CN114437415B - Rubber composition for light tire sidewall and application thereof, vulcanized rubber and preparation method and application thereof - Google Patents
Rubber composition for light tire sidewall and application thereof, vulcanized rubber and preparation method and application thereof Download PDFInfo
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L7/00—Compositions of natural rubber
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- C—CHEMISTRY; METALLURGY
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- 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
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- C08K2003/2241—Titanium dioxide
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Abstract
The invention relates to the field of rubber, and discloses a rubber composition for a light tire sidewall, application thereof, vulcanized rubber, a preparation method thereof and application thereof, wherein the composition contains the following components which are stored in a mixed manner or are stored independently: the modified rubber comprises a rubber matrix, a rubber modifier, white carbon black, titanium dioxide, talcum powder, an activating agent, an anti-aging agent, a softening agent, an accelerating agent and a vulcanizing agent, wherein the rubber modifier is a mercapto acid monomer provided by at least one of compounds shown in a formula (1), the rubber matrix is a combination of butadiene rubber and natural rubber, and the average diameter of the talcum powder is 4-5 mu m. The rubber composition provided by the invention has good processing safety and higher vulcanization efficiency, and vulcanized rubber prepared from the composition has higher strength and better yield resistance.
Description
Technical Field
The invention relates to the field of rubber, in particular to a rubber composition for a light tire sidewall and application thereof, a method for preparing vulcanized rubber, the vulcanized rubber prepared by the method and application of the vulcanized rubber in the tire sidewall.
Background
In recent years, in order to adapt to the development trend of safety, environmental protection and green of automobile tires, non-petroleum resources such as white carbon black are increasingly paid attention to in the field of tires because of the characteristics of reducing the rolling resistance of the tires, saving the fuel consumption of the automobiles and the like.
The white carbon black has a certain limit in application because of the strong surface polarity, which makes the dispersion of the white carbon black in the rubber matrix become extremely difficult. Because the white carbon black has high polarity, the surface is easy to adsorb zinc oxide, and silicon complex zinc is easy to form in the vulcanization process, and the substance can not activate the accelerator, so that the activation effect of the zinc oxide is reduced, the vulcanization hysteresis is caused, and the vulcanization efficiency in production is affected.
CN104530501a discloses a rubber composition for color tire sidewall discoloration resistance, which has bright color, better discoloration resistance, dark color tire sidewall does not have discoloration phenomenon in strong illumination and damp-heat environment within one year, and the formula has higher tearing resistance and excellent discoloration resistance under severe use conditions of strong illumination and damp-heat.
CN104311918A discloses a rubber composition for a sidewall portion of a run flat tire for a passenger car, which can improve safety performance when a vehicle runs, and reduce or eliminate traffic accidents caused by puncture and explosion of the tire.
However, in the prior art, it is disclosed that the dispersibility of the white carbon black is improved by adding a silane coupling agent Si75 or the like, and the Si75 or the like is a sulfur-containing compound, and in the high-temperature mixing process, the process control requirement is high, and improper control may cause scorching, so that the overall performance of the composite material is affected. Si75 and the like are prone to ethanol during processing, and the presence of ethanol can pose a safety hazard to tires.
CN109384964a discloses a rubber composition and vulcanized rubber for a tire sidewall, and a preparation method and application thereof, the rubber composition of the present invention has the advantages of high strength, low rolling resistance, good dynamic flexibility, and the vulcanized rubber formed from the composition can be used for a tire sidewall. But the composition generally exhibits in terms of vulcanization efficiency.
Since the above prior art cannot fully satisfy the requirements of high processing safety and high vulcanization efficiency of a tire side rubber containing a white carbon black formulation while ensuring high strength and flex resistance, it is necessary to provide a rubber composition having improved properties.
Disclosure of Invention
The invention aims to solve the problems of good processing safety and higher vulcanization efficiency on the premise of ensuring the basic application requirements of strength and bending resistance in the tire sidewall rubber containing the white carbon black formula.
