CN111333934A - Four-season all-steel snow and ice ground tire tread rubber composition - Google Patents
Four-season all-steel snow and ice ground tire tread rubber composition Download PDFInfo
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- CN111333934A CN111333934A CN202010351542.9A CN202010351542A CN111333934A CN 111333934 A CN111333934 A CN 111333934A CN 202010351542 A CN202010351542 A CN 202010351542A CN 111333934 A CN111333934 A CN 111333934A
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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
- C08L15/00—Compositions of rubber derivatives
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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
- B60C1/0016—Compositions of the tread
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- 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
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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- 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
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Abstract
The invention relates to the technical field of tire rubber, in particular to a four-season all-steel tire tread rubber composition for snowy and icy ground, which comprises the following components in parts by weight: 10-30 parts of natural rubber, 10-35 parts of liquid rubber, 65-80 parts of functionalized solution polymerized styrene-butadiene rubber, 5-25 parts of carbon black, 20-55 parts of low specific surface area white carbon black, 4.0-12.0 parts of silane coupling agent, 1.5-3.0 parts of white carbon black dispersing agent, 2.0-5.0 parts of zinc oxide, 1.0-3.0 parts of stearic acid, 40201.0-3.0 parts of anti-aging agent, 1.5-2.5 parts of anti-aging agent RD, 1.0-4.0 parts of rubber protective wax, 801.5-2.5 parts of sulfur, 1.0-3.5 parts of tear-resistant resin, NS-801.0-2.5 parts of accelerator and DPG-800-0.5 parts of accelerator. The tire tread produced by the invention not only has excellent snow gripping force on snow road surface, but also keeps excellent gripping force on all-ice road surface, and has excellent rolling resistance performance, wet skid resistance performance and abrasion resistance performance.
Description
Technical Field
The invention relates to the technical field of tire rubber, in particular to a four-season high-performance all-steel snow and ice ground tire tread rubber composition.
Background
As is well known, the winter temperature in northern areas of China is usually below minus 20 ℃, particularly in Russia, northern Europe and other areas, the snow season in winter is long, the grip between a common tire and the ground in four seasons is greatly reduced, and particularly when the tire is in contact with an ice surface, the friction between the tire and the road surface almost disappears, lateral sliding is easy to occur, and accidents are easy to happen. All-steel load-carrying snow tires designed by different tread rubber compositions are provided by tire enterprises, and compared with all-steel all-season tires, the snow tire tread has the advantages of low tread rubber hardness, low temperature resistance and better snow traction.
Because the design of the tire performance has a magic triangle mode on the aspects of wet skid resistance, wear resistance and low rolling resistance, when a snowfield tread formula is designed, the formula design hardness is low, a rubber material is soft, the tire wear resistance and rolling resistance can be greatly reduced, the use requirements of an all-steel snowfield tire and a semi-steel snowfield tire are different, the load capacity of the all-steel tire is large, a plurality of users can not change the tire after winter but continue to use the snowfield tire, the traditional snowfield tire formula cannot meet the wear resistance and rolling resistance performance of the all-season tire used all the year round, meanwhile, the design of the all-steel heavy duty tire and the semi-steel passenger car tire has certain differences and relations due to different loads, functions and running speeds, and the lateral emphasis of the design of the all-steel heavy duty tire and the semi-steel passenger car tire is different.
At present, research on all-steel snow treads is reported, and patent CN105037824B discloses that under the condition of special tread rubber composition collocation and optimized formula proportion, the tire has excellent snow slip resistance and snow grip adhesion under severe cold and severe snow environments, and the driving performance and driving safety of the snow special tire are improved.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide an all-steel snow and ice tire tread rubber composition which has excellent low temperature resistance and cold resistance, not only has excellent snow gripping force on a snow road surface, but also keeps excellent gripping force on the all-ice road surface, and has excellent rolling resistance, wet skid resistance and abrasion resistance.
The technical scheme adopted by the invention for solving the technical problems is as follows: the four-season all-steel snow and ice ground tire tread rubber composition is characterized by comprising the following components in parts by weight through mixing:
10-30 parts of natural rubber, 10-35 parts of liquid rubber, 65-80 parts of functionalized solution polymerized styrene-butadiene rubber, 5-25 parts of carbon black, 20-55 parts of low specific surface area white carbon black, 4.0-12.0 parts of silane coupling agent, 1.5-3.0 parts of white carbon black dispersing agent, 2.0-5.0 parts of zinc oxide, 1.0-3.0 parts of stearic acid, 40201.0-3.0 parts of anti-aging agent, 1.5-2.5 parts of anti-aging agent RD, 1.0-4.0 parts of rubber protective wax, 801.5-2.5 parts of sulfur, 1.0-3.5 parts of tear-resistant resin, NS-801.0-2.5 parts of accelerator and DPG-800-0.5 parts of accelerator.
