Application of SiO2 / C composite in high heat conductive base rubber of tire

Abstract

The application belongs to the technical field of tire base rubber, and provides application of SiO2 / C composite material in high-heat-conducting tire base rubber, which solves the problem of heat conduction of the tire. The composite material can effectively replace white carbon black in the tire preparation process, and the prepared tire has low heat generation and high heat conduction. The SiO2 / C aggregate formed by the organic combination of carbonization of edible fungi and SiO2 has high dispersity, plays a role in reducing the Payne of the filler, and thus reduces heat generation. Secondly, the application adopts porous silica material, so that SiO2 and C are closely combined to form a heat conduction channel, and the heat conduction performance of the filler is enhanced. In the application, the close combination of the SiO2 / C composite material and white carbon black and carbon black forms a heat conduction channel, solves the problems of poor heat conduction and static electricity of white carbon black, and makes the prepared tire base rubber composition have high heat conduction performance.

Description

TECHNICAL FIELD

[0001] The application relates to the technical field of tire base rubber, and particularly relates to application of SiO2 / C composite material in high-thermal-conductivity base rubber of a tire. BACKGROUND

[0002] In recent years, green tires are all used with high white carbon black to solve the problem of low hysteresis. The surface of the white carbon black is highly polar and is difficult to disperse. In order to solve the dispersion problem of the white carbon black, the white carbon black is modified in recent years, and particularly, silane modification has very good effect, and the prepared tire has low heat build-up. However, the thermal conductivity of the white carbon black is poor, although the heat build-up is low, the heat generated by the tire cannot be conducted out, resulting in high cumulative heat build-up of the tire, and the tire is prone to damage. Therefore, it is very important to develop a filler with low heat build-up and high thermal conductivity to solve the low heat build-up and high thermal conductivity of the base rubber, and it is a big problem in the industry. SUMMARY

[0003] The application aims at overcoming the defects in the prior art, and provides application of SiO2 / C composite material in high-thermal-conductivity base rubber of a tire.

[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 high-thermal-conductivity base rubber of a tire, and the high-thermal-conductivity base rubber of the tire comprises the following raw materials in mass fraction:

[0006] 90-110 parts of natural rubber, 0-45 parts of filler, 10-45 parts of SiO2 / C composite material, 4-10 parts of activator, 2-5 parts of vulcanizing agent, 2-5 parts of antioxidant, and 0.5-1.5 parts of microcrystalline wax.

[0007] Preferably, the filler is one or more of carbon black N220, carbon black N234, carbon black N375, carbon black N347, carbon black N339, carbon black N330, carbon black N326, carbon black N660 and pyrolytic carbon black.

[0008] Preferably, the preparation method of the SiO2 / C composite material comprises the following steps:

[0009] (A) 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 culturing is completed, the edible fungus is removed, and the waste cultivation bodies are reserved;

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

[0012] As preferred, the porous silica is one or more of silica gel powder, charcoal, diatomite, diatom shale, opal, zeolite and montmorillonite.

[0013] As preferred, the activator is one or more of stearic acid, zinc oxide, zinc stearate and lignin zinc salt.

[0014] As preferred, the vulcanizing agent is one or more of sulfur, accelerator NS and accelerator CZ; the antioxidant is antioxidant 4020 and / or antioxidant RD.

[0015] As preferred, the preparation method of the tire high-thermal-conductivity base rubber comprises the following steps:

[0016] (1) mixing natural rubber, filler, SiO2 / C composite material, activator, antioxidant and microcrystalline wax to obtain a masterbatch;

[0017] (2) mixing the masterbatch and vulcanizing agent to obtain the tire high-thermal-conductivity base rubber.

[0018] As preferred, the rotation speed of the mixing in step (1) is 45-55 rpm, the mixing time is 30-50 s, the mixing time of the lifting and pressing of the plug is 20-30 s, and the discharge temperature of the mixing is 145-165℃.

[0019] As preferred, the rotation speed of the mixing in step (2) is 25-35 rpm; the mixing time is 30-50 s, the mixing time of the lifting and pressing of the plug is 20-30 s, and the discharge temperature of the mixing is 100-113℃.

