CN114716737B - Preparation method of silicon dioxide/graphene modified rubber composite material - Google Patents
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Abstract
A preparation method of a silica/graphene modified rubber composite material comprises the following steps: dispersing graphene in a solvent to obtain a graphene dispersion solution, adding an amphiphilic polymer into the graphene dispersion solution to react to obtain a hydrophilic graphene dispersion solution, and performing spray drying to obtain powdery hydrophilic graphene with the surface modified by the amphiphilic polymer; dispersing powdery hydrophilic graphene in a silicon source compound aqueous solution to obtain a graphene-silicon source compound solution, and adjusting the pH value of the graphene-silicon source compound solution until the silicon source compound is hydrolyzed to obtain a mixed filter cake of silicon dioxide graphene-based binary particles; diluting the mixed filter cake into emulsion serving as filler, adding the emulsion into latex to obtain a mixed system, adding a flocculating agent into the mixed system to induce latex to break emulsion to obtain flocculate, and adding a processing aid into the flocculate to obtain the silicon dioxide/graphene modified rubber composite material. The invention increases the mechanical property, the wear resistance and the thermal conductivity of the rubber composite material.
Description
Technical Field
The invention relates to the field of tread rubber composite materials, in particular to a preparation method of a silica/graphene modified rubber composite material.
Background
The tread rubber is one of main components of an aircraft tire, needs to bear high speed and high load, can uniformly transmit static charge to the ground when an airplane takes off and lands, and also needs to timely release heat generated in the sliding process, so that the service condition is very harsh. This requires that the tire tread of the aircraft be designed to take into account not only the factors that are considered in a conventional tire tread, such as: besides the characteristics of wear resistance, wet skid resistance and the like, the tread rubber with more rigorous performance requirements is designed by considering a plurality of complex factors according to the special working environment of the tread rubber.
The graphene has similar reinforcing performance to white carbon black, and can be used as a reinforcing filler of a rubber material. The composite material has the advantages of large specific surface area, small particle size, stable surface chemical property, high possibility of agglomeration in rubber materials and poor reinforcing effect. Proper organic coating of graphene can help to realize high dispersion in rubber.
In recent years, various patent technologies relating to graphene for preparing natural rubber nanocomposites have been disclosed, and can be roughly classified into two main categories: one type is a single filler reinforced rubber: (1) non-covalent bond modification method: under the action of certain temperature and mechanical stirring, a polymer coating layer is formed on the surface of graphene by adopting self-polymerization monomers such as dopamine and the like so as to modify the nano material, and then the nano material is prepared by dry mixing, however, the self-polymerization compound is expensive and not beneficial to industrial production; (2) covalent bond modification method: firstly, preparing nano material emulsion, and introducing a silane coupling agent into the emulsion so as to regulate and control the surface activity of the nano material emulsion, improve the dispersibility of the nano material emulsion in a composite material and improve the comprehensive performance of the composite material, but the silane coupling agent is introduced as a filler, so that various properties of rubber cannot be improved, and certain problems exist in the application of the nano material emulsion in special fields (for example, silicon dioxide can only improve the mechanical properties of the rubber, and has no remarkable improvement effect on the antistatic and heat-conducting properties of the rubber); another class is two or more filler reinforced rubbers: firstly functionalizing each single filler, then preparing hybrid multi-element particles by utilizing the electrostatic adsorption effect or chemical reaction of functional groups on the surface of the modified filler, and utilizing the synergistic reinforcement effect of the hybrid particles to improve the comprehensive performance of the rubber composite material.
Disclosure of Invention
In order to solve the technical problems in the prior art, the invention provides a preparation method of a silica/graphene modified rubber composite material.
