CN112280127B - Low-temperature-resistant wet-skid-resistant tire tread and preparation method thereof - Google Patents
Low-temperature-resistant wet-skid-resistant tire tread and preparation method thereof Download PDFInfo
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- CN112280127B CN112280127B CN202011253292.1A CN202011253292A CN112280127B CN 112280127 B CN112280127 B CN 112280127B CN 202011253292 A CN202011253292 A CN 202011253292A CN 112280127 B CN112280127 B CN 112280127B
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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
- C08L9/06—Copolymers with styrene
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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
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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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
Abstract
The invention discloses a low-temperature-resistant wet-skid-resistant tire tread and a preparation method thereof, and belongs to the technical field of tire tread rubber compositions, wherein the tire tread comprises the low-temperature-resistant wet-skid-resistant tire tread rubber composition, and the tire tread rubber composition comprises the following components: 10-30 parts of polybutadiene rubber, 40-70 parts of SSBR with medium and low styrene and low Tg, 10-30 parts of SSBR with high styrene and high Tg, 5-20 parts of anti-wet skid resin, 80-120 parts of white carbon black, 5-15 parts of silane coupling agent and 20-60 parts of environment-friendly oil. The invention is applied to the aspect of tires, solves the problem that the existing tread rubber composition can not better improve the wet skid resistance and the low temperature resistance, and has the characteristics of being capable of simultaneously improving the low temperature resistance, the wet skid resistance and the rolling resistance of the tires and reducing the cost.
Description
Technical Field
The invention belongs to the technical field of tire tread rubber compositions, and particularly relates to a low-temperature-resistant and wet-skid-resistant tire tread and a preparation method thereof.
Background
It is generally theorized that the higher the glass transition temperature (Tg) of the tread rubber, the greater the hysteresis loss (tan. Delta. @0 ℃) at about 0 ℃, the higher the white carbon black loading fraction, and the higher the SSBR styrene content used, the better the wet skid resistance of the tire produced. However, the low temperature resistance of the rubber material is required to be low in low-temperature storage modulus (such as E' @ -20 ℃), and the Tg and the styrene content of the rubber material are also required to be low, so that the rubber material is prevented from being hardened and embrittled at low temperature, and the low-temperature gripping property of the tire is ensured. Therefore, for the common rubber combination with single glass transition peak, the low temperature resistance and the wet skid resistance are contradictory in the selection of a hydrocolloid system, and the combination is difficult to be well compatible.
Chinese patent CN107011556B discloses a tread rubber composition for all-weather tires, which adopts the technical scheme that SSBR with low styrene content (10% -20%) and low Tg is selected to ensure low temperature resistance, and 20-35 parts of anti-wet resin is added to improve the anti-wet performance of the tire, however, the cost of the anti-wet resin is higher, and the rolling resistance of the tire is improved when the parts are higher due to the deviation of the compatibility of the anti-wet resin and SSBR with low Tg; chinese patent CN110938243a discloses a tire with tread using a combination of high Tg high vinyl polybutadiene rubber and low Tg low vinyl polybutadiene rubber to balance the low temperature resistance and wet skid resistance of the rubber compound, but because of poor compatibility and large Tg difference, two peaks far from tan δ may be formed when the two are used together, and the synergistic effect of the two components is difficult to form, and the wet skid resistance and low temperature resistance cannot be improved simultaneously.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention aims to solve the technical problems that the existing tread rubber composition cannot better improve the wet skid resistance and the low temperature resistance, and provides a low-temperature-resistant wet skid-resistant tire tread capable of simultaneously improving the low temperature resistance, the wet skid resistance and the rolling resistance of the tire and reducing the cost and a preparation method thereof.
In order to solve the technical problems, the invention adopts the following technical scheme:
the present invention provides a low temperature and wet skid resistant tire tread comprising a low temperature and wet skid resistant tire tread rubber composition comprising: 10-30 parts of polybutadiene rubber, 40-70 parts of SSBR with medium and low styrene and low Tg, 10-30 parts of SSBR with high styrene and high Tg, 5-20 parts of anti-wet skid resin, 80-120 parts of white carbon black, 5-15 parts of silane coupling agent and 20-60 parts of environment-friendly oil.
