CN107325328A - A kind of preparation method of graphene/silicon dioxide compound particle - Google Patents
A kind of preparation method of graphene/silicon dioxide compound particle Download PDFInfo
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08L7/00—Compositions of natural rubber
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- C08L2205/00—Polymer mixtures characterised by other features
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Abstract
A kind of preparation method of graphene/silicon dioxide compound particle belongs to field of nanocomposite materials.Solve the problem that graphene and silica disperse in rubber.It is of the invention main using graphene aerogel is built, then silica is scattered in the micropore of aeroge.Avoid both aggregations.The present invention is using graphene oxide as presoma, by the property, electronation type, drying process that control graphene oxide, the graphene/silicon dioxide aeroge with special appearance, size and superior physical properties is obtained, with stable chemical property of low-density, high porosity, high-ratio surface, lower thermal conductivity etc..Aeroge is added in rubber, it is ensured that graphene sheet layer is dispersed in rubber matrix, improve graphene and the problems such as the interface interaction of rubber.Aeroge of the present invention is the three-dimensional carbon material with macroporosity and specific surface area, can be as excellent materials application in reinforcing rubber, and preparation technology has very big lifting compared to conventional technique.
Description
Technical field
The present invention relates to a kind of grapheme material application, belong to field of nanocomposite materials.
Background technology
Graphene is one kind by sp2The tightly packed individual layer bi-dimensional cellular shape lattice structure of the carbon atom of orbital hybridization
Carbonaceous material.An Deliehaimu and Constantine's Nuo Woxiao love adhesive tapes by Univ Manchester UK in 2004
The method of stripping high starch breeding is successfully made first really is able to self-existent two-dimensional graphene crystal.Graphene is in plane
The multiple periodic structure of freight weight limit is inside whether there is, there was only nanoscale in the direction perpendicular to plane, can be regarded as with macro-size
Nano material.Graphene has high-specific surface area, aspect ratio, high-modulus and good solvent-dispersible, be it is a kind of very
Potential rubber reinforcement filler.Cause graphene to realize the maximization of performance in rubber composite, realize graphene
Dispersed in rubber matrix and good interface is obtained, scattered in rubber matrix is the one of rubber reinforcement to ask greatly
Topic, and it is still the difficult point and key for obtaining high-performance rubber product to solve scattered in rubber matrix of graphene.
Meanwhile, the reinforcing agent that silica is used as traditional rubber, with very unique effect.Silica strengthens
Rubber in, wet-sliding resistant performance good the characteristics of low with rolling resistance.But silica has due to being nano particle simultaneously
Strong aggregation tendency, scattered in rubber is also a big difficult point.
Therefore this patent proposes to build the compounded mix of a kind of graphene and silica, while solving graphene and dioxy
The problem of SiClx disperses hardly possible in rubber, easily reunited.Main method is during graphene and silica mixing, to build
The aerogel structure of graphene.Realize that silicon dioxide granule is present in the micropore of the aeroge of graphene, finally realize two kinds
The isolation of particle mutually, reaches mutually scattered result.Most this compound particle and rubber combined at last, obtains new graphite
Alkene/silica rubber nano composite material, its combination property is higher than is doped in graphene and silica in rubber respectively
Composite performance.
The content of the invention
The purpose of the present invention is to improve a kind of preparation method of graphene/silicon dioxide compound particle, and emphasis solves graphite
The problem that alkene and silica disperse in rubber.It is of the invention main using graphene aerogel is built, then by silica
It is scattered in the micropore of aeroge.Avoid both aggregations.
