Rubber processing modified master batch for tire tread, vulcanized rubber and preparation method and application of rubber processing modified master batch and vulcanized rubber

Abstract

The invention relates to the field of rubber, and discloses a rubber processing modified master batch for tire treads, vulcanized rubber and a preparation method and application thereof, and the rubber processing modified master batch comprises maleic acid series monomers, benzoyl peroxide, solution polymerized styrene-butadiene rubber and white oil; wherein the content of the solution polymerized styrene-butadiene rubber is 30-60 parts by weight, the content of the maleic acid series monomer is 40-60 parts by weight, the content of the benzoyl peroxide is 5-12 parts by weight, and the content of the white oil is 5-10 parts by weight. The rubber processing modified master batch provided by the invention can improve the compatibility and dispersity of maleic acid series monomers in a high-viscosity rubber matrix, so that the strength of tire tread rubber can be better improved, the heat generation of the tire tread rubber is reduced, the wet skid resistance is improved, the rolling resistance is reduced, and the energy consumption in the mixing process is reduced.

Description

Technical Field

[0001] The invention relates to the field of rubber technology, and in particular to a rubber processing modified masterbatch and vulcanized rubber for tire treads, and a preparation method and application thereof. Background Art

[0002] In recent years, the dynamic hysteresis loss performance of green tires has determined the classification and grading of tires, which will also lead to a decrease in the strength and wear resistance of rubber, causing early damage to tires, and increase the rolling resistance of tires, increasing fuel consumption and carbon dioxide emissions.

[0003] CN103881161A discloses a trans-polyisoprene rubber and cis-polyisoprene rubber composition and a processing technology thereof, and specifically discloses that the total amount of rubber is 100 parts by mass, wherein the total amount of synthetic trans-polyisoprene and synthetic cis-polyisoprene is 5-60 parts by mass, natural rubber is 40-95 parts by mass, white carbon black is 5-90 parts by mass, and carbon black is 5-990 parts by mass; the masterbatch process comprises: mixing synthetic trans-polyisoprene or a composition of synthetic trans-polyisoprene and synthetic cis-polyisoprene rubber with white carbon black and a coupling agent to form white carbon black wood glue; mixing natural rubber with carbon black to form carbon black masterbatch; and the final rubber mixing process comprises: mixing the carbon black masterbatch, white carbon black wood glue, an antioxidant, an activator, an accelerator, and a vulcanizing agent to form a rubber composition. The rubber composition of the prior art and the rubber prepared by the process have the characteristics of improving wear resistance and reducing heat generation, and can be applied to rubber products, especially automobile tires, to reduce rolling resistance and heat generation.

[0004] CN103087365A discloses a rubber composition for a wet-slip and wear-resistant balanced tire tread, the rubber composition comprising a diene elastomer, an inorganic reinforcing filler, a coupling agent and a plasticizer. In the prior art, when a tire comprising the rubber composition is used, the tread of the tire has excellent wet-slip resistance, imparting a balance of wet grip and wear resistance to the tire, and the tread is used to manufacture a semi-steel radial passenger car tire.

[0005] However, the rubber provided by the above prior art still cannot meet the requirements of strength, heat generation reduction and wet skid performance required by tire tread rubber, and it is necessary to provide a rubber with improved performance.

[0006] CN107955232A discloses an application of a maleic acid monomer and its application in a tire tread. The invention can better play the bridge role of the matrix modifier between the matrix rubber and white carbon black, which is conducive to the full interaction between white carbon black and the rubber matrix, and can better improve the strength of the vulcanized rubber obtained by further vulcanization, reduce the heat generation of the vulcanized rubber, and improve the anti-slip property of the vulcanized rubber compound. However, due to the disadvantages of maleic acid monomers such as pungent odor, poor compatibility with high-viscosity rubber matrix, poor dispersibility, and inaccurate feeding, its application is subject to certain restrictions. Summary of the invention

[0007] The purpose of the present invention is to overcome the problem that the existing rubber in the prior art still cannot meet the requirements of strength, heat generation reduction and improved wet skid performance required by tire tread rubber, and to provide a rubber processing modified masterbatch and vulcanized rubber for tire tread and a preparation method and application thereof. The rubber processing modified masterbatch provided by the present invention can improve the compatibility and dispersibility of maleic acid monomers in a high-viscosity rubber matrix, thereby better improving the strength of the tire tread rubber, reducing its heat generation, improving wet skid resistance, reducing rolling resistance, and reducing energy consumption during mixing.

