A kind of styrene-butadiene rubber with high friction coefficient and preparation method thereof

Abstract

The present invention relates to a styrene-butadiene rubber with a high friction coefficient and a preparation method of such rubber, wherein the components and their mass fractions are: styrene-butadiene rubber: 100 parts, quick-pressed carbon black: 30-50 parts, light calcium carbonate: 30-50 parts, paraffin oil: 10-30 parts, zinc oxide: 4-6 parts, stearic acid: 1 part, butene derivatives: 6-12 parts, graphene: 3-6 parts, N-cyclohexyl-2-benzothiazole sulfonamide (CZ): 1-2 parts, tetramethylthiuram disulfide (TMTD): 0.5-1 parts, 4,4′-dithiodimorpholine (DTDM): 1-2 parts, and sulfur (S): 1-2 parts. The styrene-butadiene rubber obtained by the present invention has a friction coefficient of more than 3 on a wet tile surface and a friction coefficient of more than 18 on a dry tile surface, and has a good anti-slip effect.

Description

Technical Field

[0001] The invention relates to the field of nitrile rubber, in particular to styrene-butadiene rubber with a high friction coefficient and a preparation method of the rubber. Background Art

[0002] Rubber material is a material with a high friction coefficient. Rubber material is used to increase the friction coefficient in many occasions where anti-slip effect is required, such as anti-slip gloves, anti-slip mats, soles, tires, etc. As our requirements for friction increase and the use environment becomes increasingly complex, we need to continue to improve the friction coefficient of rubber materials to meet the application.

[0003] In order to solve the above problems, the industry usually adds anti-skid additives that increase the friction coefficient into rubber to increase the friction coefficient and improve the anti-skid effect. Summary of the invention

[0004] The purpose of the present invention is to provide a styrene-butadiene rubber with a higher friction coefficient, and through reasonable proportioning and reasonable selection of anti-skid additives, the product has a higher anti-skid effect.

[0005] The technical solution adopted by the present invention is:

[0006] The present invention provides a styrene-butadiene rubber with a high friction coefficient, the components and their mass fractions thereof are:

[0007]

[0008] Preferably, the flash point of paraffin oil is above 280°C.

[0009] In the present invention, styrene-butadiene rubber, quick-extrusion carbon black, paraffin oil and stearic acid are all universal materials, and any conventional materials available on the market can be used.

[0010] The zinc oxide in the present invention is indirect zinc oxide or active zinc oxide.

[0011] In the present invention, CZ, TMTD, DTDM and S are universal materials.

[0012] The butene derivatives in the present invention are low molecular weight butene oligomers with a molecular weight of less than 3,000.

[0013] Furthermore, the low molecular weight butene oligomer is a mixture of multiple polybutene substances with a molecular weight below 3000;

[0014] The D50 of the graphene in the present invention is between 5 and 50 μm.

[0015] The method for preparing styrene-butadiene rubber with high friction coefficient of the present invention comprises the following steps:

[0016] (1) mixing graphene with paraffin oil 3 to 5 times the weight of graphene, grinding and mixing by a three-roll mill, with a scale of 0.1 during grinding, and grinding three times in total;

[0017] (2) Weigh all the raw materials. After weighing the graphene, the weight of the paraffin oil mixed in the graphene needs to be calculated and deducted when weighing the paraffin oil;

[0018] (3) putting styrene-butadiene rubber into a kneading machine and kneading for (60±10) s; adding carbon black, light calcium carbonate, paraffin oil, zinc oxide, stearic acid, butene derivatives and a mixture of graphene for mixing for (300±50) s; after lifting the bolt, continue to pressurize and mix until the temperature reaches 120° C., and discharge the rubber;

[0019] (4) The mixed rubber material is placed at room temperature for 12-36 hours, and then put into a kneader. After kneading for (30±10) seconds, CZ, TMTD, DTDM, and S are added, and the kneading is continued until the temperature reaches 100°C, and the rubber is discharged;

[0020] (5) Pass the mixed rubber material through a mixing mill for 5 times and then cut it into sheets according to the required size.

