Use of a siO2 / c composite in tire cushion

Abstract

The application belongs to the technical field of tire cushion gum, and provides application of SiO2 / C composite material in tire cushion gum. The tire cushion gum comprises the following components in mass fraction: 100 parts of natural rubber, 0-45 parts of filler, 10-50 parts of SiO2 / C composite material, 0-5 parts of silane coupling agent, 4-10 parts of activator, 3-6 parts of vulcanizing agent and 2-5 parts of antioxidant. The SiO2 / C composite material is used for preparing tire cushion gum, which can effectively replace white carbon black or carbon black, and the prepared tire cushion gum has low heat build-up performance and good high temperature resistance. Specifically, the SiO2 / C aggregate has high dispersibility, can reduce the Payne effect of the filler, thereby reducing the heat build-up; the porosity of the SiO2 / C composite material promotes the close combination of rubber and filler, and the formed close combination rubber has excellent high temperature resistance.

Description

TECHNICAL FIELD

[0001] The application relates to the technical field of tire cushion rubber, and particularly relates to application of SiO2 / C composite material in tire cushion rubber. BACKGROUND

[0002] The cushion rubber is a transition layer, is called the heart of the tire, has the functions of transferring and absorbing the stress of the shoulder, and has the functions of connecting the upper and lower layers. In addition, the cushion rubber is in a high stress area and needs to continuously bear tensile and compressive stress, and the thickness of the shoulder is the thickest, and heat generation is high. Therefore, the cushion rubber formula needs to have low heat generation, good flex resistance, excellent high temperature resistance, tensile tear resistance and elasticity. In order to improve the heat resistance of the currently developed cushion rubber, the content of single sulfur bond and double sulfur bond is usually increased, which results in poor fatigue and is difficult to meet the high fatigue performance required by the cushion rubber. Therefore, it is very important to develop a cushion rubber with low heat generation, high fatigue and high temperature resistance, and it is also a big problem in the industry. SUMMARY

[0003] The application aims at overcoming the problems in the prior art, and provides application of SiO2 / C composite material in tire cushion rubber.

[0004] In order to achieve the above application purposes, the application provides the following technical scheme.

[0005] The application provides application of SiO2 / C composite material in tire cushion rubber, and the tire cushion rubber contains the following components in mass fraction:

[0006] 100 parts of natural rubber, 0-45 parts of filler, 10-50 parts of SiO2 / C composite material, 0-5 parts of silane coupling agent, 4-10 parts of activator, 3-6 parts of vulcanizing agent and 2-5 parts of antioxidant.

[0007] As a preference, the filler includes one or more of N330, N375, N234, N660 and N326.

[0008] As a preference, the preparation method of the SiO2 / C composite material includes the following steps:

[0009] (1) mixing edible fungus cultivation bodies and porous silicon dioxide to obtain silicon dioxide composite edible fungus cultivation bodies;

[0010] mixing the silicon dioxide composite edible fungus cultivation bodies and edible fungus, and culturing the edible fungus; after the culture is completed, the edible fungus is removed, and the waste cultivation bodies are reserved;

[0011] (2) carbonizing the waste cultivation bodies in step (1) to obtain SiO2 / C composite material.

[0012] Preferably, the silane coupling agent comprises one or more of Si-69, Si-75 and Si-747.

[0013] Preferably, the activator comprises one or more of stearic acid, zinc oxide, zinc stearate and lignin zinc salt.

[0014] Preferably, the vulcanizing agent comprises one or more of insoluble sulfur, accelerator NS and accelerator CZ.

[0015] Preferably, the antioxidant comprises one or more of antioxidant 4020, antioxidant RD and antioxidant DTPD.

[0016] Preferably, the method for preparing the tire cushioning rubber comprises the following steps:

[0017] The natural rubber, the filler, the SiO2 / C composite material, the activator and the antioxidant are mixed to obtain a masterbatch by first mixing; and the masterbatch and the vulcanizing agent are mixed to obtain the tire cushioning rubber by second mixing.