In order to achieve the above object, a first aspect of the present invention provides a rubber composition for a light-colored tire sidewall, the composition comprising two or more of the following components stored in admixture or each independently: the rubber modifier is a mercapto acid monomer provided by at least one of compounds shown in the formula (1), the rubber matrix is a mixture of butadiene rubber and natural rubber, and the average diameter of the talcum powder is 4-5 mu m;
wherein, in the formula (1),
x is 0, and R 2 is-SH; or alternatively
X is 1, M is a structure represented by formula (2), R 1 And R is 2 Each independently is H or-SH, and R 1 And R is 2 Not simultaneously H; or alternatively
X is 2, M is a structure represented by formula (2), R 2 R in 2M 1 Each independently is H or-SH, and R 2 R in two M 1 Not simultaneously H; or alternatively
X is 3, M is a structure represented by formula (2), R 2 R in 3M 1 Each independently is H or-SH, and R 2 R in 3M 1 Not simultaneously H;
wherein, in the rubber matrix, the content weight ratio of the butadiene rubber to the natural rubber is 40:60 to 60:40, a step of performing a;
the rubber comprises, by weight, relative to 100 parts of the rubber matrix, 5-10 parts of the rubber modifier, 40-60 parts of the white carbon black, 10-30 parts of the titanium dioxide, 10-20 parts of the talcum powder, 5-10 parts of the activator, 1-3 parts of the antioxidant, 5-15 parts of the softener, 1-5 parts of the accelerator and 0.5-4 parts of the vulcanizing agent.
In a second aspect, the present invention provides a process for producing a vulcanized rubber, the process comprising: the components of the rubber composition of the first aspect are mixed to form a final rubber compound, and the final rubber compound is subjected to vulcanization treatment.
In a third aspect, the present invention provides a vulcanized rubber prepared by the above method.
A fourth aspect of the present invention provides the use of the above-described vulcanizate in a tire sidewall.
A fifth aspect of the present invention provides the use of the rubber composition described above in the preparation of a tire sidewall rubber.
The rubber composition of the invention has good processing safety and vulcanization efficiency, higher strength and better flex resistance, and the vulcanized rubber prepared from the composition can be used for the side wall of a light-colored tire.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
As described above, the first aspect of the present invention provides a rubber composition for a light-colored tire sidewall, which comprises the following components stored in a mixture of two or more or each independently: the rubber modifier is a mercapto acid monomer provided by at least one of compounds shown in the formula (1), the rubber matrix is a mixture of butadiene rubber and natural rubber, and the average diameter of the talcum powder is 4-5 mu m;
wherein, in the formula (1),
x is 0, and R 2 is-SH; or alternatively
X is 1, M is a structure represented by formula (2), R 1 And R is 2 Each independently is H or-SH, and R 1 And R is 2 Not simultaneously H; or alternatively
X is 2, M is a structure represented by formula (2), R 2 R in 2M 1 Each independently is H or-SH, and R 2 R in two M 1 Not simultaneously H; or alternatively
X is 3, M is a structure represented by formula (2), R 2 R in 3M 1 Each independently is H or-SH, and R 2 R in 3M 1 Not simultaneously H;
wherein, in the rubber matrix, the content weight ratio of the butadiene rubber to the natural rubber is 40:60 to 60:40, a step of performing a;
the rubber comprises, by weight, relative to 100 parts of the rubber matrix, 5-10 parts of the rubber modifier, 40-60 parts of the white carbon black, 10-30 parts of the titanium dioxide, 10-20 parts of the talcum powder, 5-10 parts of the activator, 1-3 parts of the antioxidant, 5-15 parts of the softener, 1-5 parts of the accelerator and 0.5-4 parts of the vulcanizing agent.
The rubber composition provided by the invention has good processing safety and vulcanization efficiency, and the prepared vulcanized rubber has higher strength and good yield resistance.
Preferably, the cis content in the butadiene rubber is 90 to 99 wt.%.
Preferably, the natural rubber is SMR-20.
Preferably, the rubber modifier is at least one of 3-mercaptopropionic acid, 4-mercaptobutyric acid, and 2-mercaptopropionic acid.
