CN103275368A - 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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- graphene oxide
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- 239000006229 carbon black Substances 0.000 title claims abstract description 235
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- 238000000034 method Methods 0.000 title claims abstract description 125
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- Compositions Of Macromolecular Compounds (AREA)
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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 maximum, the most general filler are 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.Be used for that rubber strengthens, the equivalent material research of the non-oil resource of alternative carbon black begins progressively to become one of important topic that rubber industry faces.Comparatively successful 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 big, polymolecularity, light weight, good stability, high temperature resistant, do not burn, 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 even three agglomerates.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% is used for rubber industry at present, is good rubber reinforcing filler, can improve cementing property and tear strength.White carbon black near carbon black, especially passes through the white carbon black of surface modification to the reinforcing property of rubber, not only can provide higher modulus, can also reduce rolling resistance.But because a little less than the interaction between white carbon black and the rubber, be filled in the rubber after, wear resisting property obviously descends.Though therefore in car tyre, with the green tire widespread use of white carbon black filling butadiene-styrene rubber, in load-carrying tire and engineering tire, the consumption of white carbon black is little all the time, only be that a small amount of the filling improved tear resistance.So present research direction is by also improving the wear resisting property of white carbon black filled rubber material with other fillers, further expanding the use range of white carbon black.Common way is also with the wear resisting property of a certain amount of carbon black with the raising elastomeric material on the basis that white carbon black is filled, 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 satisfy requirements of green environmental protection again simultaneously.
Graphene be a kind of by carbon atom with sp
2The hexagonal lattice flat film that hybridized orbital is formed has only the two-dimensional material of one or more carbon atom thickness.Successfully being made first with the method for the high oriented graphite of tape stripping by the Novoselov of Univ Manchester UK and Geim in 2004 really can self-existent two-dimentional Graphene crystal.Graphene planar has or not the multiple periodic structure of freight weight limit, has only nanoscale in the direction perpendicular to the plane, can be regarded as the nano material with macro-size.Graphene has high theoretical specific surface area (about 2630m
2/ g), and big aspect ratio (＞1000) and good 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, use the high graphene oxide of peeling off partly to substitute white carbon black and come filled rubber, in the rubber nano composite material for preparing like this, because Graphene and white carbon black be the interspersed gathering that has effectively suppressed two kinds of fillers self mutually, make that their dispersion is more even, show and do not losing the original excellent properties (higher modulus of white carbon black, lower rolling resistance) time, promoted the wear resisting property of elastomeric material significantly, and further improve modulus and the tear resistance of matrix material, because laminated structure and the good automatic recovery ability of graphene oxide have also given elastomeric material good gas barrier property and self-healing ability, has the incomparable advantage of conventional filler simultaneously.Therefore, with Graphene and white carbon black and be used for strengthening or the rubber nano composite material of modification preparation has excellent comprehensive performance more, can be widely used in mechanicals and various field of sealing technology such as tire, offset plate, adhesive tape, rubber roll, conveying belt, and aerospace field.Simultaneously, graphene oxide has good automatic recovery ability and cracking resistance line extended capability, can be widely used in self-repair material and high anti-tear material field thereof.
Summary of the invention:
The purpose of this invention is to provide that height is peeled off, high dispersive, strong interfacial bond, the preparation method who has the graphene oxide/white carbon black/rubber nano composite material of high dispersive simultaneously, used Graphene is graphene oxide, (graphene oxide inevitably reassociates after being reduced into Graphene, is unfavorable for the dispersion of Graphene not pass through reduction process; And the Graphene surface functional group content after the reduction reduces significantly, and is 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 composite methods at water or solution in mutually; (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 composite methods at machining equipment.
The present invention contains the rubber nano composite material of graphene oxide/white carbon black or prepares the graphene oxide rubber master batch respectively and during the white carbon black rubber master batch in direct preparation, 201110454000.5), and " a kind of preparation method who prepares high dispersive white carbon black/rubber nano composite material " (application number: 201210001294.0) and " a kind of method for 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 fully " 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, it is scattered in water or the organic solvent, can be stripped from into graphene oxide fully by ultrasonication.A large amount of oxygen-containing functional groups is contained on the graphene oxide surface, and the Van der Waals force that makes itself and water and organic solvent commonly used have between better consistency and sheet and the sheet weakens, and has reduced congregation; The white carbon black that has grain pattern simultaneously has suspension in water character prepares graphene oxide/white carbon black water-sol; And utilize multiple rubber clone that the characteristic of emulsion form is arranged, graphene oxide/white carbon black water-sol and rubber latex blend are obtained graphene oxide/white carbon black/rubber latex mixed solution; Utilize drying process with atomizing that the mixed solution atomizing is formed small mixed solution drop; In drying medium, remove moisture content rapidly, obtain the nano composite material of graphene oxide/white carbon black/rubber.Because the fine drop that atomizing forms under drying process with atomizing makes the specific surface area of mixed solution enlarge markedly, the moisture that mixes in the drop in drying medium is removed fast, phase structure under therefore original liquid mixing state is kept in the nano composite material that obtains, and has namely obtained the graphene oxide/white carbon black/rubber nano composite material of high dispersive; Perhaps directly utilize the method for ion co-coagulation in mixed solution, to add flocculation agent, directly prepare graphene oxide/white carbon black/rubber nano composite material by stirring.
When preparation 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 fully " (application number: 201110454000.5) carry out in early stage.When preparation 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 dispersive 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 that the present invention relates to/rubber nano composite material adopts concrete implementation step is as follows:
(1) solution blending preparation method
Graphite oxide is dispensed in the deionized water, makes the graphene oxide water-sol behind ultra-sonic dispersion 10min～6h under power 0.1～1000kW, 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, perhaps pass through coupling agent modified white carbon black, ultra-sonic dispersion 10min～6h under power 0.1～1000kW, perhaps low whipping speed is to stir 30min～12h under 50～10000 r/min, obtains graphene oxide/white carbon black water-sol; In above-mentioned graphene oxide/white carbon black aqueous solution, add interfacial agents, ultra-sonic dispersion 10min～6h under power 0.1～1000kW, perhaps low whipping speed is to stir 30min～12h under 50～10000 r/min to carry out pre-treatment, obtains pretreated graphene oxide/white carbon black pretreated water colloidal sol.
