CN110551236A - Modified styrene-butadiene rubber and preparation method thereof, rubber composition, vulcanized rubber and preparation method and application thereof - Google Patents
Modified styrene-butadiene rubber and preparation method thereof, rubber composition, vulcanized rubber and preparation method and application thereof Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
- B60C1/0016—Compositions of the tread
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C19/00—Chemical modification of rubber
- C08C19/20—Incorporating sulfur atoms into the molecule
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L15/00—Compositions of rubber derivatives
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Abstract
The invention relates to the field of rubber, and discloses modified styrene-butadiene rubber, a preparation method thereof, a rubber composition, vulcanized rubber, a preparation method thereof and application thereof, wherein the modified styrene-butadiene rubber is formed by grafting a polar modifier onto styrene-butadiene rubber, the grafting ratio of the polar modifier is 0.5-5 mol% based on the total molar weight of vinyl structural units in the styrene-butadiene rubber forming the modified styrene-butadiene rubber, the gel content of the modified styrene-butadiene rubber is 3.5-10 wt%, and the polar modifier is at least one of mercapto acid monomers. The modified styrene-butadiene rubber provided by the invention can be beneficial to the interaction of white carbon black in a rubber matrix, can better improve the strength of vulcanized rubber prepared by further vulcanization, reduces the heat generation of the vulcanized rubber, and improves the wet skid resistance of a vulcanized rubber material.
Description
Technical Field
The invention relates to the field of rubber, in particular to modified styrene-butadiene rubber, a method for preparing the modified styrene-butadiene rubber, a rubber composition, a method for preparing vulcanized rubber, the vulcanized rubber prepared by the method and application of the vulcanized rubber in a tire tread of a vehicle tire.
Background
In the 90 s of the 20 th century, michelin incorporated introduced precipitated silica filler technology for the preparation of high performance tires and disclosed that silica provided good mechanical properties, high elasticity, low rolling resistance and low heat build-up upon flexing as a novel reinforcing filler. Since then, the use of white carbon black in high performance tires has attracted great interest in the industry and academia.
The styrene butadiene rubber/white carbon black composite material can well balance comprehensive performances such as mechanical strength, rebound resilience, rolling resistance and high wet skid resistance, and becomes one of the most important materials in the green color wheel tire.
the degree of dispersion of the filler and the interaction of the filler with the rubber are key factors in determining the performance of the composite. However, the surface of the silica is rich in silicon hydroxyl groups, and the surface polarity of the silica is greatly different from that of styrene-butadiene rubber, so that the silica is difficult to obtain good dispersion in a rubber matrix. To solve this problem, scholars at home and abroad do a lot of work.
At present, the most successful method is to apply the silane coupling agent to the surface of the white carbon black for modification so as to improve the dispersion effect of the white carbon black in the matrix. Although the silane coupling agent improves the compatibility of the rubber matrix and the white carbon black to a certain extent, the self-polymerization tendency of the white carbon black is still obvious due to the unique surface structure of the white carbon black.
In addition, the polar modification of the rubber matrix is also an effective way to improve filler dispersion and promote filler-matrix interaction. CN103509159A discloses a modified solution-polymerized butylbenzene prepared by a solution method, and discloses that when the gel content of the obtained modified solution-polymerized butylbenzene is 1-3 wt%, the modified solution-polymerized butylbenzene has good application performance. However, the method for preparing the modified solution polymerized butylbenzene by the solution method has the disadvantages of high energy consumption, large pollution and low efficiency.
In order to overcome the defects, the modified rubber which is simple in preparation process, low in energy consumption and low in pollution is needed, can be used for the tire tread and has excellent dynamic performance and the dispersibility of white carbon black is improved.
Disclosure of Invention
One of the purposes of the invention is to solve the problems of improving the dispersibility of white carbon black used in tire treads, reducing heat generation and improving wet skid resistance.
The second purpose of the invention is to provide a modified styrene-butadiene rubber, a preparation method thereof and a rubber composition containing the styrene-butadiene rubber.
It is a further object of the present invention to provide a vulcanized rubber formed from the above-mentioned modified styrene-butadiene rubber.
The inventor of the invention discovers in research that when the modified styrene-butadiene rubber formed by grafting the styrene-butadiene rubber with the polar modifier is used for forming vulcanized rubber, the dispersibility of white carbon black in a tire tread applying the vulcanized rubber can be improved, the heat generation can be reduced, and the wet skid resistance can be improved, wherein the gel content is within the range of 3.5-10 wt%, and the grafting ratio of the polar modifier is 0.5-5 mol%. Accordingly, the technical solution of the present invention has been completed.
the first aspect of the present invention provides a modified styrene-butadiene rubber, which is formed by grafting a polarity modifier onto styrene-butadiene rubber, wherein the grafting ratio of the polarity modifier is 0.5 to 5 mol% based on the total molar amount of vinyl structural units in the styrene-butadiene rubber forming the modified styrene-butadiene rubber, the gel content of the modified styrene-butadiene rubber is 3.5 to 10 wt%, and the polarity modifier is at least one of mercapto acid monomers.
a second aspect of the present invention provides a method for preparing a modified styrene-butadiene rubber, the method comprising:
(1) Plasticating styrene-butadiene rubber to obtain plasticated styrene-butadiene rubber;
(2) mixing a polar modifier with the plasticated styrene-butadiene rubber for mixing until the grafting ratio of the polar modifier in the obtained modified styrene-butadiene rubber is 0.5-5 mol% based on the total molar weight of vinyl structural units in the styrene-butadiene rubber, and the gel content of the modified styrene-butadiene rubber is 3.5-10 wt%,
wherein the rotation speed of the mixing process in the step (2) is controlled to be 55-75 rpm; and
The polar modifier is at least one of mercapto acid monomers, and the dosage of the polar modifier is 0.2-1.2 parts by weight relative to 100 parts by weight of the styrene butadiene rubber.
the third aspect of the invention provides a rubber composition, which contains a component A, a component B, a component C and a component D, wherein the component A, the component B, the component C and the component D are independently stored, the component A is modified styrene-butadiene rubber, the component B contains white carbon black, the component C contains an activator, an anti-aging agent, a softening agent and optionally carbon black, and the component D contains an accelerator and a vulcanizing agent, wherein the modified styrene-butadiene rubber is the modified styrene-butadiene rubber of the first aspect of the invention and/or the modified styrene-butadiene rubber prepared by the method of the second aspect of the invention.
