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

Abstract

The invention relates to the technical field of rubber, and discloses rubber processing modified master batch, vulcanized rubber, a preparation method of the rubber processing modified master batch and the vulcanized rubber and application of the vulcanized rubber in tire treads, the rubber processing modified master batch is composed of 76-81 parts by weight of a modifier, 14-17 parts by weight of a matrix material and 1-3 parts by weight of white oil, the content of the white oil is 3-7 parts by weight; the base material comprises a polyolefin elastomer, ethylene propylene diene monomer and an ethylene-vinyl acetate copolymer. 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, and the wet skid resistance is improved.

Description

Technical Field

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

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

[0003] CN102382338A discloses an isoprene rubber blend, which includes isoprene rubber, trans-1,4-polyisoprene, reinforcing filler, in-situ grafting modification aid, compounding rubber and a first additive. The in-situ grafting modification aid used in the prior art undergoes a grafting reaction with functional groups such as double bonds on the rubber molecular chain while chemically reacting with the reinforcing filler, thereby greatly improving the interface bonding force between the organic polymer and the reinforcing filler and the dispersion level of the reinforcing filler in the rubber, thereby improving the fatigue resistance of the isoprene rubber blend.

[0004] 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.

[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.

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

[0008] 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 vulcanized rubber and a preparation method thereof and an application in tire tread. The rubber processing modified masterbatch provided by the present invention can not only 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, and improving its wet skid resistance, but also improve processing safety and vulcanization efficiency.

[0009] In order to achieve the above object, 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 base material and white oil, and 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;

[0010] Wherein, the matrix material comprises polyolefin elastomer, ethylene propylene diene monomer rubber and ethylene-vinyl acetate copolymer.

[0011] 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:

[0012] (1) plasticizing a polyolefin elastomer and ethylene propylene diene monomer rubber to obtain a plasticized rubber;

[0013] (2) mixing ethylene-vinyl acetate copolymer, a modifier, white oil and the plasticized rubber; discharging the mixture to obtain a rubber masterbatch for tire tread processing;

[0014] The amount of the modifier is 76-81 parts by weight, the total amount of the polyolefin elastomer, EPDM rubber and ethylene-vinyl acetate copolymer is 14-17 parts by weight, and the amount of the white oil is 3-7 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, and improving wet skid resistance. 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 is composed of a modifier, a base material and white oil, and 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;

[0028] Wherein, the matrix material comprises polyolefin elastomer, ethylene propylene diene monomer rubber and ethylene-vinyl acetate copolymer.

[0029] The rubber processing modified masterbatch for tire tread provided by the present invention is composed of a modifier, a base material and white oil, wherein the base material comprises a polyolefin elastomer, ethylene propylene diene monomer rubber and ethylene-vinyl acetate copolymer, the polyolefin elastomer and ethylene propylene diene monomer rubber are plasticized in advance to obtain a plasticized rubber, and then the ethylene-vinyl acetate copolymer, the modifier, the white oil and the plasticized rubber are mixed, and the obtained rubber processing modified masterbatch can significantly improve the compatibility and dispersibility of maleic acid monomers in a high-viscosity rubber matrix, thereby better improving the strength of tire tread rubber, reducing its heat generation, improving anti-slip performance, reducing rolling resistance, and improving processing safety and vulcanization efficiency.

[0030] Furthermore, the rubber masterbatch for tire tread processing provided by the present invention can reduce the odor of the modifier by using the modifier, the base material and the white oil in combination, is environmentally friendly, and is convenient to weigh and accurately feed, thereby improving the stability of batch quality.

[0031] Furthermore, when the amounts of the modifier, base material 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 its processing safety and vulcanization efficiency can be improved.

[0032] In the present invention, the base material is polyolefin elastomer, referred to as POE.

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

[0034] In the present invention, the matrix material is ethylene-vinyl acetate copolymer, referred to as EVA.

[0035] In the present invention, the matrix materials are all purchased from DuPont Company of the United States.

