CN113462040A - Preparation method of graphene-silicon dioxide modified natural rubber composite material with high thermal conductivity and excellent low-thermophysical property for tire - Google Patents
Preparation method of graphene-silicon dioxide modified natural rubber composite material with high thermal conductivity and excellent low-thermophysical property for tire Download PDFInfo
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Abstract
The invention relates to the field of functional natural rubber composite materials, in particular to a preparation method of a graphene-silicon dioxide modified natural rubber composite material with high heat conductivity and low thermal-mechanical property for a tire; using GO water dispersion and SiO2Particles and Natural Rubber (NR) latex are used as raw materials, and organic compounds and GO are adopted to modify SiO twice2The GO-doped glass is prepared in the common water phase by using a latex coprecipitation methodSiO2A modified NR composite material. Not only can reduce the number of mixing segments and mixing time in the rubber preparation process, reduce mixing energy consumption and reduce dust pollution, but also can improve GO-SiO2The dispersion in a rubber matrix is improved, and GO-SiO is improved2The rubber composite material has the advantages that the rubber composite material has an interface interaction with a rubber matrix, so that the mechanical property of the finally prepared rubber composite material is obviously improved; meanwhile, frictional heat generation between the filler and the matrix and interface thermal resistance between the filler and the matrix can be reduced, and temperature rise of the tire in the driving process is reduced, so that the thermal aging speed of the rubber tire in the dynamic use process is reduced, and the service life of the rubber tire is prolonged.
Description
Technical Field
The invention relates to the field of functional natural rubber composite materials, in particular to a preparation method of a graphene-silicon dioxide modified natural rubber composite material with high heat conductivity and excellent low thermophysical properties for a tire.
Background
The natural rubber is considered as a strategic resource, has irreplaceable effects in industry, has high elasticity, high strength, high insulating property and the like, has special mechanical properties due to excellent performance, and has wide application. Statistically, there are over 70000 types of rubber articles common worldwide today, with as many as 40000 types of natural rubber being used. In common rubber products, such as tires for large airplanes, tires for engineering machinery, tires for large trucks, and building vibration isolators, natural rubber plays an irreplaceable role as synthetic rubber.
The running distance of a general pneumatic tire is 5 to 10 kilometers, the running distance of a general pneumatic load-carrying tire is about 3 kilometers, and the running distance of a solid load-carrying tire is about 1 kilometer. Rubber tires are subjected to alternating stresses during running; the tyre deforms complexly under the action of alternating external force, and during the continuous energy storage and release process, the tyre has the functions of buffering impact and damping vibration, and meanwhile, part of energy is converted into heat energy due to the internal friction of rubber, so that the temperature of the tyre is raised. The aging of the rubber is greatly accelerated by the increase of the working temperature, the service life of the tire is shortened, and when the internal temperature of the tire exceeds the damage temperature limit of the rubber, the tire is thermally damaged, namely, the natural rubber subjected to an overheating environment can generate phenomena such as blasting, bursting and the like due to accelerated aging. Therefore, the rubber tire has the advantages of reducing the compression fatigue heat generation of the rubber tire, improving the heat conductivity of the rubber material, improving the distribution of the tire section temperature field and being beneficial to improving the durability of the rubber tire.
The heat generation of the rubber tire is mainly caused by filler-filler friction, filler-rubber friction, and rubber-rubber friction. Therefore, there is a need to reduce the heat accumulation inside the tire in both terms of reducing the internal heat generation of the natural rubber composite and increasing the thermal conductivity of the natural rubber composite. The dispersibility of the filler in the matrix is improved, the interaction between the filler and the matrix is enhanced, and the friction between the filler and the dynamic friction between the filler and the matrix can be respectively reduced. Meanwhile, the enhanced interface interaction between the filler and the matrix can effectively reduce the thermal interface resistance between the filler and the matrix, thereby improving the thermal conductivity of the rubber material. Therefore, improving the filler-matrix interfacial interaction is key to achieving both high thermal conductivity and low heat build-up in rubber tires.
