CN113462038A - Formula of flexing-resistant tire sidewall - Google Patents
Formula of flexing-resistant tire sidewall Download PDFInfo
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- CN113462038A CN113462038A CN202110837297.7A CN202110837297A CN113462038A CN 113462038 A CN113462038 A CN 113462038A CN 202110837297 A CN202110837297 A CN 202110837297A CN 113462038 A CN113462038 A CN 113462038A
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- 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
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- 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
- B60C1/0025—Compositions of the sidewalls
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
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- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention belongs to the technical field of composite materials, and relates to a flexing-resistant tire side wall formula which comprises natural rubber, butadiene rubber, wollastonite, carbon black, stearic acid, zinc oxide, an anti-aging agent, microcrystalline wax, tackifying resin, an accelerant and sulfur, wherein a vulcanized product of the prepared composite material has good elasticity, and when the vulcanized product bears the damage of periodic mechanical force action, the expansion speed of a flexing fatigue crack is relatively slow, so that the expansion performance of the flexing fatigue crack of the composite material is improved, the flexing resistance of a sizing material is improved, and meanwhile, the Payne effect of mixed rubber is weakened; the wollastonite in the raw materials is low in price, so that the production cost can be further reduced, and the social and economic benefits are improved.
Description
The technical field is as follows:
the invention belongs to the technical field of composite materials, and relates to a flexing-resistant tire side wall formula, which is added with wollastonite, can improve the flexing-resistant performance of rubber materials, and is environment-friendly and energy-saving.
Background art:
the tire is one of the most important components of the automobile, is an extremely important part in the modern automobile industry, and each component of the tire has specific performance indexes, wherein the tire side part of the tire bears repeated bending deformation in the running process of the tire, also bears the damage of ambient temperature, oxygen, ozone and ultraviolet rays, and is a high-flexibility deformation device.
The flex fatigue failure resistance of the rubber is a phenomenon that when the rubber bears periodic mechanical force less than the fatigue failure strength of the rubber, initial microscopic damage is generated on the surface or inside of a material and gradually develops into macroscopic cracks until the material is broken and fails, and further the rubber product loses the use function. The flex fatigue failure resistance of rubber is a very complex dynamic development process, and is the result of the combined action of mechanical and chemical effects, environmental conditions, and factors such as rubber types and inorganic fillers in a rubber formula system. Therefore, it is very important to determine the optimized formulation system when designing the sidewall rubber with higher requirement on flex endurance.
The type of rubber is one of the important factors for restricting the dynamic fatigue performance of rubber products, the flex fatigue resistance of different types of rubber has larger difference, and at present, two or more types of rubber are usually blended to ensure that the composite material obtains more excellent flex fatigue resistance. The natural rubber has excellent rebound resilience, plasticity, insulativity, cold resistance, acid and alkali resistance and the like, and also has excellent flex crack expansion resistance in reciprocating cyclic compression and stretching movement. The regular molecular chain configuration of the butadiene rubber enables the butadiene rubber to have excellent flex crack initiation resistance, and the butadiene rubber is widely applied to the tire manufacturing industry by virtue of excellent elasticity, wear resistance, low heat generation and other properties. Therefore, the use of natural rubber in combination with butadiene rubber in the sidewall rubber has a positive influence on the improvement of the flex resistance.
The reinforcing system is one of important factors influencing the dynamic fatigue performance of the carbon black rubber product. Carbon black is a reinforcing agent commonly used in the rubber industry, the modulus, the wear resistance, the reinforcing performance and the like of a composite material can be improved by filling rubber with the carbon black, but in a pure carbon black filling system, because the interaction energy among fillers is higher and the network structure of the fillers is strong, the internal consumption of a rubber material generated in the process of flexural fatigue failure is increased, the interaction among molecular chains is stronger, the rigidity of the rubber material is increased, the movement of the molecular chains is difficult when the rubber material bears the action of periodic mechanical force, the capability of dispersing and transmitting stress is reduced, the flexural fatigue resistance of the composite material is reduced quickly, and meanwhile, in the process of producing the carbon black, the inevitable dust flying can cause serious dust pollution and is unfavorable for environmental protection.
