Rubber processing modified masterbatch and vulcanizate, and method of making and use in tire tread

Abstract

The application relates to the technical field of rubber, and discloses a rubber processing modified masterbatch, vulcanized rubber, a preparation method of the rubber processing modified masterbatch and the vulcanized rubber and application of the rubber processing modified masterbatch in a tire tread, wherein the rubber processing modified masterbatch is composed of a modifier, a base material and white oil; the content of the modifier is 76-81 parts by weight; the content of the base material is 14-17 parts by weight; and the content of the white oil is 3-7 parts by weight; and the base material comprises a polyolefin elastomer, an ethylene-propylene-diene rubber and an ethylene-vinyl acetate copolymer. The rubber processing modified masterbatch can improve the compatibility and dispersibility of maleic acid monomers in a high-viscosity rubber base, so that the strength of the tire tread rubber can be better improved, the heat generation of the tire tread rubber can be reduced, and the wet skid resistance can be improved.

Description

Rubber processing modified masterbatch and vulcanized rubber, their preparation methods and applications in tire treads Technical Field

[0001] This invention relates to the field of rubber technology, specifically to a rubber processing modified masterbatch and vulcanized rubber, their preparation method, and their application in tire treads. Background Technology

[0002] In recent years, the dynamic hysteresis loss performance of green tires has determined the tire classification and grading, as well as the tire's durability and service life. Higher dynamic hysteresis loss can lead to a decrease in the strength and wear resistance of rubber, causing premature tire damage, increasing tire rolling resistance, fuel consumption, and carbon dioxide emissions.

[0003] CN102382338A discloses an isoprene rubber blend comprising isoprene rubber, trans-1,4-polyisoprene, reinforcing filler, in-situ grafting modifier, compounded rubber, and a first additive. The in-situ grafting modifier used in this prior art reacts chemically with the reinforcing filler and simultaneously grafts onto functional groups such as double bonds on the rubber molecular chain. This significantly improves the interfacial bonding force between the organic polymer and the reinforcing filler, as well as the dispersion level of the reinforcing filler in the rubber, thereby enhancing the fatigue resistance of the isoprene rubber blend.

[0004] CN103703072A discloses a rubber composition for tire treads, comprising solution-polymerized styrene-butadiene rubber (SBR), carbon black, silica, and polyethylene glycol (PEG). The SBR content is 60% or more per 100% by mass of the rubber composition. Relative to 100 parts by mass of the rubber composition, the carbon black content is less than 10 parts by mass, the silica content is 50 parts by mass or more, and the PEG content is 0.1-3.5 parts by mass. According to this prior art, a rubber composition containing SBR, carbon black, silica, and PEG in specified amounts, when applied to tire treads, can provide a pneumatic tire with balanced improvements in fuel economy and wear resistance. Furthermore, the vulcanization speed is good during tire manufacturing, and the manufactured tire has a good appearance.

[0005] However, the rubber provided by the above-mentioned prior art still cannot meet the requirements of tire tread rubber for strength, reduced heat generation, and improved wet grip performance, so it is necessary to provide a rubber with improved performance.

[0006] CN107955232A discloses the application of maleic acid monomers and their application in tire treads. This invention can better leverage the bridging role of matrix modifiers in the matrix rubber and silica, facilitating the full interaction between silica and the rubber matrix. This results in improved strength of the vulcanized rubber obtained through further vulcanization, reduced heat generation in the vulcanized rubber, and enhanced wet skid resistance of the vulcanized rubber compound. However, the application of maleic acid monomers is somewhat limited due to their irritating odor, poor compatibility with high-viscosity rubber matrices, poor dispersibility, and inaccurate dosage.

[0007] Therefore, it is necessary to provide a rubber processing modification masterbatch for tire tread with improved performance. Summary of the Invention

[0008] The purpose of this invention is to overcome the problem that existing technologies still cannot meet the requirements of tire tread rubber for strength, heat generation reduction, and improved wet skid performance. This invention provides a rubber processing modified masterbatch, vulcanized rubber, its preparation method, and its application in tire tread. The rubber processing modified masterbatch provided by this invention can not only improve the compatibility and dispersibility of maleic acid monomers in high-viscosity rubber matrices, thereby better improving the strength of tire tread rubber, reducing its heat generation, and improving wet skid performance, but also improve processing safety and vulcanization efficiency.

