Tread rubber composition, method for producing the same, and tire

Abstract

This invention relates to the field of tire rubber manufacturing technology, and discloses a tread rubber composition, its preparation method, and a tire. The tread rubber composition incorporates anodized carbon nanosphere composite material, which is obtained by mixing natural rubber, carbon black, and anodized carbon nanospheres. The interfacial bonding between the anodized carbon nanosphere composite material and the rubber is superior to that of the anodized carbon nanospheres themselves. This invention uses precipitated silica, carbon black, and the anodized carbon nanosphere composite material as reinforcing fillers, exhibiting high reinforcing properties. With the increase of the anodized carbon nanosphere composite material, the filler's reinforcing properties are significantly improved. Simultaneously, the rubber composition exhibits high wear resistance, particularly with a significant reduction in compression heat generation, which is beneficial for reducing tire fuel consumption and increasing service life.

Description

Technical Field

[0001] This invention relates to the field of tire rubber manufacturing technology, and more specifically, to a tread rubber composition, its preparation method, and a tire. Background Technology

[0002] Rubber composite materials such as tires and conveyor belts are inevitably affected by rolling friction and sliding friction during use. Wear resistance is an important characteristic of rubber products that cannot be ignored. As the rubber product with the largest usage, tire wear resistance is particularly important. Tire wear resistance affects tire service life and the generation of rubber wear debris. Rubber wear debris is an important source of air pollutants. Therefore, the study of rubber wear is of the most important significance for the production and application of rubber products.

[0003] In recent years, researchers have explored the properties of carbon nanomaterials such as graphite, carbon nanotubes, and graphene in rubber, and the results show that they perform well in the field of friction and wear. Oxide carbon nanospheres, which are allotropes of graphite, carbon nanotubes, and graphene, hold promise as high-performance solid lubricants and anti-wear agents, and possess low Payne effect and low rolling resistance, which are not found in traditional carbon black, thus showing great promise for applications in rubber. However, the bonding interface between oxide carbon nanospheres and rubber is relatively poor.

[0004] Therefore, figuring out how to make oxidized carbon nanospheres into fillers with the same reinforcing properties as traditional fillers and apply them to rubber is a very promising direction. Summary of the Invention

[0005] To address the shortcomings of existing technologies, this invention provides a tread rubber composition in which oxidized carbon nanospheres are added. This composite material is prepared by mixing oxidized carbon nanospheres, which can act as a reinforcing filler while improving the wear resistance of the rubber and reducing the heat generated by compression.

[0006] To achieve the above objectives, the present invention adopts the following technical solution:

[0007] A tread rubber composition, said rubber composition being prepared by mixing raw materials comprising the following components in parts by weight:

[0008] 100 parts natural rubber

[0009] 20-50 parts carbon black

[0010] 20-30 parts of silica

[0011] 4-16 parts of oxidized carbon nanosphere composite material

[0012] 10-20 parts of rubber processing oil

[0013] 2-8 parts of silane coupling agent

[0014] 2-2.5 parts petroleum resin,

[0015] In addition, appropriate amounts of vulcanizing agents, antioxidants, activators, accelerators and microcrystalline waxes;

[0016] The oxidized carbon nanosphere composite material is prepared by mixing raw materials comprising the following components in parts by weight:

[0017] 20-40 parts natural rubber

[0018] 1-10 parts carbon black

[0019] 5-15 parts of oxidized carbon nanospheres;

[0020] The carbon black has a particle size of 20-40 nm;

[0021] The silica was prepared by precipitation method, and its BET specific surface area was 100-200 m². 2 / g.

[0022] Preferably, the rubber composition is prepared by mixing raw materials comprising the following components in parts by weight:

[0023] 100 parts natural rubber

[0024] 20-50 parts carbon black

[0025] 20-30 parts of silica

[0026] 14-16 parts of oxidized carbon nanosphere composite material,

[0027] 10-20 parts of rubber processing oil

[0028] 2-8 parts of silane coupling agent

[0029] 2-2.5 parts petroleum resin,

[0030] Anti-aging agent 0.5-1.5 parts,

[0031] 1-2 parts microcrystalline wax

[0032] Surfactant 4-6 parts,

[0033] Accelerator 2-5 parts,

[0034] Sulfur 1-5 parts.

