CN103408934A - Modified graphene/bismaleimide resin composite material and preparation method thereof - Google Patents
Modified graphene/bismaleimide resin composite material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a modified graphene/bismaleimide resin composite material and a preparation method thereof, and belongs to the technical field of the preparation of nanometer composite materials. The preparation method comprises the following steps: firstly preparing graphite oxide, then preparing modified graphene, and finally preparing a composite material according to 0.1-0.5wt% of modified graphene content in the composite material. The shock strength of the modified graphene/bismaleimide resin composite material disclosed by the invention is 19.557 to 26.171KJ/m<2>, and compared with the toughness of original bismaleimide resin, the toughness of the modified graphene/bismaleimide resin composite material is increased by 3.67% to 38.74%. The interfacial bonding property between the modified graphene and the bismaleimide resin is greatly improved, so that the toughness of the bismaleimide resin is improved, and the exertion of the property of the graphene is facilitated; compared with the toughness of the bismaleimide resin and a reduced graphene/bismaleimide resin composite material, the toughness of the modified graphene/bismaleimide resin composite material is greatly improved.
Description
Technical field
The invention belongs to the Nano-composite materials technical field, is a kind of modified graphene/bismaleimide resin matrix material and preparation method thereof specifically.
Background technology
Graphene is with sp by carbon atom
2The monoatomic layer that hydridization connects forms, and its basic structural unit is benzene six-ring the most stable in organic materials, and its theoretic throat be only 0.35nm, is the current the thinnest two-dimensional material of finding, 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, is the highest in test material as the intensity of Graphene, reaches 130GPa, is more than 100 times of steel; Its carrier mobility reaches 1.5 * 10
4Cm
2V
-1S
-1, be current 2 times of known indium antimonide material with high mobility, surpass 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 have caused " carbon " research boom of scientific and technological circle's new rounds.The investigator the electronic structure performance of the preparation of Graphene, Graphene with and application at microelectronic device on do a lot of work.The preparation method of Graphene has a lot, comprises micromechanics stripping method, CVD method, molecular beam epitaxy and graphite oxide method.Wherein graphite oxide method preparation method, equipment are simple, and output is larger, is conducive to realize industrialization.By the standby product of graphite oxide legal system, be graphene oxide, there is a large amount of oxygen-containing functional groups in its surface, can further by chemical reaction, prepare the derivative of Graphene.The same with most of carbon materials, Graphene also can be applied to composite additives, improves the over-all properties of matrix material.At present, the research of this respect mainly is conceived to improve the electromagnetic performance of matrix material, less for the research of mechanical property.In addition, the same with most of nano materials, Graphene exists in resin dispersed poor, and self easily reunites, with the poor problem of resin compatible, and stronger by the standby graphene oxide wetting ability of graphite oxide legal system, with resin in conjunction with also undesirable.Therefore only utilize Graphene or graphene oxide to add in resin and can not reach the purpose that improves mechanical property.
Summary of the invention
For problems of the prior art, the present invention proposes a kind of modified graphene/bismaleimide resin matrix material and preparation method thereof.The compare toughness of bismaleimide resin itself and Graphene of the prior art/bismaleimide resin matrix material of described modified graphene/bismaleimide resin matrix 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 the modified graphene that the present invention proposes/bismaleimide resin matrix material, increased the solvability of Graphene in organic solvent, is beneficial to its expansion and dispersion in matrix material.
The present invention propose a kind of modified graphene/the bismaleimide resin matrix material is the black solid of two phase structure, matrix is the bismaleimide resin matrix that original bismaleimide resin powder and thinner form, wild phase is the modified graphene of black, be dispersed in the bismaleimide resin matrix, the content of this modified graphene in matrix material is 0.1～0.5wt%.There is thickness in modified graphene in tetrahydrofuran (THF) (THF) solvent be 1～1.5nm, modified graphene particle size 0.5～1 μ m.The shock strength of the modified graphene that the present invention proposes/bismaleimide resin matrix material reaches 26.171KJ/m
2, than pure bismaleimide resin toughness reinforcing 38%.