[0009] To achieve the above objectives, the first aspect of the present invention provides a rubber processing modified masterbatch for tire tread, wherein the rubber processing modified masterbatch is composed of a modifier, a matrix material and white oil, and the content of the modifier is 76-81 parts by weight, the content of the matrix material is 14-17 parts by weight, and the content of the white oil is 3-7 parts by weight.

[0010] The matrix material comprises polyolefin elastomer, ethylene propylene diene monomer (EPDM) rubber, and ethylene-vinyl acetate copolymer.

[0011] A second aspect of the present invention provides a method for preparing a rubber processing modified masterbatch for tire tread, wherein the preparation method includes the following steps:

[0012] (1) Plasticize polyolefin elastomer and EPDM rubber to obtain plasticized rubber;

[0013] (2) The ethylene-vinyl acetate copolymer, modifier, white oil and the plasticized rubber are mixed and the mixture is discharged to obtain the rubber processing modified masterbatch for tire tread.

[0014] The modifier is used in an amount of 76-81 parts by weight, the total amount of polyolefin elastomer, EPDM rubber and ethylene-vinyl acetate copolymer is 14-17 parts by weight, and the white oil is used in an amount of 3-7 parts by weight.

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

[0016] The fourth aspect of the present invention provides the application of the aforementioned modified rubber masterbatch for tire tread in the preparation of vulcanized rubber.

[0017] A fifth aspect of the present invention provides a rubber composition comprising a base rubber and the aforementioned rubber processing modified masterbatch for tire tread.

[0018] Among them, the application of modified masterbatch for tire tread 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 includes:

[0020] (1) Mix the base rubber and rubber processing modified masterbatch to obtain the mixed rubber preform;

[0021] (2) The compounded rubber blank is vulcanized to obtain tire tread rubber;

[0022] The rubber processing modified masterbatch mentioned above is the rubber processing modified masterbatch for tire treads described above.

[0023] The seventh aspect of the present invention provides a vulcanized rubber prepared by the preparation method described above.

[0024] The eighth aspect of the present invention provides the 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 this invention can improve the compatibility and dispersibility of maleic acid monomers in high-viscosity rubber matrices, thereby better improving the strength of tire tread rubber, reducing its heat generation, and improving wet skid resistance. In addition, it can reduce the odor of the modifier, is environmentally friendly, and is convenient to weigh, accurate in feeding, and improve batch quality stability. Detailed Implementation

[0026] The endpoints and any values ​​of the ranges disclosed herein 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 the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[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 is composed of a modifier, a matrix material and white oil, and the content of the modifier is 76-81 parts by weight, the content of the matrix material is 14-17 parts by weight, and the content of the white oil is 3-7 parts by weight.

[0028] The matrix material comprises polyolefin elastomer, ethylene propylene diene monomer (EPDM) rubber, and ethylene-vinyl acetate copolymer.

[0029] The tire tread rubber processing modification masterbatch provided by this invention is composed of a modifier, a matrix material, and white oil. The matrix material includes a polyolefin elastomer, ethylene propylene diene monomer (EPDM) rubber, and an ethylene-vinyl acetate copolymer. The polyolefin elastomer and EPDM rubber are pre-plasticized to obtain a plasticized rubber. Then, the ethylene-vinyl acetate copolymer, the modifier, the white oil, and the plasticized rubber are mixed. The resulting rubber processing modification masterbatch can significantly 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 improving processing safety and vulcanization efficiency.

[0030] Furthermore, the tire tread rubber processing modified masterbatch provided by the present invention, by using modifiers, matrix materials and white oil in combination, can reduce the odor of modifiers, is environmentally friendly, and is convenient to weigh, accurate in feeding, and improves batch quality stability.

[0031] Furthermore, when the amounts of modifier, matrix material, and white oil meet the above ranges, the strength of the tire tread compound can be better improved, its heat generation reduced, its wet skid resistance improved, its rolling resistance reduced, and its processing safety and vulcanization efficiency improved.