To achieve these goals, technical scheme is as follows：Step one：(1) graphene oxide is mixed with solvent
The solution of graphene oxide is obtained after conjunction, further ultrasonic disperse is placed in Ultrasound Instrument, ultrasonic frequency is 100~5000HZ,
Temperature is 0~100 DEG C, and ultrasonic time is 0.1~4h, obtains the graphene oxide solution that concentration is 0.1mg/ml~50mg/ml；
(2) by silica and graphene oxide with mass ratio (1~50)：1 silica is added in graphene oxide solution, then
Carry out ultrasonic disperse and obtain graphene oxide/silicon dioxde solution, wherein the frequency of ultrasound is 100~5000W, the time is 0.1
~4h, temperature control is below 50 DEG C.By dispersant and silica with mass ratio (1~20)：1 dispersant adds oxidation stone
In black alkene/silicon dioxde solution, above-mentioned solution is mixed into 1-150min at room temperature, dispersant is completely dissolved, obtain uniform
Scattered graphene oxide/silicon dioxde solution；
Step 2：(1) by reducing agent and graphene oxide with mass ratio (0.1~30)：1 in graphene oxide/titanium dioxide
Silicon solution adds reducing agent, mixes 1-180 minute, mixed liquor heated constant temperature then is maintained at into 10~80 DEG C, react 0.5~
36h, obtains the gel of graphene/silicon dioxide；(2) graphene/silicon dioxide gel obtained above is first used into ethanol repeatedly
Cleaning 1~10 time；(3) by the graphene/silicon dioxide liquid gel cleaned repeatedly with ethanol, then with dissolving graphene oxide
Homogeneous solvent displacement gel in liquid, time swap be 1~3 day.
Step 3：Graphene/silicon dioxide liquid gel is dried or freeze-drying process in drying facility, most
After obtain graphene/silicon dioxide compound particle.
Solvent employed in step one of the present invention is water, methanol, ethanol, trifluoroethanol, formic acid, triethanolamine, acetic acid,
Acetone, ethyl acetate, tetrahydrofuran, N-methyl pyrrolidones, ether, expoxy propane, dichloromethane, chloroform, three ethanol
One or more in amine.
Silica employed in step one (2) of the present invention is including but not limited to precipitated silica, and vapor phase method is white
Carbon black etc..The particle diameter of silica is 10nm-10 μm.
Dispersant employed in step one (2) of the present invention is kayexalate, cetyl trimethylammonium bromide,
Dodecyl sodium sulfate, neopelex, PEO-PPOX-PEO triblock copolymer
In one or more.
Graphene oxide is mainly reduced to graphene by institute's reducing agent in step 2 (1) of the present invention, is included but is not limited to
It is several below：Ascorbic acid, benzenediol, sodium borohydride (NaBH4), hydrazine hydrate, Dimethylhydrazine, titanium trichloride, sodium citrate, three second
One or more in base aluminium, lithium aluminium hydride reduction.
Drying facility employed in step 3 of the present invention includes but are not limited to equipment：Baking oven, freeze drier, CO2
Supercritical drying instrument etc..
Freeze drying process described in step 3 kind of the present invention is not limited by freeze drying equipment, can be chilled to zero various
Under freezed or be directly placed into -60 DEG C~-10 DEG C of equipment and freezed in liquid nitrogen after, then the graphite oxide freezed
Alkene/silica liquid gel is put into freeze-dryer and is freeze-dried.
Graphene oxide and graphene aerogel preparation method system provided by the present invention, technique are simple and are easy to expand
Greatly.The preparation of aeroge is using graphene oxide as presoma, by the property (quantity, dispersiveness, the oxidation that control graphene oxide
Graphene aqueous solution concentration, size, structural intergrity etc.), electronation type (type of solvent, reaction condition), drying process,
Obtain the graphene/silicon dioxide aeroge with special appearance, size and superior physical properties.
The made graphene/silicon dioxide aeroge of the present invention has excellent characteristic and performance, low-density, high porosity
Stable chemical property of (macropore, mesopore, the mesoporous and micropore with very many interactive connection), high-ratio surface, lower thermal conductivity etc..
Especially it is added to graphene/silicon dioxide aeroge in rubber, can mainly solves to add graphite in high-performance rubber
The interface that alkene or silica disperse between uneven and graphene and rubber matrix ensures graphene sheet layer in rubber-based
The problems such as interface interaction of dispersed in body, raising graphene and rubber.
The graphene/silicon dioxide aeroge that the present invention is provided is the three-dimensional carbon materials with macroporosity and specific surface area
Material, therefore this aeroge can be as excellent materials application in reinforcing rubber, preparation technology has compared to conventional technique
Very big lifting.Graphene/silicon dioxide aeroge with superior mechanical property and self structure due to causing it in high-performance
The application potential of reinforcing rubber is huge, in addition, possess the graphene/silicon dioxide aeroge of excellent specific property and performance in material and
The application prospect in the fields such as other energy is also boundless.