The present invention proposes the preparation method of a kind of Graphene of modification/bismaleimide resin matrix material, specifically comprises following step:
Step 1: the preparation of graphite oxide:
(1) get Graphite Powder 99, KNO
3Powder and the vitriol oil (concentration is that 75wt%～concentration is 98.3wt%) mix, and blending ratio is to add 1.5g KNO in every 1.5g Graphite Powder 99
3Powder, 65～69ml vitriol oil, add KMnO during by the mixture heating in water bath to 35 that obtains～40 ℃
4Powder, adding proportion are that every 1.5g graphite adds 8.0～9.5gKMnO
4, at 100～300r/min rotating speed lower magnetic force, stir, more than reaction 6h; Then in mixture, slowly add for the first time deionized water, and bath temperature is adjusted to 60 ℃～70 ℃, after reaction 25～40min, add for the second time wherein again deionized water, for the first time described and add for the second time the add-on of deionized water still with every 1.5g graphite, to add the ratio of deionized water 100～200ml and 200～400ml to add, after continuing reaction 4～5min, be 20wt%～50wt%H to dripping concentration in mixing liquid
2O
2The aqueous solution, become glassy yellow to mixing liquid;
(2) mixing liquid is extremely neutral with deionized water wash, being configured to concentration is the graphite oxide aqueous solution of 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.Adjusting the suspension pH value is 9～10, is heated under 100 ℃ and reacts 1h in magnetic agitation, oil bath according to 120mg graphite oxide aqueous solution proportioning 1～1.5ml hydrazine hydrate (50%).Follow the ratio according to every 0.012g graphite oxide aqueous solution proportioning 0.001～0.0015mol Ursol D and 0.0015～0.002mol Isopentyl nitrite, when being heated to 80 ℃, magnetic agitation, oil bath first add Isopentyl nitrite, add again the Ursol D that is dissolved in deionized water more than 60 ℃, more than reaction 10h, cool to room temperature also with after deionized water and tetrahydrofuran (THF) (THF) washing, being kept in tetrahydrofuran (THF) (THF).
Step 3: the preparation of modified graphene/bismaleimide resin matrix material:
The tetrahydrofuran (THF) of modified graphene (THF) solution adds bismaleimide resin thinner diallyl bisphenol (DABPA), Ultrasonic Cell Disruptor 360W(power 900W, set operating power 40%) lower ultrasonic 1～2h, then under magnetic agitation, vacuum, stir emptying tetrahydrofuran (THF) (THF), temperature rises to 140 ℃ gradually by room temperature, after bubble is got rid of fully, under magnetic agitation, 140 ℃, adding with the diallyl bisphenol mol ratio is the bismaleimide resin powder of 1:1, after the solution clarification, continues to stir 0.5～1h under magnetic agitation, 140 ℃.Mixing liquid is injected to ready mould, 140 ℃ of vacuum drying ovens are bled and are steeped 15～30min, then the solidification value according to bismaleimide resin is cured, curing flow process is to be incubated 3h at 180 ℃ of temperature, at 220 ℃ of temperature, be incubated 2h, be incubated 3h at 250 ℃ of temperature, be cooled to room temperature, the demoulding after taking out, be met the modified graphene of requirement/bismaleimide resin matrix material.
The advantage that the present invention has is:
(1) the present invention proposes the preparation method of a kind of modified graphene/bismaleimide resin matrix material, in preparation process, has removed a large amount of oxy radicals in graphene oxide surface, has increased the organic solvent dissolution of Graphene after the reduction.
(2) the present invention proposes the preparation method of a kind of modified graphene/bismaleimide resin matrix material, by the 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 the preparation surface, again by two key reactions of the aniline group on modified graphene and bismaleimide resin, by chamical binding, be tied to form modified graphene and bismaleimide resin as a whole, interfacial combined function between Graphene and bismaleimide resin improves greatly like this, improved the toughness of bismaleimide resin, be conducive to the performance of the performance of Graphene own,
(3) the present invention proposes the preparation method of a kind of modified graphene/bismaleimide resin matrix material, and the compare toughness of bismaleimide resin itself and reduced graphene/bismaleimide resin matrix material of the modified graphene of gained/bismaleimide resin matrix material improves a lot.
The accompanying drawing explanation
Fig. 1: in the present invention, graphite oxide, reduction and diazotization reaction prepare modified graphene process schematic diagram;
Fig. 2: the atomic force microscope figure that graphene oxide in the present invention (a), reduced graphene (b) and modified graphene (c) disperse in deionized water for ultrasonic;
Fig. 3: graphene oxide in the present invention (a), reduced graphene (b) and modified graphene (c) infrared spectra;
Fig. 4: graphite in the present invention (a), graphene oxide (b), reduced graphene (c) and modified graphene (d) Raman spectrum;
Fig. 5-A: graphite oxide x-ray photoelectron power spectrum in the present invention: (a) complete 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) complete 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) complete spectrum, (b) O1s peak, (c) C1s swarming and (d) N1s swarming spectrum;
Fig. 6: the stereoscan photograph (* 2000) of the modified graphene of example 1,2 preparations/bismaleimide resin matrix material fracture in the present invention: (a) original bismaleimide resin; (b) 0.1%wt. modified graphene/span matrix material; (c) be 0.3%wt. modified graphene/span matrix material; (d) 0.5%wt. modified graphene/span matrix material;
Fig. 7: the stereoscan photograph (* 60000) of the 0.3wt% modified graphene of example 2 preparations/bismaleimide resin matrix material fracture in the present invention;
Fig. 8: the stereoscan photograph (* 60000) of the 0.3wt% reduced graphene of example 3 preparations/bismaleimide resin matrix material fracture in the present invention;
Fig. 9: the stereoscan photograph (* 60000) of the 0.3wt% graphene oxide of example 4 preparations/bismaleimide resin matrix material fracture in the present invention.