The graphene oxide has excellent physical, chemical and electrical properties, and due to a large number of oxygen-containing functional groups contained on the surface of the graphene oxide, active sites are provided for surface modification of the graphene oxide, so that the graphene oxide has good dispersibility in water and further functionalization conditions. Meanwhile, the carbon ring structure in the graphene oxide contains a large amount of pi electrons, and the double bonds in the molecular chain of the natural rubber also contain a large amount of pi electrons, so that the graphene oxide and the natural rubber are easy to adsorb each other due to pi-pi conjugation and hydrogen bonding, and the graphene oxide has good dispersibility in the natural rubber latex.
Among the techniques for preparing natural rubber/filler masterbatches, the emulsion blending method has significant advantages, such as the reduction of the number of mixing stages in the preparation process, the realization of a continuous mixing process, the shortening of mixing time, the reduction of mixing energy consumption, the reduction of dust pollution and the like. In addition, the method can also effectively improve the dispersion of the filler in the rubber matrix and the interface interaction between the filler and the rubber matrix, and the shorter mixing time is also beneficial to maintaining the molecular weight of rubber molecular chains and ensuring the performance of the rubber composite material. The emulsion blending method is mainly developed aiming at rubber varieties with emulsion forms, and is different from the traditional method in that the emulsion blending method requires that the modification process of the filler is carried out in a water phase, meanwhile, the rubber is suspended in water in a microsphere state, the filler water slurry and the latex are uniformly mixed, and then the rubber and the filler are co-flocculated in a flocculation mode to obtain the rubber/filler composite material.
Disclosure of Invention
The invention overcomes the defects of the prior art, and provides a preparation method of a graphene-silicon dioxide modified natural rubber composite material with high heat conduction and low raw thermal mechanical property for a tire. Thereby slowing down the thermal aging speed of the rubber tire in the dynamic use process and prolonging the service life of the rubber tire.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows: a preparation method of a graphene-silicon dioxide modified natural rubber composite material with high thermal conductivity and excellent low raw thermal mechanical property for a tire comprises the following steps:
preparation of silicon dioxide with aminated surface: fully hydrolyzing an amino-containing silane coupling agent in an alcohol-water solution, and then adding silicon dioxide into the amino-containing silane coupling agent for reaction, so that the silanol after hydrolysis of the silane coupling agent and the hydroxyl on the surface of the silicon dioxide are subjected to dehydration reaction;
preparing graphene oxide-silicon dioxide compound particles: under the condition of ice-water bath, adding a proper amount of activating agent and catalyst into the graphene oxide dispersion liquid, stirring, then adding the silicon dioxide dispersion liquid with aminated surface obtained in the step I, after reaction, washing with water for many times to remove the unreacted activating agent and catalyst, and carrying out freeze drying treatment to obtain graphene oxide-silicon dioxide compound particles;
preparing the graphene oxide-silicon dioxide modified natural rubber with high heat conductivity and excellent low raw thermal mechanical property: preparing the graphene oxide-silicon dioxide obtained in the step two and deionized water into a dispersion solution, adding the dispersion solution into the natural rubber latex, and stirring to obtain a uniformly dispersed mixed emulsion; then adding one of calcium chloride solution, sodium chloride solution, potassium chloride solution, sodium sulfate solution, hydrochloric acid solution and formic acid solution into the mixed emulsion to make the mixed emulsion break emulsion and flocculate; and placing the raw rubber without the flocculating agent in an oven for drying to constant weight to obtain the graphene oxide-silicon dioxide modified natural rubber composite material with high heat conductivity and excellent low raw thermal mechanical property.
Further, the silane coupling agent containing amino is one of gamma-aminopropyltriethoxysilane, gamma-aminopropyltrimethoxysilane, phenylaminomethyltriethoxysilane, phenylaminomethyltrimethoxysilane, N-theta (aminoethyl) -gamma-aminopropyltrimethoxysilane, N-theta (aminoethyl) -gamma-aminopropyldimethoxysilane, N-theta (aminoethyl) -gamma-aminopropyltriethoxysilane and N-theta (aminoethyl) -gamma-aminopropyldiethoxysilane.