A fourth aspect of the present invention provides a method for preparing a vulcanized rubber, the method comprising:
(1) carrying out first mixing on modified styrene-butadiene rubber serving as a component A and a component B containing white carbon black to obtain a section of master batch;
(2) carrying out second mixing on the first-stage masterbatch and a component C containing an activator, an anti-aging agent, a softener and optionally containing carbon black to obtain a second-stage masterbatch;
(3) Carrying out third mixing on the second-stage masterbatch and a component D containing an accelerator and a vulcanizing agent to obtain a final rubber compound;
(4) Vulcanizing the final rubber;
Wherein the modified styrene-butadiene rubber is the modified styrene-butadiene rubber of the first aspect of the invention and/or the modified styrene-butadiene rubber prepared by the method of the second aspect of the invention.
A fifth aspect of the present invention provides a vulcanized rubber produced by the method described in the fourth aspect.
A sixth aspect of the present invention provides the use of the vulcanized rubber described in the fifth aspect described above in a tread for a vehicle tire.
The modified styrene-butadiene rubber provided by the invention can be beneficial to the interaction of white carbon black in a rubber matrix, can better improve the strength of vulcanized rubber prepared by further vulcanization, reduces the heat generation of the vulcanized rubber, and improves the wet skid resistance of a vulcanized rubber material.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those 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 modified styrene-butadiene rubber formed by grafting a polar modifier to styrene-butadiene rubber, wherein the grafting ratio of the polar modifier is 0.5 to 5 mol% based on the total molar amount of vinyl structural units in the styrene-butadiene rubber forming the modified styrene-butadiene rubber, the gel content of the modified styrene-butadiene rubber is 3.5 to 10 wt%, and the polar modifier is at least one of mercapto acid monomers.
the "mercapto acid-based monomer" of the present invention means: alkane monomer containing both mercapto group and carboxyl group in the molecule.
In the present invention, the polar modifier is at least one of mercapto acid-based monomers, that is, in the present invention, the polar modifier may be a composition formed of two or more mercapto acid-based monomers.
in the first aspect of the present invention, in order to further improve the wet skid resistance of a vulcanized rubber compound obtained from a modified styrene-butadiene rubber, it is preferable that the mercapto acid-based monomer is provided by at least one of the compounds represented by formula (1),
in the formula (1), M is a structure shown in a formula (2), x is an integer of 0-3, R 2 is H or-SH, in the formula (2), R 1 is H or-SH, and R 1 and R 2 are not H at the same time.
In the first aspect of the present invention, in order to further improve the wet skid resistance of the vulcanized rubber compound obtained from the modified styrene-butadiene rubber, more preferably, in the mercapto acid-based monomer, in formula (1),
x is 0 and R 2 is-SH, or
x is 1, M is a structure of formula (2), R 1 and R 2 are each independently H or-SH, and R 1 and R 2 are not both H, or
x is 2, M is a structure of formula (2), R 2 and R 1 of 2M are each independently H or-SH, and R 2 and R 1 of two M are not both H, or
x is 3, M is a structure represented by formula (2), R 2 and R 1 of 3M are each independently H or-SH, and R 2 and R 1 of 3M are not both H.
in the first aspect of the present invention, in order to further improve the wet skid resistance of the vulcanized rubber compound obtained from the modified styrene-butadiene rubber, it is particularly preferable that, among the mercapto acid-based monomers, in formula (1),
x is 1, M is a structure of formula (2), R 1 and R 2 are each independently H or-SH, and R 1 and R 2 are not both H, or
x is 2, M is a structure represented by formula (2), one of the groups formed by R 2 and R 1 of 2M is-SH, the other 2 are H, or
x is 3, M is a structure represented by formula (2), one of a group formed by R 2 and R 1 out of 3M is-SH, and the other 3 are H.
In the first aspect of the present invention, it is most preferable that the polar modifier is at least one of 3-mercaptopropionic acid, 4-mercaptobutyric acid, and 2-mercaptopropionic acid.
Preferably, the styrene butadiene rubber contains 15 to 30 wt% of styrene structural units, 30 to 70 wt% of vinyl groups, and 45 to 80 Mooney viscosity.
As described above, the second aspect of the present invention provides a method for preparing a modified styrene-butadiene rubber, the method comprising:
(1) Plasticating styrene-butadiene rubber to obtain plasticated styrene-butadiene rubber;
(2) Mixing a polar modifier with the plasticated styrene-butadiene rubber for mixing until the grafting ratio of the polar modifier in the obtained modified styrene-butadiene rubber is 0.5-5 mol% based on the total molar weight of vinyl structural units in the styrene-butadiene rubber, and the gel content of the modified styrene-butadiene rubber is 3.5-10 wt%,
wherein the rotation speed of the mixing process in the step (2) is controlled to be 55-75 rpm; and
the polar modifier is at least one of mercapto acid monomers, and the dosage of the polar modifier is 0.2-1.2 parts by weight relative to 100 parts by weight of the styrene butadiene rubber.
Particularly, the inventor of the invention finds that when the rotation speed of the mixing process in the step (2) is controlled to be 55-75 rpm, the obtained modified styrene-butadiene rubber can obviously contribute to the interaction of white carbon black in a rubber matrix, the strength of vulcanized rubber prepared by further vulcanization can be better improved, the heat generation of the vulcanized rubber is reduced, and the wet skid resistance of a vulcanized rubber compound is improved.