Embodiment
The present invention is described in further detail below in conjunction with drawings and Examples.
The present invention proposes a kind of modified graphene/bismaleimide resin matrix material, this modified graphene/bismaleimide resin matrix material is black solid, it is two phase structure, main body is the bismaleimide resin matrix that bismaleimide resin powder and diallyl bisphenol form, wild phase is the modified graphene of black, described wild phase is dispersed in the bismaleimide resin matrix, and the content of this modified graphene in matrix material is 0.1～0.5wt%.There is thickness in modified graphene in tetrahydrofuran (THF) (THF) solvent be 1～1.5nm, size 0.5～1 μ m.The shock strength of described modified graphene/bismaleimide resin matrix material reaches 26.171KJ/m
2.
The present invention proposes the preparation method of a kind of Graphene of modification/bismaleimide resin matrix material, and by reference to the accompanying drawings 1, specifically comprise following step:
Step 1: the preparation of graphite oxide:
(1) get Graphite Powder 99, KNO
3(concentration is 75wt%～98.3wt%) mix, and blending ratio is to add 1.5～2g KNO in every 1.5g Graphite Powder 99 for powder and the vitriol oil
3Powder, 65～69ml vitriol oil, add KMnO during by the mixture heating in water bath to 35 that obtains～40 ℃
4Powder, adding proportion are that every 1.5g graphite adds 8.0～9.5gKMnO
4, at 100～300r/min rotating speed lower magnetic force, stir, more than reaction 6h; Then in mixture, slowly add for the first time deionized water, and bath temperature is adjusted to 60 ℃～70 ℃, after reaction 25～40min, add for the second time wherein again deionized water, add-on for the first time described and deionized water for the second time still adds the ratio of deionized water 100～200ml and 200～400ml to add with every 1.5g graphite, after continuing reaction 4～5min, be 20wt%～50wt%H to dripping concentration in mixing liquid
2O
2, become glassy yellow to mixing liquid;
(2) mixing liquid is extremely neutral with deionized water wash, add deionized water to be configured to the graphite oxide aqueous solution of 1～2mg/ml.
Step 2: the preparation of modified graphene:
Get the graphite oxide aqueous solution in step 1, after using the ultrasonic 1～2h of ultrasonic cleaning instrument, obtain the suspension of graphene oxide.In described suspension, adding sodium hydroxide solution to adjust pH value is 9～10, according to 120mg graphite oxide aqueous solution proportioning 1～1.5ml hydrazine hydrate (Hydrazine, massfraction 50%), is heated under 100 ℃ and reacts 1h in magnetic agitation, oil bath.Follow the ratio according to every 0.012g graphite oxide aqueous solution proportioning 0.001～0.0015mol Ursol D and 0.0015～0.002mol Isopentyl nitrite, when being heated to 80 ℃, magnetic agitation, oil bath first add Isopentyl nitrite, add again the Ursol D that is dissolved in deionized water more than 60 ℃, more than reaction 10h, cool to room temperature also with after deionized water and tetrahydrofuran (THF) (THF) washing, being kept in tetrahydrofuran (THF) (THF).The preparation flow of modified graphene is shown in Fig. 1.
Step 3: the preparation of modified graphene/bismaleimide resin matrix material:
Tetrahydrofuran (THF) (THF) solution at modified graphene adds bismaleimide resin thinner diallyl bisphenol (DABPA), at Ultrasonic Cell Disruptor 360W(power 900W, setting operating power 40%) ultrasonic 1～2h under power, then under magnetic agitation, vacuum, stir emptying tetrahydrofuran (THF) (THF), temperature rises to 140 ℃ gradually by room temperature, after bubble is got rid of fully, under magnetic agitation, 140 ℃, adding with the diallyl bisphenol mol ratio is the bismaleimide resin powder of 1:1, after the solution clarification, continues to stir 0.5～1h under magnetic agitation, 140 ℃.Mixing liquid is injected to ready mould, 140 ℃ of vacuum drying ovens are bled and are steeped 15～30min, then the solidification value according to bismaleimide resin is cured, curing flow process is to be incubated 3h at 180 ℃ of temperature, at 220 ℃ of temperature, be incubated 2h, be incubated 3h at 250 ℃ of temperature, be cooled to room temperature, the demoulding after taking out, be met the modified graphene of requirement/bismaleimide resin matrix material; The mass percent for preparing modified graphene in resulting matrix material is 0.1～0.5%.