Directly with graphene oxide/white carbon black water-sol or with pretreated graphene oxide/white carbon black pretreated water colloidal sol and rubber latex ultra-sonic dispersion 10min～6h under power 0.1～1000kW, perhaps low whipping speed is to stir 30min～12h under 50～10000 r/min, obtains stable composite emulsion.In the ultra-sonic dispersion operation in above-mentioned preparation process, need the monitoring system temperature, if system temperature is above 80 ℃, so earlier ultrasound procedure is suspended, mixture system is moved under the stirring of 50～500 r/min, stir 5 ~ 30min, be after system temperature reduces, to proceed ultrasound procedure again.Above preparation process needs hierarchy of control temperature less than 100 ℃, to prevent coupling agent or interfacial agents generation self-polymeric reaction;
Adopt one of following two kinds of schemes then
A) ion flocculation process: add flocculation agent in the composite emulsion and flocculate, under the speed of 50～10000 r/min, stir, make the rubber latex breakdown of emulsion through stirring, flocculation reaction takes place, obtain the flocculent gel of graphene oxide/white carbon black/rubber then, then flocculent gel is dried under 60 ~ 300 ℃, will prepare graphene oxide/white carbon black/rubber nano composite material after the oven dry of the moisture content in the flocculent gel;
B) drying process with atomizing: through spray drying unit, atomizing forms small complex liquid drop, removes moisture in drying medium, obtains graphene oxide/white carbon black/rubber nano composite material with above-mentioned composite emulsion; Perhaps by in the drying medium carrier gas of spray drying unit, introducing the flocculation agent after gasifying, make ion flocculate, 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 suppressed graphene oxide and white carbon black on the thermodynamics effectively the trend of assembling or piling up has taken place, under the dispersion phase structure of the graphene oxide/white carbon black/rubber under the feasible liquid state is kept, prepare graphene oxide/white carbon black/rubber nano composite material in dried solid particulate.The inlet temperature of spray drying unit is set to 100 ~ 350 ℃, and temperature out is 70 ~ 120 ℃; Employed drying medium is warm air, when need introducing the flocculation agent after the gasification, by the throughput ratio of carrier gas, introduces the flocculation agent gas after 1% the gasification in the carrier gas.
(2) mechanical blending method
The mechanical blending method comprises four kinds of situations altogether:
1, will place two roller mills or the Banbury mixer 1 ~ 5min that plasticates by the graphene oxide rubber master batch of emulsion method preparation, add white carbon black and coupling agent then, 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, will place two roller mills or the Banbury mixer 1 ~ 5min that plasticates by the white carbon black rubber master batch of emulsion method preparation, and add graphene oxide and interfacial agents then, blend 1-20min prepares graphene oxide/white carbon black/rubber nano composite material.
3, rubber (dried glue) is placed two roller mills or the Banbury mixer 1 ~ 5min that plasticates, add white carbon black and graphene oxide and interfacial agents through the coupling agent surface modification then, perhaps 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, will place two roller mills or Banbury mixer blend 1-20min by the graphene oxide rubber master batch of emulsion method preparation with by the female rubber of the white carbon black of emulsion method preparation, 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 ℃; Employed drying medium 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.To be 0.1 ~ 400phr(phr be the white carbon black that adds in each hundred parts of rubber and the quality of graphene oxide for 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).Wherein graphene oxide is used to equivalent and partly substitutes white carbon black, and to be 0.05 ~ 20phr(phr be the quality of the graphene oxide that adds in each hundred parts of rubber to the consumption of graphene oxide).
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%, perhaps two or more mixing latex; In the mechanical blending preparation method the 1st, 2 and 4 kind of performance in use in rubber in the rubber master batch and the mechanical blending preparation method epoxy glue that used rubber 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 the silicon rubber, perhaps two or more epoxy glue; Wt% represents mass percent.
The used interfacial agents of the present invention is carboxy terminatedpolybutadiene, aminopropyl triethoxysilane coupling agent, γ-(methacryloxypropyl) propyl trimethoxy silicane coupling agent, quaternary ammonium salt, or solid content be 10～80wt% carboxylic styrene butadiene latex, vinyl-pyridine latex, carboxyl butadiene styrene vinyl pyridine 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).
Used flocculation agent 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 the polymerize aluminum chloride among the present invention; Can introduce flocculation agent in the carrier gas for comprising nitric acid, Hydrogen bromide, hydrofluoric acid, hydrochloric acid and sulfuric acid at vaporized flocculation agent below 350 ℃.
Used coupling agent comprises two-(the silica-based propyl group of γ-triethoxy)-tetrasulfide (Si69) among the present invention; Two-(the silica-based propyl group of γ-triethoxy)-disulphide (Si75); γ-An Bingjisanyiyangjiguiwan (KH-550); γ-(2,3-epoxy, 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.
Used graphene oxide rubber master batch in the present invention, recommend request for utilization people patent of invention " preparation method of graphene oxide/rubber nano composite material of peeling off fully " (application number: the preparation method 201110454000.5) in early stage, in graphene oxide/rubber nano composite material that this method of process prepares, graphene oxide can reach fully to be peeled off, and the degree of scatter height is to obtain the even dispersion on nanoscale; Used white carbon black rubber master batch in the present invention, recommend request for utilization people patent of invention " a kind of preparation method who prepares high dispersive white carbon black/rubber nano composite material " in early stage (application number: in white carbon black/rubber nano composite material that this method of preparation method's process 201210001294.0) prepares, 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, recommend request for utilization people patent of invention " a kind of method for preparing acceptor modified white carbon black " (application number: the treatment process 201110147594.5) in early stage.The white carbon black that processing is in this way obtained, its organic degree is higher, the easier white carbon black finely dispersed matrix material in rubber matrix for preparing.
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 keep 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 kept 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, perhaps just can be easy to prepare high dispersing each other 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 that also preparation technology is simple, cost is low, non-environmental-pollution, is easy to realize large-scale industrial production.
Embodiment:
All processes of operating in solution all need hierarchy of control temperature less than 100 ℃ in following examples.
All gas of introducing in the carrier gas all measures with the volume percent of gas in following examples.
Embodiment 1
Take by weighing the 1g graphite oxide, join in the deionized water of 10kg, behind ultra-sonic dispersion 10min under the power of 0.1kw, make solid content and be 0.01% the graphene oxide water-sol.Take by weighing 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, obtain graphene oxide/white carbon black water-sol behind the stirring 30min.Be 10% styrene-butadiene latex 20kg with above-mentioned graphene oxide/white carbon black water-sol and solid content, under the stirring velocity of 50r/min, obtain stable graphene oxide/white carbon black/styrene-butadiene rubber(SBR) composite emulsion behind the dispersed with stirring 12h.With above-mentioned composite emulsion join under stirring, mass concentration is to flocculate in 1% the calcium chloride solution, stirring velocity is 50r/min, after in mixing solutions, no longer including 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 graphene oxide/white carbon black/butadiene styrene rubber nanometer composite material that the dry sample of finishing namely obtains containing the 0.1phr filler.
Obtain matrix material 100.1g by above-mentioned prepared, the matrix material that obtains in two roller mills, is carried out the mixing rubber unvulcanizate that obtains according to prescription (5 parts in 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 in sulphur).Rubber unvulcanizate is vulcanized the white carbon black/rubber nano composite material that obtains vulcanizating under 150 ℃, sulfurizing time.This nano composite material is carried out every performance test by corresponding national standard.