[0032] In this invention, the matrix material is a polyolefin elastomer, abbreviated as POE.

[0033] In this invention, the matrix material is ethylene propylene diene monomer (EPDM).

[0034] In this invention, the matrix material is ethylene-vinyl acetate copolymer, abbreviated as EVA.

[0035] In this invention, all matrix materials were purchased from DuPont, USA.

[0036] According to the present invention, preferably, the content of the modifier is 78-80 parts by weight, the content of the matrix material is 15-16 parts by weight, and the content of the white oil is 5-6 parts by weight; more preferably, the content of the modifier is 80 parts by weight, the content of the matrix material is 15 parts by weight, and the content of the white oil is 5 parts by weight. Furthermore, in the present invention, the total amount of each component is 100.

[0037] According to the present invention, the weight ratio of polyolefin elastomer, ethylene propylene diene monomer (EPDM) rubber and ethylene-vinyl acetate copolymer is (2-3):10:(2-3), preferably 3:10:2.

[0038] According to the present invention, the modifier is a maleic acid monomer; preferably, the maleic acid monomer is selected from at least one of maleic acid, maleic anhydride and dialkyl maleate.

[0039] In this invention, the maleic acid monomers were purchased from Aladdin Chemical Reagents Co., Ltd.

[0040] According to the present invention, the white oil has a kinematic viscosity of 22-28 mm² / s and a flash point ≥210℃. In this invention, the white oil is purchased from Shandong Tianfeng Chemical Technology Co., Ltd.

[0041] According to the present invention, the Mooney viscosity (100°C, 1+4 min) of the polyolefin elastomer is 10-25, preferably 15-20; the melt index at 2.16 kg and 190°C is 1-3 g / 10 min, preferably 1.5-2.5 g / 10 min. In this invention, excessively high Mooney viscosity leads to processing difficulties, while excessively low Mooney viscosity leads to poor coating of the modifier; excessively high melt index leads to poor flowability, while excessively low melt index leads to poor coating of the modifier.

[0042] According to the present invention, the EPDM rubber contains 50-60% vinyl content, 5-10% content of the third monomer ethylene-ide-norbornene (ENB) structural unit, and has a Mooney viscosity of 55-70; preferably, the EPDM rubber contains 53-56% vinyl content, 6-8% content of the third monomer ethylene-ide-norbornene (ENB) structural unit, and has a Mooney viscosity of 58-63. In the present invention, excessively high Mooney viscosity leads to processing difficulties, while excessively low Mooney viscosity leads to poor coating of the modifier; excessively high vinyl content leads to poor low-temperature resistance, while excessively low vinyl content leads to poor strength; excessively high content of the third monomer ethylene-ide-norbornene (ENB) structural unit leads to excessively fast vulcanization speed, while excessively low content leads to excessively slow vulcanization speed.

[0043] 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 at 2.16 kg and 190°C is 40-60 g / 10 min, preferably 45-60 g / 10 min. In this invention, excessively high content of vinyl acetate (VA) structural units leads to high EVA viscosity and poor dispersion of the loaded modifier in the rubber matrix; excessively low content of vinyl acetate (VA) structural units leads to high EVA melting point and limited processing capabilities; excessively high melt index leads to poor flowability and poor dispersion of the modifier; excessively low melt index leads to poor coating of the modifier.

[0044] A second aspect of the present invention provides a method for preparing a rubber processing modified masterbatch for tire tread, wherein the preparation method includes the following steps:

[0045] (1) Plasticize polyolefin elastomer and EPDM rubber to obtain plasticized rubber;

[0046] (2) The ethylene-vinyl acetate copolymer, modifier, white oil and the plasticized rubber are mixed and the mixture is discharged to obtain the rubber processing modified masterbatch for tire tread.

[0047] The modifier is used in an amount of 76-81 parts by weight, the total amount of polyolefin elastomer, EPDM rubber and ethylene-vinyl acetate copolymer is 14-17 parts by weight, and the white oil is used in an amount of 3-7 parts by weight.

