CN110551355B - 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 PDF

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CN110551355B
CN110551355B CN201810558189.4A CN201810558189A CN110551355B CN 110551355 B CN110551355 B CN 110551355B CN 201810558189 A CN201810558189 A CN 201810558189A CN 110551355 B CN110551355 B CN 110551355B
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parts
weight
rubber
butadiene rubber
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CN110551355A (en
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王丽丽
解希铭
刘苹
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
    • B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
    • C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2296—Oxides; Hydroxides of metals of zinc

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
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  • Physics & Mathematics (AREA)
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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 2-10 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 3.5-12 wt%, and the polar modifier is a maleic acid monomer. 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

Modified styrene-butadiene rubber and preparation method thereof, rubber composition, vulcanized rubber and preparation method and application thereof
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.
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, the gel content of which is within the range of 3.5-12 wt% and the grafting rate of the polar modifier is 2-10 mol%, 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. Accordingly, the technical solution of the present invention has been completed.
The first aspect of the present invention provides a modified styrene-butadiene rubber formed by grafting a polar modifier onto styrene-butadiene rubber, wherein the grafting ratio of the polar modifier is 2 to 10 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 12 wt%, and the polar modifier is a maleic acid monomer.
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 2-10 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 3.5-12 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 maleic acid monomer.
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 in the first aspect of the invention and/or the modified styrene-butadiene rubber prepared by the method in 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 in the first aspect of the invention and/or the modified styrene-butadiene rubber prepared by the method in 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 2 to 10 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 12 wt%, and the polar modifier is a maleic acid-based monomer.
The "maleic acid monomer" in the present invention means a monomer having a molecular structure containing a maleic acid dibasic acid, dibasic ester or anhydride.
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 maleic acid-based monomer is at least one selected from the group consisting of maleic acid, maleic anhydride, and dialkyl maleate.
In the present invention, it is preferable that the "alkyl group" in the "dialkyl maleate" is C1-6Alkyl group of (1).
More preferably, the maleic acid-based monomer is at least one selected from the group consisting of maleic acid, maleic anhydride, dimethyl maleate, diethyl maleate, dibutyl maleate, dipropyl maleate and diisopropyl maleate.
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 2-10 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 3.5-12 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 maleic acid monomer.
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 maleic acid-based monomer is at least one selected from the group consisting of maleic acid, maleic anhydride, and dialkyl maleate; more preferably, the maleic acid-based monomer is at least one selected from the group consisting of maleic acid, maleic anhydride, dimethyl maleate, diethyl maleate, dibutyl maleate, dipropyl maleate and diisopropyl maleate.
Preferably, the mixing conditions include: the temperature is 130-170 ℃, and the time is 3-10 min; more preferably, the mixing conditions include: the temperature is 140-150 ℃, and the time is 5-8 min.
Preferably, the polar modifier is used in an amount of 5 to 10 parts by weight, relative to 100 parts by weight of the styrene-butadiene rubber.
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 m2(ii) in terms of/g. For example, the white carbon black is 115GR (Rodiya, France) and/or 165GR (Rodiya, 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 the carbon black is contained, the CTAB adsorption specific surface area of the carbon black is 10-300 m2(ii) in terms of/g. For example, the carbon black is N330 (Zideli chemical technologies, Inc. of Dongguan) and/or N220 (Zideli chemical technologies, Inc. of 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 in the first aspect of the invention and/or the modified styrene-butadiene rubber prepared by the method in 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.