The graphene oxide prepared in step 2 (a), reduced graphene (b) and modified graphene (c) are in deionized water Atom force microscope result, as shown in Figure 2, can see that graphene oxide can disperse to become thickness at 0.8～1nm in deionized water, the graphene oxide thin slice of size 3～8 μ m, the rear Graphene of reduction thickness is reduced to 0.4～0.6nm, size is still at micron order, and Graphene surface grafting aniline group after modification, 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 the modification success.In the infrared spectra of Fig. 3, can find out that the graphite oxide (a) made is at 3420cm
-1A very wide strong peak occurs, belonged to the hydroxyl (OH) infrared absorption peak of stretching vibration generation.In figure, another wide and strong peak appears at 1260cm
-1Place is the absorption band of (C-O) key stretching vibration generation of phenolic hydroxyl group.Except the existence of further proof hydroxyl, the fully destroyed of after the strong oxidation hexa-atomic aromatic ring in graphite also proved at this peak.1720cm
-1With 1050cm
-1Locate sharp-pointed strong peak, two places and correspond respectively to the stretching vibration of the two keys (C=O) of carbon oxygen 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 is corresponding to ketone group (C=O) group, and 802cm
-1Place is the charateristic avsorption band of epoxide group (C (O) C-).The graphite oxide that makes in as can be known experiment of the information of comprehensive whole infrared spectra surface existence-OH ,-COOH ,-C=O ,-C (O) C-functional group, and-OH accounts for larger proportion, illustrates that oxidation is abundant.Graphene after hydrazine hydrate reduction (b), 3420cm
-1The wide strong hydroxyl peak at place narrows down 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
-1Carbon oxygen singly-bound C-O signal and the 802cm at place
-1The completely dissolve of epoxy charateristic avsorption band, illustrate that oxy radical is removed in a large number.Through the Graphene infared spectrum (c) of diazotization modification, at 1660cm
-1, 1500cm
-1, 1100cm
-1And 814cm
-1Stronger phenyl ring characteristic peak has appearred 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
-1The stretching vibration peak of fragrant C-N has appearred 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 has proved certain success of anilino grafting from unit structure, amino modified Graphene is had laid a good foundation in the application in matrix material next.
Raman spectrum (Fig. 4) analysis can obtain, and all samples still have the 1325.8cm of being in
-1D band and be in 1588.3cm
-1The G band at place.As previously mentioned, D band is corresponding 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 be used to meaning sp
2Carbon atom number and sp
3Carbonatoms purpose ratio is also simultaneously the strong evidence that the graphene layer electronic structure changes.By calculating, the I (D) of graphene oxide (b)/I (G) is 1.15, and the I (D) of reduction rear oxidation Graphene (c)/I (G) has reached 1.31.By the graphene oxide surface oxy radical that hydrazine reduces, remove in a large number sp
2C-structure starts to recover, and the while is broken because the chemical reaction Graphene synusia produced diminishes, so the D peak is slightly high than the G peak.The I (D) of Graphene after modification (d)/I (G) ratio is the further raising of 1.42, I (D)/I (G) ratio, and the sp of graphene-structured is described
3Carbon atom number increases, analyzes as can be known, this be due in diazo process at Graphene surface grafting aniline group, replace the structure increase, make a part of sp
2The two keys of carbon atom are opened and are become sp
3Carbon atom causes, and can successfully prove for grafting.
By the XPS result to graphite and graphite oxide (as shown in Fig. 5, table 1) as can be known, after oxidation, oxygen atom content obviously improves (C/O is 2.06), illustrates 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, the N atom appears in the modified graphene surface, and existence form is mainly-NH
2This explanation is as the reaction result of design, and diazotization reaction grafting aniline group occurs on the reduced graphene surface.After modification, C/N 32.81 after by reduction is reduced to 12.70 after modification, and C/O 5.78 after by reduction is increased to 8.27, introduces aniline group to conform to, and illustrate prepared by modified graphene comparatively successful.
Table 1 graphite, graphite oxide, reduced graphene, modified graphene XPS result
Below by embodiment, describe the preparation method of matrix material provided by the invention in detail.
