CN118240286A - Graphene rubber composition for tire tread - Google Patents
Graphene rubber composition for tire tread Download PDFInfo
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- CN118240286A CN118240286A CN202410139288.4A CN202410139288A CN118240286A CN 118240286 A CN118240286 A CN 118240286A CN 202410139288 A CN202410139288 A CN 202410139288A CN 118240286 A CN118240286 A CN 118240286A
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- graphene
- rubber
- rubber composition
- modified graphene
- tire tread
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 132
- 229920001971 elastomer Polymers 0.000 title claims abstract description 75
- 239000005060 rubber Substances 0.000 title claims abstract description 75
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 65
- 239000000203 mixture Substances 0.000 title claims abstract description 42
- 239000004594 Masterbatch (MB) Substances 0.000 claims abstract description 36
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 4
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 239000000463 material Substances 0.000 claims description 28
- 238000002156 mixing Methods 0.000 claims description 27
- 229920005989 resin Polymers 0.000 claims description 26
- 239000011347 resin Substances 0.000 claims description 26
- 238000004513 sizing Methods 0.000 claims description 25
- 239000012763 reinforcing filler Substances 0.000 claims description 22
- 229920003244 diene elastomer Polymers 0.000 claims description 20
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 18
- 239000006229 carbon black Substances 0.000 claims description 18
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 15
- 239000004816 latex Substances 0.000 claims description 15
- 229920000126 latex Polymers 0.000 claims description 15
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 8
- -1 octyl phenolic resin Chemical compound 0.000 claims description 8
- 239000011593 sulfur Substances 0.000 claims description 8
- 229910052717 sulfur Inorganic materials 0.000 claims description 8
- 244000043261 Hevea brasiliensis Species 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- 229920003052 natural elastomer Polymers 0.000 claims description 7
- 229920001194 natural rubber Polymers 0.000 claims description 7
- 239000003208 petroleum Substances 0.000 claims description 7
- 239000003223 protective agent Substances 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 238000007599 discharging Methods 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 6
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims description 5
- 230000003213 activating effect Effects 0.000 claims description 5
- 239000012065 filter cake Substances 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 3
- 239000005062 Polybutadiene Substances 0.000 claims description 3
- 239000001110 calcium chloride Substances 0.000 claims description 3
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 3
- 239000002041 carbon nanotube Substances 0.000 claims description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 3
- 150000004985 diamines Chemical class 0.000 claims description 3
- 239000000806 elastomer Substances 0.000 claims description 3
- 239000003822 epoxy resin Substances 0.000 claims description 3
- 229920003049 isoprene rubber Polymers 0.000 claims description 3
- 239000003607 modifier Substances 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 3
- 229920001568 phenolic resin Polymers 0.000 claims description 3
- 239000005011 phenolic resin Substances 0.000 claims description 3
- 229920002857 polybutadiene Polymers 0.000 claims description 3
- 229920000647 polyepoxide Polymers 0.000 claims description 3
- 239000012190 activator Substances 0.000 claims description 2
- 238000004898 kneading Methods 0.000 claims 1
- 238000002360 preparation method Methods 0.000 claims 1
- 239000007822 coupling agent Substances 0.000 abstract description 5
- 238000013040 rubber vulcanization Methods 0.000 abstract 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 14
- 238000003756 stirring Methods 0.000 description 9
- 239000011787 zinc oxide Substances 0.000 description 7
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 6
- 238000005406 washing Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 235000021355 Stearic acid Nutrition 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000003638 chemical reducing agent Substances 0.000 description 4
- 230000020169 heat generation Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 4
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 4
- 239000008117 stearic acid Substances 0.000 description 4
- 238000009210 therapy by ultrasound Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000005299 abrasion Methods 0.000 description 3
- 239000011668 ascorbic acid Substances 0.000 description 3
- 229960005070 ascorbic acid Drugs 0.000 description 3
- 235000010323 ascorbic acid Nutrition 0.000 description 3
- 239000012295 chemical reaction liquid Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000003292 glue Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 2
- 125000006702 (C1-C18) alkyl group Chemical group 0.000 description 2
- RSWGJHLUYNHPMX-UHFFFAOYSA-N 1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylic acid Chemical compound C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000003282 alkyl amino group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 125000000000 cycloalkoxy group Chemical group 0.000 description 2