Preferably, the four-season all-steel snow and ice tire tread rubber composition is characterized by comprising the following components in parts by weight:
12-30 parts of natural rubber, 15-30 parts of liquid rubber, 70-80 parts of functionalized solution polymerized styrene-butadiene rubber, 10-25 parts of carbon black, 25-50 parts of low specific surface area white carbon black, 5.0-10.0 parts of silane coupling agent, 1.5-3.0 parts of white carbon black dispersing agent, 2.0-4.0 parts of zinc oxide, 1.0-2.0 parts of stearic acid, 40201.0-2.0 parts of anti-aging agent, 1.0-2.0 parts of anti-aging agent RD, 1.5-3.5 parts of rubber protective wax, 801.5-2.5 parts of sulfur, 1.0-3.0 parts of tear-resistant resin, 2-2.0 parts of accelerator NS-801 and 800.1-0.2 parts of accelerator DPG.
Preferably, the functionalized solution-polymerized styrene-butadiene rubber is non-oil-extended terminal-modified solution-polymerized styrene-butadiene rubber with the glass transition temperature lower than-60 ℃, the content of bound styrene is 5-10%, the content of 1, 2-vinyl is 15-30%, and the ratio of the parts by weight of the solution-polymerized styrene-butadiene rubber to the parts by weight of the natural rubber is more than or equal to 2:1 is less than or equal to 3: 1.
Preferably, the liquid rubber is liquid butadiene rubber, liquid natural rubber or liquid isoprene rubber with the number average molecular weight less than 3000g/mol, and the ratio of the weight parts of the liquid rubber to the weight parts of the natural rubber is more than or equal to 1:1 and less than or equal to 3: 1.
Preferably, the silane coupling agent is a long-chain polysulfanyl modified super silane coupling agent Si-769.
Preferably, the nitrogen adsorption specific surface area of the white carbon black with the low specific surface area is 80-100m2The ratio of the parts by weight of the white carbon black with the low specific surface area to the parts by weight of the carbon black is more than or equal to 1:1 and less than or equal to 2: 1.
Preferably, the rubber protective wax has bimodal distribution, wherein the carbon number distribution is more than 20% in C20-C24, and more than 35% in C30-C34.
The invention has the beneficial effects that through the use of the functionalized solution polymerized styrene-butadiene rubber, the liquid rubber, the white carbon black with low specific surface area and the like, the related four-season high-performance all-steel snow and ice tire tread rubber composition has excellent low-temperature resistance and cold resistance, not only has excellent snow gripping force on a snow road surface, but also keeps excellent gripping force on the all-ice road surface, and has excellent rolling resistance performance, wet skid resistance performance and abrasion resistance performance.
Detailed Description
The present invention will be further described with reference to the following examples, but it should be understood that the examples described are only a part of the examples of the present invention, and not all of the examples.
The functionalized solution-polymerized styrene-butadiene rubber is non-oil-extended tail-modified solution-polymerized styrene-butadiene rubber with the glass transition temperature lower than minus 60 ℃, has the bound styrene content of between 5 and 10 percent and the 1, 2-vinyl content of between 15 and 30 percent, and is SL553R produced by JSR; the ratio of the parts of the solution polymerized styrene-butadiene rubber to the parts of the natural rubber is more than or equal to 2:1 is less than or equal to 3: 1.
The liquid rubber is liquid butadiene rubber, liquid natural rubber or liquid isoprene rubber with the number average molecular weight less than 3000g/mol, and the ratio of the parts of the liquid rubber to the parts of the natural rubber is more than or equal to 1:1 and less than or equal to 3: 1.
The silane coupling agent is a long-chain polysulfanyl modified super silane coupling agent Si-769, so that rolling resistance is reduced, and wet and slippery performance is improved.
The white carbon black has low specific surface area, and nitrogen adsorption specific surface area (NSA) of 80-100m2The low-temperature elastic modulus is reduced and the excellent low-temperature ground holding force is ensured, wherein the low-temperature elastic modulus is 1115MP or 1085MP which are products of Soervai company; the proportion of the white carbon black with the low specific surface area to the carbon black is more than or equal to 1:1 and less than or equal to 2: 1.