Embodiment 1:
Adopting method preparation quality percentage composition provided by the invention is 0.1% modified graphene/bismaleimide resin matrix material, and concrete steps are as follows:
The first step, the graphite oxide preparation:
Get Graphite Powder 99, KNO
3Powder and the vitriol oil (concentration is 98.3wt%) mix, and blending ratio is to add 1.5g KNO in every 1.5g Graphite Powder 99
3Powder, the 67ml vitriol oil, add the KMnO4 powder during by the mixture heating in water bath to 40 that obtains ℃, and adding proportion is that every 1.5g graphite adds 9.0gKMnO
4, at 220r/min rotating speed lower magnetic force, stir, more than reaction 6h; Then in mixture, slowly adding the 100mL deionized water, and bath temperature is adjusted to 60 ℃, after reaction 25min, then add wherein the 300ml deionized water, after continuing reaction 4min, is 30wt%H to dripping 9ml concentration in mixing liquid
2O
2, become glassy yellow to mixing liquid;
Mixing liquid is extremely neutral with deionized water wash, be kept in deionized water and be configured to the graphite oxide aqueous 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, adding sodium hydroxide to adjust pH value is 9, is heated under 100 ℃ and reacts 1h in magnetic agitation, oil bath according to 120mg graphite oxide aqueous solution proportioning 1ml hydrazine hydrate (massfraction 50%).Follow the ratio according to every 0.012g graphite oxide aqueous solution proportioning 0.001mol Ursol D and 0.0015mol Isopentyl nitrite, when being heated to 80 ℃, magnetic agitation, oil bath first add Isopentyl nitrite, add again the Ursol D that is dissolved in deionized water more than 60 ℃, more than reaction 10h, cool to room temperature also with after deionized water and tetrahydrofuran (THF) (THF) washing, being kept in tetrahydrofuran (THF) (THF).
Step 3: the preparation of modified graphene/bismaleimide resin matrix material:
According to the concentration of the tetrahydrofuran solution of modified graphene, calculate and measure tetrahydrofuran (THF) (THF) solution that contains the 130mg modified graphene and add 60.12g bismaleimide resin thinner diallyl bisphenol (DABPA), ultrasonic 1h under Ultrasonic Cell Disruptor 360W power, then in magnetic agitation, under vacuum, stir emptying tetrahydrofuran (THF) (THF), temperature rises to 140 ℃ gradually by room temperature, after bubble is got rid of fully, in magnetic agitation, under 140 ℃, add with the diallyl bisphenol mol ratio is the bismaleimide resin powder (69.88g) of 1:1, after the solution clarification, continue in magnetic agitation, under 140 ℃, stir 0.5h.Mixing liquid is injected to ready mould, 140 ℃ of vacuum drying ovens are bled and are steeped 15min, then the solidification value according to bismaleimide resin is cured, curing flow process is to be incubated 3h at 180 ℃ of temperature, at 220 ℃ of temperature, be incubated 2h, be incubated 3h at 250 ℃ of temperature, be cooled to room temperature, the demoulding after taking out, cutting and polishing are met the 0.1wt% modified graphene of requirement/bismaleimide resin matrix material (80 * 10 * 4mm
3).And with reference to ASTM D4812-11 resistance to impact shock testing standard, it is carried out to shock test, its resistance to impact shock is 21.042KJ/m
2, than original resin toughening 11.55%.
Embodiment 2:
Adopting preparation method provided by the invention to prepare the modified graphene mass percent concentration is 0.2% modified graphene/bismaleimide resin matrix material, and concrete steps are as follows:
Step 1: the preparation of graphite oxide:
(1) get Graphite Powder 99, KNO
3Powder and the vitriol oil (concentration is 75wt%) mix, and blending ratio is to add 1.5KNO in every 1.5g Graphite Powder 99
3Powder, the 65ml vitriol oil, add KMnO during by the mixture heating in water bath to 35 that obtains ℃
4Powder, adding proportion are that every 1.5g graphite adds 9.5gKMnO
4, at 100r/min rotating speed lower magnetic force, stir, more than reaction 6h; Then in mixture, slowly add for the first time deionized water, and bath temperature is adjusted to 70 ℃, after reaction 40min, add for the second time wherein again deionized water, add-on for the first time described and deionized water for the second time still adds the ratio of deionized water 100ml and 200ml to add with every 1.5g graphite, after continuing reaction 4min, be 50wt%H to dripping concentration in mixing liquid
2O
2, become glassy yellow to mixing liquid;
(2) mixing liquid is extremely neutral with deionized water wash, add deionized water to be configured to the graphite oxide aqueous solution of 2mg/ml.
Step 2: the preparation of modified graphene:
Get the graphite oxide aqueous solution in step 1, after using the ultrasonic 1h of ultrasonic cleaning instrument, obtain the suspension of graphene oxide.In described suspension, adding sodium hydroxide solution to adjust pH value is 10, according to 120mg graphite oxide aqueous solution proportioning 1.5ml hydrazine hydrate (Hydrazine, massfraction 50%), is heated under 100 ℃ and reacts 1h in magnetic agitation, oil bath.Follow the ratio according to every 0.012g graphite oxide aqueous solution proportioning 0.0015mol Ursol D and 0.0015mol Isopentyl nitrite, when being heated to 80 ℃, magnetic agitation, oil bath first add Isopentyl nitrite, add again the Ursol D that is dissolved in deionized water more than 60 ℃, more than reaction 10h, cool to room temperature also with after deionized water and tetrahydrofuran (THF) (THF) washing, being kept in tetrahydrofuran (THF) (THF).The preparation flow of modified graphene is shown in Fig. 1.