Embodiment 2
Take by weighing the 20g graphite oxide, join in the deionized water of 100g, ultra-sonic dispersion 6h under the power of 1000kw, while monitoring system temperature is if system temperature is above 80 ℃, so earlier ultrasound procedure is suspended, mixture system is moved under the stirring of 500 r/min, stirs 30min, system temperature is reduced after, proceed ultrasound procedure again, then make solid content and be 20% the graphene oxide water-sol.Take by weighing precipitated silica 380g and two-(the silica-based propyl group of γ-triethoxy)-disulphide 190g, join in the above-mentioned water-sol, ultra-sonic dispersion 6h under the power of 1000kw, while monitoring system temperature is if system temperature is above 80 ℃, so earlier ultrasound procedure is suspended, mixture system is moved under the stirring of 500 r/min, stirs 30min, system temperature is reduced after, proceed ultrasound procedure again, then obtain graphene oxide/white carbon black water-sol.Take by weighing the interfacial agents solid content and be 80% carboxylic styrene butadiene latex 125g, join above-mentioned graphene oxide/white carbon black water-sol, ultra-sonic dispersion 6h under the power of 1000kw, while monitoring system temperature is if system temperature is above 80 ℃, so earlier ultrasound procedure is suspended, mixture system is moved under the stirring of 500 r/min, stirs 30min, system temperature is reduced after, proceed ultrasound procedure again, then obtain through the pretreated graphene oxide of interfacial agents/white carbon black water-sol.With above-mentioned be after 80% styrene-butadiene latex 125g mixes through interfacial agents pretreated graphene oxide/white carbon black water-sol and solid content, ultra-sonic dispersion 6h under the power of 1000kw, while monitoring system temperature, if system temperature surpasses 80 ℃, so earlier ultrasound procedure is suspended, mixture system is moved under the stirring of 500 r/min, stir 30min, after system temperature is reduced, proceed ultrasound procedure again, then obtain stable graphene oxide/white carbon black/styrene-butadiene rubber(SBR) composite emulsion.With above-mentioned composite emulsion join under stirring, mass concentration is to flocculate in 1% the hydrochloric acid soln, stirring velocity is 10000r/min, after in mixing solutions, no longer including 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 graphene oxide/white carbon black/butadiene styrene rubber nanometer composite material that the dry sample of finishing namely obtains containing the 400phr filler.
Obtain matrix material 590g by above-mentioned prepared, the matrix material that obtains in two roller mills, is carried out the mixing rubber unvulcanizate that obtains according to prescription (5 parts in 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 in sulphur).Rubber unvulcanizate is vulcanized the white carbon black/rubber nano composite material that obtains vulcanizating under 150 ℃, sulfurizing time.This nano composite material is carried out every performance test by corresponding national standard.
Embodiment 3
Take by weighing the 5g graphite oxide, join in the deionized water of 500g, ultra-sonic dispersion 2h under the power of 300kw, while monitoring system temperature is if system temperature is above 80 ℃, so earlier ultrasound procedure is suspended, mixture system is moved under the stirring of 300 r/min, stirs 15min, system temperature is reduced after, proceed ultrasound procedure again, then make solid content and be 1% the graphene oxide water-sol.Take by weighing precipitated silica 70g and two-(the silica-based propyl group of γ-triethoxy)-tetrasulfide 5.6g, join in the above-mentioned water-sol, ultra-sonic dispersion 2h under the power of 300kw, while monitoring system temperature is if system temperature is above 80 ℃, so earlier ultrasound procedure is suspended, mixture system is moved under the stirring of 500 r/min, stirs 30min, system temperature is reduced after, proceed ultrasound procedure again, then obtain graphene oxide/white carbon black water-sol.Take by weighing the interfacial agents solid content and be 10% carboxyl butadiene styrene vinyl pyridine latex 200g, join above-mentioned graphene oxide/white carbon black water-sol, ultra-sonic dispersion 3h under the power of 300kw, while monitoring system temperature is if system temperature is above 80 ℃, so earlier ultrasound procedure is suspended, mixture system is moved under the stirring of 500 r/min, stirs 30min, system temperature is reduced after, proceed ultrasound procedure again, then obtain through the pretreated graphene oxide of interfacial agents/white carbon black water-sol.With above-mentioned be after 80% styrene-butadiene latex 125g mixes through interfacial agents pretreated graphene oxide/white carbon black water-sol and solid content, ultra-sonic dispersion 4h under the power of 500kw, while monitoring system temperature, if system temperature surpasses 80 ℃, so earlier ultrasound procedure is suspended, mixture system is moved under the stirring of 500 r/min, stir 30min, after system temperature is reduced, proceed ultrasound procedure again, 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 namely temperature in is 150 ℃, and this moment, temperature out was 80 ℃, by the throughput ratio of carrier gas, introduces 1% HCl gas in carrier gas simultaneously.The sample that collection is finished namely obtains containing the graphene oxide/white carbon black/butadiene styrene rubber nanometer composite material of 75phr filler.
Obtain matrix material 200.6g by above-mentioned prepared, the matrix material that obtains in two roller mills, is carried out the mixing rubber unvulcanizate that obtains according to prescription (5 parts in 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 in sulphur).Rubber unvulcanizate is vulcanized the white carbon black/rubber nano composite material that obtains vulcanizating under 150 ℃, sulfurizing time.This nano composite material is carried out every performance test by corresponding national standard.
Embodiment 4
Take by weighing the 5g graphite oxide, join in the deionized water of 500g, ultra-sonic dispersion 2h under the power of 300kw, while monitoring system temperature is if system temperature is above 80 ℃, so earlier ultrasound procedure is suspended, mixture system is moved under the stirring of 300 r/min, stirs 15min, system temperature is reduced after, proceed ultrasound procedure again, then make solid content and be 1% the graphene oxide water-sol.Take by weighing precipitated silica 50g and γ-mercaptopropyl trimethoxysilane 4g, join in the above-mentioned water-sol, ultra-sonic dispersion 2h under the power of 100kw, while monitoring system temperature is if system temperature is above 80 ℃, so earlier ultrasound procedure is suspended, mixture system is moved under the stirring of 300 r/min, stirs 30min, system temperature is reduced after, proceed ultrasound procedure again, then obtain graphene oxide/white carbon black water-sol.Take by weighing the interfacial agents solid content and be 10% epoxy natural latex 100g, join above-mentioned graphene oxide/white carbon black water-sol, ultra-sonic dispersion 3h under the power of 100kw, while monitoring system temperature is if system temperature is above 80 ℃, so earlier ultrasound procedure is suspended, mixture system is moved under the stirring of 300 r/min, stirs 10min, system temperature is reduced after, proceed ultrasound procedure again, then obtain through the pretreated graphene oxide of interfacial agents/white carbon black water-sol.With above-mentioned be after 50% natural rubber latex 200g mixes through interfacial agents pretreated graphene oxide/white carbon black water-sol and solid content, under the stirring velocity of 10000r/min, obtain stable graphene oxide/white carbon black/styrene-butadiene rubber(SBR) composite emulsion behind the dispersed with stirring 30min.Above-mentioned composite emulsion is carried out through spray drying unit, and drying medium is 100 ℃ of warm airs, and namely temperature in is 100 ℃, and this moment, temperature out was 70 ℃, by the throughput ratio of carrier gas, introduces 1% sulfuric acid gas in carrier gas simultaneously.The sample that collection is finished namely obtains containing the graphene oxide/white carbon black/natural rubber nano composite material of 55phr filler.
Obtain matrix material 169g by above-mentioned prepared, the matrix material that obtains in two roller mills, is carried out the mixing rubber unvulcanizate that obtains according to prescription (5 parts in 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 in sulphur).Rubber unvulcanizate is vulcanized the white carbon black/rubber nano composite material that obtains vulcanizating under 143 ℃, sulfurizing time.This nano composite material is carried out every performance test by corresponding national standard.