In order to achieve the above object, the present invention provides a method for preparing a silica/graphene modified rubber composite, comprising the steps of:
1) Dispersing graphene in a solvent to obtain a graphene dispersion solution, adding an amphiphilic polymer into the graphene dispersion solution to react to obtain a hydrophilic graphene dispersion solution, and performing spray drying on the hydrophilic graphene dispersion solution to obtain powdery hydrophilic graphene with the surface modified by the amphiphilic polymer;
2) Dispersing the powdery hydrophilic graphene obtained in the step 1 into a silicon source compound aqueous solution to obtain a graphene-silicon source compound solution, adjusting the pH value of the graphene-silicon source compound solution until the silicon source compound is hydrolyzed, adding a modifier prepared by mixing an organic silicon modifier and short-chain alkyl alcohol, and washing and filtering to obtain a mixed filter cake of silicon dioxide graphene-based binary particles;
3) Diluting the mixed filter cake obtained in the step 2) into emulsion serving as a filler, adding the emulsion into latex to obtain a mixed system, adding a flocculating agent into the mixed system to induce latex demulsification, or utilizing silicon dioxide/graphene modification to induce latex demulsification to obtain flocculate, adding a processing aid into the flocculate, and then carrying out mixing, sheet discharging, standing and vulcanization treatment to obtain the silicon dioxide/graphene modified rubber composite material.
As a further preferred technical solution of the present invention, step 1) specifically includes:
carrying out high-speed stirring ultrasonic dispersion on graphene in a solvent, wherein the ultrasonic frequency is 200-4000 HZ, the temperature is 25-95 ℃, the ultrasonic time is 0.5-6 h, and the stirring speed is 600-3000 r/min, so as to obtain a graphene dispersion liquid, wherein the solvent is one or a mixture of deionized water, distilled water and ethanol;
introducing an amphiphilic polymer into the graphene dispersion liquid, ultrasonically heating and stirring at a high speed, and reacting for 2-4 h to obtain a hydrophilic graphene dispersion liquid;
and carrying out suction filtration and multiple washing on the obtained hydrophilic graphene dispersion liquid, and carrying out spray drying at the outlet temperature of 70-160 ℃ to obtain powdery hydrophilic graphene.
As a further preferable technical scheme of the invention, the amphiphilic polymer in the step 1) is one or more of polyvinyl alcohol, polyethylene glycol and polyvinyl pyrrolidone containing branched chain oxygen-containing functional group polymers.
As a further preferable technical solution of the present invention, the step 2) specifically includes:
dispersing powdery hydrophilic graphene in a silicon source compound aqueous solution, and ultrasonically stirring for 1-4 hours to obtain a graphene-silicon source compound solution;
mixing an organic silicon modifier and short-chain alkyl alcohol to prepare a modifier;
and under the stirring condition of 30-90 ℃, adjusting the pH value of the graphene-silicon source compound solution until the silicon source compound is hydrolyzed, adding a modifier before or after adjusting the pH value, stirring for 2-4 hours, washing, and performing suction filtration to obtain a mixed filter cake.
As a further preferred technical solution of the present invention, in the step 2), the silicon source compound is one or more of silicate ester, sodium silicate, sodium metasilicate, and silica sol; the organic functional group of the organic silicon modifier is one or more of methyl, ethyl, amido, double bonds and epoxy groups; the short-chain alkyl alcohol is one of monohydric alcohol or polyhydric alcohol of which the alkyl alcohol is C1-C5.
As a further preferable embodiment of the present invention, in the step 2), when the pH is adjusted, one or more of an organic acid, an inorganic acid, an organic amine, ammonia water, an ammonium salt, and the like is added so that the silicon source compound is hydrolyzed.
As a further preferred embodiment of the invention, the pH value is adjusted to 8-10 or 3-4 in step 2).
As a further preferable technical solution of the present invention, the step 3) specifically includes:
diluting the mixed filter cake into emulsion, adding the emulsion into latex, and mechanically stirring to obtain a mixed system;
adding a flocculating agent into the mixed system to induce demulsification, or utilizing silicon dioxide/graphene modification induction to demulsify latex to obtain flocculate;
performing crepe, washing, crushing and drying on the flocculate to obtain a rubber composite material precursor;
adding an accelerator and an anti-aging agent as processing aids into a rubber composite material precursor, uniformly mixing on a double-roll open mill, discharging sheets, placing the mixed rubber, and vulcanizing on a flat vulcanizing machine to finally prepare the silicon dioxide/graphene modified rubber composite material.
