Rubber processing modified master batch and preparation method and application thereof, rubber composition and application thereof, vulcanized rubber and preparation method and application thereof

Abstract

The invention relates to the field of rubber, and discloses a rubber processing modified master batch and a preparation method and application thereof, a rubber composition and application thereof, and vulcanized rubber and a preparation method and application thereof, the rubber processing modified master batch comprises a mercapto acid monomer, an ethylene-vinyl acetate copolymer and white carbon black; wherein the content of the mercapto acid series monomer is 40-55 parts by weight, the content of the ethylene-vinyl acetate copolymer is 15-35 parts by weight, and the content of the white carbon black is 15-30 parts by weight. The rubber processing modified master batch provided by the invention can improve the compatibility and dispersity of a mercapto acid monomer 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 present invention relates to the field of rubber, and in particular to a rubber processing modified masterbatch and a preparation method and application thereof, a rubber composition and application thereof, a vulcanized rubber 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] CN103703072A discloses a rubber composition for tread, which contains solution-polymerized styrene-butadiene rubber, carbon black, silica and polyethylene glycol, wherein the content of the solution-polymerized styrene-butadiene rubber in 100% by mass of the rubber component is 60% by mass or more, and the content of the carbon black is less than 10 parts by mass relative to 100 parts by mass of the rubber component, the content of the silica is more than 50 parts by mass, and the content of the polyethylene glycol is 0.1-3.5 parts by mass. According to the rubber composition containing solution-polymerized styrene-butadiene rubber, carbon black, silica and polyethylene glycol in prescribed amounts respectively in accordance with the prior art, when applied to the tire tread, a pneumatic tire with balanced improvement in fuel economy and wear resistance can be provided. In addition, the vulcanization speed is good when manufacturing the tire, and the manufactured tire has a good appearance.

[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] CN107964138B discloses an application of a mercapto acid monomer and its application in tire treads. 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 the mercapto acid monomer having a bad smell, poor compatibility with a 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 rubber in the prior art still cannot meet the requirements of strength, heat generation reduction and wet skid resistance of tire tread rubber, and to provide a rubber processing modified masterbatch and its preparation method and application, a rubber composition and its application, a vulcanized rubber and its preparation method and application. The rubber processing modified masterbatch provided by the present invention can improve the compatibility and dispersibility of mercapto acid monomers in a 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.

[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 a mercapto acid monomer, an ethylene-vinyl acetate copolymer and white carbon black;

[0009] Wherein, the content of the mercapto acid monomer is 40-55 parts by weight, the content of the ethylene-vinyl acetate copolymer is 15-35 parts by weight, and the content of the white carbon black is 15-30 parts by weight.

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

[0011] (1) stirring white carbon black and mercapto acid monomers until they are uniformly mixed to obtain a preloaded mixture;

[0012] (2) mixing ethylene-vinyl acetate copolymer with the preloaded mixture to obtain a masterbatch;

[0013] (3) extruding and granulating the masterbatch to obtain a rubber processing modified masterbatch;

[0014] Wherein, the amount of the mercapto acid monomer is 40-55 parts by weight, the amount of the ethylene-vinyl acetate copolymer is 15-35 parts by weight, and the amount of the white carbon black is 15-30 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] Wherein, relative to 100 parts by weight of the base rubber, the amount of the rubber processing modified masterbatch is 0.5-4 parts by weight; preferably, relative to 100 parts by weight of the base rubber, the amount of the rubber processing modified masterbatch is 1-2 parts by weight.

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

[0020] The base rubber is mixed in the presence of a rubber processing modified masterbatch to obtain a mixed rubber blank, and the mixed rubber blank is vulcanized to obtain a vulcanized rubber;

[0021] Wherein, the rubber processing modified masterbatch is the rubber processing modified masterbatch for tire tread mentioned above.

[0022] A seventh aspect of the present invention provides a vulcanized rubber prepared by the aforementioned preparation method.

[0023] An eighth aspect of the present invention provides a use of the aforementioned rubber composition or the aforementioned vulcanized rubber in a tire tread.

[0024] Through the above technical solution, the rubber processing modified masterbatch provided by the present invention can improve the compatibility and dispersibility of mercapto acid monomers in high-viscosity rubber matrix, thereby better improving the strength of tire tread rubber, reducing its heat generation, and improving wet skid resistance. In addition, it can also reduce the odor of the modifier, be environmentally friendly, and facilitate weighing, accurately feed, and improve batch quality stability. DETAILED DESCRIPTION

[0025] 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.

