CN113736208A - Rubber composition, preparation method thereof and run-flat tire inner support - Google Patents
Rubber composition, preparation method thereof and run-flat tire inner support Download PDFInfo
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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
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
- C08L53/025—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes modified
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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
- B60C17/00—Tyres characterised by means enabling restricted operation in damaged or deflated condition; Accessories therefor
- B60C17/04—Tyres characterised by means enabling restricted operation in damaged or deflated condition; Accessories therefor utilising additional non-inflatable supports which become load-supporting in emergency
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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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- 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
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Abstract
The invention discloses a rubber composition, a preparation method thereof and an inner support of a run-flat tire, and belongs to the field of tire rubber compositions. The rubber comprises, by weight, 50-70 parts of integrated rubber and 30-50 parts of low cis-polybutadiene rubber; the integral rubber is hydrogenated and modified block type integral rubber, the weight average molecular weight of the hydrogenated and modified block type integral rubber is 30-80 ten thousand, the total hydrogenation degree of double bonds is 80% -95%, and the integral rubber before hydrogenation and modification is the integral rubber with a linear triblock structure. The invention is applied to the aspect of run-flat tires, solves the technical problems that the existing inner support rubber composition for the run-flat tires mainly uses natural rubber and butadiene rubber, cannot give consideration to heat resistance, high mechanical strength and low hysteresis, has the characteristics of excellent heat resistance, mechanical strength and lower hysteresis loss, does not lose yield resistance, low hysteresis and processability, and has the zero-air-pressure durability of more than 2.5 h.
Description
Technical Field
The invention belongs to the technical field of tire rubber compositions, and particularly relates to a rubber composition, a preparation method thereof and an inner support of a run-flat tire.
Background
A run-flat tire is a tire that has a certain ability to continue running under the condition that the tire is damaged and loses air pressure. The national regulations stipulate that run-flat tires can run for more than 1 hour at 80km/h at least under the condition of zero air pressure. The prior run-flat tire is mainly characterized in that high-hardness supporting rubber is added to the inner side of the originally soft sidewall of the tire, so that the deformation of the tire after pressure loss is reduced, and a certain stable running capability is maintained. After the run-flat tire is decompressed, most of vehicle load is borne by the inner supporting rubber, so that the supporting rubber is required to have not only higher hardness (generally Shore A hardness is 70-80), but also lower hysteresis loss, so that the dynamic temperature rise under high load is reduced, and meanwhile, the supporting rubber has mechanical properties such as bending resistance and the like corresponding to larger deformation, particularly the mechanical properties at high temperature.
The conventional supporting rubber formula generally adopts natural rubber and butadiene rubber as main materials, on one hand, the hysteresis loss of the natural rubber and the butadiene rubber is low, on the other hand, the natural rubber has excellent crack propagation resistance and mechanical strength, the butadiene rubber has excellent crack initiation resistance, and the combination of the natural rubber and the butadiene rubber has good yield resistance. However, natural rubber has poor heat resistance, is easily degraded at high temperature and high load, and has significantly reduced tensile crystallinity with increased temperature, which causes mechanical properties of the rubber material to be reduced and destroyed during long-term run-flat running, thereby limiting the zero-air pressure durability of the run-flat tire. The existing method for improving the heat resistance of the supporting rubber is mainly to add an anti-reversion agent into a vulcanization system to improve the stability of a cross-linking bond, but the method still cannot completely overcome the defect of poor heat resistance of natural rubber.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to solve the technical problems that the existing internal support rubber composition for the run-flat tire mainly uses natural rubber and butadiene rubber and cannot give consideration to heat resistance, high mechanical strength and low hysteresis, and provides a rubber composition which has excellent heat resistance, mechanical strength and lower hysteresis loss, does not lose flexibility resistance, low hysteresis and processability and can achieve the zero-air-pressure durability of more than 2.5h, a preparation method thereof and an internal support for the run-flat tire.
In order to solve the technical problem, the technical scheme adopted by the invention is as follows:
the invention provides a rubber composition for an inner support of a run-flat tire, which comprises the following components in parts by weight:
50-70 parts of integrated rubber and 30-50 parts of low cis-polybutadiene rubber;
the integral rubber is hydrogenated and modified block type integral rubber, the weight average molecular weight of the hydrogenated and modified block type integral rubber is 30-80 ten thousand, the total hydrogenation degree of double bonds is 80% -95%, and the integral rubber before hydrogenation and modification is the integral rubber with a linear triblock structure.