[0020] The application provides an application of a SiO2 / C composite material in a tire high-thermal-conductivity base rubber. The composite material can effectively replace white carbon black in the preparation of the tire, and the prepared tire has low heat generation and high thermal conductivity. The SiO2 / C aggregate formed by the organic combination of carbonization of edible fungi and SiO2 has high dispersity, plays a role in reducing the Payne of the filler, thereby reducing heat generation. In addition, the application adopts porous silica material, so that the SiO2 and C are closely combined to form a thermal conduction channel, thereby enhancing the thermal conductivity of the filler and promoting the high thermal conductivity of the prepared rubber composition.

[0021] The application also provides a high-thermal-conductivity base rubber for tires, which comprises 90-110 parts of natural rubber, 0-45 parts of filler, 10-45 parts of SiO2 / C composite material, 4-10 parts of activator, 2-5 parts of vulcanizing agent, 2-5 parts of antioxidant and 0.5-1.5 parts of microcrystalline wax.

[0022] The application solves the problem of poor thermal conductivity caused by low heat build-up of white carbon black in low-rolling-resistance tires, and solves the dispersion problem of white carbon black, so that the prepared base rubber has better low heat build-up performance. DETAILED DESCRIPTION

[0023] The application provides application of a SiO2 / C composite material in high-thermal-conductivity base rubber for tires, and the high-thermal-conductivity base rubber for tires comprises the following raw materials in mass fraction:

[0024] The application provides application of a SiO2 / C composite material in high-thermal-conductivity base rubber for tires, and the high-thermal-conductivity base rubber for tires comprises the following raw materials in mass fraction:

[0025] In the application, the mass fraction of the natural rubber is preferably 92-108 parts, further preferably 95-105 parts, and more preferably 98-102 parts.

[0026] In the application, the mass fraction of the filler is preferably 5-40 parts, further preferably 10-30 parts, and more preferably 15-25 parts.

[0027] In the application, the mass fraction of the SiO2 / C composite material is preferably 15-40 parts, further preferably 20-35 parts, and more preferably 25-30 parts.

[0028] In the application, the mass fraction of the activator is preferably 6-9 parts, further preferably 7-8 parts, and more preferably 7.3-7.7 parts.

[0029] In the present application, the mass fraction of the vulcanizing agent is preferably 2.5-4.5 parts, further preferably 3-4 parts, and more preferably 3.3-3.7 parts.

[0030] In the present application, the mass fraction of the anti-aging agent is preferably 2.5-4.5 parts, further preferably 3-4 parts, and more preferably 3.3-3.7 parts.

[0031] In the present application, the mass fraction of the microcrystalline wax is preferably 0.6-1.4 parts, further preferably 0.7-1.3 parts, and more preferably 0.8-1.2 parts.

[0032] In the present application, the filler is one or more of carbon black N220, carbon black N234, carbon black N375, carbon black N347, carbon black N339, carbon black N330, carbon black N326, carbon black N660, and pyrolytic carbon black.

[0033] In the present application, the preparation method of the SiO2 / C composite material comprises the following steps:

[0034] (A) mixing the edible mushroom cultivation body with porous silicon dioxide to obtain a silicon dioxide composite edible mushroom cultivation body;

[0035] mixing the silicon dioxide composite edible mushroom cultivation body with edible mushrooms to culture the edible mushrooms; after the culture is completed, the edible mushrooms are removed, and the waste cultivation body is retained;

[0036] (B) carbonizing the waste cultivation body of step (A) to obtain a SiO2 / C composite material.

[0037] In the present application, the edible mushroom cultivation body of step (A) preferably comprises a biomass carbon source. The biomass carbon source includes but is not limited to one or more of cottonseed hulls, corn cobs, leaf wood chips, bean straw powder, wheat straw powder, peanut shells, bran, and rice bran.

[0038] In the present application, the source of the edible mushroom cultivation body of step (A) is not limited, and commercially available or non-commercial products known to those skilled in the art can be used.