- 125000000753 cycloalkyl group Chemical group 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000003311 flocculating effect Effects 0.000 description 2
- 239000008103 glucose Substances 0.000 description 2
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 2
- 229940071870 hydroiodic acid Drugs 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 239000012279 sodium borohydride Substances 0.000 description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 description 2
- 239000001509 sodium citrate Substances 0.000 description 2
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 2
- 230000035882 stress Effects 0.000 description 2
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical class [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 238000005411 Van der Waals force Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L7/00—Compositions of natural rubber
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
- B60C1/0016—Compositions of the tread
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/80—Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
- Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The invention discloses a graphene rubber composition for tire tread, which relates to the technical field of graphene and tire rubber, and comprises the following components: the modified graphene masterbatch takes graphene oxide as a raw material, is connected with a silane coupling agent on a lamellar thereof and then reduced, the coupling agent increases the lamellar spacing of the graphene and participates in rubber vulcanization reaction.
Description
Technical Field
The invention relates to the technical field of graphene and tire rubber, in particular to a graphene rubber composition for tire treads.
Background
The emission standard in the seventh stage of Europe is required to be discharged, so that not only is the carbon emission required to be further reduced, but also the emission of automobile particles is required to be reduced, and for tires, more oil saving and wear resistance are required, and the electric automobile is a development trend, and the tires of the electric automobile have higher requirements on dry and wet land grip, oil saving and wear resistance. The tread is the contact part of the tire and the ground, the rolling resistance of the tread is about 50 percent of the rolling resistance of the tire, and the tread rubber composition with long service life, good oil saving and safety, high wear resistance, low hysteresis heat generation and good wet skid resistance is required to be produced.
The tread rubber composition comprises raw rubber, reinforcing filler, protective agent, activating agent, accelerator, sulfur and other components, wherein the reinforcing filler can increase the mechanical property, wear resistance, ageing resistance and other properties of the rubber. The reinforcing fillers commonly used are carbon black and white carbon black, and carbon black is the reinforcing filler used for the earliest time in a tire, but with carbon black as the filler, the relationship between the service life (tread wear resistance), safety (tread wet skid resistance) and oil saving (tread hysteresis heat generation) exists between the expansion and the extinction, and the phenomenon is called magic triangle of the tire. The white carbon black and the coupling agent are filler, and when the load is low, the tyre has the performances of wear resistance, oil saving and wet skid resistance. However, the rubber added with white carbon black is inferior in the strength to carbon black rubber and poor in thermal conductivity, and therefore the rubber filled with white carbon black is not suitable for tires subjected to high loads, such as aircraft tires, truck tires, and the like.
The graphene has the advantages of large specific surface area, high modulus, good heat conduction and electric conductivity, stable chemical property and capability of blocking air, and the graphene is used as a filler, so that the comprehensive performances of modulus, strength, wear resistance, heat dissipation, ageing resistance, static resistance and the like of the rubber can be improved by adding a small amount of the graphene theoretically. However, in experiments, it was found that the addition of graphene to rubber reduced the abrasion resistance of the rubber and increased the dynamic temperature rise. This phenomenon is because there are two difficulties in dispersing graphene in rubber: first, there is very strong effort between the graphene sheet layer, and the sheet layer is easy to agglomerate, is difficult to evenly disperse in rubber. If graphene is agglomerated in rubber, stress concentration can be generated, so that the mechanical property of the rubber is reduced; secondly, the acting force between the rubber molecules and the graphene is mainly van der Waals force, and the interface effect is weak; when the rubber is stressed to generate strain, the rubber molecules and the graphene sheets slide, so that on one hand, the graphene cannot effectively bear the stress acting on the rubber matrix, and on the other hand, friction heat is generated, the temperature of the rubber is increased, and the abrasion is increased. Therefore, the graphene material which can be uniformly dispersed in the rubber and has a strong interface effect with the rubber is prepared, and the mixing condition of the graphene rubber composition is defined as a necessary condition for developing the graphene tire with high wear resistance, oil saving and good safety.