[0035] Preferably, the preparation method of the oxidized carbon nanosphere composite material includes the following steps: starting the internal mixer, setting the speed to 30-45 rpm, adding natural rubber and carbon black, mixing for 20-35 seconds, adding oxidized carbon nanospheres, continuing to mix for 1-2 minutes, discharging the adhesive, and obtaining the oxidized carbon nanosphere composite material.

[0036] Preferably, the activator is zinc oxide and stearic acid: zinc oxide is 1.0-4.0 parts and stearic acid is 1.0-3.0 parts.

[0037] Preferably, the accelerator is DPG, DM and CZ: DPG is 0.1-2.0 parts, DM is 0.2-2.0 parts and CZ is 0.2-2.0 parts.

[0038] Furthermore, the present invention also discloses a method for preparing the rubber composition, comprising the following steps:

[0039] 1) First stage mixing: Mix using an internal mixer; add natural rubber, press down and hold for 55-65 seconds; raise the press, add silica, 35%-45% carbon black, oxidized nano-carbon sphere composite material, silane coupling agent, petroleum resin, microcrystalline wax, activator and antioxidant, press down and hold for 55-65 seconds; raise the press, add 55%-65% carbon black and rubber processing oil, press down and hold for 80-100 seconds; raise the press and clean.

[0040] 2) Two-stage mixing: Mixing is carried out using an open mill; discharge the rubber into the open mill, adjust the roll gap of the two-roll open mill to 0.8-1.2mm, so that the mixed rubber compound wraps around the rolls; add the accelerator and vulcanizing agent in sequence, and cut the left and right blades three times each; when the roll gap is 0.15-0.25mm, perform a triangular wrapping five times; adjust the roll gap to 1.5-2.0mm, sheet the rubber, and let it rest.

[0041] Furthermore, the present invention also discloses a tire comprising a tread, the tread being prepared by vulcanization of the aforementioned rubber composition.

[0042] The beneficial effects of this invention are as follows: the interfacial bonding between the oxidized carbon nanosphere composite material and rubber is better than that of the oxidized carbon nanospheres. This invention uses precipitated silica, carbon black and oxidized carbon nanosphere composite material as reinforcing fillers, which have high reinforcing properties. With the increase of oxidized carbon nanosphere composite material, the reinforcing properties of the filler are significantly improved. At the same time, the rubber composition has high wear resistance, especially with a significant reduction in compression heat generation, which is beneficial for tires to reduce fuel consumption and increase service life.

[0043] In the rubber composition of the present invention, in addition to the components described above, various additives may be mixed, such as other fillers commonly used in tires and other rubber compositions, vulcanizing agents, vulcanization accelerators, different types of oils, antioxidants, plasticizers, etc. These additives are mixed using conventional methods to obtain a rubber composition suitable for vulcanization. The amounts of these additives may also be conventional, typical mixing amounts, provided that this does not, in turn, affect the purpose of the present invention. Attached Figure Description

[0044] Figure 1 Scanning electron microscope images of the oxidized carbon nanosphere composite material, (a) 50,000x, (b) 100,000x.

[0045] Figure 2 Scanning electron microscope (SEM) images of cross-sections of vulcanizates of composite materials containing different amounts of oxidized carbon nanospheres: (a), (b), (c), and (d) at 50,000x magnification, (e), (f), (g), and (h) at 100,000x magnification. (a) and (e) are Example 1, (b) and (f) are Example 2, (C) and (g) are Example 3, and (d) and (h) are Comparative Example 5. Detailed Implementation

[0046] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the protection scope of the present invention.

[0047] The formulations of the examples and comparative examples are shown in Table 1 (parts by weight), and the formulations of the oxidized carbon nanosphere composite materials are shown in Table 2 (parts by weight).

[0048] The preparation methods for Examples 1-3 and Comparative Example 5 are as follows:

[0049] 1) First stage mixing: Mix using an internal mixer; add natural rubber, press down and hold for 60 seconds; raise the press, add silica, 40% carbon black, oxidized nano-carbon sphere composite material, silane coupling agent, petroleum resin, microcrystalline wax, activator and antioxidant, press down and hold for 60 seconds; raise the press, add 60% carbon black and rubber processing oil, press down and hold for 90 seconds; raise the press and clean.