[0021] The beneficial effects of the present invention are:

[0022] 1) The formula system of the present invention is used for styrene-butadiene rubber, and butene derivatives and graphene are added to the formula as anti-skid agents. The two anti-skid agents can be superimposed on the anti-skid effect and can complement each other in the influence on mechanical properties: butene derivatives have a low molecular weight and play a plasticizing role in rubber, reducing the overall hardness and strength of the rubber material; and graphene has a carbon-carbon structure and plays a reinforcing role in rubber;

[0023] 2) The graphene material added in the present invention is not easy to mix into the rubber material and is not easy to disperse well due to its light specific gravity and extremely small particle size. According to the formula in the present invention, the graphene and paraffin oil are first pre-dispersed and ground according to the corresponding preparation method, so that it can be better dispersed in the rubber to play a greater role. The flash point of paraffin oil is above 280°C to ensure that there is no precipitate affecting the friction coefficient.

[0024] 3) The styrene-butadiene rubber obtained by mixing the materials in the present application according to a specific preparation method is tested by ASTM1894, and the friction coefficient on the wet tile surface is up to 3 or more, and the friction coefficient on the dry tile surface is up to 18 or more. On the above basis, other properties can still be maintained good. The present application overcomes the technical prejudice in this field, and the styrene-butadiene rubber of the present application has a good anti-slip effect. DETAILED DESCRIPTION

[0025] The present invention will be further described below in conjunction with specific embodiments, but the protection scope of the present invention is not limited thereto.

[0026] Embodiment 1:

[0027]

[0028] The D50 of graphene is 35 μm, and the butene derivative is a low molecular weight butene oligomer, which is a mixture of various polybutene substances with a molecular weight below 3000.

[0029] The above formula is mixed according to the following process:

[0030] (1) 3 parts of graphene were mixed with 10 parts of paraffin oil, and the mixture was ground by a three-roll mill, with the grinding time scale of 0.1, and the grinding was repeated three times;

[0031] (2) Weigh all the raw materials. After weighing 13 parts of graphene, the total amount of paraffin oil is 10 parts. After deducting 10 parts of paraffin oil, there is no need to weigh additional paraffin oil;

[0032] (3) putting styrene-butadiene rubber into a kneading machine for kneading for 64 seconds; adding carbon black, light calcium carbonate, paraffin oil, zinc oxide, stearic acid, butene derivatives and a graphene mixture for mixing for 250 seconds; after lifting the bolt, continue to pressurize and mix until the temperature reaches 120° C. for rubber removal;

[0033] (4) The mixed rubber material is placed at room temperature for 24 hours, put into a kneader, and kneaded for 32 seconds. Then CZ, TMTD, DTDM, and S are added, and the kneading is continued until the temperature reaches 100°C for debonding;

[0034] (5) Pass the mixed rubber material through a mixing mill for 5 times and cut into sheets according to the required size for later use.

[0035] The material in this embodiment, referring to the ASTM1894 test method, when the friction interface is a wet tile, the dynamic friction coefficient is 2.14. When the friction interface is a dry tile, the dynamic friction coefficient is 12.46.

[0036] When the product made of the material prepared according to the formula and preparation method of the above embodiment is used as a tire for small household appliances, there is no slipping phenomenon on the wet indoor ground.

[0037] Embodiment 2:

[0038]

[0039] The D50 of graphene is 35 μm, and the butene derivative is a low molecular weight butene oligomer, which is a mixture of various polybutene substances with a molecular weight below 3000.

[0040] The above formula is mixed according to the following process:

[0041] (1) 3.5 parts of graphene were mixed with 12 parts of paraffin oil, and the mixture was ground by a three-roll mill with a grinding time of 0.1 for three times;

[0042] (2) Weigh all the raw materials, weigh 15.5 parts of graphene, and the total amount of paraffin oil is 15 parts. Deduct 12 parts of paraffin oil in graphene and only weigh 3 parts of paraffin oil;

[0043] (3) putting styrene-butadiene rubber into a kneading machine for kneading for 67 seconds; adding carbon black, light calcium carbonate, paraffin oil, zinc oxide, stearic acid, butene derivatives and graphene mixture for mixing for 250 seconds; after lifting the bolt, continue to pressurize and mix until the temperature reaches 120° C. for rubber removal;

[0044] (4) The mixed rubber material is placed at room temperature for 24 hours, put into a kneader, and kneaded for 33 seconds. Then CZ, TMTD, DTDM, and S are added, and the kneading is continued until the temperature reaches 100°C for debonding;

[0045] (5) Pass the mixed rubber material through a mixing mill for 5 times and cut into sheets according to the required size for later use.