Embodiment 5
Take by weighing the 10g graphite oxide, join in the deionized water of 1kg, ultra-sonic dispersion 2h under the power of 500kw, while monitoring system temperature is if system temperature is above 80 ℃, so earlier ultrasound procedure is suspended, mixture system is moved under the stirring of 300 r/min, stirs 30min, system temperature is reduced after, proceed ultrasound procedure again, then make solid content and be 1% the graphene oxide water-sol.Take by weighing the precipitated silica 54g through the γ-An Bingjisanyiyangjiguiwan surface modification, wherein γ-An Bingjisanyiyangjiguiwan content is 4g, joins in the above-mentioned water-sol, under the stirring velocity of 3000r/min, behind the dispersed with stirring 6h, obtain graphene oxide/white carbon black water-sol.Be after 80% natural rubber latex 125g mixes with above-mentioned graphene oxide/white carbon black water-sol and solid content, ultra-sonic dispersion 3h under the power of 300kw, while monitoring system temperature, if system temperature surpasses 80 ℃, so earlier ultrasound procedure is suspended, mixture system is moved under the stirring of 100 r/min, stir 20min, after system temperature is reduced, proceed ultrasound procedure again, 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 namely temperature in is 100 ℃, and this moment, temperature out was 70 ℃.The sample that collection is finished namely obtains containing the graphene oxide/white carbon black/natural rubber nano composite material of 60phr filler.
Obtain matrix material 164g by above-mentioned prepared, the matrix material that obtains in two roller mills, is carried out the mixing rubber unvulcanizate that obtains according to prescription (5 parts in 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 in sulphur).Rubber unvulcanizate is vulcanized the white carbon black/rubber nano composite material that obtains vulcanizating under 143 ℃, sulfurizing time.This nano composite material is carried out every performance test by corresponding national standard.
Embodiment 6
Take by weighing the 5g graphite oxide, join in the deionized water of 500g, ultra-sonic dispersion 2h under the power of 300kw, while monitoring system temperature is if system temperature is above 80 ℃, so earlier ultrasound procedure is suspended, mixture system is moved under the stirring of 300 r/min, stirs 30min, system temperature is reduced after, proceed ultrasound procedure again, then make solid content and be 1% the graphene oxide water-sol.Take by weighing 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, behind the dispersed with stirring 6h, obtain graphene oxide/white carbon black water-sol.Take by weighing the interfacial agents solid content and be 10% vinyl-pyridine latex 200g, join above-mentioned graphene oxide/white carbon black water-sol, ultra-sonic dispersion 3h under the power of 100kw, while monitoring system temperature is if system temperature is above 80 ℃, so earlier ultrasound procedure is suspended, mixture system is moved under the stirring of 300 r/min, stirs 10min, system temperature is reduced after, proceed ultrasound procedure again, then obtain through the pretreated graphene oxide of interfacial agents/white carbon black water-sol.With above-mentioned be that 80% natural rubber latex and solid content are after each 62.5g of styrene-butadiene latex of 80% mixes through interfacial agents pretreated graphene oxide/white carbon black water-sol and solid content, ultra-sonic dispersion 3h under the power of 300kw, while monitoring system temperature, if system temperature is above 80 ℃, so earlier ultrasound procedure is suspended, mixture system is moved under the stirring of 300 r/min, stir 30min, after system temperature is reduced, proceed ultrasound procedure again, 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 namely temperature in is 100 ℃, and this moment, temperature out was 70 ℃.The sample that collection is finished namely obtains containing the graphene oxide/white carbon black/natural rubber nano composite material of 55phr filler.
Obtain matrix material 179g by above-mentioned prepared, the matrix material that obtains in two roller mills, is carried out the mixing rubber unvulcanizate that obtains according to prescription (5 parts in 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 in sulphur).Rubber unvulcanizate is vulcanized the white carbon black/rubber nano composite material that obtains vulcanizating under 143 ℃, sulfurizing time.This nano composite material is carried out every performance test by corresponding national standard.
Embodiment 7
Take by weighing the 8g graphite oxide, join in the deionized water of 500g, ultra-sonic dispersion 3h under the power of 500kw, while monitoring system temperature is if system temperature is above 80 ℃, so earlier ultrasound procedure is suspended, mixture system is moved under the stirring of 300 r/min, stirs 30min, system temperature is reduced after, proceed ultrasound procedure again, then make solid content and be 1.6% the graphene oxide water-sol.Take by weighing through γ-(2,3-epoxy third oxygen) the precipitated silica 54g of propyl trimethoxy silicane surface modification, γ-(2 wherein, 3-epoxy third oxygen) content of propyl trimethoxy silicane is 4g, join in the above-mentioned water-sol, under the stirring velocity of 3000r/min, behind the dispersed with stirring 6h, obtain graphene oxide/white carbon black water-sol.Take by weighing interfacial agents carboxy terminatedpolybutadiene 20g, join above-mentioned graphene oxide/white carbon black water-sol, ultra-sonic dispersion 3h under the power of 600kw, while monitoring system temperature is if system temperature is above 80 ℃, so earlier ultrasound procedure is suspended, mixture system is moved under the stirring of 500 r/min, stirs 20min, system temperature is reduced after, proceed ultrasound procedure again, then obtain through the pretreated graphene oxide of interfacial agents/white carbon black water-sol.With above-mentioned be after 50% butadiene latex 200g mixes through interfacial agents pretreated graphene oxide/white carbon black water-sol and solid content, under the stirring velocity of 8000r/min, behind the 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 namely temperature in is 150 ℃, and this moment, temperature out was 80 ℃, by the throughput ratio of carrier gas, introduces 1% hydrochloric acid gas in carrier gas simultaneously.The sample that collection is finished namely obtains containing the graphene oxide/white carbon black/natural rubber nano composite material of 58phr filler.
Obtain matrix material 182g by above-mentioned prepared, the matrix material that obtains in two roller mills, is carried out the mixing rubber unvulcanizate that obtains according to prescription (5 parts in 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 in sulphur).Rubber unvulcanizate is vulcanized the white carbon black/rubber nano composite material that obtains vulcanizating under 150 ℃, sulfurizing time.This nano composite material is carried out every performance test by corresponding national standard.
Embodiment 8
Take by weighing the 5g graphite oxide, join in the deionized water of 500g, ultra-sonic dispersion 2h under the power of 300kw, while monitoring system temperature is if system temperature is above 80 ℃, so earlier ultrasound procedure is suspended, mixture system is moved under the stirring of 300 r/min, stirs 15min, system temperature is reduced after, proceed ultrasound procedure again, then make solid content and be 1% the graphene oxide water-sol.Take by weighing 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, ultra-sonic dispersion 3h under the power of 300kw, while monitoring system temperature, if system temperature is above 80 ℃, so earlier ultrasound procedure is suspended, mixture system is moved under the stirring of 500 r/min, stir 30min, after system temperature is reduced, proceed ultrasound procedure again, then obtain graphene oxide/white carbon black water-sol.Take by weighing interfacial agents γ-methacryloxypropyl trimethoxy silane 20g, join above-mentioned graphene oxide/white carbon black water-sol, ultra-sonic dispersion 6h under the power of 800kw, while monitoring system temperature is if system temperature is above 80 ℃, so earlier ultrasound procedure is suspended, mixture system is moved under the stirring of 500 r/min, stirs 30min, system temperature is reduced after, proceed ultrasound procedure again, then obtain through the pretreated graphene oxide of interfacial agents/white carbon black water-sol.With above-mentioned be after 80% butylbenzene/natural/butadiene latex 125g mixes through interfacial agents pretreated graphene oxide/white carbon black water-sol and solid content, ultra-sonic dispersion 4h under the power of 500kw, while monitoring system temperature, if system temperature is above 80 ℃, so earlier ultrasound procedure is suspended, mixture system is moved under the stirring of 500 r/min, stir 30min, after system temperature is reduced, proceed ultrasound procedure again, 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 namely temperature in is 150 ℃, and this moment, temperature out was 80 ℃, by the throughput ratio of carrier gas, introduces 1% HCl gas in carrier gas simultaneously.The sample that collection is finished namely obtains containing the graphene oxide/white carbon black/butylbenzene/natural/divinyl rubber nano composite material of 75phr filler.