Based on this, a graphene rubber composition for tire tread is now provided, which can eliminate the drawbacks of the existing devices.
Disclosure of Invention
The invention aims to provide a graphene rubber composition for a tire tread, and with the improvement of safety and environmental protection requirements, a tire is expected to have better oil saving, wear resistance and wet skid resistance. The tread rubber composition is required to have high wear resistance, good wet skid resistance and low dynamic temperature rise. According to the invention, the modified graphene masterbatch is added into rubber, and the mixing process is optimized, so that the graphene rubber composition with high modulus, good wear resistance and wet skid resistance and low hysteresis heat generation is prepared, and the rubber composition is suitable for tires with high running speed and high bearing load, such as aviation tires, heavy-duty tires and high-performance automobile tires.
In order to achieve the above purpose, the present invention provides the following technical solutions:
The graphene rubber composition for the tire tread comprises a diene elastomer, modified graphene masterbatch, reinforcing filler, resin, an activator, an accelerator and a vulcanizing agent;
The modified graphene masterbatch is prepared by taking graphene oxide as a raw material, modifying with a silane coupling agent, reducing, filtering, washing, uniformly dispersing a filter cake in water or an organic solvent after the reaction is finished, mixing with latex, flocculating, and drying.
Based on the technical scheme, the invention also provides the following optional technical schemes:
In one alternative: the diene elastomer is selected from one or more of natural rubber, synthetic isoprene rubber, butadiene rubber, styrene butadiene rubber and elastomer mixture.
In one alternative: the modified graphene takes graphene oxide as a raw material, the specific surface area of the graphene oxide is 100-400 m < 2 >/g, the sheet diameter is 0.05-30 mu m, and the modifier is a silane coupling agent;
The general formula of the silane coupling agent is: z- (CH 2)m-[Si-(X)a(Y)3-a]n, X is C1-C18 alkoxy or C5-C18 cycloalkoxy, a is an integer of 1-3, Y is C1-C18 alkyl, C5-C18 cycloalkyl and C6-C18 aryl, m is an integer of 0-10, n is 1 or 2, Z is one or more selected from vinyl, alkylamino, amino, epoxy, mercapto, polysulfanyl, acryloxy, and the reducing agent is one or more selected from sodium citrate, glucose, ascorbic acid, sodium borohydride, hydrazine hydrate, hydroiodic acid, polyvinylpyrrolidone, polyvinyl alcohol, ethylene glycol and formaldehyde.
In one alternative: the latex used by the modified graphene mother rubber comprises one or more of natural latex and other synthetic latex, and the flocculant of the modified graphene and the latex is one or more of sulfuric acid, acetic acid, calcium chloride and dinitrile diamine formaldehyde condensate.
In one alternative: the mass of the modified graphene in the modified graphene masterbatch is 1-10% of the mass of the dry masterbatch, and preferably 3-6%.
In one alternative: the addition amount of the modified graphene masterbatch is 100 parts, and the diene elastomer is added with 20 to 200 parts of the modified graphene masterbatch, preferably 40 to 100 parts of the modified graphene masterbatch.
In one alternative: the reinforcing filler is selected from one or more of carbon black, white carbon black and carbon nano tubes, the addition amount is 100 parts, and 50 to 160 parts of reinforcing filler, preferably 60 to 120 parts of reinforcing filler is added into the diene elastomer.
In one alternative: the resin is selected from one or more of octyl phenolic resin, phenolic epoxy resin, C5 petroleum resin, wet skid resistant resin and tear resistant resin, and the addition amount is 0 to 10 parts, preferably 2 to 6 parts.