Embodiment
With reference to embodiment, to further illustrate the present invention.But the present invention is not limited to following examples.
Embodiment 1
(1) solution of graphene oxide is obtained after 0.5g graphene oxides are mixed with water, is placed in Ultrasound Instrument further
Ultrasonic disperse, ultrasonic frequency is that 1000HZ, temperature are 25 DEG C, and ultrasonic time is 0.5h, obtains the oxidation that concentration is 1mg/ml
Graphene solution；
(2) by 1g silicon-dioxide powderies add graphene oxide solution, then carry out ultrasonic disperse obtain graphene oxide/
Silicon dioxde solution.Wherein ultrasonic frequency is 1000HZ, and the time is 0.5h, and temperature control is below 50 DEG C.Add 0.05g
Kayexalate, above-mentioned mixed liquor carries out magnetic agitation 30min at room temperature；
(3) aqueous solution of obtained graphene oxide/silica is placed into beaker, then adds 5mg benzene two
Phenol, mixes 30 minutes, mixed liquor heated constant temperature then is maintained at into 30 DEG C, react 8h, obtains the solidifying of graphene/silicon dioxide
Glue；
(4) graphene/silicon dioxide gel obtained above is first cleaned 3 times with water repeatedly；
(5) by the graphene/silicon dioxide liquid gel cleaned repeatedly with water, then with water replace gel in liquid,
Time swap is 1 day.
(6) by graphene/silicon dioxide liquid gel -20 DEG C freezing, vacuum be 15Pa under conditions of, freeze-drying
It is that can obtain graphene/silicon dioxide compound particle that machine, which dries 10h,.
Embodiment 2
(1) solution of graphene oxide is obtained after 2g graphene oxides are mixed with ethanol, is placed in Ultrasound Instrument further
Ultrasonic disperse, ultrasonic frequency is that 800HZ, temperature are 30 DEG C, and ultrasonic time is 0.8h, obtains the oxidation stone that concentration is 2mg/ml
Black alkene ethanol solution；
(2) 1g silicon-dioxide powderies are added into graphene oxide ethanol solution, then carries out ultrasonic disperse and obtain aoxidizing stone
Black alkene/silica ethanol solution.Wherein ultrasonic frequency is 750HZ, and the time is 0.5h, and temperature control is below 50 DEG C.Again
0.08g kayexalates are added, above-mentioned mixed liquor carries out magnetic agitation 30min at room temperature；
(3) ethanol solution of obtained graphene oxide/silica is placed into beaker, then adds 5mg boron
Sodium hydride, mixes 30 minutes, mixed liquor heated constant temperature then is maintained at into 30 DEG C, react 12h, obtain graphene/silicon dioxide
Gel；
(4) graphene/silicon dioxide gel obtained above is first cleaned 3 times with ethanol repeatedly；
(5) by the graphene/silicon dioxide liquid gel cleaned repeatedly with ethanol, then with the liquid in ethanol replacement gel
Body, time swap is 1 day.
(6) by graphene/silicon dioxide liquid gel -25 DEG C freezing, vacuum be 20Pa under conditions of, freeze-drying
It is that can obtain graphene/silicon dioxide compound particle that machine, which dries 8h,.
Embodiment 3
(1) solution of graphene oxide is obtained after 3g graphene oxides are mixed with ethanol, is placed in Ultrasound Instrument further
Ultrasonic disperse, ultrasonic frequency is that 600HZ, temperature are 40 DEG C, and ultrasonic time is 1h, obtains the graphite oxide that concentration is 3mg/ml
Alkene ethanol solution；
(2) 2g silicon-dioxide powderies are added into graphene oxide ethanol solution, then carries out ultrasonic disperse and obtain aoxidizing stone
Black alkene/silica ethanol solution.Wherein ultrasonic frequency is 600HZ, and the time is 1h, and temperature control is below 50 DEG C.Again plus
Enter 0.1g neopelexes, above-mentioned mixed liquor carries out magnetic agitation 30min at room temperature；
(3) ethanol solution of obtained graphene oxide/silica is placed into beaker, then adds 5mg water
Hydrazine is closed, mixes 40 minutes, mixed liquor heated constant temperature is then maintained at 25 DEG C, react 10h, obtain graphene/silicon dioxide
Gel；
(4) graphene/silicon dioxide gel obtained above is first cleaned 3 times with ethanol repeatedly；
(5) by the graphene/silicon dioxide liquid gel cleaned repeatedly with ethanol, then with the liquid in ethanol replacement gel
Body, time swap is 1 day.