[0036] According to the present invention, preferably, the content of the modifier is 78-80 parts by weight, the content of the base 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 base material is 15 parts by weight, and the content of the white oil is 5 parts by weight. In addition, in the present invention, the total amount of each component is 100.

[0037] According to the present invention, the weight ratio of the polyolefin elastomer, 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 the present invention, maleic acid monomers are purchased from Aladdin Chemical Reagent Company.

[0040] According to the present invention, the kinematic viscosity of the white oil is 22-28 mm2 / s, and the flash point is ≥210° C. In the present 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+4min) of the polyolefin elastomer is 10-25, preferably 15-20; the melt index is 1-3g / 10min, preferably 1.5-2.5g / 10min at 2.16kg and 190°C. In the present invention, too high Mooney viscosity will lead to processing difficulties, and too low Mooney viscosity will lead to poor coating of modifiers; too high melt index will lead to poor fluidity, and too low melt index will lead to poor coating of modifiers.

[0042] According to the present invention, the vinyl content of the EPDM rubber is 50-60%, the content of the third monomer ethylidene norbornene (ENB) structural unit is 5-10%, and the Mooney viscosity is 55-70; preferably, the vinyl content of the EPDM rubber is 53-56%, the content of the third monomer ethylidene norbornene (ENB) structural unit is 6-8%, and the Mooney viscosity is 58-63. In the present invention, too high Mooney viscosity will lead to processing difficulties, and too low Mooney viscosity will lead to poor coating of the modifier; too high vinyl content will lead to poor low temperature resistance, and too low vinyl content will lead to poor strength; too high content of the third monomer ethylidene norbornene (ENB) structural unit will lead to too fast vulcanization speed, and too low content of the third monomer ethylidene norbornene (ENB) structural unit will lead to too 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 is 40-60g / 10min at 2.16kg and 190°C, preferably 45-60g / 10min. 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.

[0044] 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:

[0045] (1) plasticizing a polyolefin elastomer and ethylene propylene diene monomer rubber to obtain a plasticized rubber;

[0046] (2) mixing ethylene-vinyl acetate copolymer, a modifier, white oil and the plasticized rubber; discharging the mixture to obtain a rubber masterbatch for tire tread processing;

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

[0048] In the present invention, the above method is adopted to firstly plasticize the polyolefin elastomer and EPDM rubber to obtain a plasticized rubber, and then the ethylene-vinyl acetate copolymer, the modifier, the white oil and the plasticized rubber are mixed, which can significantly improve the compatibility and dispersibility of the maleic acid monomer in the high-viscosity rubber matrix, thereby better improving the strength of the tire tread rubber, reducing its heat generation, improving the anti-skid property, reducing the rolling resistance, and improving the processing safety and vulcanization efficiency.

[0049] 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.

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

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

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

[0053] (1) Heat the internal mixer to 60-80°C and rotate at 60-80 rpm, put the matrix materials POE and EPDM into the internal mixer for plasticization for 0.5-2 min;

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

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

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

[0060] (1) mixing the base rubber and the rubber processing modified masterbatch to obtain a mixed rubber blank;

[0061] (2) vulcanizing the mixed rubber blank to obtain a tire tread rubber;

[0062] Wherein, the rubber processing modified masterbatch is the rubber processing modified masterbatch for tire tread mentioned above.

[0063] 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.

[0064] 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.

[0065] 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.

[0066] In 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.

[0067] In 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.

[0068] In 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.

[0069] In 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.

[0070] In 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.

[0071] In 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).

[0072] In 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.

[0073] A seventh aspect of the present invention provides a vulcanized rubber prepared by the aforementioned preparation method.

[0074] An eighth aspect of the present invention provides a 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 examples.

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

[0077] 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.

[0078] The amounts of components in the following examples and comparative examples are all parts by weight, and each part by weight represents 1 g.

