CN103275368B - Method for preparing graphene oxide/white carbon black/rubber nanocomposite by mechanical blending - Google Patents
Method for preparing graphene oxide/white carbon black/rubber nanocomposite by mechanical blending Download PDFInfo
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Abstract
A method for preparing a graphene oxide/white carbon black/rubber nanocomposite by mechanical blending belongs to the composite material field. In the graphene oxide/white carbon black/rubber composite prepared by the method provided by the invention, because graphene and white carbon black are inserted with each other, the self-aggregation of the two fillers is effectively suppressed, and thus a composite having high dispersion, high stripping and nanoscale dispersion is obtained. Not only while the composite has higher modulus and lower rolling resistance, but also the wear resistance of a rubber material is substantially improved, and the modulus and tear resistance of the composite are further improved; at the same time, because of the lamellar structure and good self-recovery capability of the graphene oxide, the rubber material is also imparted with good gas barrier performance and self-healing capability, and the nanocomposite has the incomparable advantages to any traditional fillers. The method provided by the invention is simple and easy to implement, low in cost and easy to industrialize, has wide suitability and better economic benefits and social benefits.
Description
Technical field
The present invention relates to that height is peeled off, the preparation method of the graphene oxide/white carbon black/rubber nano composite material of high dispersive, strong interfacial bond, be particularly related to that emulsion is compound to combine with flocculation process, or emulsion is compound combines with drying process with atomizing, and the method for mechanical blending, prepare graphene oxide/white carbon black/rubber nano composite material.
Background technology
In rubber industry, consumption is maximum, the most general filler is nano level carbon black and white carbon black.Carbon black is the most important reinforced filling of rubber industry, and still, along with the minimizing day by day of petroleum resources, production and the application of the carbon black of the oil that places one's entire reliance upon run into challenge.For the equivalent material research beginning of the non-oil resource of rubber reinforcement, alternative carbon black, progressively become one of important topic that rubber industry faces.Comparatively successfully example is white carbon black, and the chemical name of white carbon black is hydration soft silica or colloid silica (SiO
2nH2O), it is a kind of white, nontoxic, amorphous fine meal, and initial size is generally 10-40nm, have that porousness, internal surface area are large, polymolecularity, light weight, good stability, high temperature resistant, do not burn, the excellent properties such as electrical insulating property is good.White carbon black is the three dimensional structure through the random connection of covalent linkage-O-Si-O-, and structural unit can be gathered into once, secondary three agglomerates even.The main weighting agent as products such as rubber, plastics, synthetic resins and paint, also can be used as lubricant and insulating material.The white carbon black in the whole world 70%, for rubber industry, is good rubber reinforcing filler at present, can improve cementing property and tear strength.White carbon black approaches carbon black to the reinforcing property of rubber, especially passes through the white carbon black of surface modification, not only can provide higher modulus, can also reduce rolling resistance.But a little less than the interaction between white carbon black and rubber, after being filled in rubber, wear resisting property obviously declines.Although therefore, in car tyre, fill the green tire widespread use of butadiene-styrene rubber with white carbon black, in load-carrying tire and engineering tire, the consumption of white carbon black is little all the time, be only that a small amount of filling improved tear resistance.So present research direction is by also improve the wear resisting property of white carbon black filled rubber material with other fillers, further expands the use range of white carbon black.Common way is the wear resisting property with raising elastomeric material on the basis of filling at white carbon black and with a certain amount of carbon black, but do like this and often need higher carbon black loading, and can be reduced to cost with rolling resistance increase, the tear resistance of elastomeric material, can not meet the requirement of environmental protection again simultaneously.
Graphene be a kind of by carbon atom with sp
2the hexagonal lattice flat film that hybridized orbital forms, only has the two-dimensional material of one or more carbon atom thickness.The Novoselov of 2004 Nian You Univ Manchester UKs and Geim successfully make first by the method for the high oriented graphite of tape stripping really can self-existent two-dimentional Graphene crystal.Graphene planar has or not the multiple periodic structure of freight weight limit, in the direction perpendicular to plane, only has nanoscale, can be regarded as the nano material with macro-size.Graphene has high theoretical specific surface area (about 2630m
2/ g), large aspect ratio (> 1000) and well mechanical strength (Young's modulus is 1060GPa), these are indicating that Graphene efficiently strengthens direction to macromolecular material and has potential advantages.
We find by experiment, the graphene oxide of peeling off with height partly substitutes white carbon black and carrys out filled rubber, in the rubber nano composite material preparing like this, due to Graphene and the white carbon black interspersed gathering that has effectively suppressed two kinds of fillers self mutually, make their dispersion more even, show and do not losing the original excellent properties of white carbon black (higher modulus, lower rolling resistance) time, significantly promoted the wear resisting property of elastomeric material, and further improve modulus and the tear resistance of matrix material, simultaneously because laminated structure and the good automatic recovery ability of graphene oxide have also given elastomeric material good gas barrier property and self-healing capability, there is the incomparable advantage of conventional filler.Therefore, with Graphene and white carbon black and the rubber nano composite material that is used for strengthening or prepared by modification there is more excellent over-all properties, can be widely used in mechanicals and the various field of sealing technology such as tire, offset plate, adhesive tape, rubber roll, conveying belt, and aerospace field.Meanwhile, graphene oxide has good automatic recovery ability and resistance to crack extension ability, can be widely used in self-repair material and high anti-tear Material Field thereof.
Summary of the invention:
The object of this invention is to provide that height is peeled off, high dispersive, strong interfacial bond, the preparation method simultaneously with the graphene oxide/white carbon black/rubber nano composite material of high dispersive, Graphene used is graphene oxide, through reduction process, (graphene oxide does not inevitably reassociate after being reduced into Graphene, is unfavorable for the dispersion of Graphene; And the Graphene surface functional group content after reduction significantly reduces, very poor with the consistency of rubber matrix).It comprises two kinds of methods: (1) solution blended process: graphene oxide, white carbon black and rubber are carried out in water or solution phase to compound method; (2) mechanical blending method: graphene oxide or prefabricated graphene oxide rubber master batch, white carbon black or prefabricated white carbon black rubber master batch, rubber are carried out to compound method on machining equipment.
The present invention in direct preparation containing the rubber nano composite material of graphene oxide/white carbon black or prepare respectively graphene oxide rubber master batch and during white carbon black rubber master batch, 201110454000.5), and " a kind of preparation method who prepares high-dispersion white carbon black/rubber nano composite material " (application number: 201210001294.0) and " a kind of method of preparing acceptor modified white carbon black " (application number: 201110147594.5) main applicant's patent of invention " preparation method of graphene oxide/rubber nano composite material of peeling off completely " in early stage (application number: of using for reference.When directly preparation contains the rubber nano composite material of graphene oxide/white carbon black, utilize graphite oxide as the intermediate product of reduction-oxidation preparing graphite alkene, be scattered in water or organic solvent, by ultrasonication, can be stripped from into graphene oxide completely.A large amount of oxygen-containing functional groups is contained on graphene oxide surface, and the Van der Waals force that itself and water and conventional organic solvent are had between better consistency and sheet and sheet weakens, and has reduced congregation; The character that the white carbon black simultaneously with grain pattern has suspension in water prepares graphene oxide/white carbon black water-sol; And utilize multiple rubber clone to have the characteristic of emulsion form, graphene oxide/white carbon black water-sol and rubber latex blend are obtained to graphene oxide/white carbon black/rubber latex mixed solution; Utilize drying process with atomizing that mixed solution atomization is formed to small mixed solution drop; In drying medium, remove rapidly moisture content, obtain the nano composite material of graphene oxide/white carbon black/rubber.Because the fine drop that atomization forms under drying process with atomizing enlarges markedly the specific surface area of mixed solution, the moisture mixing in drying medium in drop is able to fast eliminating, phase structure under therefore original liquid mixing state is kept in the nano composite material obtaining, and has obtained the graphene oxide/white carbon black/rubber nano composite material of high dispersive; Or directly utilize the method for ion co-coagulation in mixed solution, to add flocculation agent, by stirring, directly prepare graphene oxide/white carbon black/rubber nano composite material.
When preparing graphene oxide rubber master batch, mainly take emulsion method, according to applicant's patent of invention " preparation method of graphene oxide/rubber nano composite material of peeling off completely " (application number: 201110454000.5) carry out in early stage.When preparing white carbon black rubber master batch, mainly take emulsion method, according to applicant's patent of invention " a kind of preparation method who prepares high-dispersion white carbon black/rubber nano composite material " (application number: 201210001294.0) carry out in early stage.