[0046] The material in this embodiment, referring to the ASTM1894 test method, when the friction interface is a wet tile, the dynamic friction coefficient is 2.29. When the friction interface is a dry tile, the dynamic friction coefficient is 13.22.

[0047] When the product made of the material prepared according to the formula and preparation method of the above embodiment is used as a tire for small household appliances, there is no slipping phenomenon on the wet indoor ground.

[0048] Embodiment 3:

[0049]

[0050] The D50 of graphene is 35 μm, and the butene derivative is a low molecular weight butene oligomer, which is a mixture of various polybutene substances with a molecular weight below 3000.

[0051] The above formula is mixed according to the following process:

[0052] (1) 4 parts of graphene were mixed with 20 parts of paraffin oil, and the mixture was ground by a three-roll mill, with the grinding time scale of 0.1, and the grinding was repeated three times;

[0053] (2) Weigh all the raw materials, weigh 24 parts of graphene, and the total amount of paraffin oil is 20 parts. After deducting 20 parts of paraffin oil, there is no need to weigh additional paraffin oil;

[0054] (3) putting styrene-butadiene rubber into a kneading machine for kneading for 63 seconds; adding carbon black, light calcium carbonate, paraffin oil, zinc oxide, stearic acid, butene derivatives and a graphene mixture for mixing for 300 seconds; after lifting the bolt, continue to pressurize and mix until the temperature reaches 120° C. for rubber removal;

[0055] (4) The mixed rubber material is placed at room temperature for 24 hours, put into a kneader, and kneaded for 35 seconds. Then CZ, TMTD, DTDM, and S are added, and the kneading is continued until the temperature reaches 100°C for debonding;

[0056] (5) Pass the mixed rubber material through a mixing mill for 5 times and cut into sheets according to the required size for later use.

[0057] The material in this embodiment, referring to the ASTM1894 test method, when the friction interface is a wet tile, the dynamic friction coefficient is 2.36. When the friction interface is a dry tile, the dynamic friction coefficient is 13.98.

[0058] When the product made of the material prepared according to the formula and preparation method of the above embodiment is used as a tire for small household appliances, there is no slipping phenomenon on the wet indoor ground.

[0059] Example 4

[0060]

[0061] The D50 of graphene is 35 μm, and the butene derivative is a low molecular weight butene oligomer, which is a mixture of various polybutene substances with a molecular weight below 3000.

[0062] The above formula is mixed according to the following process:

[0063] (1) 5 parts of graphene were mixed with 20 parts of paraffin oil, and the mixture was ground by a 3-roll mill, with the grinding time scale of 0.1, and the grinding was repeated three times;

[0064] (2) Weigh all the raw materials, weigh 25 parts of graphene, and the total amount of paraffin oil is 25 parts. After deducting 20 parts of paraffin oil, only 3 parts of paraffin oil are weighed;

[0065] (3) putting styrene-butadiene rubber into a kneading machine for kneading for 66 seconds; adding carbon black, light calcium carbonate, paraffin oil, zinc oxide, stearic acid, butene derivatives and a graphene mixture for mixing for 350 seconds; after lifting the bolt, continue to mix under pressure until the temperature reaches 120° C. for rubber removal;

[0066] (4) The mixed rubber material is placed at room temperature for 24 hours, put into a kneader, and kneaded for 31 seconds. Then CZ, TMTD, DTDM, and S are added, and the kneading is continued until the temperature reaches 100°C for debonding;

[0067] (5) Pass the mixed rubber material through a mixing mill for 5 times and cut into sheets according to the required size for later use.

[0068] The material in this embodiment, referring to the ASTM1894 test method, when the friction interface is a wet tile, the dynamic friction coefficient is 2.86. When the friction interface is a dry tile, the dynamic friction coefficient is 16.96.

[0069] When the product made of the material prepared according to the formula and preparation method of the above embodiment is used as a tire for small household appliances, there is no slipping phenomenon on the wet indoor ground.

[0070] Example 5

[0071]

[0072] The D50 of graphene is 35 μm, and the butene derivative is a low molecular weight butene oligomer, which is a mixture of various polybutene substances with a molecular weight below 3000.