[0026] 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 a mercapto acid monomer, an ethylene-vinyl acetate copolymer and white carbon black;

[0027] Wherein, the content of the mercapto acid monomer is 40-55 parts by weight, the content of the ethylene-vinyl acetate copolymer is 15-35 parts by weight, and the content of the white carbon black is 15-30 parts by weight.

[0028] The rubber processing modified masterbatch for tire tread provided by the present invention comprises mercapto acid monomer, ethylene-vinyl acetate copolymer and white carbon black. In the present invention, white carbon black and mercapto acid monomer are mixed in advance and then kneaded with ethylene-vinyl acetate copolymer, and then extruded and granulated, which can significantly improve the compatibility and dispersibility of mercapto acid monomer 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 kneading. .

[0029] Furthermore, the rubber processing modified masterbatch for tire tread provided by the present invention can reduce the odor of the mercapto acid monomer by using the mercapto acid monomer, ethylene-vinyl acetate copolymer and white carbon black in combination, is environmentally friendly, and is convenient to weigh, accurately feeds, and improves batch quality stability. Furthermore, when the amount of the mercapto acid monomer, ethylene-vinyl acetate copolymer and white carbon black meets the above range, it can better improve the strength of the tire tread rubber, reduce its heat generation, improve wet skid resistance, reduce rolling resistance, and reduce energy consumption during mixing.

[0030] According to the present invention, preferably, the content of the mercapto acid monomer is 45-50 parts by weight, the content of the ethylene-vinyl acetate copolymer is 20-30 parts by weight, and the content of the white carbon black is 20-25 parts by weight.

[0031] In the present invention, ethylene-vinyl acetate copolymer is referred to as EVA. In the present invention, ethylene-vinyl acetate copolymer is purchased from DuPont Company, USA.

[0032] According to the present invention, the content of vinyl acetate (VA) structural units in the ethylene-vinyl acetate copolymer is 30-40%; the melt index is 40-60g / 10min, preferably 45-55g / 10min, at 2.16kg and 190°C, and the melting point is 60°C. In the present invention, too high a content of vinyl acetate (VA) structural units will result in high viscosity of EVA and poor dispersibility of the loaded modifier in the rubber matrix; too low a content of vinyl acetate (VA) structural units will result in high melting point of EVA and limited processing technology; too high a melt index will result in poor fluidity and poor dispersibility of the modifying agent; too low a melt index will result in poor coating of the modifying agent.

[0033] According to the present invention, the type of white carbon black is not particularly limited, and can be a conventional type of white carbon black in the art, such as fumed white carbon black and / or precipitated white carbon black, preferably, the white carbon black is precipitated white carbon black. In the present invention, the white carbon black is purchased from Degussa, Germany.

[0034] According to the present invention, the mercapto acid monomer is provided by at least one of the compounds represented by formula (1):

[0035]

[0036] wherein x is 0 and R2 is -SH; or

[0037] x is 1, M is a structure represented by formula (2), R1 and R2 are each independently H or -SH, and R1 and R2 are not H at the same time; or,

[0038] x is 2, M is a structure represented by formula (2), R2 and R1 in two M are each independently H or -SH, and R2 and R1 in two M are not H at the same time; or,

[0039] x is 3, M is a structure represented by formula (2), R2 and R1 among the three M are each independently H or -SH, and R2 and R1 among the three M are not H at the same time.

[0040] In the present invention, the mercapto acid monomers are purchased from Aladdin Chemical Reagent Company.

[0041] In the present invention, the compound represented by formula (1) is selected as the mercapto acidic monomer, and the rubber processing modified masterbatch containing the mercapto acidic monomer is added to the rubber matrix, which can significantly improve the dispersibility and compatibility between ethylene-vinyl acetate copolymer, white carbon black and the mercapto acidic monomer, thereby better improving the strength of the tire tread rubber, reducing its heat generation, and improving its anti-skid property, and is suitable for use as a tire tread rubber.

[0042] In a specific embodiment of the present invention, the mercapto acid monomer is 3-mercaptoacrylic acid and / or 4-mercaptobutyric acid.