Step 3: the preparation of modified graphene/bismaleimide resin matrix material:
Tetrahydrofuran (THF) (THF) solution at modified graphene adds 60.12g bismaleimide resin thinner diallyl bisphenol (DABPA), in the tetrahydrofuran solution of described modified graphene, contain modified graphene 260mg, at Ultrasonic Cell Disruptor 360W(power 900W, setting operating power 40%) ultrasonic 2h under power, then in magnetic agitation, under vacuum, stir emptying tetrahydrofuran (THF) (THF), temperature rises to 140 ℃ gradually by room temperature, after bubble is got rid of fully, in magnetic agitation, under 140 ℃, add with the diallyl bisphenol mol ratio is the bismaleimide resin powder (69.88g) of 1:1, after the solution clarification, continue in magnetic agitation, under 140 ℃, stir 0.5h.Mixing liquid is injected to ready mould, 140 ℃ of vacuum drying ovens are bled and are steeped 15min, then the solidification value according to bismaleimide resin is cured, curing flow process is to be incubated 3h at 180 ℃ of temperature, at 220 ℃ of temperature, be incubated 2h, be incubated 3h at 250 ℃ of temperature, be cooled to room temperature, the demoulding after taking out, be met the modified graphene of requirement/bismaleimide resin matrix material; The mass percent for preparing modified graphene in resulting matrix material is 0.2%.
Embodiment 3:
Adopting preparation method provided by the invention to prepare the modified graphene mass percent concentration is 0.3% modified graphene/bismaleimide resin matrix material, and concrete steps are as follows:
Step 1: the preparation of graphite oxide:
(1) get Graphite Powder 99, KNO
3Powder and the vitriol oil (concentration is 98.3wt%) mix, and blending ratio is to add 2g KNO in every 1.5g Graphite Powder 99
3Powder, the 69ml vitriol oil, add KMnO during by the mixture heating in water bath to 40 that obtains ℃
4Powder, adding proportion are that every 1.5g graphite adds 8.0gKMnO
4, at 300r/min rotating speed lower magnetic force, stir, more than reaction 6h; Then in mixture, slowly add for the first time deionized water, and bath temperature is adjusted to 60 ℃, after reaction 25min, add for the second time wherein again deionized water, add-on for the first time described and deionized water for the second time still adds the ratio of deionized water 200ml and 400ml to add with every 1.5g graphite, after continuing reaction 5min, be 20wt%H to dripping concentration in mixing liquid
2O
2, become glassy yellow to mixing liquid;
(2) mixing liquid is extremely neutral with deionized water wash, add deionized water to be configured to the graphite oxide aqueous solution of 1mg/ml.
Step 2: the preparation of modified graphene:
Get the graphite oxide aqueous solution in step 1, after using the ultrasonic 2h of ultrasonic cleaning instrument, obtain the suspension of graphene oxide.In described suspension, adding sodium hydroxide solution to adjust pH value is 9, according to 120mg graphite oxide aqueous solution proportioning 1ml hydrazine hydrate (Hydrazine, massfraction 50%), is heated under 100 ℃ and reacts 1h in magnetic agitation, oil bath.Follow the ratio according to every 0.012g graphite oxide aqueous solution proportioning 0.001mol Ursol D and 0.002mol Isopentyl nitrite, when being heated to 80 ℃, magnetic agitation, oil bath first add Isopentyl nitrite, add again the Ursol D that is dissolved in deionized water more than 60 ℃, more than reaction 10h, cool to room temperature also with after deionized water and tetrahydrofuran (THF) (THF) washing, being kept in tetrahydrofuran (THF) (THF).The preparation flow of modified graphene is shown in Fig. 1.