[0050] 2) Two-stage mixing: Mixing is carried out using an open mill; discharge the rubber into the open mill, adjust the roller gap of the two-roll open mill to 1.0mm, so that the mixed rubber compound wraps around the rollers; add accelerator and vulcanizing agent in sequence, and cut the left and right blades three times each; when the roller gap is 0.20mm, make a triangular wrapping five times; adjust the roller gap to 1.5mm, unload the sheet, and let it rest.

[0051] The preparation methods for Comparative Examples 1-4 are the same as those in the Examples.

[0052] The preparation method of oxidized carbon nanosphere composite material is as follows: Start the internal mixer, set the speed to 30-45 rpm, add natural rubber and carbon black, mix for 20-35 seconds, add oxidized carbon nanospheres, continue mixing for 1-2 minutes, discharge the glue, and obtain oxidized carbon nanosphere composite material.

[0053] Table 1

[0054]

[0055] Table 2

[0056]

[0057] Footnotes in Tables 1 and 2

[0058] *1: SCR20, a product of Hainan Sinochem;

[0059] *2: N234, Cabot Chemicals product;

[0060] *3: 1165MP, Solvay Fine Chemicals Additives (Qingdao) Co., Ltd.;

[0061] *4: Oxide carbon nanospheres, Zibo Yideye New Material Technology Co., Ltd.;

[0062] *5: V500, a product of Ningbo Hansheng Co., Ltd.;

[0063] *6: Stearic acid, Yihai Kerry product;

[0064] *7: Antioxidant 4020 (6PPD), a product of China Petrochemical Corporation Nanjing Chemical Industry Co., Ltd.;

[0065] *8: Si69, Evonik Chemicals product;

[0066] *9: C5 / C9 resin, ExxonMobil product;

[0067] *10: Zinc oxide, a product of Qingdao Haiyan Chemical Co., Ltd.

[0068] *11: Microcrystalline wax, a product of Yanggu Huatai;

[0069] *12: Accelerator DPG(D), product of Shandong Shangshun Chemical Co., Ltd.;

[0070] *13: Accelerator DM, a product of Shandong Shangshun Chemical Co., Ltd.;

[0071] *14: Injector CBS (CZ), a product of Shandong Shangshun Chemical Co., Ltd.;

[0072] *15: Oil-extended sulfur powder, a product of Wuxi Huasheng Rubber New Material Technology Co., Ltd.

[0073] The performance of the rubber compositions obtained in the examples and comparative examples was tested, and the results are shown in Table 3.

[0074] The testing method is as follows:

[0075] 1) Vulcanization characteristics: The vulcanization curve and vulcanization characteristic parameters at 143℃ were determined using a UR-2030 rotorless vulcanizer from Taiwan Yuken Company in accordance with GB / T 9869-1997 standard, with a swing angle of 1°.

[0076] 2) Tensile properties: The tensile strength and tear strength of the rubber composition were tested in accordance with GB / T 528-2009 and GB / T 529-2008 standards. The tensile specimens were dumbbell-shaped and the tear specimens were right-angled. The tests were conducted using a U-CAN UT-2060 electronic tensile testing machine at a speed of 500 mm / min.

[0077] 3) Abrasion test: The abrasion amount of the material was tested using a GOTECH GT-7012-A Akron abrasion tester from the High-Speed ​​Railway Company in accordance with the GB / T 1689-1998 standard.

[0078] 4) Heat generation performance: The compressive fatigue heat generation performance of the material was tested according to GB / T 15584-1995 standard. The testing instrument was a U-CAN UD-3801 compressive fatigue heat generation tester. The test conditions were: frequency 30Hz, strain double amplitude 5.71mm, load force 24.5Kg, test time 25min, and the test specimen was a cylinder with a height of 25mm and a diameter of 17.8mm.

[0079] Table 3

[0080]

[0081] Analysis of Table 3 shows that Example 3 is the best embodiment, exhibiting the optimal overall performance. It can be seen that Example 3, with the addition of oxidized carbon nanospheres, demonstrates higher strength and wear resistance, particularly with a significant reduction in compression heat generation, which is beneficial for reducing tire fuel consumption and extending tire lifespan.