[0048] In this invention, the above method is used to first plasticize the polyolefin elastomer and ethylene propylene diene monomer (EPDM) rubber to obtain a plasticized rubber. Then, the ethylene-vinyl acetate copolymer, modifier, white oil, and the plasticized rubber are mixed together. This can significantly improve the compatibility and dispersibility of maleic acid monomers in high-viscosity rubber matrices, thereby better improving the strength of tire tread rubber, reducing its heat generation, improving wet skid resistance, reducing rolling resistance, and improving processing safety and vulcanization efficiency.

[0049] The amount and type of raw materials used in the preparation of the rubber processing modified masterbatch for tire tread in the second aspect of the present invention are exactly the same as those used in the first aspect of the present invention. In order to avoid repetition, the present invention will not repeat the description in this second aspect, and those skilled in the art should not understand it as a limitation of the present invention.

[0050] According to the present invention, in step (1), the plasticizing can be carried out in an internal mixer, wherein the plasticizing conditions include: a temperature of 60-80°C, a rotation speed of 60-80 rpm, and a time of 0.5-2 min; preferably, the temperature is 65-75°C, the rotation speed is 65-75 rpm, and the time is 1-1.5 min.

[0051] According to the present invention, in step (2), the mixing conditions include: a temperature of 60-80°C and a mixing time of 2-6 min; preferably, a temperature of 65-75°C and a mixing time of 3-4 min.

[0052] According to a preferred embodiment of the present invention, the preparation method of the rubber processing modified masterbatch for tire tread includes the following steps:

[0053] (1) Heat the internal mixer to 60-80℃ and rotate at 60-80rpm. Put the matrix materials POE and EPDM into the internal mixer for plasticizing for 0.5-2min.

[0054] (2) Add EVA, modifier and white oil to the internal mixer and mix with plasticized rubber for 2-6 minutes; discharge to obtain modified masterbatch for tire tread rubber processing.

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

[0056] The fourth aspect of the present invention provides the application of the aforementioned modified rubber masterbatch for tire tread in the preparation of vulcanized rubber.

[0057] A fifth aspect of the present invention provides a rubber composition comprising a base rubber and the aforementioned rubber processing modified masterbatch for tire tread.

[0058] The amount of the rubber processing modification masterbatch used is 0.2-5 parts by weight relative to 100 parts by weight of the base rubber; preferably, the amount of the rubber processing modification masterbatch used is 0.5-2 parts by weight relative to 100 parts by weight of the base rubber.

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

[0060] (1) Mix the base rubber and rubber processing modified masterbatch to obtain the mixed rubber preform;

[0061] (2) The compounded rubber blank is vulcanized to obtain tire tread rubber;

[0062] The rubber processing modified masterbatch mentioned above is the rubber processing modified masterbatch for tire treads described above.

[0063] According to another preferred embodiment of the present invention, the method for preparing the vulcanized rubber includes: mixing base rubber in the presence of rubber processing modification masterbatch to obtain a mixed rubber blank, and vulcanizing the mixed rubber blank to obtain tire tread rubber.

[0064] The main improvement of the rubber processing method provided by this invention compared to existing rubber processing methods lies in the use of the rubber processing modified masterbatch provided by this invention. Therefore, the specific process conditions and operations of the mixing and vulcanization can be carried out with reference to existing technologies. For example, specifically, the rubber processing method may include: firstly, mixing the base rubber with the rubber processing modified masterbatch of this invention for 1-5 minutes at a temperature of 60-100°C; then adding silica, carbon black, activator, softener, and antioxidant into a mixer for 5-10 minutes at a temperature of 80-160°C; after mixing, allowing the mixture to stand at room temperature for at least 4 hours; then adding vulcanizing agent and accelerator to the mixture for 3-7 minutes at a temperature not exceeding 130°C to obtain a mixed rubber preform; subsequently, subjecting the obtained mixed rubber preform to flat vulcanization at a temperature of 140-170°C for 30-40 minutes to obtain vulcanized rubber; further, applying the vulcanized rubber to tire tread to prepare tire tread rubber.

