CN116535747B - Tire tread rubber composition and preparation method thereof - Google Patents
Tire tread rubber composition and preparation method thereof Download PDFInfo
- Publication number
- CN116535747B CN116535747B CN202310718890.9A CN202310718890A CN116535747B CN 116535747 B CN116535747 B CN 116535747B CN 202310718890 A CN202310718890 A CN 202310718890A CN 116535747 B CN116535747 B CN 116535747B
- Authority
- CN
- China
- Prior art keywords
- parts
- component
- palygorskite
- tire tread
- rubber composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 229920001971 elastomer Polymers 0.000 title claims abstract description 61
- 239000005060 rubber Substances 0.000 title claims abstract description 60
- 239000000203 mixture Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 229920003052 natural elastomer Polymers 0.000 claims abstract description 34
- 229920001194 natural rubber Polymers 0.000 claims abstract description 34
- 244000043261 Hevea brasiliensis Species 0.000 claims abstract description 33
- 229920002725 thermoplastic elastomer Polymers 0.000 claims abstract description 30
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 20
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 12
- 230000003712 anti-aging effect Effects 0.000 claims abstract description 12
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 12
- 229920005549 butyl rubber Polymers 0.000 claims abstract description 11
- 239000006229 carbon black Substances 0.000 claims abstract description 11
- 239000011787 zinc oxide Substances 0.000 claims abstract description 10
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims abstract description 10
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000011593 sulfur Substances 0.000 claims abstract description 9
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 9
- 229920000181 Ethylene propylene rubber Polymers 0.000 claims abstract description 8
- 229920002302 Nylon 6,6 Polymers 0.000 claims abstract description 8
- 150000003951 lactams Chemical class 0.000 claims abstract description 8
- 229920005557 bromobutyl Polymers 0.000 claims abstract description 5
- 239000005038 ethylene vinyl acetate Substances 0.000 claims abstract description 5
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims abstract description 5
- 229910052625 palygorskite Inorganic materials 0.000 claims description 59
- 238000002156 mixing Methods 0.000 claims description 37
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 22
- 239000000725 suspension Substances 0.000 claims description 19
- 238000007599 discharging Methods 0.000 claims description 17
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 claims description 16
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 claims description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 8
- 229960002446 octanoic acid Drugs 0.000 claims description 8
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 claims description 7
- 238000010894 electron beam technology Methods 0.000 claims description 7
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- 230000003213 activating effect Effects 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000002844 melting Methods 0.000 claims description 6
- 230000008018 melting Effects 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 235000021314 Palmitic acid Nutrition 0.000 claims description 5
- 239000003292 glue Substances 0.000 claims description 5
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 238000009210 therapy by ultrasound Methods 0.000 claims description 4
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- 230000005855 radiation Effects 0.000 claims description 3
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 3
- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 claims description 2
- 239000005635 Caprylic acid (CAS 124-07-2) Substances 0.000 claims description 2
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 2
- 239000000194 fatty acid Substances 0.000 claims description 2
- 229930195729 fatty acid Natural products 0.000 claims description 2
- 238000005096 rolling process Methods 0.000 abstract description 11
- 239000000463 material Substances 0.000 abstract description 5
- 239000000446 fuel Substances 0.000 abstract description 4
- 230000000052 comparative effect Effects 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 6
- 238000005299 abrasion Methods 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 4
- 230000001678 irradiating effect Effects 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- GYSCBCSGKXNZRH-UHFFFAOYSA-N 1-benzothiophene-2-carboxamide Chemical compound C1=CC=C2SC(C(=O)N)=CC2=C1 GYSCBCSGKXNZRH-UHFFFAOYSA-N 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- DEQZTKGFXNUBJL-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)cyclohexanamine Chemical compound C1CCCCC1NSC1=NC2=CC=CC=C2S1 DEQZTKGFXNUBJL-UHFFFAOYSA-N 0.000 description 2
- 239000005543 nano-size silicon particle Substances 0.000 description 2
- 229910021392 nanocarbon Inorganic materials 0.000 description 2
- 239000012802 nanoclay Substances 0.000 description 2
- 239000002135 nanosheet Substances 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000002052 molecular layer Substances 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical group CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920006111 poly(hexamethylene terephthalamide) Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/04—Thermoplastic elastomer
-
- 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
Abstract
The application discloses a tire tread rubber composition and a preparation method thereof, and belongs to the technical field of rubber materials. A tire tread rubber composition comprising, in parts by weight: 40-60 parts of modified natural rubber, 35-50 parts of thermoplastic elastomer, 10-20 parts of carbon black, 6-10 parts of sulfur, 4-8 parts of zinc stearate, 2-6 parts of zinc oxide, 1-5 parts of silane coupling agent, 0.5-3 parts of anti-aging agent and 1-3 parts of accelerator; the thermoplastic elastomer is composed of a first component, a second component and a third component; the first component is polydodecyl lactam, polyhexamethylene adipamide or polyhexamethylene adipamide; the second component is butyl rubber or brominated butyl rubber; the third component is ethylene-vinyl acetate copolymer grafted maleic anhydride or ethylene-propylene rubber grafted maleic anhydride. The tire tread rubber composition can improve the wear resistance of the tire, reduce the rolling resistance of the tire, effectively prolong the service life of the vehicle and improve the fuel economy.