Preferably, the rubber modifier is contained in an amount of 3 to 8 parts by weight, the white carbon black is contained in an amount of 40 to 60 parts by weight, the titanium dioxide is contained in an amount of 10 to 30 parts by weight, the talc is contained in an amount of 10 to 20 parts by weight, the activator is contained in an amount of 5 to 10 parts by weight, the antioxidant is contained in an amount of 1 to 3 parts by weight, the softener is contained in an amount of 5 to 15 parts by weight, the accelerator is contained in an amount of 1 to 5 parts by weight, and the vulcanizing agent is contained in an amount of 0.5 to 4 parts by weight, relative to 100 parts by weight of the rubber substrate.
Preferably, the nitrogen adsorption specific surface area of the white carbon black is 10-200m 2 /g。
In the present invention, the white carbon black is preferably silica. Illustratively, the white carbon black may be a white carbon black having a designation of 115GR or 165GR provided by the company rotunda, france.
Preferably, the titanium dioxide is provided by titanium dioxide; more preferably, the titanium dioxide content in the titanium dioxide is greater than 98% by weight.
Preferably, the activator is a combination of a metal oxide and a fatty acid or is a fatty acid metal soap salt.
Preferably, the fatty acid metal soap salt is zinc stearate.
In the present invention, the metal oxide is preferably zinc oxide and/or magnesium oxide; the fatty acid is preferably stearic acid.
Preferably, the anti-aging agent is at least one of an amine anti-aging agent, a quinoline anti-aging agent and a benzimidazole anti-aging agent.
Preferably, the antioxidant is at least one of an antioxidant 4020, an antioxidant RD, an antioxidant 4010NA, an antioxidant D and an antioxidant MB. More preferably, the anti-aging agent is anti-aging agent 4020.
Preferably, the softener is at least one of aromatic oil, paraffin oil, naphthenic oil, petroleum resin and polyethylene glycol. More preferably, the aromatic oil is an aromatic oil TDAE V500.
Preferably, the accelerator is at least one of a sulfenamide accelerator, a thiazole accelerator, a thiuram accelerator, and a guanidine accelerator.
Preferably, the accelerator is at least one of N-tert-butyl-2-benzothiazole sulfenamide (TBBS), diphenyl guanidine (accelerator D), tetramethylthiuram disulfide (TMTD), N-cyclohexyl-2-benzothiazole sulfenamide (accelerator CZ) and dibenzothiazyl disulfide (accelerator DM).
Preferably, the vulcanizing agent is a sulfur donor. In the present invention, the sulfur donor means a substance capable of supplying sulfur. The sulfur comprises at least one of insoluble sulfur, soluble sulfur and oil-filled sulfur.
More preferably, the vulcanizing agent IS ordinary sulfur S or oil-filled insoluble sulfur IS.
As previously described, a second aspect of the present invention provides a process for producing a vulcanized rubber, the process comprising: the components of the rubber composition of the first aspect are kneaded to form a final rubber compound, and the final rubber compound is subjected to vulcanization treatment.
The manner of kneading is not particularly limited in the present invention, as long as it is possible to uniformly mix the raw materials of the respective components of the rubber composition. For example, the components in the rubber composition may be kneaded simultaneously, or several of the components may be kneaded first, and then the remaining components may be added to continue the kneading.
However, in order to obtain a vulcanized rubber having a higher strength and a better flex resistance, according to a preferred embodiment, the step of mixing the components of the rubber composition of the aforementioned first aspect comprises:
(1) Carrying out first mixing on a rubber matrix and a rubber modifier to obtain first mixed rubber;
(2) Performing second mixing on white carbon black, titanium dioxide, talcum powder, an activating agent, an anti-aging agent and a softening agent and the first mixing rubber to obtain a second mixing rubber;
(3) And thirdly mixing the second mixed rubber with a vulcanizing agent and an accelerator to obtain the final mixed rubber.
Preferably, the first mixing, the second mixing and the third mixing are each independently performed in an internal mixer and/or an open mill.