In addition, the invention also provides a preparation method of the raw rubber of graphene oxide-silicon dioxide modified natural rubber with surface organic treatment, which is different from the preparation method of the graphene-silicon dioxide modified natural rubber composite material in that in the step (iii), before being mixed with natural rubber latex, the prepared graphene oxide-silicon dioxide compound particles are subjected to surface treatment by using an organic compound to obtain the dispersion liquid of the graphene oxide-silicon dioxide compound particles with surface organic treatment, and then the dispersion liquid is mixed with the natural rubber latex to obtain the raw rubber of the graphene oxide-silicon dioxide modified natural rubber with surface organic treatment, wherein the preparation method of the dispersion liquid of the graphene oxide-silicon dioxide compound particles with surface organic treatment specifically comprises the following steps:
a. preparing a graphene oxide-silicon dioxide dispersion liquid: adding deionized water into the graphene oxide-silicon dioxide powder, and performing ultrasonic stirring to obtain a uniformly dispersed graphene oxide-silicon dioxide dispersion liquid;
b. preparing organic compound hydrolysate: adding an organic compound into a mixed solution of deionized water and any one of ethanol, methanol, ethylene glycol or glycerol, and performing ultrasonic dispersion to obtain a fully hydrolyzed organic compound hydrolysate;
c. adding organic compound hydrolysate into the graphene oxide-silicon dioxide dispersion liquid, reacting under certain conditions, washing and filtering the mixture for multiple times by using deionized water and one or more of ethanol, methanol, glycol or glycerol to remove unreacted organic compounds, and obtaining the graphene oxide-silicon dioxide particle dispersion liquid with organically treated surface.
The prepared graphene oxide-silicon dioxide particles are subjected to surface modification by using an organic compound to obtain a graphene oxide-silicon dioxide particle dispersion liquid subjected to surface organic treatment, so that the dispersibility of the compound particles in a rubber matrix is further improved, and the interfacial interaction between the graphene oxide-silicon dioxide particles and the rubber matrix is promoted, so that the heat conductivity and mechanical property of the graphene oxide-silicon dioxide modified natural rubber are further improved, and the compression fatigue heat generation of the natural rubber is reduced.
Further, the organic compound is an organic compound having a mercapto group, and has either excellent compatibility with natural rubber or can participate in a vulcanization reaction of natural rubber.
Further, the organic compound is one of gamma-mercaptopropyltriethoxysilane, gamma-mercaptopropyltrimethoxysilane, cysteine, thiophenol, N-tert-butyl-2-benzothiazolesulfenamide, 2-mercaptobenzothiazole and N-cyclohexyl-2-benzothiazolesulfenamide.
The invention also provides a method for forming a tire by using the graphene-silicon dioxide modified natural rubber raw rubber composite material prepared by the preparation method, which comprises the following steps:
placing the dried graphene oxide-silicon dioxide modified natural rubber raw rubber into an internal mixer for plasticating at 90 ℃ and 40rpm, sequentially adding zinc oxide, stearic acid, an anti-aging agent RD, an antioxidant 4010NA and a vulcanization accelerator NOBS, mixing for 5min, and discharging rubber compound; then, adjusting the temperature of a die cavity of an internal mixer to 110 ℃, putting the obtained rubber compound into the internal mixer, mixing for 5min, and discharging again; after the rubber material is cooled to room temperature, transferring the rubber material to an open mill for further mixing, adding sulfur in the mixing process, mixing the rubber material uniformly, and performing thin passing for 10 times until the rubber material has no obvious bubbles, thereby obtaining the graphene oxide-silicon dioxide modified natural rubber master batch; stopping rubber for 24 hours, then re-milling on a mill until the rubber surface is smooth and uniform, and then placing the rubber in a tire vulcanization mold for vulcanization to obtain the graphene oxide-silicon dioxide modified natural rubber tire with high heat conductivity and excellent low raw thermal mechanical property; further, a tire rubber sample was prepared by vulcanizing rubber at the same temperature, pressure and time using a sample mold.