Description
Technical Field
The application relates to a tire tread rubber composition and a preparation method thereof, belonging to the technical field of rubber materials.
Background
Rubber is a polymer material widely used in the automobile industry, has the advantages of light weight, high strength, corrosion resistance, easy molding and the like, has an important role in nonmetallic materials for automobiles, and is difficult to replace by other materials. Tires are one of the main components constituting automobiles, and are components having the largest rubber ratio used in automobiles, and play an important role in automobile systems.
In the normal running process of an automobile, the tire and the road are rubbed to cause gradual abrasion of tread rubber, so that the tire tread is shallow until the tire tread is worn down, if the tire is in contact with uneven road surfaces, sharp objects or bad weather, the abrasion is aggravated, the ground grabbing property of the tire is reduced, the braking distance of the automobile under wet skid or bad road conditions is increased, and the skid risk is increased. Natural rubber is the earliest natural elastomer found by human beings, and the annual consumption of the natural rubber is rapidly increased along with the development of the world industry, and compared with artificially synthesized rubber, the natural rubber has excellent wear resistance, insulativity, air tightness and bending resistance, and has wide application prospect in the field of automobile tires.
Chinese patent CN104672519a discloses a wear-resistant rubber tyre made from the following raw materials: natural rubber, nitrile rubber, butadiene rubber, phenolic resin, nano carbon black, nano silicon dioxide, nano clay and p-phenylenediamine. The nano carbon black, the nano silicon dioxide and the nano clay can effectively improve the strength of the tire, so that the tire has stronger wear resistance; however, the addition of these materials also increases the cohesion and tackiness of the tire, resulting in an increase in rolling resistance of the tire, reducing the fuel economy of the vehicle. Therefore, it is a great need for a person skilled in the art to provide a rubber composition that can improve the wear resistance of a tire without increasing the rolling resistance thereof.
Disclosure of Invention
In order to solve the problems, the tire tread rubber composition and the preparation method thereof are provided, so that the wear resistance of the tire can be improved, the rolling resistance of the tire can be reduced, the service life of a vehicle can be effectively prolonged, and the fuel economy can be improved.
The invention adopts the following technical scheme:
According to an aspect of the present application, there is provided a tire tread rubber composition comprising, in parts by weight: 40-60 parts of modified natural rubber, 35-50 parts of thermoplastic elastomer, 10-20 parts of carbon black, 6-10 parts of sulfur, 4-8 parts of zinc stearate, 2-6 parts of zinc oxide, 1-5 parts of silane coupling agent, 0.5-3 parts of anti-aging agent and 1-3 parts of accelerator;
The thermoplastic elastomer is composed of a first component, a second component and a third component;
the first component is polydodecyl lactam, polyhexamethylene adipamide or polyhexamethylene adipamide;
The second component is butyl rubber or brominated butyl rubber;
The third component is ethylene-vinyl acetate copolymer grafted maleic anhydride or ethylene-propylene rubber grafted maleic anhydride.
Optionally, the weight ratio of the first component, the second component and the third component is (0.3-0.5): 1: (0.1-0.3).