Preferably, the polybutadiene rubber comprises nickel-catalyzed and rare earth-catalyzed polymerized high cis-polybutadiene rubber, wherein the content of cis-1, 4-polybutadiene in the polybutadiene rubber is more than 96 percent, and the content of 1, 2-polybutadiene structure in the polybutadiene rubber is less than 40 percent;
the SSBR with low styrene and low Tg is an organolithium initiated butadiene-styrene random copolymer, wherein the styrene content accounts for 9-22% of the total mass, and the 1, 2-polybutadiene structural content accounts for 10-43% of the total mass;
the high-styrene high-Tg SSBR is an organolithium initiated butadiene-styrene random copolymer, wherein the styrene content accounts for 28-42% of the total mass, and the 1, 2-polybutadiene structural content accounts for 7-42% of the total mass.
Preferably, the polybutadiene rubber raw rubber has a glass transition temperature of-110 ℃ to-75 ℃, the low-styrene low-Tg SSBR raw rubber has a glass transition temperature of-75 ℃ to-30 ℃, and the high-styrene high-Tg SSBR raw rubber has a glass transition temperature of-40 ℃ to-15 ℃.
Preferably, the high styrene high Tg SSBR has a styrene mass fraction St of H-S Vinyl mass fraction Vi H-S Vinyl mass fraction Vi in polybutadiene rubber B Satisfy 6<24St H-S -5Vi H-S +5Vi B <9。
Preferably, the mass fraction St of styrene in the SSBR with low-medium-low styrene and low Tg L-S Vinyl mass fraction Vi L-S Satisfy 6<28St L-S +17Vi L-S <10。
Preferably, the high styrene high Tg SSBR comprises 10% to 50% mass fraction of molecular chains having a styrene content of 40% to 60%.
Preferably, the softening point of the anti-wet skid resin is 45-115 ℃ and the average molecular weight is 500-2500; the anti-wet-skid resin comprises any one of terpene resin, C5 resin, C9 resin, C5/C9 resin, coumarone resin, alpha-methylstyrene resin and copolymer thereof, dicyclopentadiene resin and hydrogenation or modification products of any one of the above resins; the environment-friendly oil comprises any one of environment-friendly aromatic oil, heavy naphthenic oil, shallow oil pumping and raffinate oil; the white carbon black has a specific surface area of 70-180m 2 Precipitation silica nanoparticles per gram; the silane coupling agent comprises any one of bis (triethoxysilylpropyl) tetrasulfide, bis (triethoxysilylpropyl) disulfide, 3-octanoylthio-1-propyltriethoxysilane, (3-octanoylthio-1-propyltriethoxysilane) - (gamma-mercaptopropyl-triethoxysilane) condensation oligomer and gamma-mercaptopropyl-ethoxybis (propane-hexapropoxy) silane.
Preferably, the anti-wet-skid resin is alpha-methyl styrene resin or hydrogenated dicyclopentadiene resin, and the softening point of the anti-wet-skid resin is 45-85 ℃; the environment-friendly oil is raffinate oil with Ca value larger than 30.
The invention also provides a preparation method of the tire tread according to any one of the technical schemes, wherein the polybutadiene rubber, the SSBR with low and medium styrene and low Tg, the white carbon black, the silane coupling agent and the environment-friendly oil are added into an internal mixer for mixing, and then the SSBR with high and high styrene and the anti-wet skid resin are added into the internal mixer for mixing.
Preferably, the method comprises the following steps:
adding the polybutadiene rubber and the SSBR with low-medium-low styrene and low Tg into an internal mixer, and carrying out bolt pressing and mixing for 5-20s, wherein the rotating speed of the internal mixer is 30-50rpm;
adding the white carbon black and the silane coupling agent into a lifting bolt, and carrying out pressing bolt mixing for 20-40s, wherein the rotating speed of an internal mixer is 30-50rpm;
putting the lifting bolt into the environment-friendly oil, pressing the bolt, mixing for 10-30s, and rotating the internal mixer at 20-40rpm;
adding the high-styrene high-Tg SSBR and the anti-wet-skid resin into a lifting bolt, and carrying out pressing bolt mixing for 10-30s, wherein the rotating speed of an internal mixer is 20-40rpm;
pressing and mixing the bolts to 135-150 ℃ after lifting the bolts, and mixing the bolts at constant temperature for 120-240s;
discharging rubber and cooling the lower piece to obtain master batch;
adding the masterbatch, the accelerator and the vulcanizing agent into an internal mixer, and mixing for 20-40s, wherein the rotating speed of the internal mixer is 20-40rpm;
pressing and mixing the bolts to 90-110 ℃ after lifting the bolts;
and discharging rubber, and cooling the lower piece to obtain final rubber.