As a further preferable technical scheme of the invention, the latex in the step 3) is natural latex or styrene-butadiene latex, or latex obtained by polymerizing monomers in solution/emulsion.
As a further preferable technical scheme of the invention, in the step 1), the concentration of graphene in the hydrophilic graphene dispersion liquid is 0.5-3 g/L, and the mass ratio of the graphene to the amphiphilic polymer is 1-20%; in the step 2), the dosage of the silicon source compound is calculated by silicon dioxide, the mass concentration of the silicon dioxide in the graphene-silicon source compound solution is 6-12 g/L, and the mass ratio of the silicon dioxide to the graphene to the organic silicon modifier and the short-chain alkyl alcohol added during the hydrolysis reaction is 1:0.03 to 2.11:0.03 to 0.4:0.04 to 0.4; the dilution concentration of the filter cake in the step 3) is 8-20 g/L.
In the method, the realization of the assistant dispersion of the silicon dioxide to the graphene is the key for preparing the silicon dioxide graphene-based binary particles, the silicon source compound aqueous solution is selected as the assistant dispersing agent and the stripping agent, and the nano-scale silicon dioxide is grown in situ on the surface or between layers of the graphene modified with the amphiphilic polymer, so that the silicon dioxide is functionalized, and the dispersibility of the graphene is further improved.
According to the invention, a silicon source compound aqueous solution is selected as an auxiliary dispersing agent and a stripping agent, so that the surface property and the surface polarity of graphene are effectively regulated and controlled, and the produced nanoscale silicon dioxide and the graphene are mutually dispersed, so that the agglomeration of nano-filler is weakened, and the synergistic reinforcement effect is obvious. Due to the functionalization of the silicon dioxide, the affinity of the silicon dioxide with a nonpolar rubber material is greatly improved. Under the action of two-phase mixing and mechanical stirring, the silica graphene-based binary particles can peel the emulsifier from the surface of the rubber molecular chain and adsorb the emulsifier on the surface of the rubber molecular chain, so that a filler-rubber network structure is quickly formed, and the demulsification of the rubber emulsion is caused.
By adopting the technical scheme, the preparation method of the silicon dioxide/graphene modified rubber composite material can achieve the following beneficial effects:
1) The preparation method disclosed by the invention is combined with the surface pretreatment or in-situ modification interface strengthening technology of graphene and silicon dioxide to realize the preparation of silicon dioxide loaded graphene, and is combined with the regulation and control of interface performance to improve the dispersibility of graphene in latex, so that the mechanical property, the wear resistance and the thermal conductivity of the silicon dioxide/graphene modified rubber composite material are remarkably improved, and the problem of tire static accumulation is favorably solved by applying the silicon dioxide/graphene modified rubber composite material disclosed by the invention to tires;
2) According to the preparation method, the silicon dioxide grows on the surface of the graphene in situ, and a liquid-phase in-situ surface modification technology is utilized, so that the large-scale preparation of the high-dispersion silicon dioxide graphene-based binary particles can be realized, namely, a green high-performance easily-dispersed loaded graphene type silicon dioxide preparation technology can be innovatively developed through the nanometer structure effects of system coordination of material component size, morphology, interface, limited domain and the like;
3) According to the invention, the silicon dioxide graphene-based binary particle filler has better affinity with natural rubber by regulating and controlling the modification group, the flocculation purpose (latex is demulsified and flocculated by utilizing silicon dioxide/graphene modification induction) can be achieved by adsorbing a natural rubber molecular chain in the emulsion, and the flocculation is thorough, so that a flocculating agent is not used in the process, the mixing energy consumption is reduced, and the dust emission and loss of graphene are reduced, thereby improving the graphene reinforcing effect; in addition, when the flocculating agent is not used for flocculation, the problem of water pollution in a creping and washing process can be avoided, the environment is friendly, and the corrosion of the flocculating agent to equipment is reduced.
