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

Abstract

The invention relates to the field of rubber, and discloses a rubber processing modified master batch, a preparation method and application thereof, a rubber composition, vulcanized rubber and a preparation method thereof, the rubber processing modified master batch comprises a methacrylic acid series monomer as shown in a formula (1), dicumyl peroxide, trimethylolpropane triacrylate, styrene butadiene rubber and white carbon black; r1 is C1-C4 alkyl or a structure as shown in a formula (2); wherein n is an integer from 1 to 2; relative to 100 parts by weight of butadiene styrene rubber, the content of the methacrylic acid series monomer is 75-400 parts by weight, the content of the dicumyl peroxide is 0.5-13 parts by weight, the content of the trimethylolpropane triacrylate is 37-200 parts by weight, and the content of the white carbon black is 50-300 parts by weight. According to the rubber processing modified masterbatch, the white carbon black has better dispersity in a rubber matrix, and the interaction between the white carbon black and the rubber matrix is stronger.

Description

Technical Field

[0001] This invention relates to the field of rubber, specifically to a rubber processing modified masterbatch and its preparation method and application, rubber compositions, vulcanized rubber and its preparation method. Background Technology

[0002] The comfort of the sole directly affects the overall quality of the shoe. Many international brands produce soles that give people a comfortable, high-end, and fashionable feeling.

[0003] In existing technologies, shoe soles are mostly made of materials such as PVC, TPR, and TPU. These materials are not as comfortable or slip-resistant as rubber soles.

[0004] In existing technologies, silica is widely used as a primary reinforcing filler in footwear. It not only provides excellent abrasion resistance, slip resistance, and adhesion to the upper, but also enables the production of colored rubber soles. It is widely used in both light-colored and colored soles (including outsoles, midsoles, and welts). Therefore, the footwear industry has always been a major user of silica.

[0005] Due to the strong surface polarity of silica, its dispersion in rubber matrices becomes exceptionally difficult, thus limiting its application to some extent.

[0006] CN105440341A discloses an anti-slip shoe sole material. This invention discloses the application of silica in shoe sole materials. In this invention, silica is improved by adding silane coupling agents. The silane coupling agents used are sulfur-containing compounds. During the high-temperature mixing process, the process control requirements are high. If the control is not properly controlled, it may cause scorching, which will affect the overall performance of the composite material.

[0007] CN104311918A discloses a composite material wear-resistant shoe sole. This invention utilizes silica grafted with toluene diisocyanate to improve the dispersibility of silica in a rubber matrix. Although the silica modification process can change the polarity of silica and increase the contact force with rubber, the process is relatively complex and consumes a lot of energy and materials.

[0008] The existing technology described above cannot fully meet the requirements of high strength, abrasion resistance, and good resilience for white shoe soles containing silica formulations. Therefore, it is necessary to provide a rubber composition with improved performance. Summary of the Invention

[0009] The purpose of this invention is to overcome the problems of low strength, poor abrasion resistance, and poor resilience of white shoe soles containing silica formulations. It provides a rubber processing modified masterbatch, its preparation method and application, a rubber composition, vulcanized rubber, and its preparation method. This rubber processing modified masterbatch enables better dispersion of silica in the rubber matrix, and strengthens the interaction between silica and the rubber matrix, thereby resulting in vulcanized rubber with high strength, high abrasion resistance, high resilience, and strong flexural strength.

[0010] To achieve the above objectives, the first aspect of the present invention provides a rubber processing modified masterbatch, wherein the rubber processing modified masterbatch comprises methacrylate monomers represented by formula (1), dicumyl peroxide, trimethylolpropane triacrylate, styrene-butadiene rubber, and silica.

[0011]

[0012] Wherein, R1 is a C1-C4 alkyl group or the structure shown in formula (2); where, n is an integer from 1 to 2;

[0013] Relative to 100 parts by weight of styrene-butadiene rubber, the content of the methacrylic acid monomer is 75-400 parts by weight, the content of dicumyl peroxide is 0.5-13 parts by weight, the content of trimethylolpropane triacrylate is 37-200 parts by weight, and the content of silica is 50-300 parts by weight.