[0008] In order to achieve the above-mentioned object, the first aspect of the present invention provides a rubber processing modified masterbatch for tire tread, wherein the rubber processing modified masterbatch comprises maleic acid monomer, benzoyl peroxide, solution polymerized styrene-butadiene rubber and white oil;

[0009] Wherein, the content of the solution-polymerized styrene-butadiene rubber is 30-60 parts by weight, the content of the maleic acid monomer is 40-60 parts by weight, the content of the benzoyl peroxide is 5-12 parts by weight, and the content of the white oil is 5-10 parts by weight.

[0010] A second aspect of the present invention provides a method for preparing a rubber masterbatch for tire tread processing modification, wherein the preparation method comprises the following steps:

[0011] (1) crushing the maleic acid monomer to obtain a crushed maleic acid monomer;

[0012] (2) plasticizing the solution polymerized styrene-butadiene rubber to obtain a plasticized rubber;

[0013] (3) mixing the crushed maleic acid monomer, benzoyl peroxide, white oil and the plasticized rubber to obtain a rubber masterbatch for tire tread processing;

[0014] Wherein, the amount of the solution-polymerized styrene-butadiene rubber is 30-60 parts by weight, the amount of the maleic acid monomer is 40-60 parts by weight, the amount of the benzoyl peroxide is 5-12 parts by weight, and the amount of the white oil is 5-10 parts by weight.

[0015] The third aspect of the present invention provides a rubber processing modified masterbatch for tire tread prepared by the aforementioned preparation method.

[0016] A fourth aspect of the present invention provides a use of the aforementioned rubber processing modified masterbatch for tire tread in the preparation of vulcanized rubber.

[0017] A fifth aspect of the present invention provides a rubber composition, wherein the rubber composition comprises a base rubber and the aforementioned rubber processing modified masterbatch for tire tread;

[0018] Among them, the application of modified masterbatch for tire tread processing in the preparation of vulcanized rubber.

[0019] A sixth aspect of the present invention provides a method for preparing vulcanized rubber, wherein the preparation method comprises:

[0020] (1) mixing the base rubber and the rubber processing modified masterbatch to obtain a mixed rubber blank;

[0021] (2) vulcanizing the mixed rubber blank to obtain a tire tread rubber;

[0022] Wherein, the rubber processing modified masterbatch is the rubber processing modified masterbatch for tire tread mentioned above.

[0023] A seventh aspect of the present invention provides a vulcanized rubber prepared by the aforementioned preparation method.

[0024] An eighth aspect of the present invention provides a use of the aforementioned rubber composition or the aforementioned vulcanized rubber in a tire tread.

[0025] Through the above technical solution, the rubber processing modified masterbatch provided by the present invention can improve the compatibility and dispersibility of maleic acid monomers in high-viscosity rubber matrix, thereby better improving the strength of tire tread rubber, reducing its heat generation, improving wet skid resistance, reducing rolling resistance, and reducing energy consumption during mixing. In addition, it can also reduce the odor of the modifier, be environmentally friendly, and facilitate weighing, accurately feed materials, and improve batch quality stability. DETAILED DESCRIPTION

[0026] The endpoints and any values ​​of the ranges disclosed in this article are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of each range, the endpoint values ​​of each range and the individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed in this article.

[0027] As mentioned above, the first aspect of the present invention provides a rubber processing modified masterbatch for tire tread, wherein the rubber processing modified masterbatch comprises maleic acid monomer, benzoyl peroxide, solution polymerized styrene-butadiene rubber and white oil;

[0028] Wherein, the content of the solution-polymerized styrene-butadiene rubber is 30-60 parts by weight, the content of the maleic acid monomer is 40-60 parts by weight, the content of the benzoyl peroxide is 5-12 parts by weight, and the content of the white oil is 5-10 parts by weight.

[0029] The rubber processing modified masterbatch for tire tread of the present invention comprises maleic acid monomer, benzoyl peroxide, solution polymerized styrene butadiene rubber and white oil, wherein the maleic acid monomer is crushed in advance, and then the solution polymerized styrene butadiene rubber is plasticized to obtain plasticized rubber, and then the crushed maleic acid monomer, benzoyl peroxide, white oil and the plasticized rubber are mixed, which can significantly improve the compatibility and dispersibility of the maleic acid monomer in a high-viscosity rubber matrix, thereby better improving the strength of the tire tread rubber, reducing its heat generation, and improving its anti-skid performance, and the energy consumption is low during the mixing process.

[0030] Furthermore, the rubber processing modified masterbatch for tire tread provided by the present invention can reduce the odor of the modifier by combining maleic acid monomers, benzoyl peroxide, solution polymerized styrene-butadiene rubber and white oil, is environmentally friendly, and is convenient to weigh and accurately feed, thereby improving batch quality stability.