Obtain matrix material 200.6g by above-mentioned prepared, the matrix material that obtains in two roller mills, is carried out the mixing rubber unvulcanizate that obtains according to prescription (5 parts in 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 in sulphur).Rubber unvulcanizate is vulcanized the white carbon black/rubber nano composite material that obtains vulcanizating under 150 ℃, sulfurizing time.This nano composite material is carried out every performance test by corresponding national standard.
Embodiment 9
Take by weighing the 2g graphite oxide, join in the deionized water of 500g, ultra-sonic dispersion 1h under the power of 300kw, while monitoring system temperature is if system temperature is above 80 ℃, so earlier ultrasound procedure is suspended, mixture system is moved under the stirring of 300 r/min, stirs 30min, system temperature is reduced after, proceed ultrasound procedure again, then make solid content and be 0.4% the graphene oxide water-sol.Take by weighing 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, behind the dispersed with stirring 6h, obtain graphene oxide/white carbon black water-sol.Take by weighing the 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, behind the dispersed with stirring 6h, obtain through the pretreated graphene oxide of interfacial agents/white carbon black water-sol.With above-mentioned be after 50% polychloroprene latex 200g mixes through interfacial agents pretreated graphene oxide/white carbon black water-sol and solid content, under the stirring velocity of 8000r/min, behind the 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 namely temperature in is 200 ℃, and this moment, temperature out was 100 ℃, by the throughput ratio of carrier gas, introduces 1% nitric acid gas in carrier gas simultaneously.The sample that collection is finished namely obtains containing the graphene oxide/white carbon black/chloroprene rubber nano composite material of 52phr filler.
Obtain matrix material 166g by above-mentioned prepared, the matrix material that obtains in two roller mills, is carried out the mixing rubber unvulcanizate that obtains according to prescription (5 parts in zinc oxide, 0.5 part of stearic acid, 4 parts in 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 the white carbon black/rubber nano composite material that obtains vulcanizating under 150 ℃, sulfurizing time.This nano composite material is carried out every performance test by corresponding national standard.
Embodiment 10
Take by weighing the 5g graphite oxide, join in the deionized water of 500g, ultra-sonic dispersion 1h under the power of 300kw, while monitoring system temperature is if system temperature is above 80 ℃, so earlier ultrasound procedure is suspended, mixture system is moved under the stirring of 300 r/min, stirs 30min, system temperature is reduced after, proceed ultrasound procedure again, then make solid content and be 1% the graphene oxide water-sol.Take by weighing 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, behind the dispersed with stirring 6h, obtain graphene oxide/white carbon black water-sol.Take by weighing interfacial agents γ-methacryloxypropyl trimethoxy silane 20g, join above-mentioned graphene oxide/white carbon black water-sol, ultra-sonic dispersion 1h under the power of 300kw, while monitoring system temperature is if system temperature is above 80 ℃, so earlier ultrasound procedure is suspended, mixture system is moved under the stirring of 300 r/min, stirs 30min, system temperature is reduced after, proceed ultrasound procedure again, then obtain through the pretreated graphene oxide of interfacial agents/white carbon black water-sol.With above-mentioned be after 80% isobutylene-isoprene latex 125g mixes through interfacial agents pretreated graphene oxide/white carbon black water-sol and solid content, ultra-sonic dispersion 6h under the power of 800kw, while monitoring system temperature, if system temperature is above 80 ℃, so earlier ultrasound procedure is suspended, mixture system is moved under the stirring of 500 r/min, stir 30min, after system temperature is reduced, proceed ultrasound procedure again, 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 namely temperature in is 200 ℃, and this moment, temperature out was 100 ℃, by the throughput ratio of carrier gas, introduces 1% nitric acid gas in carrier gas simultaneously.The sample that collection is finished namely obtains containing the graphene oxide/white carbon black/butyl rubber nanocomposites of 55phr filler.
Obtain matrix material 179g by above-mentioned prepared, the matrix material that obtains in two roller mills, is carried out the mixing rubber unvulcanizate that obtains according to prescription (5 parts in zinc oxide, 2 parts of stearic acid, 2 parts in 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 in sulphur).Rubber unvulcanizate is vulcanized the white carbon black/rubber nano composite material that obtains vulcanizating under 170 ℃, sulfurizing time.This nano composite material is carried out every performance test by corresponding national standard.
Embodiment 11
Take by weighing the 10g graphite oxide, join in the deionized water of 500g, ultra-sonic dispersion 6h under the power of 300kw, while monitoring system temperature is if system temperature is above 80 ℃, so earlier ultrasound procedure is suspended, mixture system is moved under the stirring of 300 r/min, stirs 30min, system temperature is reduced after, proceed ultrasound procedure again, then make solid content and be 2% the graphene oxide water-sol.Take by weighing 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, behind the dispersed with stirring 6h, obtain graphene oxide/white carbon black water-sol.Take by weighing the interfacial agents solid content and be 80% vinyl-pyridine latex 62.5g, join above-mentioned graphene oxide/white carbon black water-sol, ultra-sonic dispersion 4h under the power of 1000kw, while monitoring system temperature is if system temperature is above 80 ℃, so earlier ultrasound procedure is suspended, mixture system is moved under the stirring of 500 r/min, stirs 30min, system temperature is reduced after, proceed ultrasound procedure again, then obtain through the pretreated graphene oxide of interfacial agents/white carbon black water-sol.With above-mentioned be 50% after the third latex 200g mixes through interfacial agents pretreated graphene oxide/white carbon black water-sol and solid content, under the stirring velocity of 5000r/min, behind the 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 namely temperature in is 350 ℃, and this moment, temperature out was 120 ℃, by the throughput ratio of carrier gas, introduces 1% nitric acid gas in carrier gas simultaneously.The sample that collection is finished namely obtains containing third rubber nano composite material of the graphene oxide/white carbon black of 60phr filler/.
Obtain matrix material 214g by above-mentioned prepared, the matrix material that obtains in two roller mills, is carried out the mixing rubber unvulcanizate that obtains according to prescription (5 parts in zinc oxide, 2 parts of stearic acid, 1 part of protection wax, 30 parts of paraffin oils, 0.2 part of 2 parts of A151, promotor TT, 2 parts of accelerant CZs, 6 parts in sulphur).Rubber unvulcanizate is vulcanized the white carbon black/rubber nano composite material that obtains vulcanizating under 170 ℃, sulfurizing time.This nano composite material is carried out every performance test by corresponding national standard.