Two kinds of preparation methods' that the graphene oxide/white carbon black/rubber nano composite material the present invention relates to adopts concrete implementation step is as follows:
(1) solution blending preparation method
Graphite oxide is dispensed in deionized water, under power 0.1～1000kW, after ultrasonic dispersion 10min～6h, makes the graphene oxide water-sol, wherein the solid content of graphene oxide is that 0.01～20wt%(wt% represents massfraction); In the above-mentioned graphene oxide water-sol, add white carbon black and coupling agent, or through coupling agent modified white carbon black, ultrasonic dispersion 10min～6h under power 0.1～1000kW, or low whipping speed is to stir 30min～12h under 50～10000 r/min, obtain graphene oxide/white carbon black water-sol; In above-mentioned graphene oxide/white carbon black aqueous solution, add interfacial agents, ultrasonic dispersion 10min～6h under power 0.1～1000kW, or low whipping speed is under 50～10000 r/min, to stir 30min～12h to carry out pre-treatment, obtains pretreated graphene oxide/silica pretreatment water-sol.
Directly by graphene oxide/white carbon black water-sol or by pretreated graphene oxide/silica pretreatment water-sol and rubber latex ultrasonic dispersion 10min～6h under power 0.1～1000kW, or low whipping speed is to stir 30min～12h under 50～10000 r/min, obtains stable composite emulsion.In ultrasonic scatter operation in above-mentioned preparation process, need monitoring system temperature, if system temperature is over 80 ℃, so first ultrasound procedure is suspended, mixture system is moved under the stirring of 50～500 r/min, stir 5 ~ 30min, be after system temperature reduces, then proceed ultrasound procedure.Above preparation process needs hierarchy of control temperature to be less than 100 ℃, to prevent coupling agent or interfacial agents generation self-polymeric reaction;
Then adopt one of following two schemes
A) ion flocculation process: add flocculation agent to flocculate in composite emulsion, under the speed of 50～10000 r/min, stir, through stirring, make rubber latex breakdown of emulsion, there is flocculation reaction, then obtain the flocculent gel of graphene oxide/white carbon black/rubber, then flocculent gel is dried at 60 ~ 300 ℃, after the moisture content in flocculent gel is dried, prepare graphene oxide/white carbon black/rubber nano composite material;
B) drying process with atomizing: through spray drying unit, atomization forms small complex liquid drop, removes moisture in drying medium, obtains graphene oxide/white carbon black/rubber nano composite material by above-mentioned composite emulsion, or by introduce the flocculation agent after gasification in the drying medium carrier gas of spray drying unit, make ion flocculation, the process of fast dewatering is carried out at one time, the mixing drop of graphene oxide/white carbon black/rubber latex is rapider to solid-state transition process by liquid state, more efficient, thereby graphene oxide and white carbon black generation gathering or stacking trend on thermodynamics have effectively been suppressed, make under the dispersion phase structure of the graphene oxide/white carbon black/rubber under liquid kept in dried solid particulate, prepare graphene oxide/white carbon black/rubber nano composite material.The inlet temperature of spray drying unit is set to 100 ~ 350 ℃, and temperature out is 70 ~ 120 ℃; The drying medium using is warm air, while need introducing the flocculation agent after gasification, by the throughput ratio of carrier gas, to the flocculation agent gas of introducing in carrier gas after 1% gasification.
(2) mechanical blending method
Mechanical blending method comprises four kinds of situations altogether:
1, the graphene oxide rubber master batch of preparing by emulsion method is placed in to two roller mills or the Banbury mixer 1 ~ 5min that plasticates, then add white carbon black and coupling agent, or the white carbon black of process coupling agent surface modification, blend 1-20min, prepares graphene oxide/white carbon black/rubber nano composite material.
2, the white carbon black rubber master batch of preparing by emulsion method is placed in to two roller mills or the Banbury mixer 1 ~ 5min that plasticates, then adds graphene oxide and interfacial agents, blend 1-20min, prepares graphene oxide/white carbon black/rubber nano composite material.
3, rubber (dry glue) is placed in to two roller mills or the Banbury mixer 1 ~ 5min that plasticates, then add white carbon black and graphene oxide and interfacial agents through coupling agent surface modification, or white carbon black, coupling agent and graphene oxide and interfacial agents, blend 1-20min, prepares graphene oxide/white carbon black/rubber nano composite material.
4, the graphene oxide rubber master batch of preparing by emulsion method and the female rubber of the white carbon black prepared by emulsion method are placed in to two roller mills or Banbury mixer blend 1-20min, prepare graphene oxide/white carbon black/rubber nano composite material.
The inlet temperature of spray drying unit is 100 ~ 350 ℃, and temperature out is 70 ~ 120 ℃; The drying medium using is warm air.
Graphene oxide/white carbon black/rubber nano composite material that the present invention is prepared, wherein white carbon black comprises precipitated silica and thermal silica.The massfraction of the shared matrix material of quality of white carbon black and graphene oxide, the mark of white carbon black and the shared rubber matrix of graphene oxide is 0.1 ~ 400phr(phr is the white carbon black adding in each hundred parts of rubber and the quality of graphene oxide).Wherein graphene oxide is used to equivalent and partly substitutes white carbon black, and the consumption of graphene oxide is 0.05 ~ 20phr(phr is the quality of the graphene oxide adding in each hundred parts of rubber).
Rubber latex is that solid content is the mixing latex of one or both latex in the styrene-butadiene latex, natural rubber latex, polychloroprene latex, isobutylene-isoprene latex, nitrile rubber, butadiene latex, ethylene propylene rubber latex, polyisoprene latex, fluoroelastomer latex, silicone rubber latex of 10～80wt%, or two or more mixing latex; In mechanical blending preparation method the 1st, 2 and 4 kind of performance in use in rubber in rubber master batch and mechanical blending preparation method the epoxy glue that rubber used in the 3rd kind of performance comprises one or both rubber in styrene-butadiene rubber(SBR), natural rubber, chloroprene rubber, isoprene-isobutylene rubber, paracril, divinyl rubber, ethylene-propylene rubber(EPR), polyisoprene rubber, viton and silicon rubber, or two or more epoxy glue; Wt% represents mass percent.
The present invention's interfacial agents used is carboxy terminatedpolybutadiene, aminopropyl triethoxysilane coupling agent, γ-(methacryloxypropyl) propyl trimethoxy silicane coupling agent, quaternary ammonium salt, or the solid content carboxylic styrene butadiene latex that is 10～80wt%, vinyl-pyridine latex, Carboxy pyrrole latex, epoxy natural latex, carboxylic chloroprene rubber latex, carboxylic acrylonitrile butadiene rubber latex or; The consumption of interfacial agents is 0phr ~ 100phr (the interfacial agents quality of phr for adding in each hundred parts of rubber).
In the present invention, flocculation agent used is a kind of in nitric acid, sulfuric acid, hydrochloric acid, Hydrogen bromide, hydrofluoric acid, calcium chloride, sodium-chlor, Repone K, sodium sulfate, Tai-Ace S 150, iron trichloride or polymerize aluminum chloride; Can introduce flocculation agent in carrier gas for can, at vaporized flocculation agent below 350 ℃, comprising nitric acid, Hydrogen bromide, hydrofluoric acid, hydrochloric acid and sulfuric acid.
In the present invention, coupling agent used comprises two-(the silica-based propyl group of γ-triethoxy)-tetrasulfide (Si69); Two-(the silica-based propyl group of γ-triethoxy)-disulphide (Si75); γ-aminopropyl triethoxysilane (KH-550); γ-(2,3-epoxy the third oxygen) propyl trimethoxy silicane (KH-560); γ-methacryloxypropyl trimethoxy silane (KH-570); γ-mercaptopropyl trimethoxysilane (KH-590); Stearic acid; Silazane.The consumption of coupling agent is 0.01% ~ 50% of white carbon black massfraction.
Graphene oxide rubber master batch used in the present invention, recommendation applicant patent of invention " preparation method of graphene oxide/rubber nano composite material of peeling off completely " (application number: the preparation method 201110454000.5) in early stage, in the graphene oxide/rubber nano composite material preparing through this method, graphene oxide can reach completely to be peeled off, and degree of scatter is high, to obtain dispersed on nanoscale; White carbon black rubber master batch used in the present invention, recommendation applicant patent of invention " a kind of preparation method who prepares high-dispersion white carbon black/rubber nano composite material " in early stage (application number: in white carbon black/rubber nano composite material that the preparation method 201210001294.0) prepares through this method, the organic degree of white carbon black is higher, disperse more even, and better with the combination of rubber matrix; Used in the present invention, through the white carbon black of coupling agent surface modification, recommendation applicant patent of invention " a kind of method of preparing acceptor modified white carbon black " (application number: the treatment process 201110147594.5) in early stage.Make to process in this way the white carbon black obtaining, its organic degree is higher, more easily prepares white carbon black finely dispersed matrix material in rubber matrix.