Wollastonite is a natural industrial mineral with the molecular formula of CaSiO3The rubber composite material has the advantages of white color, good thermal stability, acid and alkali resistance, chemical corrosion resistance, insulativity and the like, abundant reserves, environmental protection and no toxicity, can be used as a filler and a reinforcing agent of the rubber composite material, simultaneously, the carbon black and the wollastonite belong to two fillers with different surface properties, the interaction energy between the carbon black and the wollastonite is lower, the networks of the two fillers are relatively weaker, and the addition of the wollastonite can reduce the internal consumption generated by the breaking of the filler network in the rubber fatigue process and improve the fatigue resistance life of the rubber material. Therefore, based on wollastonite, an environment-friendly flexing-resistant tire side wall formula is developed, the flexing resistance of rubber is improved, and the rubber has a good application prospect.
The invention content is as follows:
the invention aims to overcome the defects in the prior art, and develops a flexing-resistant tire side wall formula, so that the flexing-resistant performance of a tire in practical application is improved, and the fatigue life of a rubber product is prolonged.
In order to achieve the purpose, the invention relates to a flexing-resistant tire side wall formula which comprises the following components in parts by weight: 50-100 parts of natural rubber, 0-50 parts of butadiene rubber, 5-100 parts of wollastonite, 0-100 parts of carbon black, 1-5 parts of stearic acid, 1-5 parts of zinc oxide, 1-6 parts of an anti-aging agent, 1-3 parts of microcrystalline wax, 1-3 parts of tackifying resin, 1-4 parts of an accelerator and 1-3 parts of sulfur.
The natural rubber comprises standard rubber, smoked sheet rubber, crepe rubber and air-dried rubber; the length-diameter ratio of the wollastonite is 5-20: 1, the whiteness is 50-90, the median particle diameter D50 is 1-20 μm, and the structure comprises needle shape, fiber shape and bundle shape; the carbon black is one or a combination of more of N115, N234, N330 and N326; stearic acid is octadecanoic acid; the anti-aging agent is one or a combination of more of an anti-aging agent 4020, an anti-aging agent 4010NA and an anti-aging agent RD; the microcrystalline wax is a hydrocarbon mixture with 18-30 carbon atoms; the accelerant is one or a combination of more of DPG, CZ, TMTD and DM.
Compared with the prior art, the prepared vulcanized product of the composite material has better elasticity, when the vulcanized product is damaged under the action of periodic mechanical force, the expansion speed of the flexural fatigue crack is relatively slow, so that the expansion performance of the flexural fatigue crack of the composite material is improved, the flexural resistance of rubber materials can be improved, and simultaneously, the Payne effect of the rubber compound is weakened, because the filler network structure constructed by the carbon black and the wollastonite together is relatively weak, the filler network structure is easy to break and rebuild under the action of the periodic mechanical force, a molecular chain can adapt to the action of the external force more quickly, and the internal consumption generated by the break of the filler network in the rubber fatigue process is reduced; wollastonite in the raw materials is a natural industrial mineral, is rich in reserves, is environment-friendly and nontoxic, is cheaper than carbon black and white carbon black commonly used in the rubber industry, can further reduce the production cost and improve the social and economic benefits, and the prepared vulcanized product can better synchronize the deformation of rubber with the change of periodic mechanical force, ensure the good flexing resistance of rubber materials and prolong the fatigue life of rubber products.
The specific implementation mode is as follows:
the invention is further illustrated by the following examples.