Preferably, in step (1), further comprising: and plasticating the rubber matrix to obtain plasticated rubber, and then carrying out first mixing on the plasticated rubber and the rubber modifier.
The inventors have found that the vulcanized rubber produced by the method provided by this preferred embodiment of the present invention is more excellent in strength and flex resistance.
Preferably, the conditions of the first mixing at least satisfy: the mixing temperature is 70-150 ℃ and the mixing time is 1-10min; more preferably, the conditions of the first kneading satisfy at least: the mixing temperature is 90-110 ℃, and the mixing time is 2-5min.
Preferably, the conditions of the second mixing at least satisfy: the mixing temperature is 90-170 ℃, and the mixing time is 2-10min; more preferably, the conditions of the second kneading satisfy at least: the mixing temperature is 110-150 ℃ and the mixing time is 3-6min.
Preferably, the conditions of the third mixing at least satisfy: the mixing temperature is not higher than 130 ℃, and the mixing time is 5-7min.
Preferably, the conditions of the vulcanization treatment at least satisfy: the vulcanization temperature is 150-170 ℃, the vulcanization pressure is 10-20MPa, and the vulcanization time is 20-40min.
According to a more preferred embodiment, the conditions of the first mixing include at least: the mixing temperature is 90-110 ℃, and the mixing time is 2-5min; the conditions for the second kneading include at least: the mixing temperature is 110-150 ℃ and the mixing time is 3-6min; the conditions for the third kneading include at least: the mixing temperature is not higher than 130 ℃, and the mixing time is 5-7min; the vulcanization conditions include at least: the vulcanization temperature is 150-170 ℃, the vulcanization pressure is 10-20MPa, and the vulcanization time is 20-40min. The rubber composition according to the preferred embodiment is superior in processing safety and vulcanization efficiency, and the resulting vulcanized rubber is superior in strength and flex resistance.
In order to specifically explain the method for producing a vulcanized rubber of the present invention, the following provides a more preferred embodiment for explanation:
(1) Placing the rubber matrix into an internal mixer for plasticating, wherein the rotating speed is 50-120rpm, the initial mixing temperature is 60-90 ℃, and the raw rubber plasticating time is 0.1-1min; then adding a rubber modifier into the internal mixer to carry out first mixing to obtain a first mixed rubber;
(2) Adding the first rubber compound, white carbon black, titanium dioxide, talcum powder, an activating agent, an anti-aging agent and a softening agent into an internal mixer for secondary mixing, discharging and standing for 3-5 hours to obtain a second rubber compound;
(3) Placing the second rubber compound into an internal mixer for plasticating, wherein the rotating speed is 50-100rpm, the initial mixing temperature is 25-50 ℃, and the plasticating time is 0.5-1.5min; then introducing an accelerator and a vulcanizing agent into the internal mixer for third mixing to obtain final mixing;
(4) Passing the final rubber on an open mill with a roll spacing of 0.3-0.8mm once, adjusting the roll spacing to 3-7mm, and standing the obtained open mill for 12-48h at least twice;
(5) Vulcanizing the rubber compound on a flat vulcanizing machine with the vulcanizing temperature of 150-170 ℃ and the vulcanizing pressure of 10-20MPa for 20-40min to obtain vulcanized rubber.
Unless otherwise indicated, the pressures used in the present invention are gauge pressures.
As previously described, a third aspect of the present invention provides a vulcanized rubber prepared by the method of the foregoing second aspect.
As previously mentioned, a fourth aspect of the present invention provides the use of the vulcanized rubber of the foregoing third aspect in a tire sidewall.
As previously mentioned, a fifth aspect of the present invention provides the use of the aforementioned rubber composition for the preparation of a tire sidewall rubber.
The invention will be described in detail below by way of examples.
Unless otherwise specified, various commercial products used below are commercially available.
The equipment conditions for the following preparation examples and comparative examples are shown in Table 1, and the test methods are shown in Table 2.
The chemical reagents used in the preparation examples and comparative examples are commercially available, and are specifically as follows:
natural rubber: SMR-20, product of Qingdao Sirait International Logistics Co.