[0014] A second aspect of the present invention provides a method for preparing the above-mentioned rubber processing modified masterbatch, wherein the method includes:

[0015] (1) Plasticize styrene-butadiene rubber to obtain plasticized rubber;

[0016] (2) The methacrylic acid monomer, dicumyl peroxide, trimethylolpropane triacrylate, silica and plasticized rubber are mixed to obtain rubber processing modified masterbatch.

[0017] A third aspect of the present invention provides the application of the above-mentioned rubber processing modified masterbatch in a rubber composition.

[0018] A fourth aspect of the present invention provides a rubber composition comprising a base rubber and the above-mentioned rubber processing modified masterbatch;

[0019] The amount of the rubber processing modification masterbatch used is 2-10 parts by weight relative to 100 parts by weight of the base rubber.

[0020] The fifth aspect of the present invention provides a method for preparing vulcanized rubber, wherein the method comprises: mixing the components of the above-mentioned rubber composition to obtain a mixed rubber preform, and vulcanizing the mixed rubber preform.

[0021] The sixth aspect of the present invention provides a vulcanized rubber prepared by the above-described preparation method.

[0022] Through the above technical solutions, the rubber processing modified masterbatch and its preparation method and application, rubber composition, vulcanized rubber and its preparation method provided by the present invention have the following beneficial effects.

[0023] The rubber processing modified masterbatch of the present invention comprises methacrylic acid monomers as shown in formula (1), dicumyl peroxide, trimethylolpropane triacrylate, styrene-butadiene rubber, and silica. When each component is used in a specific range, the obtained rubber processing modified masterbatch can make silica have better dispersibility in the rubber matrix and stronger interaction between silica and the rubber matrix, thereby making the vulcanized rubber further produced have the characteristics of high strength, high wear resistance, high resilience, and strong flexural resistance. Detailed Implementation

[0024] 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.

[0025] The first aspect of the present invention provides a rubber processing modified masterbatch, wherein the rubber processing modified masterbatch comprises methacrylate monomers represented by formula (1), dicumyl peroxide, trimethylolpropane triacrylate, styrene-butadiene rubber and silica;

[0026]

[0027] Wherein, R1 is a C1-C4 alkyl group or the structure shown in formula (2); where, n is an integer from 1 to 2;

[0028] Relative to 100 parts by weight of styrene-butadiene rubber, the content of the methacrylic acid monomer is 75-400 parts by weight, the content of dicumyl peroxide is 0.5-13 parts by weight, the content of trimethylolpropane triacrylate is 37-200 parts by weight, and the content of silica is 50-300 parts by weight.

[0029] In this invention, the rubber processing modified masterbatch includes methacrylic acid monomers as shown in formula (1), dicumyl peroxide, trimethylolpropane triacrylate, styrene-butadiene rubber, and silica. When each component is used in a specific range, the obtained rubber processing modified masterbatch can make silica have better dispersibility in the rubber matrix and stronger interaction between silica and the rubber matrix, thereby making the vulcanized rubber further produced have the characteristics of high strength, high wear resistance, high resilience, and strong flexural resistance.

[0030] In this invention, in formula (2), "*" refers to the chemical bond connected to formula (1).

[0031] Furthermore, relative to 100 parts by weight of styrene-butadiene rubber, the content of the methacrylic acid monomer is 133-250 parts by weight, the content of dicumyl peroxide is 1.5-5 parts by weight, the content of trimethylolpropane triacrylate is 66-125 parts by weight, and the content of silica is 100-200 parts by weight.

[0032] According to the present invention, the methacrylate monomer is selected from at least one of glycidyl methacrylate, methyl methacrylate and butyl methacrylate.

[0033] According to the present invention, the styrene-butadiene rubber contains 10-25 wt% styrene and 40-70% vinyl content.

[0034] Furthermore, the styrene-butadiene rubber contains 18-25 wt% styrene and 55-65 wt% vinyl content.

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

[0036] Furthermore, the Mooney viscosity ML (100℃, 1+4min) of the styrene-butadiene rubber is 58-73.

[0037] According to the present invention, the nitrogen adsorption specific surface area of ​​the silica is 100-200 m². 2 / g.

[0038] According to the present invention, the average particle size of the silica is 10-100 nm.