In the second aspect of the present invention, it is preferable that the mercapto acid-based monomer is provided by at least one of the compounds represented by formula (1),
In the formula (1), M is a structure shown in a formula (2), x is an integer of 0-3, R 2 is H or-SH, in the formula (2), R 1 is H or-SH, and R 1 and R 2 are not H at the same time.
in the second aspect of the present invention, more preferably, in the mercapto acid-based monomer, in formula (1),
x is 0 and R 2 is-SH, or
x is 1, M is a structure of formula (2), R 1 and R 2 are each independently H or-SH, and R 1 and R 2 are not both H, or
x is 2, M is a structure of formula (2), R 2 and R 1 of 2M are each independently H or-SH, and R 2 and R 1 of two M are not both H, or
x is 3, M is a structure represented by formula (2), R 2 and R 1 of 3M are each independently H or-SH, and R 2 and R 1 of 3M are not both H.
In the second aspect of the present invention, it is particularly preferable that, among the mercapto acid-based monomers, in formula (1),
x is 1, M is a structure of formula (2), R 1 and R 2 are each independently H or-SH, and R 1 and R 2 are not both H, or
x is 2, M is a structure represented by formula (2), one of the groups formed by R 2 and R 1 of 2M is-SH, the other 2 are H, or
x is 3, M is a structure represented by formula (2), one of a group formed by R 2 and R 1 out of 3M is-SH, and the other 3 are H.
In the second aspect of the present invention, it is most preferable that the polar modifier is at least one of 3-mercaptopropionic acid, 4-mercaptobutyric acid, and 2-mercaptopropionic acid.
Preferably, the mixing conditions include: the temperature is 70-130 ℃, and the time is 1-5 min; more preferably, the mixing conditions include: the temperature is 90-110 ℃, and the time is 2-3 min.
Preferably, the conditions of the mastication include: the rotation speed is 40-100 rpm, the temperature is 80-120 ℃, and the time is 0.5-5 min.
the characteristics of the modified styrene-butadiene rubber, the styrene-butadiene rubber forming the modified styrene-butadiene rubber, and the polar modifier referred to in the second aspect of the present invention are the same as those in the first aspect of the present invention, unless otherwise specified, and the present invention is not described in detail herein.
as described above, the third aspect of the present invention provides a rubber composition, which contains a component a, a component B, a component C and a component D, each of which is independently stored, wherein the component a is a modified styrene-butadiene rubber, the component B contains white carbon black, the component C contains an activator, an anti-aging agent, a softener and optionally carbon black, and the component D contains an accelerator and a vulcanizing agent, wherein the modified styrene-butadiene rubber is the modified styrene-butadiene rubber according to the first aspect of the present invention and/or the modified styrene-butadiene rubber prepared by the method according to the second aspect of the present invention.
The expression "optionally containing carbon black" means that carbon black may or may not be contained in the rubber composition of the present invention, and preferably, carbon black is contained in the rubber composition.
Preferably, the white carbon black is contained in an amount of 20 to 120 parts by weight, more preferably 50 to 100 parts by weight, based on 100 parts by weight of the modified styrene-butadiene rubber.
preferably, the content of the activating agent is 1 to 15 parts by weight, the content of the anti-aging agent is 0.5 to 10 parts by weight, the content of the softening agent is 5 to 30 parts by weight, the content of the carbon black is 0 to 30 parts by weight, the content of the accelerator is 0.5 to 10 parts by weight, and the content of the vulcanizing agent is 0.1 to 5 parts by weight, based on 100 parts by weight of the modified styrene-butadiene rubber.
More preferably, the content of the activating agent is 3 to 8 parts by weight, the content of the anti-aging agent is 1 to 6 parts by weight, the content of the softening agent is 10 to 20 parts by weight, the content of the carbon black is 0 to 20 parts by weight, the content of the accelerator is 1 to 6 parts by weight, and the content of the vulcanizing agent is 0.5 to 3 parts by weight, based on 100 parts by weight of the modified styrene-butadiene rubber.
in the present invention, the content of the carbon black is 0 to 20 parts by weight, and represents: when no carbon black is contained, the content of the carbon black is 0 part by weight; when carbon black is contained, the content of the carbon black is more than 0 and 20 parts by weight or less.
Preferably, the white carbon black is silicon dioxide, more preferably, the nitrogen adsorption specific surface area of the white carbon black is 10-200 m 2/g, for example, the white carbon black is 115GR (Rodia, France) and/or 165GR (Rodia, France).
Preferably, the activator is a combination of a metal oxide and a fatty acid or a fatty acid metal soap salt. The metal oxide is preferably zinc oxide and/or magnesium oxide; the fatty acid is preferably stearic acid; the fatty acid metal soap salt is zinc stearate and/or zinc borate.
Preferably, the anti-aging agent is at least one of amine anti-aging agents, quinoline anti-aging agents and benzimidazole anti-aging agents. For example, the antioxidant is antioxidant 4020 or antioxidant RD.
Preferably, the softening agent is at least one of aromatic oil, paraffin oil, naphthenic oil, petroleum resin and polyethylene glycol. Wherein the weight average molecular weight of the polyethylene glycol is 3000-5000. And the polyethylene glycol with the weight-average molecular weight of 3000-5000 enables the material to have better processing performance and physical and mechanical properties. The aromatic oil may be, for example, aromatic oil TDAE V500, and the polyethylene glycol may be, for example, polyethylene glycol PEG 4000.
Preferably, when carbon black is contained, the carbon black has a CTAB adsorption specific surface area of 10 to 300m 2/g, for example, the carbon black is N330 (Zideli chemical technology Co., Ltd., Dongguan) and/or N220 (Zideli chemical technology Co., Ltd., Dongguan).
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 N-tert-butyl-2-benzothiazolesulfenamide (TBBS), diphenylguanidine (accelerator D), tetramethylthiuram disulfide (TMTD).