Butadiene rubber: BR9000 (hereinafter referred to as butadiene rubber I) having a cis content of 97.8% by weight, a yankee petrochemical product; 015H (hereinafter referred to as butadiene rubber II) with a cis content of 92% by weight, as per the product of the company Tadall.
White carbon black: 165GR, nitrogen adsorption specific surface area of 170m 2 /g, product of the company Rodiola, france.
Titanium dioxide: titanium dioxide, titanium dioxide 98 wt%, is a product of the middling chemical industry limited company.
Kaolin (component a): 2 μm, jiangxi Jiangyuan technology Co., ltd.
Talc powder: the average diameter was 5. Mu.m, a product of Jinan Yubang chemical Co., ltd.
Calcium carbonate (component b): 6.5 μm, product of the company, gallery silver Ma Yanliao, inc.
Si69: analytically pure, xudi chemical Co., ltd.
Rubber modifier:
3-mercaptopropionic acid, a product of Shandong Xinchang chemical technology Co., ltd.
4-mercaptobutyric acid, a product of Zhengzhou Kouzuku Dacron chemical products Co., ltd.
2-mercaptopropionic acid, a product of the technical Co.Ltd.
Softening agent: environment-friendly aromatic oil TDAE V500 (TDAE for short), new Youyang (Ningbo) limited company product.
An activating agent: zinc oxide, stearic acid, a product of Weifang Hengfeng chemical industry Co., ltd.
Anti-aging agent: n- (1, 3-dimethylbutyl) -N' -phenyl-p-phenylenediamine (anti-aging agent 4020), a product of Jiangsu san Orthochemistry Co., ltd.
Vulcanizing agent: sulfur, a product of a constant chemical company, weifang.
And (3) an accelerator: n-tert-butyl-2-benzothiazole sulfenamide (TBBS), diphenyl guanidine (accelerator D), tetramethylthiuram disulfide (TMTD), shanghai Yongyangzhi chemical technology Co., ltd.
Unless otherwise specified, each part by weight in the examples below represents 1g.
TABLE 1
| Sequence number | Device name | Model number | Manufacturing factories |
| 1 | Banbury mixer | BR1600 | America Rayleigh Corp |
| 2 | Open mill | XK-160 | Qingdao Xincheng Yi Ming mechanical Co Ltd |
| 3 | Flat vulcanizing machine | XLB-D400*400*2 | First rubber machinery plant of Shanghai |
| 4 | Universal pulling machine | SHIMADZU，AG-20KNG | Shimadzu corporation of Japan |
| 5 | Rubber deflection testing machine | GT-7011-GLH | Taiwan high-speed rail Co Ltd |
| 6 | Vulcanizing instrument | GT-M2000A | Taiwan high-speed rail Co Ltd |
TABLE 2
Preparation example 1: preparation of vulcanized rubber
First mixing:
placing the rubber matrix into an internal mixer for plasticating, setting the rotation speed of the internal mixer to be 80rpm, setting the initial plasticating temperature of the internal mixer to be 80 ℃, and setting the raw rubber plasticating time to be 0.5min; and then adding the rubber modifier into the internal mixer, setting the mixing temperature of the internal mixer, and carrying out first mixing to obtain a first mixed compound.
And (3) secondary mixing:
lifting an upper top bolt of the internal mixer for the first mixing, adding white carbon black, titanium dioxide, talcum powder, an activating agent, an anti-aging agent and a softening agent into the internal mixer for the second mixing, discharging and standing for 4 hours to obtain a second mixed rubber.
And (3) third mixing:
and placing the second rubber compound into an internal mixer for plasticating, setting the rotation speed of the internal mixer to be 80rpm, setting the initial plasticating temperature of the internal mixer to be 40 ℃, setting the plasticating time of the second rubber compound to be 1min, and then adding a vulcanizing agent and an accelerator into the internal mixer for third mixing to obtain final rubber compound.
The final rubber was passed through an open mill with a roll gap of 0.5mm once, then the roll gap was adjusted to 5mm, and the obtained mill was parked for 24 hours by passing twice.