Advantage of the present invention is to utilize solution blended process or mechanical blending method all can prepare graphene oxide/white carbon black/rubber nano composite material, ion flocculation process in the inventive method or drying process with atomizing can retain the phase structure of graphene oxide/white carbon black/rubber combined emulsion under liquid state effectively, thereby obtained high dispersing, highly peel off and be graphene oxide/white carbon black/rubber nano composite material that nanoscale disperses; In prefabricated graphene oxide rubber master batch and prefabricated white carbon black rubber master batch, all retain graphene oxide/rubber combined emulsion and the phase structure of white carbon black/rubber combined emulsion under liquid state, thereby obtained high dispersing, highly peel off and be graphene oxide/white carbon black/rubber nano composite material that nanoscale disperses.When both and filler blend, or just can be easy to each other prepare high dispersing during blend, highly peel off and be graphene oxide/white carbon black/rubber nano composite material that nanoscale disperses.This is the technique means that the present invention is set up.
In addition, advantage of the present invention is also that preparation technology is simple, cost is low, non-environmental-pollution, is easy to realize large-scale industrial production.
Embodiment:
In following examples, all processes operating in solution all need hierarchy of control temperature to be less than 100 ℃.
In following examples, all gas to introducing in carrier gas all measures with the volume percent of gas.
Embodiment 1
Take 1g graphite oxide, join in the deionized water of 10kg, under the power of 0.1kw after ultrasonic dispersion 10min, make solid content and be 0.01% the graphene oxide water-sol.Take precipitated silica 1g and two-(the silica-based propyl group of γ-triethoxy)-tetrasulfide 0.01g, join in the above-mentioned water-sol, under the stirring velocity of 50r/min, after stirring 30min, obtain graphene oxide/white carbon black water-sol.The styrene-butadiene latex 20kg that is 10% by above-mentioned graphene oxide/white carbon black water-sol and solid content, under the stirring velocity of 50r/min, obtains stable graphene oxide/white carbon black/styrene-butadiene rubber(SBR) composite emulsion after dispersed with stirring 12h.Above-mentioned composite emulsion is joined in calcium chloride solution under stirring, that mass concentration is 1% and flocculated, stirring velocity is 50r/min, until no longer include in mixing solutions after new throw out generation, after the micelle trickle washing of graphene oxide/white carbon black/styrene-butadiene rubber(SBR) that flocculation is obtained, dry in 60 ℃ of baking ovens.Collect the sample being dried and obtain the graphene oxide/white carbon black/butadiene styrene rubber nanometer composite material containing 0.1phr filler.
By above-mentioned technique, prepare matrix material 100.1g, the matrix material obtaining, in two roller mills, is carried out to the mixing rubber unvulcanizate that obtains according to formula (5 parts, zinc oxide, 2 parts of stearic acid, 0.5 part of vulkacit D, 0.5 part of altax, 0.2 part of promotor TT, 1 part of antioxidant 4010NA, 1 part of anti-aging agent RD, 2 parts, sulphur).Rubber unvulcanizate is vulcanized to the white carbon black/rubber nano composite material that obtains vulcanizating under 150 ℃, sulfurizing time.This nano composite material is carried out to properties test by corresponding national standard.
Embodiment 2
Take 20g graphite oxide, join in the deionized water of 100g, ultrasonic dispersion 6h under the power of 1000kw, while monitoring system temperature, if system temperature is over 80 ℃, so first ultrasound procedure is suspended, mixture system is moved under the stirring of 500 r/min, stir 30min, after system temperature is reduced, proceed again ultrasound procedure, then make solid content and be 20% the graphene oxide water-sol.Take precipitated silica 380g and two-(the silica-based propyl group of γ-triethoxy)-disulphide 190g, join in the above-mentioned water-sol, ultrasonic dispersion 6h under the power of 1000kw, while monitoring system temperature, if system temperature is over 80 ℃, so first ultrasound procedure is suspended, mixture system is moved under the stirring of 500 r/min, stir 30min, after system temperature is reduced, proceed again ultrasound procedure, then obtain graphene oxide/white carbon black water-sol.Take interfacial agents solid content and be 80% carboxylic styrene butadiene latex 125g, join above-mentioned graphene oxide/white carbon black water-sol, ultrasonic dispersion 6h under the power of 1000kw, while monitoring system temperature, if system temperature is over 80 ℃, so first ultrasound procedure is suspended, mixture system is moved under the stirring of 500 r/min, stir 30min, after system temperature is reduced, proceed again ultrasound procedure, then obtain through the pretreated graphene oxide/white carbon black of the interfacial agents water-sol.After the above-mentioned styrene-butadiene latex 125g that is 80% through the pretreated graphene oxide/white carbon black of the interfacial agents water-sol with solid content is mixed, ultrasonic dispersion 6h under the power of 1000kw, while monitoring system temperature, if system temperature surpasses 80 ℃, so first ultrasound procedure is suspended, mixture system is moved under the stirring of 500 r/min, stir 30min, after system temperature is reduced, then proceed ultrasound procedure, then obtain stable graphene oxide/white carbon black/styrene-butadiene rubber(SBR) composite emulsion.Above-mentioned composite emulsion is joined in hydrochloric acid soln under stirring, that mass concentration is 1% and flocculated, stirring velocity is 10000r/min, until no longer include in mixing solutions after new throw out generation, after the micelle trickle washing of graphene oxide/white carbon black/styrene-butadiene rubber(SBR) that flocculation is obtained, dry in 300 ℃ of baking ovens.Collect the sample being dried and obtain the graphene oxide/white carbon black/butadiene styrene rubber nanometer composite material containing 400phr filler.
By above-mentioned technique, prepare matrix material 590g, the matrix material obtaining, in two roller mills, is carried out to the mixing rubber unvulcanizate that obtains according to formula (5 parts, zinc oxide, 2 parts of stearic acid, 0.5 part of vulkacit D, 0.5 part of altax, 0.2 part of promotor TT, 1 part of antioxidant 4010NA, 1 part of anti-aging agent RD, 2 parts, sulphur).Rubber unvulcanizate is vulcanized to the white carbon black/rubber nano composite material that obtains vulcanizating under 150 ℃, sulfurizing time.This nano composite material is carried out to properties test by corresponding national standard.
Embodiment 3
Take 5g graphite oxide, join in the deionized water of 500g, ultrasonic dispersion 2h under the power of 300kw, while monitoring system temperature, if system temperature is over 80 ℃, so first ultrasound procedure is suspended, mixture system is moved under the stirring of 300 r/min, stir 15min, after system temperature is reduced, proceed again ultrasound procedure, then make solid content and be 1% the graphene oxide water-sol.Take precipitated silica 70g and two-(the silica-based propyl group of γ-triethoxy)-tetrasulfide 5.6g, join in the above-mentioned water-sol, ultrasonic dispersion 2h under the power of 300kw, while monitoring system temperature, if system temperature is over 80 ℃, so first ultrasound procedure is suspended, mixture system is moved under the stirring of 500 r/min, stir 30min, after system temperature is reduced, proceed again ultrasound procedure, then obtain graphene oxide/white carbon black water-sol.Take interfacial agents solid content and be 10% Carboxy pyrrole latex 200g, join above-mentioned graphene oxide/white carbon black water-sol, ultrasonic dispersion 3h under the power of 300kw, while monitoring system temperature, if system temperature is over 80 ℃, so first ultrasound procedure is suspended, mixture system is moved under the stirring of 500 r/min, stir 30min, after system temperature is reduced, proceed again ultrasound procedure, then obtain through the pretreated graphene oxide/white carbon black of the interfacial agents water-sol.After the above-mentioned styrene-butadiene latex 125g that is 80% through the pretreated graphene oxide/white carbon black of the interfacial agents water-sol with solid content is mixed, ultrasonic dispersion 4h under the power of 500kw, while monitoring system temperature, if system temperature surpasses 80 ℃, so first ultrasound procedure is suspended, mixture system is moved under the stirring of 500 r/min, stir 30min, after system temperature is reduced, then proceed ultrasound procedure, then obtain stable graphene oxide/white carbon black/styrene-butadiene rubber(SBR) composite emulsion.Above-mentioned composite emulsion is carried out through spray drying unit, and drying medium is 150 ℃ of warm airs, and temperature in is 150 ℃, and now temperature out is 80 ℃, by the throughput ratio of carrier gas, in carrier gas, introduces 1% HCl gas simultaneously.The sample that collection completes obtains the graphene oxide/white carbon black/butadiene styrene rubber nanometer composite material containing 75phr filler.
By above-mentioned technique, prepare matrix material 200.6g, the matrix material obtaining, in two roller mills, is carried out to the mixing rubber unvulcanizate that obtains according to formula (5 parts, zinc oxide, 2 parts of stearic acid, 0.5 part of vulkacit D, 0.5 part of altax, 0.2 part of promotor TT, 1 part of antioxidant 4010NA, 1 part of anti-aging agent RD, 2 parts, sulphur).Rubber unvulcanizate is vulcanized to the white carbon black/rubber nano composite material that obtains vulcanizating under 150 ℃, sulfurizing time.This nano composite material is carried out to properties test by corresponding national standard.