Preferably, the vulcanizing agent is sulfur and/or a sulfur donor. The sulfur donor is a substance capable of providing sulfur. The sulfur comprises at least one of insoluble sulfur, soluble sulfur and oil-extended sulfur. For example, the vulcanizing agent IS ordinary sulfur S, oil-extended insoluble sulfur IS, or the like.
As previously mentioned, a fourth aspect of the present invention provides a method for preparing a vulcanized rubber, the method comprising:
(1) carrying out first mixing on modified styrene-butadiene rubber serving as a component A and a component B containing white carbon black to obtain a section of master batch;
(2) carrying out second mixing on the first-stage masterbatch and a component C containing an activator, an anti-aging agent, a softener and optionally containing carbon black to obtain a second-stage masterbatch;
(3) carrying out third mixing on the second-stage masterbatch and a component D containing an accelerator and a vulcanizing agent to obtain a final rubber compound;
(4) vulcanizing the final rubber;
Wherein the modified styrene-butadiene rubber is the modified styrene-butadiene rubber of the first aspect of the invention and/or the modified styrene-butadiene rubber prepared by the method of the second aspect of the invention.
In fact, in the process for preparing the vulcanized rubber, the amounts of the components involved in the preparation of the vulcanized rubber may be the same as the amounts of the corresponding components in the rubber composition involved in the third aspect of the present invention, and therefore, in the fourth aspect of the present invention, in order to avoid repetition, the amounts of the components involved in the preparation of the vulcanized rubber are not individually listed, and the skilled person should not be construed as limiting the present invention.
Preferably, the conditions of the first mixing include: the temperature is 100-150 ℃, and the time is 3-10 min. More preferably, the conditions of the first mixing include: the temperature is 110-120 ℃, and the time is 5-7 min.
Preferably, the second mixing conditions include: the temperature is 80-140 ℃, and the time is 3-12 min; more preferably, the conditions of the second mixing include: the temperature is 110-130 ℃, and the time is 3-5 min.
Preferably, the conditions of the third mixing include: the temperature is not more than 130 ℃, and the time is 5-7 min. More preferably, the temperature of the third mixing is 110 to 130 ℃.
Preferably, the vulcanization conditions include: the temperature is 150-170 ℃, the pressure is 10-20 MPa, and the time is 30-50 min.
The vulcanized rubber is obtained by a novel mixing method, wherein a section of white carbon black master batch is prepared by adopting modified styrene-butadiene rubber with specific gel content and grafting rate; then adding an activating agent, an anti-aging agent, a softening agent and the like into the white carbon black master batch, mixing to prepare a second-stage master batch, adding a vulcanizing agent and an accelerator into the second-stage master batch to prepare a final rubber, and finally vulcanizing the final rubber to prepare the vulcanized rubber. The vulcanized rubber thus obtained has excellent wet skid resistance.
As previously mentioned, a fifth aspect of the present invention provides a vulcanizate prepared by the method of the fourth aspect described above.
As previously mentioned, a sixth aspect of the present invention provides the use of the vulcanizate described by the fifth aspect described above in a tread for a vehicle tire.
the pressures used in the present invention are gage pressures.
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 equipment conditions of the following preparation examples, examples and comparative examples are shown in Table 1.
The test instruments of the preparation examples, examples and comparative examples are shown in Table 2, and the test conditions are shown in Table 3.
The chemicals used in the preparation examples, examples and comparative examples were commercially available, specifically as follows:
solution polymerized styrene-butadiene rubber: 2506, a Yanshan petrochemical (wherein the styrene structural unit content is 23 wt%, the vinyl content is 63 wt%, and the Mooney viscosity is 60);
165GR, Rodiya France, nitrogen adsorption specific surface area is 170m 2/g;
n330, Zideli chemical technology Co., Ltd, Dongguan, CTAB adsorption specific surface area is 75m 2/g;
polar modifier: 3-mercaptopropionic acid (New Chang chemical science and technology Co., Ltd., Shandong), 4-mercaptobutyric acid (Henan chemical products Co., Ltd., Zheng Zhou Keyu), 2-mercaptopropionic acid (Bailingwei science and technology Co., Ltd.);
softening agent: environmental aromatic oil TDAE V500 (TDAE for short), xindayang (ningbo) limited;
Activating agent: zinc oxide, stearic acid, Weifang Heng Feng chemical Limited;
an anti-aging agent: n- (1, 3-dimethylbutyl) -N' -phenyl-p-phenylenediamine (antioxidant 4020), 2,2, 4-trimethyl-1, 2-dihydroquinoline polymer (antioxidant RD), saint ao chemical technology ltd, jiang su;
vulcanizing agent: sulfur, Heicheng Hechenghuai chemical Limited;
Accelerator (b): n-tert-butyl-2-benzothiazolesulfenamide (TBBS), diphenylguanidine (accelerator D), tetramethylthiuram disulfide (TMTD), Shanghai Yongyan chemical science and technology Co., Ltd;
PEG 4000: huaihean petrochemical plant.
The amounts of the components used in the following preparation examples, examples and comparative examples are all parts by weight, each representing 1 g.
TABLE 1
| Serial number | device name | Model number | Manufacturer of the product |
| 1 | Internal mixer | BR1600 | farrel America Ltd |
| 2 | flat vulcanizing machine | XLB-D400*400*2 | Shanghai first rubber machinery plant |
TABLE 2
| Serial number | Test items | Model of the test apparatus | Manufacturer of the product |
| 1 | tensile strength | Universal tensile machine, SHIMADZU, AG-20KNG | Shimadzu Japan Ltd |
| 2 | Rebound resilience | ZWICK 5109 | ZWICK, Germany |
| 3 | DIN abrasion | GT-7012-A | High speed railway instrumentation Co Ltd |
| 4 | Dynamic viscoelastometer | EPLEXOR 500N | german Gaobao Co |
| 5 | rubber processing analyzer | RPA2000 | Alpha company of USA |
| 6 | Dynamic compression fatigue heating | Compression thermogenesis experimental machine Y3000E | Beijing Youth deep electronics Instrument Co Ltd |
TABLE 3
Preparation example 1: preparation of modified styrene-butadiene rubber G1
Adding 100 parts by weight of solution-polymerized styrene-butadiene rubber into an internal mixer, setting the rotating speed of the internal mixer to be 55rpm, the plasticating temperature to be 80 ℃, and the plasticating time of raw rubber to be 0.5min, keeping the rotating speed of the internal mixer to be 55rpm, then adding 0.2 part by weight of polar modifier 2-mercaptopropionic acid into the internal mixer for mixing, wherein the mixing temperature is 90 ℃ and the mixing time is 3min, and obtaining the modified styrene-butadiene rubber G1.