[0065] In this invention, the base rubber can be any type of rubber that requires vulcanization, such as natural rubber and / or synthetic rubber, and the synthetic rubber can include, but is not limited to, butadiene rubber and / or styrene-butadiene rubber.

[0066] In this invention, the silica can be any existing precipitated silica that can be used as rubber reinforcement, including but not limited to: silica 200MP, 1165MP, 165GR, 115GR, and the content of silica can be selected within a wide range; specifically, relative to 100 parts by weight of base rubber, the content of silica can be 40-100 parts by weight.

[0067] In this 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 in a wide range; specifically, the content of the carbon black can be 0-70 parts by weight relative to 100 parts by weight of base rubber.

[0068] In this invention, the type and amount of the activator are well known to those skilled in the art. The activator may be zinc oxide and / or stearic acid. Specifically, the content of the activator may be 2-10 parts by weight relative to 100 parts by weight of natural rubber and synthetic rubber.

[0069] In this invention, the softener is at least one selected from aromatic oil, paraffin oil, naphthenic oil, petroleum resin, and polyethylene glycol. The polyethylene glycol, with a weight-average molecular weight of 3000-5000, imparts good processability and physical-mechanical properties to the composite material. The aromatic oil can be, for example, TDAE V500, and the polyethylene glycol can be, for example, PEG4000.

[0070] In this invention, the antioxidant is at least one selected from amine antioxidants, quinoline antioxidants, and benzimidazole antioxidants. For example, the antioxidant is antioxidant 4020.

[0071] In this invention, the accelerator is at least one selected from sulfenamide accelerators, thiazole accelerators, thiuram accelerators, and guanidine accelerators. The accelerator may be N-tert-butyl-2-benzothiazole sulfenamide (TBBS) or diphenylguanidine (accelerator D).

[0072] In this invention, preferably, the vulcanizing agent is sulfur and / or a sulfur donor. The sulfur donor refers to a substance capable of providing 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.

[0073] The seventh aspect of the present invention provides a vulcanized rubber prepared by the preparation method described above.

[0074] The eighth aspect of the present invention provides the use of the aforementioned rubber composition or the aforementioned vulcanized rubber in a tire tread.

[0075] The present invention will be described in detail below through embodiments.

[0076] The equipment used for preparing vulcanized rubber in the following examples and comparative examples is shown in Table 1.

[0077] The testing instruments for the vulcanized rubbers prepared in the examples and comparative examples are shown in Table 2, and the testing conditions are shown in Table 3.

[0078] In the following examples and comparative examples, the amounts of components are all parts by weight, with each part by weight representing 1g.

[0079] Table 1

[0080] Serial Number Equipment Name Model Manufacturer 1 Internal Mixer BR1600 Farrell, USA 2 Flat Vulcanizing Machine XLB-D400*400*2 Shanghai No.1 Rubber Machinery Factory 3 Rotorless Vulcanizing Machine MDR 3000basic Montech, Germany surface

[0081] Table 2

[0082]

[0083] Table 3

[0084]

[0085]

[0086] The preparation examples illustrate the prepared rubber processing modified masterbatch.

[0087] Preparation Example 1

[0088] Heat the internal mixer to 60°C and rotate at 80 rpm. Add 10 parts by weight of EPDM (60% ethylene content, 10% ENB content, Mooney viscosity 70) and 3 parts by weight of POE (Mouney viscosity 25, melt index 1 g / 10 min) to the internal mixer and masticate for 0.5 min. Then add 2 parts by weight of EVA (40% VA content, melt index 60 g / 10 min), 80 parts by weight of maleic anhydride and 5 parts by weight of white oil to the internal mixer and mix with the masticated rubber for 6 min. Discharge the material to obtain tire tread rubber processing modified masterbatch X1.

[0089] Preparation Example 2

[0090] Heat the internal mixer to 70°C and rotate at 70 rpm. Add 10 parts by weight of EPDM (ethylene content 50%, ENB content 8%, Mooney viscosity 55) and 2 parts by weight of POE (Mouney viscosity 10, melt index 3g / 10min) to the internal mixer and masticate for 1 min. Then add 3 parts by weight of EVA (VA content 30%, melt index 40g / 10min), 80 parts by weight of maleic acid, and 5 parts by weight of white oil to the internal mixer and mix with the masticated rubber for 4 min. Discharge the material to obtain tire tread rubber processing modified masterbatch X2.

