CN103408934B - A kind of modified graphene/bismaleimide resin composite material and preparation method thereof - Google Patents
A kind of modified graphene/bismaleimide resin composite material and preparation method thereof Download PDFInfo
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- CN103408934B CN103408934B CN201310283358.5A CN201310283358A CN103408934B CN 103408934 B CN103408934 B CN 103408934B CN 201310283358 A CN201310283358 A CN 201310283358A CN 103408934 B CN103408934 B CN 103408934B
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Abstract
The invention discloses a kind of modified graphene/bismaleimide resin composite material and preparation method thereof, belong to Nano-composite materials technical field.First described preparation method prepares graphite oxide, then prepares modified graphene, is finally that 0.1 ~ 0.5wt% prepares matrix material according to meeting modified graphene content in material.The resistance to impact shock of modified graphene/bismaleimide resin composite material that the present invention proposes is 19.557 ~ 26.171KJ/m
2, toughness reinforcing compared to original bismaleimide resin 3.67% ~ 38.74%.Interfacial combined function between the middle modified graphene of matrix material of the present invention and bismaleimide resin improves greatly, improves the toughness of bismaleimide resin, is conducive to the performance of the performance of Graphene own; The compare toughness of bismaleimide resin itself and reduced graphene/bismaleimide resin composite material of the matrix material of gained improves a lot.
Description
Technical field
The invention belongs to Nano-composite materials technical field, specifically a kind of modified graphene/bismaleimide resin composite material and preparation method thereof.
Background technology
Graphene is with sp by carbon atom
2the monoatomic layer that hydridization connects is formed, and its basic structural unit is benzene six-ring the most stable in organic materials, and its theoretic throat is only 0.35nm, and being the thinnest two-dimensional material found at present, is the two-dimentional allotropic substance of the carbon found in recent years.This special construction has contained abundant and peculiar physical phenomenon, makes Graphene show the physicochemical property of many excellences, and the intensity as Graphene is the highest in test material, and reaching 130GPa, is more than 100 times of steel; Its carrier mobility reaches 1.5 × 10
4cm
2v
-1s
-1, be known at present 2 times with the indium antimonide materials of most high mobility, exceed 10 times of commercial silicon chip mobility; The thermal conductivity of Graphene can reach 5 × 10
3wm
-1k
-1, be adamantine 3 times; In addition, Graphene also has the special propertys such as room-temperature quantum Hall effect.These excellent specific properties of Graphene cause " carbon " research boom of scientific and technological circle's new round.Investigator the preparation of Graphene, the electronic structure performance of Graphene and its do a lot of work in the application of microelectronic device.The preparation method of Graphene has a lot, comprises micromechanics stripping method, CVD, molecular beam epitaxy and graphite oxide method.Wherein graphite oxide method preparation method, equipment are simply, and output is comparatively large, is conducive to realizing industrialization.Be graphene oxide by the product that graphite oxide legal system is standby, there is a large amount of oxygen-containing functional groups in its surface, can prepare the derivative of Graphene further by chemical reaction.The same with most of carbon material, Graphene also can be applied to composite additives, improves the over-all properties of matrix material.At present, the research of this respect is mainly conceived to the electromagnetic performance improving matrix material, and the research for mechanical property is less.In addition, the same with most of nano material, Graphene also exists in resin dispersed poor, and self easily reunites, with the problem that resin compatible is poor, and comparatively strong by the graphene oxide wetting ability that graphite oxide legal system is standby, also undesirable with the combination of resin.Therefore only utilize Graphene or graphene oxide to add in resin and can not reach the object improving mechanical property.
Summary of the invention
For problems of the prior art, the present invention proposes a kind of modified graphene/bismaleimide resin composite material and preparation method thereof.The compare toughness of bismaleimide resin itself and Graphene/bismaleimide resin composite material of the prior art of described modified graphene/bismaleimide resin composite material improves a lot, interfacial combined function between modified graphene and bismaleimide resin improves greatly, is conducive to the performance of the performance of Graphene own.And the preparation method of modified graphene/bismaleimide resin composite material that the present invention proposes, increase Graphene solvability in organic solvent, be beneficial to its expansion in the composite and dispersion.
A kind of modified graphene/bismaleimide resin composite material that the present invention proposes is the black solid of two phase structure, matrix is the bismaleimide resin matrix of original bismaleimide resin powder and thinner composition, wild phase is the modified graphene of black, be dispersed in bismaleimide resin matrix, this modified graphene content is in the composite 0.1 ~ 0.5wt%.It is 1 ~ 1.5nm that modified graphene exists thickness in tetrahydrofuran (THF) (THF) solvent, modified graphene particle size 0.5 ~ 1 μm.The shock strength of modified graphene/bismaleimide resin composite material that the present invention proposes reaches 26.171KJ/m
2, more toughness reinforcing than pure bismaleimide resin 38%.