Compared with the prior art, the invention has the beneficial effects that:
the invention provides a low-temperature-resistant wet-skid-resistant tire tread, which can simultaneously improve the low-temperature resistance, the wet skid resistance and the rolling resistance of the tire and reduce the cost.
Drawings
FIG. 1 shows DMA temperature scan curves (tan delta and E') for example 1 and comparative example 1 of the present invention.
Detailed Description
The following detailed description of the technical solutions in the specific embodiments of the present invention will be given with reference to the accompanying drawings. It is apparent that the described embodiments are only some specific implementations, but not all implementations, of the general technical solution of the present invention. All other embodiments, which are obtained by those skilled in the art based on the general inventive concept, fall within the scope of the present invention.
The present invention provides a low temperature and wet skid resistant tire tread comprising a low temperature and wet skid resistant tire tread rubber composition comprising: 10-30 parts of polybutadiene rubber, 40-70 parts of SSBR with medium and low styrene and low Tg, 10-30 parts of SSBR with high styrene and high Tg, 5-20 parts of anti-wet skid resin, 80-120 parts of white carbon black, 5-15 parts of silane coupling agent and 20-60 parts of environment-friendly oil. The technical scheme limits that the tire tread rubber composition comprises polybutadiene rubber (BR), SSBR (L-SSBR) with low and medium styrene and low Tg, SSBR (H-SSBR) with high styrene and high Tg and anti-wet skid resin, and the combination of the polybutadiene rubber (BR) with medium and low styrene and the SSBR with high styrene and the anti-wet skid resin can realize a bimodal curve of two tan delta peaks at a low temperature and a high temperature, and has the potential of improving the wet skid resistance and the low temperature resistance simultaneously.
Specifically, when the styrene content in H-SSBR is increased and the vinyl content is decreased, the compatibility with BR may be deteriorated, and a two-phase structure is formed, so that the two tan delta peaks are represented as a high temperature and a low temperature on a DMA temperature scanning curve. The L-SSBR has certain compatibility with BR and H-SSBR, so that the two tan delta peaks are distributed in two phases, so that the two tan delta peaks are close to each other and are not fused, and the defects of poor low temperature resistance and poor wet skid resistance of the blended H-SSBR are overcome. The highly aromatic wet skid resistant resin is more compatible with H-SSBR and therefore preferentially partitions in the H-SSBR phase, as a plasticizer, reduces the modulus of this phase, thereby further reducing the adverse effect of H-SSBR on low temperature resistance and improving wet skid resistance. On the other hand, when the L-SSBR and the H-SSBR are used in binary combination, because the compatibility between the SSBRs is better, the Tg is also closer, only one tan delta peak appears on the DMA curve, and the peak type is also narrower. At this time, the contradiction between the wet skid resistance (tan. Delta. At 0 ℃) and the low temperature resistance (-20 ℃ E') cannot be avoided regardless of the microstructure and the combination ratio of the two. When BR and anti-slippery resin are added into the system, the BR has better compatibility with L-SSBR and poorer compatibility with H-SSBR, so that the original single tan delta peak is split into two peaks, and the two peaks respectively move towards the low temperature and the high temperature, and when the structure and the dosage of the BR/L-SSBR/H-SSBR/anti-slippery resin are accurately adjusted, the contradiction between the anti-slippery property (tan delta at 0 ℃) and the low temperature resistance (-20 ℃ E') can be avoided. Finally, an ideal curve with a low-temperature tan delta peak value of about minus 30 ℃ and a high-temperature tan delta peak value of about minus 10 ℃ and a low peak value and a wide peak value is realized, meanwhile, the wet skid resistance and the low temperature resistance are improved, and the improvement of the low temperature resistance, the wet skid resistance and the rolling resistance of the tire and the reduction of the cost are realized.