[0031] Furthermore, when the amounts of maleic acid monomer, benzoyl peroxide, solution polymerized styrene-butadiene rubber and white oil meet the above ranges, the strength of the tire tread rubber can be better improved, its heat generation can be reduced, its anti-skid performance can be improved, its rolling resistance can be reduced, and the energy consumption during the mixing process can be reduced.

[0032] According to the present invention, preferably, the content of the solution-polymerized styrene-butadiene rubber is 40-50 parts by weight, the content of the maleic acid-based monomer is 45-55 parts by weight, the content of the benzoyl peroxide is 8-10 parts by weight, and the content of the white oil is 6-8 parts by weight.

[0033] According to the present invention, the maleic acid monomer is maleic acid and / or maleic anhydride. In the present invention, the maleic acid monomer is purchased from Aladdin Chemical Reagent Company.

[0034] According to the present invention, the styrene structural unit content of the solution polymerized styrene butadiene rubber is 10-25% and the vinyl content is 40-70%; further, the styrene structural unit content of the solution polymerized styrene butadiene rubber is 20-25wt% and the vinyl content is 55-65wt%. In the present invention, the solution polymerized styrene butadiene rubber is purchased from Yanshan Petrochemical Company.

[0035] According to the present invention, preferably, the Mooney viscosity (100° C., 1+4 min) of the solution-polymerized styrene-butadiene rubber is 55-75, preferably 60-65.

[0036] According to the present invention, the kinematic viscosity of the white oil is 22-28 mm 2 / s, flash point ≥210° C. In the present invention, white oil is purchased from Shandong Tianfeng Chemical Technology Co., Ltd.

[0037] A second aspect of the present invention provides a method for preparing a rubber masterbatch for tire tread processing modification, wherein the preparation method comprises the following steps:

[0038] (1) crushing the maleic acid monomer to obtain a crushed maleic acid monomer;

[0039] (2) plasticizing the solution polymerized styrene-butadiene rubber to obtain a plasticized rubber;

[0040] (3) mixing the crushed maleic acid monomer, benzoyl peroxide, white oil and the plasticized rubber to obtain a rubber masterbatch for tire tread processing;

[0041] Wherein, the amount of the solution-polymerized styrene-butadiene rubber is 30-60 parts by weight, the amount of the maleic acid monomer is 40-60 parts by weight, the amount of the benzoyl peroxide is 5-12 parts by weight, and the amount of the white oil is 5-10 parts by weight.

[0042] In the present invention, the above method is adopted to mix the crushed maleic acid monomer, benzoyl peroxide, white oil and the plasticized rubber of solution polymerized styrene-butadiene rubber to obtain the rubber processing modified masterbatch for tire tread as described in the first aspect of the present invention, which can significantly improve the compatibility and dispersibility of the maleic acid monomer with the rubber matrix. When the rubber processing modified masterbatch for tire tread is used to prepare vulcanized rubber, it can further improve the strength of the tire tread rubber, reduce its heat generation, and improve its anti-skid performance.

[0043] The amount and type of raw materials for preparing the rubber processing modified masterbatch for tire tread in the second aspect of the present invention are exactly the same as the type and amount of raw materials described in the first aspect of the present invention. In order to avoid repetition, the present invention will not be repeated in the second aspect, and those skilled in the art should not understand it as a limitation of the present invention.

[0044] According to the present invention, in step (1), the pulverization can be carried out in a pulverizer, wherein the rotation speed of the pulverizer can be 18000-20000 rpm and the time is 20-25 s.

[0045] According to the present invention, in step (2), the plasticizing can be carried out in an internal mixer, wherein the plasticizing conditions include: temperature of 20-40°C, rotation speed of 30-60rpm, and time of 1-2min; preferably, temperature of 25-35°C, rotation speed of 40-50rpm, and time of 1-1.5min.

[0046] According to the present invention, in step (3), the mixing conditions include: mixing temperature of 60-90°C, preferably, temperature of 60-80°C, mixing time of 3-6 min; more preferably, temperature of 65-75°C, mixing time of 3-4 min.

[0047] According to a preferred embodiment of the present invention, the method for preparing the tire tread rubber modified masterbatch comprises the following steps:

[0048] (1) The maleic acid monomer is crushed in a crusher at a speed of 20000 rpm for 20 seconds;

[0049] (2) heating the internal mixer to 20-40° C. and rotating at 30-60 rpm, and placing the solution polymerized styrene-butadiene rubber into the internal mixer for plasticization for 1-2 min;

[0050] (3) adding crushed maleic acid monomer, benzoyl peroxide and white oil into an internal mixer, and mixing with the plasticized matrix for 3-6 minutes; discharging the material to obtain a rubber modified masterbatch for tire tread.