Optionally, the preparation method of the thermoplastic elastomer comprises the following steps:
stirring and melting the first component at 180-220 ℃, adding the third component, mixing uniformly, then adding the second component, and radiating with electron beam at a radiation dose of 35-60kGy to obtain the thermoplastic elastomer.
Optionally, the preparation method of the modified natural rubber comprises the following steps:
S1, heating and activating palygorskite at 100-200 ℃ for 1-4 hours, then dissolving C 6-C12 fatty acid in an organic solvent, ultrasonically mixing the activated palygorskite for 6-10 hours, and drying to obtain pretreated palygorskite;
S2, dispersing the pretreated palygorskite in an ultrasonic treatment solvent, performing ultrasonic stripping treatment with the power of 170-250w and the time of 1.5-3h, and centrifuging to obtain palygorskite suspension with the concentration of 1.8-2.5 mg/mL;
S3, adding the palygorskite suspension into the natural latex, fully stirring at 130-300rpm, then rapidly pouring into a calcium chloride solution, and crushing, washing and drying to obtain the modified natural rubber.
Optionally, the C 6-C12 fatty acid accounts for 2.5-6% of the total weight of the palygorskite.
Optionally, the palygorskite suspension comprises 0.5-1.5% of the total weight of the natural latex.
Optionally, the C 6-C12 fatty acid is one or a combination of more than two of palmitic acid, caprylic acid, caproic acid and capric acid;
The ultrasonic treatment solvent is dimethylformamide, sodium dodecyl benzene sulfonate aqueous solution or chloroform.
Alternatively, the organic solvent is ethanol or dichloromethane.
Optionally, the anti-aging agent is one or more than two of 4010, RD, 2246 and DFC-34;
the accelerator is one or the combination of more than two of NS, DPG, CZ;
The silane coupling agent is one or the combination of more than two of Si-69, KH550 and NXT.
According to still another aspect of the present application, there is provided a method for producing the tire tread rubber composition as described in any one of the above, comprising the steps of:
(1) Adding the modified natural rubber and the thermoplastic elastomer into an internal mixer, and mixing for 40-65 seconds to obtain a first masterbatch;
(2) Adding the first masterbatch, carbon black, zinc stearate, zinc oxide and an anti-aging agent in the step (1) into an internal mixer, mixing for 20-30 seconds, adding a silane coupling agent, and mixing for 75-200 seconds to obtain a second masterbatch;
(3) Adding the second masterbatch, sulfur and accelerator in the step (2) into an internal mixer, and mixing for 50-75 seconds to obtain the tire tread rubber composition.
Optionally, in the step (1), the glue discharging temperature is 125-140 ℃;
in the step (2), the glue discharging temperature is 105-115 ℃;
in the step (3), the glue discharging temperature is 95-100 ℃.
The beneficial effects of the application include, but are not limited to:
1. According to the tire tread rubber composition, the addition of palygorskite in the modified natural rubber increases the hardness and rigidity of the rubber, so that the wear resistance of the tire can be improved, the deformation of the tire in the rolling process can be resisted, and the rolling resistance of the tire can be reduced; the addition of the thermoplastic elastomer can improve the fatigue performance of the tire, so that the tire can still keep good elasticity and durability under the working conditions of long-time use, frequent bending and the like; the added zinc stearate and zinc oxide are used for filling pores and defects in rubber, and the compactness and the firmness of the tire are improved, so that the rubber abrasion under severe conditions is improved, and the service life of the tire is prolonged; the hardness of the tire tread rubber composition is 63-65, the tensile strength is 28.0-28.4MPa, the elongation at break is 481-485%, the rebound performance is 64-68%, the Aldrich wear is 0.117-0.121cm 3/1.61 km, the Tan delta @60 ℃ is 0.062-0.067, the balance between the wear resistance and the rolling resistance is realized, the fuel efficiency and the running stability are improved, and the performance requirement of the tire is met.