Preferably, the integrated rubber structure of the linear triblock structure is:
the two ends of the polymer are provided with styrene-butadiene rubber chain segments which are randomly copolymerized, and the polymer accounts for 20-60% of the total mass of the polymer, wherein styrene units account for 15-40% of the mass of the styrene-butadiene rubber chain segments, and 1, 4-butadiene units account for 55-80% of the mass of the styrene-butadiene rubber chain segments; the middle part is an isoprene rubber chain segment which accounts for 40-80% of the total mass of the polymer, and the 1, 4-isoprene unit accounts for 80-95% of the mass of the isoprene rubber chain segment.
Preferably, the weight-average molecular weight of the low cis-polybutadiene rubber is 50-100 ten thousand, and the mass fraction of the 1, 4-butadiene structure is 75-95%.
Preferably, the composition further comprises the following components in parts by weight:
15-35 parts of carbon black, 15-35 parts of high-dispersion white carbon black, 1-3 parts of silane coupling agent, 2-4 parts of filler dispersant, 3-6 parts of anti-aging agent, 3-6 parts of activating agent, 1-3 parts of insoluble sulfur, 1-2 parts of accelerator and 0.5-2 parts of anti-reversion agent.
Preferably, the carbon black iodine absorption value is 30g/kg-60g/kg, and the DBP absorption value is 120 multiplied by 10-5m3/kg-150×10-5m3/kg。
Preferably, the specific surface area of the high-dispersion white carbon black is 85m2/g-115m2/g。
Preferably, the silane coupling agent is selected from at least one of 3-octanoylthio-1-propyltriethoxysilane, gamma-mercaptopropyl-ethoxybis (propyl-hexapropoxy) silane, and gamma-mercaptopropyltriethoxysilane;
the filler dispersing agent is selected from at least one of fatty acid zinc soap, fatty acid ester and low molecular weight ether;
the anti-reversion agent is at least one selected from tetrabenzylthiuram disulfide, 1, 6-bis (N, N '-dibenzylthiocarbamoyldithio) hexane, N' -m-methylphenyl bis (3-methylmaleimide) and N, N-m-phenylene bismaleimide.
In another aspect, the present invention provides a method for preparing a rubber composition according to any one of the above technical solutions, comprising the steps of:
first-stage mixing: adding the low cis-polybutadiene rubber, the high dispersion white carbon black, the silane coupling agent and the 1/2 carbon black into a closed rubber mixing mill according to the weight part ratio, uniformly mixing, and then discharging rubber to obtain a first-section masterbatch;
and (3) second-stage mixing: adding the hydrogenated and modified block type integrated rubber into a closed rubber mixing mill according to the weight part ratio for plastication, adding the first-stage masterbatch, the filler dispersant, the anti-aging agent, the activator and the residual 1/2 carbon black, uniformly mixing, and discharging rubber to obtain second-stage masterbatch;
three-stage mixing: and adding the second-stage masterbatch, insoluble sulfur, an accelerant and an anti-reversion agent into a closed rubber mixing mill, uniformly mixing, and discharging rubber to obtain the final rubber.
The invention also provides an inner support of a run-flat tire, which is prepared from the rubber composition of any technical scheme.
Compared with the prior art, the invention has the beneficial effects that:
the present invention provides a rubber composition having excellent heat resistance, mechanical strength and low hysteresis loss without losing its flex resistance, low hysteresis and processability;
the invention also provides a preparation method of the rubber composition, which effectively solves the problem of mixing difficulty caused by huge difference of Mooney viscosities of hydrogenated integral rubber and polybutadiene rubber and is beneficial to industrial implementation;
the invention also provides the run-flat tire inner support, the run-flat tire prepared from the run-flat tire inner support has the zero-air-pressure durability of more than 2.5h, is obviously superior to the prior art, and the inner support rubber is not the first failure point.
Detailed Description
The technical solutions in the embodiments of the present invention will be fully described in detail below. It is obvious that the described embodiments are only some specific embodiments, not all embodiments, of the general technical solution of the present invention. All other embodiments, which can be derived by a person skilled in the art from the general idea of the invention, fall within the scope of protection of the invention.