[0079] Table 1

[0080] 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 3 Rotorless Rheometer MDR 3000basic Montech, Germany

[0081] Table 2

[0082]

[0083] Table 3

[0084]

[0085]

[0086] The preparation example is used to illustrate the prepared rubber processing modified masterbatch.

[0087] Preparation Example 1

[0088] The internal mixer was heated to 60°C and the rotation speed was 80 rpm. 10 parts by weight of EPDM (ethylene content 60%, ENB content 10%, Mooney 70) and 3 parts by weight of POE (Mooney viscosity 25, melt index 1 g / 10 min) were put into the internal mixer and plasticized for 0.5 min. Then, 2 parts by weight of EVA (VA content 40%, melt index 60 g / 10 min), 80 parts by weight of maleic anhydride and 5 parts by weight of white oil were added into the internal mixer and mixed with the plasticized rubber for 6 min. The material was discharged to obtain rubber processing modified masterbatch X1 for tire tread.

[0089] Preparation Example 2

[0090] The internal mixer was heated to 70°C and the rotation speed was 70 rpm. 10 parts by weight of EPDM (ethylene content 50%, ENB content 8%, Mooney 55) and 2 parts by weight of POE (Mooney viscosity 10, melt index 3 g / 10 min) were put into the internal mixer and plasticized for 1 min. Then 3 parts by weight of EVA (VA content 30%, melt index 40 g / 10 min), 80 parts by weight of maleic acid and 5 parts by weight of white oil were added into the internal mixer and mixed with the plasticized rubber for 4 min. The material was discharged to obtain rubber processing modified masterbatch X2 for tire tread.

[0091] Preparation Example 3

[0092] The internal mixer was heated to 80°C and the rotation speed was 60rpm. 10 parts by weight of EPDM (ethylene content 55%, ENB content 5%, Mooney 65) and 3 parts by weight of POE (Mooney viscosity 19, melt index 1.3g / 10min) were put into the internal mixer and plasticized for 2 minutes. Then, 2 parts by weight of EVA (VA content 33%, melt index 45g / 10min), 80 parts by weight of diethyl maleate and 5 parts by weight of white oil were added to the internal mixer and mixed with the plasticized rubber for 2 minutes. The material was discharged to obtain rubber processing modified masterbatch X3 for tire tread.

[0093] Comparative Preparation Example 4

[0094] The internal mixer was heated to 80°C and the rotation speed was 60 rpm. 10 parts by weight of EPDM (ethylene content 59%, ENB content 1.5%, Mooney 38) and 3 parts by weight of POE (Mooney viscosity 37, melt index 0.5 g / 10 min) were put into the internal mixer and plasticized for 2 minutes. Then, 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 were added to the internal mixer and mixed with the plasticized rubber for 2 minutes. The material was discharged to obtain rubber processing modified masterbatch X4 for tire tread.

[0095] Comparative Preparation Example 5

[0096] The rubber processing modified masterbatch was prepared in the same manner as in Preparation Example 1, except that the amounts of the modifier, base 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] As a result, the rubber modified masterbatch X5 for tire tread was obtained.

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

[0100] Example 1

[0101] 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 2 parts by weight of 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.

[0102] The performance of the 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 (product of Yanshan Petrochemical, SSBR2636) and 40 parts by weight of cis-1,4-butadiene rubber (product of Yanshan Petrochemical, BR9000) and 0.5 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.

[0105] The performance of the 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 (product of Yanshan Petrochemical, SSBR2636) and 30 parts by weight of cis-1,4-butadiene rubber (product of Yanshan Petrochemical, BR9000) and 1 part 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.

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

[0109] Example 4

[0110] The rubber was prepared according to the method of Example 1, except that the rubber processing modified masterbatch was added in an amount of 4 parts by weight of the rubber processing modified masterbatch X1 prepared in Preparation Example 1, to obtain a vulcanized rubber sample S4.

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

[0112] Comparative Example 1

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

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

[0115] Comparative Example 2

[0116] 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.

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

[0118] Comparative Example 3

[0119] 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 the vulcanized rubber DS3 was obtained after vulcanization.