The present invention proposes a kind of preparation method of Graphene/bismaleimide resin composite material of modification, specifically comprises following step:
Step one: the preparation of graphite oxide:
(1) Graphite Powder 99, KNO is got
3powder and the vitriol oil (concentration is 75wt% ~ concentration is 98.3wt%) mix, and blending ratio is add 1.5g KNO in every 1.5g Graphite Powder 99
3powder, 65 ~ 69ml vitriol oil, add KMnO by during mixture heating in water bath to 35 ~ 40 DEG C obtained
4powder, adding proportion is that every 1.5g graphite adds 8.0 ~ 9.5gKMnO
4, stir at 100 ~ 300r/min rotating speed lower magnetic force, reaction more than 6h; Then in mixture, slowly first time adds deionized water, and bath temperature is adjusted to 60 DEG C ~ 70 DEG C, after reaction 25 ~ 40min, second time adds deionized water wherein again, the ratio that the add-on that described first time and second time add deionized water still adds deionized water 100 ~ 200ml and 200 ~ 400ml with every 1.5g graphite adds, after continuing reaction 4 ~ 5min, in mixing liquid, drip concentration is 20wt% ~ 50wt%H
2o
2the aqueous solution, becomes glassy yellow to mixing liquid;
(2) mixing liquid is extremely neutral with deionized water wash, be configured to the graphene oxide water solution that concentration is 1 ~ 2mg/ml.
Step 2: the preparation of modified graphene:
After using ultrasonic cleaning instrument ultrasonic oxidation graphene aqueous solution 1 ~ 2h, obtain the suspension of graphene oxide.Adjustment suspension pH value is 9 ~ 10, reacts 1h according to 120mg graphene oxide water solution proportioning 1 ~ 1.5ml hydrazine hydrate (50%) in magnetic agitation, oil bath at being heated to 100 DEG C.Then according to the ratio of every 0.012g graphene oxide water solution proportioning 0.001 ~ 0.0015mol Ursol D and 0.0015 ~ 0.002mol Isopentyl nitrite, first Isopentyl nitrite is added when being heated to 80 DEG C in magnetic agitation, oil bath, add the Ursol D being dissolved in more than 60 DEG C deionized waters again, reaction more than 10h, cools to room temperature and is kept in tetrahydrofuran (THF) (THF) with after deionized water and tetrahydrofuran (THF) (THF) washing.
Step 3: the preparation of modified graphene/bismaleimide resin composite material:
Tetrahydrofuran (THF) (THF) solution of modified graphene adds bismaleimide resin thinner diallyl bisphenol (DABPA), Ultrasonic Cell Disruptor 360W(power 900W, setting operating power 40%) under ultrasonic 1 ~ 2h, then under magnetic agitation, vacuum, emptying tetrahydrofuran (THF) (THF) is stirred, temperature from ambient rises to 140 DEG C gradually, after bubble is got rid of completely, in magnetic agitation, to add with diallyl bisphenol mol ratio at 140 DEG C be the bismaleimide resin powder of 1:1, continues to stir 0.5 ~ 1h in magnetic agitation, at 140 DEG C after solution clarification.Mixing liquid is injected ready mould, 140 DEG C of vacuum drying ovens are bled bubble 15 ~ 30min, then be cured according to the solidification value of bismaleimide resin, solidification flow process is be incubated 3h at 180 DEG C of temperature, be incubated 2h at 220 DEG C of temperature, be incubated 3h at 250 DEG C of temperature, be cooled to room temperature, the demoulding after taking out, is met the modified graphene/bismaleimide resin composite material of requirement.
The advantage that the present invention has is:
(1) the present invention proposes a kind of preparation method of modified graphene/bismaleimide resin composite material, in preparation process, eliminates a large amount of oxy radical of surface of graphene oxide, increases the organic solvent solubility of the rear Graphene of reduction.
(2) the present invention proposes a kind of preparation method of modified graphene/bismaleimide resin composite material, by hydrazine hydrate reduction graphene oxide, and utilize Ursol D and Isopentyl nitrite to carry out diazotization reaction to it, there is the modified graphene of aniline group on preparation surface, reacted by the double bond of the aniline group on modified graphene and bismaleimide resin again, modified graphene and bismaleimide resin are tied to form as a whole by chamical binding, interfacial combined function between such Graphene and bismaleimide resin improves greatly, improve the toughness of bismaleimide resin, be conducive to the performance of the performance of Graphene own,
(3) the present invention proposes a kind of preparation method of modified graphene/bismaleimide resin composite material, and the compare toughness of bismaleimide resin itself and reduced graphene/bismaleimide resin composite material of the modified graphene/bismaleimide resin composite material of gained improves a lot.