The invention provides a rubber composition for an inner support of a run-flat tire, which comprises the following components in parts by weight: 50-70 parts of integrated rubber and 30-50 parts of low cis-polybutadiene rubber; the integral rubber is hydrogenated and modified block type integral rubber, the weight average molecular weight of the hydrogenated and modified block type integral rubber is 30-80 ten thousand, the total hydrogenation degree of double bonds is 80% -95%, and the integral rubber before hydrogenation and modification is the integral rubber with a linear triblock structure. The integrated rubber and the hydrogenated modified product thereof are originally rubber specially developed for the tread rubber of the tire, wherein the integrated rubber subjected to anionic polymerization contains three comonomers of styrene, butadiene and isoprene, the sequence structure of the integrated rubber also has random copolymerization, block copolymerization, hybrid arm coupling and the like, the height of the microstructure is adjustable, and the dynamic performance and the heat resistance of the integrated rubber are more excellent by adding a hydrogenation modification technology. Chinese patent CN104628901 discloses a partially hydrogenated terpolymer rubber with a star-shaped block structure, a preparation method and an application thereof, wherein the lower hydrogenation degree is beneficial to improving the heat resistance and aging resistance, and simultaneously, the rubber material is kept to have better elasticity, faster vulcanization speed and good processability, and the partially hydrogenated terpolymer rubber is suitable for tire tread rubber. However, although the partially hydrogenated terpolymer rubber with a star-shaped block structure improves the heat and aging resistance, and keeps the rubber material with better elasticity, faster vulcanization speed and good processability, the mechanical properties of the rubber material cannot be obviously improved. The technical scheme mainly adopts the integrated rubber and the low cis-polybutadiene rubber, further limits the type and the structure of the integrated rubber, is beneficial to greatly improving the heat resistance and the mechanical strength of the rubber material, simultaneously does not lose the low hysteresis quality and the flexibility resistance of the rubber material, and particularly ensures that the rubber material has excellent heat resistance and tensile crystallization property by higher hydrogenation degree, but still keeps partial double bonds to provide necessary vulcanization speed and elasticity; moderate molecular weight can compromise processability and mechanical strength. The technical scheme also limits the usage amount of the integral rubber and the low cis-polybutadiene rubber, and can be understood that the usage amount of the integral rubber can be 55 parts, 60 parts and 65 parts and any value in the range, and the usage amount of the low cis-polybutadiene rubber can be 35 parts, 40 parts and 45 parts and any value in the range.
Compared with the traditional scheme (such as natural rubber is taken as the main component), the high-hydrogenation modified block type integrated rubber adopted by the technical scheme of the invention has excellent heat resistance, mechanical strength and lower hysteresis loss, but has general crack initiation resistance and relatively difficult processing and vulcanization. The present invention thus achieves performance complementation with low cis-polybutadiene rubber without losing yield flexibility, low hysteresis, and processability while achieving high heat resistance goals. By blending other ingredients which are preferred in terms of the compatibility, the highly heat-resistant run-flat tire inner support rubber composition having greatly improved overall performance is finally obtained. The zero-air-pressure durability of the run-flat tire prepared from the inner support rubber composition can reach more than 2.5h, and is remarkably superior to the prior art, and the inner support rubber is not the first failure point, which further shows the excellent performance of the scheme.
In a preferred embodiment, the integrated rubber structure of the linear triblock structure is: the two ends of the polymer are provided with styrene-butadiene rubber chain segments which are randomly copolymerized, and the polymer accounts for 20-60% of the total mass of the polymer, wherein styrene units account for 15-40% of the mass of the styrene-butadiene rubber chain segments, and 1, 4-butadiene units account for 55-80% of the mass of the styrene-butadiene rubber chain segments; the middle part is an isoprene rubber chain segment which accounts for 40-80% of the total mass of the polymer, and the 1, 4-isoprene unit accounts for 80-95% of the mass of the isoprene rubber chain segment. The styrene butadiene rubber chain segments at the two ends of the molecular chain can provide higher mechanical strength after hydrogenation, wherein the low styrene content is used for balancing internal rotation resistance and structural regularity, and the higher 1, 4-butadiene content is used for ensuring the tensile crystallization characteristic after hydrogenation; the hydrogenation activity of the isoprene rubber chain segment in the middle of the molecular chain is slightly lower than that of the styrene-butadiene rubber chain segments at two ends, so that better elasticity and crosslinkability can be provided, and the higher content of the 1, 4-isoprene is also used for ensuring the tensile crystallization characteristic after hydrogenation.
In a preferred embodiment, the weight average molecular weight of the low-cis polybutadiene rubber is 50-100 ten thousand, and the mass fraction of the 1, 4-butadiene structure is 75-95%. The low cis-polybutadiene with higher molecular weight has Mooney viscosity closer to that of hydrogenated integral rubber, is beneficial to uniform mixing, and simultaneously, the higher content of 1, 4-butadiene can improve the crack initiation resistance of rubber materials.
