CN105131359A - Graphene/carbon nano tube hybridized filler network enhanced rubber material and preparation method thereof - Google Patents
Graphene/carbon nano tube hybridized filler network enhanced rubber material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a graphene/carbon nano tube hybridized filler network enhanced rubber material and a preparation method thereof. According to the rubber material, graphene and carbon nano tubes are taken as filler, a hybridized filler network is formed in a rubber material matrix, wherein 100 parts by mass of the rubber material matrix are adopted, and 0.1-20 parts by mass of graphene and the carbon nano tubes are adopted. The rubber material is prepared according to steps as follows: oxidized graphene and the carbon nano tubes are added to water, and a hybridized suspension liquid is prepared; the prepared hybridized suspension liquid is added to an emulsion of the rubber material matrix and mixed, a demulsifier is added for demulsification, an oxidized graphene/carbon nano tube/rubber particle suspension liquid is prepared, then, a reducing agent is added for a reduction reaction, solid-liquid separation is performed after sufficient reaction, an obtained solid phase is washed and dried, and the rubber material is prepared. The graphene and the carbon nano tubes form the hybridized filler network in the rubber material and have an energy dissipation function, so that the rubber material has excellent mechanical property, fatigue resistance, crack growth resistance and conductive property.
Description
Technical field
The present invention relates to technical field of rubber material, being specifically related to Graphene, carbon nanotube is elastomeric material of filler modified enhancing and preparation method thereof.
Background technology
The mechanical property of elastomeric material is most important to Rubber use properties.The mechanical property improving elastomeric material is the problem of scientific worker's concern in affiliated field always.Common practice doses mineral filler in elastomeric material matrix, improved the mechanical property of elastomeric material by filler.Graphene and carbon nanotube have bigger serface, excellent mechanical property, conductivity and barrier property, are a kind of desirable elastomeric material modified fillers, have been successfully used to the mechanical property of Reinforced Rubber material.Mainly as filler, modification is carried out to elastomeric material mechanical property using Graphene or carbon nanotube at present.Wu Jinrong etc. adopt emulsion dispersion to prepare Graphene/natural rubber nano composite material, under best Graphene addition, the tensile strength of Graphene/natural rubber nano composite material can reach 24.5MPa, with pure natural rubber phase ratio, improve 48% (W.Xing, J.R.Wu, G.S.Huang, H.Li, M.Z.Tang, X.Fu.PolymerInternational2014,63,1674-1681).Bhattacharyya etc. adopt surfactant-dispersed carbon nanotube, again with natural rubber compound, when content of carbon nanotubes is 8.3%, the tensile strength of carbon nanotube/natural rubber is 7.3MPa (S.Bhattacharyya, C.Sinturel, O.Bahloul, M.Saboungi, S.Thomas, J.Salvetat.Carbon, 2008,46,1037-1045).Graphene and carbon nanotube are as in single filler filled rubber material matrix, improve the tensile mechanical properties of elastomeric material all to a certain extent, but its reinforced effects is limited, and the performance such as the toughness of single filler Reinforced Rubber, antifatigue and opposing crack growth is not ideal enough.Therefore, the new filler Reinforced Rubber method of exploration is needed badly.
Application number be 201110203850.8 patent document disclose a kind of polymer composites and its manufacture method of graphene/carbon nanotube hybrid, the method takes polymer composites Graphene, carbon nanotube and polymer matrix material being prepared graphene/carbon nanotube hybrid with the method for solution blending or mechanical blending.Obtained polymer composites has higher conductivity and strong mechanical performance, can as antistatic material, electromagnetic shielding material, in order to be made into packaging, the parts of mobile phone, the antistatic tread rubber of conduction carpet, electronic product, and the electromagnetic screen coating etc. of aerospace equipment.If the method adopts its solution blended process to produce polymer composites, need in a large number with an organic solvent, its Problems existing is that cost is high, can bring pollution to environment; If the method adopts its mechanical blending legal system to get polymer composites, Graphene and carbon nanotube disperse bad in polymer matrix material, and reunite obviously, polymer composites performance is uneven.In addition, no matter be solution blended process or mechanical blending method, be all unfavorable for that filler network is formed, significant reinforced effects can not be obtained.Therefore, how realizing simple and effective dispersed graphite alkene/carbon nano-tube hybridization filler in rubber matrix, and make filler form filler network in rubber matrix, is a difficult problem of preparation graphene/carbon nano-tube/rubber nano composite material.