Accompanying drawing explanation
Fig. 1: in the present invention, graphite oxide, reduction and diazotization reaction prepare modified graphene process schematic;
Fig. 2: the atomic force microscope figure of graphene oxide (a), reduced graphene (b) and modified graphene (c) ultrasonic disperse in deionized water in the present invention;
Fig. 3: graphene oxide (a), reduced graphene (b) and modified graphene (c) infrared spectra in the present invention;
Fig. 4: graphite (a), graphene oxide (b), reduced graphene (c) and modified graphene (d) Raman spectrum in the present invention;
Fig. 5-A: graphite oxide x-ray photoelectron power spectrum in the present invention: (a) full spectrum, (b) O1s peak, (c) C1s peak and (d) C1s swarming spectrum;
Fig. 5-B: reduced graphene x-ray photoelectron power spectrum in the present invention: (a) full spectrum, (b) O1s peak, (c) C1s peak and (d) C1s swarming spectrum;
Fig. 5-C: modified graphene x-ray photoelectron power spectrum in the present invention: (a) full spectrum, (b) O1s peak, (c) C1s swarming and (d) N1s swarming spectrum;
Fig. 6: the stereoscan photograph (× 2000) of modified graphene/bismaleimide resin composite material fracture prepared by example 1,2 in the present invention: (a) original bismaleimide resin; (b) 0.1%wt. modified graphene/span matrix material; C () is 0.3%wt. modified graphene/span matrix material; (d) 0.5%wt. modified graphene/span matrix material;
Fig. 7: the stereoscan photograph (× 60000) of 0.3wt% modified graphene/bismaleimide resin composite material fracture prepared by example 2 in the present invention;
Fig. 8: the stereoscan photograph (× 60000) of 0.3wt% reduced graphene/bismaleimide resin composite material fracture prepared by example 3 in the present invention;
Fig. 9: the stereoscan photograph (× 60000) of 0.3wt% graphene oxide/bismaleimide resin composite material fracture prepared by example 4 in the present invention.
Embodiment
Below in conjunction with drawings and Examples, the present invention is described in further detail.
The present invention proposes a kind of modified graphene/bismaleimide resin composite material, this modified graphene/bismaleimide resin composite material is black solid, it is two phase structure, main body is the bismaleimide resin matrix of bismaleimide resin powder and diallyl bisphenol composition, wild phase is the modified graphene of black, described wild phase is dispersed in bismaleimide resin matrix, and this modified graphene content is in the composite 0.1 ~ 0.5wt%.It is 1 ~ 1.5nm that modified graphene exists thickness in tetrahydrofuran (THF) (THF) solvent, size 0.5 ~ 1 μm.The shock strength of described modified graphene/bismaleimide resin composite material reaches 26.171KJ/m
2.
The present invention proposes a kind of preparation method of Graphene/bismaleimide resin composite material of modification, and by reference to the accompanying drawings 1, specifically comprise following step:
Step one: the preparation of graphite oxide:
(1) Graphite Powder 99, KNO is got
3powder and the vitriol oil (concentration is 75wt% ~ 98.3wt%) mix, and blending ratio is add 1.5 ~ 2g KNO in every 1.5g Graphite Powder 99
3powder, 65 ~ 69ml vitriol oil, add KMnO by during mixture heating in water bath to 35 ~ 40 DEG C obtained
4powder, adding proportion is that every 1.5g graphite adds 8.0 ~ 9.5gKMnO
4, stir at 100 ~ 300r/min rotating speed lower magnetic force, reaction more than 6h; Then in mixture, slowly first time adds deionized water, and bath temperature is adjusted to 60 DEG C ~ 70 DEG C, after reaction 25 ~ 40min, second time adds deionized water wherein again, the ratio that the add-on of described first time and second time deionized water still adds deionized water 100 ~ 200ml and 200 ~ 400ml with every 1.5g graphite adds, after continuing reaction 4 ~ 5min, in mixing liquid, drip concentration is 20wt% ~ 50wt%H
2o
2, become glassy yellow to mixing liquid;
(2) mixing liquid is extremely neutral with deionized water wash, add the graphite oxide aqueous solution that deionized water is configured to 1 ~ 2mg/ml.
Step 2: the preparation of modified graphene:
Get the graphite oxide aqueous solution in step one, after using the ultrasonic 1 ~ 2h of ultrasonic cleaning instrument, obtain the suspension of graphene oxide.In described suspension, add sodium hydroxide solution adjustment pH value is 9 ~ 10, according to 120mg graphene oxide water solution proportioning 1 ~ 1.5ml hydrazine hydrate (Hydrazine, massfraction 50%), reacts 1h in magnetic agitation, oil bath at being heated to 100 DEG C.Then according to the ratio of every 0.012g graphene oxide water solution proportioning 0.001 ~ 0.0015mol Ursol D and 0.0015 ~ 0.002mol Isopentyl nitrite, first Isopentyl nitrite is added when being heated to 80 DEG C in magnetic agitation, oil bath, add the Ursol D being dissolved in more than 60 DEG C deionized waters again, reaction more than 10h, cools to room temperature and is kept in tetrahydrofuran (THF) (THF) with after deionized water and tetrahydrofuran (THF) (THF) washing.The preparation flow of modified graphene is shown in Fig. 1.
Step 3: the preparation of modified graphene/bismaleimide resin composite material:
Bismaleimide resin thinner diallyl bisphenol (DABPA) is added at tetrahydrofuran (THF) (THF) solution of modified graphene, at Ultrasonic Cell Disruptor 360W(power 900W, setting operating power 40%) ultrasonic 1 ~ 2h under power, then under magnetic agitation, vacuum, emptying tetrahydrofuran (THF) (THF) is stirred, temperature from ambient rises to 140 DEG C gradually, after bubble is got rid of completely, in magnetic agitation, to add with diallyl bisphenol mol ratio at 140 DEG C be the bismaleimide resin powder of 1:1, continues to stir 0.5 ~ 1h in magnetic agitation, at 140 DEG C after solution clarification.Mixing liquid is injected ready mould, 140 DEG C of vacuum drying ovens are bled bubble 15 ~ 30min, then be cured according to the solidification value of bismaleimide resin, solidification flow process is be incubated 3h at 180 DEG C of temperature, be incubated 2h at 220 DEG C of temperature, be incubated 3h at 250 DEG C of temperature, be cooled to room temperature, the demoulding after taking out, is met the modified graphene/bismaleimide resin composite material of requirement; The mass percent preparing modified graphene in the matrix material obtained is 0.1 ~ 0.5%.