[0039] In this invention, when the nitrogen adsorption specific surface area and / or average particle size of silica meet the above-mentioned range, silica can support a high content of methacrylic acid monomers, which not only improves the efficiency of rubber processing modification masterbatch, but also allows silica to have better dispersibility in the rubber matrix. The interaction between silica and the rubber matrix is ​​stronger, thereby enabling the further vulcanized rubber to have the characteristics of high strength, high wear resistance, high resilience, and strong flexural resistance.

[0040] Furthermore, the nitrogen adsorption specific surface area of ​​the precipitated silica is 130-180 m². 2 / g.

[0041] Furthermore, the average particle size of the silica is 30-80 nm.

[0042] A second aspect of the present invention provides a method for preparing the above-mentioned rubber processing modified masterbatch, wherein the method includes:

[0043] (1) Plasticize styrene-butadiene rubber to obtain plasticized rubber;

[0044] (2) The methacrylic acid monomer, dicumyl peroxide, trimethylolpropane triacrylate, silica and plasticized rubber are mixed to obtain rubber processing modified masterbatch.

[0045] According to the present invention, in step (1), the plasticizing temperature is 50-80℃, the plasticizing speed is 30-60rpm, and the plasticizing time is 1-2min.

[0046] According to the present invention, in step (2), the mixing temperature is 60-100℃ and the mixing time is 3-6 min.

[0047] A third aspect of the present invention provides the application of the above-mentioned rubber processing modified masterbatch in a rubber composition.

[0048] Furthermore, the application of the rubber processing modified masterbatch in rubber compositions for footwear materials.

[0049] In this invention, when the rubber processing modified masterbatch provided in the first aspect of this invention is used in a rubber composition for footwear materials, the abrasion resistance, durability and comfort of the footwear materials can be improved.

[0050] A fourth aspect of the present invention provides a rubber composition comprising a base rubber and the above-mentioned rubber processing modified masterbatch;

[0051] The amount of the rubber processing modification masterbatch used is 2-10 parts by weight relative to 100 parts by weight of the base rubber.

[0052] Furthermore, the amount of the rubber processing modification masterbatch used is 3-6 parts by weight relative to 100 parts by weight of the base rubber.

[0053] In this invention, the base rubber can be any conventional rubber used in shoe materials that requires vulcanization, including but not limited to: natural rubber and / or synthetic rubber, wherein the synthetic rubber can include but not limited to: butadiene rubber and / or styrene-butadiene rubber.

[0054] In this invention, the rubber composition further includes conventional additive components in the art, such as fillers (fumed silica and / or titanium dioxide), silane coupling agents, activators, softeners, antioxidants, accelerators, vulcanizing agents, etc.

[0055] In this invention, the silica can be any existing precipitated silica that can be used for 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.

[0056] In this invention, the titanium dioxide can be any existing titanium dioxide that can be used as a rubber additive, and the TiO2 content is ≥90%; specifically, the content of the titanium dioxide can be 0-50 parts by weight relative to 100 parts by weight of base rubber.

[0057] In this invention, the silane coupling agent can be silane coupling agent Si69. Specifically, the content of the silane coupling agent can be 0.2-10 parts by weight relative to 100 parts by weight of the base rubber.

[0058] 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 2-15 parts by weight relative to 100 parts by weight of natural rubber and synthetic rubber.

[0059] 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 has a weight-average molecular weight of 3000-5000, which gives the composite material good processability and physical and mechanical properties. The naphthenic oil can be, for example, ASTM 103#, and the polyethylene glycol can be, for example, polyethylene glycol PEG4000. Specifically, the content of the softener relative to 100 parts by weight of the base rubber can be 5-20 parts by weight.

[0060] In this invention, the antioxidant is a phenolic antioxidant. For example, the antioxidant is antioxidant 264. Specifically, the content of the antioxidant relative to 100 parts by weight of the base rubber can be 1-8 parts by weight.

[0061] In this invention, the accelerator is at least one selected from sulfenamide accelerators, thiazole accelerators, thiuram accelerators, and guanidine accelerators. Preferably, the accelerator can be tetramethylthiuram disulfide (TMTD) and dibenzothiazole disulfide (accelerator DM). Specifically, the content of the accelerator can be 2-6 parts by weight relative to 100 parts by weight of base rubber.

[0062] In this invention, 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. Specifically, the content of the vulcanizing agent can be 1-5 parts by weight relative to 100 parts by weight of the base rubber.