The method for forming the tire by using the graphene-silicon dioxide modified natural rubber raw rubber composite material prepared by the preparation method comprises the following steps: placing the dried graphene oxide-silicon dioxide modified natural rubber raw rubber subjected to surface organic treatment into an internal mixer for plasticating at 90 ℃ and 40rpm, sequentially adding zinc oxide, stearic acid, an antioxidant RD, an antioxidant 4010NA and a vulcanization accelerator NOBS, mixing for 5min, and discharging rubber mixed rubber; then, adjusting the temperature of a die cavity of an internal mixer to 110 ℃, putting the obtained rubber compound into the internal mixer, mixing for 5min, and discharging again; after the rubber material is cooled to room temperature, transferring the rubber material to an open mill for further mixing, adding sulfur in the mixing process, mixing the rubber material uniformly, and performing thin passing for 10 times until the rubber material has no obvious bubbles, thereby obtaining the organic matter modified graphene oxide-silicon dioxide modified natural rubber masterbatch; stopping rubber for 24 hours, then re-milling on a mill until the rubber surface is smooth and uniform, and then placing the rubber in a tire vulcanization mold for vulcanization to obtain the graphene oxide-silicon dioxide modified natural rubber tire with high heat conductivity, low raw thermal mechanical property and excellent surface organic treatment; further, a tire rubber sample was prepared by vulcanizing rubber at the same temperature, pressure and time using a sample mold.
The surface-organically-treated graphene oxide-silica modified natural rubber designed by the invention can enable carboxyl in graphene oxide and amino in aminated silica to carry out amidation reaction, and the graphene oxide and silica particles are connected through covalent bonds, so that the dispersibility of the silica particles in a rubber matrix is improved. Meanwhile, the organic matter with both the mercapto terminal group and the hydroxyl terminal group is adopted to modify the graphene oxide-silicon dioxide compound particles, the hydroxyl terminal group in the organic matter can be subjected to dehydration reaction with the hydroxyl group on the surface of the graphene oxide-silicon dioxide compound particles, and the mercapto terminal group can participate in the vulcanization reaction of rubber to form a single sulfur bond, so that the mechanical property of the finally prepared rubber composite material is obviously improved, in addition, the interface interaction between the reduced graphene oxide and the natural rubber can be improved, and meanwhile, the frictional heat generation between the filler and the matrix and the interface thermal resistance between the filler and the matrix are reduced, so that the heat accumulation of the tire in the using process is reduced.
Furthermore, the mass ratio of the natural rubber, the zinc oxide, the stearic acid, the antioxidant RD, the antioxidant 4010NA, the vulcanization accelerator NOBS, the sulfur and the silicon dioxide is 100: 5: 2: 1: 2: 50.
Compared with the prior art, the invention has the following beneficial effects:
the graphene oxide modified natural rubber master batch is prepared by taking the graphene oxide aqueous dispersion, the silicon dioxide particles and the natural rubber latex as raw materials and adopting an emulsion blending method which is high in efficiency, energy-saving and easy for continuous production, so that the number of mixing stages in the rubber preparation process can be reduced, the continuous mixing process is facilitated to be realized, the mixing time is shortened, the mixing energy consumption is reduced, the dust pollution is reduced and the like; but also can effectively improve the dispersion performance of the silicon dioxide in the rubber matrix, promote the interface interaction between the filler and the rubber matrix, and the shorter mixing time is also beneficial to keeping the molecular weight of the rubber molecular chain and ensuring the performance of the rubber composite material. Therefore, the mechanical property of the rubber for the tire is improved, and meanwhile, the heat conductivity of the natural rubber is improved and the heat buildup property is reduced, so that the heat aging speed of the rubber tire in the dynamic use process is reduced, and the service life of the rubber tire is prolonged.
In order to further exert the excellent performance of the graphene filler, the organic matter modified graphene oxide-silicon dioxide compound particles with both sulfydryl and hydroxyl are adopted, the hydroxyl end group in the organic matter can be subjected to dehydration reaction with the hydroxyl on the surface of the graphene oxide-silicon dioxide compound particles, and the sulfydryl end group can participate in the vulcanization reaction of rubber to form a single sulfur bond, so that the mechanical property of the finally prepared rubber composite material is obviously improved, in addition, the interface interaction between the reduced graphene oxide and the natural rubber can be improved, and meanwhile, the frictional heat generation between the filler and the matrix and the interface thermal resistance between the filler and the matrix are reduced, so that the heat accumulation of the tire in the using process is further reduced.
Drawings
FIG. 1 is a SEM cross-section of vulcanizates prepared in examples 1 and 2 and comparative example, wherein a is comparative example 1, b is example 1, and c is example 2.
Detailed Description
The present invention is further illustrated by the following specific examples.