The graphene oxide (a) prepared in step 2, reduced graphene (b) and modified graphene (c) atomic force microscope result in deionized water, as shown in Figure 2, can see that graphene oxide dispersibles in deionized water and become thickness at 0.8 ~ 1nm, the graphene oxide thin slice of size 3 ~ 8 μm, the rear Graphene of reduction then thickness is reduced to 0.4 ~ 0.6nm, size is still at micron order, and modified graphenic surface grafting aniline group, synusia thickness is increased to 1 ~ 1.5nm.
The result of infrared spectra (Fig. 3), Raman spectrum (Fig. 4) and XPS test (Fig. 5, table 1) shows modification success.In the infrared spectra of Fig. 3, can find out that obtained graphite oxide (a) is at 3420cm
-1there is a very wide strong peak, belong to the infrared absorption peak that hydroxyl (-OH) stretching vibration produces.In figure, another wide and strong peak appears at 1260cm
-1place is the absorption band that the stretching vibration of phenolic hydroxyl group (C-O) key produces.Except proving the existence of hydroxyl further, the completely not destroyed of hexa-atomic aromatic ring after oxidation strongly in graphite has also been proved at this peak.1720cm
-1with 1050cm
-1locate sharp-pointed strong peak, two places and then correspond respectively to the stretching vibration of the C=O bond (C=O) in carboxyl and the absorption of vibrations of carbon oxygen singly-bound (C-O) key, corresponding 3700 ~ 2000cm
-1the broad peak occurred in scope, can prove the existence of carboxyl in graphite oxide.In addition, 1620cm
-1the absorption peak that place occurs corresponds to ketone group (C=O) group, and 802cm
-1place is then the charateristic avsorption band of epoxide group (-C (O) C-).There is-OH ,-COOH ,-C=O ,-C (O) C-functional group in graphite oxide surface obtained in known of the information experiment of comprehensive whole infrared spectra, and-OH accounts for larger proportion, illustrates that oxidation fully.Graphene (b) after hydrazine hydrate reduction, 3420cm
-1the wide strong hydroxyl peak at place narrows greatly, and 1720cm
-1c=O signal, the 1260cm of the carboxyl at place
-1c-O signal, the 1050cm of the phenolic hydroxyl group at place
-1the carbon oxygen singly-bound C-O signal at place and 802cm
-1the completely dissolve of epoxy charateristic avsorption band, illustrate that oxy radical is removed in a large number.Through Graphene infared spectrum (c) of diazotization modification, at 1660cm
-1, 1500cm
-1, 1100cm
-1and 814cm
-1having there is stronger phenyl ring characteristic peak in place, comprises the skeletal vibration of phenyl ring and in-plane bending vibration, the out-of-plane deformation vibration of CH, and at 1380cm
-1there is the stretching vibration peak of fragrant C-N in place, and the characteristic peak 3500-3300cm of N-H
-1the hydroxyl peak 3430cm caused with inevitable water
-1coincide, be difficult to distinguish.Fig. 3 demonstrates certain success of anilino grafting from unit structure, amino modifiedly haves laid a good foundation to the application of Graphene in following matrix material.
Raman spectrum (Fig. 4) analysis can obtain, and all samples still have and are in 1325.8cm
-1d band and be in 1588.3cm
-1the G band at place.As previously mentioned, D band corresponds to the defect of graphite (a), it and sp
3the vibration of carbon atom is relevant.And G band and sp
2the vibration of carbon atom is relevant.So peak intensity I (G) ratio of the peak intensity I (D) of D band and G band is usually for representing sp
2carbon atom number and sp
3carbonatoms object ratio is also the strong evidence of graphene layer electronic structure change simultaneously.By calculating, I (the D)/I (G) of graphene oxide (b) is 1.15, and I (the D)/I (G) of reduction rear oxidation Graphene (c) reaches 1.31.The surface of graphene oxide oxy radical reduced by hydrazine is removed in a large number, sp
2c-structure starts to recover, and the chemical reaction Graphene synusia simultaneously owing to producing diminishes broken, and therefore comparatively G peak is slightly high at D peak.I (D)/I (G) ratio of modified Graphene (d) is the further raising of 1.42, I (D)/I (G) ratio, and the sp of graphene-structured is described
3carbon atom number increase, analyze known, this be due in diazo process at graphenic surface grafting aniline group, replace structure increase, make a part of sp
2carbon atom double bond is opened and is become sp
3carbon atom causes, and successfully can prove for grafting.