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 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 110-130 ℃, and the time is 3-5 min; the conditions of the third mixing include: the temperature is 110-130 ℃ and the time is 5-7 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);
white carbon black: 165GR, Rodiya, France, nitrogen adsorption specific surface area 170m2/g；
Carbon black: n330, Zideli chemical technology Co., Ltd, Dongguan, CTAB adsorption specific surface area of 75m2/g；
Polar modifier: maleic anhydride (Jessie Ka chemical Co., Ltd., Hangzhou), diethyl maleate (Jinnan Zi Anhua chemical Co., Ltd.), maleic acid (Bailingwei science and technology Co., Ltd.), diisopropyl maleate (Shaanxi Baoyu Jade chemical 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
Figure BDA0001682107870000111
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 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 55rpm, adding 5 parts by weight of polar modifier maleic acid into the internal mixer for mixing at the mixing temperature of 140 ℃ for 8min to obtain the modified styrene-butadiene rubber G1.
The grafting ratio of the polar modifier was 2 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 75rpm, the plasticating temperature to be 80 ℃, and the plasticating time of raw rubber to be 0.5 min; and keeping the rotating speed of the internal mixer at 75rpm, adding 8 parts by weight of a polar modifier diethyl maleate into the internal mixer, and mixing at 145 ℃ for 6min to obtain the modified styrene-butadiene rubber G2.
The grafting ratio of the polar modifier is 6 mol% and the gel content of the modified styrene-butadiene rubber G2 is 8 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 10 parts by weight of polar modifier maleic anhydride into the internal mixer to be mixed, wherein the mixing temperature is 150 ℃, and the mixing time is 5min, and obtaining the modified styrene-butadiene rubber G3.
The grafting ratio of the polar modifier was 10 mol% and the gel content of the modified styrene-butadiene rubber G3 was 12 wt% based on the total molar amount of vinyl structural units in the styrene-butadiene rubber forming the modified styrene-butadiene rubber G3.
Preparation example 4: preparation of modified styrene-butadiene rubber G4
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 10 parts by weight of diisopropyl maleate serving as a polar modifier into the internal mixer for mixing, wherein the mixing temperature is 160 ℃, and the mixing time is 4min, and obtaining the modified styrene-butadiene rubber G4.
The grafting ratio of the polar modifier was 10 mol% and the gel content of the modified styrene-butadiene rubber G4 was 12 wt% based on the total molar amount of vinyl structural units in the styrene-butadiene rubber forming the modified styrene-butadiene rubber G4.
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 composition formulation of this example is similar to that of example 3 except that 100 parts by weight of modified styrene-butadiene rubber G4 is used in place of 100 parts by weight of modified styrene-butadiene rubber G3 in example 3.
The process for the preparation of the vulcanizates in this example was exactly the same as in example 3. A vulcanized rubber sample S4 was obtained.
The cured rubber sample S4 was subjected to the performance test, and the results are shown in Table 4.
Example 5: composition formulation and preparation of vulcanized rubber S5
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 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 maleic anhydride into the internal mixer for mixing, wherein the mixing temperature is 180 ℃, and the mixing time is 2min, 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 1 mol%, and the gel content of the modified styrene-butadiene rubber DG1 is 18 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 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 2.
The cured rubber sample DS2 was subjected to performance testing and the results are shown in Table 4.
TABLE 4
Figure BDA0001682107870000161
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 and 2, it can be seen that vulcanizates DS1 and DS2 prepared using the same rubber composition formulation and preparation method as example 3 but using 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 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 and DS 2.
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 (26)