In one alternative: the mixing condition of the graphene rubber composition comprises the following steps:
Firstly, putting a diene elastomer into an internal mixer at the temperature of 80-90 ℃ at the rotor speed of 60-90 r/min for plasticating time of 20-60 seconds;
step two, putting the modified graphene masterbatch into an internal mixer to mix the modified graphene masterbatch with a diene elastomer, wherein the rotating speed of a rotor is 60-90 r/min, and the mixing time is 20-60 seconds;
Step three, adding reinforcing filler, resin and protective agent into an internal mixer to mix the reinforcing filler, resin and protective agent with the sizing material in the step two, wherein the rotating speed of a rotor is 30-70 r/min, the mixing time is 60-240 seconds, and the sizing material discharging temperature is 130-160 ℃;
And step four, cooling the mixed sizing material to room temperature, adding an activating agent, an accelerating agent and sulfur into the sizing material by using an open mill or an internal mixer, and uniformly mixing the mixed sizing material with the sizing material after the step three, wherein the temperature of the mixing process is not more than 110 ℃.
Compared with the prior art, the invention has the following beneficial effects:
The modified graphene masterbatch added by the invention can be uniformly dispersed in rubber, has good interface effect with the rubber, has the advantages of large specific surface area, high modulus, good heat conduction and electric conductivity and the like, can fully play, obviously improves the mechanical property, wear resistance and dynamic property of the graphene rubber composition, and is suitable for being used as tread rubber materials of aviation tires, heavy-duty tires, high-performance automobile tires and the like.
Drawings
FIG. 1 is a DMA chart of the rubber compositions of the examples and comparative examples.
FIG. 2 is a table showing the correlation between the rubber compositions of examples and comparative examples.
FIG. 3 is an SEM image of brittle fracture interface of the rubber compositions of the examples and comparative examples.
FIG. 4 is a table of properties of the rubber compositions of examples and comparative examples.
Detailed Description
The present invention will be described in further detail with reference to the drawings and examples, in order to make the objects, technical solutions and advantages of the present invention more apparent.
In one embodiment, as shown in fig. 1-4, a graphene rubber composition for a tire tread, comprises the steps of:
Dispersing graphene oxide in water, wherein the specific surface area of the graphene oxide is 100-400 m < 2 >/g, the sheet diameter is 0.05-30 mu m, the pH value is adjusted to 8-14, stirring is carried out to uniformly disperse the graphene oxide, ultrasonic treatment is carried out for 0.3-3 hours, and the pH value is adjusted to 5-7; dripping ethanol solution of a modifier silane coupling agent into graphene oxide dispersion liquid, and heating to 70-100 ℃ for reaction after dripping, wherein the reaction time is 1-4 h, so as to obtain a reaction liquid from graphene oxide to the coupling agent; cooling the reaction liquid to below 40 ℃, adjusting the pH value to 7-10, adding a reducing agent into the reaction liquid, heating to 50-100 ℃ for carrying out reduction reaction, reacting for 2-10 hours, cooling, filtering and washing to obtain modified graphene; dispersing the modified graphene in water or an organic solvent, stirring, and performing ultrasonic treatment to obtain a modified graphene dispersion liquid; adding the modified graphene dispersion liquid into the latex under stirring, stirring for 0.1 to 1 hour, flocculating the latex, washing, and drying to obtain the modified graphene masterbatch.
The general formula of the silane coupling agent is: z- (CH 2)m-[Si-(X)a(Y)3-a]n, X is C1-C18 alkoxy or C5-C18 cycloalkoxy, a is an integer from 1 to 3, Y is C1-C18 alkyl, C5-C18 cycloalkyl and C6-C18 aryl, m is an integer from 0 to 10, n is 1 or 2, Z is one or more selected from vinyl, alkylamino, amino, epoxy, mercapto, polysulphanyl, acryloxy, and the reducing agent is one or more selected from sodium citrate, glucose, ascorbic acid, sodium borohydride, hydrazine hydrate, hydroiodic acid, polyvinylpyrrolidone, polyvinyl alcohol, ethylene glycol and formaldehyde.