[0018] The present application has the following advantages:

[0019] The present application provides an application of a SiO2 / C composite material in a tire cushioning rubber, wherein the tire cushioning rubber comprises the following components in mass fraction: 100 parts of natural rubber, 0-45 parts of a filler, 10-50 parts of the SiO2 / C composite material, 0-5 parts of a silane coupling agent, 4-10 parts of an activator, 3-6 parts of a vulcanizing agent and 2-5 parts of an antioxidant. The SiO2 / C composite material can effectively replace white carbon black or carbon black in the preparation of the tire cushioning rubber, and the prepared tire cushioning rubber has low heat build-up and good high-temperature resistance. Specifically, the SiO2 / C aggregate formed by the organic combination of carbonization of edible fungi and silicon dioxide has high dispersibility and can reduce the Payne effect of the filler, thereby reducing heat build-up. In addition, the porous silicon dioxide material is selected in the preparation of the SiO2 / C composite material, so that the SiO2 and C can be closely combined, and the porosity of the SiO2 / C composite material promotes the close combination of the rubber and the filler, so that the prepared tire cushioning rubber composition has excellent high-temperature resistance. The rubber composition prepared by the present application has the characteristics of low heat build-up, good flex resistance, good high-temperature resistance, excellent tensile tear resistance and elasticity when used in the tire cushioning rubber. DETAILED DESCRIPTION

[0020] The present application provides an application of a SiO2 / C composite material in a tire cushioning rubber, wherein the tire cushioning rubber comprises the following components in mass fraction:

[0021] Natural rubber 100 parts, filler 0-45 parts, SiO2 / C composite material 10-50 parts, silane coupling agent 0-5 parts, activator 4-10 parts, vulcanizing agent 3-6 parts and antioxidant 2-5 parts.

[0022] In the application, the mass fraction of the filler is 0-45 parts, preferably 5-35 parts, further preferably 10-30 parts, and more preferably 15-20 parts.

[0023] In the application, the mass fraction of the SiO2 / C composite material is 10-50 parts, preferably 15-45 parts, further preferably 20-40 parts, and more preferably 30-32 parts.

[0024] In the application, the mass fraction of the silane coupling agent is 0-5 parts, preferably 1-4 parts, further preferably 2-3 parts, and more preferably 2.5 parts.

[0025] In the application, the mass fraction of the activator is 4-10 parts, preferably 5-9 parts, further preferably 6-8 parts, and more preferably 7-7.5 parts.

[0026] In the application, the mass fraction of the vulcanizing agent is 3-6 parts, preferably 3.5-5.5 parts, further preferably 4-5 parts, and more preferably 4.5-4.7 parts.

[0027] In the application, the mass fraction of the antioxidant is 2-5 parts, preferably 2.5-4.5 parts, further preferably 3-4 parts, and more preferably 3.5-3.7 parts.

[0028] In the application, the filler is preferably carbon black, and the carbon black preferably includes one or more of N330, N375, N234, N660 and N326.

[0029] In the application, the preparation method of the SiO2 / C composite material preferably comprises the following steps:

[0030] (1) mixing edible fungus cultivation bodies and porous silicon dioxide to obtain silicon dioxide composite edible fungus cultivation bodies;

[0031] mixing the silicon dioxide composite edible fungus cultivation bodies with edible fungus for edible fungus cultivation; after cultivation is completed, removing the edible fungus and retaining the waste cultivation bodies;

[0032] (2) carbonizing the waste cultivation bodies of step (1) to obtain SiO2 / C composite materials.

[0033] In the application, the edible fungus cultivation bodies of step (1) preferably include a biomass carbon source. The biomass carbon source includes but is not limited to one or more of cottonseed hulls, corn cobs, leaf tree sawdust, bean straw powder, wheat straw powder, peanut shells, bran and rice bran.

[0034] In the present application, the source of the edible fungus cultivation body in step (1) is not limited, and commercially available or non-commercial products known to those skilled in the art can be used.

[0035] In the present application, the porous silicon dioxide in step (1) preferably includes one or more of silicagel, carbon nanotubes, diatomite, diatom shale, opal, zeolite and montmorillonite, further preferably includes silicagel, diatomite, diatom shale, opal, zeolite or montmorillonite, and more preferably is silicagel.

[0036] In the present application, the grade of the carbon nanotubes is preferably TSI-A5008.

[0037] In the present application, the particle size of the porous silicon dioxide in step (1) is preferably 500 nm to 100 μm, further preferably 500 nm to 50 μm, and more preferably 500 nm to 10 μm; the specific surface area is preferably 60 to 500 m 2 / g, further preferably 60 to 300 m 2 / g, and more preferably 60 to 200 m 2 / g; the pore size is preferably 2 to 100 nm; and the porosity is preferably 0.1 to 5 cm 3 / g, further preferably 0.1 to 3 cm 3 / g, and more preferably 0.1 to 2 cm 3 / g.