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

[0121] Comparative Example 4

[0122] The rubber was prepared according to the method of Example 1, except that the rubber processing modified masterbatch was added in an amount of 2 parts by weight of X4 prepared in Comparative Preparation Example 4, to obtain a vulcanized rubber sample DS4.

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

[0124] Comparative Example 5

[0125] The rubber was prepared according to the method of Example 1, except that the same weight portion of X5 prepared in Comparative Preparation Example 5 was added to the rubber processing modified masterbatch to obtain a vulcanized rubber sample DS5.

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

[0127] Table 4

[0128]

[0129]

[0130] Table 4 (continued)

[0131]

[0132] 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.

[0133] Further, by comparing the data of Examples 1-4 with Comparative Examples 1-5, it can be seen that the vulcanized rubber DS1-DS5 prepared in Comparative Examples 1-5 is obviously inferior to the vulcanized rubber S1-S4 in terms of performance. For example, the tear 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 wear of DS1-DS5 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, and 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-DS5. From the perspective 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 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.

[0135] 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 is composed of a modifier, a base material and white oil, wherein 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; Wherein, the matrix material comprises polyolefin elastomer, ethylene propylene diene monomer rubber and ethylene-vinyl acetate copolymer.

2. The rubber processing modified masterbatch according to claim 1, wherein: The content of the modifier is 78-80 parts by weight, the content of the base material is 15-16 parts by weight, and the content of the white oil is 5-6 parts by weight; Preferably, the weight ratio of the polyolefin elastomer, EPDM rubber and ethylene-vinyl acetate copolymer is (2-3):10:(2-3).

3. The rubber processing modified masterbatch according to claim 1 or 2, wherein: 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.

4. The rubber processing modified masterbatch according to any one of claims 1 to 3, wherein: The Mooney viscosity of the polyolefin elastomer is 10-25, and the melt index is 1-3 g / 10 min at 2.16 kg and 190° C.; And / or, the vinyl content of the EPDM rubber is 50-60%, the content of the third monomer ethylidene norbornene structural unit is 5-10%, and the Mooney viscosity is 55-70; And / or, 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.

5. A method for preparing a rubber masterbatch for tire tread, characterized in that: The preparation method comprises the following steps: (1) plasticizing a polyolefin elastomer and ethylene propylene diene monomer rubber to obtain a plasticized rubber; (2) mixing ethylene-vinyl acetate copolymer, a modifier, white oil and the plasticized rubber; discharging the mixture to obtain a rubber masterbatch for tire tread processing; The amount of the modifier is 76-81 parts by weight, the total amount of the polyolefin elastomer, EPDM rubber and ethylene-vinyl acetate copolymer is 14-17 parts by weight, and the amount of the white oil is 3-7 parts by weight.

6. The preparation method according to claim 5, wherein: The amount of the modifier is 78-80 parts by weight, the amount of the base material is 15-16 parts by weight, and the amount of the white oil is 5-6 parts by weight; Preferably, the weight ratio of the polyolefin elastomer, EPDM rubber and ethylene-vinyl acetate copolymer is (2-3):10:(2-3); Preferably, 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; Preferably, the Mooney viscosity of the polyolefin elastomer is 10-25, and the melt index is 1-3 g / 10 min at 2.16 kg and 190° C.; And / or, the vinyl content of the EPDM rubber is 50-60%, the content of the third monomer ethylidene norbornene structural unit is 5-10%, and the Mooney viscosity is 55-70; And / or, 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.

7. The preparation method according to claim 5, wherein: In step (1), the conditions for plasticizing include: temperature of 60-80°C, rotation speed of 60-80 rpm, and time of 0.5-2 min; And / or, in step (2), the mixing conditions include: temperature of 60-80° C., and mixing time of 2-6 min.

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 0.2-5 parts by weight; preferably, relative to 100 parts by weight of the base rubber, the amount of the rubber processing modified masterbatch is 0.5-2 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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