(6) by graphene/silicon dioxide liquid gel in CO2Supercritical drying instrument be dried can obtain graphene/
Silica dioxide composite particles.
Embodiment 4
(1) solution of graphene oxide is obtained after 3g graphene oxides are mixed with ethanol, is placed in Ultrasound Instrument further
Ultrasonic disperse, ultrasonic frequency is that 700HZ, temperature are 40 DEG C, and ultrasonic time is 1h, obtains the graphite oxide that concentration is 3mg/ml
Alkene ethanol solution；
(2) 1.5g silicon-dioxide powderies are added into graphene oxide ethanol solution, then carries out ultrasonic disperse and aoxidized
Graphene/silicon dioxide ethanol solution.Wherein ultrasonic frequency is 700HZ, and the time is 1h, and temperature control is below 50 DEG C.Again
0.1g neopelexes are added, above-mentioned mixed liquor carries out magnetic agitation 30min at room temperature；
(3) ethanol solution of obtained graphene oxide/silica is placed into beaker, then adds 5mg lemon
Lemon acid sodium, mixes 30 minutes, mixed liquor heated constant temperature then is maintained at into 40 DEG C, react 14h, obtain graphene/silicon dioxide
Gel；
(4) graphene/silicon dioxide gel obtained above is first cleaned 3 times with water repeatedly；
(5) by the graphene/silicon dioxide liquid gel cleaned repeatedly with water, then with the liquid in ethanol replacement gel
Body, time swap is 1 day.
(6) graphene/silicon dioxide liquid gel is being placed into 12h, graphene/silicon dioxide water-setting in 60 DEG C of baking ovens
Colloid product is obvious to shrink, you can obtain graphene/silicon dioxide compound particle.
Embodiment 5
(1) solution of graphene oxide is obtained after 2g graphene oxides are mixed with ethanol, is placed in Ultrasound Instrument further
Ultrasonic disperse, ultrasonic frequency is that 800HZ, temperature are 30 DEG C, and ultrasonic time is 0.8h, obtains the oxidation stone that concentration is 2mg/ml
Black alkene ethanol solution；
(2) 1g silicon-dioxide powderies are added into graphene oxide ethanol solution, then carries out ultrasonic disperse and obtain aoxidizing stone
Black alkene/silica ethanol solution.Wherein ultrasonic frequency is 600HZ, and the time is 1h, and temperature control is below 50 DEG C.Again plus
Enter 0.05g neopelexes, above-mentioned mixed liquor carries out magnetic agitation 30min at room temperature；
(3) ethanol solution of obtained graphene oxide/silica is placed into beaker, then adds 5mg boron
Sodium hydride, mixes 30 minutes, mixed liquor heated constant temperature then is maintained at into 30 DEG C, react 12h, obtain graphene/silicon dioxide
Gel；
(4) graphene/silicon dioxide gel obtained above is first cleaned 3 times with ethanol repeatedly；
(5) by the graphene/silicon dioxide liquid gel cleaned repeatedly with ethanol, then with the liquid in ethanol replacement gel
Body, time swap is 1 day.
(6) by graphene/silicon dioxide liquid gel -25 DEG C freezing, vacuum be 20Pa under conditions of, freeze-drying
It is that can obtain graphene/silicon dioxide compound particle that machine, which dries 8h,.