[0063] The fifth aspect of the present invention provides a method for preparing vulcanized rubber, wherein the method comprises: mixing the components of the above-mentioned rubber composition to obtain a mixed rubber preform, and vulcanizing the mixed rubber preform.

[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, titanium dioxide, silane coupling agent, 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, a pressure of 10-20 MPa, and a time of 30-40 minutes to obtain vulcanized rubber.

[0065] The sixth aspect of the present invention provides a vulcanized rubber prepared by the above-described preparation method.

[0066] The present invention will be described in detail below through embodiments.

[0067] The equipment used for preparing vulcanized rubber in the following examples and comparative examples is shown in Table 1.

[0068] 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.

[0069] In the following examples and comparative examples, the amounts of components are all parts by weight, with each part by weight representing 1g.

[0070] Table 1

[0071] Serial Number Equipment Name model Manufacturer 1 Internal mixer BR1600 Farrell Company, USA 2 Flat vulcanizing machine XLB-D400*400*2 Shanghai No.1 Rubber Machinery Factory

[0072] Table 2

[0073]

[0074] Table 3

[0075]

[0076] Preparation Examples 1-4 illustrate the rubber processing modified masterbatch and its preparation method of the present invention.

[0077] Preparation Example 1

[0078] Set the internal mixer to 50°C and 30 rpm. Add 100 parts by weight of SSBR (styrene content 10 wt%, vinyl content 40 wt%, Mooney viscosity 55) to the internal mixer and masticate for 1 min. Then add 167 parts by weight of glycidyl methacrylate, 3 parts by weight of dicumyl peroxide, 83 parts by weight of trimethylolpropane triacrylate, and 133 parts by weight of silica (1165 MPa, adsorption specific surface area 165 m²). 2 / g (average particle size of 65nm) is added to an internal mixer and mixed with the plasticized matrix. The mixture is then mixed at 80℃ for 3 minutes. The resulting material is rubber processing modified masterbatch X1.

[0079] Preparation Example 2

[0080] Set the internal mixer to 50°C and 30 rpm. Add 100 parts by weight of SSBR (20 wt% styrene, 70 wt% vinyl, Mooney viscosity 75) to the internal mixer and masticate for 1 min. Then add 133 parts by weight of methyl methacrylate, 1.5 parts by weight of dicumyl peroxide, 92 parts by weight of trimethylolpropane triacrylate, and 140 parts by weight of silica (grade 1165MP, adsorption specific surface area 165 m²). 2 / g (average particle size of 65nm) is added to a mixer and mixed with the plasticized matrix. The mixture is then mixed at 80℃ for 3 minutes. The resulting material is rubber processing modified masterbatch X2.

[0081] Preparation Example 3

[0082] Set the internal mixer to 50°C and 30 rpm. Add 100 parts by weight of SSBR (25 wt% styrene, 55 wt% vinyl content, Mooney viscosity 65) to the internal mixer and masticate for 1 min. Then add 125 parts by weight of glycidyl methacrylate, 5 parts by weight of dicumyl peroxide, 100 parts by weight of trimethylolpropane triacrylate, and 150 parts by weight of silica (grade 1165MP, adsorption specific surface area 165 m²). 2 / g (average particle size of 65nm) is added to a mixer and mixed with the plasticized matrix. The mixture is then mixed at 80℃ for 3 minutes. The resulting material is rubber processing modified masterbatch X3.

[0083] Preparation Example 4

[0084] Set the internal mixer to 50°C and 30 rpm. Add 100 parts by weight of SSBR (styrene content 25 wt%, vinyl content 55 wt%, Mooney viscosity 65) to the internal mixer and plasticize for 1 min. Then add 75 parts by weight of glycidyl methacrylate, 5 parts by weight of dicumyl peroxide, 57 parts by weight of trimethylolpropane triacrylate, and 90 parts by weight of silica (grade 1165MP, adsorption specific surface area 165 m²). 2 / g (average particle size of 65nm) is added to a mixer and mixed with the plasticized matrix. The mixture is then mixed at 80℃ for 3 minutes. The resulting material is rubber processing modified masterbatch X4.