The grafting ratio of the polar modifier was 0.5 mol% and the gel content of the modified styrene-butadiene rubber G1 was 3.5 wt% based on the total molar amount of vinyl structural units in the styrene-butadiene rubber forming the modified styrene-butadiene rubber G1.
Preparation example 2: preparation of modified styrene-butadiene rubber G2
Adding 100 parts by weight of solution polymerized styrene-butadiene rubber into an internal mixer, setting the rotating speed of the internal mixer to be 80rpm, the plasticating temperature to be 80 ℃, and the plasticating time of raw rubber to be 0.5 min; and adjusting the rotating speed of the internal mixer to 75rpm, adding 0.5 part by weight of a polar modifier 4-mercaptobutyric acid into the internal mixer for mixing at the mixing temperature of 100 ℃ for 2.5min to obtain the modified styrene-butadiene rubber G2.
the grafting ratio of the polar modifier was 3 mol% and the gel content of the modified styrene-butadiene rubber G2 was 6 wt% based on the total molar amount of vinyl structural units in the styrene-butadiene rubber forming the modified styrene-butadiene rubber G2.
preparation example 3: preparation of modified styrene-butadiene rubber G3
Adding 100 parts by weight of solution-polymerized styrene-butadiene rubber into an internal mixer, setting the rotating speed of the internal mixer to be 60rpm, the plasticating temperature to be 80 ℃, and the plasticating time of raw rubber to be 0.5min, keeping the rotating speed of the internal mixer to be 60rpm, then adding 1.2 parts by weight of polar modifier 3-mercaptopropionic acid into the internal mixer for mixing, wherein the mixing temperature is 110 ℃, and the mixing time is 2min, so as to obtain the modified styrene-butadiene rubber G3.
The grafting ratio of the polar modifier is 5 mol% and the gel content of the modified styrene-butadiene rubber G3 is 10 wt% based on the total molar amount of vinyl structural units in the styrene-butadiene rubber forming the modified styrene-butadiene rubber G3.
example 1: composition formulation and preparation of vulcanized rubber S1
the formula is as follows: 100 parts of modified styrene-butadiene rubber G1, 50 parts of white carbon black, 30 parts of carbon black, 15 parts of TDAE (softening agent), 1.5 parts of zinc oxide, 1.5 parts of stearic acid, 0.5 part of sulfur (vulcanizing agent), 2 parts of TBBS (accelerator), 4 parts of D (accelerator), 1 part of anti-aging agent 4020 (anti-aging agent) and 5 parts of PEG4000 (softening agent).
The preparation of the vulcanized rubber is carried out by adopting the process in the specific embodiment of the invention, and the specific process conditions are as follows:
In the process of preparing the first-stage masterbatch, the temperature of first mixing is 110 ℃, and the time is 7 min;
In the process of preparing the second-stage masterbatch, the temperature of second mixing is 110 ℃, and the time is 5 min;
in the process of preparing the final rubber compound, the temperature (rubber discharge temperature) of the third mixing is 130 ℃, and the time is 5 min;
And (3) putting the final rubber compound into a flat vulcanizing machine for vulcanization, wherein the vulcanization temperature is 150 ℃, the vulcanization pressure is 20MPa, and the vulcanization time is 50min, so that a vulcanized rubber sample S1 is obtained.
the cured rubber sample S1 was subjected to the performance test, and the results are shown in Table 4.
Example 2: composition formulation and preparation of vulcanized rubber S2
The formula is as follows: 100 parts of modified styrene-butadiene rubber G2, 77 parts of white carbon black, 8 parts of carbon black, 10 parts of TDAE (softening agent), 2 parts of zinc oxide, 3 parts of stearic acid, 1.7 parts of sulfur (vulcanizing agent), 1.8 parts of TBBS (accelerator), 1.8 parts of D (accelerator), 2 parts of anti-aging agent 4020 and 4 parts of PEG4000 (softening agent).
The preparation of the vulcanized rubber is carried out by adopting the process in the specific embodiment of the invention, and the specific process conditions are as follows:
In the process of preparing the first-stage masterbatch, the temperature of first mixing is 120 ℃ and the time is 5 min;
In the process of preparing the second-stage masterbatch, the temperature of second mixing is 120 ℃, and the time is 4 min;
In the process of preparing the final rubber compound, the temperature of the third mixing is 110 ℃, and the time is 7 min;
and (3) putting the final rubber compound into a flat vulcanizing machine for vulcanization, wherein the vulcanization temperature is 170 ℃, the vulcanization pressure is 10MPa, and the vulcanization time is 30min, so that a vulcanized rubber sample S2 is obtained.
The cured rubber sample S2 was subjected to the performance test, and the results are shown in Table 4.
Example 3: composition formulation and preparation of vulcanized rubber S3
The formula is as follows: 100 parts of modified styrene-butadiene rubber G3, 100 parts of white carbon black, 8 parts of TDAE (softening agent), 5 parts of zinc oxide, 3 parts of stearic acid, 3 parts of sulfur (vulcanizing agent), 0.5 part of TBBS (accelerator), 0.5 part of D (accelerator), 6 parts of anti-aging agent 4020 and 2 parts of PEG4000 (softening agent).