In a preferred embodiment, the method further comprises the following steps of: 15-35 parts of carbon black, 15-35 parts of high-dispersion white carbon black, 1-3 parts of silane coupling agent, 2-4 parts of filler dispersant, 3-6 parts of anti-aging agent, 3-6 parts of activating agent, 1-3 parts of insoluble sulfur, 1-2 parts of accelerator and 0.5-2 parts of anti-reversion agent. The technical scheme specifically limits the specific use amounts of the carbon black, the high-dispersion white carbon black, the silane coupling agent, the filler dispersant, the anti-aging agent, the activating agent, the insoluble sulfur, the accelerator and the anti-reversion agent, and it can be understood that the use amount of the carbon black can be any value within the ranges of 20 parts, 25 parts and 30 parts, and the use amount of the high-dispersion white carbon black can be any value within the ranges of 20 parts, 25 parts and 30 parts.
In a preferred embodiment, the carbon black iodine absorption value is 30g/kg-60g/kg, and the DBP absorption value is 120 x 10-5m3/kg-150×10-5m3In terms of/kg. The carbon black with large particle size and high structure can reduce the hysteresis loss of the sizing material and improve the crack propagation resistance of the sizing material.
In a preferred embodiment, the specific surface area of the high-dispersion white carbon black is 85m2/g-115m2(ii) in terms of/g. The white carbon black with low specific surface area and high dispersion can further reduce the hysteresis loss of the sizing material.
In a preferred embodiment, the silane coupling agent is selected from at least one of 3-octanoylthio-1-propyltriethoxysilane, gamma-mercaptopropyl-ethoxybis (propyl-hexapropoxy) silane, and gamma-mercaptopropyltriethoxysilane, and the high activity silane containing mercapto groups or derivatives thereof is particularly suitable for use in high hydrogenation rubber systems to further reduce compound hysteresis loss; the filler dispersing agent is selected from at least one of fatty acid zinc soap, fatty acid ester and low molecular weight ether, and can improve the processing performance and the flexing resistance of the rubber material; the anti-reversion agent is at least one selected from tetrabenzylthiuram disulfide, 1, 6-bis (N, N '-dibenzylthiocarbamoyldithio) hexane, N' -m-methylphenyl bis (3-methylmaleimide) and N, N-m-phenylene bismaleimide, and can improve the thermal stability of cross-links and further improve the heat resistance of the rubber compound.
In another aspect, the present invention provides a method for preparing a rubber composition according to any one of the above technical solutions, comprising the steps of:
first-stage mixing: adding the low cis-polybutadiene rubber, the high dispersion white carbon black, the silane coupling agent and the 1/2 carbon black into a closed rubber mixing mill according to the weight part ratio, uniformly mixing, and then discharging rubber to obtain a first-section masterbatch;
and (3) second-stage mixing: adding the hydrogenated and modified block type integrated rubber into a closed rubber mixing mill according to the weight part ratio for plastication, adding the first-stage masterbatch, the filler dispersant, the anti-aging agent, the activator and the residual 1/2 carbon black, uniformly mixing, and discharging rubber to obtain second-stage masterbatch;
three-stage mixing: and adding the second-stage masterbatch, insoluble sulfur, an accelerant and an anti-reversion agent into a closed rubber mixing mill, uniformly mixing, and discharging rubber to obtain the final rubber.
The preparation method firstly prepares the high-filling polybutadiene rubber master batch, and then mixes the high-filling polybutadiene rubber master batch with the plasticated hydrogenated integral rubber together, effectively solves the mixing difficulty caused by the huge difference of the Mooney viscosities of the hydrogenated integral rubber and the polybutadiene rubber, and is beneficial to industrial implementation.
The invention also provides an inner support of a run-flat tire, which is prepared from the rubber composition of any technical scheme. The zero-air-pressure durability of the run-flat tire obtained by the inner support of the run-flat tire can reach more than 2.5h, the run-flat tire is obviously superior to the prior art, and the inner support rubber is not the first failure point.
In order to more clearly and specifically describe the rubber composition, the preparation method thereof and the run-flat tire inner support provided in the examples of the present invention, the following description will be given with reference to specific examples.
Example 1
The embodiment provides a high-heat-resistance run-flat tire inner support rubber composition and a preparation method thereof, and the preparation method specifically comprises the following steps:
the formula of the inner support rubber composition comprises the following components in parts by weight:
60 parts of hydrogenated modified block-type integral rubber, 40 parts of low cis-polybutadiene rubber, 35 parts of N550 carbon black, 20 parts of 1115MP white carbon black, 2.4 parts of TESPT silane coupling agent, 2 parts of SL5050 filler dispersing agent, 3.5 parts of anti-aging agent, 5 parts of activating agent, 1.6 parts of insoluble sulfur, 1.5 parts of NS accelerator and 1 part of TBzTD anti-reversion agent.