Drawings
The present invention will be described in further detail with reference to the accompanying drawings and specific embodiments.
Fig. 1 is a scanning electron microscope image of graphene dry powder and silica graphene-based binary particles in example 1;
FIG. 2 is a scanning electron micrograph of the samples obtained in examples 1 to 4.
The objects, features and advantages of the present invention will be further explained with reference to the accompanying drawings.
Detailed Description
The invention will be further described with reference to the accompanying drawings and specific embodiments. In the preferred embodiments, the terms "upper", "lower", "left", "right", "middle" and "a" are used for clarity of description only, and are not used to limit the scope of the invention, and the relative relationship between the terms and the terms is not changed or modified substantially without changing the technical content of the invention.
Example 1
Taking out dry graphene powder, 5phr of ethanol and 2phr of polyvinylpyrrolidone based on 100phr of the content of the dry graphene powder (shown in figure 1 (a)), adding 3900phr of distilled water, ultrasonically stirring for 3 hours, and performing suction filtration, multiple times of washing and drying to obtain functionalized graphene with a surface modified with polyvinylpyrrolidone, namely powdered hydrophilic graphene;
according to the content of the functionalized graphene dry powder of 12phr, 1278phr of sodium silicate (n = 3.2) and 1566phr of distilled water are taken, the temperature is raised to 68 ℃, and the mixture is stirred for 20min to obtain a graphene-sodium silicate aqueous solution; stirring at the rotating speed of 600rad/min, slowly dropwise adding a dilute sulfuric acid solution (wt = 20%) into a graphene-sodium silicate aqueous solution until the pH of the solution is =8-9, then heating to 80 ℃ and keeping the temperature constant for 3 hours, then slowly adding 72phr of a modifier (gamma-glycidyl ether oxypropyl trimethoxysilane: ethanol = 1) into a reaction system, continuously reacting for 2 hours at the constant temperature after the modifier is completely added, carrying out suction filtration on the reaction solution, washing for multiple times, and drying to obtain silica graphene-based binary particles (see (b) in fig. 1), namely a mixed filter cake;
taking 50phr of prepared silica graphene-based binary particles, calculated by the dry glue content of 100phr in the concentrated latex, adding the silica graphene-based binary particles into 200phr of distilled water, ultrasonically stirring for 20min, preparing a silica graphene-based binary particle water solution with 20% of solid content, pumping the prepared silica graphene-based binary particle water solution and the concentrated latex (the dry glue content is 61%) at 164g under the condition of 25 ℃, controlling the flow (being adjustable according to actual conditions) and simultaneously pumping the obtained solution into a reaction kettle to form a mixed system, stirring for 5min at the rotating speed of 400rad/min, and performing modification induction by using silica/graphene to flocculate the latex to obtain a composite micelle (flocculate); and (4) carrying out crepe, washing, crushing and drying on the flocculate to obtain the rubber composite material precursor.
100phr of rubber composite precursor, 5phr of Si69, 5phr of zinc oxide, 3phr of stearic acid, 1.5phr of microcrystalline wax, 1.5phr of anti-aging agent 4020.5 phr, 1.5phr of accelerator CZ, 2phr of accelerator D and 1.5phr of sulfur are mixed and placed for vulcanization under the conditions of 12h,160 ℃ multiplied by 20MPa multiplied by Tc90 to obtain a sample, namely the silicon dioxide/graphene modified rubber composite material, and the mechanical property, the heat conduction antistatic property and the results are shown in tables 1 and 2.
Referring to fig. 1, comparing (a) and (b), it can be seen that the silicon dioxide is uniformly loaded on the surface and between the layers of the graphene, and further functionalizes the silicon dioxide.