Example 1:
the flex-resistant tire side wall formula related in the embodiment comprises the following components in parts by weight: 2050 parts of natural rubber STR, 900050 parts of butadiene rubber BR, 5 parts of wollastonite, 49 parts of carbon black, 2 parts of stearic acid, 3 parts of zinc oxide, 40205 parts of anti-aging agent, 0.5 part of anti-aging agent RD, 1.8 parts of microcrystalline wax, 2 parts of C5 resin, 0.9 part of accelerator NS and 202.8 parts of sulfur OT.
Example 2:
the environment-friendly flexing-resistant tire side wall formula related to the embodiment comprises the following components in parts by weight: 2050 parts of natural rubber STR, 900050 parts of butadiene rubber BR, 10 parts of wollastonite, 44 parts of carbon black, 2 parts of stearic acid, 3 parts of zinc oxide, 40205 parts of anti-aging agent RD, 0.5 part of anti-aging agent RD, 1.8 parts of microcrystalline wax, 2 parts of C5 resin, 0.9 part of accelerator NS and 202.8 parts of sulfur OT.
Example 3:
the environment-friendly flexing-resistant tire side wall formula related to the embodiment comprises the following components in parts by weight: 2050 parts of natural rubber STR, 900050 parts of butadiene rubber BR, 15 parts of wollastonite, 39 parts of carbon black, 2 parts of stearic acid, 3 parts of zinc oxide, 40205 parts of anti-aging agent RD, 0.5 part of anti-aging agent RD, 1.8 parts of microcrystalline wax, 2 parts of C5 resin, 0.9 part of accelerator NS and 202.8 parts of sulfur OT.
Example 4:
this example relates to performance testing of composites prepared with flex resistant tire sidewall formulations,
the flex-resistant tire sidewall formulations of examples 1, 2 and 3 were first prepared into composites, the specific process for preparing the composites was as follows:
mixing: putting natural rubber STR20 and butadiene rubber BR9000 into an internal mixer, dropping an upper plug, opening the upper plug after 40 seconds, adding zinc oxide, stearic acid, an antioxidant 4020, an antioxidant RD, microcrystalline wax and C5 resin, and dropping the upper plug; after 30 seconds, the upper plug is opened, 2/3 carbon black is added, and the upper plug falls down; after 30 seconds, opening the upper top bolt, adding wollastonite and the rest carbon black, dropping the upper top bolt, lifting the bolt every other minute to clean leaked rubber, mixing for 5 minutes, discharging the rubber at the temperature of 145 ℃, discharging the master rubber, and discharging the master rubber through an open mill for cooling;
and (3) final refining: thinning the master batch through an open mill, wrapping the rubber with a roller, adding an accelerator NS and sulfur OT20, cutting twice with a left cutter and a right cutter, after finishing feeding, alternately performing rolling and triangular wrapping for four times, and discharging sheets;
and (3) vulcanization: the vulcanization characteristic of the rubber material is measured by a rotor-free vulcanizer, the vulcanization temperature is set to be 150 ℃, the vulcanization pressure is set to be 11MPa, and the vulcanization time is set to be 1.3 Xt 90.
The wollastonite in the formulation of example 1 was then replaced entirely with carbon black as the formulation of comparative example 1: the composite material is prepared from 2050 parts of natural rubber STR, 900050 parts of butadiene rubber BR, 54 parts of carbon black, 2 parts of stearic acid, 3 parts of zinc oxide, 40205 parts of an anti-aging agent, 0.5 part of an anti-aging agent RD, 1.8 parts of microcrystalline wax, 2 parts of C5 resin, 0.9 part of an accelerator NS and 202.8 parts of sulfur OT according to the process.