Wherein, the weight average molecular weight of the block type integral rubber modified by hydrogenation is 65 ten thousand, the degree of double bond hydrogenation is 92 percent, and the integral rubber before hydrogenation is a linear triblock structure: the two ends of the polymer are provided with styrene-butadiene rubber chain segments which are randomly copolymerized, and the styrene units account for 40 percent of the total mass of the polymer, and the 1, 4-butadiene units account for 70 percent of the mass of the styrene-butadiene rubber chain segments; the middle part is an isoprene rubber chain segment which accounts for 60 percent of the total mass of the polymer, and the 1, 4-isoprene unit accounts for 90 percent of the mass of the isoprene rubber chain segment. The low cis-polybutadiene rubber has a weight average molecular weight of 75 ten thousand and a 1, 4-butadiene structure content of 90%.
The preparation method of the inner support rubber comprises the following steps:
(1) adding low cis-polybutadiene rubber into an internal mixer, carrying out bolt pressing and mixing for 20s, and controlling the rotating speed of the internal mixer to be 70 rpm;
(2) adding white carbon black, a silane coupling agent and 1/2 carbon black into the mixture, and carrying out plug pressing and mixing for 40s at the rotating speed of 50rpm of an internal mixer;
(3) after extracting the plug, pressing the plug and mixing to 160 ℃, controlling the rotating speed of an internal mixer to be 90rpm, and discharging the rubber and cooling the lower piece to obtain a section of master batch;
(4) adding hydrogenated modified block type integral rubber into an internal mixer, performing bolt pressing and mixing for 20s, and controlling the rotating speed of the internal mixer to be 70 rpm;
(5) adding a section of masterbatch, the rest 1/2 carbon black, a filler dispersant, an anti-aging agent and an activator into the mixture for plug extraction, mixing the mixture for 40s by pressing, and controlling the rotating speed of an internal mixer to be 50 rpm;
(6) mixing the mixture to 145 ℃ after bolt extraction, controlling the rotating speed of the internal mixer to 90rpm, mixing the mixture at the constant temperature of 150 ℃ for 180s after bolt extraction, removing rubber, and cooling to obtain a second-stage master batch;
(7) adding the second-stage masterbatch after extracting the plug, pressing and mixing for 20s, and controlling the rotating speed of an internal mixer to be 40 rpm;
(8) adding an accelerant, insoluble sulfur and an anti-reversion agent into the mixture, carrying out bolt pressing and mixing for 40s or 90 ℃, controlling the rotating speed of the internal mixer to be 40rpm, carrying out bolt pressing and mixing to be 100 ℃ after bolt extraction, discharging rubber, and cooling to obtain final rubber.
Example 2
The embodiment provides a high-heat-resistance run-flat tire inner support rubber composition and a preparation method thereof, and the preparation method specifically comprises the following steps:
the formula of the inner support rubber composition comprises the following components in parts by weight:
60 parts of hydrogenated modified block type integral rubber, 40 parts of low cis-polybutadiene rubber, 25 parts of BC2123 carbon black, 25 parts of 1085MP white carbon black, 2 parts of NXT silane coupling agent, 2 parts of AEO-9 filler dispersing agent, 3.5 parts of anti-aging agent, 5 parts of activating agent, 1.6 parts of insoluble sulfur, 1.5 parts of NS accelerator and 1 part of WY9188 anti-reversion agent.
Wherein the molecular structures of the block type integral rubber and the low cis polybutadiene rubber modified by hydrogenation are the same as those of example 1.
The preparation method is the same as example 1.
Example 3
The embodiment provides a high-heat-resistance run-flat tire inner support rubber composition and a preparation method thereof, and the preparation method specifically comprises the following steps:
the formula of the inner support rubber composition comprises the following components in parts by weight:
70 parts of hydrogenated modified block type integral rubber, 30 parts of low cis-polybutadiene rubber, 15 parts of BC2123 carbon black, 35 parts of 1085MP white carbon black, 3 parts of Si-747 silane coupling agent, 4 parts of SL5044 filler dispersing agent, 6 parts of anti-aging agent, 3 parts of activating agent, 1 part of insoluble sulfur, 1 part of CZ accelerator and 2 parts of PK900 anti-reversion agent.
Wherein, the weight average molecular weight of the block type integral rubber modified by hydrogenation is 80 ten thousand, the degree of double bond hydrogenation is 80 percent, and the integral rubber before hydrogenation is a linear triblock structure: the two ends of the polymer are provided with styrene-butadiene rubber chain segments which are randomly copolymerized, and the styrene units account for 60 percent of the total mass of the polymer, and the 1, 4-butadiene units account for 55 percent of the mass of the styrene-butadiene rubber chain segments; the middle part is an isoprene rubber chain segment which accounts for 40 percent of the total mass of the polymer, and the 1, 4-isoprene unit accounts for 95 percent of the mass of the isoprene rubber chain segment. The weight average molecular weight of the low cis-polybutadiene rubber is 50 ten thousand, and the content of a 1, 4-butadiene structure is 75%.