[0043] The second aspect of the present invention provides a method for preparing a rubber processing modified masterbatch for tire tread, wherein the preparation method comprises the following steps:

[0044] (1) stirring white carbon black and mercapto acid monomers until they are uniformly mixed to obtain a preloaded mixture;

[0045] (2) mixing ethylene-vinyl acetate copolymer with the preloaded mixture to obtain a masterbatch;

[0046] (3) extruding and granulating the masterbatch to obtain a rubber processing modified masterbatch;

[0047] Wherein, the amount of the mercapto acid monomer is 40-55 parts by weight, the amount of the ethylene-vinyl acetate copolymer is 15-35 parts by weight, and the amount of the white carbon black is 15-30 parts by weight.

[0048] In the present invention, the above method is adopted to mix white carbon black and mercapto acid monomers and then knead them with ethylene-vinyl acetate copolymer, and then extrusion granulation is performed to obtain the rubber processing modified masterbatch for tire tread according to the first aspect of the present invention. The mercapto acid monomers can be fully and evenly mixed with white carbon black and EVA in advance, thereby significantly improving the compatibility and dispersibility of the mercapto acid monomers and EVA. When the rubber processing aid 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.

[0049] The amount and type of raw materials used to prepare the rubber processing modified masterbatch 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 described in detail in the second aspect, and those skilled in the art should not understand it as a limitation of the present invention.

[0050] In the present invention, there is no particular limitation on the mixing method of white carbon black and mercapto acid monomers, as long as white carbon black and mercapto acid monomers can form a uniform preloaded mixture.

[0051] According to the present invention, in step (2), the mixing is carried out in an internal mixer.

[0052] According to the present invention, in step (2), the mixing conditions include: temperature of 85-90°C, rotation speed of 55-65rpm, and time of 3-5min; preferably, temperature of 86-89°C, rotation speed of 57-63rpm, and time of 4-4.5min.

[0053] According to the present invention, in step (3), the basic granulation is extruded and granulated in a single screw extruder.

[0054] According to the present invention, in step (3), the temperature of the single screw is set to 85-90°C, the die temperature is 90-95°C, the motor power is 8-10Hz; the pelletizer power is 7-10Hz; preferably, the temperature of the single screw is set to 86-89°C, the die temperature is 92-94°C, the motor power is 8.5-9Hz; the pelletizer power is 8-9Hz.

[0055] The third aspect of the present invention provides a rubber processing modified masterbatch for tire tread prepared by the aforementioned preparation method.

[0056] 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.

[0057] 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;

[0058] Wherein, relative to 100 parts by weight of the base rubber, the amount of the rubber processing modified masterbatch is 0.5-4 parts by weight; preferably, relative to 100 parts by weight of the base rubber, the amount of the rubber processing modified masterbatch is 1-2 parts by weight.

[0059] A sixth aspect of the present invention provides a method for preparing vulcanized rubber, wherein the preparation method comprises:

[0060] The base rubber is mixed in the presence of a rubber processing modified masterbatch to obtain a mixed rubber blank, and the mixed rubber blank is vulcanized to obtain a vulcanized rubber;

[0061] Wherein, the rubber processing modified masterbatch is the rubber processing modified masterbatch for tire tread mentioned above.

[0062] The main improvement of the rubber processing method provided by the present invention over the existing rubber processing method is that the above-mentioned 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 prior art. For example, specifically, the rubber processing method may include, firstly, mixing the base rubber with the rubber processing modified masterbatch of the present invention for the first time, the mixing time may be 1-5 minutes, and the temperature may be 60-100°C; then adding white carbon black, carbon black, activator, softener, and antioxidant into an internal mixer for mixing, the mixing time may be 5-10 minutes, the temperature may be 80-160°C, after the mixing is completed, placing it at room temperature for at least 4 hours, then adding a vulcanizing agent and an accelerator to the above mixture, the mixing time may be 3-7 minutes, the temperature does not exceed 130°C, and a mixed rubber blank is obtained, and then the obtained mixed rubber blank is subjected to plate vulcanization, the plate vulcanization temperature may be 140-170°C, and the plate vulcanization time may be 30-40 minutes, thereby obtaining a vulcanized rubber.

[0063] 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.

[0064] 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.

[0065] 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. 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.

[0066] 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.

[0067] The softener is at least one of aromatic oil, paraffin oil, naphthenic oil, petroleum resin and polyethylene glycol. 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.

[0068] The antioxidant is at least one of an amine antioxidant, a quinoline antioxidant and a benzimidazole antioxidant. For example, the antioxidant is antioxidant 4020.