Finally, the test results of the composite material are shown in the following table:
as can be seen from the table: the Mooney viscosities of examples 1, 2 and 3 are reduced from that of comparative example 1; t10 for examples 1, 2 and 3 is greater than for comparative example 1, indicating that the addition of wollastonite improves the processing safety of the compound; the hardness and the stress at definite elongation of examples 1, 2 and 3 are slightly reduced compared with those of comparative example 1, the elongation at break and the product coefficient of tensile are slightly improved, and the tensile strength is at the same level; the rebound resilience of examples 1, 2 and 3 is improved compared with that of comparative example 1, wherein the rebound resilience of example 3 is improved by 11.3 percent compared with that of comparative example 1; the Δ G' for examples 1, 2 and 3 are all less than that of comparative example 1, indicating that the filler network structure is weaker and the filler is better dispersed in the rubber matrix in examples 1, 2 and 3.
Example 5:
the embodiment relates to a test of the flexing resistance of a composite material prepared by a flexing-resistant tire side wall formula, wherein a notch tool is used for puncturing a flexing-resistant test sample of the composite material prepared in the examples 1, 2 and 3 and the comparative example 1 respectively, so that a notch with the length of 2.5mm is positioned at the center of the sample, the sample is placed in a Delxi subtype flexing-resistant tester for testing, the length of a surface crack of each group of samples under the same fatigue times is measured, and the obtained flexing-resistant crack expansion performance is shown as the following table:
| number of fatigues times 103Length of crack/mm | Comparative example 1 | Example 1 | Example 2 | Example 3 |
| 3 | 6 | 5.5 | 5 | 5.5 |
| 6 | 9 | 8 | 7.5 | 8 |
| 9 | 11 | 10.5 | 9.5 | 9 |
| 12 | 12.5 | 12 | 11 | 11 |
| 15 | 14 | 13 | 12 | 11.5 |
| 18 | 16 | 14.5 | 13.5 | 13 |
As can be seen from the table: when the fatigue times are 3000-12000 times, the length of the flexion fatigue crack is increased by 1.5-3mm, the damage of the material by the destructive action of periodic mechanical force and oxidation reaction is obvious, and the extension of the flexion fatigue crack length is rapid; when the fatigue frequency is 12000-18000 times, the increase of the length of the flexion fatigue crack is 0.5-1.5mm, and because the length of the crack is larger, the damage effect of the periodic mechanical force on the deformation of the flexion fatigue crack is reduced, and the crack expansion speed is relatively slow.
Specifically, the flex fatigue crack lengths of examples 1, 2 and 3 are all less than the flex fatigue crack length of comparative example 1 at the same number of fatigue times, and the flex fatigue crack lengths of examples 1, 2 and 3 are all less increased than the flex fatigue crack length of comparative example 1 at the same interval of fatigue times, wherein the flex resistance performance of example 3 is the best, indicating that: the addition of wollastonite has a blocking effect on the development process of the flex fatigue crack, and along with the weakening of Payne effect, the improvement of elongation at break and rebound rate, the improvement of filler dispersibility and the improvement of rubber elasticity, the deformation of the rubber can be more synchronous with the change of periodic mechanical force, so that the expansion performance of the flex fatigue crack resistance of the composite material is improved, the flex resistance of the rubber material is improved, and the fatigue life of the rubber material is prolonged.
Claims (10)
1. The flexing-resistant tire side wall formula is characterized by comprising natural rubber, butadiene rubber, wollastonite, carbon black, stearic acid, zinc oxide, an anti-aging agent, microcrystalline wax, tackifying resin, an accelerator and sulfur.
2. The flex-resistant tire side-wall formulation of claim 1, wherein the natural rubber is present in an amount of 50 to 100 parts by weight, the butadiene rubber is present in an amount of 0 to 50 parts by weight, the wollastonite is present in an amount of 5 to 100 parts by weight, the carbon black is present in an amount of 0 to 100 parts by weight, the stearic acid is present in an amount of 1 to 5 parts by weight, the zinc oxide is present in an amount of 1 to 5 parts by weight, the antioxidant is present in an amount of 1 to 6 parts by weight, the microcrystalline wax is present in an amount of 1 to 3 parts by weight, the tackifying resin is present in an amount of 1 to 3 parts by weight, the accelerator is present in an amount of 1 to 4 parts by weight, and the sulfur is present in an amount of 1 to 3 parts by weight.