2. In the process of preparing the elastomer by blending the first component and the second component, the introduced third component not only serves as a solubilizer to enhance the compatibility and the adhesion between the first component and the second component and improve the uniformity and the stability of the thermoplastic elastomer, but also has maleic anhydride functional groups capable of reacting with amine groups in the first component and/or double bonds in the second component to form a crosslinked structure, so that the flexibility and the tensile strength of the thermoplastic elastomer are enhanced; after electron beam irradiation, the crosslinking reaction degree is increased, the mechanical property of the thermoplastic elastomer is further enhanced, and the elongation at break is not influenced, so that the abrasion resistance and rolling resistance of the tire are balanced.
3. According to the tire tread rubber composition disclosed by the application, the surface of the pretreated palygorskite is covered with the fatty acid molecular layer, wherein the hydrophobic alkyl chain extends between the palygorskite layers, and the hydrophilic carboxyl part faces to the interface, so that the interaction between the palygorskite and the natural rubber is enhanced, the occurrence of agglomeration phenomenon is reduced, the palygorskite is more easily and uniformly dispersed in the natural rubber, the arrangement structure of the natural rubber is improved, and the deformation of the natural rubber is reduced, so that the wear resistance of the tire is improved, and the rolling resistance of the tire is reduced; hydrophilic carboxyl is introduced into the surface of the pretreated palygorskite, so that the hydrophilic property of the palygorskite is enhanced, the palygorskite is easier to interact with water molecules in a solvent in the ultrasonic stripping process, the adsorption force between palygorskite nano-sheets is weakened, and the palygorskite nano-sheets are easier to strip from a layered stacking structure, so that a dispersed suspension is formed.
4. The preparation method of the tire tread rubber composition is simple to operate and high in practicability, and by reasonably controlling the mixing sequence, mixing time and rubber discharging temperature of the raw materials, the tread rubber composition can be fully mixed in an internal mixer, so that good fluidity and plasticity of the tread rubber composition are ensured, subsequent forming processing is facilitated, the uniform distribution of the raw materials in the tread rubber composition is ensured, and the performance consistency and stability of the tire are improved.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The raw materials or instruments used are conventional products available commercially without identifying the manufacturer.
Example 1
A method of preparing a tire tread rubber composition comprising the steps of:
(1) Adding 40 parts of modified natural rubber and 50 parts of thermoplastic elastomer into an internal mixer, mixing for 40 seconds, and obtaining a first masterbatch, wherein the rubber discharging temperature is 140 ℃;
(2) Adding the first masterbatch, 10 parts of carbon black, 8 parts of zinc stearate, 2 parts of zinc oxide and 3 parts of anti-aging agent 4010 in the step (1) into an internal mixer, mixing for 20 seconds, adding 1 part of silane coupling agent KH550, mixing for 75 seconds, and obtaining a second masterbatch at a rubber discharging temperature of 115 ℃;
(3) Adding the second masterbatch, 6 parts of sulfur and 3 parts of accelerator NS in the step (2) into an internal mixer, and mixing for 50 seconds, wherein the rubber discharging temperature is 100 ℃, so as to obtain a tire tread rubber composition;
the preparation method of the thermoplastic elastomer comprises the following steps:
stirring and melting polyhexamethylene adipamide at 180 ℃, adding ethylene-propylene rubber grafted maleic anhydride, uniformly mixing, and then adding butyl rubber, wherein the weight ratio of the polyhexamethylene adipamide to the butyl rubber to the ethylene-propylene rubber grafted maleic anhydride is 0.3:1:0.1, and irradiating with electron beam at a dose of 35kGy to obtain a thermoplastic elastomer.
The preparation method of the modified natural rubber comprises the following steps:
S1, heating and activating palygorskite at 100 ℃ for 4 hours, then dissolving caproic acid in dichloromethane, ultrasonically mixing the solution with the activated palygorskite for 6 hours, wherein the caproic acid accounts for 2.5% of the total weight of the palygorskite, and drying to obtain pretreated palygorskite;
s2, dispersing the pretreated palygorskite in dimethylformamide, performing ultrasonic stripping treatment with the power of 170w and the time of 3h, and centrifuging to obtain palygorskite suspension with the concentration of 1.8 mg/mL;
S3, adding the palygorskite suspension into the natural latex, fully stirring at 130rpm, wherein the palygorskite suspension accounts for 0.5% of the total weight of the natural latex, rapidly pouring into a calcium chloride solution, and crushing, washing and drying to obtain the modified natural rubber.