[0069] The accelerator is at least one of sulfenamide accelerators, thiazole accelerators, thiuram accelerators and guanidine accelerators. The accelerator may be N-tert-butyl-2-benzothiazole sulfenamide (TBBS) or diphenylguanidine (accelerator D).

[0070] 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.

[0071] A seventh aspect of the present invention provides a vulcanized rubber prepared by the aforementioned preparation method.

[0072] An eighth aspect of the present invention provides a use of the aforementioned rubber composition or the aforementioned vulcanized rubber in a tire tread.

[0073] The present invention will be described in detail below through examples.

[0074] The equipment conditions for preparing the vulcanized rubber in the following examples and comparative examples are shown in Table 1.

[0075] 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.

[0076] The amounts of components in the following examples and comparative examples are all parts by weight, and each part by weight represents 1 g.

[0077] Table 1

[0078]

[0079]

[0080] Table 2

[0081]

[0082] Table 3

[0083]

[0084] The preparation example is used to illustrate the rubber processing modified masterbatch and its preparation method.

[0085] Preparation Example 1

[0086] At room temperature (25°C), 20 parts by weight of precipitated silica (1165MP) and 45 parts by weight of 3-mercaptopropionic acid were uniformly stirred to obtain a preloaded mixture; the internal mixer was set to 85°C and the speed was 55rpm, 20 parts by weight of EVA (VA content 30%, melting point 60°C, melt index 40g / 10min.) was put into the internal mixer for mixing for 3min, and a masterbatch was obtained by discharging the material; a masterbatch was extruded and granulated in a single screw extruder, the temperature of the single screw was set to 85°C, the temperature of the die head was 95°C, the motor power was 8HZ; the power of the pelletizer was 7HZ. The rubber modified masterbatch X1 for tire tread was obtained by discharging the material.

[0087] Preparation Example 2

[0088] At room temperature (25°C), 23 parts by weight of precipitated silica (165GR) and 48 parts by weight of 4-mercaptobutyric acid were uniformly stirred to obtain a preloaded mixture; the internal mixer was set at 88°C and the speed was 60rpm, 25 parts by weight of EVA (VA content 30%, melting point 60°C, melt index 40g / 10min.) was put into the internal mixer for mixing for 4 minutes, and a masterbatch was obtained by discharging the material; a masterbatch was extruded and granulated in a single screw extruder, the temperature of the single screw was set at 88°C, the temperature of the die head was 93°C, the motor power was 9HZ; the power of the pelletizer was 8.5HZ. The rubber modified masterbatch X2 for tire tread was obtained by discharging the material.

[0089] Preparation Example 3

[0090] At room temperature (25°C), 25 parts by weight of precipitated silica (1165MP) and 50 parts by weight of 3-mercaptopropionic acid were uniformly stirred to obtain a preloaded mixture; the internal mixer was set at 90°C and the speed was 65rpm, 30 parts by weight of EVA (VA content 30%, melting point 60°C, melt index 40g / 10min.) was put into the internal mixer for mixing for 5 minutes, and a masterbatch was obtained by discharging the material; a masterbatch was extruded and granulated in a single screw extruder, the temperature of the single screw was set at 90°C, the temperature of the die head was 90°C, the motor power was 10HZ; the pelletizer power was 10HZ. The rubber modified masterbatch X3 for tire tread was obtained by discharging the material.

[0091] Preparation Example 4

[0092] At room temperature (25°C), 30 parts by weight of precipitated silica (1165MP) and 55 parts by weight of 3-mercaptopropionic acid were uniformly stirred to obtain a preloaded mixture; the internal mixer was set at 90°C and the speed was 65rpm, 35 parts by weight of EVA (VA content 30%, melting point 60°C, melt index 40g / 10min.) was put into the internal mixer for mixing for 5 minutes, and a masterbatch was obtained by discharging the material; a masterbatch was extruded and granulated in a single screw extruder, the temperature of the single screw was set at 90°C, the temperature of the die head was 90°C, the motor power was 10HZ; the pelletizer power was 10HZ. The rubber modified masterbatch X4 for tire tread was obtained by discharging the material.