The latex includes one or more of natural latex and other synthetic latex; the flocculant of the modified graphene and the latex is one or more of sulfuric acid, acetic acid, calcium chloride and dinitrile diamine formaldehyde condensate.
The mass of the modified graphene in the modified graphene masterbatch is 1-10% of the mass of the dry masterbatch, and preferably 3-6%.
Preparing a graphene rubber composition:
The graphene rubber composition for the tire tread consists of a diene elastomer, modified graphene masterbatch, reinforcing filler, resin, an activating agent, an accelerating agent and a vulcanizing agent.
The diene elastomer is selected from natural rubber, synthetic isoprene rubber, butadiene rubber, styrene butadiene rubber and elastomer mixtures.
The addition amount of the modified graphene masterbatch is 100 parts, and 20 to 200 parts of the modified graphene masterbatch, preferably 40 to 100 parts of the modified graphene masterbatch, are added to the diene elastomer.
The reinforcing filler is selected from one or more of carbon black, white carbon black and carbon nano tubes, the addition amount is 100 parts, and 50 to 160 parts of reinforcing filler, preferably 60 to 120 parts of reinforcing filler is added into the diene elastomer.
The resin is selected from one or more of octyl phenolic resin, phenolic epoxy resin, C5 petroleum resin, wet skid resistant resin and tear resistant resin, and the addition amount is 0 to 10 parts, preferably 2 to 6 parts.
Mixing conditions of the graphene rubber composition:
Firstly, putting a diene elastomer into an internal mixer at the temperature of 80-90 ℃ at the rotor speed of 60-90 r/min for plasticating time of 20-60 seconds;
step two, putting the modified graphene masterbatch into an internal mixer to mix the modified graphene masterbatch with a diene elastomer, wherein the rotating speed of a rotor is 60-90 r/min, and the mixing time is 20-60 seconds;
Step three, adding reinforcing filler, resin and protective agent into an internal mixer to mix the reinforcing filler, resin and protective agent with the sizing material in the step two, wherein the rotating speed of a rotor is 30-70 r/min, the mixing time is 60-240 seconds, and the sizing material discharging temperature is 130-160 ℃;
And step four, cooling the mixed sizing material to room temperature, adding an activating agent, an accelerating agent and sulfur into the sizing material by using an open mill or an internal mixer, and uniformly mixing the mixed sizing material with the sizing material after the step three, wherein the temperature of the mixing process is not more than 110 ℃.
According to the modified graphene masterbatch used in the invention, firstly graphene oxide reacts with a silane coupling agent, then most of residual oxygen-containing functional groups are removed through a reducing agent, so that the polarity of the modified graphene is reduced, and the interface compatibility of the modified graphene with rubber molecules is enhanced; the coupling agent increases the lamellar spacing of the modified graphene, reduces the acting force between lamellar layers, and enables the lamellar layers of the modified graphene to be easily peeled off; the modified graphene is directly dispersed in a solvent after being filtered and washed, and is mixed with latex, rubber molecules are intercalated between modified graphene sheets, lamination of sheets is prevented, the characteristic of large specific surface area of a graphene material can be fully utilized, and rubber can be covered by adding a small amount of the modified graphene. When the graphene sizing material is mixed, zinc oxide and a vulcanization system are added in the fourth step, so that the modified graphene is prevented from being activated during mixing by an internal mixer, and local scorching is generated at a lower temperature; the glue discharging temperature of the internal mixer is controlled, so that the problem that the performance is reduced due to local scorching of graphene glue stock at high temperature is avoided; under the mixing condition, the modified graphene can be uniformly dispersed in the rubber composition, has good interface compatibility with rubber, can fully exert the excellent property of the graphene, and obviously improves the mechanical property, wear resistance and dynamic property of the graphene rubber composition.