Example 1
Graphene oxide-silicon dioxide modified natural rubber
Preparation of silicon dioxide with aminated surface: ethanol and water are fully mixed according to the mass ratio of 7:1 at room temperature, and then 3g to 5g of silane coupling agent KH550 are dropwise added into 100ml of mixed solution of ethanol and water for full hydrolysis, wherein the hydrolysis time is 2 hours. Then the raw material SiO2Adding the powder into KH550 ethanol water solution, stirring and reacting at 70 deg.C for 8 hr to obtain KH550 modified SiO2. Finally, after filtering and washing for three times by absolute ethyl alcohol and water, unreacted KH550 is removed, and the obtained modified SiO2In a vacuum oven at 60 deg.CAnd treating for 24 hours to obtain aminated silicon dioxide.
Preparing graphene oxide-silicon dioxide compound particles: 100g of 0.5 wt.% aqueous GO (graphene oxide) solution is mixed with deionized water, and the graphene oxide is fully dispersed in the aqueous solution by ultrasonic treatment for 30 min. The aqueous GO solution was cooled to 0 ℃ in an ice-water bath, then 0.01g of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (EDC) and 0.01g N-hydroxysuccinimide (NHS) were added to the aqueous GO solution in sequence and stirred for 1 h. 50g of SiO2-NH2Adding the powder into 500g of deionized water, and performing ultrasonic treatment for 30min to obtain SiO2-NH2Followed by dispersing the SiO2-NH2Adding the dispersion into 100g of activated GO aqueous solution, stirring and reacting for 12h under the condition of ice-water bath to obtain GO and SiO2The compound particle GO-SiO2. Filtering and washing with deionized water for three times to remove unreacted EDC (1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride) and NHS (N-hydroxysuccinimide), and mixing with deionized water to obtain GO-SiO with concentration of 10 wt%2。
Preparing the graphene oxide-silicon dioxide modified natural rubber raw rubber with high heat conductivity, low heat generation and excellent mechanical property: 500g of GO-SiO obtained in the second step2Adding 340ml of 30 wt.% natural rubber latex, and stirring to obtain uniformly dispersed mixed emulsion; adding calcium chloride solution to make the mixed emulsion break emulsion and flocculate; and placing the raw rubber without the flocculating agent in an oven for drying to constant weight to obtain the graphene oxide-silicon dioxide modified natural rubber with high heat conductivity and excellent low raw thermal mechanical property.
Placing the dried graphene oxide-silicon dioxide modified natural rubber raw rubber into an internal mixer for plasticating at 90 ℃ and 40rpm, sequentially adding zinc oxide, stearic acid, an antioxidant RD, an antioxidant 4010NA and a vulcanization accelerator N-tert-butyl-2-benzothiazole sulfonamide for mixing for 5min, and discharging rubber mixed rubber; then, adjusting the temperature of a die cavity of an internal mixer to 110 ℃, putting the obtained rubber compound into the internal mixer, mixing for 5min, and discharging again; and (3) after the rubber material is cooled to room temperature, transferring the rubber material to an open mill for further mixing, adding sulfur in the mixing process, mixing the rubber material uniformly, and performing thin passing for 10 times until the rubber material has no obvious bubbles, thus obtaining the organic matter modified graphene oxide-silicon dioxide modified natural rubber master batch. And (5) after the rubber is stopped for 24 hours, re-milling on the open mill until the rubber surface is smooth and uniform. And vulcanizing at the temperature of 150 ℃ and under the pressure of 15MPa for 25min to obtain the organic matter modified graphene oxide-silicon dioxide modified natural rubber vulcanized rubber.
The tensile strength test was carried out on an AI-7000 stretcher of Taiwan high-speed railway science and technology, Inc., with the test standard of ISO 37-2005, a tensile rate of 500mm/min, and the mechanical property data shown in Table 1.
Example 2
3-mercaptopropyltriethoxysilane-modified graphene oxide-silicon dioxide modified natural rubber
Preparation of silicon dioxide with aminated surface: ethanol and water are fully mixed according to the mass ratio of 7:1 at room temperature, and then 3g to 5g of silane coupling agent KH550 are dropwise added into 100ml of mixed solution of ethanol and water for full hydrolysis, wherein the hydrolysis time is 2 hours. Then the raw material SiO2Adding the powder into KH550 ethanol water solution, stirring and reacting at 70 deg.C for 8 hr to obtain KH550 modified SiO2. Finally, after filtering and washing for three times by absolute ethyl alcohol and water, unreacted KH550 is removed, and the obtained modified SiO2And treating the mixture for 24 hours in a vacuum oven at the temperature of 60 ℃ to obtain the aminated silicon dioxide.