[0038] In the present application, the mass ratio of the porous silicon dioxide in step (1) to the edible fungus cultivation body is preferably 1:1 to 10, further preferably 1:2 to 4, and more preferably 1:2.

[0039] In the present application, the silicon dioxide composite edible fungus cultivation body in step (1) further preferably includes sterilization treatment of the silicon dioxide composite edible fungus cultivation body before mixing with the edible fungus.

[0040] In the present application, the conditions for the sterilization treatment are not limited, and the methods known to those skilled in the art can be used. In the embodiments of the present application, the sterilization treatment is performed at 120°C for 1.5 h or more.

[0041] In the present application, the edible fungus in step (1) preferably includes, but is not limited to, shiitake mushrooms, oyster mushrooms or wood ear fungus. Preferably, the embodiments of the present application are cultured with wood ear fungus as an example.

[0042] In the present application, the time for completing the culture in step (1) is preferably ≥3 months, further preferably ≥3.5 months, and more preferably 4 months.

[0043] In the present application, step (2) before the carbonization preferably further comprises: naturally drying the waste cultivation body of step (1). The time of the natural drying is preferably 5-24 h, further preferably 12-24 h, and more preferably 24 h.

[0044] In the present application, the equipment used for the carbonization of step (2) is preferably a carbonization furnace.

[0045] In the present application, in step (2), the carbonization is preferably carried out under a protective atmosphere; the protective atmosphere is preferably at least one of nitrogen or argon, further preferably nitrogen or argon, and more preferably nitrogen.

[0046] In the present application, in step (2), the temperature of the carbonization is preferably 600-950℃, further preferably 700-900℃, and more preferably 800℃; the time is preferably 10-60 min, further preferably 30-60 min, and more preferably 60 min; the rate of heating to the required carbonization temperature is preferably 5-15℃ / min, further preferably 5-10℃ / min, and more preferably 5℃ / min.

[0047] In the present application, after the carbonization of step (2), preferably further comprises: sequentially carrying out crushing and screening.

[0048] In the present application, the equipment for the crushing is preferably a planetary ball mill.

[0049] In the present application, the rotation speed of the crushing of step (2) is preferably 300-700 r / min, further preferably 400-600 r / min, and more preferably 500 r / min; the time is preferably 15-60 min, further preferably 20-40 min, and more preferably 30 min.

[0050] In the present application, the equipment for the screening is preferably a centrifugal classifier.

[0051] In the present application, the particle size D 50 of the screening of step (2) is preferably 500 nm-45 μm, further preferably 500 nm-20 μm, and more preferably 500 nm-10 μm.

[0052] In the present application, the silane coupling agent preferably comprises one or more of Si-69, Si-75, and Si-747.

[0053] In the present application, the activator preferably comprises one or more of stearic acid, zinc oxide, zinc stearate, and a lignin zinc salt; the preparation method of the lignin zinc salt is referred to patent CN115678038B.

[0054] In the present application, the vulcanizing agent preferably comprises one or several of insoluble sulfur, accelerator NS and accelerator CZ.

[0055] In the present application, the anti-aging agent preferably comprises one or several of anti-aging agent 4020, anti-aging agent RD and anti-aging agent DTPD.

[0056] In the present application, the method for preparing the tire cushion preferably comprises the following steps:

[0057] The natural rubber, the filler, the SiO2 / C composite material, the activator and the anti-aging agent are mixed to obtain the masterbatch by first mixing; the masterbatch and the vulcanizing agent are mixed to obtain the tire cushion by second mixing.

[0058] In the present application, the first mixing preferably comprises the following steps: starting the internal mixer, setting the rotating speed of the internal mixer to 45-55 r / min, adding the natural rubber, the filler, the SiO2 / C composite material, the activator and the anti-aging agent, mixing for 30-50 s, after mixing, pressing the ram to carry out ram pressing mixing for 20-30 s, carrying out ram pressing mixing to 145-165 ℃ to discharge the rubber, and obtaining the masterbatch; the rotating speed of the internal mixer is preferably 45-55 r / min, further preferably 47-53 r / min, and more preferably 50 r / min; the mixing time is preferably 30-50 s, further preferably 35-45 s, and more preferably 40 s; the ram pressing mixing time is preferably 20-30 s, further preferably 22-28 s, and more preferably 25 s; and the discharging temperature is preferably 145-165 ℃, further preferably 150-160 ℃, and more preferably 152-155 ℃.