Embodiment 6
(1) solution of graphene oxide is obtained after 2g graphene oxides are mixed with acetone, is placed in Ultrasound Instrument further
Ultrasonic disperse, ultrasonic frequency is that 600HZ, temperature are 30 DEG C, and ultrasonic time is 0.8h, obtains the oxidation stone that concentration is 2mg/ml
Black allydione solution；
(2) 1g silicon-dioxide powderies are added into graphene oxide acetone soln, then carries out ultrasonic disperse and obtain aoxidizing stone
Black alkene/silicon dioxde acetone solution.Wherein ultrasonic frequency is 800HZ, and the time is 0.8h, and temperature control is below 50 DEG C.Again
0.05g neopelexes are added, above-mentioned mixed liquor carries out magnetic agitation 30min at room temperature；
(3) acetone soln of obtained graphene oxide/silica is placed into beaker, then adds 5mg boron
Sodium hydride, mixes 30 minutes, mixed liquor heated constant temperature then is maintained at into 30 DEG C, react 12h, obtain graphene/silicon dioxide
Gel；
(4) graphene/silicon dioxide gel obtained above is first cleaned 3 times with water repeatedly；
(5) by the graphene/silicon dioxide liquid gel cleaned repeatedly with water, then with the liquid in ethanol replacement gel
Body, time swap is 2 days.
(6) it is that can obtain graphene/silicon dioxide graphene/silicon dioxide liquid gel to be dried into 8h in vacuum drying chamber
Compound particle.
Embodiment 7
(1) solution of graphene oxide is obtained after 1.5g graphene oxides are mixed with water, is placed in Ultrasound Instrument further
Ultrasonic disperse, ultrasonic frequency is that 800HZ, temperature are 30 DEG C, and ultrasonic time is 1.5h, obtains the oxidation that concentration is 1.5mg/ml
Graphene solution；
(2) 1g precipitated silicas silicon powder is added into graphene oxide solution, then carries out ultrasonic disperse and obtain aoxidizing stone
Black alkene/silicon dioxde solution.Wherein ultrasonic frequency is 800HZ, and the time is 1h, and temperature control is below 50 DEG C.Add
0.05g PEOs-PPOX-PEO, above-mentioned mixed liquor carries out magnetic agitation 30min at room temperature；
(3) aqueous solution of obtained graphene oxide/silica is placed into beaker, then adds 5mg trichlorine
Change titanium, mix 30 minutes, mixed liquor heated constant temperature is then maintained at 30 DEG C, react 13h, obtain graphene/silicon dioxide
Gel；
(4) graphene/silicon dioxide gel obtained above is first cleaned 3 times with ethanol repeatedly；
(5) by the graphene/silicon dioxide liquid gel cleaned repeatedly with ethanol, then with the liquid in ethanol replacement gel
Body, time swap is 1 day.
(6) by graphene/silicon dioxide liquid gel -25 DEG C freezing, vacuum be 10Pa under conditions of, freeze-drying
It is that can obtain graphene/silicon dioxide compound particle that machine, which dries 24h,.
Embodiment 8
(1) solution of graphene oxide is obtained after 2g graphene oxides are mixed with tetrahydrofuran, is placed in Ultrasound Instrument
One step ultrasonic disperse, ultrasonic frequency is that 1000HZ, temperature are 40 DEG C, and ultrasonic time is 1h, obtains the oxygen that concentration is 2mg/ml
Graphite alkene ethanol solution；
(2) by 1g silicon-dioxide powderies add graphene oxide solution, then carry out ultrasonic disperse obtain graphene oxide/
Silicon dioxde solution.Wherein ultrasonic frequency is 1000HZ, and the time is 1h, and temperature control is below 50 DEG C.Add 0.05g ten
Dialkyl benzene sulfonic acids sodium, above-mentioned mixed liquor carries out magnetic agitation 30min at room temperature；
(3) tetrahydrofuran solution of obtained graphene oxide/silica is placed into beaker, then adds 5mg
Sodium borohydride, mix 30 minutes, mixed liquor heated constant temperature be then maintained at 30 DEG C, react 12h, obtain graphene/dioxy
The gel of SiClx；
(4) graphene/silicon dioxide gel obtained above is first cleaned 3 times with tetrahydrofuran repeatedly；
(5) by the graphene/silicon dioxide liquid gel cleaned repeatedly with tetrahydrofuran, then with ethanol replacement gel
Liquid, time swap be 2 days.