[0073] The above formula is mixed according to the following process:

[0074] (1) 6 parts of graphene were mixed with 20 parts of paraffin oil, and the mixture was ground by a three-roll mill, with the grinding time scale of 0.1, and the grinding was repeated three times;

[0075] (2) Weigh all the raw materials, weigh 26 parts of graphene, and the total amount of paraffin oil is 30 parts. After deducting 20 parts of paraffin oil, only 10 parts of paraffin oil are weighed;

[0076] (3) putting styrene-butadiene rubber into a kneading machine for kneading for 58 seconds; adding carbon black, light calcium carbonate, paraffin oil, zinc oxide, stearic acid, butene derivatives and graphene mixture for mixing for 350 seconds; after lifting the bolt, continue to pressurize and mix until the temperature reaches 120° C. for rubber removal;

[0077] (4) The mixed rubber material is placed at room temperature for 24 hours, put into a kneader, and kneaded for 35 seconds. Then CZ, TMTD, DTDM, and S are added, and the kneading is continued until the temperature reaches 100°C for debonding;

[0078] (5) Pass the mixed rubber material through a mixing mill for 5 times and cut into sheets according to the required size for later use.

[0079] The material in this embodiment, referring to the ASTM1894 test method, when the friction interface is a wet tile, the dynamic friction coefficient is 3.21. When the friction interface is a dry tile, the dynamic friction coefficient is 18.72.

[0080] When the product made of the material prepared according to the formula and preparation method of the above embodiment is used as a tire for small household appliances, there is no slipping phenomenon on the wet indoor ground.

[0081] Comparative Example 1:

[0082] Without using butene derivatives and light calcium carbonate

[0083]

[0084] The D50 of graphene is 35 μm, and the butene derivative is a low molecular weight butene oligomer, which is a mixture of various polybutene substances with a molecular weight below 3000.

[0085] The above formula is mixed according to the following process:

[0086] (1) 4 parts of graphene were mixed with 20 parts of paraffin oil, and the mixture was ground by a three-roll mill, with the grinding time scale of 0.1, and the grinding was repeated three times;

[0087] (2) Weigh all the raw materials, weigh 24 parts of graphene, and the total amount of paraffin oil is 30 parts. After deducting 20 parts of paraffin oil, only 10 parts of paraffin oil are weighed;

[0088] (3) putting styrene-butadiene rubber into a kneading machine for kneading for 65 seconds; adding carbon black, light calcium carbonate, paraffin oil, zinc oxide, stearic acid, butene derivatives and a graphene mixture for mixing for 350 seconds; after lifting the bolt, continue to mix under pressure until the temperature reaches 120° C. for rubber removal;

[0089] (4) The mixed rubber material is placed at room temperature for 24 hours, put into a kneader, and kneaded for 33 seconds. Then CZ, TMTD, DTDM, and S are added, and the kneading is continued until the temperature reaches 100°C for debonding;

[0090] (5) Pass the mixed rubber material through a mixing mill for 5 times and cut into sheets according to the required size for later use.

[0091] The material in this embodiment, referring to the ASTM1894 test method, when the friction interface is a wet tile, the dynamic friction coefficient is 1.29. When the friction interface is a dry tile, the dynamic friction coefficient is 6.67.

[0092] When a product made of the material prepared according to the formula and preparation method of the above embodiment is used as a tire for a small household appliance, the tire cannot drive the entire appliance to move when it is started on a wet indoor floor.

[0093] Comparative Example 2:

[0094] Without the use of graphene

[0095]

[0096] Butene derivatives are low molecular weight butene oligomers, which are mixtures of various polybutene substances with a molecular weight of less than 3000.

[0097] The above formula is mixed according to the following process:

[0098] (1) Weigh all raw materials;

[0099] (2) putting styrene-butadiene rubber into a kneading machine for kneading for 66 seconds; adding carbon black, light calcium carbonate, paraffin oil, zinc oxide, stearic acid, butene derivatives and a graphene mixture for mixing for 350 seconds; after lifting the bolt, continue to pressurize and mix until the temperature reaches 120° C. for rubber removal;

[0100] (3) The mixed rubber material is placed at room temperature for 24 hours, put into a kneading machine, and kneaded for 35 seconds. Then CZ, TMTD, DTDM, and S are added, and the kneading is continued until the temperature reaches 100°C for debonding;

[0101] (4) Pass the mixed rubber material through a mixing mill for 5 times and cut into sheets according to the required size for later use.