[0051] The third aspect of the present invention provides a rubber processing modified masterbatch for tire tread prepared by the aforementioned preparation method.

[0052] A fourth aspect of the present invention provides a use of the aforementioned rubber processing modified masterbatch for tire tread in the preparation of vulcanized rubber.

[0053] A fifth aspect of the present invention provides a rubber composition, wherein the rubber composition comprises a base rubber and the aforementioned rubber processing modified masterbatch for tire tread;

[0054] Wherein, relative to 100 parts by weight of the base rubber, the amount of the rubber processing modified masterbatch is 5-15 parts by weight; preferably, relative to 100 parts by weight of the base rubber, the amount of the rubber processing modified masterbatch is 8-10 parts by weight.

[0055] A sixth aspect of the present invention provides a method for preparing vulcanized rubber, wherein the preparation method comprises:

[0056] (1) mixing the base rubber and the rubber processing modified masterbatch to obtain a mixed rubber blank;

[0057] (2) vulcanizing the mixed rubber blank to obtain a tire tread rubber;

[0058] Wherein, the rubber processing modified masterbatch is the rubber processing modified masterbatch for tire tread mentioned above.

[0059] According to another preferred embodiment of the present invention, the method for preparing the vulcanized rubber comprises: mixing the base rubber in the presence of a rubber processing modified masterbatch to obtain a mixed rubber blank, and vulcanizing the mixed rubber blank to obtain a rubber for tire tread.

[0060] The main improvement of the rubber processing method provided by the present invention over the existing rubber processing method is that the rubber processing modified masterbatch provided by the present invention is used, so the specific process conditions and operations of the mixing and vulcanization can be carried out with reference to the existing technology. For example, specifically, the rubber processing method can include, firstly, mixing the base rubber with the rubber processing modified masterbatch of the present invention for the first time, the mixing time can be 1-5 minutes, and the temperature can be 60-100°C; then, adding white carbon black, carbon black, activator, softener, and antioxidant into an internal mixer for mixing, the mixing time can be 5-10 minutes, the temperature can be 80-160°C, after the mixing is completed, it is placed at room temperature for at least 4 hours, then adding a vulcanizing agent and an accelerator to the above mixture, the mixing time can be 3-7 minutes, and the temperature does not exceed 130°C, to obtain a mixed rubber blank, and then the obtained mixed rubber blank is subjected to plate vulcanization, the plate vulcanization temperature can be 140-170°C, and the plate vulcanization time can be 30-40 minutes, so as to obtain a vulcanized rubber, and further, the vulcanized rubber is applied to the tire tread to prepare a tire tread rubber.

[0061] In the present invention, the base rubber may be any conventional tire tread rubber that requires vulcanization, including but not limited to natural rubber and / or synthetic rubber, and the synthetic rubber may include but not limited to butadiene rubber and / or styrene-butadiene rubber.

[0062] According to the present invention, the white carbon black can be any existing precipitated white carbon black that can be used for rubber reinforcement, including but not limited to: white carbon black 200MP, 1165MP, 165GR, 115GR, and the content of the white carbon black can be selected within a large range; specifically, relative to 100 parts by weight of the base rubber, the content of the carbon black can be 40-100 parts by weight.

[0063] According to the present invention, the carbon black can be any existing carbon black that can be used as a rubber additive, including but not limited to: carbon black N550, N774 and N330, and the content of the carbon black can be selected within a large range; specifically, relative to 100 parts by weight of the base rubber, the content of the carbon black can be 0-70 parts by weight.

[0064] According to the present invention, the type and amount of the active agent are also well known to those skilled in the art. The active agent may be zinc oxide and / or stearic acid; specifically, relative to 100 parts by weight of natural rubber and synthetic rubber, the content of the active agent may be 2-10 parts by weight.

[0065] According to the present invention, the softener 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 so that the composite material has good processing performance and physical and mechanical properties. The aromatic oil can be, for example, aromatic oil TDAE V500, and the polyethylene glycol can be, for example, polyethylene glycol PEG4000.

[0066] According to the present invention, the antioxidant is at least one of an amine antioxidant, a quinoline antioxidant and a benzimidazole antioxidant. For example, the antioxidant is antioxidant 4020.