[0091] Preparation Example 3

[0092] Heat the internal mixer to 80°C and rotate at 60 rpm. Add 10 parts by weight of EPDM (ethylene content 55%, ENB content 5%, Mooney viscosity 65) and 3 parts by weight of POE (Mouney viscosity 19, melt index 1.3 g / 10 min) to the internal mixer and masticate for 2 min. Then add 2 parts by weight of EVA (VA content 33%, melt index 45 g / 10 min), 80 parts by weight of diethyl maleate and 5 parts by weight of white oil to the internal mixer and mix with the masticated rubber for 2 min. Discharge the material to obtain tire tread rubber processing modified masterbatch X3.

[0093] Comparative preparation example 4

[0094] Heat the internal mixer to 80°C and rotate at 60 rpm. Add 10 parts by weight of EPDM (ethylene content 59%, ENB content 1.5%, Mooney viscosity 38) and 3 parts by weight of POE (Mouney viscosity 37, melt index 0.5 g / 10 min) to the internal mixer and masticate for 2 min. Then add 2 parts by weight of EVA (VA content 28%, melt index 25 g / 10 min), 80 parts by weight of diethyl maleate and 5 parts by weight of white oil to the internal mixer and mix with the masticated rubber for 2 min. Discharge to obtain 4 tire tread rubber processing modified masterbatch.

[0095] Comparative preparation example 5

[0096] The rubber processing modified masterbatch was prepared using the same method as in Preparation Example 1, except that the amounts of modifier, matrix material, and white oil were different. Specifically:

[0097] 7 parts by weight of EPDM, 4 parts by weight of POE, 4 parts by weight of EVA, 75 parts by weight of diethyl maleate and 10 parts by weight of white oil;

[0098] The final product was 5 units of modified masterbatch for tire tread processing.

[0099] Examples 1-4 illustrate the rubber processing method provided by the present invention.

[0100] Example 1

[0101] 85 parts by weight of solution-polymerized styrene-butadiene rubber (Yanshan Petrochemical product, SSBR2636) and 15 parts by weight of butadiene rubber (Yanshan Petrochemical product, BR9000) were added to a mixing mill along with 2 parts by weight of the rubber processing modified masterbatch X1 prepared in Preparation Example 1. The mixture was mixed at 70°C for 3 minutes. Then, 60 parts by weight of silica (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.), and 10 parts by weight of aromatic oil (Xinda Yang) were added. Ningbo Co., Ltd., TDAEV500), and 3 parts by weight of antioxidant (Jiangsu Shengao Chemical Technology Co., Ltd., 4020) were added to a mixer and mixed for 7 minutes. After mixing, the mixture was placed 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-benzothiazole sulfenamide) were added to a first-stage masterbatch and mixed at 60°C for 5 minutes to obtain a compound rubber preform. Subsequently, the obtained compound rubber preform was subjected to flat vulcanization at a vulcanization temperature of 160°C, a vulcanization pressure of 10MPa, and a vulcanization time of 40 minutes to obtain vulcanized rubber sample S1.

[0102] The performance of vulcanized rubber sample S1 was tested, and the results are shown in Table 4.

[0103] Example 2

[0104] 60 parts by weight of solution-polymerized styrene-butadiene rubber (Yanshan Petrochemical product, SSBR2636) and 40 parts by weight of butadiene rubber (Yanshan Petrochemical product, BR9000) were added to a mixing mill along with 0.5 parts by weight of the rubber processing modified masterbatch X2 prepared in Preparation Example 2. The mixture was then mixed at 70°C for 3 minutes. Next, 60 parts by weight of silica (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.), and 10 parts by weight of aromatic oil (Xinda Yang) were added. (Ningbo) Co., Ltd., TDAEV500), 3 parts by weight of antioxidant (Jiangsu Shengao Chemical Technology Co., Ltd., 4020) were added to a mixer and mixed for 7 minutes. After mixing, the mixture was placed 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-benzothiazole sulfenamide) were added to a first-stage masterbatch and mixed at 60°C for 5 minutes to obtain a compound rubber preform. Subsequently, the obtained compound rubber preform was subjected to flat vulcanization at a vulcanization temperature of 160°C, a vulcanization pressure of 10MPa, and a vulcanization time of 40 minutes to obtain vulcanized rubber sample S2.