The technical scheme specifically limits the dosage of BR, L-SSBR, H-SSBR, anti-wet-slip resin, white carbon black, silane coupling agent and environment-friendly oil, it is understood that the dosage of BR can be 15, 20, 25 parts and any point value in the range of BR, the dosage of L-SSBR can be 45, 50, 55, 60, 65 parts and any point value in the range of L-SSBR, the dosage of H-SSBR can be 15, 20, 25 parts and any point value in the range of H-SSBR, the dosage of anti-wet-slip resin can be 10, 15 parts and any point value in the range of white carbon black, the dosage of white carbon black can be 90, 100, 110 parts and any point value in the range of white carbon black, the dosage of silane coupling agent can be 8, 10, 12 parts and any point value in the range of silane coupling agent, and the dosage of environment-friendly oil can be 30, 40, 50 parts and any point value in the range of environment-friendly oil.
In a preferred embodiment, the polybutadiene rubber comprises a nickel-catalyzed, rare earth-catalyzed polymeric high cis polybutadiene rubber having a cis-1, 4-polybutadiene content of 96% or more and an organolithium initiated medium or low vinyl polybutadiene rubber having a 1, 2-polybutadiene structure content of 40% or less; the SSBR with low styrene and low Tg is an organolithium initiated butadiene-styrene random copolymer, wherein the styrene content accounts for 9-22% of the total mass, and the 1, 2-polybutadiene structural content accounts for 10-43% of the total mass; the high-styrene high-Tg SSBR is an organolithium initiated butadiene-styrene random copolymer, wherein the styrene content accounts for 28-42% of the total mass, and the 1, 2-polybutadiene structural content accounts for 7-42% of the total mass. The technical scheme specifically limits the structures and the compositions of BR, L-SSBR and H-SSBR, is beneficial to further improving the wet skid resistance and the low temperature resistance at the same time, and realizes the improvement of the low temperature resistance, the wet skid resistance and the rolling resistance of the tire and the reduction of the cost.
In a preferred embodiment, the polybutadiene rubber raw has a glass transition temperature of-110 ℃ to-75 ℃, the medium-low styrene low Tg SSBR raw has a glass transition temperature of-75 ℃ to-30 ℃, and the high styrene high Tg SSBR raw has a glass transition temperature of-40 ℃ to-15 ℃. The technical proposal further limits the glass transition temperatures of BR, L-SSBR and H-SSBR, because the proper glass transition temperature of the sizing material is the key for improving the wet skid resistance and the low temperature resistance.
In a preferred embodiment, the high styrene high Tg SSBR has a styrene mass fraction St H-S Vinyl mass fraction Vi H-S Vinyl mass fraction Vi in polybutadiene rubber B Satisfy 6<24St H-S -5Vi H-S +5Vi B <9. The technical scheme further limits the structural composition relation of the H-SSBR and the BR, because the H-SSBR and the BR meeting the limitation have proper compatibility, and are beneficial to realizing a bimodal DMA curve, thereby further improving the wet skid resistance and the low temperature resistance.
In a preferred embodiment, the mass fraction St of styrene in the medium-low styrene low Tg SSBR L-S Vinyl mass fraction Vi L-S Satisfy 6<28St L-S +17Vi L-S <10. The present solution further defines the structural composition of the L-SSBR, since an L-SSBR satisfying this definition has a suitable Tg, as well as a suitable compatibility with both H-SSBR and BR.
In a preferred embodiment, the high styrene high Tg SSBR comprises 10% to 50% mass fraction of molecular chains having a styrene content of 40% to 60%. The technical scheme further limits the structural composition of the H-SSBR, because the H-SSBR meeting the limit is more beneficial to realizing a bimodal DMA curve, thereby further improving the wet skid resistance and the low temperature resistance. It should be noted that some commercial H-SSBRs are formed by compounding two molecular chains with different styrene contents, and the nominal styrene content is the overall average value (i.e. "the high-styrene high-Tg SSBR is an organolithium-initiated butadiene-styrene random copolymer defined in the above technical scheme, wherein the styrene content is 28% -42% of the total mass, and the 1, 2-polybutadiene structural content is 7% -42% of the total mass), but actually comprises a portion with the styrene content higher than the nominal value, i.e. a portion defined in the technical scheme of the present application.