[0085] Comparative Preparation Example 1

[0086] Set the internal mixer to 50°C and 30 rpm. Add 100 parts by weight of SSBR (styrene content 25 wt%, vinyl content 55 wt%, Mooney viscosity 65) to the internal mixer and masticate for 1 min. Then add 267 parts by weight of glycidyl methacrylate, 27 parts by weight of dicumyl peroxide, 267 parts by weight of trimethylolpropane triacrylate, and 333 parts by weight of silica (grade 1165MP, adsorption specific surface area 165 m²). 2 / g (average particle size of 65nm) is added to a mixer and mixed with the plasticized matrix. The mixture is then mixed at 80℃ for 3 minutes. The resulting material is rubber processing modified masterbatch DX1.

[0087] Comparative Preparation Example 2

[0088] Rubber processing modified masterbatch was prepared according to the method of Preparation Example 1, except that trimethylolpropane triacrylate was replaced with an equal mass of styrene; the rubber processing modified masterbatch DX2 was obtained by discharge.

[0089] Examples 1-7 illustrate the rubber processing method provided by the present invention.

[0090] Example 1

[0091] 20 parts by weight of solution-polymerized styrene-butadiene rubber (Yanshan Petrochemical product, SSBR2636) and 80 parts by weight of butadiene rubber (Yanshan Petrochemical product, BR9000) and 6 parts by weight of rubber processing modification masterbatch X1 were added to a mixer and mixed at 70°C for 3 minutes. Then, 40 parts by weight of silica (Rhodia, France, 165GR), 20 parts by weight of titanium dioxide (Weifang Hengze Chemical Co., Ltd., TiO2 content % 96%), 4 parts by weight of Si69 (Huachen New Materials Co., Ltd.), 10 parts by weight of zinc oxide (Weifang Hengfeng Chemical Co., Ltd.), 4 parts by weight of stearic acid (Weifang Hengfeng Chemical Co., Ltd.), 2 parts by weight of polyethylene glycol PEG4000 (Dow Chemical Company, USA, industrial grade), and 10 parts by weight of naphthenic oil (Shandong Taichang Petrochemical) were added. The following ingredients were added to a mixing mill: ASTM 103# naphthenic oil, 4 parts by weight of microcrystalline wax (Shanghai Qiju Chemical Co., Ltd.), and 1 part by weight of antioxidant (Jiangsu Shengao Chemical Technology Co., Ltd., 264). The mixture was mixed for 7 minutes at an initial mixing temperature of 80℃. After mixing, the mixture was allowed to stand at room temperature for 5 hours. Then, 5 parts by weight of sulfur (Weifang Zhongheng Chemical Co., Ltd.), 1 part by weight of DM (2,2'-dithiodibenzothiazole), and 1 part by weight of TMTD (tetramethylthiuram disulfide) were added to a masterbatch. The mixture was mixed at 60℃ for 5 minutes to obtain a compounded rubber preform. The obtained compounded rubber preform was then subjected to flat vulcanization at a vulcanization temperature of 160℃, a vulcanization pressure of 10MPa, and a vulcanization time of 40min to obtain vulcanized rubber sample S1.

[0092] The performance of vulcanized rubber sample S1 was tested, and the results are shown in Table 4.

[0093] Example 2

[0094] 20 parts by weight of solution-polymerized styrene-butadiene rubber (Yanshan Petrochemical product, SSBR2636) and 80 parts by weight of butadiene rubber (Yanshan Petrochemical product, BR9000) and 3 parts by weight of rubber processing modification masterbatch X1 were added to a mixer and mixed at 70°C for 3 minutes. Then, 40 parts by weight of silica (Rhodia, France, 165GR), 20 parts by weight of titanium dioxide (Weifang Hengze Chemical Co., Ltd., TiO2 content % 96%), 4 parts by weight of Si69 (Huachen New Materials Co., Ltd.), 10 parts by weight of zinc oxide (Weifang Hengfeng Chemical Co., Ltd.), 4 parts by weight of stearic acid (Weifang Hengfeng Chemical Co., Ltd.), 2 parts by weight of polyethylene glycol PEG4000 (Dow Chemical Company, USA, industrial grade), and 10 parts by weight of naphthenic oil (Shandong Taichang Stone) were added. The following ingredients were added to a mixing mill: ASTM 103# naphthenic oil, 4 parts by weight of microcrystalline wax (Shanghai Qiju Chemical Co., Ltd.), and 1 part by weight of antioxidant (Jiangsu Shengao Chemical Technology Co., Ltd., 264). The mixture was mixed for 7 minutes at an initial mixing temperature of 80℃. After mixing, the mixture was allowed to stand at room temperature for 5 hours. Then, 5 parts by weight of sulfur (Weifang Zhongheng Chemical Co., Ltd.), 1 part by weight of DM (2,2'-thiodibenzothiazole), and 1 part by weight of TMTD (tetramethylthiuram disulfide) were added to a masterbatch. The mixture was mixed at 60℃ for 5 minutes to obtain a compounded rubber preform. The obtained compounded rubber preform was then subjected to flat vulcanization at a vulcanization temperature of 160℃, a vulcanization pressure of 10MPa, and a vulcanization time of 40 minutes to obtain vulcanized rubber sample S2.