Embodiment 12
Take by weighing the 10g graphite oxide, join in the deionized water of 500g, ultra-sonic dispersion 3h under the power of 400kw, while monitoring system temperature is if system temperature is above 80 ℃, so earlier ultrasound procedure is suspended, mixture system is moved under the stirring of 300 r/min, stirs 30min, system temperature is reduced after, proceed ultrasound procedure again, then make solid content and be 2% the graphene oxide water-sol.Take by weighing 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, behind the dispersed with stirring 6h, obtain graphene oxide/white carbon black water-sol.Take by weighing interfacial agents quaternary ammonium salt 20g, join above-mentioned graphene oxide/white carbon black water-sol, ultra-sonic dispersion 4h under the power of 1000kw, while monitoring system temperature is if system temperature is above 80 ℃, so earlier ultrasound procedure is suspended, mixture system is moved under the stirring of 500 r/min, stirs 30min, system temperature is reduced after, proceed ultrasound procedure again, then obtain through the pretreated graphene oxide of interfacial agents/white carbon black water-sol.With above-mentioned be after 80% polyisoprene latex 125g mixes through interfacial agents pretreated graphene oxide/white carbon black water-sol and solid content, ultra-sonic dispersion 6h under the power of 800kw, while monitoring system temperature, if system temperature is above 80 ℃, so earlier ultrasound procedure is suspended, mixture system is moved under the stirring of 500 r/min, stir 30min, after system temperature is reduced, proceed ultrasound procedure again, 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 namely temperature in is 150 ℃, and this moment, temperature out was 80 ℃, by the throughput ratio of carrier gas, introduces 1% hydrochloric acid gas in carrier gas simultaneously.The sample that collection is finished namely obtains containing the graphene oxide/white carbon black/polyisoprene rubber nano composite material of 60phr filler.
Obtain matrix material 184g by above-mentioned prepared, the matrix material that obtains in two roller mills, is carried out the mixing rubber unvulcanizate that obtains according to prescription (5 parts in 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 in sulphur).Rubber unvulcanizate is vulcanized the white carbon black/rubber nano composite material that obtains vulcanizating under 143 ℃, sulfurizing time.This nano composite material is carried out every performance test by corresponding national standard.
Embodiment 13
Take by weighing the 10g graphite oxide, join in the deionized water of 500g, ultra-sonic dispersion 3h under the power of 400kw, while monitoring system temperature is if system temperature is above 80 ℃, so earlier ultrasound procedure is suspended, mixture system is moved under the stirring of 300 r/min, stirs 30min, system temperature is reduced after, proceed ultrasound procedure again, then make solid content and be 2% the graphene oxide water-sol.Take by weighing the thermal silica 77g through the perstearic acid surface modification, wherein stearic acid content is 7g, joins in the above-mentioned water-sol ultra-sonic dispersion 2h under the power of 500kw, while monitoring system temperature, if system temperature surpasses 80 ℃, so earlier ultrasound procedure is suspended, mixture system is moved under the stirring of 300 r/min, stir 15min, after system temperature is reduced, proceed ultrasound procedure again, then obtain graphene oxide/white carbon black water-sol.Take by weighing the interfacial agents solid content and be 50% carboxylic acrylonitrile butadiene rubber latex 40g, join above-mentioned graphene oxide/white carbon black water-sol, ultra-sonic dispersion 4h under the power of 600kw, while monitoring system temperature is if system temperature is above 80 ℃, so earlier ultrasound procedure is suspended, mixture system is moved under the stirring of 500 r/min, stirs 30min, system temperature is reduced after, proceed ultrasound procedure again, then obtain through the pretreated graphene oxide of interfacial agents/white carbon black water-sol.With above-mentioned be after 80% nitrile rubber 125g mixes through interfacial agents pretreated graphene oxide/white carbon black water-sol and solid content, ultra-sonic dispersion 6h under the power of 800kw, while monitoring system temperature, if system temperature surpasses 80 ℃, so earlier ultrasound procedure is suspended, mixture system is moved under the stirring of 500 r/min, stir 30min, after system temperature is reduced, proceed ultrasound procedure again, 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 namely temperature in is 350 ℃, and this moment, temperature out was 120 ℃, by the throughput ratio of carrier gas, introduces 1% hydrochloric acid gas in carrier gas simultaneously.The sample that collection is finished namely obtains containing the graphene oxide/white carbon black/nitrile rubber nanocomposites of 80phr filler.
Obtain matrix material 207g by above-mentioned prepared, the matrix material that obtains in two roller mills, is carried out the mixing rubber unvulcanizate that obtains according to prescription (3 parts in 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 in sulphur).Rubber unvulcanizate is vulcanized the white carbon black/rubber nano composite material that obtains vulcanizating under 170 ℃, sulfurizing time.This nano composite material is carried out every performance test by corresponding national standard.
Embodiment 14
Take by weighing the 10g graphite oxide, join in the deionized water of 500g, ultra-sonic dispersion 3h under the power of 400kw, while monitoring system temperature is if system temperature is above 80 ℃, so earlier ultrasound procedure is suspended, mixture system is moved under the stirring of 300 r/min, stirs 30min, system temperature is reduced after, proceed ultrasound procedure again, then make solid content and be 2% the graphene oxide water-sol.Take by weighing the thermal silica 77g through the perstearic acid surface modification, wherein stearic acid content is 7g, joins in the above-mentioned water-sol ultra-sonic dispersion 2h under the power of 500kw, while monitoring system temperature, if system temperature surpasses 80 ℃, so earlier ultrasound procedure is suspended, mixture system is moved under the stirring of 300 r/min, stir 15min, after system temperature is reduced, proceed ultrasound procedure again, then obtain graphene oxide/white carbon black water-sol.Take by weighing the quaternary ammonium salt of interfacial agents 10g, join above-mentioned graphene oxide/white carbon black water-sol, ultra-sonic dispersion 4h under the power of 600kw, while monitoring system temperature is if system temperature is above 80 ℃, so earlier ultrasound procedure is suspended, mixture system is moved under the stirring of 500 r/min, stirs 30min, system temperature is reduced after, proceed ultrasound procedure again, then obtain through the pretreated graphene oxide of interfacial agents/white carbon black water-sol.With above-mentioned be after 80% fluoroelastomer latex 125g mixes through interfacial agents pretreated graphene oxide/white carbon black water-sol and solid content, ultra-sonic dispersion 6h under the power of 1000kw, while monitoring system temperature, if system temperature surpasses 80 ℃, so earlier ultrasound procedure is suspended, mixture system is moved under the stirring of 500 r/min, stir 30min, after system temperature is reduced, proceed ultrasound procedure again, 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 namely temperature in is 150 ℃, and this moment, temperature out was 120 ℃, by the throughput ratio of carrier gas, introduces 1% hydrofluoric acid gas in carrier gas simultaneously.The sample that collection is finished namely obtains containing the graphene oxide/white carbon black/viton nano composite material of 80phr filler.
Obtain matrix material 197g by above-mentioned prepared, the matrix material that obtains in two roller mills, is carried out the mixing rubber unvulcanizate that obtains according to prescription (1 part of sodium stearate, 5 parts of TAIC, 1 part of 1,4 bis tert butyl peroxy isopropyl benzene).With rubber unvulcanizate at one section 170 ℃, under two sections 230 ℃, vulcanize the white carbon black/rubber nano composite material that obtains vulcanizating under the sulfurizing time.This nano composite material is carried out every performance test by corresponding national standard.