The preparation method is the same as example 1.
Example 4
The embodiment provides a high-heat-resistance run-flat tire inner support rubber composition and a preparation method thereof, and the preparation method specifically comprises the following steps:
the formula of the inner support rubber composition comprises the following components in parts by weight:
50 parts of hydrogenated modified block type integrated rubber, 50 parts of low cis-polybutadiene rubber, 35 parts of BC1029 carbon black, 15 parts of 1115MP white carbon black, 1 part of KH-580 silane coupling agent, 3 parts of EF-44 filler dispersing agent, 3 parts of anti-aging agent, 6 parts of activating agent, 3 parts of insoluble sulfur, 2 parts of CZ promoter and 0.5 part of HVA-2 anti-reversion agent.
Wherein, the weight average molecular weight of the block type integral rubber modified by hydrogenation is 30 ten thousand, the degree of double bond hydrogenation is 95 percent, and the integral rubber before hydrogenation is a linear triblock structure: the two ends of the polymer are provided with styrene-butadiene rubber chain segments which are randomly copolymerized, and the styrene units account for 20 percent of the total mass of the polymer, and the 1, 4-butadiene units account for 80 percent of the mass of the styrene-butadiene rubber chain segments; the middle part is an isoprene rubber chain segment, which accounts for 80 percent of the total mass of the polymer, and the 1, 4-isoprene unit accounts for 80 percent of the mass of the isoprene rubber chain segment. The weight average molecular weight of the low cis-polybutadiene rubber is 100 ten thousand, and the content of the 1, 4-butadiene structure is 95%.
The preparation method is the same as example 1.
Comparative example 1
The comparative example provides an inner support rubber composition and a preparation method thereof, and the preparation method specifically comprises the following steps:
the formula of the inner support rubber composition comprises the following components in parts by weight:
50 parts of natural rubber, 50 parts of neodymium butadiene rubber, 35 parts of N550 carbon black, 20 parts of 1115MP white carbon black, 2.4 parts of TESPT silane coupling agent, 2 parts of SL5050 filler dispersant, 3.5 parts of anti-aging agent, 5 parts of activator, 1.6 parts of insoluble sulfur, 1.5 parts of NS accelerator and 1 part of TBzTD anti-reversion agent. The preparation method is carried out according to the conventional processes of first-stage masterbatch preparation and first-stage final rubber preparation.
Comparative example 2
The comparative example provides an inner support rubber composition and a preparation method thereof, and the preparation method specifically comprises the following steps:
the formula of the inner support rubber composition comprises the following components in parts by weight:
60 parts of unhydrogenated modified block-type integral rubber, 40 parts of low cis-polybutadiene rubber, 35 parts of N550 carbon black, 20 parts of 1115MP white carbon black, 2.4 parts of TESPT silane coupling agent, 2 parts of SL5050 filler dispersing agent, 3.5 parts of anti-aging agent, 5 parts of activating agent, 1.6 parts of insoluble sulfur, 1.5 parts of NS accelerator and 1 part of TBzTD anti-reversion agent.
Wherein the weight-average molecular weight of the block type integral rubber which is not hydrogenated and modified is 65 ten thousand, and the block type integral rubber is of a linear triblock structure: the two ends of the polymer are provided with styrene-butadiene rubber chain segments which are randomly copolymerized, and the styrene units account for 40 percent of the total mass of the polymer, and the 1, 4-butadiene units account for 70 percent of the mass of the styrene-butadiene rubber chain segments; the middle part is an isoprene rubber chain segment which accounts for 60 percent of the total mass of the polymer, and the 1, 4-isoprene unit accounts for 90 percent of the mass of the isoprene rubber chain segment. The low cis-polybutadiene rubber has a weight average molecular weight of 75 ten thousand and a 1, 4-butadiene structure content of 90%.
The preparation method is the same as example 1.
Comparative example 3
The comparative example provides an inner support rubber composition and a preparation method thereof, and the preparation method specifically comprises the following steps:
the formula of the inner support rubber composition comprises the following components in parts by weight:
60 parts of hydrogenated modified random integral rubber, 40 parts of low cis-polybutadiene rubber, 35 parts of N550 carbon black, 20 parts of 1115MP white carbon black, 2.4 parts of TESPT silane coupling agent, 2 parts of SL5050 filler dispersing agent, 3.5 parts of anti-aging agent, 5 parts of activating agent, 1.6 parts of insoluble sulfur, 1.5 parts of NS accelerator and 1 part of TBzTD anti-reversion agent.