Example 2
Taking out dry graphene powder, 5phr of ethanol and 2phr of polyvinylpyrrolidone, adding the dry graphene powder, the 5phr of ethanol and the 2phr of polyvinylpyrrolidone into 3900phr of distilled water, performing ultrasonic stirring for 3 hours, performing suction filtration, washing for multiple times and drying to obtain functionalized graphene with the surface modified with the polyvinylpyrrolidone, namely powdered hydrophilic graphene;
taking 639phr of sodium silicate (n = 3.2) and 783phr of distilled water according to the content of the functionalized graphene dry powder of 12phr, heating to 70 ℃, and stirring for 20min to obtain a graphene-sodium silicate aqueous solution; stirring at the rotating speed of 600rad/min, slowly dropwise adding a dilute sulfuric acid solution (wt = 20%) into a graphene-sodium silicate aqueous solution until the pH of the solution is =8-10, then heating to 80 ℃, keeping the temperature constant for 3 hours, then slowly adding 36phr of a modifier (gamma-glycidyl ether oxypropyl trimethoxysilane: ethanol = 1) into a reaction system, continuously reacting for 2 hours at the constant temperature after the modifier is completely added, carrying out suction filtration on the reaction solution, washing for multiple times, and drying to obtain a mixed filter cake of silica graphene-based binary particles;
taking 50phr of prepared silica-graphene-based binary particles according to the dry glue content of 100phr in the concentrated latex, adding the silica-graphene-based binary particles into 200phr of distilled water, ultrasonically stirring for 20min, preparing a 20% solid content silica-graphene-based binary particle aqueous solution, pumping the aqueous solution and the concentrated latex (the dry glue content is 61%) 164g at 25 ℃, controlling the flow (being adjustable according to actual conditions), simultaneously pumping the aqueous solution and the concentrated latex into a reaction kettle, stirring for 7min at the rotating speed of 300rad/min, adding a proper amount of acid into a system after uniform mixing to demulsify the aqueous solution and obtain a composite micelle (floc); and (4) carrying out crepe, washing, crushing and drying on the flocculate to obtain the rubber composite material precursor.
100phr of rubber composite material precursor, 5phr of Si69, 5phr of zinc oxide, 3phr of stearic acid, 1.5phr of microcrystalline wax, 1.5phr of anti-aging agent 4020.5 phr, 1.5phr of accelerator CZ, 2phr of accelerator D and 1.5phr of sulfur are mixed and placed for vulcanization under the conditions of 12h,160 ℃ multiplied by 20MPa multiplied by Tc90 to obtain a sample, namely the silicon dioxide/graphene modified rubber composite material, and the mechanical property and the heat conduction antistatic property are tested, and the results are shown in tables 1 and 2.
Example 3
Adding 5phr of ethanol and 2phr of polyvinylpyrrolidone into 3900phr of distilled water according to 100phr of the content of the graphene dry powder, ultrasonically stirring for 3 hours, performing suction filtration, washing for multiple times, and drying to obtain functionalized graphene with the surface modified with the polyvinylpyrrolidone, namely powdery hydrophilic graphene;
taking 319.5phr of sodium silicate (n = 3.2) and 391.5phr of distilled water according to the content of the functionalized graphene dry powder of 12phr, heating to 69 ℃, and stirring for 20min to obtain a graphene-sodium silicate aqueous solution; stirring at the rotating speed of 600rad/min, slowly dropwise adding a dilute sulfuric acid solution (wt = 20%) into a graphene-sodium silicate aqueous solution until the pH of the solution is =8-10, then heating to 80 ℃, keeping the temperature constant for 3 hours, slowly adding 18phr of a modifier (gamma-glycidyl ether oxypropyl trimethoxysilane: ethanol = 1) into a reaction system, continuously reacting for 2 hours at the constant temperature after the modifier is completely added, and carrying out suction filtration, multiple washing and drying on the reaction solution to obtain a mixed filter cake of silica graphene-based binary particles;
taking 50phr of prepared silicon dioxide graphene-based binary particles based on 100phr of dry glue content in the concentrated latex, adding the silicon dioxide graphene-based binary particles into 200phr of distilled water, and preparing a silicon dioxide graphene-based binary particle aqueous solution with 20% of solid content after ultrasonic stirring for 20 min; 164g with concentrated latex (the dry glue content is 61 percent), pumping into a reaction kettle at the same time of controlling the flow (being adjustable according to the actual condition) under the condition of 25 ℃, stirring for 6min at the rotating speed of 400rad/min, and performing emulsion breaking and flocculation on the latex by utilizing the modification induction of silicon dioxide/graphene to obtain a composite micelle (flocculate); and (4) carrying out crepe, washing, crushing and drying on the flocculate to obtain the rubber composite material precursor.