Embodiment 4
Take 5g graphite oxide, join in the deionized water of 500g, ultrasonic dispersion 2h under the power of 300kw, while monitoring system temperature, if system temperature is over 80 ℃, so first ultrasound procedure is suspended, mixture system is moved under the stirring of 300 r/min, stir 15min, after system temperature is reduced, proceed again ultrasound procedure, then make solid content and be 1% the graphene oxide water-sol.Take precipitated silica 50g and γ-mercaptopropyl trimethoxysilane 4g, join in the above-mentioned water-sol, ultrasonic dispersion 2h under the power of 100kw, while monitoring system temperature, if system temperature is over 80 ℃, so first ultrasound procedure is suspended, mixture system is moved under the stirring of 300 r/min, stir 30min, after system temperature is reduced, proceed again ultrasound procedure, then obtain graphene oxide/white carbon black water-sol.Take interfacial agents solid content and be 10% epoxy natural latex 100g, join above-mentioned graphene oxide/white carbon black water-sol, ultrasonic dispersion 3h under the power of 100kw, while monitoring system temperature, if system temperature is over 80 ℃, so first ultrasound procedure is suspended, mixture system is moved under the stirring of 300 r/min, stir 10min, after system temperature is reduced, proceed again ultrasound procedure, then obtain through the pretreated graphene oxide/white carbon black of the interfacial agents water-sol.After the above-mentioned natural rubber latex 200g that is 50% through the pretreated graphene oxide/white carbon black of the interfacial agents water-sol with solid content is mixed, under the stirring velocity of 10000r/min, after dispersed with stirring 30min, obtain stable graphene oxide/white carbon black/styrene-butadiene rubber(SBR) composite emulsion.Above-mentioned composite emulsion is carried out through spray drying unit, and drying medium is 100 ℃ of warm airs, and temperature in is 100 ℃, and now temperature out is 70 ℃, by the throughput ratio of carrier gas, in carrier gas, introduces 1% sulfuric acid gas simultaneously.The sample that collection completes obtains the graphene oxide/white carbon black/natural rubber nano composite material containing 55phr filler.
By above-mentioned technique, prepare matrix material 169g, the matrix material obtaining, in two roller mills, is carried out to the mixing rubber unvulcanizate that obtains according to formula (5 parts, zinc oxide, 2 parts of stearic acid, 3 parts of altaxs, 2 parts of antioxidant 4010NAs, 2 parts of anti-aging agent RDs, 2 parts, sulphur).Rubber unvulcanizate is vulcanized to the white carbon black/rubber nano composite material that obtains vulcanizating under 143 ℃, sulfurizing time.This nano composite material is carried out to properties test by corresponding national standard.
Embodiment 5
Take 10g graphite oxide, join in the deionized water of 1kg, ultrasonic dispersion 2h under the power of 500kw, while monitoring system temperature, if system temperature is over 80 ℃, so first ultrasound procedure is suspended, mixture system is moved under the stirring of 300 r/min, stir 30min, after system temperature is reduced, proceed again ultrasound procedure, then make solid content and be 1% the graphene oxide water-sol.Take the precipitated silica 54g through γ-aminopropyl triethoxysilane surface modification, wherein γ-aminopropyl triethoxysilane content is 4g, joins in the above-mentioned water-sol, under the stirring velocity of 3000r/min, after dispersed with stirring 6h, obtain graphene oxide/white carbon black water-sol.After the natural rubber latex 125g that is 80% with solid content by above-mentioned graphene oxide/white carbon black water-sol mixes, ultrasonic dispersion 3h under the power of 300kw, while monitoring system temperature, if system temperature surpasses 80 ℃, so first ultrasound procedure is suspended, mixture system is moved under the stirring of 100 r/min, stir 20min, after system temperature is reduced, then proceed ultrasound procedure, then obtain stable graphene oxide/white carbon black/styrene-butadiene rubber(SBR) composite emulsion.Above-mentioned composite emulsion is carried out through spray drying unit, and drying medium is 100 ℃ of warm airs, and temperature in is 100 ℃, and now temperature out is 70 ℃.The sample that collection completes obtains the graphene oxide/white carbon black/natural rubber nano composite material containing 60phr filler.
By above-mentioned technique, prepare matrix material 164g, the matrix material obtaining, in two roller mills, is carried out to the mixing rubber unvulcanizate that obtains according to formula (5 parts, zinc oxide, 2 parts of stearic acid, 3 parts of altaxs, 2 parts of antioxidant 4010NAs, 2 parts of anti-aging agent RDs, 2 parts, sulphur).Rubber unvulcanizate is vulcanized to the white carbon black/rubber nano composite material that obtains vulcanizating under 143 ℃, sulfurizing time.This nano composite material is carried out to properties test by corresponding national standard.
Embodiment 6
Take 5g graphite oxide, join in the deionized water of 500g, ultrasonic dispersion 2h under the power of 300kw, while monitoring system temperature, if system temperature is over 80 ℃, so first ultrasound procedure is suspended, mixture system is moved under the stirring of 300 r/min, stir 30min, after system temperature is reduced, proceed again ultrasound procedure, then make solid content and be 1% the graphene oxide water-sol.Take the precipitated silica 54g through two-(the silica-based propyl group of γ-triethoxy)-tetrasulfide surface modification, wherein the content of two-(the silica-based propyl group of γ-triethoxy)-tetrasulfide is 4g, join in the above-mentioned water-sol, under the stirring velocity of 3000r/min, after dispersed with stirring 6h, obtain graphene oxide/white carbon black water-sol.Take interfacial agents solid content and be 10% vinyl-pyridine latex 200g, join above-mentioned graphene oxide/white carbon black water-sol, ultrasonic dispersion 3h under the power of 100kw, while monitoring system temperature, if system temperature is over 80 ℃, so first ultrasound procedure is suspended, mixture system is moved under the stirring of 300 r/min, stir 10min, after system temperature is reduced, proceed again ultrasound procedure, then obtain through the pretreated graphene oxide/white carbon black of the interfacial agents water-sol.After each 62.5g of styrene-butadiene latex that is 80% by the above-mentioned natural rubber latex that is 80% through the pretreated graphene oxide/white carbon black of the interfacial agents water-sol with solid content and solid content mixes, ultrasonic dispersion 3h under the power of 300kw, while monitoring system temperature, if system temperature is over 80 ℃, so first ultrasound procedure is suspended, mixture system is moved under the stirring of 300 r/min, stir 30min, after system temperature is reduced, proceed again ultrasound procedure, then obtain stable graphene oxide/white carbon black/butylbenzene/natural rubber composite emulsion.Above-mentioned composite emulsion is carried out through spray drying unit, and drying medium is 100 ℃ of warm airs, and temperature in is 100 ℃, and now temperature out is 70 ℃.The sample that collection completes obtains the graphene oxide/white carbon black/natural rubber nano composite material containing 55phr filler.
By above-mentioned technique, prepare matrix material 179g, the matrix material obtaining, in two roller mills, is carried out to the mixing rubber unvulcanizate that obtains according to formula (5 parts, zinc oxide, 2 parts of stearic acid, 3 parts of altaxs, 2 parts of antioxidant 4010NAs, 2 parts of anti-aging agent RDs, 2 parts, sulphur).Rubber unvulcanizate is vulcanized to the white carbon black/rubber nano composite material that obtains vulcanizating under 143 ℃, sulfurizing time.This nano composite material is carried out to properties test by corresponding national standard.
Embodiment 7
Take 8g graphite oxide, join in the deionized water of 500g, ultrasonic dispersion 3h under the power of 500kw, while monitoring system temperature, if system temperature is over 80 ℃, so first ultrasound procedure is suspended, mixture system is moved under the stirring of 300 r/min, stir 30min, after system temperature is reduced, proceed again ultrasound procedure, then make solid content and be 1.6% the graphene oxide water-sol.Take through γ-(2,3-epoxy the third oxygen) the precipitated silica 54g of propyl trimethoxy silicane surface modification, γ-(2 wherein, 3-epoxy the third oxygen) content of propyl trimethoxy silicane is 4g, join in the above-mentioned water-sol, under the stirring velocity of 3000r/min, after dispersed with stirring 6h, obtain graphene oxide/white carbon black water-sol.Take interfacial agents carboxy terminatedpolybutadiene 20g, join above-mentioned graphene oxide/white carbon black water-sol, ultrasonic dispersion 3h under the power of 600kw, while monitoring system temperature, if system temperature is over 80 ℃, so first ultrasound procedure is suspended, mixture system is moved under the stirring of 500 r/min, stir 20min, after system temperature is reduced, proceed again ultrasound procedure, then obtain through the pretreated graphene oxide/white carbon black of the interfacial agents water-sol.After the above-mentioned butadiene latex 200g that is 50% through the pretreated graphene oxide/white carbon black of the interfacial agents water-sol with solid content is mixed, under the stirring velocity of 8000r/min, after dispersed with stirring 8h, obtain stable graphene oxide/white carbon black/divinyl rubber composite emulsion.Above-mentioned composite emulsion is carried out through spray drying unit, and drying medium is 150 ℃ of warm airs, and temperature in is 150 ℃, and now temperature out is 80 ℃, by the throughput ratio of carrier gas, in carrier gas, introduces 1% hydrochloric acid gas simultaneously.The sample that collection completes obtains the graphene oxide/white carbon black/natural rubber nano composite material containing 58phr filler.