[0093] Comparative Preparation Example 5

[0094] At room temperature (25°C), 10 parts by weight of precipitated silica (1165MP) and 60 parts by weight of 3-mercaptopropionic acid were uniformly stirred to obtain a preloaded mixture; the internal mixer was set at 90°C and the speed was 65rpm, 40 parts by weight of EVA (VA content 30%, melting point 60°C, melt index 40g / 10min.) was put into the internal mixer for mixing for 5 minutes, and a masterbatch was obtained by discharging the material; a masterbatch was extruded and granulated in a single screw extruder, the temperature of the single screw was set at 90°C, the temperature of the die head was 90°C, the motor power was 10HZ; the pelletizer power was 10HZ. The rubber modified masterbatch X5 for tire tread was obtained by discharging the material.

[0095] Examples 1-4 are used to illustrate the rubber processing method provided by the present invention.

[0096] Example 1

[0097] 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 1 part 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.

[0098] The performance of the vulcanized rubber sample S1 was tested, and the results are shown in Table 4.

[0099] Example 2

[0100] 60 parts by weight of solution-polymerized styrene-butadiene rubber (product of Yanshan Petrochemical, SSBR2636) and 40 parts by weight of butadiene rubber (product of Yanshan Petrochemical, BR9000) and 1.5 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 Chemical Co., Ltd.) were added. (Ningbo) Co., Ltd., TDAEV500), 3 parts by weight of antioxidant (Jiangsu Shengao Chemical Technology Co., Ltd., 4020) were added into an internal mixer for mixing for 7 minutes. After mixing, the mixture was allowed to stand at room temperature for 5 hours. Then, 2 parts by weight of sulfur (Weifang Zhongheng Chemical Co., Ltd.) and 3 parts by weight of TBBS (N-tert-butyl-2-benzothiazolesulfonamide) were added into a masterbatch and mixed at 60°C for 5 minutes to obtain a mixed rubber blank. The obtained 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.

[0101] The performance of the vulcanized rubber sample S2 was tested, and the results are shown in Table 4.

[0102] Example 3

[0103] 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 2 parts by weight of the 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.

[0104] The performance of the vulcanized rubber sample S3 was tested, and the results are shown in Table 4.

[0105] Example 4

[0106] 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 4 parts by weight of the 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.

[0107] The performance of the vulcanized rubber sample S4 was tested, and the results are shown in Table 4.

[0108] Comparative Example 1

[0109] The rubber was processed according to the method of Example 1, except that the added amount of the rubber processing modified masterbatch X1 was 6 parts by weight, to obtain a vulcanized rubber sample DS1.

[0110] The performance of the vulcanized rubber sample DS1 was tested, and the results are shown in Table 4.

[0111] Comparative Example 2

[0112] The rubber was processed according to the method of Example 1, except that the rubber processing modified masterbatch X1 was replaced by the same amount of pure 3-mercaptopropionic acid in the rubber processing, and the vulcanized rubber DS2 was obtained after vulcanization.

[0113] The performance of the vulcanized rubber sample DS2 was tested, and the results are shown in Table 4.

[0114] Comparative Example 3

[0115] The rubber was prepared according to the method of Example 1, except that the rubber processing modified masterbatch was added in an amount of 1 part by weight of X5 prepared in Comparative Preparation Example 5, to obtain a vulcanized rubber sample DS3.

[0116] The vulcanized rubber sample DS3 was subjected to performance tests, and the results are shown in Table 4.

[0117] Comparative Example 4

[0118] 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.

[0119] The vulcanized rubber sample DS4 was subjected to performance tests, and the results are shown in Table 4.

[0120] Table 4

[0121]

[0122]

[0123] Table 4 (continued)

[0124]

[0125] 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.

[0126] Furthermore, by comparing the data of Example 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 abrasion of DS1-DS4 is higher than that of S1-S4. The dynamic mechanical properties of the vulcanized rubber of 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 of Examples 1-4 is significantly better than that of DS1-DS4. During the mixing process, S1-S4 has a smaller power loss and a lower energy consumption than DS1-DS4.

[0127] 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.

[0128] The preferred embodiments of the present invention are described in detail above. However, the present invention is not limited to the specific details in the above embodiments. Within the technical concept of the present invention, a variety of simple modifications can be made to the technical solution of the present invention, and these simple modifications all belong to the protection scope of the present invention.

[0129] 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 processing modified masterbatch for tire tread, characterized in that: The rubber processing modified masterbatch comprises mercapto acid monomer, ethylene-vinyl acetate copolymer and white carbon black; Wherein, the content of the mercapto acid monomer is 40-55 parts by weight, the content of the ethylene-vinyl acetate copolymer is 15-35 parts by weight, and the content of the white carbon black is 15-30 parts by weight.