By to the XPS result of graphite and graphite oxide known (as shown in Fig. 5, table 1), be oxidized rear oxygen atom content and significantly improve (C/O is 2.06), illustrate that graphite is oxidized.After reduction, Graphene C/O increases to 5.78, and wherein the main existence form of C element is sp
2c, there is atom N in modified graphene surface, and existence form is mainly-NH
2this illustrates the reaction result as design, and diazotization reaction grafting aniline group occurs on reduced graphene surface.Modified, C/N is reduced to modified 12.70 by 32.81 after reducing, and C/O is increased to 8.27 by 5.78 after reducing, and introducing aniline group conforms to, and illustrates that modified graphene is prepared comparatively successful.
Table 1 graphite, graphite oxide, reduced graphene, modified graphene XPS result
The preparation method of matrix material provided by the invention is described in detail below by embodiment.
Embodiment 1:
Adopt method preparation quality percentage composition provided by the invention be 0.1% modified graphene/bismaleimide resin composite material, concrete steps are as follows:
The first step, prepared by graphite oxide:
Get Graphite Powder 99, KNO
3powder and the vitriol oil (concentration is 98.3wt%) mix, and blending ratio is add 1.5g KNO in every 1.5g Graphite Powder 99
3powder, the 67ml vitriol oil, add KMnO4 powder by during the mixture heating in water bath to 40 DEG C obtained, adding proportion is that every 1.5g graphite adds 9.0gKMnO
4, stir at 220r/min rotating speed lower magnetic force, reaction more than 6h; Then in mixture, slowly add 100mL deionized water, and bath temperature is adjusted to 60 DEG C, after reaction 25min, then add 300ml deionized water wherein, after continuing reaction 4min, in mixing liquid, drip 9ml concentration is 30wt%H
2o
2, become glassy yellow to mixing liquid;
Mixing liquid is extremely neutral with deionized water wash, preserve in deionized water and be configured to the graphene oxide water solution that concentration is 1mg/ml.
Second step, the preparation of modified graphene:
After using ultrasonic cleaning instrument ultrasonic oxidation graphene aqueous solution 1h, obtain the suspension of graphene oxide.In described suspension, add sodium hydroxide adjustment pH value is 9, reacts 1h according to 120mg graphene oxide water solution proportioning 1ml hydrazine hydrate (massfraction 50%) in magnetic agitation, oil bath at being heated to 100 DEG C.Then according to the ratio of every 0.012g graphene oxide water solution proportioning 0.001mol Ursol D and 0.0015mol Isopentyl nitrite, first Isopentyl nitrite is added when being heated to 80 DEG C in magnetic agitation, oil bath, add the Ursol D being dissolved in more than 60 DEG C deionized waters again, reaction more than 10h, cools to room temperature and is kept in tetrahydrofuran (THF) (THF) with after deionized water and tetrahydrofuran (THF) (THF) washing.
Step 3: the preparation of modified graphene/bismaleimide resin composite material:
To calculate according to the concentration of the tetrahydrofuran solution of modified graphene and tetrahydrofuran (THF) (THF) solution measured containing 130mg modified graphene adds 60.12g bismaleimide resin thinner diallyl bisphenol (DABPA), ultrasonic 1h under Ultrasonic Cell Disruptor 360W power, then in magnetic agitation, emptying tetrahydrofuran (THF) (THF) is stirred under vacuum, temperature from ambient rises to 140 DEG C gradually, after bubble is got rid of completely, in magnetic agitation, adding at 140 DEG C with diallyl bisphenol mol ratio is the bismaleimide resin powder (69.88g) of 1:1, continue in magnetic agitation after solution clarification, 0.5h is stirred at 140 DEG C.Mixing liquid is injected ready mould, 140 DEG C of vacuum drying ovens are bled and are steeped 15min, then be cured according to the solidification value of bismaleimide resin, solidification flow process is be incubated 3h at 180 DEG C of temperature, be incubated 2h at 220 DEG C of temperature, be incubated 3h at 250 DEG C of temperature, be cooled to room temperature, the demoulding after taking out, cutting and polishing are met 0.1wt% modified graphene/bismaleimide resin composite material (80 × 10 × 4mm of requirement
3).And with reference to ASTM D4812-11 resistance to impact shock testing standard, shock test is carried out to it, its resistance to impact shock is 21.042KJ/m
2, more toughness reinforcing than initial resin 11.55%.
Embodiment 2:
Adopt preparation method provided by the invention to prepare modified graphene/bismaleimide resin composite material that modified graphene mass percent concentration is 0.2%, concrete steps are as follows:
Step one: the preparation of graphite oxide:
(1) Graphite Powder 99, KNO is got
3powder and the vitriol oil (concentration is 75wt%) mix, and blending ratio is add 1.5KNO in every 1.5g Graphite Powder 99
3powder, the 65ml vitriol oil, add KMnO by during the mixture heating in water bath to 35 DEG C obtained
4powder, adding proportion is that every 1.5g graphite adds 9.5gKMnO
4, stir at 100r/min rotating speed lower magnetic force, reaction more than 6h; Then in mixture, slowly first time adds deionized water, and bath temperature is adjusted to 70 DEG C, after reaction 40min, second time adds deionized water wherein again, the ratio that the add-on of described first time and second time deionized water still adds deionized water 100ml and 200ml with every 1.5g graphite adds, after continuing reaction 4min, in mixing liquid, drip concentration is 50wt%H
2o
2, become glassy yellow to mixing liquid;
(2) mixing liquid is extremely neutral with deionized water wash, add the graphite oxide aqueous solution that deionized water is configured to 2mg/ml.