The preparation of the vulcanized rubber is carried out by adopting the process in the specific embodiment of the invention, and the specific process conditions are as follows:
In the process of preparing the first-stage masterbatch, the temperature of first mixing is 115 ℃ and the time is 6 min;
In the process of preparing the second-stage masterbatch, the temperature of second mixing is 130 ℃, and the time is 3 min;
In the process of preparing the final rubber compound, the temperature of the third mixing is 120 ℃, and the time is 6 min;
And (3) putting the final rubber compound into a flat vulcanizing machine for vulcanization, wherein the vulcanization temperature is 160 ℃, the vulcanization pressure is 15MPa, and the vulcanization time is 40min, so that a vulcanized rubber sample S3 is obtained.
The cured rubber sample S3 was subjected to the performance test, and the results are shown in Table 4.
Example 4: composition formulation and preparation of vulcanized rubber S4
The formula is as follows: 100 parts of modified styrene-butadiene rubber G3, 100 parts of white carbon black, 15 parts of TDAE (softening agent), 5 parts of zinc oxide, 5 parts of stearic acid, 4 parts of sulfur (vulcanizing agent), 3.5 parts of TBBS (accelerator), 3.5 parts of D (accelerator), 7 parts of anti-aging agent 4020 and 5 parts of PEG4000 (softening agent).
The preparation of the vulcanized rubber is carried out by adopting the process in the specific embodiment of the invention, and the specific process conditions are as follows:
In the process of preparing the first-stage masterbatch, the temperature of first mixing is 140 ℃ and the time is 4 min;
In the process of preparing the second-stage masterbatch, the temperature of second mixing is 140 ℃ and the time is 3 min;
In the process of preparing the final rubber compound, the temperature of the third mixing is 120 ℃, and the time is 6 min;
And (3) putting the final rubber compound into a flat vulcanizing machine for vulcanization, wherein the vulcanization temperature is 160 ℃, the vulcanization pressure is 15MPa, and the vulcanization time is 40min, so that a vulcanized rubber sample S4 is obtained.
The cured rubber sample S4 was subjected to the performance test, and the results are shown in Table 4.
Comparative example 1
the preparation process of the modified styrene-butadiene rubber comprises the following steps: adding 100 parts by weight of solution polymerized styrene-butadiene rubber into an internal mixer, setting the rotating speed of the internal mixer at 80rpm, the plasticating temperature at 80 ℃, and the raw rubber plasticating time at 0.5min, keeping the rotating speed of the internal mixer at 80rpm, then adding 0.1 part by weight of a polar modifier 3-mercaptopropionic acid into the internal mixer for mixing, wherein the mixing temperature is 130 ℃, and the mixing time is 5min, and obtaining the modified styrene-butadiene rubber DG 1.
Based on the total molar amount of vinyl structural units in the styrene-butadiene rubber forming the modified styrene-butadiene rubber DG1, the grafting rate of the polar modifier is 0.2 mol%, and the gel content of the modified styrene-butadiene rubber DG1 is 3 wt%.
The formulation of the rubber composition of this comparative example was: 100 parts of modified styrene-butadiene rubber DG1, 100 parts of white carbon black, 8 parts of TDAE (softening agent), 5 parts of zinc oxide, 3 parts of stearic acid, 3 parts of sulfur (vulcanizing agent), 0.5 part of TBBS (accelerator), 0.5 part of D (accelerator), 6 parts of anti-aging agent 4020 (anti-aging agent) and 2 parts of PEG4000 (softening agent).
The preparation of the vulcanizate was carried out using the same procedure as in example 3 to give vulcanizate sample DS 1.
the cured rubber sample DS1 was subjected to performance testing and the results are shown in Table 4.
Comparative example 2
The preparation process of the modified styrene-butadiene rubber comprises the following steps: adding 100 parts by weight of solution-polymerized styrene-butadiene rubber into an internal mixer, setting the rotating speed of the internal mixer to be 80rpm, the plasticating temperature to be 80 ℃, and the plasticating time of raw rubber to be 0.5min, keeping the rotating speed of the internal mixer to be 80rpm, then adding 2 parts by weight of polar modifier 3-mercaptopropionic acid into the internal mixer for mixing, wherein the mixing temperature is 130 ℃, and the mixing time is 5min, and obtaining the modified styrene-butadiene rubber DG 2.
based on the total molar weight of vinyl structural units in the styrene-butadiene rubber forming the modified styrene-butadiene rubber DG2, the grafting rate of the polar modifier is 7 mol%, and the gel content of the modified styrene-butadiene rubber DG1 is 15 wt%.
The formulation of the rubber composition of this comparative example was: 100 parts of modified styrene-butadiene rubber DG2, 100 parts of white carbon black, 8 parts of TDAE (softening agent), 5 parts of zinc oxide, 3 parts of stearic acid, 3 parts of sulfur (vulcanizing agent), 0.5 part of TBBS (accelerator), 0.5 part of D (accelerator), 6 parts of anti-aging agent 4020 (anti-aging agent) and 2 parts of PEG4000 (softening agent).
The preparation of the vulcanizate was carried out using the same procedure as in example 3 to give vulcanizate sample DS 2.
The cured rubber sample DS2 was subjected to performance testing and the results are shown in Table 4.
Comparative example 3
the rubber composition of this comparative example was formulated in the same manner as in example 3 except that the rubber matrix was the unmodified styrene-butadiene rubber (i.e., the raw solution-polymerized styrene-butadiene rubber) used in preparation example 3, to give a vulcanized rubber sample DS 3.
the cured rubber sample DS3 was subjected to performance testing and the results are shown in Table 4.