Summary of the invention
For the deficiencies in the prior art and present situation, first object of the present invention is to provide the graphene/carbon nano-tube hydridization filler network Reinforced Rubber material that a kind of mechanical property obtains obviously strengthening; Second object of the present invention is to provide a kind of method preparing graphene/carbon nano-tube hydridization filler network Reinforced Rubber material.
Basic ideas of the present invention are by forming graphene/carbon nano-tube hydridization filler network to realize the mechanical property of Reinforced Rubber material in elastomeric material matrix.The present invention prepares the basic ideas of graphene/carbon nano-tube hydridization filler network Reinforced Rubber material, it is the surface active function dispersing Nano carbon tubes utilizing graphene oxide, obtain graphene oxide/carbon nano-tube hybridization suspension, and then by graphene oxide/carbon nano-tube hybridization suspension and latex blended, mix rear breakdown of emulsion, form graphene oxide/carbon nanotube/rubber grain suspension, by reductive agent, graphene oxide is reduced into Graphene afterwards, through solid-liquid separation, washing, obtained graphene/carbon nano-tube/rubber nano composite rubber material after dry.
Graphene/carbon nano-tube hydridization filler network Reinforced Rubber material provided by the invention, it is formed is for filler with Graphene and carbon nanotube, be dispersed in elastomeric material matrix and form hydridization filler network, with the mechanical property of Reinforced Rubber material, elastomeric material component is formed: elastomeric material matrix 100 mass parts, as Graphene and carbon nanotube totally 0.1 ~ 20 mass parts of filler, and the mass ratio of Graphene and carbon nanotube is (1:10) ~ (10:1).
In technique scheme of the present invention, as Graphene and the carbon nanotube of filler, their shared amount is preferably 0.5 ~ 20 mass parts.
In technique scheme of the present invention, described elastomeric material matrix is selected from natural gum, butadiene-styrene rubber, ABS glue, butadiene-acrylonitrile rubber, neoprene latex, urethane, Voncoat R 3310 or multipolymer and methacrylate homopolymer or multipolymer etc., namely can be the one in them, also can be two or more in them.
Above-mentioned graphene/carbon nano-tube hydridization filler network Reinforced Rubber material of the present invention, is prepared by the method comprising following processing step:
(1) preparation of graphene oxide/carbon nano-tube hybridization suspension: will add in the water of 100 mass parts according to the graphene oxide of Graphene determined amounts of formula ratio and the carbon nanotube of formula ratio, the fully obtained graphene oxide/carbon nano-tube hybridization suspension of mixing;
(2) preparation of graphene oxide/carbon nanotube/rubber grain suspension: it is in the elastomeric material matrix emulsion of 5 ~ 70% formula ratios that graphene oxide/carbon nano-tube hybridization suspension step (1) prepared joins solid content, add after abundant mixing mass concentration be 5 ~ 80% emulsion splitter 0.1 ~ 100 mass parts carry out breakdown of emulsion, obtained graphene oxide/carbon nanotube/rubber grain suspension;
(3) preparation of hydridization filler network Reinforced Rubber material: add 0.1 ~ 50 weight part reductive agent in graphene oxide/carbon nanotube/rubber grain suspension that step (2) is obtained, reduction reaction is carried out at 20 ~ 100 DEG C, solid-liquid separation is carried out after abundant reduction reaction, drying after gained solid phase washing removing emulsion splitter, reductive agent and unreacted component, namely obtains the elastomeric material that graphene/carbon nano-tube hydridization filler network strengthens.