By above-mentioned technique, prepare matrix material 182g, the matrix material obtaining, in two roller mills, is carried out to the mixing rubber unvulcanizate that obtains according to formula (5 parts, zinc oxide, 3 parts of stearic acid, 2 parts of accelerant CZs, 10 parts of dioctyl phthalate (DOP)s, 0.2 part of promotor TT, 1 part of antioxidant 4010NA, 1 part of antioxidant D, 4 parts, sulphur).Rubber unvulcanizate is vulcanized to the white carbon black/rubber nano composite material that obtains vulcanizating under 150 ℃, sulfurizing time.This nano composite material is carried out to properties test by corresponding national standard.
Embodiment 8
Take 5g graphite oxide, join in the deionized water of 500g, ultrasonic dispersion 2h under the power of 300kw, while monitoring system temperature, if system temperature is over 80 ℃, so first ultrasound procedure is suspended, mixture system is moved under the stirring of 300 r/min, stir 15min, after system temperature is reduced, proceed again ultrasound procedure, then make solid content and be 1% the graphene oxide water-sol.Take the precipitated silica 75.6g through γ-methacryloxypropyl trimethoxy silane surface modification, wherein the content of γ-methacryloxypropyl trimethoxy silane is 5.6g, join in the above-mentioned water-sol, ultrasonic dispersion 3h under the power of 300kw, while monitoring system temperature, if system temperature is over 80 ℃, so first ultrasound procedure is suspended, mixture system is moved under the stirring of 500 r/min, stir 30min, after system temperature is reduced, then proceed ultrasound procedure, then obtain graphene oxide/white carbon black water-sol.Take interfacial agents γ-methacryloxypropyl trimethoxy silane 20g, join above-mentioned graphene oxide/white carbon black water-sol, ultrasonic dispersion 6h under the power of 800kw, while monitoring system temperature, if system temperature is over 80 ℃, so first ultrasound procedure is suspended, mixture system is moved under the stirring of 500 r/min, stir 30min, after system temperature is reduced, proceed again ultrasound procedure, then obtain through the pretreated graphene oxide/white carbon black of the interfacial agents water-sol.After the above-mentioned butylbenzene/natural/butadiene latex 125g that is 80% through the pretreated graphene oxide/white carbon black of the interfacial agents water-sol with solid content is mixed, ultrasonic dispersion 4h under the power of 500kw, while monitoring system temperature, if system temperature is over 80 ℃, so first ultrasound procedure is suspended, mixture system is moved under the stirring of 500 r/min, stir 30min, after system temperature is reduced, proceed again ultrasound procedure, then obtain stable graphene oxide/white carbon black/styrene-butadiene rubber(SBR) composite emulsion.Above-mentioned composite emulsion is carried out through spray drying unit, and drying medium is 150 ℃ of warm airs, and temperature in is 150 ℃, and now temperature out is 80 ℃, by the throughput ratio of carrier gas, in carrier gas, introduces 1% HCl gas simultaneously.The sample that collection completes obtains the graphene oxide/white carbon black/butylbenzene/natural/divinyl rubber nano composite material containing 75phr filler.
By above-mentioned technique, prepare matrix material 200.6g, the matrix material obtaining, in two roller mills, is carried out to the mixing rubber unvulcanizate that obtains according to formula (5 parts, zinc oxide, 2 parts of stearic acid, 0.5 part of vulkacit D, 0.5 part of altax, 0.2 part of promotor TT, 1 part of antioxidant 4010NA, 1 part of anti-aging agent RD, 2 parts, sulphur).Rubber unvulcanizate is vulcanized to the white carbon black/rubber nano composite material that obtains vulcanizating under 150 ℃, sulfurizing time.This nano composite material is carried out to properties test by corresponding national standard.
Embodiment 9
Take 2g graphite oxide, join in the deionized water of 500g, ultrasonic dispersion 1h under the power of 300kw, while monitoring system temperature, if system temperature is over 80 ℃, so first ultrasound procedure is suspended, mixture system is moved under the stirring of 300 r/min, stir 30min, after system temperature is reduced, proceed again ultrasound procedure, then make solid content and be 0.4% the graphene oxide water-sol.Take the precipitated silica 54g through γ-methacryloxypropyl trimethoxy silane surface modification, wherein the content of γ-methacryloxypropyl trimethoxy silane is 4g, join in the above-mentioned water-sol, under the stirring velocity of 3000r/min, after dispersed with stirring 6h, obtain graphene oxide/white carbon black water-sol.Take interfacial agents solid content and be 50% carboxylic chloroprene rubber latex 20g, join above-mentioned graphene oxide/white carbon black water-sol, under the stirring velocity of 5000r/min, after dispersed with stirring 6h, obtain through the pretreated graphene oxide/white carbon black of the interfacial agents water-sol.After the above-mentioned polychloroprene latex 200g that is 50% through the pretreated graphene oxide/white carbon black of the interfacial agents water-sol with solid content is mixed, under the stirring velocity of 8000r/min, after dispersed with stirring 8h, obtain stable graphene oxide/white carbon black/divinyl rubber composite emulsion.Above-mentioned composite emulsion is carried out through spray drying unit, and drying medium is 200 ℃ of warm airs, and temperature in is 200 ℃, and now temperature out is 100 ℃, by the throughput ratio of carrier gas, in carrier gas, introduces 1% nitric acid gas simultaneously.The sample that collection completes obtains the graphene oxide/white carbon black/chloroprene rubber nano composite material containing 52phr filler.
By above-mentioned technique, prepare matrix material 166g, the matrix material obtaining, in two roller mills, is carried out to the mixing rubber unvulcanizate that obtains according to formula (5 parts, zinc oxide, 0.5 part of stearic acid, 4 parts, magnesium oxide, 0.5 part of accelerant N A-22,10 parts of naphthenic oils, 2 parts of antioxidant 4010NAs, 2 parts of anti-aging agent TPPD).Rubber unvulcanizate is vulcanized to the white carbon black/rubber nano composite material that obtains vulcanizating under 150 ℃, sulfurizing time.This nano composite material is carried out to properties test by corresponding national standard.
Embodiment 10
Take 5g graphite oxide, join in the deionized water of 500g, ultrasonic dispersion 1h under the power of 300kw, while monitoring system temperature, if system temperature is over 80 ℃, so first ultrasound procedure is suspended, mixture system is moved under the stirring of 300 r/min, stir 30min, after system temperature is reduced, proceed again ultrasound procedure, then make solid content and be 1% the graphene oxide water-sol.Take the precipitated silica 54g through γ-methacryloxypropyl trimethoxy silane surface modification, wherein the content of γ-methacryloxypropyl trimethoxy silane is 4g, join in the above-mentioned water-sol, under the stirring velocity of 3000r/min, after dispersed with stirring 6h, obtain graphene oxide/white carbon black water-sol.Take interfacial agents γ-methacryloxypropyl trimethoxy silane 20g, join above-mentioned graphene oxide/white carbon black water-sol, ultrasonic dispersion 1h under the power of 300kw, while monitoring system temperature, if system temperature is over 80 ℃, so first ultrasound procedure is suspended, mixture system is moved under the stirring of 300 r/min, stir 30min, after system temperature is reduced, proceed again ultrasound procedure, then obtain through the pretreated graphene oxide/white carbon black of the interfacial agents water-sol.After the above-mentioned isobutylene-isoprene latex 125g that is 80% through the pretreated graphene oxide/white carbon black of the interfacial agents water-sol with solid content is mixed, ultrasonic dispersion 6h under the power of 800kw, while monitoring system temperature, if system temperature is over 80 ℃, so first ultrasound procedure is suspended, mixture system is moved under the stirring of 500 r/min, stir 30min, after system temperature is reduced, proceed again ultrasound procedure, then obtain stable graphene oxide/white carbon black/divinyl rubber composite emulsion.Above-mentioned composite emulsion is carried out through spray drying unit, and drying medium is 200 ℃ of warm airs, and temperature in is 200 ℃, and now temperature out is 100 ℃, by the throughput ratio of carrier gas, in carrier gas, introduces 1% nitric acid gas simultaneously.The sample that collection completes obtains the graphene oxide/white carbon black/butyl rubber nanocomposites containing 55phr filler.