Example 2
A method of preparing a tire tread rubber composition comprising the steps of:
(1) Adding 50 parts of modified natural rubber and 43 parts of thermoplastic elastomer into an internal mixer, mixing for 50 seconds, and obtaining a first masterbatch, wherein the rubber discharging temperature is 132 ℃;
(2) Adding the first masterbatch, 15 parts of carbon black, 6 parts of zinc stearate, 4 parts of zinc oxide, 1 part of an anti-aging agent RD and 0.8 part of an anti-aging agent DFC-34 in the step (1) into an internal mixer, mixing for 25 seconds, adding 2 parts of a silane coupling agent Si-69 and 1 part of a silane coupling agent NXT, mixing for 140 seconds, and obtaining a second masterbatch at a rubber discharging temperature of 110 ℃;
(3) Adding the second masterbatch, 8 parts of sulfur, 1 part of accelerator DPG, 0.5 part of accelerator NS and 0.5 part of accelerator CZ in the step (2) into an internal mixer, mixing for 60 seconds, and obtaining a tire tread rubber composition at a rubber discharging temperature of 98 ℃;
the preparation method of the thermoplastic elastomer comprises the following steps:
Stirring and melting the polydodecyl lactam at 200 ℃, adding ethylene-propylene rubber grafted maleic anhydride, uniformly mixing, and then adding butyl rubber, wherein the weight ratio of the polydodecyl lactam, the ethylene-propylene rubber grafted maleic anhydride and the butyl rubber is 0.4:1:0.2, and irradiating with electron beam at a dose of 45kGy to obtain a thermoplastic elastomer.
The preparation method of the modified natural rubber comprises the following steps:
S1, heating and activating palygorskite at 150 ℃ for 2.5 hours, dissolving octanoic acid and palmitic acid in ethanol, ultrasonically mixing the mixture with the activated palygorskite for 8 hours, wherein the octanoic acid and the palmitic acid account for 4.5% of the total weight of the palygorskite, and drying to obtain pretreated palygorskite;
S2, dispersing the pretreated palygorskite in a sodium dodecyl benzene sulfonate aqueous solution, performing ultrasonic stripping treatment with the power of 200w and the time of 2.5h, and centrifuging to obtain a palygorskite suspension with the concentration of 2 mg/mL;
S3, adding the palygorskite suspension into the natural latex, fully stirring at 200rpm, wherein the palygorskite suspension accounts for 1% of the total weight of the natural latex, rapidly pouring into a calcium chloride solution, and crushing, washing and drying to obtain the modified natural rubber.
Example 3
A method of preparing a tire tread rubber composition comprising the steps of:
(1) Adding 60 parts of modified natural rubber and 35 parts of thermoplastic elastomer into an internal mixer, mixing for 65 seconds, and obtaining a first masterbatch, wherein the rubber discharging temperature is 125 ℃;
(2) Adding the first masterbatch, 20 parts of carbon black, 4 parts of zinc stearate, 6 parts of zinc oxide and 0.5 part of anti-aging agent 2246 in the step (1) into an internal mixer, mixing for 30 seconds, adding 5 parts of silane coupling agent NXT, mixing for 200 seconds, and obtaining a second masterbatch at a rubber discharging temperature of 105 ℃;
(3) Adding the second masterbatch, 10 parts of sulfur and 1 part of accelerator CZ in the step (2) into an internal mixer, mixing for 75 seconds, wherein the rubber discharging temperature is 95 ℃, and obtaining a tire tread rubber composition;
the preparation method of the thermoplastic elastomer comprises the following steps:
stirring and melting the polydodecyl hexamethylenediamine at 220 ℃, adding ethylene-vinyl acetate copolymer grafted maleic anhydride, uniformly mixing, and then adding brominated butyl rubber, wherein the weight ratio of the polydodecyl hexamethylenediamine to the brominated butyl rubber to the ethylene-vinyl acetate copolymer grafted maleic anhydride is 0.5:1:0.3, and irradiating with electron beam at a dose of 60kGy to obtain a thermoplastic elastomer.
