of 50r/min~500r/min
Solution B；
4., mixed solution B is placed in wide mouth beaker, then in the constant temperature oil bath that temperature is 80 DEG C~150 DEG C with 50r/min~
Mixing speed heating stirring 4h~12h of 600r/min obtains situ-formed graft graphene oxide/asphalt mixtures modified by epoxy resin containing residual solvent
Resin blends；
Two, situ-formed graft graphene oxide modified, high temperature resistant epoxy resin composite material is prepared:
1., situ-formed graft graphene oxide/epoxy resin for containing using three-roll grinder or ball mill grinding residual solvent it is total
Mixed object, then residual solvent is removed under conditions of temperature is for 80 DEG C~120 DEG C and less than 1000Pa, until situ-formed graft aoxidizes stone
The quality of black alkene/epoxy resin blend is no longer changed, and obtains situ-formed graft graphene oxide/asphalt mixtures modified by epoxy resin of removing solvent
Resin blends；
2., to removing solvent situ-formed graft graphene oxide/epoxy resin blend in curing agent is added, be stirred for uniformly,
Solidification 3h~6h is carried out at being again 60 DEG C~180 DEG C in temperature, obtains situ-formed graft graphene oxide modified, high temperature resistant asphalt mixtures modified by epoxy resin
Resin composite material；
Step 2 2. described in removing solvent situ-formed graft graphene oxide/epoxy resin blend and curing agent quality
Than for 100:(10~100).
2. a kind of system of situ-formed graft graphene oxide modified, high temperature resistant epoxy resin composite material according to claim 1
Preparation Method, it is characterised in that step 1 1. described in liquid-state epoxy resin be cycloaliphatic epoxy resin.
3. a kind of system of situ-formed graft graphene oxide modified, high temperature resistant epoxy resin composite material according to claim 2
Preparation Method, it is characterised in that the cycloaliphatic epoxy resin is 3,4- epoxycyclohexyl-methyl 3,4- epoxycyclohexyl formic acid
Ester, bis- ((3,4- epoxycyclohexyl) methyl) adipate esters, 4,5- 7-oxa-bicyclo[4.1.0-1,2- dicarboxylic acid diglycidyl ester, 4-
One of vinyl -1- cyclohexene dicyclic oxide and bis- (the 3,4- 7-oxa-bicyclo[4.1.0 formic acid) esters of 1,4 cyclohexane dimethanol or
Wherein several mixture.
4. a kind of system of situ-formed graft graphene oxide modified, high temperature resistant epoxy resin composite material according to claim 1
Preparation Method, it is characterised in that step 1 1. described in organic solvent be dimethyl sulfoxide, n,N-Dimethylformamide, N, N- bis-
One of methylacetamide and N-Methyl pyrrolidone or in which several mixtures.
5. a kind of system of situ-formed graft graphene oxide modified, high temperature resistant epoxy resin composite material according to claim 1
Preparation Method, it is characterised in that step 1 1. described in mass fraction be 0.001%~2% graphene oxide aqueous dispersions
The preparation method is as follows:
1., graphite powder is added in reaction vessel, adding the concentrated sulfuric acid that mass fraction is 98% and mass fraction is 85%
Phosphoric acid is added potassium permanganate under conditions of ice-water bath and stirring, is stirred to react 20min~60min under conditions of ice-water bath,
System is heated to 45 DEG C~50 DEG C using heating device later, 8h~20h is kept the temperature under conditions of 45 DEG C~50 DEG C, it is naturally cold
But to room temperature, distilled water is added under conditions of ice-water bath and is diluted, hydrogen peroxide to color is added dropwise at normal temperature becomes golden yellow
Color and without bubble generate until, revolving speed be 2000rpm~4000rpm under conditions of be centrifuged 10min~30min, by supernatant
Liquid is poured out, and the removal of bottom black substance obtains graphene dispersing solution；
Step 1. described in graphite powder and mass fraction be 98% the mass ratio of the concentrated sulfuric acid be 1:(30~150)；
Step 1. described in graphite powder and mass fraction be 85% the mass ratio of phosphoric acid be 1:(3~15)；
Step 1. described in graphite powder and potassium permanganate mass ratio be 1:(5~15)；
Step 1. described in graphite powder quality and distilled water volume ratio be 1g:(500mL~1000mL)；
2., using distilled water graphene dispersing solution is washed, then under conditions of revolving speed is 8000rpm~10000rpm
Supernatant is outwelled after centrifugation 20min~60min；
3., until the supernatant pH after the step of repeating step 2. to centrifugation is greater than 6, last time outwells supernatant after being centrifuged,
Distilled water is added, the graphene oxide aqueous dispersions that mass fraction is 0.001%~2% are obtained.
6. a kind of system of situ-formed graft graphene oxide modified, high temperature resistant epoxy resin composite material according to claim 1
Preparation Method, it is characterised in that step 1 3. described in acid solution be hydrochloric acid solution that mass fraction is 1%~10%.
7. a kind of system of situ-formed graft graphene oxide modified, high temperature resistant epoxy resin composite material according to claim 1
Preparation Method, it is characterised in that step 1 3. described in dropwise addition speed be 5 drops/min~30 drops/min.
8. a kind of system of situ-formed graft graphene oxide modified, high temperature resistant epoxy resin composite material according to claim 1
Preparation Method, it is characterised in that step 2 1. described in the parameter of three-roll grinder grinding be the ratio between three roller rates be 1:3:9, three
Gap between roller is 0.1 μm~10 μm, and milling time is 0.5h~2h.
9. a kind of system of situ-formed graft graphene oxide modified, high temperature resistant epoxy resin composite material according to claim 1
Preparation Method, it is characterised in that step 2 1. described in the parameter of ball mill grinding be ratio of grinding media to material (1~4): 1, ball milling speed is
100r/min~600r/min, Ball-milling Time are 2h~4h.
10. a kind of situ-formed graft graphene oxide modified, high temperature resistant epoxy resin composite material according to claim 1
Preparation method, it is characterised in that step 2 2. described in curing agent be polyamide, fatty amine, polyetheramine, aliphatic cyclic amine, anhydride
One of compound, glyoxaline compound and piperazine compounds or in which several mixtures.
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