Step 3: the preparation of modified graphene/bismaleimide resin matrix material:
Tetrahydrofuran (THF) (THF) solution at modified graphene adds 60.12g bismaleimide resin thinner diallyl bisphenol (DABPA), in the tetrahydrofuran solution of described modified graphene, contains modified graphene 390mg; At Ultrasonic Cell Disruptor 360W(power 900W, setting operating power 40%) ultrasonic 1h under power, then under magnetic agitation, vacuum, stir emptying tetrahydrofuran (THF) (THF), temperature rises to 140 ℃ gradually by room temperature, after bubble is got rid of fully, under magnetic agitation, 140 ℃, adding with the diallyl bisphenol mol ratio is the bismaleimide resin powder (69.88g) of 1:1, after the solution clarification, continues to stir 1h under magnetic agitation, 140 ℃.Mixing liquid is injected to ready mould, 140 ℃ of vacuum drying ovens are bled and are steeped 30min, then the solidification value according to bismaleimide resin is cured, curing flow process is to be incubated 3h at 180 ℃ of temperature, at 220 ℃ of temperature, be incubated 2h, be incubated 3h at 250 ℃ of temperature, be cooled to room temperature, the demoulding after taking out, be met the modified graphene of requirement/bismaleimide resin matrix material; The mass percent for preparing modified graphene in resulting matrix material is 0.3%.
Embodiment 4:
By in embodiment 1 or embodiment 2 or embodiment 3,130mg modified graphene in step 3 changes respectively 520mg and 650mg into, other step is constant, the method that adopts invention to provide prepares content and is respectively 0.4%, 0.5% modified graphene/bismaleimide resin matrix material, and with reference to ASTM D4812-11 resistance to impact shock testing standard, it is carried out to shock test.
Gained matrix material shock strength and with respect to the toughness reinforcing per-cent of bismaleimide resin in Table 2, when the content of modified graphene was 0.3%, the bismaleimide resin resistance to impact shock reached the highest, was 26.171KJ/m
2, than original bismaleimide resin toughness reinforcing 38%.Continue to increase modified graphene content, the impact property increase rate descends.Under scanning electronic microscope, amplify 2000 times, impact specimen fracture photo such as Fig. 6 without modified graphene content, 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 can obviously be found out the introducing of modified graphene synusia, and the thick resin of nano ply surface parcel, introduce free volume, hindered crack propagation.Think, modified graphene be added in the bismaleimide resin matrix a large amount of interfaces of introducing, bismaleimide resin is wrapped in the Graphene surface and is cured, when the modified graphene massfraction increases, when the interface of namely introducing is more, this parcel caused because of interface is more, thereby makes fracture apperance more coarse.Two keys of the aniline group on modified graphene surface and bismaleimide resin react, make between the toughness reinforcing synusia of nanometer and matrix and produce chemistry and be connected, strengthen greatly interface in conjunction with making the character of nano ply be brought into play, therefore the increase composite material toughness along with modified graphene content increases, yet 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 descend.
Table 2 different content modified graphene/bismaleimide resin matrix material impact property
To sum up, when the mass percent of modified graphene in matrix material was 0.1%～0.5%, matrix material resistance to impact shock value was 19.557～26.171KJ/m
2, than original bismaleimide resin toughness reinforcing 3.67%～38.74%.
Embodiment 5:
Change the 130mg modified graphene in step 3 in embodiment 1 or embodiment 2 or embodiment 3 into the 390mg reduced graphene, other each steps and embodiment 1 are identical, the reduced graphene for preparing/bismaleimide resin matrix material reference standard ASTM D4812-11 is carried out to Impact Test, and the shock strength of Graphene after reduction/bismaleimide resin matrix material is 18.241KJ/m
2.Under scanning electron microscope, amplify impact specimen fracture apperance such as Fig. 8 of 60000 times, as seen from the figure after modification Graphene in resin in the form of sheets, certain dispersiveness is arranged.Dispersiveness due to reduced graphene in Fig. 8 is weaker than modified graphene, and is easy to reunite, thus at resin surface, form weak interface, destructible during impact, and produce the crackle that similar lamella is extracted.
Embodiment 6:
Change the 130mg modified graphene in step 3 in embodiment 1 or embodiment 2 or embodiment 3 into the 390mg graphene oxide, other each steps and embodiment 1 are identical, the graphene oxide for preparing/bismaleimide resin matrix material reference standard ASTM D4812-11 is carried out to Impact Test, in preparation process, gather discovery, because a large amount of epoxide groups are contained on the graphene oxide surface, two key additions of itself and bismaleimide resin, make the too high processing characteristics that causes of curing front soltion viscosity descend, bubble is difficult to discharge, the matrix material of preparing will inevitably contain more bubble, the matrix material resistance to impact shock that contains this kind defect is extremely low, at 10KJ/m
2left and right.Under scanning electron microscope, amplify impact specimen fracture apperance such as Fig. 9 of 60000 times, as seen from the figure after modification Graphene in resin in the form of sheets, certain dispersiveness is arranged.And graphene oxide is high due to surperficial epoxide group concentration, many with the chemical bond chalaza of bismaleimide resin, and polarity is large, more easily launches in resin matrix, therefore in Fig. 9 visual field, more easily observes.