3. The flex-resistant tire sidewall formulation of claims 1 or 2, wherein the natural rubber comprises standard gum, smoked sheet gum, creped gum and air dried gum.
4. The flex resistant tire sidewall formulation of claims 1 or 2, wherein the wollastonite has a structure comprising needles, fibers and strands.
5. The flex resistant tire sidewall formulation of claim 4, wherein the wollastonite has an aspect ratio of 5 to 20: 1, the whiteness is 50-90, and the median particle diameter D50 is 1-20 μm.
6. The flex resistant tire sidewall formulation of claims 1 or 2, wherein the carbon black is one or a combination of N115, N234, N330, N326.
7. The flex resistant tire sidewall formulation of claims 1 or 2, wherein stearic acid is octadecanoic acid.
8. The flex-resistant tire side-wall formulation of claim 1 or 2, wherein the anti-aging agent is one or a combination of anti-aging agent 4020, anti-aging agent 4010NA and anti-aging agent RD.
9. The flex resistant tire sidewall formulation of claim 2, wherein the microcrystalline wax is a hydrocarbon mixture having from 18 to 30 carbon atoms.
10. The flex resistant tire sidewall formulation of claims 1 or 2, wherein the accelerator is one or a combination of DPG, CZ, TMTD and DM.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN202110837297.7A CN113462038A (en) | 2021-07-23 | 2021-07-23 | Formula of flexing-resistant tire sidewall |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202110837297.7A CN113462038A (en) | 2021-07-23 | 2021-07-23 | Formula of flexing-resistant tire sidewall |
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| CN113462038A true CN113462038A (en) | 2021-10-01 |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005232356A (en) * | 2004-02-20 | 2005-09-02 | Yokohama Rubber Co Ltd:The | Rubber composition for tire |
| JP2009062439A (en) * | 2007-09-05 | 2009-03-26 | Yokohama Rubber Co Ltd:The | Rubber composition for tire side tread |
| CN103772762A (en) * | 2014-01-13 | 2014-05-07 | 肇庆骏鸿实业有限公司 | Automobile tire sidewall rubber for preventing starved joint |
| CN109942910A (en) * | 2019-03-21 | 2019-06-28 | 山东华聚高分子材料有限公司 | A kind of high flexing fatigue service life aviation sidewall rubber, preparation method and application |
| CN110382255A (en) * | 2016-12-23 | 2019-10-25 | 倍耐力轮胎股份公司 | The elastic composition of the silicate fiber with needle-shaped pattern containing nano-scale and vehicle tyre including them |
-
2021
- 2021-07-23 CN CN202110837297.7A patent/CN113462038A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005232356A (en) * | 2004-02-20 | 2005-09-02 | Yokohama Rubber Co Ltd:The | Rubber composition for tire |
| JP2009062439A (en) * | 2007-09-05 | 2009-03-26 | Yokohama Rubber Co Ltd:The | Rubber composition for tire side tread |
| CN103772762A (en) * | 2014-01-13 | 2014-05-07 | 肇庆骏鸿实业有限公司 | Automobile tire sidewall rubber for preventing starved joint |
| CN110382255A (en) * | 2016-12-23 | 2019-10-25 | 倍耐力轮胎股份公司 | The elastic composition of the silicate fiber with needle-shaped pattern containing nano-scale and vehicle tyre including them |
| CN109942910A (en) * | 2019-03-21 | 2019-06-28 | 山东华聚高分子材料有限公司 | A kind of high flexing fatigue service life aviation sidewall rubber, preparation method and application |
Non-Patent Citations (2)
| Title |
|---|
| 张殿荣等: "《现代橡胶配方设计》", 31 October 2001, 化学工业出版社 * |
| 李永河: "《橡胶硫化技术》", 31 May 2012, 黄河水利出版社 * |
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Application publication date: 20211001 |