The above-mentioned rubber compounds were vulcanized on a press vulcanizer at a set temperature and pressure to obtain vulcanized rubber, which was designated as Z1, and the performance test was conducted, and the results are shown in Table 6. Also, the information on the necessary process conditions and the like in this preparation example are shown in tables 3 and 4.
Preparation example 7
And (3) raw rubber plasticating:
the rubber matrix is put into an internal mixer for plasticating, the rotating speed of the internal mixer is set to be 60rpm, the initial plasticating temperature of the internal mixer is set to be 60 ℃, and the raw rubber plasticating time is set to be 0.5min.
And (3) secondary mixing:
lifting an upper top bolt of the internal mixer for plasticating the raw rubber, adding a rubber modifier, white carbon black, titanium dioxide, talcum powder, an activating agent, an anti-aging agent and a softening agent into the internal mixer for secondary mixing, discharging and standing for 4 hours to obtain a secondary mixed rubber.
And (3) third mixing:
and (3) placing the second rubber compound into an internal mixer for plasticating, setting the rotating speed of the internal mixer to be 80rpm, setting the initial plasticating temperature of the internal mixer to be 40 ℃, plasticating the second rubber compound for 1min, and then adding a vulcanizing agent and an accelerator into the internal mixer for third mixing to obtain final rubber compound.
The final rubber was passed through an open mill with a roll gap of 0.5mm once, then the roll gap was adjusted to 5mm, and the obtained mill was parked for 24 hours by passing twice.
The above-mentioned rubber compounds were vulcanized on a press vulcanizer at a set temperature and pressure to obtain vulcanized rubber, which was designated as Z7, and the performance test was conducted, and the results are shown in Table 6. Also, the information on the necessary process conditions and the like in this preparation example are shown in tables 3 and 4.
The other preparation examples, unless otherwise specified, used the same procedure as in preparation example 1, except that the process conditions and the component formulations were as shown in Table 3, the specific process conditions were as shown in Table 4, and the results of the performance test are as shown in Table 6.
TABLE 3 Table 3
| Preparation example 1 | Preparation example 2 | Preparation example 3 | Preparation example 4 | Preparation example 5 | Preparation example 6 | Preparation example 7 | |
| Plasticating raw rubber | |||||||
| Initial temperature (. Degree. C.) | 80 | 80 | 80 | 80 | 80 | 80 | 60 |
| Rotating speed (rpm) | 80 | 80 | 80 | 80 | 80 | 80 | 60 |
| Time (min) | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 |
| First mixing | |||||||
| Mixing temperature (. Degree. C.) | 90 | 100 | 110 | 130 | 70 | 90 | / |
| Mixing time (min) | 5 | 3.5 | 2 | 1.5 | 10 | 5 | / |
| Second mixing | |||||||
| Mixing temperature (. Degree. C.) | 110 | 130 | 150 | 160 | 90 | 110 | 130 |
| Mixing time (min) | 6 | 4 | 3 | 2 | 10 | 6 | 7 |
| Parking time (h) | 4 | 4 | 4 | 4 | 4 | 4 | 4 |
| Plasticating the second rubber compound | |||||||
| Initial temperature (. Degree. C.) | 40 | 40 | 40 | 40 | 40 | 40 | 40 |
| Rotating speed (rpm) | 80 | 80 | 80 | 80 | 80 | 80 | 80 |
| Time (min) | 1 | 1 | 1 | 1 | 1 | 1 | 1 |
| Third mixing | |||||||
| Mixing temperature (. Degree. C.) | 105 | 110 | 120 | 130 | 130 | 105 | 130 |
| Mixing time (min) | 7 | 6 | 5 | 6 | 5 | 7 | 5 |
| Open mill | |||||||
| Initial roll gap (mm) | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 |
| Final roll gap (mm) | 5 | 5 | 5 | 5 | 5 | 5 | 5 |
| Parking time (h) | 24 | 24 | 24 | 24 | 24 | 24 | 24 |
| Vulcanization treatment | |||||||
| Vulcanization temperature (. Degree. C.) | 150 | 170 | 160 | 160 | 150 | 150 | 150 |
| Vulcanizing pressure (MPa) | 20 | 10 | 15 | 15 | 20 | 20 | 20 |
| Vulcanizing time (min) | 40 | 20 | 30 | 30 | 40 | 40 | 40 |
| Vulcanized rubber naming | Z1 | Z2 | Z3 | Z4 | Z5 | Z6 | Z7 |
TABLE 4 Table 4
Comparative example 1
Vulcanized rubber was prepared according to the formulation and method of preparation example 3, except that: the finally obtained vulcanized rubber was designated as D1 by replacing 4 parts by weight of Si69 with 2-mercaptopropionic acid, and the results of the performance test are shown in Table 5.
Unless otherwise specified, the rest of comparative examples were prepared as in preparation example 3, specifically as shown in Table 5, and the results of the performance test are shown in Table 6.
TABLE 5
TABLE 6
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As can be seen from the results obtained in Table 6, the rubber composition provided by the invention can meet the requirement of better dispersion of each component of the rubber composition in a rubber matrix, the processing safety and the vulcanization efficiency of the rubber compound are further improved, and the prepared vulcanized rubber has higher strength and good yield resistance. Also, from the above properties, it can be seen that the vulcanized rubber of the present invention can be used for tire sidewalls.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (26)
1. A rubber composition for a light tire sidewall, characterized in that the composition comprises the following components stored in a mixture or independently of each other: the rubber modifier is a mercapto acid monomer provided by at least one of compounds shown in the formula (1), the rubber matrix is a combination of butadiene rubber and natural rubber, and the average diameter of the talcum powder is 4-5 mu m;
wherein, in the formula (1),
x is 0, and R 2 is-SH; or alternatively
X is 1, M isA structure represented by formula (2), R 1 And R is 2 Each independently is H or-SH, and R 1 And R is 2 Not simultaneously H; or alternatively
X is 2, M is a structure represented by formula (2), R 2 R in 2M 1 Each independently is H or-SH, and R 2 R in two M 1 Not simultaneously H; or alternatively
X is 3, M is a structure represented by formula (2), R 2 R in 3M 1 Each independently is H or-SH, and R 2 R in 3M 1 Not simultaneously H;
wherein, in the rubber matrix, the content weight ratio of the butadiene rubber to the natural rubber is 40:60 to 60:40, a step of performing a;
the rubber comprises, by weight, relative to 100 parts of the rubber matrix, 5-10 parts of the rubber modifier, 40-60 parts of the white carbon black, 10-30 parts of the titanium dioxide, 10-20 parts of the talcum powder, 5-10 parts of the activator, 1-3 parts of the antioxidant, 5-15 parts of the softener, 1-5 parts of the accelerator and 0.5-4 parts of the vulcanizing agent.
2. The composition of claim 1, wherein the cis content of the butadiene rubber is 90-99 wt%.
3. The composition of claim 1, wherein the natural rubber is SMR-20.
4. The composition of claim 1, wherein the rubber modifier is at least one of 3-mercaptopropionic acid, 4-mercaptobutyric acid, and 2-mercaptopropionic acid.
5. The composition according to any one of claims 1 to 4, wherein the rubber modifier is contained in an amount of 3 to 8 parts by weight, the white carbon black is contained in an amount of 40 to 60 parts by weight, the titanium dioxide is contained in an amount of 10 to 30 parts by weight, the talc is contained in an amount of 10 to 20 parts by weight, the activator is contained in an amount of 5 to 10 parts by weight, the antioxidant is contained in an amount of 1 to 3 parts by weight, the softener is contained in an amount of 5 to 15 parts by weight, the accelerator is contained in an amount of 1 to 5 parts by weight, and the vulcanizing agent is contained in an amount of 0.5 to 4 parts by weight, relative to 100 parts by weight of the rubber substrate.