[0095] The performance of vulcanized rubber sample S2 was tested, and the results are shown in Table 4.

[0096] Example 3

[0097] 20 parts by weight of solution-polymerized styrene-butadiene rubber (Yanshan Petrochemical product, SSBR2636) and 80 parts by weight of butadiene rubber (Yanshan Petrochemical product, BR9000) were added to a mixing mill along with 4.5 parts by weight of rubber processing modification masterbatch X1 and mixed at 70°C for 3 minutes. Then, 40 parts by weight of silica (Rhodia, France, 165GR), 20 parts by weight of titanium dioxide (Weifang Hengze Chemical Co., Ltd., TiO2 content % 96%), 4 parts by weight of Si69 (Huachen New Materials Co., Ltd.), 10 parts by weight of zinc oxide (Weifang Hengfeng Chemical Co., Ltd.), 4 parts by weight of stearic acid (Weifang Hengfeng Chemical Co., Ltd.), 2 parts by weight of polyethylene glycol PEG4000 (Dow Chemical Company, USA, industrial grade), and 10 parts by weight of naphthenic oil (Shandong Taichang Petrochemical Co., Ltd.) were added. The following ingredients were added to a mixing mill: ASTM 103# naphthenic oil, 4 parts by weight of microcrystalline wax (Shanghai Qiju Chemical Co., Ltd.), and 1 part by weight of antioxidant (Jiangsu Shengao Chemical Technology Co., Ltd., 264). The mixture was mixed for 7 minutes at an initial mixing temperature of 80℃. After mixing, the mixture was allowed to stand at room temperature for 5 hours. Then, 5 parts by weight of sulfur (Weifang Zhongheng Chemical Co., Ltd.), 1 part by weight of DM (2,2'-dithiodibenzothiazole), and 1 part by weight of TMTD (tetramethylthiuram disulfide) were added to a masterbatch. The mixture was mixed at 60℃ for 5 minutes to obtain a compounded rubber preform. The obtained compounded rubber preform was then subjected to flat vulcanization at a vulcanization temperature of 160℃, a vulcanization pressure of 10MPa, and a vulcanization time of 40 minutes to obtain vulcanized rubber sample S3.

[0098] The performance of vulcanized rubber sample S3 was tested, and the results are shown in Table 4.

[0099] Example 4

[0100] 20 parts by weight of solution-polymerized styrene-butadiene rubber (Yanshan Petrochemical product, SSBR2636) and 80 parts by weight of butadiene rubber (Yanshan Petrochemical product, BR9000) and 10 parts by weight of rubber processing modification masterbatch X1 were added to a mixer and mixed at 70°C for 3 minutes. Then, 40 parts by weight of silica (Rhodia, France, 165GR), 20 parts by weight of titanium dioxide (Weifang Hengze Chemical Co., Ltd., TiO2 content % 96%), 4 parts by weight of Si69 (Huachen New Materials Co., Ltd.), 10 parts by weight of zinc oxide (Weifang Hengfeng Chemical Co., Ltd.), 4 parts by weight of stearic acid (Weifang Hengfeng Chemical Co., Ltd.), 2 parts by weight of polyethylene glycol PEG4000 (Dow Chemical Company, USA, industrial grade), and 10 parts by weight of naphthenic oil (Shandong Taichang Stone) were added. The following ingredients were added to a mixing mill: ASTM 103# naphthenic oil, 4 parts by weight of microcrystalline wax (Shanghai Qiju Chemical Co., Ltd.), and 1 part by weight of antioxidant (Jiangsu Shengao Chemical Technology Co., Ltd., 264). The mixture was mixed for 7 minutes at an initial mixing temperature of 80℃. After mixing, the mixture was allowed to stand at room temperature for 5 hours. Then, 5 parts by weight of sulfur (Weifang Zhongheng Chemical Co., Ltd.), 1 part by weight of DM (2,2'-dithiodibenzothiazole), and 1 part by weight of TMTD (tetramethylthiuram disulfide) were added to a masterbatch. The mixture was mixed at 60℃ for 5 minutes to obtain a compounded rubber preform. The obtained compounded rubber preform was then subjected to flat vulcanization at a vulcanization temperature of 160℃, a vulcanization pressure of 10MPa, and a vulcanization time of 40 minutes to obtain vulcanized rubber sample S4.