100phr of rubber composite precursor, 5phr of Si69, 5phr of zinc oxide, 3phr of stearic acid, 1.5phr of microcrystalline wax, 1.5phr of anti-aging agent 4020.5 phr, 1.5phr of accelerator CZ, 2phr of accelerator D and 1.5phr of sulfur are mixed and placed for vulcanization under the conditions of 12h,160 ℃ multiplied by 20MPa multiplied by Tc90, so that a sample, namely the silicon dioxide/graphene modified rubber composite material is obtained, and the mechanical property, the heat conduction antistatic property and the results are shown in tables 1 and 2.
Example 4
Adding 5phr of ethanol and 2phr of polyvinylpyrrolidone into 3900phr of distilled water according to 100phr of the content of the graphene dry powder, ultrasonically stirring for 3 hours, performing suction filtration, washing for multiple times, and drying to obtain functionalized graphene with the surface modified with the polyvinylpyrrolidone, namely powdery hydrophilic graphene;
taking 159.75phr of sodium silicate (n = 3.2) and 195.75phr of distilled water according to the content of the functionalized graphene dry powder of 12phr, heating to 68 ℃, and stirring for 20min to obtain a graphene-sodium silicate aqueous solution; stirring at the rotating speed of 600rad/min, slowly dropwise adding a dilute sulfuric acid solution (wt = 20%) into a graphene-sodium silicate aqueous solution until the pH of the solution is =8-10, then heating to 80 ℃, keeping the temperature constant for 3 hours, slowly adding 9phr of a modifier (gamma-glycidyl ether oxypropyl trimethoxysilane: ethanol = 1) into a reaction system, continuously reacting for 2 hours at the constant temperature after the modifier is completely added, and carrying out suction filtration, multiple washing and drying on the reaction solution to obtain a mixed filter cake of silica graphene-based binary particles;
taking 50phr of prepared silicon dioxide graphene-based binary particles based on 100phr of dry glue content in the concentrated latex, adding the silicon dioxide graphene-based binary particles into 200phr of distilled water, and preparing a silicon dioxide graphene-based binary particle aqueous solution with 20% of solid content after ultrasonic stirring for 20 min; 164g with concentrated latex (the dry glue content is 61 percent), pumping into a reaction kettle at the same time of controlling the flow (being adjusted according to the actual condition) under the condition of 25 ℃, stirring for 8min at the rotating speed of 200rad/min, adding a proper amount of acid into a system after uniform mixing to be used as a flocculating agent to break the emulsion, and obtaining a composite micelle (flocculate); performing crepe, washing, crushing and drying on the flocculate to obtain a rubber composite material precursor;
100phr of rubber composite precursor, 5phr of Si69, 5phr of zinc oxide, 3phr of stearic acid, 1.5phr of microcrystalline wax, 1.5phr of anti-aging agent 4020.5 phr, 1.5phr of accelerator CZ, 2phr of accelerator D and 1.5phr of sulfur are mixed and placed for vulcanization under the conditions of 12h,160 ℃ multiplied by 20MPa multiplied by Tc90 to obtain a sample, namely the silicon dioxide/graphene modified rubber composite material, and the mechanical property, the heat conduction antistatic property and the results are shown in tables 1 and 2.