In above-mentioned preparation method of the present invention, described emulsion splitter is preferentially selected from sodium chloride solution, Klorvess Liquid, calcium chloride solution, magnesium chloride solution, liquor alumini chloridi, polymeric aluminum chlorides solution, ferric chloride Solution, solution of ferrous chloride, Cupric Chloride Solution, calcium sulphate soln, metabisulfite solution, copper-bath, ferrum sulfuricum oxydatum solutum, copperas solution, formic acid, acetic acid, hydrochloric acid and sulfuric acid etc., namely can be the one in them, also can be two or more in them.
In above-mentioned preparation method of the present invention, described reductive agent is preferentially selected from hydrazine, hydrazine hydrate, dimethylhydrazine, sodium borohydride, Resorcinol, n-Butyl Amine 99, quadrol, vitamins C, natrium hydrocitricum, iron powder, lithium aluminum hydride, nitrous acid hydrogen sodium, hydrogen sulfide, kalium carbide and aluminium powder, namely can be the one in them, also can be two or more in them.
In above-mentioned preparation method of the present invention, described carbon nanotube can be multi-walled carbon nano-tubes or the Single Walled Carbon Nanotube that length-to-diameter ratio is 10 ~ 1000; Graphene oxide can be one or more layers, and diameter is 50 nanometer ~ 500 micron.
In above-mentioned preparation method of the present invention, add in graphene oxide/carbon nanotube/rubber grain suspension at 0.1 ~ 50 weight part reductive agent has precedence over 50 DEG C ~ 100 DEG C and carry out reduction reaction.
In above-mentioned preparation method of the present invention, the preferential employing after washing of separating obtained solid phase is inserted in vacuum drying oven and is carried out drying in 20 DEG C ~ 180 DEG C, is better than 50 DEG C ~ 90 DEG C most and carries out drying.
In above-mentioned preparation method of the present invention, the graphene oxide of determined amounts and the carbon nanotube filler of formula ratio are added in the water of 100 mass parts, for mechanical stirring mixing, is generally uniformly mixed 1 ~ 72 hour, for ultrasonic disperse mixing, General Decentralized mixes 30 minutes ~ 5 hours; It is in the elastomeric material matrix emulsion of 5 ~ 70% formula ratios that graphene oxide/carbon nano-tube hybridization suspension joins solid content, mechanical stirring is mixed, generally be uniformly mixed 5 minutes ~ 10 hours, for ultrasonic disperse mixing, General Decentralized mixes 1 minute ~ 2 hours.
Graphene/carbon nano-tube hydridization filler network Reinforced Rubber material provided by the invention is particulate state, in order to check its mechanical property, need be processed into type, to carry out Mechanics Performance Testing.The rubber vulcanization processes machine-shaping that shaping usual employing is traditional.By graphene/carbon nano-tube hydridization filler network Reinforced Rubber material 100 mass parts, filler 0 ~ 100 mass parts, vulcanizing agent 0 ~ 20 mass parts, vulcanization aid 0 ~ 20 mass parts, oxidation inhibitor 0 ~ 10 mass parts, softening agent 0 ~ 50 mass parts, fire retardant 0 ~ 50 mass parts, anti-aging agent 0 ~ 10 mass parts, add in two rod mill or Banbury mixer, in temperature 10 ~ 70 DEG C mixing 2 ~ 50 minutes, mixing uniform material is put into mould, adopt vulcanizing press, in temperature 30 ~ 170 DEG C of sulfurations 3 ~ 100 minutes.Wherein, the known materials that vulcanizing agent, vulcanization aid, oxidation inhibitor, softening agent, fire retardant and anti-aging agent adopt this area usually to adopt, adding of these additives be its precondition do not produce detrimentally affect to realizing object of the present invention and obtaining excellent results of the present invention.