[0082] However, with the increase of the amount of oxidized carbon nanospheres, the aggregates in the dumbbell-shaped sample cross-section became larger and the number of aggregates increased. This indicates that the more oxidized carbon nanosphere composite material is used, the less easily it is dispersed in the rubber matrix, and excessive use is actually detrimental to the performance of the rubber.

[0083] The foregoing description of embodiments of the present invention, through which those skilled in the art are able to implement or use the present invention, will be readily apparent to those skilled in the art. Various modifications to these embodiments will be readily apparent to those skilled in the art. The general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the invention. Therefore, the present invention is not to be limited to the embodiments shown herein, but is to be accorded the widest scope consistent with the principles and novelty disclosed herein.

Claims

1. A tread rubber composition characterized in that, The rubber composition is prepared by mixing raw materials comprising the following components in parts by weight: 100 parts natural rubber 20-50 parts carbon black 20-30 parts of silica 4-16 parts of oxidized carbon nanosphere composite material 10-20 parts of rubber processing oil 2-8 parts of silane coupling agent 2-2.5 parts petroleum resin, In addition, appropriate amounts of vulcanizing agents, antioxidants, activators, accelerators and microcrystalline waxes; The oxidized carbon nanosphere composite material is prepared by mixing raw materials comprising the following components in parts by weight: 20-40 parts natural rubber 1-10 parts carbon black 5-15 parts of oxidized carbon nanospheres; The carbon black has a particle size of 20-40 nm; The white carbon black is prepared by a precipitation method, and has a BET specific surface area of 100-200 m 2 / g.

2. The rubber composition according to claim 1, characterized in that, The rubber composition is prepared by mixing raw materials comprising the following components in parts by weight: 100 parts natural rubber 20-50 parts carbon black 20-30 parts of silica 14-16 parts of oxidized carbon nanosphere composite material, 10-20 parts of rubber processing oil 2-8 parts of silane coupling agent 2-2.5 parts petroleum resin, Anti-aging agent 0.5-1.5 parts, 1-2 parts microcrystalline wax Surfactant 4-6 parts, Accelerator 2-5 parts, Sulfur 1-5 parts.

3. Rubber composition according to claim 1 or 2, characterized in that, The preparation method of the oxidized carbon nanosphere composite material includes the following steps: start the internal mixer, set the speed to 30-45 rpm, add natural rubber and carbon black, mix for 20-35 seconds, add oxidized carbon nanospheres, continue mixing for 1-2 minutes, discharge the glue, and obtain the oxidized carbon nanosphere composite material.

4. The rubber composition according to claim 1 or 2, characterized in that, The activator is zinc oxide and stearic acid: zinc oxide is 1.0-4.0 parts and stearic acid is 1.0-3.0 parts.

5. The rubber composition according to claim 1 or 2, characterized in that, The accelerators used are DPG, DM and CZ: DPG is 0.1-2.0 parts, DM is 0.2-2.0 parts and CZ is 0.2-2.0 parts.

6. The method for preparing the rubber composition according to any one of claims 1-5, characterized in that, Includes the following steps: 1) First stage mixing: Mix using an internal mixer; add natural rubber, press down and hold for 55-65 seconds; raise the press, add silica, 35%-45% carbon black, oxidized nano-carbon sphere composite material, silane coupling agent, petroleum resin, microcrystalline wax, activator and antioxidant, press down and hold for 55-65 seconds; raise the press, add 55%-65% carbon black and rubber processing oil, press down and hold for 80-100 seconds; raise the press and clean. 2) Two-stage mixing: Mixing is carried out using an open mill; discharge the rubber into the open mill, adjust the roll gap of the two-roll open mill to 0.8-1.2mm, so that the mixed rubber compound wraps around the rolls; add the accelerator and vulcanizing agent in sequence, and cut the left and right blades three times each; when the roll gap is adjusted to 0.15-0.25mm, perform a triangular wrapping five times; adjust the roll gap to 1.5-2.0mm, sheet the rubber, and let it rest.

7. A tire, characterized in that, The tire includes a tread, which is prepared by vulcanization using the rubber composition according to any one of claims 1-5.

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