Comparative example 1
Mixing graphene oxide with water to obtain a graphene oxide solution, and further performing ultrasonic dispersion in an ultrasonic instrument at the ultrasonic frequency of 1000HZ and the temperature of 25 ℃ for 0.5h to obtain a graphene oxide solution with the concentration of 1 mg/ml; mixing ethyl orthosilicate and ethanol in a mass ratio of 1:20 to obtain a mixed solution. Stirring with a magnetic stirrer at 30 deg.C for 0.5h; and (3) oxidizing the graphene by using the mixed solution of the aqueous solution of the graphene oxide and tetraethoxysilane: adding ethyl orthosilicate into the mixture according to a mass ratio of 1: adding a surfactant into hexadecyl trimethyl ammonium bromide according to a mass ratio of 1; repeatedly soaking the obtained graphene oxide/silicon dioxide gel in ethanol for 3 times; placing the graphene oxide/silicon dioxide liquid gel repeatedly soaked by the ethanol at room temperature for aging for 1 day; placing the graphene oxide/silicon dioxide liquid gel in a vacuum drying oven, and vacuumizing and drying for 5 hours at the temperature of 25 ℃; and crushing the obtained graphene/silicon dioxide composite material to obtain a powdery composite material, and adding the powdery composite material into a natural rubber material to obtain a rubber composite material precursor. 100phr of the obtained rubber composite precursor, 5phr of zinc oxide, 2phr of stearic acid, 1phr of microcrystalline wax, 3phr of anti-aging agent 4010NA, 1.5phr of accelerator CZ, 1.2phr of accelerator D1.2phr and 1.5phr of sulfur are mixed and vulcanized under the conditions of being parked at 12h,160 ℃ multiplied by 20MPa multiplied by Tc90, so as to obtain a comparison sample, and the mechanical properties of the comparison sample are tested, and the results are shown in Table 2.
TABLE 1 volume resistivity and thermal conductivity of the samples obtained in examples 1-4
TABLE 2 mechanical properties of the samples obtained in examples 1 to 4 and the comparative sample obtained in comparative example 1
As can be seen from Table 2, compared with the comparative sample prepared by the prior art, the sample prepared by the invention basically shows consistent tensile strength and elongation at break, particularly tear strength, and the invention is obviously higher than the prior art, so that the performance of the tire is greatly improved when the silica/graphene modified rubber composite material is applied to the tire.
The method for preparing the silica graphene-based binary particles in the method is a liquid-phase in-situ method, the problem that graphene is difficult to disperse and easy to agglomerate in latex serving as a rubber matrix is solved by the liquid-phase in-situ method, and as can be seen from fig. 2 ((a) - (d) correspond to samples obtained in examples 1-4 in sequence), graphene does not agglomerate in the latex and is uniformly dispersed in the rubber matrix; meanwhile, the problem of tearing and peeling of graphene is solved, and the interface combination of the filler and the rubber is further improved, so that the rubber composite material has a good application effect. The silica graphene-based binary particles can improve the mechanical property, the heat conduction property and the electric conduction property of the rubber composite material, and as can be seen from tables 1 and 2, the tensile strength of the silica graphene-based binary particles can reach more than 24MPa, the elongation at break is more than 400%, particularly, the tearing strength can reach 100KN/m, in addition, the volume resistivity of a sample prepared in the embodiment 4 reaches 1.7 multiplied by 109 omega cm, the antistatic requirement is met, the heat conduction coefficient is 0.483W/mK, and compared with pure rubber, the heat conduction capability is improved by 260%, namely, the heat dissipation capability of the material is obviously improved, and a basis is provided for the optimal scheme of the invention, namely the design of a high-performance tire tread rubber material and the preparation of a high-efficiency binary filler.
Although specific embodiments of the present invention have been described above, it will be appreciated by those skilled in the art that these are merely examples and that many variations or modifications may be made to the embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims.