[0067] According to the present invention, the accelerator is at least one of a sulfonamide accelerator, a thiazole accelerator, a thiuram accelerator and a guanidine accelerator. The accelerator may be N-tert-butyl-2-benzothiazole sulfonamide (TBBS) or diphenylguanidine (accelerator D).

[0068] According to the present invention, preferably, the vulcanizing agent is sulfur and / or a sulfur donor. The sulfur donor refers to a substance that can provide sulfur. The sulfur includes 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, etc.

[0069] A seventh aspect of the present invention provides a vulcanized rubber prepared by the aforementioned preparation method.

[0070] An eighth aspect of the present invention provides a use of the aforementioned rubber composition or the aforementioned vulcanized rubber in a tire tread.

[0071] The present invention will be described in detail below through examples.

[0072] The equipment conditions for preparing the vulcanized rubber in the following examples and comparative examples are shown in Table 1.

[0073] The testing instruments of the vulcanized rubbers prepared in the examples and comparative examples are shown in Table 2, and the testing conditions are shown in Table 3.

[0074] The amounts of components in the following examples and comparative examples are all parts by weight, and each part by weight represents 1 g.

[0075] Table 1

[0076] Serial number Device Name model Manufacturer 1 Internal Mixer BR1600 Farrell Corporation 2 Plate vulcanizing press XLB-D400*400*2 Shanghai First Rubber Machinery Factory

[0077] Table 2

[0078]

[0079] Table 3

[0080]

[0081] The preparation example is used to illustrate the rubber processing modified masterbatch and its preparation method.

[0082] Preparation Example 1

[0083] At room temperature (25° C.), 55 parts by weight of maleic anhydride are crushed in a pulverizer; the internal mixer is set at 20° C. and the rotation speed is 60 rpm, and 50 parts by weight of solution styrene butadiene rubber SSBR (styrene structural unit content 10%, vinyl content 40%, Mooney viscosity 55) are put into the internal mixer for plastication for 1 minute; then 55 parts by weight of the crushed maleic anhydride, 10 parts by weight of benzoyl peroxide and 8 parts by weight of white oil are added to the internal mixer and mixed with the plasticated matrix for 6 minutes; the material is discharged to obtain rubber modified masterbatch X1 for tire tread.

[0084] Preparation Example 2

[0085] At room temperature (25°C), 50 parts by weight of maleic acid are crushed in a pulverizer; the internal mixer is set at 30°C and the rotation speed is 45 rpm, and 45 parts by weight of SSBR (styrene structural unit content 20%, vinyl content 70%, Mooney viscosity 75) are put into the internal mixer for plasticization for 1.5 minutes; then 50 parts by weight of crushed maleic anhydride, 9 parts by weight of benzoyl peroxide and 7 parts by weight of white oil are added to the internal mixer and mixed with the plasticized matrix for 4 minutes; the material is discharged to obtain rubber modified masterbatch X2 for tire tread.

[0086] Preparation Example 3

[0087] At room temperature (25°C), 45 parts by weight of maleic anhydride are crushed in a pulverizer; the internal mixer is set to 40°C and the rotation speed is 30rpm, and 40 parts by weight of SSBR (styrene structural unit content 25%, vinyl content 55%, Mooney viscosity 65) are put into the internal mixer for plasticization for 2 minutes; then 45 parts by weight of the crushed maleic anhydride, 8 parts by weight of benzoyl peroxide and 6 parts by weight of white oil are added to the internal mixer and mixed with the plasticized matrix for 3 minutes; the material is discharged to obtain rubber modified masterbatch X3 for tire tread.

[0088] Preparation Example 4

[0089] At room temperature (25° C.), 60 parts by weight of maleic anhydride are crushed in a pulverizer; the internal mixer is set at 40° C. and the rotation speed is 30 rpm, and 60 parts by weight of SSBR (styrene structural unit content 25%, vinyl content 55%, Mooney viscosity 65) are put into the internal mixer for plasticization for 2 minutes; then 60 parts by weight of the crushed maleic anhydride, 12 parts by weight of benzoyl peroxide and 10 parts by weight of white oil are added to the internal mixer and mixed with the plasticized matrix for 3 minutes; the material is discharged to obtain rubber modified masterbatch X4 for tire tread.

[0090] Comparative Preparation Example 5

[0091] At room temperature (25° C.), 70 parts by weight of maleic anhydride are crushed in a pulverizer; the internal mixer is set at 40° C. and the rotation speed is 30 rpm, and 25 parts by weight of SSBR (styrene structural unit content 25%, vinyl content 55%, Mooney viscosity 65) are put into the internal mixer for plasticization for 2 minutes; then 70 parts by weight of the crushed maleic anhydride, 15 parts by weight of benzoyl peroxide and 3 parts by weight of white oil are added to the internal mixer and mixed with the plasticized matrix for 3 minutes; the material is discharged to obtain rubber modified masterbatch X5 for tire tread.