[0039] In the present application, the porous silicon dioxide of step (A) preferably comprises one or more of silicon powder, carbon black, diatomite, diatom shale, opal, zeolite, and montmorillonite, further preferably comprises silicon powder, diatomite, diatom shale, opal, zeolite, or montmorillonite, and more preferably is silicon powder.

[0040] In the present application, the grade of the carbon black is preferably TSI-A5008.

[0041] In this invention, the particle size of the porous silica in step (A) is preferably 500 nm to 100 μm, more preferably 500 nm to 50 μm, and even more preferably 500 nm to 10 μm; the specific surface area is preferably 60 to 500 m². 2 / g, further preferably 60-300m 2 / g, more preferably 60-200m 2 / g; pore size preferably 2–100 nm; porosity preferably 0.1–5 cm³. 3 / g, more preferably 0.1–3cm 3 / g, more preferably 0.1-2cm 3 / g.

[0042] In this invention, the mass ratio of the porous silica to the edible fungus culture medium in step (A) is preferably 1:1 to 10, more preferably 1:2 to 4, and even more preferably 1:2.

[0043] In this invention, step (A) preferably includes sterilizing the silica composite edible fungus culture before mixing it with edible fungi.

[0044] In this invention, the sterilization conditions are not limited, and any method well known to those skilled in the art can be used. Specifically, in this embodiment of the invention, the sterilization process is performed at 120°C for 1.5 hours or more.

[0045] In this invention, the edible fungi mentioned in step (A) are preferably including, but not limited to, shiitake mushrooms, oyster mushrooms, or wood ear mushrooms. Preferably, in this embodiment of the invention, wood ear mushrooms are used as an example for cultivation.

[0046] In this invention, the time required to complete the culture in step (A) is preferably ≥3 months, more preferably ≥3.5 months, and even more preferably 4 months.

[0047] In this invention, step (B) preferably further includes, before carbonization, naturally drying the waste culture medium from step (A). The natural drying time is preferably 5–24 hours, more preferably 12–24 hours, and even more preferably 24 hours.

[0048] In this invention, the equipment used for carbonization in step (B) is preferably a carbonization furnace.

[0049] In this invention, in step (B), the carbonization is preferably carried out under a protective atmosphere; the protective atmosphere is preferably at least one of nitrogen or argon, more preferably nitrogen or argon, and even more preferably nitrogen.

[0050] In this invention, in step (B), the carbonization temperature is preferably 600-950°C, more preferably 700-900°C, and even more preferably 800°C; the time is preferably 10-60 min, more preferably 30-60 min, and even more preferably 60 min; the rate of heating to the desired carbonization temperature is preferably 5-15°C / min, more preferably 5-10°C / min, and even more preferably 5°C / min.

[0051] In this invention, the carbonization process described in step (B) preferably further includes sequential crushing and sieving.

[0052] In this invention, the crushing equipment is preferably a planetary ball mill.

[0053] In this invention, the crushing speed in step (B) is preferably 300-700 r / min, more preferably 400-600 r / min, and even more preferably 500 r / min; the time is preferably 15-60 min, more preferably 20-40 min, and even more preferably 30 min.

[0054] In this invention, the screening equipment is preferably a centrifugal classifier.

[0055] In this invention, the particle size D of the sieving in step (B) is... 50 Preferably, the wavelength is 500 nm to 45 μm, more preferably 500 nm to 20 μm, and even more preferably 500 nm to 10 μm.

[0056] In this invention, the activator is one or more of stearic acid, zinc oxide, zinc stearate and zinc lignin salt; the zinc lignin salt was purchased from Zhongce Rubber Tire Co., Ltd.

[0057] In this invention, the vulcanizing agent is one or more of sulfur, accelerator NS and accelerator CZ; the antioxidant is antioxidant 4020 and / or antioxidant RD.

[0058] In this invention, the method for preparing the high thermal conductivity base adhesive for tires includes the following steps:

[0059] (1) Natural rubber, filler, SiO2 / C composite material, activator, antioxidant and microcrystalline wax are mixed to obtain masterbatch;

[0060] (2) Mix the masterbatch and vulcanizing agent to obtain the high thermal conductivity base rubber of the tire.