In a preferred embodiment, the anti-wet skid resin has a softening point of 45 ℃ to 115 ℃ and an average molecular weight of 500 to 2500; the anti-wet-skid resin comprises any one of terpene resin, C5 resin, C9 resin, C5/C9 resin, coumarone resin, alpha-methylstyrene resin and copolymer thereof, dicyclopentadiene resin and hydrogenation or modification products of any one of the above resins; the environment-friendly oil comprises any one of environment-friendly aromatic oil, heavy naphthenic oil, shallow oil pumping and raffinate oil; the white carbon black has a specific surface area of 70-180m 2 Per gram (g)Precipitation method silica nanoparticles; the silane coupling agent comprises any one of bis (triethoxysilylpropyl) tetrasulfide, bis (triethoxysilylpropyl) disulfide, 3-octanoylthio-1-propyltriethoxysilane, (3-octanoylthio-1-propyltriethoxysilane) - (gamma-mercaptopropyl-triethoxysilane) condensation oligomer and gamma-mercaptopropyl-ethoxybis (propane-hexapropoxy) silane. The technical scheme defines the wet skid resistant resin, the white carbon black and the environment-friendly oil, and it is understood that the substances can be other substances reasonably selected by a person skilled in the art.
In a preferred embodiment, the anti-wet skid resin is an alpha-methylstyrene resin or a hydrogenated dicyclopentadiene resin, and the softening point of the anti-wet skid resin is 45-85 ℃; the environment-friendly oil is raffinate oil with Ca value larger than 30. The technical scheme specifically limits the anti-skidding resin to be alpha-methyl styrene resin or hydrogenated dicyclopentadiene resin, because the two types of anti-skidding resin have better compatibility with the H-SSBR, and further limits the softening point of the anti-skidding resin to be 45-85 ℃, because the lower softening point is favorable for avoiding the damage of the anti-skidding resin to low temperature resistance and rolling resistance; the technical scheme selects the raffinate oil with the Ca value larger than 30 as the environment-friendly oil, and has the advantages that the raffinate oil with high aromaticity has better compatibility with H-SSBR, is beneficial to reducing the modulus of the H-SSBR part and improves the low temperature resistance.
The invention also provides a preparation method of the tire tread according to any one of the technical schemes, wherein the polybutadiene rubber, the SSBR with low and medium styrene and low Tg, the white carbon black, the silane coupling agent and the environment-friendly oil are added into an internal mixer for mixing, and then the SSBR with high and high styrene and the anti-wet skid resin are added into the internal mixer for mixing. The technical scheme limits the mixing of the H-SSBR and the wet skid resistant resin after the delay, and is characterized in that the wet skid resistant resin is preferentially distributed in the H-SSBR phase, white carbon black in the H-SSBR phase is reduced, and the double-peak DMA curve is realized, so that the wet skid resistance and the low temperature resistance are further improved.
In a preferred embodiment, the method comprises the steps of:
adding the polybutadiene rubber and the SSBR with low-medium-low styrene and low Tg into an internal mixer, and carrying out bolt pressing and mixing for 5-20s, wherein the rotating speed of the internal mixer is 30-50rpm;
adding the white carbon black and the silane coupling agent into a lifting bolt, and carrying out pressing bolt mixing for 20-40s, wherein the rotating speed of an internal mixer is 30-50rpm;
putting the lifting bolt into the environment-friendly oil, pressing the bolt, mixing for 10-30s, and rotating the internal mixer at 20-40rpm;
adding the high-styrene high-Tg SSBR and the anti-wet-skid resin into a lifting bolt, and carrying out pressing bolt mixing for 10-30s, wherein the rotating speed of an internal mixer is 20-40rpm;
pressing and mixing the bolts to 135-150 ℃ after lifting the bolts, and mixing the bolts at constant temperature for 120-240s;
discharging rubber and cooling the lower piece to obtain master batch;
adding the masterbatch, the accelerator and the vulcanizing agent into an internal mixer, and mixing for 20-40s, wherein the rotating speed of the internal mixer is 20-40rpm;
pressing and mixing the bolts to 90-110 ℃ after lifting the bolts;
and discharging rubber, and cooling the lower piece to obtain final rubber.