The preparation method of the modified natural rubber comprises the following steps:
S1, heating and activating palygorskite at 200 ℃ for 1h, dissolving decanoic acid in ethanol, ultrasonically mixing the decanoic acid with the activated palygorskite for 10h, wherein the decanoic acid accounts for 6% of the total weight of the palygorskite, and drying to obtain pretreated palygorskite;
S2, dispersing the pretreated palygorskite in chloroform, performing ultrasonic stripping treatment with the power of 250w and the time of 1.5h, and centrifuging to obtain a palygorskite suspension with the concentration of 2.5 mg/mL;
S3, adding the palygorskite suspension into the natural latex, fully stirring at 300rpm, wherein the palygorskite suspension accounts for 1.5% of the total weight of the natural latex, rapidly pouring into a calcium chloride solution, and crushing, washing and drying to obtain the modified natural rubber.
Comparative example 1
A method of preparing a tire tread rubber composition comprising the steps of:
(1) Adding 75 parts of modified natural rubber, 20 parts of thermoplastic elastomer, 30 parts of carbon black, 10 parts of zinc oxide and 5 parts of anti-aging agent 616 into an internal mixer, mixing for 30 seconds, adding 7 parts of silane coupling agent KH570, mixing for 250 seconds, and discharging the rubber at 105 ℃ to obtain master batch;
(2) Adding the masterbatch, 4 parts of sulfur and4 parts of accelerator DM in the step (1) into an internal mixer, and mixing for 35 seconds, wherein the rubber discharging temperature is 90 ℃, so as to obtain the tire tread rubber composition.
Comparative example 2
The preparation method of the thermoplastic elastomer comprises the following steps:
stirring and melting the polydodecyl lactam at 250 ℃, and then adding butyl rubber, wherein the weight ratio of the polydodecyl lactam to the butyl rubber is 1:1, and irradiating with electron beam at a radiation dose of 30kGy to obtain a thermoplastic elastomer.
Comparative example 3
The preparation method of the modified natural rubber comprises the following steps:
S1, heating and activating palygorskite at 250 ℃ for 0.5h, dissolving octanoic acid in ethanol, ultrasonically mixing the octanoic acid with the activated palygorskite for 4h, wherein the octanoic acid accounts for 8% of the total weight of the palygorskite, and drying to obtain pretreated palygorskite;
S2, dispersing the pretreated palygorskite in an aqueous solution, performing ultrasonic stripping treatment with the power of 150w and the time of 5h, and centrifuging to obtain a palygorskite suspension with the concentration of 1 mg/mL;
S3, adding the palygorskite suspension into the natural latex, fully stirring at 350rpm, wherein the palygorskite suspension accounts for 2% of the total weight of the natural latex, rapidly pouring into a calcium chloride solution, and crushing, washing and drying to obtain the modified natural rubber.
Comparative example 4
The difference from example 2 is that: the modified natural rubber is replaced with natural rubber, and a method for producing the modified natural rubber is not disclosed.
Comparative example 5
The difference from example 2 is that: the thermoplastic elastomer is replaced with butyl rubber, and a method for preparing the thermoplastic elastomer is not disclosed.
Comparative example 6
The difference from example 2 is that: zinc stearate is replaced with stearic acid.
Comparative example 7
The difference from example 2 is that: the ethylene-propylene rubber grafted maleic anhydride was replaced with an acrylate.
Comparative example 8
The difference from example 2 is that: the polydodecyl lactam is replaced by the poly (hexamethylene terephthalamide); butyl rubber is replaced with styrene butadiene rubber.
Comparative example 9
The difference from example 2 is that: octanoic acid and palmitic acid are replaced by butyric acid.
Comparative example 10
The difference from example 2 is that: palygorskite is replaced by montmorillonite.
Test examples
The tire tread rubber compositions of examples 1 to 3 and comparative examples 1 to 10 were tested for performance;
Hardness, tensile properties, resilience properties and acle abrasion were tested according to GB/T531.1-2008, GB/T528-2009, GB/T1681-2009 and GB/T1689-2014, respectively;
the rolling resistance is tested by adopting RPA, the frequency is 10Hz and the strain is 7% in terms of tan delta value at 60 ℃;
The test results are shown in Table 1.