Wherein, the weight average molecular weight of the hydrogenated and modified random integral rubber is 65 ten thousand, the degree of double bond hydrogenation is 92 percent, and the integral rubber before hydrogenation is in a linear random structure: styrene units accounted for 8.8% of the total mass of the polymer; the butadiene unit accounts for 31.2 percent of the total mass of the polymer, wherein the 1, 4-butadiene unit accounts for 28 percent of the total mass of the polymer; the isoprene unit accounts for 60% of the total mass of the polymer, wherein the 1, 4-isoprene unit accounts for 54% of the total mass of the polymer. The low cis-polybutadiene rubber has a weight average molecular weight of 75 ten thousand and a 1, 4-butadiene structure content of 90%.
The preparation method is the same as example 1.
Performance testing
The invention carries out a plurality of performance tests on the rubber compounds prepared in the above examples 1-4 and comparative examples 1-3, and the specific test methods and test results are as follows:
(1) the test method comprises the following steps: the rubber material is vulcanized under the condition of 161 ℃ multiplied by 20 min; the hardness test of the sizing material is carried out according to GB/T531, and the tensile property of the sizing material is carried out according to GB/T528, and the tests are divided into room temperature test, high temperature test (70 ℃) and test after aging (100 ℃ multiplied by 48 h); the rubber compound RPA test conditions are as follows: after vulcanization at 161 ℃ for 15min, strain scanning is carried out at 100 ℃ under the condition of 10Hz, and the strain range is 0.28-42 percent; the compression fatigue temperature rise thermostat is 100 ℃, the load is 2MPa, the stroke is 4.45mm, and the test time is 1 h; the compound flex resistance was performed according to GB/T13934, observing a vent rating every 1000 times; the tire test was carried out using the specification 225/45R17 and the zero air pressure endurance test was carried out in accordance with GB/T30196.
(2) The test results are shown in Table 1.
TABLE 1 results of the Performance test of the compounds prepared in examples 1 to 4 and comparative examples 1 to 3
On the basis of the rubber composition formulas shown in the examples and the comparative examples, the performance test data shown in the table 1 are combined, so that the comparative example 1 is the conventional common rubber composition formula, the raw rubber system adopts natural rubber and butadiene rubber, the room-temperature mechanical property of the raw rubber system is good, but the mechanical property of the raw rubber system is remarkably reduced after high temperature and aging; the hysteresis loss and the compression fatigue temperature rise are lower, but the final compression rate is higher, which is also caused by the reduction of the mechanical property of the sizing material at high temperature; the zero-air-pressure endurance time of the trial-manufactured tire is 1.15h, the failure mode is that the inner support rubber is damaged, and the performance of the inner support rubber is a main factor for limiting the zero-air-pressure endurance of the tire. After the technical scheme is adopted in the embodiment, the mechanical property of the sizing material at room temperature is improved, and the high-temperature mechanical property and the aging resistance are obviously improved; although the hysteresis loss and the compression fatigue temperature rise of the rubber compound slightly fluctuate with the change of the formula, the final compression ratio is obviously lower than that of the comparative example; the crack initiation resistance and crack propagation resistance of the rubber are greatly improved; the zero-air-pressure endurance time of the tire is remarkably prolonged, and the inner supporting rubber is no longer a weak link for limiting endurance performance. Therefore, the rubber composition formula and the preparation method thereof provided by the invention are utilized to finally prepare the run-flat tire inner supporting rubber with high heat resistance, high mechanical strength, low hysteresis loss and flex resistance, and the technical problem that the mechanical property of the run-flat tire inner supporting rubber in the prior art is greatly reduced at high temperature can be solved.
Claims (9)
1. A rubber composition for use in a run-flat tire inner support, comprising: comprises the following components in parts by weight:
50-70 parts of integrated rubber and 30-50 parts of low cis-polybutadiene rubber;
the integral rubber is hydrogenated and modified block type integral rubber, the weight average molecular weight of the hydrogenated and modified block type integral rubber is 30-80 ten thousand, the total hydrogenation degree of double bonds is 80% -95%, and the integral rubber before hydrogenation and modification is the integral rubber with a linear triblock structure.
2. The rubber composition according to claim 1, characterized in that: the integrated rubber structure of the linear triblock structure is as follows:
the two ends of the polymer are provided with styrene-butadiene rubber chain segments which are randomly copolymerized, and the polymer accounts for 20-60% of the total mass of the polymer, wherein styrene units account for 15-40% of the mass of the styrene-butadiene rubber chain segments, and 1, 4-butadiene units account for 55-80% of the mass of the styrene-butadiene rubber chain segments; the middle part is an isoprene rubber chain segment which accounts for 40-80% of the total mass of the polymer, and the 1, 4-isoprene unit accounts for 80-95% of the mass of the isoprene rubber chain segment.