In order to more clearly and in detail describe the low temperature resistant and wet skid resistant tire tread and the preparation method thereof provided by the embodiment of the invention, the following description will be made with reference to specific embodiments.
Example 1
The composition of the tire tread rubber composition is shown in Table 1.
Table 1 example 1 tire tread rubber composition formulation
| Raw materials | Number plate | Example 1 | |
| | CB24 | 20 parts of | |
| L-SSBR | SLR 3402 | 60 parts of | |
| H-SSBR | SLR 918S | 25 parts of | |
| Wet skid resistant resin | CSR6009 | 15 parts of | |
| High dispersion white carbon black | 1115MP | 105 parts of | |
| Silane coupling agent | Si-75 | 6.3 parts of | |
| Carbon black | N375 | 5 parts of | |
| Naphthenic oil | N4700 | 28 parts of | |
| White carbon black dispersant | CSP908 | 3 parts of | |
| Activating agent | Precipitation method zinc oxide | 2 parts of | |
| Activating | Stearic acid | 1 part of | |
| Anti-aging agent | 6PPD | 2.5 parts of | |
| | RD | 1 part of | |
| Anti-aging agent | RW287 | 2 parts of | |
| Accelerating agent | CZ | 1.6 parts of | |
| Accelerating agent | DPG | 2 parts of | |
| Vulcanizing agent | S | 1.25 parts of |
The tire tread rubber composition is mixed according to the following steps:
1) Adding CB24 and SLR 3402 into an internal mixer, and carrying out bolt pressing and mixing for 10 seconds, wherein the rotation speed of the internal mixer is 50rpm;
2) Adding white carbon black, a silane coupling agent, an anti-aging agent and an activating agent into a bolt, pressing and mixing for 20 seconds, and rotating the internal mixer at 50rpm;
3) Adding environment-friendly oil into the lifting bolt, pressing the bolt, mixing for 30 seconds, and rotating the internal mixer at 40rpm;
4) Adding SLR 918S and anti-wet resin into a lifting bolt, pressing and mixing for 20S, wherein the rotating speed of an internal mixer is 30rpm;
5) Pressing and mixing the bolts to 145 ℃ after lifting the bolts, and mixing the bolts at constant temperature for 180 seconds;
6) Discharging rubber and cooling the lower piece to obtain master batch;
7) Adding the masterbatch, the accelerator and the vulcanizing agent into an internal mixer, and mixing for 30 seconds, wherein the rotating speed of the internal mixer is 25rpm;
8) Pressing and mixing to 100 ℃ after lifting the bolts;
9) And discharging rubber, and cooling the lower piece to obtain final rubber.
Comparative example 1
The tire tread rubber composition compositions are shown in table 2.
Table 2 comparative example 1 tire tread rubber composition formulation
| Raw materials | Number plate | Comparative example 1 | |
| | CB24 | 40 parts of | |
| G- | 2550H | 60 parts of | |
| High dispersion white carbon black | 1115MP | 105 parts of | |
| Silane coupling agent | Si-75 | 6.3 parts of | |
| Carbon black | N375 | 5 parts of | |
| Naphthenic oil | N4700 | 24 parts of | |
| White carbon black dispersant | CSP908 | 3 parts of | |
| Activating agent | Precipitation method zinc oxide | 2 parts of | |
| Activating | Stearic acid | 1 part of | |
| Anti-aging agent | 6PPD | 2.5 parts of | |
| | RD | 1 part of | |
| Anti-aging agent | RW287 | 2 parts of | |
| Accelerating agent | CZ | 1.6 parts of | |
| Accelerating agent | DPG | 2 parts of | |
| Vulcanizing agent | S | 1.25 parts of |
The tire tread rubber composition is mixed according to the following steps:
1) Adding CB24 and 2550H into an internal mixer, pressing and mixing for 10 seconds, wherein the rotation speed of the internal mixer is 50rpm;
2) Adding white carbon black, a silane coupling agent, an anti-aging agent and an activating agent into a bolt, pressing and mixing for 20 seconds, and rotating the internal mixer at 50rpm;
3) Adding environment-friendly oil into the lifting bolt, pressing the bolt, mixing for 30 seconds, and rotating the internal mixer at 40rpm;
4) Lifting bolts, pressing bolts, mixing for 20 seconds, and rotating the internal mixer at 30rpm;
5) Pressing and mixing the bolts to 145 ℃ after lifting the bolts, and mixing the bolts at constant temperature for 180 seconds;
6) Discharging rubber and cooling the lower piece to obtain master batch;
7) Adding the masterbatch, the accelerator and the vulcanizing agent into an internal mixer, and mixing for 30 seconds, wherein the rotating speed of the internal mixer is 25rpm;
8) Pressing and mixing to 100 ℃ after lifting the bolts;
9) And discharging rubber, and cooling the lower piece to obtain final rubber.