By above-mentioned technique, prepare matrix material 179g, the matrix material obtaining, in two roller mills, is carried out to the mixing rubber unvulcanizate that obtains according to formula (5 parts, zinc oxide, 2 parts of stearic acid, 2 parts, paraffin, 2 parts of accelerant CZs, 0.2 part of promotor TT, 10 parts of aromatic hydrocarbon oil, 1 part of antioxidant 4010NA, 1 part of anti-aging agent RD, 2 parts, sulphur).Rubber unvulcanizate is vulcanized to the white carbon black/rubber nano composite material that obtains vulcanizating under 170 ℃, sulfurizing time.This nano composite material is carried out to properties test by corresponding national standard.
Embodiment 11
Take 10g graphite oxide, join in the deionized water of 500g, ultrasonic dispersion 6h under the power of 300kw, while monitoring system temperature, if system temperature is over 80 ℃, so first ultrasound procedure is suspended, mixture system is moved under the stirring of 300 r/min, stir 30min, after system temperature is reduced, proceed again ultrasound procedure, then make solid content and be 2% the graphene oxide water-sol.Take the precipitated silica 54g through two-(the silica-based propyl group of γ-triethoxy)-tetrasulfide surface modification, wherein the content of two-(the silica-based propyl group of γ-triethoxy)-tetrasulfide is 4g, join in the above-mentioned water-sol, under the stirring velocity of 3000r/min, after dispersed with stirring 6h, obtain graphene oxide/white carbon black water-sol.Take interfacial agents solid content and be 80% vinyl-pyridine latex 62.5g, join above-mentioned graphene oxide/white carbon black water-sol, ultrasonic dispersion 4h under the power of 1000kw, while monitoring system temperature, if system temperature is over 80 ℃, so first ultrasound procedure is suspended, mixture system is moved under the stirring of 500 r/min, stir 30min, after system temperature is reduced, proceed again ultrasound procedure, then obtain through the pretreated graphene oxide/white carbon black of the interfacial agents water-sol.By above-mentioned through the pretreated graphene oxide/white carbon black of the interfacial agents water-sol, be 50% with solid content the third latex 200g mixes after, under the stirring velocity of 5000r/min, after dispersed with stirring 12h, obtain the third rubber combined emulsion of stable graphene oxide/white carbon black/.Above-mentioned composite emulsion is carried out through spray drying unit, and drying medium is 350 ℃ of warm airs, and temperature in is 350 ℃, and now temperature out is 120 ℃, by the throughput ratio of carrier gas, in carrier gas, introduces 1% nitric acid gas simultaneously.The sample that collection completes obtains containing the third rubber nano composite material of the graphene oxide/white carbon black of 60phr filler/.
By above-mentioned technique, prepare matrix material 214g, the matrix material obtaining, in two roller mills, is carried out to the mixing rubber unvulcanizate that obtains according to formula (5 parts, zinc oxide, 2 parts of stearic acid, 1 part of protection wax, 30 parts of paraffin oils, 2 parts of A151,0.2 part of promotor TT, 2 parts of accelerant CZs, 6 parts, sulphur).Rubber unvulcanizate is vulcanized to the white carbon black/rubber nano composite material that obtains vulcanizating under 170 ℃, sulfurizing time.This nano composite material is carried out to properties test by corresponding national standard.
Embodiment 12
Take 10g graphite oxide, join in the deionized water of 500g, ultrasonic dispersion 3h under the power of 400kw, while monitoring system temperature, if system temperature is over 80 ℃, so first ultrasound procedure is suspended, mixture system is moved under the stirring of 300 r/min, stir 30min, after system temperature is reduced, proceed again ultrasound procedure, then make solid content and be 2% the graphene oxide water-sol.Take the precipitated silica 54g through two-(the silica-based propyl group of γ-triethoxy)-tetrasulfide surface modification, wherein the content of two-(the silica-based propyl group of γ-triethoxy)-tetrasulfide is 4g, join in the above-mentioned water-sol, under the stirring velocity of 3000r/min, after dispersed with stirring 6h, obtain graphene oxide/white carbon black water-sol.Take interfacial agents quaternary ammonium salt 20g, join above-mentioned graphene oxide/white carbon black water-sol, ultrasonic dispersion 4h under the power of 1000kw, while monitoring system temperature, if system temperature is over 80 ℃, so first ultrasound procedure is suspended, mixture system is moved under the stirring of 500 r/min, stir 30min, after system temperature is reduced, proceed again ultrasound procedure, then obtain through the pretreated graphene oxide/white carbon black of the interfacial agents water-sol.After the above-mentioned polyisoprene latex 125g that is 80% through the pretreated graphene oxide/white carbon black of the interfacial agents water-sol with solid content is mixed, ultrasonic dispersion 6h under the power of 800kw, while monitoring system temperature, if system temperature is over 80 ℃, so first ultrasound procedure is suspended, mixture system is moved under the stirring of 500 r/min, stir 30min, after system temperature is reduced, proceed again ultrasound procedure, then obtain stable graphene oxide/white carbon black/polyisoprene rubber composite emulsion.Above-mentioned composite emulsion is carried out through spray drying unit, and drying medium is 150 ℃ of warm airs, and temperature in is 150 ℃, and now temperature out is 80 ℃, by the throughput ratio of carrier gas, in carrier gas, introduces 1% hydrochloric acid gas simultaneously.The sample that collection completes obtains the graphene oxide/white carbon black/polyisoprene rubber nano composite material containing 60phr filler.
By above-mentioned technique, prepare matrix material 184g, the matrix material obtaining, in two roller mills, is carried out to the mixing rubber unvulcanizate that obtains according to formula (5 parts, zinc oxide, 2 parts of stearic acid, 3 parts of altaxs, 2 parts of antioxidant 4010NAs, 2 parts of anti-aging agent RDs, 2 parts, sulphur).Rubber unvulcanizate is vulcanized to the white carbon black/rubber nano composite material that obtains vulcanizating under 143 ℃, sulfurizing time.This nano composite material is carried out to properties test by corresponding national standard.
Embodiment 13
Take 10g graphite oxide, join in the deionized water of 500g, ultrasonic dispersion 3h under the power of 400kw, while monitoring system temperature, if system temperature is over 80 ℃, so first ultrasound procedure is suspended, mixture system is moved under the stirring of 300 r/min, stir 30min, after system temperature is reduced, proceed again ultrasound procedure, then make solid content and be 2% the graphene oxide water-sol.Take the thermal silica 77g through perstearic acid surface modification, wherein stearic acid content is 7g, joins in the above-mentioned water-sol ultrasonic dispersion 2h under the power of 500kw, while monitoring system temperature, if system temperature surpasses 80 ℃, so first ultrasound procedure is suspended, mixture system is moved under the stirring of 300 r/min, stir 15min, after system temperature is reduced, then proceed ultrasound procedure, then obtain graphene oxide/white carbon black water-sol.Take interfacial agents solid content and be 50% carboxylic acrylonitrile butadiene rubber latex 40g, join above-mentioned graphene oxide/white carbon black water-sol, ultrasonic dispersion 4h under the power of 600kw, while monitoring system temperature, if system temperature is over 80 ℃, so first ultrasound procedure is suspended, mixture system is moved under the stirring of 500 r/min, stir 30min, after system temperature is reduced, proceed again ultrasound procedure, then obtain through the pretreated graphene oxide/white carbon black of the interfacial agents water-sol.After the above-mentioned nitrile rubber 125g that is 80% through the pretreated graphene oxide/white carbon black of the interfacial agents water-sol with solid content is mixed, ultrasonic dispersion 6h under the power of 800kw, while monitoring system temperature, if system temperature surpasses 80 ℃, so first ultrasound procedure is suspended, mixture system is moved under the stirring of 500 r/min, stir 30min, after system temperature is reduced, then proceed ultrasound procedure, then obtain stable graphene oxide/white carbon black/paracril composite emulsion.Above-mentioned composite emulsion is carried out through spray drying unit, and drying medium is 350 ℃ of warm airs, and temperature in is 350 ℃, and now temperature out is 120 ℃, by the throughput ratio of carrier gas, in carrier gas, introduces 1% hydrochloric acid gas simultaneously.The sample that collection completes obtains the graphene oxide/white carbon black/nitrile rubber nanocomposites containing 80phr filler.