[0101] The performance of vulcanized rubber sample S4 was tested, and the results are shown in Table 4.

[0102] Example 5

[0103] Rubber was prepared according to the method of Example 1, except that the amount of rubber processing modification masterbatch added was 6 parts by weight X2, and vulcanized rubber sample S5 was obtained.

[0104] The performance of vulcanized rubber sample S5 was tested, and the results are shown in Table 4.

[0105] Example 6

[0106] Rubber was prepared according to the method of Example 1, except that the amount of rubber processing modification masterbatch added was 6 parts by weight of X3, and vulcanized rubber sample S6 was obtained.

[0107] The performance of vulcanized rubber sample S6 was tested, and the results are shown in Table 4.

[0108] Example 7

[0109] Rubber was prepared according to the method of Example 1, except that the amount of rubber processing modification masterbatch added was 6 parts by weight X4, and vulcanized rubber sample S7 was obtained.

[0110] The performance of vulcanized rubber sample S7 was tested, and the results are shown in Table 4.

[0111] Comparative Example 1

[0112] Rubber was processed according to the method of Example 1, except that the amount of rubber processing modified masterbatch X1 added was 15 parts by weight, and vulcanized rubber sample DS1 was obtained.

[0113] The performance of vulcanized rubber sample DS1 was tested, and the results are shown in Table 4.

[0114] Comparative Example 2

[0115] 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 methacrylate monomers, dicumyl peroxide, trimethylolpropane triacrylate, silica, and SSBR, and vulcanized to obtain vulcanized rubber DS2.

[0116] The performance of vulcanized rubber sample DS2 was tested, and the results are shown in Table 4.

[0117] Comparative Example 3

[0118] Rubber was prepared according to the method of Example 1, except that the amount of rubber processing modification masterbatch added was 6 parts by weight of DX1, and vulcanized rubber sample DS3 was obtained.

[0119] The performance of vulcanized rubber sample DS3 was tested, and the results are shown in Table 4.

[0120] Comparative Example 4

[0121] Rubber is processed according to the method of Example 1, except that rubber processing modifier masterbatch is not added during the rubber processing, and vulcanized rubber DS4 is obtained after vulcanization.

[0122] The performance of the vulcanized rubber sample DS4 was tested, and the results are shown in Table 4.

[0123] Comparative Example 5

[0124] Rubber was prepared according to the method of Example 1, except that the amount of rubber processing modification masterbatch added was 6 parts by weight of DX2, and vulcanized rubber sample DS5 was obtained.

[0125] The performance of the vulcanized rubber sample DS5 was tested, and the results are shown in Table 4.

[0126] Table 4

[0127] Sample number S1 S2 S3 S4 S5 S6 S7 Hardness (°) 73 74 72 75 73 76 78 Tensile strength (MPa) 16 16.2 16.5 15.1 16.2 14.9 14.5 Tear strength (kN / m) 45 48 47 42 46 41 39 <![CDATA[DIN Wear (mm 3 )]]> 60 61 59 68 59 70 72 Rebound value (%) 38.2 37.9 38.0 35.4 38.3 37.0 36.7 Compression temperature rise (°C) 16.5 16.7 16.3 17.1 16.4 17.3 17.8

[0128] Continued from Table 4

[0129] Sample number DS1 DS2 DS3 DS4 DS5 Hardness (°) 78 77 80 83 79 Tensile strength (MPa) 12 12.5 11.3 10.2 12.3 Tear strength (kN / m) 32 35 30 23 34 <![CDATA[DIN Wear (mm 3 )]]> 81 84 92 99 88 Rebound value (%) 26.3 29.1 30.2 23.9 30.5 Compression temperature rise (°C) 20.3 20.5 22.4 25.8 21.3

[0130] 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 and enhance the interaction between silica and the rubber matrix, thereby enabling the further vulcanized rubber to have high strength, high wear resistance, and high resilience. Furthermore, the vulcanized rubber of the present invention has a lower compression temperature, indicating that it has strong flexural resistance.