[0105] The performance of vulcanized rubber sample S2 was tested, and the results are shown in Table 4.

[0106] Example 3

[0107] 70 parts by weight of solution-polymerized styrene-butadiene rubber (Yanshan Petrochemical product, SSBR2636) and 30 parts by weight of butadiene rubber (Yanshan Petrochemical product, BR9000) were added to a mixing mill along with 1 part by weight of the rubber processing modified masterbatch X3 prepared in Preparation Example 3. The mixture was mixed at 70°C for 3 minutes. Then, 60 parts by weight of silica (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.), and 10 parts by weight of aromatic oil (Xinda Yang) were added. Ningbo Co., Ltd., TDAEV500), and 3 parts by weight of antioxidant (Jiangsu Shengao Chemical Technology Co., Ltd., 4020) were added to a mixer and mixed for 7 minutes. After mixing, the mixture was placed 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-benzothiazole sulfenamide) were added to a first-stage masterbatch and mixed at 60°C for 5 minutes to obtain a compound rubber preform. Subsequently, the obtained compound rubber preform was subjected to flat vulcanization at a vulcanization temperature of 160°C, a vulcanization pressure of 10MPa, and a vulcanization time of 40 minutes to obtain vulcanized rubber sample S3.

[0108] The performance of vulcanized rubber sample S3 was tested, and the results are shown in Table 4.

[0109] Example 4

[0110] Rubber was prepared according to the method of Example 1, except that the amount of rubber processing modified masterbatch added was 4 parts by weight of rubber processing modified masterbatch X1 prepared in Example 1, and vulcanized rubber sample S4 was obtained.

[0111] The performance of vulcanized rubber sample S4 was tested, and the results are shown in Table 4.

[0112] Comparative Example 1

[0113] Rubber was processed according to the method of Example 1, except that the amount of rubber processing modified masterbatch X1 added was 8 parts by weight, and vulcanized rubber sample DS1 was obtained.

[0114] The performance of vulcanized rubber sample DS1 was tested, and the results are shown in Table 4.

[0115] Comparative Example 2

[0116] Rubber was processed according to the method of Example 1, except that pure maleic anhydride was added in the same proportion instead of rubber processing modified masterbatch X1, and vulcanized rubber DS2 was obtained after vulcanization.

[0117] The performance of vulcanized rubber sample DS2 was tested, and the results are shown in Table 4.

[0118] Comparative Example 3

[0119] Rubber is processed according to the method of Example 1, except that no rubber processing modifier masterbatch is added during the rubber processing, and vulcanized rubber DS3 is obtained after vulcanization.

[0120] The performance of the vulcanized rubber sample DS3 was tested, and the results are shown in Table 4.

[0121] Comparative Example 4

[0122] Rubber was prepared according to the method of Example 1, except that the amount of rubber processing modification masterbatch added was 2 parts by weight of X4 prepared in Comparative Preparation Example 4, and vulcanized rubber sample DS4 was obtained.

[0123] The performance of the vulcanized rubber sample DS4 was tested, and the results are shown in Table 4.

[0124] Comparative Example 5

[0125] Rubber was prepared according to the method of Example 1, except that the rubber processing and modification masterbatch was added to the same weight parts of X5 prepared in Comparative Preparation Example 5 to obtain vulcanized rubber sample DS5.

[0126] The performance of the vulcanized rubber sample DS5 was tested, and the results are shown in Table 4.

[0127] Table 4

[0128]

[0129]

[0130] Table 4 (continued)

[0131]

[0132] The results above show that using the rubber processing modified masterbatch provided by the present invention can improve the dispersion of silica in the rubber matrix, strengthen the interaction between silica and the rubber matrix, thereby better improving the strength of vulcanized rubber, reducing its heat generation, and improving its wet slip resistance.