By above-mentioned technique, prepare matrix material 207g, the matrix material obtaining, in two roller mills, is carried out to the mixing rubber unvulcanizate that obtains according to formula (3 parts, zinc oxide, 2 parts of stearic acid, 1 part of vulkacit D, 2 parts of altaxs, 30 parts of dioctyl phthalate (DOP)s, 2 parts of protection waxes, 2 parts of antioxidant 4010NAs, 2 parts of anti-aging agent RDs, 4 parts, sulphur).Rubber unvulcanizate is vulcanized to the white carbon black/rubber nano composite material that obtains vulcanizating under 170 ℃, sulfurizing time.This nano composite material is carried out to properties test by corresponding national standard.
Embodiment 14
Take 10g graphite oxide, join in the deionized water of 500g, ultrasonic dispersion 3h under the power of 400kw, while monitoring system temperature, if system temperature is over 80 ℃, so first ultrasound procedure is suspended, mixture system is moved under the stirring of 300 r/min, stir 30min, after system temperature is reduced, proceed again ultrasound procedure, then make solid content and be 2% the graphene oxide water-sol.Take the thermal silica 77g through perstearic acid surface modification, wherein stearic acid content is 7g, joins in the above-mentioned water-sol ultrasonic dispersion 2h under the power of 500kw, while monitoring system temperature, if system temperature surpasses 80 ℃, so first ultrasound procedure is suspended, mixture system is moved under the stirring of 300 r/min, stir 15min, after system temperature is reduced, then proceed ultrasound procedure, then obtain graphene oxide/white carbon black water-sol.Take the quaternary ammonium salt of interfacial agents 10g, join above-mentioned graphene oxide/white carbon black water-sol, ultrasonic dispersion 4h under the power of 600kw, while monitoring system temperature, if system temperature is over 80 ℃, so first ultrasound procedure is suspended, mixture system is moved under the stirring of 500 r/min, stir 30min, after system temperature is reduced, proceed again ultrasound procedure, then obtain through the pretreated graphene oxide/white carbon black of the interfacial agents water-sol.After the above-mentioned fluoroelastomer latex 125g that is 80% through the pretreated graphene oxide/white carbon black of the interfacial agents water-sol with solid content is mixed, ultrasonic dispersion 6h under the power of 1000kw, while monitoring system temperature, if system temperature surpasses 80 ℃, so first ultrasound procedure is suspended, mixture system is moved under the stirring of 500 r/min, stir 30min, after system temperature is reduced, then proceed ultrasound procedure, then obtain stable graphene oxide/white carbon black/viton composite emulsion.Above-mentioned composite emulsion is carried out through spray drying unit, and drying medium is 150 ℃ of warm airs, and temperature in is 150 ℃, and now temperature out is 120 ℃, by the throughput ratio of carrier gas, in carrier gas, introduces 1% hydrofluoric acid gas simultaneously.The sample that collection completes obtains the graphene oxide/white carbon black/viton nano composite material containing 80phr filler.
By above-mentioned technique, prepare matrix material 197g, the matrix material obtaining, in two roller mills, is carried out to the mixing rubber unvulcanizate that obtains according to formula (1 part of sodium stearate, 5 parts of TAIC, 1 part of 1,4 bis tert butyl peroxy isopropyl benzene).By rubber unvulcanizate at one section 170 ℃, at two sections 230 ℃, vulcanize the white carbon black/rubber nano composite material that obtains vulcanizating under sulfurizing time.This nano composite material is carried out to properties test by corresponding national standard.
Embodiment 15
Take 20g graphite oxide, join in the deionized water of 1000g, ultrasonic dispersion 4h under the power of 300kw, while monitoring system temperature, if system temperature is over 80 ℃, so first ultrasound procedure is suspended, mixture system is moved under the stirring of 300 r/min, stir 20min, after system temperature is reduced, proceed again ultrasound procedure, then make solid content and be 2% the graphene oxide water-sol.Take the thermal silica 88g through silazane surface modification, wherein silazane content is 8g, joins in the above-mentioned water-sol ultrasonic dispersion 2h under the power of 500kw, while monitoring system temperature, if system temperature surpasses 80 ℃, so first ultrasound procedure is suspended, mixture system is moved under the stirring of 300 r/min, stir 15min, after system temperature is reduced, then proceed ultrasound procedure, then obtain graphene oxide/white carbon black water-sol.Take the aminopropyl triethoxysilane coupling agent of interfacial agents 40g, join above-mentioned graphene oxide/white carbon black water-sol, ultrasonic dispersion 4h under the power of 600kw, while monitoring system temperature, if system temperature is over 80 ℃, so first ultrasound procedure is suspended, mixture system is moved under the stirring of 500 r/min, stir 30min, after system temperature is reduced, proceed again ultrasound procedure, then obtain through the pretreated graphene oxide/white carbon black of the interfacial agents water-sol.After the above-mentioned silicone rubber latex 200g that is 50% through the pretreated graphene oxide/white carbon black of the interfacial agents water-sol with solid content is mixed, ultrasonic dispersion 4h under the power of 500kw, while monitoring system temperature, if system temperature surpasses 80 ℃, so first ultrasound procedure is suspended, mixture system is moved under the stirring of 300 r/min, stir 30min, after system temperature is reduced, then proceed ultrasound procedure, then obtain stable graphene oxide/white carbon black/silicon rubber composite emulsion.Above-mentioned composite emulsion is carried out through spray drying unit, and drying medium is 200 ℃ of warm airs, and temperature in is 200 ℃, and now temperature out is 100 ℃.The sample that collection completes obtains the graphene oxide/white carbon black/silicon rubber nano composite material containing 100phr filler.
By above-mentioned technique, prepare matrix material 248g, the matrix material obtaining, in two roller mills, is carried out to the mixing rubber unvulcanizate that obtains according to formula (1.5 parts of DCP).Rubber unvulcanizate is vulcanized to the white carbon black/rubber nano composite material that obtains vulcanizating under 160 ℃, sulfurizing time.This nano composite material is carried out to properties test by corresponding national standard.
Embodiment 16
By the graphene oxide rubber master batch 105g preparing by emulsion method, wherein base glue is 100g natural rubber, graphene oxide is 5g, be placed in the 1min that plasticates in two roller mills, then add the precipitated silica 58g through two-(the silica-based propyl group of γ-triethoxy)-tetrasulfide surface modification, wherein the content of two-(the silica-based propyl group of γ-triethoxy)-tetrasulfide is 8g, and mixing 8min obtains the graphene oxide/white carbon black/natural rubber nano composite material containing 55phr filler.
By above-mentioned technique, prepare matrix material 163g, the matrix material obtaining, in two roller mills, is carried out to the mixing rubber unvulcanizate that obtains according to formula (5 parts, zinc oxide, 2 parts of stearic acid, 3 parts of altaxs, 2 parts of antioxidant 4010NAs, 2 parts of anti-aging agent RDs, 2 parts, sulphur).Rubber unvulcanizate is vulcanized to the white carbon black/rubber nano composite material that obtains vulcanizating under 143 ℃, sulfurizing time.This nano composite material is carried out to properties test by corresponding national standard.
Embodiment 17
By the graphene oxide rubber master batch 125g preparing by emulsion method, wherein base glue is 100g styrene-butadiene rubber(SBR), graphene oxide is 5g, interfacial agents is the carboxylic styrene-butadiene rubber of 20g, be placed in the Banbury mixer 5min that plasticates, then add the precipitated silica 75.6g through two-(the silica-based propyl group of γ-triethoxy)-tetrasulfide surface modification, wherein the content of two-(the silica-based propyl group of γ-triethoxy)-tetrasulfide is 5.6g, mixing 20min, obtains the graphene oxide/white carbon black/butadiene styrene rubber nanometer composite material containing 75phr filler.
By above-mentioned technique, prepare matrix material 200.6g, the matrix material obtaining, in two roller mills, is carried out to the mixing rubber unvulcanizate that obtains according to formula (5 parts, zinc oxide, 2 parts of stearic acid, 0.5 part of vulkacit D, 0.5 part of altax, 0.2 part of promotor TT, 1 part of antioxidant 4010NA, 1 part of anti-aging agent RD, 2 parts, sulphur).Rubber unvulcanizate is vulcanized to the white carbon black/rubber nano composite material that obtains vulcanizating under 150 ℃, sulfurizing time.This nano composite material is carried out to properties test by corresponding national standard.
Embodiment 18
By the white carbon black rubber master batch 181g preparing by emulsion method, wherein base glue is 100g styrene-butadiene rubber(SBR), precipitated silica 75g, coupling agent is two-(the silica-based propyl group of γ-triethoxy)-tetrasulfide 6g, be placed in the 5min that plasticates in two roller mills, then add graphene oxide 5g, mixing 20min, obtains the graphene oxide/white carbon black/butadiene styrene rubber nanometer composite material containing 80phr filler.