Step 2: the preparation of modified graphene:
Get the graphite oxide aqueous solution in step one, after using the ultrasonic 1h of ultrasonic cleaning instrument, obtain the suspension of graphene oxide.In described suspension, add sodium hydroxide solution adjustment pH value is 10, according to 120mg graphene oxide water solution proportioning 1.5ml hydrazine hydrate (Hydrazine, massfraction 50%), reacts 1h in magnetic agitation, oil bath at being heated to 100 DEG C.Then according to the ratio of every 0.012g graphene oxide water solution proportioning 0.0015mol Ursol D and 0.0015mol Isopentyl nitrite, first Isopentyl nitrite is added when being heated to 80 DEG C in magnetic agitation, oil bath, add the Ursol D being dissolved in more than 60 DEG C deionized waters again, reaction more than 10h, cools to room temperature and is kept in tetrahydrofuran (THF) (THF) with after deionized water and tetrahydrofuran (THF) (THF) washing.The preparation flow of modified graphene is shown in Fig. 1.
Step 3: the preparation of modified graphene/bismaleimide resin composite material:
60.12g bismaleimide resin thinner diallyl bisphenol (DABPA) is added at tetrahydrofuran (THF) (THF) solution of modified graphene, containing modified graphene 260mg in the tetrahydrofuran solution of described modified graphene, at Ultrasonic Cell Disruptor 360W(power 900W, setting operating power 40%) ultrasonic 2h under power, then in magnetic agitation, emptying tetrahydrofuran (THF) (THF) is stirred under vacuum, temperature from ambient rises to 140 DEG C gradually, after bubble is got rid of completely, in magnetic agitation, adding at 140 DEG C with diallyl bisphenol mol ratio is the bismaleimide resin powder (69.88g) of 1:1, continue in magnetic agitation after solution clarification, 0.5h is stirred at 140 DEG C.Mixing liquid is injected ready mould, 140 DEG C of vacuum drying ovens are bled and are steeped 15min, then be cured according to the solidification value of bismaleimide resin, solidification flow process is be incubated 3h at 180 DEG C of temperature, be incubated 2h at 220 DEG C of temperature, be incubated 3h at 250 DEG C of temperature, be cooled to room temperature, the demoulding after taking out, is met the modified graphene/bismaleimide resin composite material of requirement; The mass percent preparing modified graphene in the matrix material obtained is 0.2%.
Embodiment 3:
Adopt preparation method provided by the invention to prepare modified graphene/bismaleimide resin composite material that modified graphene mass percent concentration is 0.3%, concrete steps are as follows:
Step one: the preparation of graphite oxide:
(1) Graphite Powder 99, KNO is got
3powder and the vitriol oil (concentration is 98.3wt%) mix, and blending ratio is add 2g KNO in every 1.5g Graphite Powder 99
3powder, the 69ml vitriol oil, add KMnO by during the mixture heating in water bath to 40 DEG C obtained
4powder, adding proportion is that every 1.5g graphite adds 8.0gKMnO
4, stir at 300r/min rotating speed lower magnetic force, reaction more than 6h; Then in mixture, slowly first time adds deionized water, and bath temperature is adjusted to 60 DEG C, after reaction 25min, second time adds deionized water wherein again, the ratio that the add-on of described first time and second time deionized water still adds deionized water 200ml and 400ml with every 1.5g graphite adds, after continuing reaction 5min, in mixing liquid, drip concentration is 20wt%H
2o
2, become glassy yellow to mixing liquid;
(2) mixing liquid is extremely neutral with deionized water wash, add the graphite oxide aqueous solution that deionized water is configured to 1mg/ml.
Step 2: the preparation of modified graphene:
Get the graphite oxide aqueous solution in step one, after using the ultrasonic 2h of ultrasonic cleaning instrument, obtain the suspension of graphene oxide.In described suspension, add sodium hydroxide solution adjustment pH value is 9, according to 120mg graphene oxide water solution proportioning 1ml hydrazine hydrate (Hydrazine, massfraction 50%), reacts 1h in magnetic agitation, oil bath at being heated to 100 DEG C.Then according to the ratio of every 0.012g graphene oxide water solution proportioning 0.001mol Ursol D and 0.002mol Isopentyl nitrite, first Isopentyl nitrite is added when being heated to 80 DEG C in magnetic agitation, oil bath, add the Ursol D being dissolved in more than 60 DEG C deionized waters again, reaction more than 10h, cools to room temperature and is kept in tetrahydrofuran (THF) (THF) with after deionized water and tetrahydrofuran (THF) (THF) washing.The preparation flow of modified graphene is shown in Fig. 1.