[0133] Furthermore, comparing the data from Example 1 and Comparative Example 2, it can be seen that when the same rubber composition formulation as in Example 1 is used, but the rubber processing modifier is added in a different manner, the vulcanized rubber DS2 prepared further is significantly inferior to vulcanized rubber S1 in terms of performance. S1 has higher strength, abrasion resistance, resilience and flexural strength.

[0134] Since the rubber processing modification masterbatch and preparation method provided by the present invention can make the obtained vulcanized rubber have better performance, when the vulcanized rubber of the present invention is applied to shoe materials, the abrasion resistance, durability and comfort of the shoe materials can be improved.

[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 rubber processing modifying masterbatch, characterized by, The rubber processing modification masterbatch comprises a methyl methacrylate monomer shown in formula (1), dicumyl peroxide, trimethylolpropane triacrylate, styrene butadiene rubber and white carbon black; R1 is a C1-C4 alkyl group or a structure shown in formula (2); n is an integer of 1-2; The content of the methyl methacrylate monomer is 75-400 parts by weight, the content of the dicumyl peroxide is 0.5-13 parts by weight, the content of the trimethylolpropane triacrylate is 37-200 parts by weight, and the content of the white carbon black is 50-300 parts by weight, relative to 100 parts by weight of the styrene butadiene rubber.

2. The rubber processing modifying masterbatch of claim 1, wherein, The content of the methyl methacrylate monomer is 133-250 parts by weight, the content of the dicumyl peroxide is 1.5-5 parts by weight, the content of the trimethylolpropane triacrylate is 66-125 parts by weight, and the content of the white carbon black is 100-200 parts by weight, relative to 100 parts by weight of the styrene butadiene rubber.

3. Rubber processing modifying masterbatch according to claim 1 or 2, wherein, The methyl methacrylate monomer is selected from at least one of glycidyl methacrylate, methyl methacrylate and butyl methacrylate.

4. The rubber processing modifying masterbatch according to any one of claims 1 to 3, wherein, The content of styrene in the styrene butadiene rubber is 10-25 wt%, preferably 18-25 wt%, and the content of vinyl is 40-70%, preferably 55-65 wt%; Preferably, the styrene butadiene rubber has a Mooney viscosity ML (100℃, 1+4min) of 55-75, preferably 58-73. Preferably, the nitrogen adsorption specific surface area of the white carbon black is 100-200 m 2 / g; Preferably, the white carbon black has an average particle size of 10-100 nm, preferably 30-80 nm.

5. A process for preparing the rubber processing modifying masterbatch according to any one of claims 1 to 4, characterized in that The method comprises: (1) plasticizing the styrene butadiene rubber to obtain plasticized rubber; (2) mixing the methyl methacrylate monomer, dicumyl peroxide, trimethylolpropane triacrylate, white carbon black and plasticized rubber to obtain a rubber processing modification masterbatch.

6. The method of claim 5, wherein, In step (1), the plasticizing temperature is 50-80℃, the plasticizing speed is 30-60 rpm, and the plasticizing time is 1-2 min. Preferably, in step (2), the mixing temperature is 60-100℃, and the mixing time is 3-6 min.

7. Use of the rubber processing modification masterbatch of any one of claims 1-4 in a rubber composition. Preferably, use in a shoe material rubber composition.

8. A rubber composition characterized in that, The rubber composition comprises a base rubber and the rubber processing modification masterbatch of any one of claims 1-4. Preferably, the amount of the rubber processing modification masterbatch is 3-6 parts by weight, relative to 100 parts by weight of the base rubber.

9. A method for producing a vulcanized rubber, characterized by, The preparation method comprises mixing the components in the rubber composition of claim 8 to obtain a mixed rubber blank, and vulcanizing the mixed rubber blank.

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

Images