TABLE 1
As can be seen from Table 1, the tire tread rubber compositions of examples 1 to 3 were less varied in hardness (63 to 65) than comparative examples 1 to 10, and were excellent in tensile strength (28.0 to 28.4 MPa), elongation at break (481 to 485%) and rebound resilience (64 to 68%), respectively, improved by at least 2.6%, 2.8% and 12.3%, respectively, and had lower Aldrich wear (0.117 to 0.121cm 3/1.61 km) and Tanδ@60 ℃ (0.062 to 0.067), respectively, reduced by 5.0% and 6.0%, respectively, wherein the tire tread rubber composition of example 2 was excellent in overall performance, and had a hardness of 64, a tensile strength of 28.4MPa, an elongation at break of 485%, an Aldrich wear of 0.117cm 3/1.61 km, a Tan@60 ℃ of 0.062 60%, and an rebound resilience of 68%, and was favorable for balancing the wear resistance and rolling resistance of the tire, and had significant advantages when applied to a tire tread.
The above description is only an example of the present application, and the scope of the present application is not limited to the specific examples, but is defined by the claims of the present application. Various modifications and variations of the present application will be apparent to those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the technical idea and principle of the present application should be included in the protection scope of the present application.
Claims (7)
1. A tire tread rubber composition characterized by comprising, in parts by weight: 40-60 parts of modified natural rubber, 35-50 parts of thermoplastic elastomer, 10-20 parts of carbon black, 6-10 parts of sulfur, 4-8 parts of zinc stearate, 2-6 parts of zinc oxide, 1-5 parts of silane coupling agent, 0.5-3 parts of anti-aging agent and 1-3 parts of accelerator;
The thermoplastic elastomer is composed of a first component, a second component and a third component;
the first component is polydodecyl lactam, polyhexamethylene adipamide or polyhexamethylene adipamide;
The second component is butyl rubber or brominated butyl rubber;
The third component is ethylene-vinyl acetate copolymer grafted maleic anhydride or ethylene-propylene rubber grafted maleic anhydride;
The weight ratio of the first component, the second component and the third component is (0.3-0.5): 1: (0.1-0.3);
the preparation method of the thermoplastic elastomer comprises the following steps:
Stirring and melting the first component at 180-220 ℃, adding the third component, uniformly mixing, then adding the second component, and radiating with electron beam, wherein the radiation dose is 35-60kGy, thus obtaining a thermoplastic elastomer;
the preparation method of the modified natural rubber comprises the following steps:
S1, heating and activating palygorskite at 100-200 ℃ for 1-4 hours, then dissolving C 6-C12 fatty acid in an organic solvent, ultrasonically mixing the activated palygorskite for 6-10 hours, and drying to obtain pretreated palygorskite;
S2, dispersing the pretreated palygorskite in an ultrasonic treatment solvent, performing ultrasonic stripping treatment with the power of 170-250w and the time of 1.5-3h, and centrifuging to obtain palygorskite suspension with the concentration of 1.8-2.5 mg/mL;
S3, adding the palygorskite suspension into the natural latex, fully stirring at 130-300rpm, then rapidly pouring into a calcium chloride solution, and crushing, washing and drying to obtain the modified natural rubber.
2. The tire tread rubber composition of claim 1, wherein the C 6-C12 fatty acids comprise 2.5-6% by total weight of palygorskite.
3. The tire tread rubber composition of claim 1, wherein the palygorskite suspension comprises 0.5 to 1.5% by weight of the total natural latex.
4. The tire tread rubber composition of claim 1, wherein the C 6-C12 fatty acid is one or a combination of two or more of palmitic acid, caprylic acid, caproic acid, capric acid;
The ultrasonic treatment solvent is dimethylformamide, sodium dodecyl benzene sulfonate aqueous solution or chloroform.
5. The tire tread rubber composition of claim 1, wherein the anti-aging agent is one or a combination of two or more of 4010, RD, 2246, DFC-34;
the accelerator is one or the combination of more than two of NS, DPG, CZ;
The silane coupling agent is one or the combination of more than two of Si-69, KH550 and NXT.