(6) by graphene/silicon dioxide liquid gel in -25 DEG C of freezings, vacuum is under conditions of 300Pa, freezing is dry
It is that can obtain graphene/silicon dioxide compound particle that dry machine, which dries 12h,.
Embodiment 9
(1) solution of graphene oxide is obtained after 2g graphene oxides are mixed with ethanol, is placed in Ultrasound Instrument further
Ultrasonic disperse, ultrasonic frequency is that 800HZ, temperature are 30 DEG C, and ultrasonic time is 0.8h, obtains the oxidation stone that concentration is 2mg/ml
Black alkene ethanol solution；
(2) 1g silicon-dioxide powderies are added into graphene oxide ethanol solution, then carries out ultrasonic disperse and obtain aoxidizing stone
Black alkene/silica ethanol solution.Wherein ultrasonic frequency is 800HZ, and the time is 1h, and temperature control is below 50 DEG C.Again plus
Enter 0.05g neopelexes, above-mentioned mixed liquor carries out magnetic agitation 30min at room temperature；
(3) ethanol solution of obtained graphene oxide/silica is placed into beaker, then adds 5mg boron
Sodium hydride, mixes 30 minutes, mixed liquor heated constant temperature then is maintained at into 30 DEG C, react 12h, obtain graphene/silicon dioxide
Gel；
(4) graphene/silicon dioxide gel obtained above is first cleaned 3 times with ethanol repeatedly；
(5) by the graphene/silicon dioxide liquid gel cleaned repeatedly with ethanol, then with the liquid in ethanol replacement gel
Body, time swap is 1 day.
(6) by graphene/silicon dioxide liquid gel 40 DEG C freezing, vacuum be 5Pa under conditions of, freeze drier
It is that can obtain graphene/silicon dioxide compound particle to dry 20h.
Embodiment 10
(1) solution of graphene oxide is obtained after 4g graphene oxides are mixed with water, is placed in Ultrasound Instrument and further surpasses
Sound disperses, and ultrasonic frequency is that 500HZ, temperature are 50 DEG C, and ultrasonic time is 1h, obtains the graphene oxide that concentration is 4mg/ml
Solution；
(2) 1g aerosils powder is added into graphene oxide solution, then carries out ultrasonic disperse and obtain aoxidizing stone
Black alkene/silicon dioxde solution.Wherein ultrasonic frequency is 600HZ, and the time is 0.5h, and temperature control is below 50 DEG C.Add
0.05g kayexalates, above-mentioned mixed liquor carries out magnetic agitation 20min at room temperature；
(3) aqueous solution of obtained graphene oxide/silica is placed into beaker, then adds 5mg boron hydrogen
Change sodium, mix 30 minutes, mixed liquor heated constant temperature is then maintained at 30 DEG C, react 10h, obtain graphene/silicon dioxide
Gel；
(4) graphene/silicon dioxide gel obtained above is first cleaned 3 times with ethanol repeatedly；
(5) by the graphene/silicon dioxide liquid gel cleaned repeatedly with ethanol, then with the liquid in ethanol replacement gel
Body, time swap is 1 day.
(6) by graphene/silicon dioxide liquid gel -40 DEG C freezing, vacuum be 10Pa under conditions of, freeze-drying
It is that can obtain graphene/silicon dioxide compound particle that machine, which dries 36h,.
Comparative example 1
(1) solution of graphene oxide is obtained after 5g graphene oxides are mixed with water, is placed in Ultrasound Instrument and further surpasses
Sound disperses, and ultrasonic frequency is that 1000HZ, temperature are 50 DEG C, and ultrasonic time is 1h, obtains the graphite oxide that concentration is 5mg/ml
Alkene solution；
(2) 2g precipitated silicas powder is added into graphene oxide solution, then carries out ultrasonic disperse and aoxidized
Graphene/silicon dioxide solution.Wherein ultrasonic frequency is 600HZ, and the time is 0.5h, and temperature control is below 50 DEG C.Again plus
Enter 0.2g kayexalates, above-mentioned mixed liquor carries out magnetic agitation 30min at room temperature；
(3) aqueous solution of obtained graphene oxide/silica is placed into beaker, then adds the anti-bad of 5mg
Hematic acid, mixes 30 minutes, mixed liquor heated constant temperature then is maintained at into 40 DEG C, react 15h, obtain graphene/titanium dioxide
The gel of silicon；
(4) graphene/silicon dioxide gel obtained above is first cleaned 3 times with water repeatedly；
(5) by the graphene/silicon dioxide liquid gel cleaned repeatedly with water, then with water replace gel in liquid,
Time swap is 1 day.