[0133] Furthermore, comparing the data from Examples 1-4 with those from Comparative Examples 1-5, it can be seen that the vulcanized rubbers DS1-DS5 prepared in Comparative Examples 1-5 are significantly inferior to vulcanized rubbers S1-S4 in terms of performance. For example, the tensile strength of DS1-DS5 is lower than that of S1-S4, the compression temperature rise of DS1-DS5 is higher than that of S1-S4, and the DIN abrasion of DS1-DS5 is higher than that of S1-S4. The dynamic mechanical properties of the vulcanized rubbers prepared in Examples 1-4 show lower rolling resistance and better wet skid resistance. The Penney effect data also indicate that the carbon black dispersion of the vulcanized rubbers S1-S4 in Examples 1-4 is significantly better than that of DS1-DS5. In terms of processing performance, the scorch time of DS1-DS5 is shorter than that of Examples S1-S4, and the vulcanization time of DS1-DS5 is longer than that of Examples S1-S4, indicating that the processing safety and vulcanization efficiency of Examples 1-4 are better than those of DS1-DS5.

[0134] Since the rubber processing modification masterbatch and preparation method provided by the present invention can give the obtained vulcanized rubber better performance, when the vulcanized rubber of the present invention is applied to the tread of automobile tires, it can improve the durability of the tires, improve the fuel economy of automobiles, and improve the safety of automobiles.

[0135] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A modified masterbatch for tire tread processing, characterized in that, The rubber processing modified masterbatch is composed of a modifier, a matrix material, and white oil. The modifier content is 76-81 parts by weight, the matrix material content is 14-17 parts by weight, and the white oil content is 3-7 parts by weight. The matrix material comprises a polyolefin elastomer, EPDM rubber, and ethylene-vinyl acetate copolymer, with a weight ratio of (2-3):10:(2-3). The polyolefin elastomer has a Mooney viscosity of 10-25 and a melt index of 1-3 g / 10 at 2.16 kg and 190°C. min; the vinyl content in the EPDM rubber is 50-60%, the content of the third monomer ethyleneide norbornene structural unit is 5-10%, and the Mooney viscosity is 55-70; the vinyl acetate structural unit 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; wherein the modifier is a maleic acid monomer; wherein the preparation method of the rubber processing modification masterbatch for tire tread includes the following steps: (1) plasticizing the polyolefin elastomer and EPDM rubber to obtain plasticized rubber; (2) mixing the ethylene-vinyl acetate copolymer, modifier, white oil and the plasticized rubber; and discharging to obtain the rubber processing modification masterbatch for tire tread.

2. The rubber processing modified masterbatch according to claim 1, wherein, The modifier is present in a content of 78-80 parts by weight, the matrix material is present in a content of 15-16 parts by weight, and the white oil is present in a content of 5-6 parts by weight.

3. The rubber processing modified masterbatch according to claim 1 or 2, wherein, The maleic acid monomers are selected from at least one of maleic acid, maleic anhydride, and dialkyl maleic acid esters.

4. The rubber processing modified masterbatch according to claim 1, wherein, In step (1), the plasticizing conditions include: a temperature of 60-80℃, a rotation speed of 60-80 rpm, and a time of 0.5-2 min; and / or, in step (2), the mixing conditions include: a temperature of 60-80℃ and a mixing time of 2-6 min.

5. The application of the rubber processing modified masterbatch for tire tread as described in any one of claims 1-4 in the preparation of vulcanized rubber.

6. A rubber composition, characterized in that, The rubber composition comprises a base rubber and a rubber processing modified masterbatch for tire tread as described in any one of claims 1-4; wherein the amount of the rubber processing modified masterbatch is 0.2-5 parts by weight relative to 100 parts by weight of the base rubber.

7. The rubber composition according to claim 6, wherein, The amount of the rubber processing modification masterbatch used is 0.5-2 parts by weight relative to 100 parts by weight of base rubber.

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

9. A vulcanized rubber prepared by the preparation method of claim 8.

10. The use of a rubber composition according to claim 6 or 7 or a vulcanized rubber according to claim 9 in a tire tread.

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