TABLE 4
From the results, the modified styrene-butadiene rubber provided by the invention is more beneficial to the dispersion of white carbon black, so that the strength of vulcanized rubber can be improved, the heat generation of the vulcanized rubber can be reduced, and the wet skid resistance can be improved.
further, comparing the data of example 3 with comparative examples 1,2 and 3, it can be seen that the vulcanizates DS1, DS2 and DS3 prepared using the same rubber composition formulation and preparation method as example 3 but with different rubber matrices are significantly inferior in performance to vulcanizate S3, e.g., tensile strength at break is lower than S3, compression temperature is higher than S3, rebound resilience is lower than S3, DIN abrasion is higher than S3; the dynamic mechanical properties of the vulcanizate of example 3 show less rolling resistance, better wet skid resistance, and the Peltier effect data also show that the vulcanizate S3 of example 3 has a significantly better filler dispersion than DS1, DS2 and DS 3.
because the vulcanized rubber has better performance, when the vulcanized rubber is applied to the tread of an automobile tire, the durability of the tire can be improved, the fuel economy of the automobile can be improved, and the safety of the automobile can be improved.
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 (17)
1. A modified styrene-butadiene rubber is formed by grafting a styrene-butadiene rubber with a polar modifier, and is characterized in that the grafting rate of the polar modifier is 0.5-5 mol% based on the total molar amount of vinyl structural units in the styrene-butadiene rubber forming the modified styrene-butadiene rubber, the gel content of the modified styrene-butadiene rubber is 3.5-10 wt%, and the polar modifier is at least one of mercapto acid monomers.
2. The modified styrene-butadiene rubber according to claim 1, wherein the mercapto acid-based monomer is provided by at least one of compounds represented by formula (1),
in the formula (1), M is a structure shown in a formula (2), x is an integer of 0-3, R 2 is H or-SH, in the formula (2), R 1 is H or-SH, and R 1 and R 2 are not H at the same time.
3. the modified styrene-butadiene rubber according to claim 2, wherein, in the mercapto acid-based monomer, in formula (1),
x is 0 and R 2 is-SH, or
x is 1, M is a structure of formula (2), R 1 and R 2 are each independently H or-SH, and R 1 and R 2 are not both H, or
x is 2, M is a structure of formula (2), R 2 and R 1 of 2M are each independently H or-SH, and R 2 and R 1 of two M are not both H, or
x is 3, M is a structure shown in formula (2), R 2 and R 1 in 3M are each independently H or-SH, and R 2 and R 1 in 3M are not H at the same time;
preferably, the first and second electrodes are formed of a metal,
Among the mercapto acid-based monomers, in formula (1),
x is 1, M is a structure of formula (2), R 1 and R 2 are each independently H or-SH, and R 1 and R 2 are not both H, or
x is 2, M is a structure represented by formula (2), one of the groups formed by R 2 and R 1 of 2M is-SH, the other 2 are H, or
x is 3, M is a structure represented by formula (2), one of a group formed by R 2 and R 1 out of 3M is-SH, and the other 3 are H.
4. the modified styrene-butadiene rubber according to any one of claims 1 to 3, wherein the styrene-butadiene rubber contains 15 to 30% by weight of a styrene structural unit, 30 to 70% by weight of a vinyl group, and has a Mooney viscosity of 45 to 80.
5. a method for preparing a modified styrene-butadiene rubber, the method comprising:
(1) Plasticating styrene-butadiene rubber to obtain plasticated styrene-butadiene rubber;
(2) Mixing a polar modifier with the plasticated styrene-butadiene rubber for mixing until the grafting ratio of the polar modifier in the obtained modified styrene-butadiene rubber is 0.5-5 mol% based on the total molar weight of vinyl structural units in the styrene-butadiene rubber, and the gel content of the modified styrene-butadiene rubber is 3.5-10 wt%,
Wherein the rotation speed of the mixing process in the step (2) is controlled to be 55-75 rpm; and
The polar modifier is at least one of mercapto acid monomers, and the dosage of the polar modifier is 0.2-1.2 parts by weight relative to 100 parts by weight of the styrene butadiene rubber.
6. the method of claim 5, wherein said mercapto-acid-based monomer is provided by at least one of the compounds represented by formula (1),
In the formula (1), M is a structure shown in a formula (2), x is an integer of 0-3, R 2 is H or-SH, in the formula (2), R 1 is H or-SH, and R 1 and R 2 are not H at the same time.
7. The method according to claim 6, wherein, in said mercapto acid-based monomer, in formula (1),
x is 0 and R 2 is-SH, or
x is 1, M is a structure of formula (2), R 1 and R 2 are each independently H or-SH, and R 1 and R 2 are not both H, or
x is 2, M is a structure of formula (2), R 2 and R 1 of 2M are each independently H or-SH, and R 2 and R 1 of two M are not both H, or
x is 3, M is a structure shown in formula (2), R 2 and R 1 in 3M are each independently H or-SH, and R 2 and R 1 in 3M are not H at the same time;
Preferably, the first and second electrodes are formed of a metal,
Among the mercapto acid-based monomers, in formula (1),
x is 1, M is a structure of formula (2), R 1 and R 2 are each independently H or-SH, and R 1 and R 2 are not both H, or
x is 2, M is a structure represented by formula (2), one of the groups formed by R 2 and R 1 of 2M is-SH, the other 2 are H, or
x is 3, M is a structure represented by formula (2), one of a group formed by R 2 and R 1 out of 3M is-SH, and the other 3 are H.
8. the method of any one of claims 5-7, wherein the mixing conditions comprise: the temperature is 70-130 ℃, and the time is 1-5 min; preferably, the first and second electrodes are formed of a metal,
the mixing conditions comprise: the temperature is 90-110 ℃, and the time is 2-3 min.
9. The method of claim 5, wherein the conditions of the mastication include: the rotation speed is 40-100 rpm, the temperature is 80-120 ℃, and the time is 0.5-5 min.