[0059] In the present application, the second mixing preferably comprises the following steps: starting the internal mixer, setting the rotating speed of the internal mixer to 25-35 r / min, adding the masterbatch and the vulcanizing agent, mixing for 30-50 s, after mixing, pressing the ram to carry out ram pressing mixing for 20-30 s, carrying out ram pressing mixing to 95-110 ℃ to discharge the rubber, and obtaining the tire cushion; the rotating speed of the internal mixer is preferably 25-35 r / min, further preferably 27-33 r / min, and more preferably 30 r / min; the mixing time is preferably 30-50 s, further preferably 35-45 s, and more preferably 40 s; the ram pressing mixing time is preferably 20-30 s, further preferably 22-28 s, and more preferably 25 s; and the discharging temperature is preferably 95-110 ℃, further preferably 100-105 ℃, and more preferably 102-103 ℃.

[0060] The technical solutions provided by the present application are described in detail below in combination with examples, but they should not be understood as limiting the scope of protection of the present application.

[0061] Example 1

[0062] The components and their mass parts in this example are as follows:

[0063] 100 parts of natural rubber, 0 parts of filler (carbon black N330), 32 parts of SiO2 / C composite material, 0 parts of silane coupling agent (Si-69), 6 parts of activator (2 parts of stearic acid and 4 parts of zinc oxide), 4.7 parts of vulcanizing agent (3.7 parts of insoluble sulfur and 1 part of accelerator NS), and 2.5 parts of antioxidant (1.5 parts of antioxidant 4020 and 1 part of antioxidant RD);

[0064] The preparation method of the SiO2 / C composite material comprises the following steps:

[0065] 2 kg of agaric cultivation bodies (from Heilongjiang Dongjingcheng Forestry Bureau Science and Technology Demonstration Garden) and 200 g of silicon powder (D 50 -8 μm, model TSI-1, manufacturer Harbin Silicon New Material Co., Ltd., particle size 500 nm-10 μm, specific surface area 60-200 m 2 / g, pore size 2-100 nm, porosity 0.1-2 cm 3 / g) are uniformly mixed to obtain a silicon dioxide composite edible mushroom cultivation body;

[0066] After sterilization treatment of the silicon dioxide composite edible mushroom cultivation body at 120°C for 1.5 h, the silicon dioxide composite edible mushroom cultivation body is inoculated with agaric fungi for cultivation. After the agaric fungi are cultivated for 3 months, the mature agaric fungi are removed, and the waste cultivation body is retained;

[0067] The waste cultivation body is naturally dried for 24 h, and then the waste cultivation body is placed in a carbonization furnace and carbonized at a temperature increasing rate of 5°C / min to 800°C for 60 min under nitrogen protection. The silicon-carbon composite obtained by carbonization is ball milled in a planetary ball mill at a rotating speed of 500 r / min for 30 min. Then, the sample after ball milling is sieved by a centrifugal classifier to obtain a sample with a particle size D 50 ≤3 μm, to obtain a SiO2 / C composite material;

[0068] Start the internal mixer, set the rotating speed of the internal mixer to 50 r / min, add the natural rubber, filler, SiO2 / C composite material, activator, and antioxidant, mix for 35 s, after mixing is completed, press the bolt and mix for 20 s, press the bolt and mix to 152°C to discharge the glue, to obtain the masterbatch;

[0069] Start the internal mixer, set the rotating speed of the internal mixer to 25 r / min, add the masterbatch and vulcanizing agent, mix for 30 s, after mixing is completed, press the bolt and mix for 20 s, press the bolt and mix to 105°C to discharge the glue, to obtain the tire cushion.

[0070] Example 2

[0071] The mass fraction of the filler (carbon black N330) was modified to 10 parts, the mass fraction of the SiO2 / C composite material was modified to 30 parts, and the mass fraction of the silane coupling agent (Si-69) was modified to 3 parts in Example 1, and a tire cushion was obtained.

[0072] Comparative Example 1

[0073] The mass fraction of the filler (carbon black N330) was modified to 32 parts in Example 1, and a tire cushion was obtained.

[0074] Comparative Example 2

[0075] The mass fraction of the silane coupling agent (Si-69) was modified to 3 parts in Example 1, the type of the filler was modified to carbon black N330 and white carbon black GR175 (purchased from Wacker Chemie AG), the mass fraction of the carbon black N330 was modified to 10 parts, the mass fraction of the white carbon black GR175 was modified to 30 parts, and the mass fraction of the SiO2 / C composite material was modified to 0 parts, and a tire cushion was obtained.