The rubber protective wax has bimodal distribution, the carbon number distribution of C20-C24 accounts for more than 20%, the low-temperature protective performance is good, the tire aging and cracking in winter are prevented, the carbon number distribution of C30-C34 accounts for more than 35%, and the cracking protective performance used throughout the year except in winter is guaranteed.
The tear-resistant resin is small organic molecules with Mw less than or equal to 100, acrochemical Acroad EN-01, a non-commercial common dicyclopentadiene or modified alicyclic resin mixture, the modulus of the tread rubber is reduced, the tear resistance and the cutting resistance of the tread rubber are improved, and the heat generation is reduced, so that the rolling resistance of the tire is reduced.
The glass transition temperature of the tread rubber composition is less than or equal to minus 60 ℃, the DIN relative abrasion index is more than or equal to 110, the rolling resistance coefficient of a tire produced by using the tread rubber composition is less than or equal to 6.5, the snow gripping index is more than or equal to 1.25, and the wet gripping index is more than or equal to 0.95.
The preparation method of the four-season high-performance all-steel snow and ice ground tire tread rubber composition comprises the following steps: adopting a GK320/GK550 series internal mixer produced by Krupp company of Germany to carry out low-temperature one-time rubber mixing, wherein the rotating speed of the internal mixer is 40-50rpm, and the top plug pressure is 40-50N/cm2The first internal mixing process comprises the following steps: functional solution polymerized styrene-butadiene rubber, natural rubber, liquid rubber, low-specific-surface-area white carbon black, silane coupling agent, stearic acid, white carbon black dispersing agent, anti-tear resin and low-temperature protectionPutting wax and rubber anti-aging agent into an internal mixer, pressing a top bolt for 15 seconds, lifting the top bolt, adding zinc oxide carbon black to heat the rubber material to 120 ℃, pressing the top bolt to heat the rubber material to 145 ℃, and discharging the rubber material to a lower internal mixer; (II) internal mixer technology: heating the rubber material to 145 ℃, mixing for 160s at constant temperature, and performing low-temperature vulcanization process on a rubber discharge (III) open mill: discharging rubber to a main open mill, smashing the rubber and cooling the rubber to be below 100 ℃, adding S-80, NS-80 and DPG-80 into the rubber on a vulcanizing open mill, wherein the roller distance of the open mill is 3.0-4.0mm, the two times of smashing the rubber are accumulated for 13-15 min, mixing uniformly, tabletting and cooling to room temperature.
The key technology of the invention is that the traditional all-steel snowfield tire is changed by using natural rubber and butadiene rubber together, the structural functional solution polymerized styrene-butadiene rubber with the glass transition temperature of the natural rubber being lower than minus 60 ℃ and close to the butadiene rubber is adopted, the styrene content is low, and the vinyl content is low, thereby not only providing the low-temperature grip of the tire on the ice and snow road surface, but also ensuring the wear resistance and low rolling resistance of the tire used throughout the year; the traditional mode of filling a large amount of oil is changed, liquid rubber is adopted to completely replace oil, the glass transition temperature and the low-temperature modulus are reduced, and the situation that the grip force is reduced due to the increase of the hardness of the tire tread after the oil migrates to the surface in the later period of the tire is avoided; application 100m2The white carbon black with low specific surface area below/g ensures low-temperature modulus and low-temperature grip; the low-temperature protective wax with bimodal distribution is suitable for preventing the tire from cracking at low temperature in winter and is also suitable for protecting climate in four seasons; the rubber composition prepared by the method can meet the use requirement of an ice and snow road surface environment, can also avoid tire replacement after winter, and has wear resistance and rolling resistance performance suitable for four seasons.
Table one: formulation matching table of the invention (examples, unit: parts by weight)
In order to verify the reliability of the effect of the invention, the formula of the invention is compared with the formula of the snow tread and various performance indexes, and the result is shown in the table I, the table II and the table III: the second table is the comparison of the physical and mechanical properties of the comparative example and the example, and the third table is the low-temperature and dynamic properties, and the elastic modulus E' at-25 ℃ is generally considered to represent the grip force of the ice and snow land, and the lower the value is, the lower the modulus is, the better the grip performance of the ice and snow land is; the rolling resistance of the tire is represented by tan delta at 60 ℃, and the smaller the value is, the lower the hysteresis loss is, and the lower the rolling resistance is; the abrasion resistance of the rubber material is represented by DIN abrasion index, and the higher the numerical value is, the better the abrasion resistance is.