[0102] The material in this embodiment, referring to the ASTM1894 test method, when the friction interface is a wet tile, the dynamic friction coefficient is 1.57. When the friction interface is a dry tile, the dynamic friction coefficient is 10.08.

[0103] When the product made of the material prepared according to the above-mentioned embodiment formula and preparation method is used as a tire for small household appliances, it slips on a wet indoor floor and gets stuck severely when moving forward and turning.

[0104] Comparative Example 3:

[0105] The amount of graphene and butene derivatives used in the solution of the present invention is reduced, and the formula is as follows:

[0106]

[0107] The D50 of graphene is 35 μm, and the butene derivative is a low molecular weight butene oligomer, which is a mixture of various polybutene substances with a molecular weight below 3000.

[0108] The above formula is mixed according to the following process:

[0109] (1) 1.5 parts of graphene and 6 parts of paraffin oil were mixed, and the mixture was ground by a three-roll mill, with the grinding time scale of 0.1, and the grinding was repeated three times;

[0110] (2) Weigh all the raw materials, weigh 7.5 parts of graphene, and the total amount of paraffin oil is 20 parts. After deducting 6 parts of paraffin oil, only 14 parts of paraffin oil are weighed;

[0111] (3) putting styrene-butadiene rubber into a kneading machine for kneading for 65 seconds; adding carbon black, light calcium carbonate, paraffin oil, zinc oxide, stearic acid, butene derivatives and a graphene mixture for mixing for 350 seconds; after lifting the bolt, continue to mix under pressure until the temperature reaches 120° C. for rubber removal;

[0112] (4) The mixed rubber material is placed at room temperature for 24 hours, put into a kneader, and kneaded for 35 seconds. Then CZ, TMTD, DTDM, and S are added, and the kneading is continued until the temperature reaches 100°C for debonding;

[0113] (5) Pass the mixed rubber material through a mixing mill for 5 times and cut into sheets according to the required size for later use.

[0114] The material in this embodiment, referring to the ASTM1894 test method, when the friction interface is a wet tile, the dynamic friction coefficient is 1.64. When the friction interface is a dry tile, the dynamic friction coefficient is 10.44.

[0115] When the product made of the material prepared according to the formula and preparation method of the above embodiment is used as a tire for small household appliances, it slips on a wet indoor floor, and the state is similar to that of Comparative Example 2.

[0116] Comparative Example 4:

[0117] Using graphene material with larger particle size, the formula is as follows:

[0118]

[0119] The above formula is mixed according to the following process:

[0120] (1) 4 parts of graphene were mixed with 20 parts of paraffin oil, and the mixture was ground by a three-roll mill, with the grinding time scale of 0.1, and the grinding was repeated three times;

[0121] (2) Weigh all the raw materials, weigh 24 parts of graphene, and the total amount of paraffin oil is 20 parts. After deducting 20 parts of paraffin oil, there is no need to weigh additional paraffin oil;

[0122] (3) putting styrene-butadiene rubber into a kneading machine for kneading for 65 seconds; adding carbon black, light calcium carbonate, paraffin oil, zinc oxide, stearic acid, butene derivatives and a graphene mixture for mixing for 300 seconds; after the bolt is raised, the kneading is continued under pressure until the temperature reaches 120° C. for rubber removal;

[0123] (4) The mixed rubber material is placed at room temperature for 24 hours, put into a kneader, and kneaded for 35 seconds. Then CZ, TMTD, DTDM, and S are added, and the kneading is continued until the temperature reaches 100°C for debonding;

[0124] (5) Pass the mixed rubber material through a mixing mill for 5 times and cut into sheets according to the required size for later use.

[0125] The material in this embodiment, referring to the ASTM1894 test method, when the friction interface is a wet tile, the dynamic friction coefficient is 1.98. When the friction interface is a dry tile, the dynamic friction coefficient is 11.24.

[0126] When a product made from the material prepared according to the formula and preparation method of the above embodiment is used as a tire for small household appliances, a temporary jam occurs when the tire moves forward on a wet indoor floor.