(6) by graphene/silicon dioxide liquid gel -20 DEG C freezing, vacuum be 15Pa under conditions of, freeze-drying
It is that can obtain graphene/silicon dioxide compound particle that machine, which dries 20h,.
Comparative example 2
Any filler is not added with, NR/SBR Blend rubbers are prepared.
Experimental formula and mass fraction are as follows：NR (1# standard rubbers) 50, SBR (1502) 50, zinc oxide 5, stearic acid 2 is prevented
Old agent 4010NA 3, paraffin 1, aromatic naphtha 6, accelerant CZ 1.5 promotees D 1.2, sulphur 1.5.
According to above-mentioned formula, NR, SBR are put into Φ 160mm × 320mm two-roll mills and plasticated, work is sequentially added
Property agent, age resistor, plasticizer, accelerator, sulphur, slice after mixing.Electrothermal plate vulcanizer tabletting vulcanization is obtained at 150 DEG C
Vulcanizate simultaneously tests every basic performance.
Comparative example 3
Using direct blending, graphene and precipitated silica powder are added separately to rubber, graphite is prepared
Alkene/silica/rubber composite.
(1) the graphene/silicon dioxide aeroge prepared in comparative example 1 is taken as reinforcing material.Experimental formula and quality
Number is as follows：NR (1# standard rubbers) 50, SBR (1502) 50, zinc oxide 5, stearic acid 2, antioxidant 4010NA 3, paraffin 1, aromatic hydrocarbons
Oil 6, accelerant CZ 1.5 promotees D 1.2, sulphur 1.5, silica 2, graphene 1.
(2) according to above-mentioned formula, NR, SBR is put into Φ 160mm × 320mm two-roll mills and plasticated, activity is sequentially added
Agent, age resistor, graphene/silicon dioxide aeroge compound particle, plasticizer, accelerator, sulphur mixing slice.At 150 DEG C
The molding vulcanization of electrothermal plate vulcanizer obtains vulcanizate and tests every basic property.
Embodiment 11
Graphene/silicon dioxide aeroge compound particle is added into rubber, the rubber combined material of graphene/silicon dioxide is prepared
Material.
(1) the graphene/silicon dioxide nano-composite fiber prepared in Example 1 is as reinforcing material.Experimental formula
And the following NR of mass fraction (1# standard rubbers) 50, SBR (1502) 50, zinc oxide 5, stearic acid 2, antioxidant 4010NA 3, paraffin
1, aromatic naphtha 6, accelerant CZ 1.5 promotees D 1.2, sulphur 1.5, graphene/silicon dioxide nano-composite fiber 4.
(2) according to above-mentioned formula, NR, SBR is put into Φ 160mm × 320mm two-roll mills and plasticated, activity is sequentially added
Agent, age resistor, graphene/silicon dioxide aeroge compound particle, plasticizer, accelerator, sulphur, knead slice.At 150 DEG C
The molding vulcanization of electrothermal plate vulcanizer obtains vulcanizate and tests properties.
Embodiment 12
Graphene/silicon dioxide aeroge compound particle is added into rubber, the rubber combined material of graphene/silicon dioxide is prepared
Material.
(1) the graphene/silicon dioxide aeroge compound particle prepared respectively in Example 2~10 is as strengthening material
Material.Experimental formula and mass fraction are as follows：NR (1# standard rubbers) 50, SBR (1502) 50, zinc oxide 5, stearic acid 2, age resistor
4010NA 3, paraffin 1, aromatic naphtha 6, accelerant CZ 1.5 promotees D 1.2, and sulphur 1.5, graphene/silicon dioxide aeroge is combined
Particle 4.
(2) according to above-mentioned formula, NR, SBR is put into Φ 160mm × 320mm two-roll mills and plasticated, activity is sequentially added
Agent, age resistor, graphene/silicon dioxide aeroge compound particle, plasticizer, accelerator, sulphur, knead slice.In 150 DEG C of electricity
The molding vulcanization of flat plate heat vulcanizer obtains vulcanizate and tests every basic property.