Performance testing
The compounds obtained in example 1 and comparative example 1 were subjected to performance test, and the test results are shown in table 3 and fig. 1.
Table 3 performance test data
| Project | Comparative example 1 | Example 1 |
| Shore A hardness/degree | 61 | 58 |
| 300% stress/MPa | 9.7 | 10.3 |
| Tensile Strength/MPa | 14.8 | 17.7 |
| Elongation at break/% | 429 | 454 |
| Rebound resilience/% | 34.1 | 38.8 |
| Tg/℃ | -29 | -31 |
| -20℃E’/MPa | 57 | 61 |
| 0℃tanδ | 0.336 | 0.410 |
| 70℃tanδ | 0.154 | 0.132 |
From the above data, it can be found that example 1 significantly improved the wet skid resistance (0 ℃ tan δ) and reduced the rolling resistance (70 ℃ tan δ) while maintaining the low temperature resistance (-20 ℃ E') at the same level as comparative example 1. The stress at definite elongation, tensile strength, elongation at break and rebound resilience are all improved. The DMAtan delta curve shows a rare bimodal trend and is critical for improving low temperature resistance and wet skid resistance of the compound.
In order to further clearly and in detail describe the tire tread with low temperature resistance and wet skid resistance and the preparation method thereof provided by the embodiment of the present invention, the structural compositions of the main components in the above-mentioned embodiment 1 and comparative embodiment 1 are given below, and the main formulation compositions and performance test data of the embodiments 2 to 5 are further listed, see table 4.
TABLE 4 Main component formulations and Performance test data for examples 1-5, comparative example 1
Claims (8)
1. A low temperature and wet skid resistant tire tread, the tire tread comprising a low temperature and wet skid resistant tire tread rubber composition comprising: 10-30 parts of polybutadiene rubber, 40-70 parts of SSBR with medium and low styrene and low Tg, 10-30 parts of SSBR with high styrene and high Tg, 5-20 parts of anti-wet skid resin, 80-120 parts of white carbon black, 5-15 parts of silane coupling agent and 20-60 parts of environment-friendly oil;
styrene mass fraction St in the high styrene high Tg SSBR H-S Vinyl mass fraction Vi H-S Vinyl mass fraction Vi in polybutadiene rubber B Satisfy 6<24St H-S -5Vi H-S +5Vi B <9；
The polybutadiene rubber comprises high cis-polybutadiene rubber polymerized by rare earth catalysis, wherein the content of cis-1, 4-polybutadiene in the polybutadiene rubber is more than 96 percent, and the content of 1, 2-polybutadiene structure in the polybutadiene rubber is less than 40 percent;
the SSBR with low styrene and low Tg is an organolithium initiated butadiene-styrene random copolymer, wherein the styrene content accounts for 9-22% of the total mass, and the 1, 2-polybutadiene structural content accounts for 10-43% of the total mass;
the high-styrene high-Tg SSBR is an organolithium initiated butadiene-styrene random copolymer, wherein the styrene content accounts for 28-42% of the total mass, and the 1, 2-polybutadiene structural content accounts for 7-42% of the total mass;
the tire tread is prepared by the following method:
firstly, adding the polybutadiene rubber, the SSBR with low and medium styrene and low Tg, the white carbon black, the silane coupling agent and the environment-friendly oil into an internal mixer for mixing, and then adding the SSBR with high and high styrene and high Tg and the anti-wet skid resin into the internal mixer for mixing.
2. The tire tread of claim 1, wherein the polybutadiene rubber green has a glass transition temperature of-110 ℃ to-75 ℃, the low-medium styrene low Tg SSBR green has a glass transition temperature of-75 ℃ to-30 ℃, and the high-styrene high Tg SSBR green has a glass transition temperature of-40 ℃ to-15 ℃.