Preparing graphene oxide-silicon dioxide compound particles: 100g of 0.5 wt.% aqueous GO solution is mixed with deionized water and the graphene oxide is fully dispersed in the aqueous solution by ultrasonic treatment for 30 min. The aqueous GO solution was cooled to 0 ℃ in an ice-water bath, then 0.01g EDC and 0.01g NHS were added to the aqueous GO solution in sequence and stirred for 1 h. 50g of SiO2-NH2Adding the powder into 500g of deionized water, and performing ultrasonic treatment for 30min to obtain SiO2-NH2Followed by dispersing the SiO2-NH2Adding the dispersion into 100g of activated GO aqueous solution, stirring and reacting for 12h under the condition of ice-water bath to obtain GO and SiO2The compound particle GO-SiO2. Filtering and washing with deionized water for three times to remove unreacted EDC and NHS, and mixing with deionized water to obtain GO-SiO with concentration of 10 wt%2。
Preparing 3-mercaptopropyltriethoxysilane-modified graphene oxide-silicon dioxide compound particles: 5g of 3-mercaptopropyltriethoxysilane was added to an aqueous ethanol solution having a pure water ratio of 7:1, and sufficient hydrolysis was performed at normal temperature. And adding the dispersion liquid of the 3-mercaptopropyltriethoxysilane into the graphene oxide-silicon dioxide dispersion liquid, and carrying out water bath reaction for 8 hours at the temperature of 75 ℃ to obtain the graphene oxide-silicon dioxide subjected to surface organic treatment. Filtering and washing with absolute ethyl alcohol and water for three times to remove unreacted organic compounds, and mixing with deionized water to obtain GO-SiO with surface organic compound treatment concentration of 10 wt%2And (3) dispersing the mixture.
Preparing 3-mercaptopropyltriethoxysilane-modified graphene oxide-silica modified natural rubber raw rubber: adding 500g of 3-mercaptopropyltriethoxysilane-modified graphene oxide-silicon dioxide dispersion liquid obtained in the step (c) into 340g of 30 wt.% natural rubber latex, and stirring to obtain uniformly dispersed mixed emulsion; adding 60g of 10 wt.% calcium chloride aqueous solution to demulsify and flocculate the mixed emulsion; and (3) drying the crude rubber without the flocculating agent in an oven to constant weight to obtain the 3-mercaptopropyltriethoxysilane-modified graphene oxide-silicon dioxide natural rubber crude rubber.
Placing the dried 3-mercaptopropyltriethoxysilane-modified graphene oxide-silicon dioxide modified natural rubber raw rubber into an internal mixer for plastication at the temperature of 90 ℃ and the speed of 40rpm, sequentially adding zinc oxide, stearic acid, an anti-aging agent RD, an antioxidant 4010NA and a vulcanization accelerator N-tert-butyl-2-benzothiazole sulfenamide, mixing for 5min, and discharging rubber mixed rubber; then, adjusting the temperature of a die cavity of an internal mixer to 110 ℃, putting the obtained rubber compound into the internal mixer, mixing for 5min, and discharging again; and (3) cooling the rubber material to room temperature, transferring the rubber material to an open mill for further mixing, adding sulfur in the mixing process, mixing the rubber material uniformly, and performing thin passing for 10 times until the rubber material has no obvious bubbles, thus obtaining the 3-mercaptopropyltriethoxysilane modified graphene oxide-silicon dioxide modified natural rubber master batch. And (4) stopping the rubber of the obtained rubber compound for 24 hours, and then re-milling the rubber compound on the open mill until the rubber surface is smooth and uniform. And vulcanizing at the temperature of 150 ℃ and under the pressure of 15MPa for 25min to obtain the 3-mercaptopropyltriethoxysilane-modified graphene oxide-silicon dioxide natural rubber vulcanized rubber.
The tensile strength test was carried out on an AI-7000 stretcher of Taiwan high-speed railway science and technology, Inc., with the test standard of ISO 37-2005, a tensile rate of 500mm/min, and the mechanical property data shown in Table 1.