The invention will be further illustrated by the following examples, but the invention is not limited thereby.
Preparing modified graphene masterbatch:
Dispersing 4g of graphene oxide in 2000ml of aqueous solution, uniformly stirring, adding sodium hydroxide aqueous solution to adjust the pH value to 9-10, performing ultrasonic treatment for 2 hours, and then adjusting the pH value to 6 by using acetic acid to obtain aqueous dispersion liquid of the graphene oxide; adding 756g of coupling agent Si into 100ml of ethanol, uniformly mixing, dripping into aqueous dispersion of graphene oxide, heating to 80 ℃ under stirring, reacting for 2h, adding 8g of ascorbic acid, heating to 90 ℃ and reacting for 3h. Cooling to normal temperature, filtering and washing to obtain a modified graphene filter cake; adding the modified graphene filter cake into 400ml of water, stirring, and performing ultrasonic treatment to uniformly disperse the modified graphene filter cake; pouring 333g (solid content 200 g) of natural latex into a beaker, diluting for 1 time, adding the aqueous dispersion of the modified graphene under stirring, and stirring for 30min to uniformly disperse the modified graphene in the latex; preparing 3% acetic acid aqueous solution, pouring modified graphene or natural latex into the acetic acid aqueous solution to flocculate, washing flocculate, and vacuum drying at 60 ℃ to obtain modified graphene master batch.
Preparing a graphene rubber composition:
Examples
Graphene rubber composition components: 100g of natural rubber, 83.2g of modified graphene masterbatch (prepared in example 1), N23486.8g of carbon black, 5.4g of C5 petroleum resin, 5.4g of zinc oxide, 3.6g of stearic acid, 2.7g of sulfur powder and 1.8g of accelerator NS1.
Adding natural rubber into an internal mixer at 88 ℃ for mixing for 30 seconds at 80 rpm, and then adding modified graphene masterbatch into the internal mixer for mixing for 30 seconds at 80 rpm; the rotor is rotated and adjusted to 60 revolutions per minute, carbon black, C5 petroleum resin and stearic acid are added into an internal mixer, when the temperature is raised to 125 ℃, the weight is lifted for cleaning, and the temperature is raised to 155 ℃ for discharging glue. And cooling the mixed sizing material to room temperature, and when the temperature of the open mill is raised to 60 ℃, mixing the sizing material, zinc oxide, sulfur and accelerator NS until the sizing material, the zinc oxide, the sulfur and the accelerator NS are uniformly dispersed, wherein the temperature of the mixing process is not more than 110 ℃.
Comparative example
Rubber composition components: 180g of natural rubber, 23490g of carbon black N, 5.4g of C5 petroleum resin, 5.4g of zinc oxide, 3.6g of stearic acid, 2.7g of sulfur powder and 1.8g of accelerator NS1.
When the temperature of the internal mixer is 88 ℃, adding natural rubber into the internal mixer, mixing for 30 seconds at 80 revolutions per minute, regulating the rotor speed to 60 revolutions per minute, adding carbon black, C5 petroleum resin and stearic acid into the internal mixer, cleaning a lifting weight when the temperature is increased to 125 ℃, and discharging the rubber when the temperature is increased to 155 ℃. And cooling the mixed sizing material to room temperature, and when the temperature of the open mill is raised to 60 ℃, mixing the sizing material, zinc oxide, sulfur and accelerator NS until the sizing material, the zinc oxide, the sulfur and the accelerator NS are uniformly dispersed, wherein the temperature of the mixing process is not more than 110 ℃.
It can be seen from examples and comparative examples that the DIN abrasion resistance and wet skid resistance of the rubber compound are improved, the hysteresis heat generation is reduced, and the modulus and the tearing strength of the rubber compound are also greatly improved by adding the graphene masterbatch.