The section bar of the graphene/carbon nano-tube hydridization filler network Reinforced Rubber material adopting aforesaid method to obtain, mechanical property adopts the test of GB/T529-1999 prescriptive procedure, its tensile strength is 15 ~ 40MPa, and elongation at break is 300 ~ 900%, and fracture toughness property is 3 ~ 8GJ; Energy dissipation capability characterizes the sample size and rate of extension that adopt and specify in GB/T529-1999, the hysteresis loop of test sample, calculate area of hysteresis loop size, for the size of Characterization Energy dissipation capabilities, the rubber nano composite material that the energy dissipation capability of the bright Graphene/carbon nanotube/rubber nanocomposite of table with test results strengthens than single-component carbon nanotube or Graphene is high 2 ~ 6 times; Opposing crack growth ability adopts dynamic fatigue test machine test, and the crack growth rate of the bright Graphene/carbon nanotube/rubber nanocomposite of table with test results is 60 ~ 10% of the rubber nano composite material that single-component carbon nanotube or Graphene strengthen; Conductivity adopts resistance instrument to test, and the specific conductivity of graphene/carbon nano-tube/rubber nano composite material is 0.001 ~ 1000S/m.The rubber nano composite material that the bright Graphene of above table with test results/carbon nano-tube hybridization filler network strengthens has good mechanical property, fatigue performance, opposing crack growth performance, waste of energy performance and conductivity.
Graphene can not be scattered in water equably, and carbon nanotube can not be scattered in water equably, and graphene oxide can be scattered in equably in water and form homogeneous suspension.Contriver finds in the research of graphene/carbon nano-tube hydridization filler network Reinforced Rubber material, is joined by carbon nanotube in graphene oxide aqeous suspension, can disperse equably.This is because the aromatic hydrocarbons structure of graphene oxide can produce π-π molecular interaction with carbon nanotube, carbon nanotube joins in graphene oxide water solution, graphene oxide is actual becomes a kind of tensio-active agent, makes not to be dispersed in water with itself not can be uniformly dispersed in the even carbon nanotube in water.Contriver completes the present invention based on above-mentioned just, graphene oxide and carbon nanotube is taked to be added to the water, by stirring or supersound process acquisition graphene oxide/carbon nano-tube hybridization suspension, and then by graphene oxide/carbon nano-tube hybridization suspension and latex blended, mix rear breakdown of emulsion, form graphene oxide/carbon nanotube/rubber grain suspension, by reductive agent, graphene oxide is reduced into Graphene afterwards, obtained graphene/carbon nano-tube/rubber nano composite rubber material after solid-liquid separation, washing, drying.
Graphene/carbon nano-tube hydridization filler network Reinforced Rubber material provided by the invention, adopting with graphene oxide is that surfactant-dispersed carbon nanotube prepares graphene oxide/carbon nano-tube hybridization aqeous suspension, Graphene is realized and carbon nanotube hydridization in rubber matrix is dispersed by the emulsion dispersion improved, Graphene and carbon nanotube are interacted by π-π-electron and forms hydridization filler network, this hydridization filler network preferentially ruptures under stress, dissipation energy, elastomeric material is made to have good mechanical property, fatigue performance, opposing crack growth performance and conductivity.Completely avoid prior art adopts the methods such as organic solvent blending method, surface-modification method, dispersing auxiliary method to produce Graphene, carbon nanotube filler Reinforced Rubber material, a large amount of organic solvent is used not only to increase production cost, easily cause environmental pollution, also destroy the performance of the finished product simultaneously, limit the range of application that product is potential.Graphene/carbon nano-tube hydridization filler network Reinforced Rubber material provided by the invention, has good mechanical property, fatigue performance, opposing crack growth performance and conductivity.And production cost is low, preparation technology is simple, and non-environmental-pollution, is easy to realize large-scale industrial production.
Accompanying drawing explanation
Accompanying drawing 1 is the stress-strain correlation curve of the elastomeric material of embodiment 1 and comparative example 1, the breaking tenacity of reaction elastomeric material and elongation at break, as seen from the figure, the breaking tenacity of elastomeric material of the present invention and elongation at break are obviously better than breaking tenacity and the elongation at break of Graphene/rubber composite.
Accompanying drawing 2 is fracture toughness property histograms of the elastomeric material of embodiment 1 and comparative example 1, and as seen from the figure, the fracture toughness property of elastomeric material of the present invention is obviously better than the fracture toughness property of Graphene/rubber composite.