3. The rubber composition according to claim 1, characterized in that: the weight average molecular weight of the low cis-polybutadiene rubber is 50-100 ten thousand, and the mass fraction of the 1, 4-butadiene structure is 75% -95%.
4. The rubber composition according to claim 1, characterized in that: the adhesive also comprises the following components in parts by weight:
15-35 parts of carbon black, 15-35 parts of high-dispersion white carbon black, 1-3 parts of silane coupling agent, 2-4 parts of filler dispersant, 3-6 parts of anti-aging agent, 3-6 parts of activating agent, 1-3 parts of insoluble sulfur, 1-2 parts of accelerator and 0.5-2 parts of anti-reversion agent.
5. The rubber composition according to claim 4, wherein: the iodine absorption value of the carbon black is 30g/kg-60g/kg, and the DBP absorption value is 120 multiplied by 10-5m3/kg-150×10-5m3/kg。
6. The rubber composition according to claim 4, wherein: the specific surface area of the high-dispersion white carbon black is 85m2/g-115m2/g。
7. The rubber composition according to claim 4, wherein: the silane coupling agent is selected from at least one of 3-octanoylthio-1-propyltriethoxysilane, gamma-mercaptopropyl-ethoxybis (propyl-hexapropoxy) silane and gamma-mercaptopropyltriethoxysilane;
the filler dispersing agent is selected from at least one of fatty acid zinc soap, fatty acid ester and low molecular weight ether;
the anti-reversion agent is at least one selected from tetrabenzylthiuram disulfide, 1, 6-bis (N, N '-dibenzylthiocarbamoyldithio) hexane, N' -m-methylphenyl bis (3-methylmaleimide) and N, N-m-phenylene bismaleimide.
8. The method for producing a rubber composition according to any one of claims 1 to 7, characterized in that: the method comprises the following steps:
first-stage mixing: adding the low cis-polybutadiene rubber, the high dispersion white carbon black, the silane coupling agent and the 1/2 carbon black into a closed rubber mixing mill according to the weight part ratio, uniformly mixing, and then discharging rubber to obtain a first-section masterbatch;
and (3) second-stage mixing: adding the hydrogenated and modified block type integrated rubber into a closed rubber mixing mill according to the weight part ratio for plastication, adding the first-stage masterbatch, the filler dispersant, the anti-aging agent, the activator and the residual 1/2 carbon black, uniformly mixing, and discharging rubber to obtain second-stage masterbatch;
three-stage mixing: and adding the second-stage masterbatch, insoluble sulfur, an accelerant and an anti-reversion agent into a closed rubber mixing mill, uniformly mixing, and discharging rubber to obtain the final rubber.
9. An in-flight tire inner support, characterized by: is produced by using the rubber composition according to any one of claims 1 to 7.
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| CN1156467A (en) * | 1994-08-08 | 1997-08-06 | 旭化成工业株式会社 | Hydrogenated rubber composition |
| CN103012873A (en) * | 2011-09-26 | 2013-04-03 | 北京橡胶工业研究设计院 | Rubber composition for tire sidewall part of run-flat tire |
| CN110050024A (en) * | 2016-12-15 | 2019-07-23 | 通伊欧轮胎株式会社 | Rubber composition for tire and the pneumatic tire for having used the rubber composition for tire |
| CN111607136A (en) * | 2020-06-30 | 2020-09-01 | 山东金宇轮胎有限公司 | All-steel radial tire base rubber formula and preparation method thereof |
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2021
- 2021-09-28 CN CN202111143098.2A patent/CN113736208B/en active Active
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1156467A (en) * | 1994-08-08 | 1997-08-06 | 旭化成工业株式会社 | Hydrogenated rubber composition |
| US5804644A (en) * | 1994-08-08 | 1998-09-08 | Asahi Kasei Kabushiki Kaisha | Hydrogenerated rubber composition |
| CN103012873A (en) * | 2011-09-26 | 2013-04-03 | 北京橡胶工业研究设计院 | Rubber composition for tire sidewall part of run-flat tire |
| CN110050024A (en) * | 2016-12-15 | 2019-07-23 | 通伊欧轮胎株式会社 | Rubber composition for tire and the pneumatic tire for having used the rubber composition for tire |
| CN111607136A (en) * | 2020-06-30 | 2020-09-01 | 山东金宇轮胎有限公司 | All-steel radial tire base rubber formula and preparation method thereof |
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