Claims (6)
1. A preparation method of a silica/graphene modified rubber composite material is characterized by comprising the following steps:
1) Carrying out high-speed stirring and ultrasonic dispersion on graphene in a solvent, wherein the ultrasonic frequency is 200-4000 Hz, the temperature is 25-95 ℃, the ultrasonic time is 0.5-6 h, and the stirring speed is 600-3000 r/min, so as to obtain a graphene dispersion liquid, wherein the solvent is one or a mixture of deionized water, distilled water and ethanol; introducing an amphiphilic polymer into the graphene dispersion liquid, ultrasonically heating, stirring at a high speed, and reacting for 2 to 4 hours to obtain a hydrophilic graphene dispersion liquid; carrying out suction filtration and multiple washing on the obtained hydrophilic graphene dispersion liquid, and carrying out spray drying at an outlet temperature of 70-160 ℃ to obtain powdery hydrophilic graphene with the surface modified by an amphiphilic polymer;
2) Dispersing powdery hydrophilic graphene in a silicon source compound aqueous solution, and ultrasonically stirring for 1 to 4 hours to obtain a graphene-silicon source compound solution; mixing an organic silicon modifier and short-chain alkyl alcohol to prepare a modifier; adjusting the pH value of the graphene-silicon source compound solution under the stirring condition of 30-90 ℃ until the silicon source compound is hydrolyzed, adding a modifier before or after adjusting the pH value, stirring for 2-4 hours, washing, and performing suction filtration to obtain a mixed filter cake;
3) Diluting the mixed filter cake into emulsion, adding the emulsion into latex, and mechanically stirring to obtain a mixed system; adding a flocculating agent into the mixed system to induce demulsification, or utilizing silicon dioxide/graphene modification induction to demulsify latex to obtain flocculate; performing crepe, washing, crushing and drying on the flocculate to obtain a rubber composite material precursor; adding an accelerator and an anti-aging agent as processing aids into a rubber composite material precursor, uniformly mixing on a double-roll open mill, discharging, standing the mixed rubber, and vulcanizing on a flat vulcanizing machine to finally prepare the silicon dioxide/graphene modified rubber composite material;
in the step 1), the concentration of graphene in the hydrophilic graphene dispersion liquid is 0.5-3g/L, and the mass ratio of the graphene to the amphiphilic polymer is 1-20%; in the step 2), the dosage of the silicon source compound is calculated by silicon dioxide, the mass concentration of the silicon dioxide in the graphene-silicon source compound solution is 6-12g/L, and the mass ratio of the silicon dioxide to the graphene to the organic silicon modifier and the short-chain alkyl alcohol added during the hydrolysis reaction is 1:0.03 to 2.11:0.03 to 0.4:0.04 to 0.4; in the step 3), the dilution concentration of the mixed filter cake is 8-20g/L.
2. The method for preparing a silica/graphene-modified rubber composite according to claim 1, wherein the amphiphilic polymer in the step 1) is one or more of polyvinyl alcohol, polyethylene glycol, and polyvinyl pyrrolidone containing a branched polymer having an oxygen functional group.
3. The method for preparing a silica/graphene-modified rubber composite according to claim 1, wherein in the step 2), the silicon source compound is one or more of silicate ester, sodium silicate, sodium metasilicate, and silica sol; the organic functional group of the organic silicon modifier is one or more of methyl, ethyl, amido, double bond and epoxy; the short-chain alkyl alcohol is alkyl alcohol which is monohydric alcohol or polyhydric alcohol in C1-C5.
4. The method of claim 1, wherein the silicon source compound is hydrolyzed by adding one or more of organic acid, inorganic acid, organic amine, ammonia water, and ammonium salt when adjusting the pH in step 2).
5. The method for preparing a silica/graphene-modified rubber composite according to claim 1, wherein the pH is adjusted to 8 to 10 or 3 to 4 in the step 2).
6. The method for preparing a silica/graphene-modified rubber composite according to claim 1, wherein the latex in the step 3) is natural latex or styrene-butadiene latex, or latex obtained by polymerizing monomers in solution/emulsion.
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