[0092] Examples 1-4 are used to illustrate the rubber processing method provided by the present invention.

[0093] Example 1

[0094] 85 parts by weight of solution-polymerized styrene-butadiene rubber (product of Yanshan Petrochemical, SSBR2636) and 15 parts by weight of butadiene rubber (product of Yanshan Petrochemical, BR9000) and 10 parts by weight of the rubber processing modified masterbatch X1 prepared in Preparation Example 1 were added to an internal mixer and mixed at 70°C for 3 minutes; then 60 parts by weight of white carbon black (Rhodia, France, 165GR), 15 parts by weight of carbon black (Dongguan Qideli Chemical Technology Co., Ltd., N330), 3 parts by weight of zinc oxide (Weifang Hengfeng Chemical Co., Ltd.), 2 parts by weight of stearic acid (Weifang Hengfeng Chemical Co., Ltd.), 10 parts by weight of aromatic oil (Xindayan ( The mixture was added with 2 parts by weight of sulfur (Weifang Zhongheng Chemical Co., Ltd.) and 3 parts by weight of TBBS (N-tert-butyl-2-benzothiazole sulfonamide) into a masterbatch and mixed at 60°C for 5 minutes to obtain a mixed rubber blank. The mixed rubber blank was then subjected to flat vulcanization at a vulcanization temperature of 160°C, a vulcanization pressure of 10 MPa and a vulcanization time of 40 min to obtain a vulcanized rubber sample S1.

[0095] The performance of the vulcanized rubber sample S1 was tested, and the results are shown in Table 4.

[0096] Example 2

[0097] 60 parts by weight of solution-polymerized styrene-butadiene rubber (product of Yanshan Petrochemical, SSBR2636) and 40 parts by weight of cis-1,4-dimethoxy-1-butyl rubber (product of Yanshan Petrochemical, BR9000) and 8 parts by weight of the rubber processing modified masterbatch X2 prepared in Preparation Example 2 were added to an internal mixer and mixed at 70° C. for 3 minutes; then 60 parts by weight of white carbon black (Rhodia, France, 165GR), 15 parts by weight of carbon black (Dongguan Qideli Chemical Technology Co., Ltd., N330), 3 parts by weight of zinc oxide (Weifang Hengfeng Chemical Co., Ltd.), 2 parts by weight of stearic acid (Weifang Hengfeng Chemical Co., Ltd.), 10 parts by weight of aromatic oil (Xindayan ( The mixture was added with 2 parts by weight of sulfur (Weifang Zhongheng Chemical Co., Ltd.) and 3 parts by weight of TBBS (N-tert-butyl-2-benzothiazole sulfonamide) into a masterbatch and mixed at 60°C for 5 minutes to obtain a mixed rubber blank. The mixed rubber blank was then subjected to flat vulcanization at a vulcanization temperature of 160°C, a vulcanization pressure of 10 MPa and a vulcanization time of 40 min to obtain a vulcanized rubber sample S2.

[0098] The performance of the vulcanized rubber sample S2 was tested, and the results are shown in Table 4.

[0099] Example 3

[0100] 70 parts by weight of solution-polymerized styrene-butadiene rubber (product of Yanshan Petrochemical, SSBR2636) and 30 parts by weight of butadiene rubber (product of Yanshan Petrochemical, BR9000) and 9 parts by weight of rubber processing modified masterbatch X3 prepared in Preparation Example 3 were added to an internal mixer and mixed at 70° C. for 3 minutes; then 60 parts by weight of white carbon black (Rhodia, France, 165GR), 15 parts by weight of carbon black (Dongguan Qideli Chemical Technology Co., Ltd., N330), 3 parts by weight of zinc oxide (Weifang Hengfeng Chemical Co., Ltd.), 2 parts by weight of stearic acid (Weifang Hengfeng Chemical Co., Ltd.), 10 parts by weight of aromatic oil (Xindayan ( The mixture was added with 2 parts by weight of sulfur (Weifang Zhongheng Chemical Co., Ltd.) and 3 parts by weight of TBBS (N-tert-butyl-2-benzothiazole sulfonamide) into a masterbatch and mixed at 60°C for 5 minutes to obtain a mixed rubber blank. The mixed rubber blank was then subjected to flat vulcanization at a vulcanization temperature of 160°C, a vulcanization pressure of 10 MPa and a vulcanization time of 40 min to obtain a vulcanized rubber sample S3.