Accompanying drawing 3 is graphene oxide, carbon nanotube and graphene oxide/carbon nanotube deployment conditions in water, wherein numbering 1 is the deployment conditions of graphene oxide in water, numbering 2 is carbon nanotube deployment conditions in water, numbering 3 is the deployment conditions of graphene oxide/carbon nanotube in water, as can be seen from Figure, graphene oxide can make even carbon nanotube disperse as tensio-active agent, forms uniform graphene oxide/carbon nano-tube hybridization suspension.
Embodiment
Below by embodiment, the present invention is specifically described.What be necessary to herein means out is; following examples are only used to further illustrate the present invention; can not be interpreted as limiting the scope of the invention, the person skilled in the art in this field can make some nonessential improvement and adjustment according to the content of the invention described above.
Embodiment 1
0.5g graphene oxide, 1g multi-walled carbon nano-tubes are added in 100g water, ultrasonic disperse 1 hour, obtain graphene oxide/carbon nano-tube hybridization suspension, hydridization suspension being added 200g solid content is again in the natural rubber latex of 50%, and mechanical stirring 30 minutes adds the sodium chloride solution that 50g mass concentration is 20%, obtain graphene oxide/carbon nanotube/natural rubber particle suspension liquid, add 2g sodium borohydride reduction graphene oxide, the recovery time is 24 hours, and reduction temperature is 50 DEG C.Reduzate after filtering, washes 10 times with water, dries to constant weight, obtains graphene/carbon nano-tube/natural rubber nano composite material.This matrix material adopts traditional rubber vulcanization processes shaping, and the tensile strength of obtained sheet material is 35MPa, and elongation at break is 600%, and fracture toughness property is 7GJ, is 1600J/m at tearing energy
2condition under crack growth rate be 20nm/Cycle.
Comparative example 1
1.5g graphene oxide is added in 100g water, ultrasonic disperse 1 hour, obtain graphene oxide suspension, this suspension being added 200g solid content is again in the natural rubber latex of 50%, and mechanical stirring 30 minutes adds the sodium chloride solution that 50g mass concentration is 20%, obtain graphene oxide/natural rubber particle suspension liquid, add 2g sodium borohydride reduction graphene oxide, the recovery time is 24 hours, and reduction temperature is 50 DEG C.Reduzate after filtering, washes 10 times with water, dries to constant weight, obtains Graphene/natural rubber nano composite material.This matrix material adopts traditional rubber vulcanization processes shaping, and the tensile strength of obtained sheet material is 20MPa, and elongation at break is 520%, and fracture toughness property is 3.5GJ, is 1600J/m at tearing energy
2condition under crack growth rate be 42nm/Cycle.
Embodiment 2
1g graphene oxide, 5g multi-walled carbon nano-tubes are added in 100g water, ultrasonic disperse 2 hours, obtain graphene oxide/carbon nano-tube hybridization suspension, hydridization suspension being added 1000g solid content is again in the styrene-butadiene latex of 10%, mechanical stirring 5 hours, add the calcium chloride solution that 100g mass concentration is 10%, obtain graphene oxide/carbon nanotube/styrene-butadiene rubber(SBR) particle suspension liquid, add 5g hydrazine hydrate reduction graphene oxide, recovery time is 5 hours, and reduction temperature is 100 DEG C.Reduzate after filtering, washes 20 times with water, dries to constant weight, obtains graphene/carbon nano-tube/butadiene styrene rubber nanometer composite material.This matrix material adopts traditional rubber vulcanization processes shaping, and the energy dissipation capability under obtained sheet material stretching to 400% strains is 12MJ/m
3, fracture toughness property is 6GJ.