Comparative example 1
Firstly, plasticating 100g of No. 10 rubber (SCR 10) natural rubber in an internal mixer at the temperature of 90 ℃ and the speed of 40rpm, sequentially adding 5g of zinc oxide, 2g of stearic acid, 2g of antioxidant 4010NA, 2g of antioxidant RD, 2g of vulcanization accelerator N-tert-butyl-2-benzothiazole sulfenamide and 50g of silicon dioxide, mixing for 15min, and discharging rubber compound. Then, the temperature of a mold cavity of the internal mixer is adjusted to 110 ℃, the rubber compound obtained in the previous step is placed into the internal mixer, and the rubber compound is discharged after being mixed for 5 min. And (3) after the rubber material is cooled to room temperature, transferring the rubber material to an open mill for further mixing, adding 2g of sulfur in the mixing process, and mixing the rubber material uniformly to obtain the natural rubber compound. And (4) stopping the rubber of the obtained rubber compound for 24 hours, and then re-milling the rubber compound on the open mill until the rubber surface is smooth and uniform. Vulcanizing at 150 ℃ and 15MPa for 25min to obtain the silicon dioxide modified natural rubber vulcanized rubber.
The tensile strength test was carried out on an AI-7000 stretcher of Taiwan high-speed railway science and technology, Inc., with the test standard of ISO 37-2005, a tensile rate of 500mm/min, and the mechanical property data shown in Table 1.
TABLE 1 mechanical Properties of rubber composites
| Sample (I) | Comparative example 1 | Example 1 | Example 2 |
| Sample number | 1 | 2 | 3 |
| Tensile Strength (MPa) | 16.5 | 21.7 | 27.1 |
| Elongation at Break (%) | 461 | 480 | 500 |
| M100(MPa) | 1.32 | 1.6 | 2.2 |
| M300(MPa) | 7.4 | 8 | 12.8 |
| Tear Strength (N/mm) | 28 | 33 | 60 |
| Hardness (HA) | 60 | 54 | 60 |
| Coefficient of thermal conductivity (Wm)-1K-1) | 0.40 | 0.46 | 0.55 |
| Heat generation by compression fatigue (. degree. C.) | 33 | 27 | 21 |
Claims (8)
1. The preparation method of the graphene-silicon dioxide modified natural rubber composite material with high thermal conductivity and low raw thermal mechanical property for the tire is characterized by comprising the following steps:
2. The method for preparing a graphene-silica modified natural rubber composite material with high thermal conductivity and excellent low thermodynamic property for a tire as claimed in claim 1, wherein the amino group-containing silane coupling agent is one of γ -aminopropyltriethoxysilane, γ -aminopropyltrimethoxysilane, phenylaminomethyltriethoxysilane, phenylaminomethyltrimethoxysilane, N- θ (aminoethyl) - γ -aminopropyltrimethoxysilane, N- θ (aminoethyl) - γ -aminopropyldimethoxysilane, N- θ (aminoethyl) - γ -aminopropyltriethoxysilane, and N- θ (aminoethyl) - γ -aminopropyldiethoxysilane.
3. The method for preparing the graphene-silica modified natural rubber composite material with high thermal conductivity and excellent low thermodynamic properties for the tire as claimed in claim 1, wherein the step of preparing the graphene-silica modified natural rubber composite material is
In the method, before mixing with natural rubber latex, an organic compound is used for carrying out surface modification on the prepared graphene oxide-silicon dioxide compound particles to obtain graphene oxide-silicon dioxide compound particle dispersion liquid with organically treated surface, and then the graphene oxide-silicon dioxide compound particle dispersion liquid is mixed with the natural rubber latex to obtain graphene oxide-silicon dioxide modified natural rubber raw rubber with organically treated surface, wherein the preparation method of the graphene oxide-silicon dioxide compound particle dispersion liquid with organically treated surface specifically comprises the following steps:
a. preparing a graphene oxide-silicon dioxide dispersion liquid: adding deionized water into the graphene oxide-silicon dioxide powder, and performing ultrasonic stirring to obtain a uniformly dispersed graphene oxide-silicon dioxide dispersion liquid;
b. preparing organic compound hydrolysate: adding an organic compound into a mixed solution of deionized water and any one of ethanol, methanol, ethylene glycol or glycerol, and performing ultrasonic dispersion to obtain a fully hydrolyzed organic compound hydrolysate;
c. adding organic compound hydrolysate into the graphene oxide-silicon dioxide dispersion liquid, reacting under certain conditions, washing and filtering the mixture for multiple times by using deionized water and one or more of ethanol, methanol, glycol or glycerol to remove unreacted organic compounds, and obtaining the graphene oxide-silicon dioxide particle dispersion liquid with organically treated surface.