Table two: physical and mechanical properties of the sizing materials of examples 1-2 and comparative examples of the invention
| Test items | Comparative formulation | Example 1 | Example 2 |
| Hardness of | 60 | 58 | 59 |
| Tensile strength/MPa | 28.0 | 27.0 | 27.8 |
| Elongation at break/%) | 525 | 510 | 536 |
| 100% stress at definite elongation, MPa | 3.2 | 2.9 | 3.0 |
| 300% stress at definite elongation, MPa | 12.0 | 11.5 | 10.9 |
| DIN relative abrasion index | 97 | 120 | 118 |
The performance of the rubber compound is tested according to national standard or industry standard, and the vulcanization condition of the rubber compound is 150 ℃ for 30min
Table three: low temperature and dynamic mechanical properties of the rubber compositions of examples 1-2 and comparative examples
| Test items | Comparative formulation | Example 1 | Example 2 |
| Tg，℃ | -48 | -60 | -62 |
| E’(-25℃) | 31.3 | 18.5 | 15.6 |
| E’(0℃) | 28.0 | 27.0 | 27.8 |
| Tanδ(60℃) | 0.15 | 0.10 | 0.09 |
A dynamic viscoelasticity analyzer DMA produced by Germany GABO is adopted to carry out temperature scanning on vulcanized rubber, and the test conditions are as follows: static strain is 1%, dynamic strain is 0.25%, frequency is 10Hz, temperature range is-60-120 ℃, and heating rate is 2 ℃/min.
Table four: data from performance testing of tires prepared from examples 1-2 and comparative example compounds
The compounds of examples 1-2 and comparative example were used to produce 285/70R22.5 gauge all steel truck snow tires, the rolling resistance of which was tested in the national engineering laboratory data; the snow performance test is carried out in the automobile test center of the red river valley of Heilongjiang according to the ECE-R117 regulation. The specific tire test data of each scheme are shown in the fourth table, and it can be seen that the tires prepared by the rubber materials of examples 1 and 2 have obvious advantages in the aspects of rolling resistance, wet skid performance and snow performance, and can meet the performance requirements of ECE-117 regulations on common four-season tires.
As can be seen from the second table and the third table, the abrasion resistance of the embodiment is obviously improved by more than 20 percent compared with the comparative example, the low temperature resistance is improved, the glass transition temperature is less than or equal to minus 60 ℃, the ice-snow road surface can resist an extremely cold environment below minus 60 ℃, the low-temperature elastic modulus is reduced, and the ice-snow road surface grip force is favorably improved; from the test data of the tires of the four examples and the comparative examples in the table, the snow grip of the examples is obviously improved compared with the comparative examples, and the rolling resistance and the wet skid resistance can meet the performance requirements of ECE-R117 regulations on the common all-season tires. The above invention has been described only for the preferred embodiments and is not limited to the above examples, and various modifications within the technical scope of the present invention are included in the claims of the present invention.
Claims (7)
1. The four-season all-steel snow and ice ground tire tread rubber composition is characterized by comprising the following components in parts by weight through mixing:
10-30 parts of natural rubber, 10-35 parts of liquid rubber, 65-80 parts of functionalized solution polymerized styrene-butadiene rubber, 5-25 parts of carbon black, 20-55 parts of low specific surface area white carbon black, 4.0-12.0 parts of silane coupling agent, 1.5-3.0 parts of white carbon black dispersing agent, 2.0-5.0 parts of zinc oxide, 1.0-3.0 parts of stearic acid, 40201.0-3.0 parts of anti-aging agent, 1.5-2.5 parts of anti-aging agent RD, 1.0-4.0 parts of rubber protective wax, 801.5-2.5 parts of sulfur, 1.0-3.5 parts of tear-resistant resin, NS-801.0-2.5 parts of accelerator and DPG-800-0.5 parts of accelerator.
2. The four-season all-steel snow and ice tire tread rubber composition as claimed in claim 1, which is prepared by mixing the following components in parts by weight:
12-30 parts of natural rubber, 15-30 parts of liquid rubber, 70-80 parts of functionalized solution polymerized styrene-butadiene rubber, 10-25 parts of carbon black, 25-50 parts of low specific surface area white carbon black, 5.0-10.0 parts of silane coupling agent, 1.5-3.0 parts of white carbon black dispersing agent, 2.0-4.0 parts of zinc oxide, 1.0-2.0 parts of stearic acid, 40201.0-2.0 parts of anti-aging agent, 1.0-2.0 parts of anti-aging agent RD, 1.5-3.5 parts of rubber protective wax, 801.5-2.5 parts of sulfur, 1.0-3.0 parts of tear-resistant resin, 2-2.0 parts of accelerator NS-801 and 800.1-0.2 parts of accelerator DPG.