By above-mentioned technique, prepare matrix material 186g, the matrix material obtaining, in two roller mills, is carried out to the mixing rubber unvulcanizate that obtains according to formula (5 parts, zinc oxide, 2 parts of stearic acid, 0.5 part of vulkacit D, 0.5 part of altax, 0.2 part of promotor TT, 1 part of antioxidant 4010NA, 1 part of anti-aging agent RD, 2 parts, sulphur).Rubber unvulcanizate is vulcanized to the white carbon black/rubber nano composite material that obtains vulcanizating under 150 ℃, sulfurizing time.This nano composite material is carried out to properties test by corresponding national standard.
Embodiment 19
By the white carbon black rubber master batch 155g preparing by emulsion method, wherein base glue is 100g butylbenzene/natural/divinyl mixed rubber, precipitated silica 50g, coupling agent is two-(the silica-based propyl group of γ-triethoxy)-tetrasulfide 5g, be placed in the Banbury mixer 3min that plasticates, then add graphene oxide 5g, the carboxy terminatedpolybutadiene that interfacial agents is 10g, mixing 10min, obtains the graphene oxide/white carbon black/butylbenzene/natural/divinyl rubber nano composite material containing 55phr filler.
By above-mentioned technique, prepare matrix material 170g, the matrix material obtaining, in two roller mills, is carried out to the mixing rubber unvulcanizate that obtains according to formula (5 parts, zinc oxide, 2 parts of stearic acid, 0.5 part of vulkacit D, 0.5 part of altax, 0.2 part of promotor TT, 1 part of antioxidant 4010NA, 1 part of anti-aging agent RD, 2 parts, sulphur).Rubber unvulcanizate is vulcanized to the white carbon black/rubber nano composite material that obtains vulcanizating under 150 ℃, sulfurizing time.This nano composite material is carried out to properties test by corresponding national standard.
Embodiment 20
Will be by 100g silicon rubber, be placed in the 5min that plasticates in two roller mills, then add graphene oxide 5g, interfacial agents is the aminopropyl triethoxysilane coupling agent of 10g, and 81g is through the thermal silica of silazane modification, wherein silazane content is 6g, and mixing 20min obtains the graphene oxide/white carbon black/silicon rubber nano composite material containing 80phr filler.
By above-mentioned technique, prepare matrix material 196g, the matrix material obtaining, in two roller mills, is carried out to the mixing rubber unvulcanizate that obtains according to formula (1.5 parts of DCP).Rubber unvulcanizate is vulcanized to the white carbon black/rubber nano composite material that obtains vulcanizating under 160 ℃, sulfurizing time.This nano composite material is carried out to properties test by corresponding national standard.
Embodiment 21
By the white carbon black rubber master batch 131g preparing by emulsion method, wherein base glue is 50g styrene-butadiene rubber(SBR), precipitated silica 75g, coupling agent is two-(the silica-based propyl group of γ-triethoxy)-tetrasulfide 6g, and the graphene oxide rubber master batch 75g preparing by emulsion method, wherein base glue is 50g styrene-butadiene rubber(SBR), graphene oxide is 5g, interfacial agents is the carboxylic styrene-butadiene rubber of 20g, is placed in mixing 15min in two roller mills, obtains the graphene oxide/white carbon black/butadiene styrene rubber nanometer composite material containing 80phr filler.
By above-mentioned technique, prepare matrix material 206g, the matrix material obtaining, in two roller mills, is carried out to the mixing rubber unvulcanizate that obtains according to formula (5 parts, zinc oxide, 2 parts of stearic acid, 0.5 part of vulkacit D, 0.5 part of altax, 0.2 part of promotor TT, 1 part of antioxidant 4010NA, 1 part of anti-aging agent RD, 2 parts, sulphur).Rubber unvulcanizate is vulcanized to the white carbon black/rubber nano composite material that obtains vulcanizating under 150 ℃, sulfurizing time.This nano composite material is carried out to properties test by corresponding national standard.
Embodiment 22
By the white carbon black rubber master batch 104g preparing by emulsion method, wherein base glue is 50g paracril, thermal silica 50g, coupling agent stearic acid 4g, and the graphene oxide rubber master batch 75g preparing by emulsion method, wherein base glue is 50g styrene-butadiene rubber(SBR), graphene oxide is 5g, interfacial agents is the carboxy nitrile rubber of 20g, is placed in the mixing 15min of Banbury mixer, obtains the graphene oxide/white carbon black/nitrile rubber nanocomposites containing 55phr filler.
By above-mentioned technique, prepare matrix material 179g, the matrix material obtaining, in two roller mills, is carried out to the mixing rubber unvulcanizate that obtains according to formula (3 parts, zinc oxide, 2 parts of stearic acid, 1 part of vulkacit D, 2 parts of altaxs, 30 parts of dioctyl phthalate (DOP)s, 2 parts of protection waxes, 2 parts of antioxidant 4010NAs, 2 parts of anti-aging agent RDs, 4 parts, sulphur).Rubber unvulcanizate is vulcanized to the white carbon black/rubber nano composite material that obtains vulcanizating under 170 ℃, sulfurizing time.This nano composite material is carried out to properties test by corresponding national standard.
Comparative example
Comparative example is under same process condition, and graphene oxide equivalent substitution is returned to white carbon black, and removes interfacial agents, and keeps the sample of proportionlity between original coupling agent and white carbon black.Other fillers and small powder, and the course of processing all remains unchanged.
Concrete outcome is as follows
Table 1 is containing each performance data table of graphene oxide and oxygen-free functionalized graphene sample
Below preferred embodiment of the present invention is illustrated, but the present invention is not limited to described embodiment, those of ordinary skill in the art also can make all modification being equal to or replacement under the prerequisite without prejudice to spirit of the present invention, and the modification that these are equal to or replacement are all included in the application's claim limited range.
Claims (4)
1. mechanical blending is prepared the method for graphene oxide/white carbon black/rubber nano composite material, it is characterized in that the method comprises following four kinds of performances altogether:
1, graphene oxide rubber master batch is placed in to two roller mills or the Banbury mixer 1～5min that plasticates, then add white carbon black and coupling agent, or the white carbon black of process coupling agent surface modification, blend 1-20min, prepares graphene oxide/white carbon black/rubber nano composite material;
2, white carbon black rubber master batch is placed in to two roller mills or the Banbury mixer 1～5min that plasticates, then adds graphene oxide and interfacial agents, blend 1-20min, prepares graphene oxide/white carbon black/rubber nano composite material;
3, rubber is placed in to two roller mills or the Banbury mixer 1～5min that plasticates, then add white carbon black and graphene oxide and interfacial agents through coupling agent surface modification, or white carbon black, coupling agent and graphene oxide and interfacial agents, blend 1-20min, prepares graphene oxide/white carbon black/rubber nano composite material;
4, graphene oxide rubber master batch and the female rubber of white carbon black are placed in to two roller mills or Banbury mixer blend 1-20min, prepare graphene oxide/white carbon black/rubber nano composite material; Interfacial agents is carboxy terminatedpolybutadiene, aminopropyl triethoxysilane, γ-(methacryloxypropyl) propyl trimethoxy silicane coupling agent, quaternary ammonium salt, or solid content be 10～80wt% carboxylic styrene butadiene latex, vinyl-pyridine latex, Carboxy pyrrole latex, epoxy natural latex, carboxylic chloroprene rubber latex or carboxylic acrylonitrile butadiene rubber latex.
2. method according to claim 1, is characterized in that in prepared graphene oxide/white carbon black/rubber nano composite material, white carbon black comprises precipitated silica and thermal silica; The consumption of white carbon black and graphene oxide is 0.1～400phr, and phr represents the white carbon black that adds in each hundred parts of rubber and the quality of graphene oxide.
3. according to profit, require the method described in 1, it is characterized in that wherein the 1st, 2 and 4 kind of performance in use in rubber in rubber master batch and mechanical blending preparation method the epoxy glue that rubber used in the 3rd kind of performance comprises one or both rubber in styrene-butadiene rubber(SBR), natural rubber, chloroprene rubber, isoprene-isobutylene rubber, paracril, divinyl rubber, ethylene-propylene rubber(EPR), polyisoprene rubber, viton and silicon rubber, or two or more epoxy glue; Wt% represents mass percent.
4. according to profit, require the method described in 1, it is characterized in that coupling agent used comprises two-(the silica-based propyl group of γ-triethoxy)-tetrasulfide, two-(the silica-based propyl group of γ-triethoxy)-disulphide, γ-aminopropyl triethoxysilane, γ-(2,3-epoxy the third oxygen) propyl trimethoxy silicane, γ-methacryloxypropyl trimethoxy silane, γ-mercaptopropyl trimethoxysilane, stearic acid or silazane; The consumption of coupling agent is 0.01%～50% of white carbon black massfraction.
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