Claims (7)
1. modified graphene/bismaleimide resin matrix material, it is characterized in that: modified graphene/bismaleimide resin matrix material is the black solid of two phase structure, matrix is the bismaleimide resin matrix that bismaleimide resin powder and thinner form, wild phase is the modified graphene of black, be dispersed in the bismaleimide resin matrix, the content of modified graphene in matrix material is 0.1～0.5wt%; There is thickness in modified graphene in tetrahydrofuran solvent be 1～1.5nm, modified graphene particle size 0.5～1 μ m.
2. a kind of modified graphene according to claim 1/bismaleimide resin matrix material, it is characterized in that: the resistance to impact shock value of described modified graphene/bismaleimide resin matrix material is 19.557～26.171KJ/m
2, than original bismaleimide resin toughness reinforcing 3.67%～38.74%.
3. the preparation method of modified graphene/bismaleimide resin matrix material, is characterized in that, described preparation method comprises the steps:
Step 1: the preparation of graphite oxide;
Step 2: the preparation of modified graphene;
Step 3: the preparation of modified graphene/bismaleimide resin matrix material:
The tetrahydrofuran solution of choosing modified graphene adds bismaleimide resin thinner diallyl bisphenol, ultrasonic 1～2h, then under magnetic agitation, vacuum, stir emptying tetrahydrofuran (THF), temperature rises to 140 ℃ gradually by room temperature, after bubble is got rid of fully, under magnetic agitation, 140 ℃, adding with the diallyl bisphenol mol ratio is the bismaleimide resin powder of 1:1, after the solution clarification, continues to stir 0.5～1h under magnetic agitation, 140 ℃; Mixing liquid is injected to ready mould, 140 ℃ of vacuum drying ovens are bled and are steeped 15～30min, then the solidification value according to bismaleimide resin is cured, curing flow process is to be incubated 3h at 180 ℃ of temperature, at 220 ℃ of temperature, be incubated 2h, be incubated 3h at 250 ℃ of temperature, be cooled to room temperature, the demoulding after taking out, be met the modified graphene of requirement/bismaleimide resin matrix material; The mass percent 0.1～0.5% of modified graphene in described matrix material.
4. the preparation method of a kind of modified graphene according to claim 3/bismaleimide resin matrix material, it is characterized in that: described step 1 is specially:
(1) get Graphite Powder 99, KNO
3Powder and the vitriol oil mix, and blending ratio is to add 1.5g KNO in every 1.5g Graphite Powder 99
3Powder, 65～69ml vitriol oil, add KMnO during by the mixture heating in water bath to 35 that obtains～40 ℃
4Powder, adding proportion are that every 1.5g graphite adds 8.0～9.5gKMnO
4, at 100～300r/min rotating speed lower magnetic force, stir, more than reaction 6h; Then in mixture, slowly add for the first time deionized water, and bath temperature is adjusted to 60 ℃～70 ℃, after reaction 25～40min, add for the second time wherein again deionized water, for the first time described and add for the second time the add-on of deionized water to add the ratio of deionized water 100～200ml and 200～400ml to add with every 1.5g graphite, after continuing reaction 4～5min, be 20wt%～50wt%H to dripping concentration in mixing liquid
2O
2The aqueous solution, become glassy yellow to mixing liquid;
(2) mixing liquid is extremely neutral with deionized water wash, being configured to concentration is the graphite oxide aqueous solution of 1～2mg/ml.
5. the preparation method of a kind of modified graphene according to claim 4/bismaleimide resin matrix material, it is characterized in that: the concentration of the described vitriol oil is that 75wt%～concentration is 983wt%.
6. the preparation method of a kind of modified graphene according to claim 3/bismaleimide resin matrix material, it is characterized in that: described step 2 is specially: after using ultrasonic cleaning instrument ultrasonic oxidation graphene aqueous solution 1～2h, obtain the suspension of graphene oxide; Adjusting the suspension pH value is 9～10, is heated under 100 ℃ and reacts 1h in magnetic agitation, oil bath according to 120mg graphite oxide aqueous solution proportioning 1～1.5ml hydrazine hydrate; Follow the ratio according to every 0.012g graphite oxide aqueous solution proportioning 0.001～0.0015mol Ursol D and 0.0015～0.002mol Isopentyl nitrite, when being heated to 80 ℃, magnetic agitation, oil bath first add Isopentyl nitrite, add again the Ursol D that is dissolved in deionized water more than 60 ℃, more than reaction 10h, cool to room temperature also with after deionized water and tetrahydrofuran (THF) washing, being kept in tetrahydrofuran (THF).
7. the preparation method of a kind of modified graphene according to claim 6/bismaleimide resin matrix material, it is characterized in that: the mass percent concentration of described hydrazine hydrate is 50%.
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