The foregoing is merely specific embodiments of the disclosure, but the protection scope of the disclosure is not limited thereto, and any person skilled in the art can easily think about changes or substitutions within the technical scope of the disclosure, and it is intended to cover the scope of the disclosure. Therefore, the protection scope of the present disclosure shall be subject to the protection scope of the claims.
Claims (10)
1. The graphene rubber composition for the tire tread comprises a diene elastomer, modified graphene masterbatch, reinforcing filler, resin, an activator, an accelerator and a vulcanizing agent;
The preparation method is characterized in that the modified graphene masterbatch takes graphene oxide as a raw material, is modified by a silane coupling agent, is reduced, is filtered and washed after the reaction is finished, uniformly disperses filter cakes in water or an organic solvent, and is mixed with latex, flocculated and dried to obtain the modified graphene masterbatch.
2. The graphene rubber composition for tire tread according to claim 1, wherein the diene elastomer is one or more selected from the group consisting of natural rubber, synthetic isoprene rubber, butadiene rubber, styrene butadiene rubber and elastomer mixtures.
3. The graphene rubber composition for tire tread according to claim 1, wherein the modified graphene is prepared from graphene oxide, the specific surface area of the graphene oxide is 100-400 m2/g, the sheet diameter is 0.05-30 μm, and the modifier is a silane coupling agent.
4. The graphene rubber composition for tire tread according to claim 1, wherein the latex used for the modified graphene mother rubber comprises one or more of natural latex and other synthetic latex, and the flocculant of the modified graphene and latex is one or more of sulfuric acid, acetic acid, calcium chloride and dinitrile diamine formaldehyde condensate.
5. The graphene rubber composition for a tire tread according to claim 1, wherein the mass of the modified graphene in the modified graphene masterbatch is 1% to 10% of the mass of the dry rubber.
6. The graphene rubber composition for a tire tread according to claim 5, wherein the modified graphene masterbatch is added in an amount of 100 parts, and the diene elastomer is added in an amount of 20 to 200 parts.
7. The graphene rubber composition for tire tread according to claim 6, wherein the reinforcing filler is one or more selected from carbon black, white carbon black and carbon nanotubes, and the diene elastomer is added in an amount of 50 to 160 parts of the reinforcing filler.
8. The graphene rubber composition for tire tread according to claim 7, wherein the resin is one or more selected from octyl phenolic resin, phenolic epoxy resin, C5 petroleum resin, anti-wet-skid resin and anti-tear resin, and the addition amount is 0 to 10 parts.
9. The graphene rubber composition for a tire tread according to claim 8, wherein the mass of the modified graphene in the modified graphene masterbatch is 3% to 6% of the mass of the dry rubber, 40 to 100 parts of the modified graphene masterbatch is added to the diene elastomer, 60 to 120 parts of the reinforcing filler is added to the diene elastomer, and the resin is added in an amount of 2 to 6 parts.
10. A graphene rubber composition for tire tread according to any one of claims 1 to 9, wherein the conditions for kneading the graphene rubber composition comprise the steps of:
Firstly, putting a diene elastomer into an internal mixer at the temperature of 80-90 ℃ at the rotor speed of 60-90 r/min for plasticating time of 20-60 seconds;
step two, putting the modified graphene masterbatch into an internal mixer to mix the modified graphene masterbatch with a diene elastomer, wherein the rotating speed of a rotor is 60-90 r/min, and the mixing time is 20-60 seconds;
step three, adding reinforcing filler, resin and protective agent into an internal mixer to mix the reinforcing filler, resin and protective agent with the sizing material in the step two, wherein the rotating speed of a rotor is 30-70 r/min, the mixing time is 60-240 seconds, and the sizing material discharging temperature is 130-160 ℃;
And step four, cooling the mixed sizing material to room temperature, adding an activating agent, an accelerating agent and sulfur into the sizing material by using an open mill or an internal mixer, and uniformly mixing the mixed sizing material with the sizing material after the step three, wherein the temperature of the mixing process is not more than 110 ℃.
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