[0127] Comparative Example 5:

[0128] Polyisobutylene with a molecular weight distribution of about 1300 is used to replace the butene oligomer with a lower molecular chain. The formula is as follows:

[0129]

[0130] The above formula is mixed according to the following process:

[0131] (1) 4 parts of graphene were mixed with 20 parts of paraffin oil, and the mixture was ground by a three-roll mill, with the grinding time scale of 0.1, and the grinding was repeated three times;

[0132] (2) Weigh all the raw materials, weigh 24 parts of graphene, and the total amount of paraffin oil is 20 parts. After deducting 20 parts of paraffin oil, there is no need to weigh additional paraffin oil;

[0133] (3) putting styrene-butadiene rubber into a kneading machine for kneading for 65 seconds; adding carbon black, light calcium carbonate, paraffin oil, zinc oxide, stearic acid, butene derivatives and a graphene mixture for mixing for 300 seconds; after the bolt is raised, the kneading is continued under pressure until the temperature reaches 120° C. for rubber removal;

[0134] (4) The mixed rubber material is placed at room temperature for 24 hours, put into a kneader, and kneaded for 35 seconds. Then CZ, TMTD, DTDM, and S are added, and the kneading is continued until the temperature reaches 100°C for debonding;

[0135] (5) Pass the mixed rubber material through a mixing mill for 5 times and cut into sheets according to the required size for later use.

[0136] Polyisobutylene, with a molecular weight distribution of about 1300, acts as a plasticizer in rubber. Due to its molecular structure, it cannot migrate to the surface of the product to form a fuzzy surface.

[0137] The material in this embodiment, referring to the ASTM1894 test method, when the friction interface is a wet tile, the dynamic friction coefficient is 1.52. When the friction interface is a dry tile, the dynamic friction coefficient is 9.96.

[0138] When the product made of the material prepared according to the above-mentioned embodiment formula and preparation method is used as a tire for small household appliances, it slips on a wet indoor floor and has severe jamming when moving forward and turning.

Claims

1. A styrene-butadiene rubber with a high friction coefficient, characterized in that: Its components and their mass fractions are: The low molecular weight butene oligomer has a molecular weight of less than 3000; the low molecular weight butene oligomer is a mixture of multiple polybutene substances with a molecular weight of less than 3000; the butene oligomer does not contain polyisobutylene; The D50 of graphene is between 5 and 50 μm.

2. The styrene-butadiene rubber with a high friction coefficient according to claim 1, characterized in that: The flash point of paraffin oil is above 280℃.

3. The styrene-butadiene rubber with a high friction coefficient according to claim 1 or 2, characterized in that: Styrene-butadiene rubber, quick-extrusion carbon black, paraffin oil, and stearic acid are all general-purpose materials; Zinc oxide is indirect zinc oxide or active zinc oxide; Accelerator CZ, Accelerator TMTD, Accelerator DTDM and sulfur are universal materials.

4. The styrene-butadiene rubber with a high friction coefficient according to claim 1 or 2, characterized in that:

5. The method for preparing the high friction coefficient styrene-butadiene rubber according to claim 1 or 2, characterized in that: The steps include: (1) mixing graphene with paraffin oil 3 to 5 times the weight of graphene, grinding and mixing by a three-roll mill, with a scale of 0.1 during grinding, and grinding three times in total; (2) Weigh all the raw materials. After weighing the graphene, the weight of the paraffin oil mixed in the graphene needs to be calculated and deducted when weighing the paraffin oil; (3) putting styrene-butadiene rubber into a kneading machine for kneading; putting in carbon black, light calcium carbonate, paraffin oil, zinc oxide, stearic acid, low molecular weight butene oligomer and graphene mixture for mixing and kneading; after lifting the bolt, continue to pressurize and mix, and discharge the rubber; (4) The mixed rubber material is placed at room temperature, put into a kneading machine for kneading, and then accelerator CZ, accelerator TMTD, accelerator DTDM and sulfur are added, and the kneading is continued to discharge the rubber material; (5) Pass the mixed rubber material through a mixing mill for 5 times and then cut it into sheets according to the required size.

6. The method for preparing styrene-butadiene rubber with high friction coefficient according to claim 5, characterized in that: The steps include: In step (3), the styrene-butadiene rubber is put into a kneading machine and kneaded for 60±10 seconds; the low molecular weight butene polymer and the graphene mixture are mixed for 300±50 seconds; after the bolt is raised, the pressure mixing is continued to reach 120° C., and the rubber is discharged; In step (4), the mixed rubber material is placed at room temperature for 12-36 hours, put into a kneader, and kneaded for 30±10 seconds, and then accelerator CZ, accelerator TMTD, accelerator DTDM and sulfur are added, and the kneading is continued to 100° C. to discharge the rubber material.

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