4. The method for preparing a graphene-silica modified natural rubber composite material with high thermal conductivity and low thermodynamic properties for a tire as claimed in claim 3, wherein the organic compound is an organic compound containing a mercapto group, and the organic compound has either excellent compatibility with natural rubber or can participate in a vulcanization reaction of natural rubber.
5. The method for preparing a graphene-silica modified natural rubber composite material with high thermal conductivity and excellent low thermodynamic properties for a tire as claimed in claim 4, wherein the organic compound is one of γ -mercaptopropyltriethoxysilane, γ -mercaptopropyltrimethoxysilane, cysteine, thiophenol, N-tert-butyl-2-benzothiazolesulfenamide, 2-mercaptobenzothiazole and N-cyclohexyl-2-benzothiazolesulfenamide.
6. The method for molding the tire by using the graphene-silica modified natural rubber raw rubber composite material prepared by the preparation method of claim 1, is characterized by comprising the following steps of:
placing the dried graphene oxide-silicon dioxide modified natural rubber raw rubber into an internal mixer for plasticating at 90 ℃ and 40rpm, sequentially adding zinc oxide, stearic acid, an anti-aging agent RD, an antioxidant 4010NA and a vulcanization accelerator NOBS, mixing for 5min, and discharging rubber compound; then, adjusting the temperature of a die cavity of an internal mixer to 110 ℃, putting the obtained rubber compound into the internal mixer, mixing for 5min, and discharging again; after the rubber material is cooled to room temperature, transferring the rubber material to an open mill for further mixing, adding sulfur in the mixing process, mixing the rubber material uniformly, and performing thin passing for 10 times until the rubber material has no obvious bubbles, thereby obtaining the graphene oxide-silicon dioxide modified natural rubber master batch; stopping rubber for 24 hours, then re-milling on a mill until the rubber surface is smooth and uniform, and then placing the rubber in a tire vulcanization mold for vulcanization to obtain the graphene oxide-silicon dioxide modified natural rubber tire with high heat conductivity and excellent low raw thermal mechanical property; further, a tire rubber sample was prepared by vulcanizing rubber at the same temperature, pressure and time using a sample mold.
7. The method for forming the tire by using the graphene-silica modified natural rubber raw rubber composite material prepared by the preparation method of claim 3 is characterized by comprising the following steps of: placing the dried graphene oxide-silicon dioxide modified natural rubber raw rubber subjected to surface organic treatment into an internal mixer for plasticating at 90 ℃ and 40rpm, sequentially adding zinc oxide, stearic acid, an antioxidant RD, an antioxidant 4010NA and a vulcanization accelerator NOBS, mixing for 5min, and discharging rubber mixed rubber; then, adjusting the temperature of a die cavity of an internal mixer to 110 ℃, putting the obtained rubber compound into the internal mixer, mixing for 5min, and discharging again; after the rubber material is cooled to room temperature, transferring the rubber material to an open mill for further mixing, adding sulfur in the mixing process, mixing the rubber material uniformly, and performing thin passing for 10 times until the rubber material has no obvious bubbles, thereby obtaining the organic matter modified graphene oxide-silicon dioxide modified natural rubber masterbatch; stopping rubber for 24 hours, then re-milling on a mill until the rubber surface is smooth and uniform, and then placing the rubber in a tire vulcanization mold for vulcanization to obtain the graphene oxide-silicon dioxide modified natural rubber tire with high heat conductivity, low raw thermal mechanical property and excellent surface organic treatment; further, a tire rubber sample was prepared by vulcanizing rubber at the same temperature, pressure and time using a sample mold.
8. The process for producing a tire as claimed in claim 6 or 7, wherein the mass ratio of natural rubber, zinc oxide, stearic acid, antioxidant RD, antioxidant 4010NA, vulcanization accelerator NOBS, sulfur and silica is 100: 5: 2: 1: 2: 50.
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