3. The tire tread of claim 2, wherein the tire tread comprisesStyrene mass fraction St in the SSBR with low-medium-low styrene and low Tg L-S Vinyl mass fraction Vi L-S Satisfy 6<28St L-S +17Vi L-S <10。
4. The tire tread of claim 2, wherein the high styrene high Tg SSBR comprises 10% to 50% mass fraction of molecular chains having a styrene content of 40% to 60%.
5. The tire tread of claim 1, wherein the anti-wet resin has a softening point of 45 ℃ to 115 ℃ and an average molecular weight of 500 to 2500; the anti-wet-skid resin comprises any one of terpene resin, C5 resin, C9 resin, C5/C9 resin, coumarone resin, alpha-methylstyrene resin and copolymer thereof, dicyclopentadiene resin and hydrogenation or modification products of any one of the above resins; the environment-friendly oil comprises any one of environment-friendly aromatic oil, heavy naphthenic oil, shallow oil pumping and raffinate oil; the white carbon black has a specific surface area of 70-180m 2 Precipitation silica nanoparticles per gram; the silane coupling agent comprises any one of bis (triethoxysilylpropyl) tetrasulfide, bis (triethoxysilylpropyl) disulfide, 3-octanoylthio-1-propyltriethoxysilane, (3-octanoylthio-1-propyltriethoxysilane) - (gamma-mercaptopropyl-triethoxysilane) condensation oligomer and gamma-mercaptopropyl-ethoxybis (propane-hexapropoxy) silane.
6. The tire tread of claim 5, wherein the anti-wet resin is an alpha-methylstyrene resin or a hydrogenated dicyclopentadiene resin, the softening point of the anti-wet resin being 45-85 ℃; the environment-friendly oil is raffinate oil with Ca value larger than 30.
7. The method for producing a tire tread according to any one of claims 1 to 6, wherein the polybutadiene rubber, the SSBR with low and medium styrene and low Tg, the white carbon black, the silane coupling agent, and the environmental friendly oil are first added to an internal mixer to be mixed, and then the SSBR with high and high styrene and the anti-wet skid resin are added to the internal mixer to be mixed.
8. A method of preparing a tire tread according to claim 7, comprising the steps of:
adding the polybutadiene rubber and the SSBR with low-medium-low styrene and low Tg into an internal mixer, and carrying out bolt pressing and mixing for 5-20s, wherein the rotating speed of the internal mixer is 30-50rpm;
adding the white carbon black and the silane coupling agent into a lifting bolt, and carrying out pressing bolt mixing for 20-40s, wherein the rotating speed of an internal mixer is 30-50rpm;
putting the lifting bolt into the environment-friendly oil, pressing the bolt, mixing for 10-30s, and rotating the internal mixer at 20-40rpm;
adding the high-styrene high-Tg SSBR and the anti-wet-skid resin into a lifting bolt, and carrying out pressing bolt mixing for 10-30s, wherein the rotating speed of an internal mixer is 20-40rpm;
pressing and mixing the bolts to 135-150 ℃ after lifting the bolts, and mixing the bolts at constant temperature for 120-240s;
discharging rubber and cooling the lower piece to obtain master batch;
adding the masterbatch, the accelerator and the vulcanizing agent into an internal mixer, and mixing for 20-40s, wherein the rotating speed of the internal mixer is 20-40rpm;
pressing and mixing the bolts to 90-110 ℃ after lifting the bolts;
and discharging rubber, and cooling the lower piece to obtain final rubber.
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| CN113788994A (en) * | 2021-08-26 | 2021-12-14 | 中策橡胶集团有限公司 | Outer rubber protection rubber composition with excellent appearance, mixing method thereof and tire |
| CN113736155B (en) * | 2021-09-02 | 2023-01-24 | 赛轮集团股份有限公司 | Anti-slippery rubber composition, mixing method and application thereof |
| CN114921001A (en) * | 2022-06-16 | 2022-08-19 | 山东科技大学 | High-adhesion-grip-force polymer matrix composition for shipboard aircraft and preparation method thereof |
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| CN110372929B (en) * | 2019-07-16 | 2021-08-10 | 赛轮集团股份有限公司 | High-grip high-handling-performance racing tire tread rubber composition |
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