Comparative example 2, comparative example 3, the test result of embodiment 11 and embodiment 12 are as follows：
Specific implementation process of the above example to the present invention is described in detail, but the present invention be not limited to it is described
Embodiment, those skilled in the art can make a variety of equal replacements, such as with different modifying agent to graphene oxide
Or silica carries out functional modification etc..These equal modifications or replacement belong to this application claims scope
It is interior.
Claims (7)
1. a kind of preparation method of graphene/silicon dioxide compound particle, it is characterised in that specific steps are proceeded as follows：
Step one：(1) solution of graphene oxide is obtained after graphene oxide is mixed with solvent, is placed in Ultrasound Instrument further
Ultrasonic disperse, ultrasonic frequency is that 100~5000HZ, temperature are 0~100 DEG C, and ultrasonic time is 0.1~4h, and obtaining concentration is
0.1mg/ml~50mg/ml graphene oxide solution；(2) by silica and graphene oxide with mass ratio (1~50)：1
Silica is added in graphene oxide solution, ultrasonic disperse is then carried out and obtains graphene oxide/silicon dioxde solution, its
Middle ultrasonic frequency is 100~5000W, and the time is 0.1~4h, and temperature control is below 50 DEG C；By dispersant and silica
With mass ratio (1~20)：1 dispersant is added in graphene oxide/silicon dioxde solution, and above-mentioned solution is mixed at room temperature
1-150min, is completely dissolved dispersant, obtains dispersed graphene oxide/silicon dioxde solution；
Step 2：(1) by reducing agent and graphene oxide with mass ratio (0.1~30)：1 is molten in graphene oxide/silica
Liquid adds reducing agent, mixes 1-180 minutes, mixed liquor heated constant temperature then is maintained at into 10~80 DEG C, react 0.5~36h, obtain
To the gel of graphene/silicon dioxide；(2) graphene/silicon dioxide gel obtained above is first cleaned 1 with ethanol repeatedly~
10 times；(3) by the graphene/silicon dioxide liquid gel cleaned repeatedly with ethanol, then with dissolving graphene oxide it is of the same race
Liquid in solvent displacement gel, time swap is 1~3 day；
Step 3：Graphene/silicon dioxide liquid gel is dried or freeze-drying process in drying facility, finally
To graphene/silicon dioxide compound particle.
2. in accordance with the method for claim 1, it is characterised in that the solvent employed in step one is water, methanol, ethanol,
Trifluoroethanol, formic acid, triethanolamine, acetic acid, acetone, ethyl acetate, tetrahydrofuran, N-methyl pyrrolidones, ether, epoxy third
One or more in alkane, dichloromethane, chloroform, triethanolamine.
3. in accordance with the method for claim 1, it is characterised in that the silica employed in step one (2) includes precipitation
Method silica, fumed silica；The particle diameter of silica is 10nm-10 μm.
4. in accordance with the method for claim 1, it is characterised in that the dispersant employed in step one (3) is polystyrene
Sodium sulfonate, cetyl trimethylammonium bromide, dodecyl sodium sulfate, neopelex, PEO-polycyclic oxygen
One or more in propane-PEO triblock copolymer.
5. in accordance with the method for claim 1, it is characterised in that institute's reducing agent includes ascorbic acid, benzene two in step 2 (1)
One or more in phenol, sodium borohydride, hydrazine hydrate, Dimethylhydrazine, titanium trichloride, sodium citrate, triethyl aluminum, lithium aluminium hydride reduction.
6. in accordance with the method for claim 1, it is characterised in that the drying facility employed in step 3 includes baking oven, cold
Freeze drying instrument or CO2Supercritical drying instrument.
7. in accordance with the method for claim 1, it is characterised in that freeze drying process described in step 3 kind is in various freezings
Freezed or be directly placed into subzero -60 DEG C~-10 DEG C of equipment after being freezed in liquid nitrogen, then the oxidation stone freezed
Black alkene/silica liquid gel is put into freeze-dryer and is freeze-dried.
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