Step 3: the preparation of modified graphene/bismaleimide resin composite material:
60.12g bismaleimide resin thinner diallyl bisphenol (DABPA) is added, containing modified graphene 390mg in the tetrahydrofuran solution of described modified graphene at tetrahydrofuran (THF) (THF) solution of modified graphene; At Ultrasonic Cell Disruptor 360W(power 900W, setting operating power 40%) ultrasonic 1h under power, then under magnetic agitation, vacuum, emptying tetrahydrofuran (THF) (THF) is stirred, temperature from ambient rises to 140 DEG C gradually, after bubble is got rid of completely, in magnetic agitation, to add with diallyl bisphenol mol ratio at 140 DEG C be the bismaleimide resin powder (69.88g) of 1:1, continues to stir 1h in magnetic agitation, at 140 DEG C after solution clarification.Mixing liquid is injected ready mould, 140 DEG C of vacuum drying ovens are bled and are steeped 30min, then be cured according to the solidification value of bismaleimide resin, solidification flow process is be incubated 3h at 180 DEG C of temperature, be incubated 2h at 220 DEG C of temperature, be incubated 3h at 250 DEG C of temperature, be cooled to room temperature, the demoulding after taking out, is met the modified graphene/bismaleimide resin composite material of requirement; The mass percent preparing modified graphene in the matrix material obtained is 0.3%.
Embodiment 4:
By in embodiment 1 or embodiment 2 or embodiment 3,130mg modified graphene in step 3 changes 520mg and 650mg into respectively, other step is constant, the method adopting invention to provide prepares modified graphene/bismaleimide resin composite material that content is respectively 0.4%, 0.5%, and carries out shock test with reference to ASTM D4812-11 resistance to impact shock testing standard to it.
Gained composite impact intensity and relative to the toughness reinforcing per-cent of bismaleimide resin in table 2, when the content of modified graphene is 0.3%, bismaleimide resin resistance to impact shock reaches the highest, is 26.171KJ/m
2, comparatively toughness reinforcing than original bismaleimide resin 38%.Continue to increase modified graphene content, impact property increase rate declines.Amplify 2000 times under a scanning electron microscope, without the impact specimen fracture photo of modified graphene content as Fig. 6, impact fracture surface in Fig. 6 in (b), (c), (d) becomes very coarse, along with the progressively increase of modified graphene content, the smooth region of fracture surface reduces gradually.In Fig. 7,0.3wt% modified graphene/span matrix material obviously can find out the introducing of modified graphene synusia, the resin that nano ply surface parcel is thick, introduces free volume, hinders crack propagation.Think, modified graphene be added in bismaleimide resin matrix a large amount of interfaces of introducing, bismaleimide resin is wrapped in graphenic surface and is cured, when modified graphene massfraction increases, when the interface of namely introducing is more, this parcel caused because of interface is more, thus makes fracture apperance more coarse.The aniline group on modified graphene surface and the double bond of bismaleimide resin react, make the toughness reinforcing synusia of nanometer and between matrix, produce chemical connection, strengthening interface cohesion greatly makes the character of nano ply be played, therefore along with the increase composite material toughness of modified graphene content increases, but when modified graphene content is increased to a certain degree, nanoparticle produces inevitably reunites, and between bismaleimide resin, degree of crosslinking decline makes toughness reinforcing degree decline.
Table 2 different content modified graphene/bismaleimide resin composite material impact property
To sum up, when the mass percent of modified graphene in matrix material is 0.1% ~ 0.5%, matrix material resistance to impact shock value is 19.557 ~ 26.171KJ/m
2, toughness reinforcing compared to original bismaleimide resin 3.67% ~ 38.74%.
Embodiment 5:
Change the 130mg modified graphene in step 3 in embodiment 1 or embodiment 2 or embodiment 3 into 390mg reduced graphene, other each steps are identical with embodiment 1, the reduced graphene prepared/bismaleimide resin composite material reference standard ASTM D4812-11 is carried out Impact Test, and after reduction, the shock strength of Graphene/bismaleimide resin composite material is 18.241KJ/m
2.Under scanning electron microscope, amplify the impact specimen fracture apperance of 60000 times as Fig. 8, as seen from the figure modified Graphene in resin in the form of sheets, have certain dispersiveness.Dispersiveness due to reduced graphene in Fig. 8 is weaker than modified graphene, and is easy to reunite, therefore forms weak interface at resin surface, destructible during impact, and produces the crackle that similar lamella extracts.
Embodiment 6:
Change the 130mg modified graphene in step 3 in embodiment 1 or embodiment 2 or embodiment 3 into 390mg graphene oxide, other each steps are identical with embodiment 1, the graphene oxide prepared/bismaleimide resin composite material reference standard ASTM D4812-11 is carried out Impact Test, discovery is gathered in preparation process, because surface of graphene oxide contains a large amount of epoxide group, the double bond addition of itself and bismaleimide resin, make to solidify the too high processing characteristics that causes of front soltion viscosity to decline, bubble is difficult to discharge, the matrix material prepared inevitably will contain more bubble, matrix material resistance to impact shock containing this kind of defect is extremely low, at 10KJ/m
2left and right.Under scanning electron microscope, amplify the impact specimen fracture apperance of 60000 times as Fig. 9, as seen from the figure modified Graphene in resin in the form of sheets, have certain dispersiveness.And graphene oxide due to the epoxide group concentration on surface high, many with the chemical bond chalaza of bismaleimide resin, and polarity is large, more easily launches, therefore more easily observe in Fig. 9 visual field in resin matrix.