1. A rubber composition is characterized by comprising 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 softening agent and optionally carbon black, and the component D contains an accelerator and a vulcanizing agent, wherein the content of the white carbon black is 20-120 parts by weight relative to 100 parts by weight of the modified styrene-butadiene rubber, and the modified styrene-butadiene rubber is prepared by a method comprising the following steps:
(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 2-10 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 3.5-12 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 maleic acid monomer.
2. The rubber composition according to claim 1, wherein the maleic acid-based monomer is at least one selected from the group consisting of maleic acid, maleic anhydride, and dialkyl maleate.
3. The rubber composition according to claim 2, wherein the number of carbons of the alkyl group in the dialkyl maleate is 1 to 6.
4. The rubber composition according to claim 1, wherein the maleic acid-based monomer is at least one selected from the group consisting of maleic acid, maleic anhydride, dimethyl maleate, diethyl maleate, dibutyl maleate, dipropyl maleate and diisopropyl maleate.
5. The rubber composition according to any one of claims 1 to 4, wherein in the process for producing the modified styrene-butadiene rubber, the styrene-butadiene rubber has a styrene structural unit content of 15 to 30% by weight, a vinyl group content of 30 to 70% by weight, and a Mooney viscosity of 45 to 80.
6. The rubber composition according to any one of claims 1 to 4, wherein in the process for producing the modified styrene-butadiene rubber, the mixing conditions include: the temperature is 130-170 ℃ and the time is 3-10 min.
7. The rubber composition according to any one of claims 1 to 4, wherein in the process for producing the modified styrene-butadiene rubber, the mixing conditions include: the temperature is 140-150 ℃, and the time is 5-8 min.
8. The rubber composition according to any one of claims 1 to 4, wherein the polar modifier is used in an amount of 5 to 10 parts by weight per 100 parts by weight of the styrene-butadiene rubber in the process for producing the modified styrene-butadiene rubber.
9. The rubber composition according to any one of claims 1 to 4, wherein in the process for producing the modified styrene-butadiene rubber, the conditions for the mastication include: the rotation speed is 40-100 rpm, the temperature is 80-120 ℃, and the time is 0.5-5 min.
10. The rubber composition according to any one of claims 1 to 4, wherein the white carbon is contained in an amount of 50 to 100 parts by weight based on 100 parts by weight of the modified styrene-butadiene rubber.
11. The rubber composition according to any one of claims 1 to 4, 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.
12. The rubber composition according to any one of claims 1 to 4, wherein the activator is contained in an amount of 3 to 8 parts by weight, the antioxidant is contained in an amount of 1 to 6 parts by weight, the softener is contained in an amount of 10 to 20 parts by weight, the carbon black is contained in an amount of 0 to 20 parts by weight, the accelerator is contained in an amount of 1 to 6 parts by weight, and the vulcanizing agent is contained in an amount of 0.5 to 3 parts by weight, based on 100 parts by weight of the modified styrene-butadiene rubber.
13. The rubber composition according to any one of claims 1 to 4, wherein the silica has a nitrogen adsorption specific surface area of 10 to 200m2/g。
14. The rubber composition according to any one of claims 1 to 4, wherein the activator is a combination of a metal oxide and a fatty acid or a fatty acid metal soap salt.
15. The rubber 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.
16. The rubber composition according to any one of claims 1 to 4, wherein the softening agent is at least one of aromatic oil, paraffin oil, naphthenic oil, petroleum resin, and polyethylene glycol.
17. The rubber composition according to any one of claims 1 to 4, wherein the carbon black has a CTAB adsorption specific surface area of 10 to 300m2/g。
18. The rubber composition according to any one of claims 1 to 4, wherein the accelerator is at least one of a sulfenamide accelerator, a thiazole accelerator, a thiuram accelerator, and a guanidine accelerator.
19. The rubber composition according to any one of claims 1 to 4, wherein the vulcanizing agent is sulfur and/or a sulfur donor.
20. A process for preparing a vulcanized rubber using the rubber composition of any one of claims 1 to 19, the process 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.
21. The method according to claim 20, wherein the activator is used in an amount of 1 to 15 parts by weight, the antioxidant is used in an amount of 0.5 to 10 parts by weight, the softener is used in an amount of 5 to 30 parts by weight, the carbon black is used in an amount of 0 to 30 parts by weight, the accelerator is used in an amount of 0.5 to 10 parts by weight, and the vulcanizing agent is used in an amount of 0.1 to 5 parts by weight, based on 100 parts by weight of the modified styrene-butadiene rubber.
22. The method according to claim 20, wherein the activator is used in an amount of 3 to 8 parts by weight, the antioxidant is used in an amount of 1 to 6 parts by weight, the softener is used in an amount of 10 to 20 parts by weight, the carbon black is used in an amount of 0 to 20 parts by weight, the accelerator is used in an amount of 1 to 6 parts by weight, and the vulcanizing agent is used in an amount of 0.5 to 3 parts by weight, based on 100 parts by weight of the modified styrene-butadiene rubber.
23. A method according to any one of claims 20 to 22, wherein the conditions of the first mixing comprise: the temperature is 100-150 ℃, and the time is 3-10 min;
the conditions of the second mixing include: the temperature is 80-140 ℃, and the time is 3-12 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.
24. A method according to any one of claims 20 to 22, wherein the conditions of the first mixing comprise: the temperature is 110-120 ℃, and the time is 5-7 min;
the conditions of the second mixing include: the temperature is 110-130 ℃, and the time is 3-5 min.
25. A vulcanized rubber produced by the process of any one of claims 20-24.
26. Use of the vulcanizate of claim 25 in a tire tread.
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EP1262510A1 (en) * 1999-12-03 2002-12-04 China Petro-Chemical Corporation Full vulcanized powdered rubber with controllable particle diameter, preparing method and uses thereof
CN103509159A (en) * 2013-09-23 2014-01-15 北京石油化工学院 Grafting modification method for solution-polymerized styrene-butadiene rubber with low gel rate
CN107057205A (en) * 2017-05-30 2017-08-18 温州市小林鞋材有限公司 Tasteless elastomeric material and preparation method thereof

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EP1262510A1 (en) * 1999-12-03 2002-12-04 China Petro-Chemical Corporation Full vulcanized powdered rubber with controllable particle diameter, preparing method and uses thereof
CN103509159A (en) * 2013-09-23 2014-01-15 北京石油化工学院 Grafting modification method for solution-polymerized styrene-butadiene rubber with low gel rate
CN107057205A (en) * 2017-05-30 2017-08-18 温州市小林鞋材有限公司 Tasteless elastomeric material and preparation method thereof

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