[0076] The tire cushions obtained in Examples 1-2 and Comparative Examples 1-2 were subjected to performance testing, and the performance test results of the tire cushions obtained in Examples 1-2 and Comparative Examples 1-2 are shown in Table 1.

[0077] Table 1 Performance test results of tire cushions obtained in Examples 1-2 and Comparative Examples 1-2

[0078]

[0079] As can be seen from the above Comparative Examples 1 and 2 and Examples 1 and 2, the reinforcing effect of the SiO2 / C composite material is similar to that of the white carbon black GR175 and the carbon black N330, the heat generation of the SiO2 / C composite material is as low as 24% ((0.075-0.057) / 0.075), and the high temperature resistance is improved by 24% ((9.7-7.8) / 7.8). That is, the tire cushion prepared by using the SiO2 / C composite material according to the present application has low heat generation and good high temperature resistance.

[0080] From the above embodiments, the application provides an application of the SiO2 / C composite material in the tire cushion rubber, and the tire cushion rubber comprises the following components in mass fraction: 100 parts of natural rubber, 0-40 parts of fillers, 10-50 parts of the SiO2 / C composite material, 4-10 parts of an activator, 3-6 parts of a vulcanizing agent and 2-5 parts of an antioxidant. The SiO2 / C composite material is used for preparing the tire cushion rubber, and the white carbon black or carbon black can be effectively replaced, the prepared tire cushion rubber has the low heat build-up performance and also has good high temperature resistance. Specifically, the SiO2 / C aggregate formed by the organic combination of the carbonization of the edible mushroom and the silicon dioxide has high dispersibility, and can reduce the Payne effect of the fillers, thereby reducing the heat build-up. Secondly, the porous silicon dioxide material is selected when the SiO2 / C composite material is prepared, so that the SiO2 and C can be closely combined, the close combination of the rubber and the fillers is promoted through the porosity of the SiO2 / C composite material, and the prepared close combination rubber makes the prepared tire cushion rubber composition have excellent high temperature resistance. The rubber composition prepared by the application is used in the tire cushion rubber, and has the characteristics of low heat build-up, good flex resistance, good high temperature resistance, excellent tensile tear resistance and elasticity.

[0081] The above only describes the preferred embodiments of the application, and it should be noted that the ordinary skilled in the art can make several improvements and refinements without departing from the principles of the application, and these improvements and refinements should also be considered as the protection scope of the application.

Claims

1. Use of a SiO2 / C composite material in the tire cushion gum, characterized in that, The tire cushion rubber comprises the following components in mass fraction: 100 parts of natural rubber, 0-45 parts of filler, 10-50 parts of SiO2 / C composite material, 0-5 parts of silane coupling agent, 4-10 parts of activator, 3-6 parts of vulcanizing agent and 2-5 parts of antioxidant; The preparation method of the SiO2 / C composite material comprises the following steps: (1) mixing edible mushroom cultivation body and porous silicon dioxide to obtain silicon dioxide composite edible mushroom cultivation body; Mixing the silicon dioxide composite edible mushroom cultivation body with edible mushroom to culture the edible mushroom; after the culture is completed, the edible mushroom is removed and the waste cultivation body is reserved; (2) carbonizing the waste cultivation body in step (1) to obtain SiO2 / C composite material.

2. Use of the SiO2 / C composite material according to claim 1 in the tyre cushioning gum, characterized in that, The filler comprises one or more of N330, N375, N234, N660 and N326.

3. Use of the SiO2 / C composite material according to claim 1 in the tyre cushioning gum, characterized in that, The silane coupling agent comprises one or more of Si-69, Si-75 and Si-747.

4. Use of the SiO2 / C composite material according to claim 3 in the tyre cushioning gum, characterized in that, The activator comprises one or more of stearic acid, zinc oxide, zinc stearate and lignin zinc salt.

5. Use of the SiO2 / C composite material according to claim 4 in the tyre cushioning gum, characterized in that, The vulcanizing agent comprises one or more of insoluble sulfur, accelerator NS and accelerator CZ.

6. Use of the SiO2 / C composite material according to claim 5 in the tyre cushioning gum, characterized in that, The antioxidant comprises one or more of antioxidant 4020, antioxidant RD and antioxidant DTPD.

7. Use of the SiO2 / C composite material according to claim 6 in the tyre cushioning gum, characterized in that, The preparation method of the tire cushion rubber comprises the following steps: Mixing natural rubber, filler, SiO2 / C composite material, activator and antioxidant to obtain masterbatch by first mixing; mixing the masterbatch and vulcanizing agent to obtain the tire cushion rubber by second mixing.

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