Embodiment 15
Take by weighing the 20g graphite oxide, join in the deionized water of 1000g, ultra-sonic dispersion 4h under the power of 300kw, while monitoring system temperature is if system temperature is above 80 ℃, so earlier ultrasound procedure is suspended, mixture system is moved under the stirring of 300 r/min, stirs 20min, system temperature is reduced after, proceed ultrasound procedure again, then make solid content and be 2% the graphene oxide water-sol.Take by weighing the thermal silica 88g through the silazane surface modification, wherein silazane content is 8g, joins in the above-mentioned water-sol ultra-sonic dispersion 2h under the power of 500kw, while monitoring system temperature, if system temperature surpasses 80 ℃, so earlier ultrasound procedure is suspended, mixture system is moved under the stirring of 300 r/min, stir 15min, after system temperature is reduced, proceed ultrasound procedure again, then obtain graphene oxide/white carbon black water-sol.Take by weighing the aminopropyl triethoxysilane coupling agent of interfacial agents 40g, join above-mentioned graphene oxide/white carbon black water-sol, ultra-sonic dispersion 4h under the power of 600kw, while monitoring system temperature is if system temperature is above 80 ℃, so earlier ultrasound procedure is suspended, mixture system is moved under the stirring of 500 r/min, stirs 30min, system temperature is reduced after, proceed ultrasound procedure again, then obtain through the pretreated graphene oxide of interfacial agents/white carbon black water-sol.With above-mentioned be after 50% silicone rubber latex 200g mixes through interfacial agents pretreated graphene oxide/white carbon black water-sol and solid content, ultra-sonic dispersion 4h under the power of 500kw, while monitoring system temperature, if system temperature surpasses 80 ℃, so earlier ultrasound procedure is suspended, mixture system is moved under the stirring of 300 r/min, stir 30min, after system temperature is reduced, proceed ultrasound procedure again, 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 namely temperature in is 200 ℃, and this moment, temperature out was 100 ℃.The sample that collection is finished namely obtains containing the graphene oxide/white carbon black/silicon rubber nano composite material of 100phr filler.
Obtain matrix material 248g by above-mentioned prepared, the matrix material that obtains in two roller mills, is carried out the mixing rubber unvulcanizate that obtains according to prescription (1.5 parts of DCP).Rubber unvulcanizate is vulcanized the white carbon black/rubber nano composite material that obtains vulcanizating under 160 ℃, sulfurizing time.This nano composite material is carried out every performance test by corresponding national standard.
Embodiment 16
Will be by the graphene oxide rubber master batch 105g of emulsion method preparation, wherein basic glue is the 100g natural rubber, graphene oxide is 5g, place the 1min that plasticates in two roller mills, add the precipitated silica 58g through two-(the silica-based propyl group of γ-triethoxy)-tetrasulfide surface modification then, wherein the content of two-(the silica-based propyl group of γ-triethoxy)-tetrasulfide is 8g, and mixing 8min obtains containing the graphene oxide/white carbon black/natural rubber nano composite material of 55phr filler.
Obtain matrix material 163g by above-mentioned prepared, the matrix material that obtains in two roller mills, is carried out the mixing rubber unvulcanizate that obtains according to prescription (5 parts in 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 in sulphur).Rubber unvulcanizate is vulcanized the white carbon black/rubber nano composite material that obtains vulcanizating under 143 ℃, sulfurizing time.This nano composite material is carried out every performance test by corresponding national standard.
Embodiment 17
Will be by the graphene oxide rubber master batch 125g of emulsion method preparation, wherein basic glue is 100g styrene-butadiene rubber(SBR), graphene oxide is 5g, interfacial agents is the carboxylic styrene-butadiene rubber of 20g, place the Banbury mixer 5min that plasticates, add the precipitated silica 75.6g through two-(the silica-based propyl group of γ-triethoxy)-tetrasulfide surface modification then, wherein the content of two-(the silica-based propyl group of γ-triethoxy)-tetrasulfide is 5.6g, mixing 20min obtains containing the graphene oxide/white carbon black/butadiene styrene rubber nanometer composite material of 75phr filler.
Obtain matrix material 200.6g by above-mentioned prepared, the matrix material that obtains in two roller mills, is carried out the mixing rubber unvulcanizate that obtains according to prescription (5 parts in 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 in sulphur).Rubber unvulcanizate is vulcanized the white carbon black/rubber nano composite material that obtains vulcanizating under 150 ℃, sulfurizing time.This nano composite material is carried out every performance test by corresponding national standard.
Embodiment 18
Will be by the white carbon black rubber master batch 181g of emulsion method preparation, wherein basic glue is 100g styrene-butadiene rubber(SBR), precipitated silica 75g, coupling agent is two-(the silica-based propyl group of γ-triethoxy)-tetrasulfide 6g, place the 5min that plasticates in two roller mills, add graphene oxide 5g then, mixing 20min obtains containing the graphene oxide/white carbon black/butadiene styrene rubber nanometer composite material of 80phr filler.
Obtain matrix material 186g by above-mentioned prepared, the matrix material that obtains in two roller mills, is carried out the mixing rubber unvulcanizate that obtains according to prescription (5 parts in 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 in sulphur).Rubber unvulcanizate is vulcanized the white carbon black/rubber nano composite material that obtains vulcanizating under 150 ℃, sulfurizing time.This nano composite material is carried out every performance test by corresponding national standard.
Embodiment 19
Will be by the white carbon black rubber master batch 155g of emulsion method preparation, wherein basic 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, place the Banbury mixer 3min that plasticates, add graphene oxide 5g then, interfacial agents is the carboxy terminatedpolybutadiene of 10g, mixing 10min obtains containing the graphene oxide/white carbon black/butylbenzene/natural/divinyl rubber nano composite material of 55phr filler.
Obtain matrix material 170g by above-mentioned prepared, the matrix material that obtains in two roller mills, is carried out the mixing rubber unvulcanizate that obtains according to prescription (5 parts in 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 in sulphur).Rubber unvulcanizate is vulcanized the white carbon black/rubber nano composite material that obtains vulcanizating under 150 ℃, sulfurizing time.This nano composite material is carried out every performance test by corresponding national standard.
Embodiment 20
Will be by 100g silicon rubber, place the 5min that plasticates in two roller mills, add graphene oxide 5g then, 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 containing the graphene oxide/white carbon black/silicon rubber nano composite material of 80phr filler.
Obtain matrix material 196g by above-mentioned prepared, the matrix material that obtains in two roller mills, is carried out the mixing rubber unvulcanizate that obtains according to prescription (1.5 parts of DCP).Rubber unvulcanizate is vulcanized the white carbon black/rubber nano composite material that obtains vulcanizating under 160 ℃, sulfurizing time.This nano composite material is carried out every performance test by corresponding national standard.
Embodiment 21
Will be by the white carbon black rubber master batch 131g of emulsion method preparation, wherein basic 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 by the emulsion method preparation, and wherein basic glue is 50g styrene-butadiene rubber(SBR), graphene oxide is 5g, interfacial agents is the carboxylic styrene-butadiene rubber of 20g, places mixing 15min in two roller mills, obtains containing the graphene oxide/white carbon black/butadiene styrene rubber nanometer composite material of 80phr filler.
Obtain matrix material 206g by above-mentioned prepared, the matrix material that obtains in two roller mills, is carried out the mixing rubber unvulcanizate that obtains according to prescription (5 parts in 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 in sulphur).Rubber unvulcanizate is vulcanized the white carbon black/rubber nano composite material that obtains vulcanizating under 150 ℃, sulfurizing time.This nano composite material is carried out every performance test by corresponding national standard.