Comparative example 2
6g carbon nanotube is added in 100g water, ultrasonic disperse 2 hours, obtain carbon nano tube suspension, this suspension being added 1000g solid content is again in the styrene-butadiene latex of 10%, mechanical stirring 5 hours, add the calcium chloride solution that 100g mass concentration is 10%, obtain carbon nanotube/styrene-butadiene rubber(SBR) particle suspension liquid, add 5g hydrazine hydrate reduction, recovery time is 5 hours, and reduction temperature is 100 DEG C.Reduzate after filtering, washes 20 times with water, dries to constant weight, obtains carbon nanotube/butadiene styrene rubber nanometer composite material.This matrix material adopts traditional rubber vulcanization processes shaping, and the energy dissipation capability under obtained sheet material stretching to 400% strains is 5MJ/m
3, fracture toughness property is 3GJ.
Embodiment 3
2.5g graphene oxide, 5g multi-walled carbon nano-tubes are added in 100g water, ultrasonic disperse 2 hours, obtain graphene oxide/carbon nano-tube hybridization suspension, hydridization suspension being added 100g solid content is in the polyethyl acrylate emulsion of 50% again, mechanical stirring 10 minutes, add the liquor alumini chloridi that 10g mass concentration is 20%, obtain graphene oxide/carbon nanotube/polypropylene acetoacetic ester particle suspension liquid, add 20g vitamins C redox graphene, recovery time is 24 hours, and reduction temperature is 50 DEG C.Reduzate after filtering, washes 5 times with water, dries to constant weight, obtains graphene/carbon nano-tube/polyethyl acrylate nano composite material.This matrix material adopts traditional rubber vulcanization processes shaping, and the specific conductivity of obtained sheet material is 10S/m.
Comparative example 3
7.5g graphene oxide is added in 100g water, ultrasonic disperse 2 hours, obtain graphene oxide suspension, this suspension being added 100g solid content is in the polyethyl acrylate emulsion of 50% again, and mechanical stirring 10 minutes, adds the liquor alumini chloridi that 10g mass concentration is 20%, obtain graphene oxide/polyethyl acrylate particle suspension liquid, add 20g vitamins C redox graphene, the recovery time is 24 hours, and reduction temperature is 50 DEG C.Reduzate after filtering, washes 5 times with water, dries to constant weight, obtains Graphene/polyethyl acrylate nano composite material.This matrix material adopts traditional rubber vulcanization processes shaping, and the specific conductivity of obtained sheet material is 0.1S/m.
As can be seen from the data of embodiment 1 and comparative example 1 and embodiment 2 and comparative example 2, under the condition that packing quality mark is identical with preparation process condition, adopt the tensile strength of one-component Graphene or one-component carbon nanotube Reinforced Rubber material, elongation at break, fracture toughness property, cracking growth resistance ability and energy dissipation capability all poor, the graphene/carbon nano-tube hybridization network filler Reinforced Rubber material prepared with the present invention does not have a comparability.From embodiment 3 and comparative example 3 relatively, the conductivity of graphene/carbon nano-tube hybridization network filler Reinforced Rubber prepared by the present invention is significantly better than the elastomeric material that adopts Graphene one-component to strengthen.
Claims (10)
1. a graphene/carbon nano-tube hydridization filler network Reinforced Rubber material, it is characterized in that, with Graphene and carbon nanotube for filler, be dispersed in elastomeric material matrix and form hydridization filler network, with the mechanical property of Reinforced Rubber material, elastomeric material component is formed: elastomeric material matrix 100 mass parts, as Graphene and carbon nanotube totally 0.1 ~ 20 mass parts of filler, and the mass ratio of Graphene and carbon nanotube is (1:10) ~ (10:1).
2. graphene/carbon nano-tube hydridization filler network Reinforced Rubber material as claimed in claim 1, it is characterized in that, described Graphene and carbon nanotube be totally 0.5 ~ 20 mass parts.
3. graphene/carbon nano-tube hydridization filler network Reinforced Rubber material as claimed in claim 1, it is characterized in that, described elastomeric material matrix is selected from natural gum, butadiene-styrene rubber, ABS glue, butadiene-acrylonitrile rubber, neoprene latex, urethane, Voncoat R 3310 or multipolymer and methacrylate homopolymer or multipolymer.