[0061] In this invention, the mixing speed in step (1) is preferably 45-55 rpm, more preferably 46-54 rpm, and even more preferably 48-52 rpm; the mixing time is preferably 30-50 s, more preferably 35-45 s, and even more preferably 38-42 s; the mixing time for lifting and pressing the plug is preferably 20-30 s, more preferably 22-28 s, and even more preferably 24-26 s; the mixing discharge temperature is preferably 145-165℃, more preferably 150-160℃, and even more preferably 152-158℃.

[0062] In this invention, the mixing speed in step (2) is preferably 25-35 rpm, more preferably 26-34 rpm, and even more preferably 28-32 rpm; the mixing time is preferably 30-50 s, more preferably 35-45 s, and even more preferably 38-42 s; the mixing time for lifting and pressing the plug is preferably 20-30 s, more preferably 22-28 s, and even more preferably 24-26 s; the mixing discharge temperature is preferably 100-113℃, more preferably 102-110℃, and even more preferably 104-106℃.

[0063] The technical solutions provided by the present invention will be described in detail below with reference to the embodiments, but they should not be construed as limiting the scope of protection of the present invention.

[0064] Example 1

[0065] Preparation of SiO2 / C composite materials

[0066] 2 kg of Auricularia auricula-judae culture medium (source: Science and Technology Demonstration Park of Dongjingcheng Forestry Bureau, Heilongjiang Province) was mixed with 200 g of silica powder (D 50 -8μm, model TSI-1, manufactured by Harbin Silicon Ge New Materials Co., Ltd., particle size 500nm~10μm, specific surface area 60~200m² 2 / g, pore size 2–100 nm, porosity 0.1–2 cm³ 3 Mix (g) evenly to obtain silica composite edible fungi culture medium;

[0067] After sterilizing the silica composite edible fungus culture at 120℃ for 1.5 hours, Auricularia auricula-judae was inoculated into the silica composite edible fungus culture for cultivation. After 3 months of cultivation, the mature Auricularia auricula-judae was removed and the waste culture was retained.

[0068] The waste culture medium was naturally dried for 24 hours, then placed in a carbonization furnace and carbonized at 800℃ for 60 minutes under nitrogen protection at a heating rate of 5℃ / min. The resulting silicon-carbon composite was then ball-milled in a planetary ball mill at 500 rpm for 30 minutes. The ball-milled sample was then sieved by a centrifugal classifier to determine the particle size D. 50 Samples with a diameter ≤3μm were used to obtain SiO2 / C composite materials.

[0069] Take 100 parts of natural rubber, 45 parts of SiO2 / C composite material, 6 parts of activator (2 parts of stearic acid and 4 parts of zinc oxide), 2.5 parts of antioxidant (1.5 parts of antioxidant 4020 and 1 part of RD), 1 part of microcrystalline wax and 4 parts of vulcanizing agent (1 part of oil-extended 10% sulfur, 1 part of insoluble sulfur 7020 and 2 parts of accelerator NS).

[0070] Natural rubber, SiO2 / C composite material, activator, antioxidant and microcrystalline wax are put into a mixer, the speed is set to 50 rpm, and the mixture is mixed for 35 seconds. Then, the mixture is mixed for 20 seconds with the plug lifted and pressed, until the discharge temperature is 155℃, and the masterbatch is obtained.

[0071] Start the internal mixer, set the speed to 30 rpm, add the masterbatch and vulcanizing agent, mix for 30 seconds, then mix for 20 seconds with the piston lifting and pressing, until the discharge temperature is 105℃, to obtain the high thermal conductivity base rubber for tires.

[0072] Example 2

[0073] The difference between Example 2 and Example 1 is that 25 parts of carbon black N330 were added, and the SiO2 / C composite material was adjusted to 25 parts.

[0074] Comparative Example 1

[0075] The difference between Comparative Example 1 and Example 1 is that SiO2 / C composite material was not added, but 45 parts of silica GR175 were added.