2. The rubber processing modified masterbatch according to claim 1, wherein The content of the mercapto acid monomer is 45-50 parts by weight, the content of the ethylene-vinyl acetate copolymer is 20-30 parts by weight, and the content of the white carbon black is 20-25 parts by weight.

3. The rubber processing modified masterbatch according to claim 1 or 2, wherein: The content of vinyl acetate structural units in the ethylene-vinyl acetate copolymer is 30-40%, and the melt index is 40-60 g / 10 min at 2.16 kg and 190° C.

4. The rubber processing modified masterbatch according to any one of claims 1 to 3, wherein: The mercapto acid monomer is provided by at least one of the compounds represented by formula (1): wherein x is 0 and R2 is -SH; or x is 1, M is a structure represented by formula (2), R1 and R2 are each independently H or -SH, and R1 and R2 are not H at the same time; or, x is 2, M is a structure represented by formula (2), R2 and R1 in two M are each independently H or -SH, and R2 and R1 in two M are not H at the same time; or, x is 3, M is a structure represented by formula (2), R2 and R1 among the three M are each independently H or -SH, and R2 and R1 among the three M are not H at the same time.

5. A method for preparing a rubber masterbatch for tire tread, characterized in that: The preparation method comprises the following steps: (1) stirring white carbon black and mercapto acid monomers until they are uniformly mixed to obtain a preloaded mixture; (2) mixing ethylene-vinyl acetate copolymer with the preloaded mixture to obtain a masterbatch; (3) extruding and granulating the masterbatch to obtain a rubber processing modified masterbatch; Wherein, the amount of the mercapto acid monomer is 40-55 parts by weight, the amount of the ethylene-vinyl acetate copolymer is 15-35 parts by weight, and the amount of the white carbon black is 15-30 parts by weight.

6. The preparation method according to claim 5, wherein: The amount of the mercapto acid monomer is 45-50 parts by weight, the amount of the ethylene-vinyl acetate copolymer is 20-30 parts by weight, and the amount of the white carbon black is 20-25 parts by weight; Preferably, the content of vinyl acetate structural units in the ethylene-vinyl acetate copolymer is 30-40%, and the melt index is 40-60 g / 10 min at 2.16 kg and 190° C.; And / or, the white carbon black is precipitated white carbon black.

7. The preparation method according to claim 5, wherein the mercapto acid monomer is provided by at least one of the compounds represented by formula (1): in, x is 0, and R2 is -SH; or, x is 1, M is a structure represented by formula (2), R1 and R2 are each independently H or -SH, and R1 and R2 are not H at the same time; or, x is 2, M is a structure represented by formula (2), R2 and R1 in two M are each independently H or -SH, and R2 and R1 in two M are not H at the same time; or, x is 3, M is a structure represented by formula (2), R2 and R1 in the three M are each independently H or -SH, and R2 and R1 in the three M are not H at the same time; Preferably, the mercapto acid monomer is 3-mercaptoacrylic acid and / or 4-mercaptobutyric acid.

8. The preparation method according to claim 5, wherein: In step (2), the mixing conditions include: temperature of 85-90°C, rotation speed of 55-65 rpm, and time of 3-5 min; Preferably, the mixing is carried out in an internal mixer; Preferably, the extrusion granulation conditions include: the temperature of the single screw is set to 85-90°C, the temperature of the die head is 90-95°C, the motor power is 8-10Hz; and the pelletizer power is 7-10Hz.

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

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

11. A rubber composition, characterized in that: The rubber composition comprises a base rubber and a rubber processing and modified masterbatch for tire tread according to any one of claims 1 to 4 and 9; Wherein, relative to 100 parts by weight of the base rubber, the amount of the rubber processing modified masterbatch is 0.5-4 parts by weight; preferably, relative to 100 parts by weight of the base rubber, the amount of the rubber processing modified masterbatch is 1-2 parts by weight.

12. A method for preparing vulcanized rubber, characterized in that: The preparation method comprises: The base rubber is mixed in the presence of a rubber processing modified masterbatch to obtain a mixed rubber blank, and the mixed rubber blank is vulcanized to obtain a vulcanized rubber; Wherein, the rubber processing modified masterbatch is the rubber processing modified masterbatch for tire tread according to any one of claims 1 to 4 and 9.

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

14. Use of the rubber composition according to claim 11 or the vulcanized rubber according to claim 13 in a tire tread.

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