4. the preparation method of one of claims 1 to 3 described graphene/carbon nano-tube hydridization filler network Reinforced Rubber material, is characterized in that comprising following processing step:
(1) preparation of graphene oxide/carbon nano-tube hybridization suspension: will add in the water of 100 mass parts according to the graphene oxide of Graphene determined amounts of formula ratio and the carbon nanotube of formula ratio, the fully obtained graphene oxide/carbon nano-tube hybridization suspension of mixing;
(2) preparation of graphene oxide/carbon nanotube/rubber grain suspension: it is in the elastomeric material base emulsions of 5 ~ 70% formula ratios that graphene oxide/carbon nano-tube hybridization suspension step (1) prepared joins solid content, add after abundant mixing mass concentration be 5 ~ 80% emulsion splitter 0.1 ~ 100 mass parts carry out breakdown of emulsion, obtained graphene oxide/carbon nanotube/rubber grain suspension;
(3) preparation of hydridization filler network Reinforced Rubber material: add 0.1 ~ 50 weight part reductive agent in graphene oxide/carbon nanotube/rubber grain suspension that step (2) is obtained, reduction reaction is carried out at 20 ~ 100 DEG C, solid-liquid separation is carried out after abundant reduction reaction, drying after gained solid phase washing removing emulsion splitter, reductive agent and unreacted component, namely obtains the elastomeric material that graphene/carbon nano-tube hydridization filler network strengthens.
5. the preparation method of graphene/carbon nano-tube hydridization filler network Reinforced Rubber material according to claim 4, it is characterized in that, described emulsion splitter is selected from sodium chloride solution, Klorvess Liquid, calcium chloride solution, magnesium chloride solution, liquor alumini chloridi, polymeric aluminum chlorides solution, ferric chloride Solution, solution of ferrous chloride, Cupric Chloride Solution, calcium sulphate soln, metabisulfite solution, copper-bath, ferrum sulfuricum oxydatum solutum, copperas solution, formic acid, acetic acid, hydrochloric acid and sulfuric acid.
6. the preparation method of graphene/carbon nano-tube hydridization filler network Reinforced Rubber material according to claim 4, it is characterized in that, described reductive agent is selected from hydrazine, hydrazine hydrate, dimethylhydrazine, sodium borohydride, Resorcinol, n-Butyl Amine 99, quadrol, vitamins C, natrium hydrocitricum, iron powder, lithium aluminum hydride, nitrous acid hydrogen sodium, hydrogen sulfide and kalium carbide.
7. graphene/carbon nano-tube hydridization filler network Reinforced Rubber material as claimed in claim 4, it is characterized in that, described carbon nanotube to be length-to-diameter ratio be 10 ~ 1000 multi-walled carbon nano-tubes or Single Walled Carbon Nanotube, graphene oxide is one or more layers, and diameter is 50 nanometer ~ 500 micron.
8. the preparation method of graphene/carbon nano-tube hydridization filler network Reinforced Rubber material according to claim 4, it is characterized in that, add 0.1 ~ 50 weight part reductive agent in graphene oxide/carbon nanotube/rubber grain suspension and carry out reduction reaction at 50 DEG C ~ 90 DEG C.
9. the preparation method of graphene/carbon nano-tube hydridization filler network Reinforced Rubber material according to claim 4, is characterized in that, separating obtained solid phase is inserted in vacuum drying oven and carried out drying in 20 DEG C ~ 180 DEG C after washing.
10. according to the preparation method of the graphene/carbon nano-tube hydridization filler network Reinforced Rubber material one of claim 5 to 9 Suo Shu, it is characterized in that, the graphene oxide of determined amounts and the carbon nanotube of formula ratio are added mechanical stirring mixing 1 ~ 72 hour or ultrasonic disperse in the water of 100 mass parts and mix 30 minutes ~ 5 hours; It is that in the elastomeric material base emulsions of 5 ~ 70% formula ratios, mechanical stirring mixes 5 minutes ~ 10 hours or ultrasonic disperse mixes 1 minute ~ 2 hours that graphene oxide/carbon nano-tube hybridization suspension joins solid content.
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