[0076] Comparative Example 2

[0077] The difference between Comparative Example 2 and Example 2 is that SiO2 / C composite material was not added, but 25 parts of silica GR175 were added.

[0078] The base adhesives of Examples 1 and 2 and Comparative Examples 1 and 2 were subjected to performance tests according to GB / T528-1998, and the results are recorded in Table 1.

[0079] Table 1 Test Results

[0080] Case Comparative Example 1 Comparative Example 2 Example 1 Example 2 Tan δ / 60°C 0.066 0.078 0.062 0.073 M300 12.5 13.3 12.1 13.2 TB 27.5 27.7 27.0 27.2 E.B% 523 520 532 515 Thermal conductivity 0.178 0.210 0.256 0.258

[0081] Note: DMA test tanδ / 60℃ conditions 151℃×30min (test conditions frequency 20Hz, strain 10±2%, temperature scan 0℃~80℃).

[0082] As can be seen from the above examples, the reinforcing effect of SiO2 / C composite materials is similar to that of silica, and the heat generation of SiO2 / C composite materials is similar, but the thermal conductivity is significantly improved. These examples demonstrate that rubber compositions prepared using SiO2 / C composite materials possess both low heat generation and high thermal conductivity.

[0083] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. The application of a SiO2 / C composite material in a high thermal conductivity base adhesive for tires, characterized in that, The high thermal conductivity base rubber of the tire comprises the following raw materials in parts by weight: 90-110 parts natural rubber, 0-45 parts filler, 10-45 parts SiO2 / C composite material, 4-10 parts activator, 2-5 parts vulcanizing agent, 2-5 parts antioxidant, and 0.5-1.5 parts microcrystalline wax; The preparation method of the SiO2 / C composite material includes the following steps: (A) Mix edible fungus culture medium with porous silica to obtain silica composite edible fungus culture medium; The silica composite edible fungus culture medium is mixed with edible fungi for edible fungus cultivation; after cultivation is completed, the edible fungi are removed and the waste culture medium is retained. (B) Carbonize the waste culture medium described in step (A) to obtain a SiO2 / C composite material; The porous silica is one or more of the following: silica lattice powder, diatomaceous earth, diatom shale, opal, zeolite, and montmorillonite.

2. The application of the SiO2 / C composite material as described in claim 1 in the high thermal conductivity base adhesive of tires, characterized in that, The filler is one or more of carbon black N220, carbon black N234, carbon black N375, carbon black N347, carbon black N339, carbon black N330, carbon black N326, carbon black N660, and pyrolysis carbon black.

3. The application of the SiO2 / C composite material as described in claim 2 in the high thermal conductivity base adhesive of tires, characterized in that, The activator is one or more of stearic acid, zinc oxide, zinc stearate, and zinc lignin salt.

4. The application of the SiO2 / C composite material as described in claim 3 in the high thermal conductivity base adhesive of tires, characterized in that, The vulcanizing agent is one or more of sulfur, accelerator NS and accelerator CZ; the antioxidant is antioxidant 4020 and / or antioxidant RD.

5. The application of the SiO2 / C composite material as described in claim 4 in the high thermal conductivity base adhesive of tires, characterized in that, The method for preparing the high thermal conductivity base adhesive for tires includes the following steps: (1) Natural rubber, filler, SiO2 / C composite material, activator, antioxidant and microcrystalline wax are mixed to obtain masterbatch; (2) Mix the masterbatch and vulcanizing agent to obtain the high thermal conductivity base rubber of the tire.

6. The application of the SiO2 / C composite material as described in claim 5 in the high thermal conductivity base adhesive of tires, characterized in that, The mixing speed in step (1) is 45~55 rpm, the mixing time is 30~50 s, the mixing time for lifting and pressing the plug is 20~30 s, and the discharging temperature of the compound is 145~165℃.

7. The application of the SiO2 / C composite material as described in claim 6 in the high thermal conductivity base adhesive of tires, characterized in that, The mixing speed in step (2) is 25~35 rpm; the mixing time is 30~50s; the mixing time for lifting and pressing the plug is 20~30s; and the discharging temperature of the compound is 100~113℃.