[0101] The performance of the vulcanized rubber sample S3 was tested, and the results are shown in Table 4.

[0102] Example 4

[0103] 70 parts by weight of solution-polymerized styrene-butadiene rubber (product of Yanshan Petrochemical, SSBR2636) and 30 parts by weight of cis-1,4-butadiene rubber (product of Yanshan Petrochemical, BR9000) and 12 parts by weight of rubber processing modified masterbatch X4 prepared in Preparation Example 4 were added to an internal mixer and mixed at 70°C for 3 minutes; then 60 parts by weight of white carbon black (Rhodia, France, 165GR), 15 parts by weight of carbon black (Dongguan Qideli Chemical Technology Co., Ltd., N330), 3 parts by weight of zinc oxide (Weifang Hengfeng Chemical Co., Ltd.), 2 parts by weight of stearic acid (Weifang Hengfeng Chemical Co., Ltd.), 10 parts by weight of aromatic oil (Xindayan ( The mixture was added with 2 parts by weight of sulfur (Weifang Zhongheng Chemical Co., Ltd.) and 3 parts by weight of TBBS (N-tert-butyl-2-benzothiazole sulfonamide) into a masterbatch and mixed at 60°C for 5 minutes to obtain a mixed rubber blank. The mixed rubber blank was then subjected to flat vulcanization at a vulcanization temperature of 160°C, a vulcanization pressure of 10 MPa and a vulcanization time of 40 min to obtain a vulcanized rubber sample S4.

[0104] The performance of the vulcanized rubber sample S4 was tested, and the results are shown in Table 4.

[0105] Comparative Example 1

[0106] The rubber was processed according to the method of Example 1, except that the addition amount of the rubber processing modified masterbatch X1 prepared in Preparation Example 1 was 20 parts by weight, to obtain a vulcanized rubber sample DS1.

[0107] The performance of the vulcanized rubber sample DS1 was tested, and the results are shown in Table 4.

[0108] Comparative Example 2

[0109] The rubber was processed according to the method of Example 1, except that the rubber modified masterbatch X1 was replaced by the same amount of pure maleic anhydride added in the rubber processing, and the vulcanized rubber DS2 was obtained after vulcanization.

[0110] The performance of the vulcanized rubber sample DS2 was tested, and the results are shown in Table 4.

[0111] Comparative Example 3

[0112] The rubber was prepared according to the method of Example 1, except that the rubber processing modified masterbatch was added in an amount of 5 parts by weight of the rubber processing modified masterbatch X5 prepared in Comparative Preparation Example 5, to obtain a vulcanized rubber sample DS3.

[0113] The vulcanized rubber sample DS3 was subjected to performance tests, and the results are shown in Table 4.

[0114] Comparative Example 4

[0115] The rubber was processed according to the method of Example 1, except that no rubber processing modified masterbatch was added during the rubber processing, and vulcanized rubber DS4 was obtained after vulcanization.

[0116] The vulcanized rubber sample DS4 was subjected to performance tests, and the results are shown in Table 4.

[0117] Table 4

[0118]

[0119] It can be seen from the above results that the use of the rubber processing modified masterbatch provided by the present invention can make the white carbon black have better dispersibility in the rubber matrix, and the interaction between the white carbon black and the rubber matrix is ​​stronger, thereby being able to better improve the strength of the vulcanized rubber, reduce its heat generation, and improve its anti-skid performance.

[0120] Further, by comparing the data of Examples 1-4 with Comparative Examples 1-4, it can be seen that the vulcanized rubber DS1-DS4 prepared in Comparative Examples 1-4 is obviously inferior to the vulcanized rubber S1-S4 in performance. For example, the tear strength of DS1-DS4 is lower than that of S1-S4, the compression temperature rise of DS1-DS4 is higher than that of S1-S4, and the DIN wear of DS1-DS4 is higher than that of S1-S4. The dynamic mechanical properties of the vulcanized rubber prepared in Examples 1-4 show smaller rolling resistance and better anti-slip properties. The Penny effect data also show that the carbon black dispersion of the vulcanized rubber S1-S4 in Examples 1-4 is significantly better than that of DS1-DS4. At the same time, during the mixing process, S1-S4 has a smaller power loss and lower energy consumption than DS1-DS4.

[0121] Since the rubber processing modified masterbatch and preparation method provided by the present invention can make the obtained vulcanized rubber have better performance, therefore, when the vulcanized rubber of the present invention is applied to the tread of automobile tires, the durability of the tires can be improved, the fuel economy of the automobile can be improved, and the safety of the automobile can be improved.