Claims (3)
1. a preparation method for modified graphene/bismaleimide resin composite material, is characterized in that, described preparation method comprises the steps:
Step one: the preparation of graphite oxide; Be specially:
(1) Graphite Powder 99, KNO is got
3powder and the vitriol oil mix, and blending ratio is add 1.5g KNO in every 1.5g Graphite Powder 99
3powder, 65 ~ 69ml vitriol oil, add KMnO by during mixture heating in water bath to 35 ~ 40 DEG C obtained
4powder, adding proportion is that every 1.5g graphite adds 8.0 ~ 9.5gKMnO
4, stir at 100 ~ 300r/min rotating speed lower magnetic force, reaction more than 6h; Then in mixture, slowly first time adds deionized water, and bath temperature is adjusted to 60 DEG C ~ 70 DEG C, after reaction 25 ~ 40min, second time adds deionized water wherein again, the ratio that the add-on that described first time and second time add deionized water adds deionized water 100 ~ 200ml and 200 ~ 400ml with every 1.5g graphite adds, after continuing reaction 4 ~ 5min, in mixing liquid, drip concentration is 20wt% ~ 50wt%H
2o
2the aqueous solution, becomes glassy yellow to mixing liquid;
(2) mixing liquid is extremely neutral with deionized water wash, be configured to the graphene oxide water solution that concentration is 1 ~ 2mg/ml;
Step 2: the preparation of modified graphene; Be specially: after using ultrasonic cleaning instrument ultrasonic oxidation graphene aqueous solution 1 ~ 2h, obtain the suspension of graphene oxide; Adjustment suspension pH value is 9 ~ 10, reacts 1h according to 120mg graphene oxide water solution proportioning 1 ~ 1.5ml hydrazine hydrate in magnetic agitation, oil bath at being heated to 100 DEG C; Then according to the ratio of every 0.012g graphene oxide water solution proportioning 0.001 ~ 0.0015mol Ursol D and 0.0015 ~ 0.002mol Isopentyl nitrite, first Isopentyl nitrite is added when being heated to 80 DEG C in magnetic agitation, oil bath, add the Ursol D being dissolved in more than 60 DEG C deionized waters again, reaction more than 10h, cools to room temperature also with being kept in tetrahydrofuran (THF) after deionized water and tetrahydrofuran (THF) washing;
Step 3: the preparation of modified graphene/bismaleimide resin composite material:
The tetrahydrofuran solution choosing modified graphene adds bismaleimide resin thinner diallyl bisphenol, ultrasonic 1 ~ 2h, then under magnetic agitation, vacuum, emptying tetrahydrofuran (THF) is stirred, temperature from ambient rises to 140 DEG C gradually, after bubble is got rid of completely, in magnetic agitation, to add with diallyl bisphenol mol ratio at 140 DEG C be the bismaleimide resin powder of 1:1, continues to stir 0.5 ~ 1h in magnetic agitation, at 140 DEG C after solution clarification; Mixing liquid is injected ready mould, 140 DEG C of vacuum drying ovens are bled bubble 15 ~ 30min, then be cured according to the solidification value of bismaleimide resin, solidification flow process is be incubated 3h at 180 DEG C of temperature, be incubated 2h at 220 DEG C of temperature, be incubated 3h at 250 DEG C of temperature, be cooled to room temperature, the demoulding after taking out, is met the modified graphene/bismaleimide resin composite material of requirement; The mass percent 0.1 ~ 0.5% of modified graphene in described matrix material.
2. the preparation method of a kind of modified graphene/bismaleimide resin composite material according to claim 1, is characterized in that: the concentration of the described vitriol oil is 75wt% ~ 98.3wt%.
3. the preparation method of a kind of modified graphene/bismaleimide resin composite material according to claim 1, is characterized in that: the mass percent concentration of described hydrazine hydrate is 50%.
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| CN105218815B (en) * | 2015-09-15 | 2017-05-10 | 沈阳航空航天大学 | Preparation method for maleic anhydride modified graphene oxide/bismaleimide nanometer composite material |
| CN106589962A (en) * | 2016-11-25 | 2017-04-26 | 湖北三江航天江北机械工程有限公司 | Bismaleimide resin/silicone rubber ablation-resistant thermal insulation composite material and preparation method thereof |
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| CN107298858A (en) * | 2017-07-12 | 2017-10-27 | 中国航发北京航空材料研究院 | A kind of graphene oxide toughening model+composition and preparation method thereof |
| CN108535336A (en) * | 2018-04-24 | 2018-09-14 | 南京信息工程大学 | A kind of preparation method of graphene/molybdenum disulfide/cadmium sulfide composite sensing material |
| CN109206905B (en) * | 2018-08-29 | 2021-03-05 | 中航复合材料有限责任公司 | Graphene bismaleimide resin composite material and preparation method thereof |
| CN110283528A (en) * | 2019-06-27 | 2019-09-27 | 浙江儒商科技有限公司 | A kind of preparation method of the wear-resistant self-lubricating swash plate based on bismaleimide |
| CN114685990A (en) * | 2020-12-31 | 2022-07-01 | 洛阳尖端技术研究院 | Modified graphene/bismaleimide resin and preparation method thereof |
| CN114276165B (en) * | 2021-12-24 | 2022-10-21 | 中国人民解放军陆军装甲兵学院 | Method for reducing surface brittleness of hard and brittle material |
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