Embodiment 22
Will be by the white carbon black rubber master batch 104g of emulsion method preparation, wherein basic glue is the 50g paracril, thermal silica 50g, coupling agent stearic acid 4g and the graphene oxide rubber master batch 75g for preparing by emulsion method, wherein basic glue is 50g styrene-butadiene rubber(SBR), graphene oxide is 5g, interfacial agents is the carboxy nitrile rubber of 20g, places the mixing 15min of Banbury mixer, obtains containing the graphene oxide/white carbon black/nitrile rubber nanocomposites of 55phr filler.
Obtain matrix material 179g by above-mentioned prepared, the matrix material that obtains in two roller mills, is carried out the mixing rubber unvulcanizate that obtains according to prescription (3 parts in 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 in sulphur).Rubber unvulcanizate is vulcanized the white carbon black/rubber nano composite material that obtains vulcanizating under 170 ℃, sulfurizing time.This nano composite material is carried out every performance test by corresponding national standard.
Comparative Examples
Comparative Examples is under the same process condition, and the graphene oxide equivalent substitution is returned white carbon black, and removes interfacial agents, and keeps the sample of proportionlity between original coupling agent and the white carbon black.Other fillers and small powder, and the course of processing all remains unchanged.
Concrete outcome is as follows
Table 1 contains each performance data table of graphene oxide and oxygen-free Graphene sample
Below preferred embodiment of the present invention is specified, but the present invention is not limited to described embodiment, those of ordinary skill in the art also can make all modification that is equal to or replacement under the prerequisite of spirit of the present invention, the modification that these are equal to or replacement all are included in the application's claim institute restricted portion.
Claims (4)
1. mechanical blending prepares the method for graphene oxide/white carbon black/rubber nano composite material, it is characterized in that this method comprises following four kinds of performances altogether:
(1) the graphene oxide rubber master batch is placed two roller mills or the Banbury mixer 1 ~ 5min that plasticates, add white carbon black and coupling agent then, 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 is placed two roller mills or the Banbury mixer 1 ~ 5min that plasticates, add graphene oxide and interfacial agents then, blend 1-20min prepares graphene oxide/white carbon black/rubber nano composite material;
(3) rubber is placed two roller mills or the Banbury mixer 1 ~ 5min that plasticates, add white carbon black and graphene oxide and interfacial agents through the coupling agent surface modification then, perhaps 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 two roller mills or Banbury mixer blend 1-20min, prepare graphene oxide/white carbon black/rubber nano composite material.
2. method according to claim 1 is characterized in that white carbon black comprises precipitated silica and thermal silica in prepared graphene oxide/white carbon black/rubber nano composite material; 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. require 1 described method according to profit, it is characterized in that wherein the 1st, 2 and 4 kind of performance in use in rubber in the rubber master batch and the mechanical blending preparation method epoxy glue that used rubber 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 the silicon rubber, perhaps two or more epoxy glue; Wt% represents mass percent.
4. require 1 described method according to profit, two-(the silica-based propyl group of γ-triethoxy)-tetrasulfide that it is characterized in that used coupling agent comprises, two-(the silica-based propyl group of γ-triethoxy)-disulphide, γ-An Bingjisanyiyangjiguiwan, γ-(2,3-epoxy, 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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Cited By (21)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103772760A (en) * | 2014-01-23 | 2014-05-07 | 怡维怡橡胶研究院有限公司 | Rubber composition taking natural rubber/carbon black and synthesized isoprene rubber/white carbon black as rubber master batch and preparation technique thereof |
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| CN103772760A (en) * | 2014-01-23 | 2014-05-07 | 怡维怡橡胶研究院有限公司 | Rubber composition taking natural rubber/carbon black and synthesized isoprene rubber/white carbon black as rubber master batch and preparation technique thereof |
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| CN105175953A (en) * | 2015-09-29 | 2015-12-23 | 中国航空工业集团公司北京航空材料研究院 | Preparation method of graphene oxide micro-restrained fluororubber nanocomposite material |
| CN105175954A (en) * | 2015-09-29 | 2015-12-23 | 中国航空工业集团公司北京航空材料研究院 | Graphene-containing fluororubber nanocomposite with low gas permeability and preparation method |
| CN105400025A (en) * | 2015-12-10 | 2016-03-16 | 北京化工大学 | Acid and alkali resisting chloroprene rubber |
| CN105542228A (en) * | 2016-01-31 | 2016-05-04 | 华南理工大学 | Preparation method of functionalized nano-silica based on graphene |
| CN106317901A (en) * | 2016-08-22 | 2017-01-11 | 广东纳路纳米科技有限公司 | Modified nano composite silicon rubber seal ring and preparation thereof |
| CN106905702A (en) * | 2017-04-11 | 2017-06-30 | 哈尔滨理工大学 | The method for preparing nano modification silicon rubber |
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| CN108794830B (en) * | 2017-04-27 | 2021-07-02 | 中国石油化工股份有限公司 | Rubber composition, vulcanized rubber, and preparation method and application thereof |
| CN107325343B (en) * | 2017-08-10 | 2019-01-04 | 青岛科技大学 | A kind of graphene/rubber composite material preparation method |
| CN107325343A (en) * | 2017-08-10 | 2017-11-07 | 青岛科技大学 | A kind of graphene/rubber composite preparation method |
| CN109081961A (en) * | 2018-08-06 | 2018-12-25 | 三角轮胎股份有限公司 | tire tread rubber composition and preparation method thereof |
| CN111499926A (en) * | 2019-01-31 | 2020-08-07 | 山东欧铂新材料有限公司 | Graphene/white carbon black nano composite material and preparation method thereof |
| CN109867832A (en) * | 2019-03-07 | 2019-06-11 | 江苏康普印刷科技有限公司 | A kind of graphene oxide/nitrile rubber nanocomposite and preparation method thereof |
| CN111218068A (en) * | 2019-04-23 | 2020-06-02 | 烟台桑尼橡胶有限公司 | Formula and preparation process of graphene-containing high-wear-resistance rubber dam and gas shield dam |
| CN110408088A (en) * | 2019-08-13 | 2019-11-05 | 江苏通用科技股份有限公司 | A kind of resistance to puncture and tear-proof tread slab base and preparation method thereof |
| CN110343298A (en) * | 2019-08-19 | 2019-10-18 | 江苏通用科技股份有限公司 | All steel snow tyre tread glue and preparation method thereof |
| CN111253643A (en) * | 2020-03-18 | 2020-06-09 | 泉州市泉石通智能科技有限公司 | Preparation method of graphene oxide reinforced styrene butadiene rubber material |
| CN114316397A (en) * | 2020-09-28 | 2022-04-12 | 中国石油天然气股份有限公司 | Bifunctional polybutadiene rubber/graphene oxide composite material and preparation method thereof |
| CN114316397B (en) * | 2020-09-28 | 2024-03-01 | 中国石油天然气股份有限公司 | Double-functional polybutadiene rubber/graphene oxide composite material and preparation method thereof |
| CN114921004A (en) * | 2022-05-16 | 2022-08-19 | 安徽大学 | Nitrile rubber with high mechanical property and low compression deformation and preparation method thereof |
| CN114921004B (en) * | 2022-05-16 | 2024-04-19 | 安徽大学 | Nitrile rubber with low compression deformation and high mechanical property and preparation method thereof |
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