[0122] The preferred embodiments of the present invention are described in detail above, but the present invention is not limited thereto. Within the technical concept of the present invention, the technical solution of the present invention can be subjected to a variety of simple modifications, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be regarded as the contents disclosed by the present invention and belong to the protection scope of the present invention.

Claims

1. A rubber masterbatch for tire tread processing and modification, characterized in that: The rubber processing modified masterbatch comprises maleic acid monomer, benzoyl peroxide, solution polymerized styrene-butadiene rubber and white oil; Wherein, the content of the solution-polymerized styrene-butadiene rubber is 30-60 parts by weight, the content of the maleic acid monomer is 40-60 parts by weight, the content of the benzoyl peroxide is 5-12 parts by weight, and the content of the white oil is 5-10 parts by weight.

2. The rubber processing modified masterbatch according to claim 1, wherein: The content of the solution-polymerized styrene-butadiene rubber is 40-50 parts by weight, the content of the maleic acid monomer is 45-55 parts by weight, the content of the benzoyl peroxide is 8-10 parts by weight, and the content of the white oil is 6-8 parts by weight.

3. The rubber processing modified masterbatch according to claim 1 or 2, wherein: The maleic acid monomer is maleic acid and / or maleic anhydride.

4. The rubber processing modified masterbatch according to any one of claims 1 to 3, wherein: In the solution-polymerized styrene-butadiene rubber, the content of styrene structural units is 10-25%, and the content of vinyl groups is 40-70%; Preferably, the Mooney viscosity of the solution polymerized styrene butadiene rubber is 55-75.

5. A method for preparing a rubber masterbatch for tire tread, characterized in that: The preparation method comprises the following steps: (1) crushing the maleic acid monomer to obtain a crushed maleic acid monomer; (2) plasticizing the solution polymerized styrene-butadiene rubber to obtain a plasticized rubber; (3) mixing the crushed maleic acid monomer, benzoyl peroxide, white oil and the plasticized rubber to obtain a rubber masterbatch for tire tread processing; Wherein, the amount of the solution-polymerized styrene-butadiene rubber is 30-60 parts by weight, the amount of the maleic acid monomer is 40-60 parts by weight, the amount of the benzoyl peroxide is 5-12 parts by weight, and the amount of the white oil is 5-10 parts by weight.

6. The preparation method according to claim 5, wherein: The amount of the solution polymerized styrene-butadiene rubber is 40-50 parts by weight, the amount of the maleic acid monomer is 45-55 parts by weight, the amount of the benzoyl peroxide is 8-10 parts by weight, and the amount of the white oil is 6-8 parts by weight; Preferably, the maleic acid monomer is selected from at least one of maleic acid and maleic anhydride; Preferably, in the solution-polymerized styrene-butadiene rubber, the content of styrene structural units is 10-25%, and the content of vinyl groups is 40-70%; Preferably, the Mooney viscosity of the solution polymerized styrene butadiene rubber is 55-75.

7. The preparation method according to claim 5, wherein: The plasticizing conditions include: plasticizing temperature of 20-40°C, rotation speed of 30-60rpm, and plasticizing time of 1-2min; Preferably, the plasticating is carried out in an internal mixer; Preferably, the mixing conditions include: mixing time of 3-6 min, and mixing temperature of 60-90°C.

8. A rubber masterbatch for tire tread prepared by the preparation method according to any one of claims 5 to 7.

9. Use of the rubber masterbatch for tire tread processing modified according to any one of claims 1 to 4 and 8 in the preparation of vulcanized rubber.

10. A rubber composition, characterized in that: The rubber composition comprises a base rubber and a rubber processing modified masterbatch for tire tread according to any one of claims 1 to 4 and 7; Wherein, relative to 100 parts by weight of the base rubber, the amount of the rubber processing modified masterbatch is 5-15 parts by weight; preferably, relative to 100 parts by weight of the base rubber, the amount of the rubber processing modified masterbatch is 8-10 parts by weight.

11. A method for preparing vulcanized rubber, characterized in that: The preparation method comprises: (1) mixing the base rubber and the rubber processing modified masterbatch to obtain a mixed rubber blank; (2) vulcanizing the mixed rubber blank to obtain a tire tread rubber; Wherein, the rubber processing modified masterbatch is the rubber processing modified masterbatch for tire tread according to any one of claims 1-4 and 8.

12. A vulcanized rubber prepared by the preparation method according to claim 11.

13. Use of the rubber composition according to claim 10 or the vulcanized rubber according to claim 12 in a tire tread.

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