10. A rubber composition, which comprises a component A, a component B, a component C and a component D which are independently stored, wherein the component A is modified styrene-butadiene rubber, the component B contains white carbon black, the component C contains an activator, an anti-aging agent, a softener and optionally carbon black, and the component D contains an accelerator and a vulcanizing agent, wherein the modified styrene-butadiene rubber is the modified styrene-butadiene rubber as defined in any one of claims 1 to 4 and/or the modified styrene-butadiene rubber prepared by the method as defined in any one of claims 5 to 9.
11. the rubber composition according to claim 10, wherein the white carbon is contained in an amount of 20 to 120 parts by weight, preferably 50 to 100 parts by weight, based on 100 parts by weight of the modified styrene-butadiene rubber.
12. the rubber composition according to claim 10, wherein the activator is contained in an amount of 1 to 15 parts by weight, the antioxidant is contained in an amount of 0.5 to 10 parts by weight, the softener is contained in an amount of 5 to 30 parts by weight, the carbon black is contained in an amount of 0 to 30 parts by weight, the accelerator is contained in an amount of 0.5 to 10 parts by weight, and the vulcanizing agent is contained in an amount of 0.1 to 5 parts by weight, based on 100 parts by weight of the modified styrene-butadiene rubber; preferably, the first and second electrodes are formed of a metal,
The modified styrene-butadiene rubber comprises, by weight, 100 parts of modified styrene-butadiene rubber, 3-8 parts of an activating agent, 1-6 parts of an anti-aging agent, 10-20 parts of a softening agent, 0-20 parts of carbon black, 1-6 parts of an accelerating agent and 0.5-3 parts of a vulcanizing agent.
13. the rubber composition according to claim 10, wherein the silica has a nitrogen adsorption specific surface area of 10 to 200m 2/g, preferably,
The activator is a composition of metal oxide and fatty acid or fatty acid metal soap salt; preferably, the first and second electrodes are formed of a metal,
the anti-aging agent is at least one of amine anti-aging agent, quinoline anti-aging agent and benzimidazole anti-aging agent; preferably, the first and second electrodes are formed of a metal,
The softener is at least one of aromatic oil, paraffin oil, naphthenic oil, petroleum resin and polyethylene glycol; preferably, the first and second electrodes are formed of a metal,
the carbon black has a CTAB adsorption specific surface area of 10-300 m 2/g, preferably,
the accelerator is at least one of sulfenamide accelerator, thiazole accelerator, thiuram accelerator and guanidine accelerator; preferably, the first and second electrodes are formed of a metal,
The vulcanizing agent is sulfur and/or a sulfur donor.
14. A method of preparing a vulcanized rubber, the method comprising:
(1) Carrying out first mixing on modified styrene-butadiene rubber serving as a component A and a component B containing white carbon black to obtain a section of master batch;
(2) Carrying out second mixing on the first-stage masterbatch and a component C containing an activator, an anti-aging agent, a softener and optionally containing carbon black to obtain a second-stage masterbatch;
(3) Carrying out third mixing on the second-stage masterbatch and a component D containing an accelerator and a vulcanizing agent to obtain a final rubber compound;
(4) Vulcanizing the final rubber;
Wherein the modified styrene-butadiene rubber is the modified styrene-butadiene rubber of any one of claims 1 to 4 and/or the modified styrene-butadiene rubber prepared by the method of any one of claims 5 to 9; preferably, the first and second electrodes are formed of a metal,
the modified styrene-butadiene rubber composition comprises, by weight, 100 parts of modified styrene-butadiene rubber, 1-15 parts of an activating agent, 0.5-10 parts of an anti-aging agent, 5-30 parts of a softening agent, 0-30 parts of carbon black, 0.5-10 parts of an accelerating agent and 0.1-5 parts of a vulcanizing agent; preferably, the first and second electrodes are formed of a metal,
The modified styrene-butadiene rubber is characterized in that the amount of the activating agent is 3-8 parts by weight, the amount of the anti-aging agent is 1-6 parts by weight, the amount of the softening agent is 10-20 parts by weight, the amount of the carbon black is 0-20 parts by weight, the amount of the accelerator is 1-6 parts by weight, and the amount of the vulcanizing agent is 0.5-3 parts by weight, based on 100 parts by weight of the modified styrene-butadiene rubber.
15. the method of claim 14, wherein the conditions of the first mixing comprise: the temperature is 100-150 ℃, and the time is 3-10 min; preferably, the conditions of the first mixing include: the temperature is 110-120 ℃, and the time is 5-7 min;
the conditions of the second mixing include: the temperature is 80-140 ℃, and the time is 3-12 min; preferably, the conditions of the second mixing include: the temperature is 110-130 ℃, and the time is 3-5 min;
The conditions of the third mixing include: the temperature is not more than 130 ℃, and the time is 5-7 min;
the vulcanization conditions include: the temperature is 150-170 ℃, the pressure is 10-20 MPa, and the time is 30-50 min.
16. a vulcanized rubber produced by the process of any one of claims 14-15.
17. Use of the vulcanizate of claim 16 in a tire tread.
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| JP2020189958A (en) * | 2019-05-23 | 2020-11-26 | ハンコック タイヤ アンド テクノロジー カンパニー リミテッドＨａｎｋｏｏｋ Ｔｉｒｅ ＆ Ｔｅｃｈｎｏｌｏｇｙ Ｃｏ．， Ｌｔｄ． | Rubber composition for tire tread and tire manufactured by using same |
| JP7050040B2 (en) | 2019-05-23 | 2022-04-07 | ハンコック タイヤ アンド テクノロジー カンパニー リミテッド | Rubber composition for tire tread and tires manufactured using it |
| JP7050040B6 (en) | 2019-05-23 | 2022-05-06 | ハンコック タイヤ アンド テクノロジー カンパニー リミテッド | Rubber composition for tire tread and tires manufactured using it |
| CN115710413A (en) * | 2023-01-09 | 2023-02-24 | 广东品凡派塑胶实业有限公司 | Chemical-resistant injection-molding-grade super-tough PET make-up package material and dynamic variable-mold-temperature injection molding method thereof |
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