6. The method for producing a tire tread rubber composition as claimed in any one of claims 1 to 5, comprising the steps of:
(1) Adding the modified natural rubber and the thermoplastic elastomer into an internal mixer, and mixing for 40-65 seconds to obtain a first masterbatch;
(2) Adding the first masterbatch, carbon black, zinc stearate, zinc oxide and an anti-aging agent in the step (1) into an internal mixer, mixing for 20-30 seconds, adding a silane coupling agent, and mixing for 75-200 seconds to obtain a second masterbatch;
(3) Adding the second masterbatch, sulfur and accelerator in the step (2) into an internal mixer, and mixing for 50-75 seconds to obtain the tire tread rubber composition.
7. The method for producing a tire tread rubber composition according to claim 6, wherein in the step (1), the rubber discharge temperature is 125 to 140 ℃;
in the step (2), the glue discharging temperature is 105-115 ℃;
in the step (3), the glue discharging temperature is 95-100 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310718890.9A CN116535747B (en) | 2023-06-16 | 2023-06-16 | Tire tread rubber composition and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310718890.9A CN116535747B (en) | 2023-06-16 | 2023-06-16 | Tire tread rubber composition and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN116535747A CN116535747A (en) | 2023-08-04 |
| CN116535747B true CN116535747B (en) | 2024-04-23 |
Family
ID=87443832
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310718890.9A Active CN116535747B (en) | 2023-06-16 | 2023-06-16 | Tire tread rubber composition and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116535747B (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108410033A (en) * | 2018-04-20 | 2018-08-17 | 刘凡领 | A kind of preparation method of modified natural rubber type tire tread glue |
| CN111333931A (en) * | 2020-03-05 | 2020-06-26 | 山东阳谷华泰化工股份有限公司 | High-performance environment-friendly tire tread rubber material and preparation method thereof |
-
2023
- 2023-06-16 CN CN202310718890.9A patent/CN116535747B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108410033A (en) * | 2018-04-20 | 2018-08-17 | 刘凡领 | A kind of preparation method of modified natural rubber type tire tread glue |
| CN111333931A (en) * | 2020-03-05 | 2020-06-26 | 山东阳谷华泰化工股份有限公司 | High-performance environment-friendly tire tread rubber material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN116535747A (en) | 2023-08-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5706863B2 (en) | Masterbatch, rubber composition and pneumatic tire | |
| EP3075775B1 (en) | Rubber composition for tires and pneumatic tire | |
| WO2016199555A1 (en) | Pneumatic tire and motorcycle tire | |
| US9732165B2 (en) | Rubber composition for tires and pneumatic tire | |
| JP3392249B2 (en) | Rubber composition and method for producing the same | |
| WO2004067625A1 (en) | Diene rubber composition and process for producing the same | |
| CN114292450A (en) | Dry mixing method of tire rubber composition, tread composition and low rolling resistance high-performance tire | |
| CN111073067A (en) | Antistatic and wear-resistant aircraft tire tread rubber material and preparation method thereof | |
| JP6050433B1 (en) | Pneumatic tire | |
| JP2019151743A (en) | Rubber composition for tire | |
| CN116535747B (en) | Tire tread rubber composition and preparation method thereof | |
| KR102357628B1 (en) | Rubber composition for tire and tire manufactured by using the same | |
| CN111100343A (en) | Automobile tire rubber material with excellent sound absorption performance and preparation method thereof | |
| CN114921002B (en) | Winter tire tread rubber with hard lamellar structure metal salt, mixing method thereof and tire | |
| Kim et al. | Effects of zinc-free processing AIDS on silica-reinforced tread compounds for green tires | |
| CN111918915A (en) | Rubber composition and tire | |
| KR20050046851A (en) | Rubber composition for tire tread | |
| CN101508800A (en) | Rubber material containing branched stripping type organic montmorillonite and preparation thereof | |
| JP6050434B1 (en) | Tires for motorcycles | |
| CN114196090A (en) | Non-pneumatic tire rubber material and modified carbon black for non-pneumatic tire rubber production | |
| KR100332684B1 (en) | Rubber Composition with Activated Zinc Oxide | |
| KR101074336B1 (en) | Rubber composition of tire tread | |
| CN112210134B (en) | Automobile tire tread composition and manufacturing method thereof | |
| JP3392246B2 (en) | Rubber composition and method for producing the same | |
| KR100863682B1 (en) | Studless snow tire tread rubber composition with snow sensor |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |