CN114437415A - Rubber composition for light-color tire sidewall and application thereof, vulcanized rubber and preparation method and application thereof - Google Patents
Rubber composition for light-color tire sidewall and application thereof, vulcanized rubber and preparation method and application thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L7/00—Compositions of natural rubber
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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
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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
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
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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
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
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Abstract
The invention relates to the field of rubber, and discloses a rubber composition for a light-color tire sidewall and application thereof, vulcanized rubber and a preparation method and application thereof, wherein the composition contains the following components which are stored in a mixed manner or are respectively and independently stored: rubber matrix, rubber modifier, white carbon black, titanium dioxide and talcum powderThe 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 microns. The rubber composition provided by the invention has good processing safety and higher vulcanization efficiency, and the vulcanized rubber prepared from the composition has higher strength and better bending resistance.
Description
Technical Field
The invention relates to the field of rubber, in particular to a rubber composition for a light-colored tire side wall 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 side wall.
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 more and more emphasized in the field of tires due to the characteristics of reducing the rolling resistance of the tires, saving the fuel consumption of automobiles and the like.
The dispersion of white carbon black in a rubber matrix becomes extremely difficult due to the strong surface polarity of the white carbon black, so that the application is limited to a certain extent. The white carbon black is easy to adsorb zinc oxide due to high polarity, 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 is delayed, and the vulcanization efficiency in production is influenced.
CN104530501A discloses a rubber composition for color tire sidewall discoloration resistance, which has bright colors and better discoloration resistance, wherein a dark color sidewall tire does not have discoloration phenomenon within one year under the environment of strong illumination and damp heat, and the formula has higher tearing resistance and excellent discoloration resistance under the severe use conditions of strong illumination and damp heat.
CN104311918A discloses a rubber composition for a sidewall part of a run-flat tire for a passenger car, which can improve the safety performance of a vehicle in running and reduce or eliminate traffic accidents caused by puncture and explosion of the tire.
However, in the above prior art, it is disclosed that the silica white is added with silane coupling agent Si75, etc. to improve the dispersibility, while Si75, etc. is a sulfur-containing compound, and during the high-temperature mixing process, the requirement for process control is high, and improper control thereof may cause scorching, which may further affect the overall performance of the composite material. Si75 and the like are easy to generate ethanol in the processing process, and the existence of the ethanol brings hidden danger to the safety of the tire.
CN109384964A discloses a rubber composition and a vulcanized rubber for a tire side wall, and a preparation method and application thereof, wherein the rubber composition has the advantages of high strength, low rolling resistance and good dynamic flexibility, and the vulcanized rubber formed by the composition can be used for the tire side wall. But the composition generally performs in terms of vulcanization efficiency.
Since the above prior art can not completely satisfy the requirements of high processing safety and high vulcanization efficiency of tire sidewall rubber containing white carbon black formula under the precondition of ensuring high strength and bending resistance, there is a need to provide a rubber composition with improved properties.
Disclosure of Invention
The invention aims to solve the problems of good processing safety and higher vulcanization efficiency in the tire side wall rubber containing the white carbon black formula on the premise of ensuring the basic application requirements of strength and flexibility resistance.
In order to achieve the above object, a first aspect of the present invention provides a rubber composition for a light-colored tire sidewall, which contains two or more of the following components stored in admixture or separately: 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 mixture of butadiene rubber and natural rubber, and the average diameter of the talcum powder is 4-5 microns;
wherein, in the formula (1),
x is 0, and R2is-SH; or
x is 1, M is a structure represented by the formula (2), R1And R2Each independently is H or-SH, and R1And R2Not H at the same time; or
x is 2, M is a structure represented by the formula (2), R2And R in 2M1Each independently is H or-SH, and R2And R in two M1Not H at the same time; or
x is 3, M is a structure represented by the formula (2), R2And R in 3M1Each independently is H or-SH, and R2And R in 3M1Not H at the same time;
wherein in the rubber matrix, the weight ratio of the cis-butadiene rubber to the natural rubber is 40: 60 to 60: 40;
relative to 100 parts by weight of the rubber matrix, the rubber modifier is 5-10 parts by weight, the white carbon black is 40-60 parts by weight, the titanium dioxide is 10-30 parts by weight, the talcum powder is 10-20 parts by weight, the activator is 5-10 parts by weight, the anti-aging agent is 1-3 parts by weight, the softener is 5-15 parts by weight, the accelerator is 1-5 parts by weight, and the vulcanizing agent is 0.5-4 parts by weight.
A second aspect of the present invention provides a method of preparing a vulcanized rubber, the method comprising: the respective components in the rubber composition of the aforementioned first aspect are kneaded to form a final batch, and the final batch is subjected to a vulcanization treatment.
A third aspect of the present invention provides a vulcanized rubber prepared by the above-described method.
A fourth aspect of the invention provides the use of the above-described vulcanized rubber in a tire sidewall.
A fifth aspect of the present invention provides the use of the above rubber composition for the preparation of a tire sidewall rubber.
The rubber composition 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 of the ranges and any values disclosed herein are not limited to the precise range or value, and these ranges or values should be understood to encompass values close to these ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should 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 contains two or more of the following components stored in admixture or separately: 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 mixture of butadiene rubber and natural rubber, and the average diameter of the talcum powder is 4-5 microns;
wherein, in the formula (1),
x is 0, and R2is-SH; or
x is 1, M is a structure represented by the formula (2), R1And R2Each independently is H or-SH, and R1And R2Not H at the same time; or
x is 2, M is a structure represented by the formula (2), R2And R in 2M1Each independently is H or-SH, and R2And R in two M1Not H at the same time; or
x is 3, M is a structure represented by the formula (2), R2And R in 3M1Each independently is H or-SH, and R2And R in 3M1Not H at the same time;
wherein, in the rubber matrix, the weight ratio of the cis-butadiene rubber to the natural rubber is 40: 60 to 60: 40;
relative to 100 parts by weight of the rubber matrix, the rubber modifier is 5-10 parts by weight, the white carbon black is 40-60 parts by weight, the titanium dioxide is 10-30 parts by weight, the talcum powder is 10-20 parts by weight, the activator is 5-10 parts by weight, the anti-aging agent is 1-3 parts by weight, the softener is 5-15 parts by weight, the accelerator is 1-5 parts by weight, and the vulcanizing agent is 0.5-4 parts by weight.
The rubber composition has good processing safety and vulcanization efficiency, and the prepared vulcanized rubber has high strength and good bending 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 3-8 parts by weight, the white carbon black is 40-60 parts by weight, the titanium dioxide is 10-30 parts by weight, the talcum powder is 10-20 parts by weight, the activator is 5-10 parts by weight, the anti-aging agent is 1-3 parts by weight, the softener is 5-15 parts by weight, the accelerator is 1-5 parts by weight, and the vulcanizing agent is 0.5-4 parts by weight, relative to 100 parts by weight of the rubber matrix.
Preferably, the nitrogen adsorption specific surface area of the white carbon black is 10-200m2/g。
In the present invention, preferably, the white carbon is silica. For example, the white carbon black may be white carbon black with a mark number of 115GR or 165GR provided by the company rosidi, france.
Preferably, the titanium dioxide is provided by titanium dioxide; more preferably, the content of titanium dioxide in the titanium dioxide is more than 98 wt%.
Preferably, the activator is a combination of a metal oxide and a fatty acid or 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 amine anti-aging agents, quinoline anti-aging agents and benzimidazole anti-aging agents.
Preferably, the antioxidant is at least one of antioxidant 4020, antioxidant RD, antioxidant 4010NA, antioxidant D and antioxidant MB. More preferably, the antioxidant is antioxidant 4020.
Preferably, the softening agent is at least one of aromatic oil, paraffin oil, naphthenic oil, petroleum resin, and polyethylene glycol. More preferably, the aromatic oil is 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-benzothiazolesulfenamide (TBBS), diphenylguanidine (accelerator D), tetramethylthiuram disulfide (TMTD), N-cyclohexyl-2-benzothiazolesulfenamide (accelerator CZ), and dibenzothiazyl disulfide (accelerator DM).
Preferably, the vulcanizing agent is a sulfur donor. In the present invention, the sulfur donor refers to a substance capable of providing sulfur. The sulfur comprises at least one of insoluble sulfur, soluble sulfur and oil-extended sulfur.
More preferably, the vulcanizing agent IS ordinary sulfur S or oil-extended insoluble sulfur IS.
As previously mentioned, a second aspect of the present invention provides a process for preparing a vulcanized rubber, the process comprising: the respective components in the rubber composition of the first aspect are kneaded to form a final batch, and the final batch is subjected to a vulcanization treatment.
In the present invention, the kneading method is not particularly limited as long as the raw materials of the components of the rubber composition can be uniformly mixed. For example, the components of the rubber composition may be simultaneously kneaded, or several of the components may be kneaded first, and then the remaining components may be added to continue kneading.
However, in order to obtain a vulcanized rubber having higher strength and better flex resistance, according to a preferred embodiment, the step of subjecting the respective components in the rubber composition of the aforementioned first aspect to said compounding comprises:
(1) carrying out first mixing on a rubber matrix and a rubber modifier to obtain first mixed rubber;
(2) carrying out second mixing on white carbon black, titanium dioxide, talcum powder, an activating agent, an anti-aging agent and a softening agent with the first mixed rubber to obtain second mixed rubber;
(3) and carrying out third mixing on the second mixed rubber, a vulcanizing agent and an accelerator to obtain the final rubber.
Preferably, the first mixing, the second mixing and the third mixing are each independently carried out in an internal mixer and/or an open mill.
Preferably, step (1) further comprises: firstly 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 obtained by the method provided by this preferred embodiment of the present invention is more excellent in strength and flex resistance.
Preferably, the first mixing conditions at least satisfy: the mixing temperature is 70-150 ℃, and the mixing time is 1-10 min; more preferably, the first mixing conditions at least satisfy: the mixing temperature is 90-110 ℃, and the mixing time is 2-5 min.
Preferably, the second mixing conditions at least satisfy: the mixing temperature is 90-170 ℃, and the mixing time is 2-10 min; more preferably, the second mixing conditions at least satisfy: the mixing temperature is 110-150 ℃, and the mixing time is 3-6 min.
Preferably, the third mixing conditions at least satisfy: the mixing temperature is not higher than 130 ℃, and the mixing time is 5-7 min.
Preferably, the conditions of the vulcanization treatment at least satisfy: the vulcanization temperature is 150 ℃ and 170 ℃, the vulcanization pressure is 10-20MPa, and the vulcanization time is 20-40 min.
According to a more preferred embodiment, the conditions of the first mixing comprise at least: the mixing temperature is 90-110 ℃, and the mixing time is 2-5 min; the conditions of the second mixing include at least: the mixing temperature is 110-150 ℃, and the mixing time is 3-6 min; the third mixing conditions include at least: the mixing temperature is not higher than 130 ℃, and the mixing time is 5-7 min; the conditions of the vulcanization treatment include at least: the vulcanization temperature is 150 ℃ and 170 ℃, the vulcanization pressure is 10-20MPa, and the vulcanization time is 20-40 min. The rubber composition of the preferred embodiment has better processing safety and vulcanization efficiency, and the prepared vulcanized rubber has higher strength and better flex resistance.
To specifically illustrate the process of the present invention for preparing vulcanizates, a more preferred embodiment is provided below for illustration:
(1) plasticating the rubber matrix in an internal mixer at the rotation speed of 50-120rpm, the initial mixing temperature of 60-90 ℃ for raw rubber plasticating time of 0.1-1 min; then adding a rubber modifier into the internal mixer for first mixing to obtain 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 second mixing, discharging and standing for 3-5 hours to obtain a second rubber compound;
(3) plasticating the second rubber compound in an internal mixer at the rotation speed of 50-100rpm, the initial mixing temperature of 25-50 ℃ and the plastication time of 0.5-1.5 min; then introducing an accelerator and a vulcanizing agent into the internal mixer for third mixing to obtain final mixed rubber;
(4) the final rubber is passed through an open mill with the roller spacing of 0.3-0.8mm once, then the roller spacing is adjusted to 3-7mm, and the obtained open mill rubber is placed for 12-48h after passing through the open mill at least twice;
(5) and vulcanizing the open rubber for 20-40min on a flat vulcanizing machine with the vulcanization temperature of 150-170 ℃ and the vulcanization pressure of 10-20MPa to obtain the vulcanized rubber.
The pressures used in the present invention are gauge pressures unless otherwise specified.
As previously mentioned, a third aspect of the present invention provides a vulcanizate prepared by the method of the second aspect described above.
As previously mentioned, a fourth aspect of the present invention provides the use of the vulcanizate of the third aspect described above in a tire sidewall.
As previously mentioned, a fifth aspect of the present invention provides the use of the aforementioned rubber composition in the preparation of a tire sidewall rubber.
The present invention will be described in detail below by way of examples.
Unless otherwise specified, various commercial products used below are commercially available.
The following preparation examples and comparative examples relate to the apparatus shown in Table 1 and the test methods shown in Table 2.
The chemicals used in the preparation examples and comparative examples were commercially available, specifically as follows:
natural rubber: SMR-20, product of International Logistics Co., Ltd, Serratite, Qingdao.
Butadiene rubber: BR9000 (hereinafter referred to as butadiene rubber I), having a cis content of 97.8% by weight, a Yanshan petrochemical; 015H (hereinafter referred to as butadiene rubber II), having a cis content of 92% by weight, a product of Dadall.
White carbon black: 165GR, nitrogen adsorption specific surface area 170m2G, product of Rodiya, France.
Titanium dioxide: titanium dioxide, titanium dioxide content is 98% by weight, the product of the Zhongtai chemical industry Co.
Kaolin (component a): 2 μm, a product of science and technology Limited of Jiangxi Garden establishment.
Talc powder: average diameter of 5 μm, a product of chemical Limited of Jinan Yubang.
Calcium carbonate (component b): 6.5 μm, product of gallery silver horse pigment Limited.
Si 69: analytically pure, product of Asahi chemical Co., Ltd.
Rubber modifier:
3-mercaptopropionic acid, a product of chemical technology, Inc. of Xinchang, Shandong.
4-mercaptobutanoic acid, a product of Zhengzhou Keyu chemical Limited.
2-mercaptopropionic acid, a product of Bailingwei science and technology Co.
Softening agent: environmental-friendly aromatic oil TDAE V500 (TDAE for short), a product of Ningbo company Limited.
Activating agent: zinc oxide, stearic acid, Weifang Heng Feng chemical products.
An anti-aging agent: n- (1, 3-dimethylbutyl) -N' -phenyl-p-phenylenediamine (antioxidant 4020), a product of san Oao chemical Co., Ltd, Jiangsu.
Vulcanizing agent: sulfur, a product of the Hechenochuan chemical industry Limited company.
Accelerator (b): n-tert-butyl-2-benzothiazolesulfenamide (TBBS), diphenylguanidine (accelerator D), tetramethylthiuram disulfide (TMTD), a product of Shanghai Yongyan chemical science and technology Co., Ltd.
Unless otherwise specified, 1g is represented per part by weight in the following examples.
TABLE 1
| Serial number | Device name | Model number | Manufacturer of the product |
| 1 | Internal mixer | BR1600 | Farrel America Ltd |
| 2 | Open mill | XK-160 | Qingdao Xincheng Yiming mechanical Co Ltd |
| 3 | Flat vulcanizing machine | XLB-D400*400*2 | Shanghai first rubber machinery plant |
| 4 | Universal tensile machine | SHIMADZU，AG-20KNG | Shimadzu Japan Ltd |
| 5 | Rubber bending tester | GT-7011-GLH | Taiwan high speed railway, China |
| 6 | Vulcanizing instrument | GT-M2000A | Taiwan high speed railway, China |
TABLE 2
Preparation example 1: preparation of vulcanized rubber
First mixing:
placing the rubber matrix in an internal mixer for plasticating, wherein the rotating speed of the internal mixer is set to be 80rpm, the initial plasticating temperature of the internal mixer is set to be 80 ℃, and the raw rubber plasticating time is set to be 0.5 min; 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 rubber.
And (3) second mixing:
and lifting the upper top bolt of the internal mixer for the first mixing, adding the white carbon black, the titanium dioxide, the talcum powder, the activating agent, the anti-aging agent and the softening agent into the internal mixer for second mixing, discharging and standing for 4 hours to obtain second mixed rubber.
And (3) third mixing:
and plasticating the second rubber compound in an internal mixer at the rotation speed of 80rpm, the initial plasticating temperature of the internal mixer is 40 ℃, the plasticating time of the second rubber compound is 1min, and then adding a vulcanizing agent and an accelerator into the internal mixer for third mixing to obtain the final rubber compound.
And (3) passing the final rubber compound on an open mill with the roller spacing of 0.5mm once, adjusting the roller spacing to 5mm, passing twice, and standing the obtained open mill rubber for 24 hours.
The above-mentioned starting rubber was vulcanized on a press vulcanizer having a temperature and a pressure set therein to obtain a vulcanized rubber, which was designated as Z1, and subjected to a performance test, the results of which are shown in Table 6. Information on the necessary process conditions and the like in the preparation examples are shown in tables 3 and 4.
Preparation example 7
Plasticating raw rubber:
placing the rubber matrix in an internal mixer for plastication, setting the rotating speed of the internal mixer to be 60rpm, the initial plastication temperature of the internal mixer to be 60 ℃, and the plastication time of raw rubber to be 0.5 min.
And (3) second mixing:
and lifting the upper top bolt of the internal mixer for plasticating the raw rubber, adding the rubber modifier, the white carbon black, the titanium dioxide, the talcum powder, the activator, the anti-aging agent and the softener into the internal mixer for second mixing, discharging and standing for 4 hours to obtain second mixed rubber.
And (3) third mixing:
and plasticating the second rubber compound in an internal mixer at the rotation speed of 80rpm and the initial plasticating temperature of 40 ℃ for 1min, and adding a vulcanizing agent and an accelerator into the internal mixer for third mixing to obtain the final rubber compound.
And (3) passing the final rubber compound on an open mill with the roller spacing of 0.5mm once, adjusting the roller spacing to 5mm, passing twice, and standing the obtained open mill rubber for 24 hours.
The unvulcanized rubber was vulcanized on a press vulcanizer having a temperature and a pressure set therein to obtain a vulcanized rubber, which was designated as Z7, and the results of the performance test were shown in table 6. Information on the necessary process conditions and the like in the present production examples are shown in tables 3 and 4.
Unless otherwise specified, the same procedures as in preparation example 1 were followed for the other preparation examples, except that the process conditions and the component formulations were as shown in Table 3, the component formulations were as shown in Table 4, and the results of the performance tests were as shown in Table 6.
TABLE 3
| Preparation example 1 | Preparation example 2 | Preparation example 3 | Preparation example 4 | Preparation example 5 | Preparation example 6 | Preparation example 7 | |
| Raw rubber plastication | |||||||
| Initial temperature (. degree. C.) | 80 | 80 | 80 | 80 | 80 | 80 | 60 |
| Rotational 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 | |||||||
| Kneading temperature (. degree. C.) | 90 | 100 | 110 | 130 | 70 | 90 | / |
| Mixing time (min) | 5 | 3.5 | 2 | 1.5 | 10 | 5 | / |
| Second mixing of | |||||||
| 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 of the second elastomeric compound | |||||||
| Initial temperature (. degree. C.) | 40 | 40 | 40 | 40 | 40 | 40 | 40 |
| Rotational 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 nip (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 |
| Vulcanization pressure (MPa) | 20 | 10 | 15 | 15 | 20 | 20 | 20 |
| Vulcanization time (min) | 40 | 20 | 30 | 30 | 40 | 40 | 40 |
| Nomenclature for vulcanized rubber | Z1 | Z2 | Z3 | Z4 | Z5 | Z6 | Z7 |
TABLE 4
Comparative example 1
A vulcanizate was prepared according to the formulation and method of preparation example 3, except that: the final vulcanizate was designated D1, as shown in Table 5, with the 2-mercaptopropionic acid replaced by 4 parts by weight of Si69, and the results of the performance tests are shown in Table 6.
The remaining comparative examples were prepared in the same manner as in preparation example 3, except that no particular reference was made, as shown in Table 5, and the results of the property tests are shown in Table 6.
TABLE 5
TABLE 6
As can be seen from the results shown in Table 6, the rubber composition provided by the present invention can meet the requirement of better dispersion of the components of the rubber composition in the rubber matrix, the processing safety and the vulcanization efficiency of the rubber compound are further improved, and the prepared vulcanized rubber has high strength and good flexing resistance. Also, as can be seen from the above properties, the vulcanized rubber of the present invention can be used for a tire side wall.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (14)
1. A rubber composition for a light-colored tire sidewall, characterized by comprising the following components stored in admixture or independently of each other: 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 microns;
wherein, in the formula (1),
x is 0, and R2is-SH; or
x is 1, M is a structure represented by the formula (2), R1And R2Each independently is H or-SH, and R1And R2Not H at the same time; or
x is 2, M is a structure represented by the formula (2), R2And R in 2M1Each independently is H or-SH, and R2And R in two M1Not H at the same time; or
x is 3, M is a structure represented by the formula (2), R2And R in 3M1Each independently is H or-SH, and R2And R in 3M1Not H at the same time;
wherein, in the rubber matrix, the weight ratio of the cis-butadiene rubber to the natural rubber is 40: 60 to 60: 40;
relative to 100 parts by weight of the rubber matrix, the rubber modifier is 5-10 parts by weight, the white carbon black is 40-60 parts by weight, the titanium dioxide is 10-30 parts by weight, the talcum powder is 10-20 parts by weight, the activator is 5-10 parts by weight, the anti-aging agent is 1-3 parts by weight, the softener is 5-15 parts by weight, the accelerator is 1-5 parts by weight, and the vulcanizing agent is 0.5-4 parts by weight.
2. The composition of claim 1, wherein the cis content in the butadiene rubber is 90-99 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.
3. The composition according to claim 1 or 2, 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 base.
4. The composition according to any one of claims 1 to 3, wherein the silica has a nitrogen adsorption specific surface area of 10 to 200m2/g；
Preferably, the titanium dioxide is provided by titanium dioxide; preferably, the content of titanium dioxide in the titanium dioxide is more than 98 wt%;
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.
5. The composition according to any one of claims 1 to 4, wherein the antioxidant is at least one of an amine antioxidant, a quinoline antioxidant and a benzimidazole antioxidant;
preferably, 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 and anti-aging agent MB;
preferably, the softening agent is at least one of aromatic oil, paraffin oil, naphthenic oil, petroleum resin and polyethylene glycol;
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-benzothiazolesulfenamide, diphenylguanidine, tetramethylthiuram disulfide, N-cyclohexyl-2-benzothiazolesulfenamide, and dibenzothiazyl disulfide;
preferably, the vulcanizing agent is a sulfur donor.
6. A method of preparing a vulcanizate, the method comprising: mixing the components of the rubber composition of any one of claims 1 to 5 to form a final batch, and subjecting the final batch to a vulcanization treatment.
7. The method of claim 6, wherein said step of mixing the components comprises:
(1) carrying out first mixing on a rubber matrix and a rubber modifier to obtain first mixed rubber;
(2) carrying out second mixing on the white carbon black, the titanium dioxide, the talcum powder, the activating agent, the anti-aging agent and the softening agent with the first mixed rubber to obtain second mixed rubber;
(3) and carrying out third mixing on the second mixed rubber, a vulcanizing agent and an accelerator to obtain the final rubber.
8. The method of claim 7, wherein step (1) further comprises: firstly plasticating a rubber matrix to obtain plasticated rubber, and then carrying out first mixing on the plasticated rubber and a rubber modifier;
preferably, the first mixing conditions at least satisfy: the mixing temperature is 90-110 ℃, and the mixing time is 2-5 min.
9. The method according to any one of claims 7, wherein in step (2), the conditions of the second mixing are at least satisfied: the mixing temperature is 110-150 ℃, and the mixing time is 3-6 min.
10. The method according to any one of claims 7, wherein in step (3), the conditions of the third mixing are at least satisfied: the mixing temperature is not higher than 130 ℃, and the mixing time is 5-7 min.
11. The method according to any one of claims 6 to 10, wherein the conditions of the vulcanization process at least satisfy: the vulcanization temperature is 150 ℃ and 170 ℃, the vulcanization pressure is 10-20MPa, and the vulcanization time is 20-40 min.
12. A vulcanized rubber produced by the method of any one of claims 6 to 11.
13. Use of the vulcanizate of claim 12 in a sidewall of a tire.
14. Use of the rubber composition of any one of claims 1 to 5 in the preparation of a tire sidewall rubber.
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| CN109384965A (en) * | 2017-08-03 | 2019-02-26 | 中国石油化工股份有限公司 | For the rubber composition on tire sidewall and vulcanized rubber and its preparation method and application |
| 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 |
| CN101755002A (en) * | 2007-06-08 | 2010-06-23 | 住友橡胶工业株式会社 | Rubber composition for sidewall and pneumatic tire made with the same |
| 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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