3. The four-season all-steel snow and ice tire tread rubber composition as claimed in claim 1, wherein the functionalized solution-polymerized styrene-butadiene rubber is non-oil-extended terminal modified solution-polymerized styrene-butadiene rubber with a glass transition temperature of less than-60 ℃, the bound styrene content is 5-10%, the 1, 2-vinyl content is 15-30%, and the ratio of the parts by weight of the solution-polymerized styrene-butadiene rubber to the parts by weight of the natural rubber is more than or equal to 2:1 is less than or equal to 3: 1.
4. The four-season all-steel snow and ice tire tread rubber composition as claimed in claim 1, wherein the liquid rubber is liquid butadiene rubber, liquid natural rubber or liquid isoprene rubber with the number average molecular weight less than 3000g/mol, and the ratio of the weight part of the liquid rubber to the weight part of the natural rubber is greater than or equal to 1:1 and less than or equal to 3: 1.
5. The all-season-all-steel snow and ice tire tread rubber composition as claimed in claim 1, wherein the silane coupling agent is a long-chain polysulfanyl modified super silane coupling agent Si-769.
6. The four-season all-steel snow and ice ground tire tread rubber composition as claimed in claim 1, wherein the low specific surface area white carbon black has a nitrogen adsorption specific surface area of 80-100m2The ratio of the parts by weight of the white carbon black with the low specific surface area to the parts by weight of the carbon black is more than or equal to 1:1 and less than or equal to 2: 1.
7. The tire tread rubber composition for all-steel snow and ice road in four seasons as claimed in claim 1, wherein the rubber protective wax has a bimodal distribution, the carbon number distribution is more than 20% from C20 to C24, and the carbon number distribution is more than 35% from C30 to C34.
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| CN113321856A (en) * | 2021-06-10 | 2021-08-31 | 正新橡胶（中国）有限公司 | Rubber composition for improving performance of tire in ice and snow fields and tire |
| CN113402783A (en) * | 2021-06-25 | 2021-09-17 | 徐州工业职业技术学院 | Preparation method of sheet rubber anti-slip belt for tire |
| CN114479206A (en) * | 2020-11-11 | 2022-05-13 | 赛轮集团股份有限公司 | Low-heat-generation tear-resistant rubber composition for engineering tire and preparation method thereof |
| CN115109325A (en) * | 2022-07-16 | 2022-09-27 | 海安橡胶集团股份公司 | All-steel giant engineering radial tire base rubber with high cutting resistance and high tear resistance and preparation method thereof |
| CN115216071A (en) * | 2022-08-23 | 2022-10-21 | 正新橡胶（中国）有限公司 | Rubber composition for winter tire and winter tire |
| CN115490935A (en) * | 2022-09-30 | 2022-12-20 | 四川远星橡胶有限责任公司 | Ultralow-temperature high-grip-area snow tire rubber material and preparation method thereof |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114479206A (en) * | 2020-11-11 | 2022-05-13 | 赛轮集团股份有限公司 | Low-heat-generation tear-resistant rubber composition for engineering tire and preparation method thereof |
| CN113321856A (en) * | 2021-06-10 | 2021-08-31 | 正新橡胶（中国）有限公司 | Rubber composition for improving performance of tire in ice and snow fields and tire |
| CN113402783A (en) * | 2021-06-25 | 2021-09-17 | 徐州工业职业技术学院 | Preparation method of sheet rubber anti-slip belt for tire |
| CN115109325A (en) * | 2022-07-16 | 2022-09-27 | 海安橡胶集团股份公司 | All-steel giant engineering radial tire base rubber with high cutting resistance and high tear resistance and preparation method thereof |
| CN115109325B (en) * | 2022-07-16 | 2023-10-31 | 海安橡胶集团股份公司 | High-cutting-resistance high-tearing-resistance all-steel giant engineering radial tire base rubber and preparation method thereof |
| CN115216071A (en) * | 2022-08-23 | 2022-10-21 | 正新橡胶（中国）有限公司 | Rubber composition for winter tire and winter tire |
| CN115490935A (en) * | 2022-09-30 | 2022-12-20 | 四川远星橡胶有限责任公司 | Ultralow-temperature high-grip-area snow tire rubber material and preparation method thereof |
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