6. The composition according to any one of claims 1 to 4, wherein the silica has a nitrogen adsorption specific surface area of 10 to 200m 2 /g。
7. The composition of any of claims 1-4, wherein the titanium dioxide is provided by titanium dioxide.
8. The composition of claim 7 wherein the titanium dioxide is present in the titanium dioxide in an amount greater than 98% by weight.
9. The composition of any of claims 1-4, wherein the activator is a combination of a metal oxide and a fatty acid or is a fatty acid metal soap salt.
10. The composition of claim 9, wherein the fatty acid metal soap salt is zinc stearate.
11. The composition of any of claims 1-4, wherein the anti-aging agent is at least one of an amine anti-aging agent, a quinoline anti-aging agent, and a benzimidazole anti-aging agent.
12. The composition of any one of claims 1-4, wherein the anti-aging agent is at least one of anti-aging agent 4020, anti-aging agent RD, anti-aging agent 4010NA, anti-aging agent D, anti-aging agent MB.
13. The composition of any of claims 1-4, wherein the softening agent is at least one of aromatic oil, paraffinic oil, naphthenic oil, petroleum resin, and polyethylene glycol.
14. The composition of any of claims 1-4, wherein the accelerator is at least one of a sulfenamide accelerator, a thiazole accelerator, a thiuram accelerator, and a guanidine accelerator.
15. The composition of any of claims 1-4, wherein the accelerator is at least one of N-tert-butyl-2-benzothiazole sulfenamide, diphenyl guanidine, tetramethylthiuram disulfide, N-cyclohexyl-2-benzothiazole sulfenamide, and dibenzothiazyl disulfide.
16. The composition of any of claims 1-4, wherein the vulcanizing agent is a sulfur donor.
17. A process for preparing a vulcanized rubber, comprising: mixing the components of the rubber composition of any one of claims 1-16 to form a final rubber compound, and curing the final rubber compound.
18. A method as claimed in claim 17, wherein the step of mixing the components comprises:
(1) First mixing the rubber matrix and the rubber modifier to obtain a first mixed rubber;
(2) Performing second mixing on white carbon black, titanium dioxide, talcum powder, an activating agent, an anti-aging agent and a softening agent and the first mixing rubber to obtain a second mixing rubber;
(3) And thirdly mixing the second mixed rubber with a vulcanizing agent and an accelerator to obtain the final mixed rubber.
19. The method of claim 18, wherein in step (1) further comprises: and plasticating the rubber matrix to obtain plasticated rubber, and then carrying out first mixing on the plasticated rubber and the rubber modifier.
20. The method of claim 18, wherein the conditions of the first mixing at least satisfy: the mixing temperature is 90-110 ℃, and the mixing time is 2-5min.
21. The method of claim 18, wherein in step (2), the conditions of the second mixing at least satisfy: the mixing temperature is 110-150 ℃ and the mixing time is 3-6min.
22. The method of claim 18, wherein in step (3), the conditions of the third mixing at least satisfy: the mixing temperature is not higher than 130 ℃, and the mixing time is 5-7min.
23. The method according to any one of claims 17-22, wherein the vulcanization conditions at least satisfy: the vulcanization temperature is 150-170 ℃, the vulcanization pressure is 10-20MPa, and the vulcanization time is 20-40min.
24. A vulcanized rubber prepared by the process of any one of claims 17-23.
25. Use of the vulcanized rubber of claim 24 in a tire sidewall.
26. Use of the rubber composition of any one of claims 1 to 16 for the preparation of a tire sidewall rubber.
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| CN109575387A (en) * | 2017-09-29 | 2019-04-05 | 中国石油化工股份有限公司 | Tire tread rubber composition and vulcanized rubber and its preparation method and application |
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| JP2008088381A (en) * | 2006-10-05 | 2008-04-17 | Sumitomo Rubber Ind Ltd | Rubber composition for white sidewall and tire having white sidewall using the same |
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| WO2010000294A1 (en) * | 2008-06-30 | 2010-01-07 | Pirelli Tyre S.P.A. | Tyre and crosslinkable elastomeric composition comprising an oxetane derivative and a carboxylic acid |
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