Application of SiO2 / C composite material in tire cushion rubber

Abstract

The invention belongs to the technical field of tire cushion rubber, and provides application of a SiO2 / C composite material in tire cushion rubber. The tire cushion rubber comprises the following components in parts by mass: 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 activating agent, 3-6 parts of vulcanizing agent and 2-5 parts of anti-aging agent. The SiO2 / C composite material is used for preparing the tire cushion rubber and can effectively replace white carbon black or carbon black, and the prepared tire cushion rubber has low heat generation performance and also has good high temperature resistance. Specifically, the SiO2 / C aggregate has high dispersity and can play a role in reducing the Payne effect of the filler, so that heat generation is reduced; the porosity of the SiO2 / C composite material promotes the tight combination of the rubber and the filler, and the formed tight combination rubber enables the prepared tire cushion rubber composition to have excellent high temperature resistance.

Description

Technical Field

[0001] The invention relates to the technical field of tire cushion rubber, and in particular to application of a SiO2 / C composite material in tire cushion rubber. Background Art

[0002] The cushion rubber is a transition layer, known as the heart of the tire. It has the function of transferring and absorbing the stress of the shoulder and connecting the upper and lower parts. In addition, the cushion rubber is in a high stress area and needs to be continuously subjected to tensile and compressive stress. It is thickest at the shoulder and generates high heat. Therefore, the cushion rubber formula not only needs to have low heat generation and good flex resistance, but also needs to have excellent high temperature resistance, tensile tearing and elasticity. In order to improve heat resistance, the cushion rubber currently developed usually increases the content of single sulfur bonds and disulfide bonds. The result is poor fatigue, which makes it difficult to meet the high fatigue performance required for the cushion rubber. Therefore, it is very important to develop a cushion rubber with low heat generation, high fatigue and high temperature resistance, which is also a major problem in the industry. Summary of the invention

[0003] The purpose of the present invention is to overcome the problems existing in the prior art and provide an application of a SiO2 / C composite material in tire cushion rubber.

[0004] In order to achieve the above-mentioned object of the invention, the present invention provides the following technical solutions:

[0005] The present invention provides an application of a SiO2 / C composite material in a tire cushion rubber, wherein the tire cushion rubber comprises the following components in parts by mass:

[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 vulcanizer and 2-5 parts of antioxidant.

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

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

[0009] (1) mixing the edible fungus cultivation body with porous silica to obtain a silica composite edible fungus cultivation body;

[0010] The silicon dioxide composite edible fungus cultivation body is mixed with edible fungi to culture the edible fungi; after the culture is completed, the edible fungi are removed and the discarded cultivation body is retained;

[0011] (2) Carbonizing the discarded culture medium in step (1) to obtain a SiO2 / C composite material.

[0012] Preferably, the silane coupling agent includes 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 includes one or more of insoluble sulfur, accelerator NS and accelerator CZ.

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

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

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

[0018] The beneficial effects of the present invention are:

[0019] The present invention provides an application of SiO2 / C composite material in tire cushion rubber, wherein the tire cushion rubber comprises the following components in parts by mass: 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 vulcanizer and 2-5 parts of antioxidant. The SiO2 / C composite material is used to prepare tire cushion rubber, which can effectively replace white carbon black or carbon black, and the prepared tire cushion rubber has low heat generation performance and good high temperature resistance performance. Specifically, the present invention utilizes the carbonization of edible fungi to organically combine with silicon dioxide, and the formed SiO2 / C aggregate has high dispersibility, which can play a role in reducing the Payne effect of filler, thereby reducing heat generation; secondly, since porous silicon dioxide material is selected when preparing SiO2 / C composite material, SiO2 and C can be tightly combined, and the porosity of SiO2 / C composite material promotes the tight combination of rubber and filler, and the formed tight combination glue makes the prepared tire cushion rubber composition have excellent high temperature resistance. The rubber composition prepared by the present invention is used for tire cushion rubber, which has the characteristics of low heat generation, good flex resistance, good high temperature resistance, excellent tensile tearing resistance and elasticity. DETAILED DESCRIPTION

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

[0021] 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 vulcanizer and 2-5 parts of antioxidant.

[0022] In the present invention, the mass fraction of the filler is 0 to 45 parts, preferably 5 to 35 parts, more preferably 10 to 30 parts, and even more preferably 15 to 20 parts.

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

[0024] In the present invention, the mass fraction of the silane coupling agent is 0 to 5 parts, preferably 1 to 4 parts, more preferably 2 to 3 parts, and even more preferably 2.5 parts.

[0025] In the present invention, the mass fraction of the activator is 4 to 10 parts, preferably 5 to 9 parts, more preferably 6 to 8 parts, and even more preferably 7 to 7.5 parts.

[0026] In the present invention, the mass fraction of the vulcanizing agent is 3 to 6 parts, preferably 3.5 to 5.5 parts, more preferably 4 to 5 parts, and even more preferably 4.5 to 4.7 parts.

[0027] In the present invention, the weight percentage of the antioxidant is 2 to 5 parts, preferably 2.5 to 4.5 parts, more preferably 3 to 4 parts, and even more preferably 3.5 to 3.7 parts.

[0028] In the present invention, 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 present invention, the preparation method of the SiO2 / C composite material preferably comprises the following steps:

[0030] (1) mixing the edible fungus cultivation body with porous silica to obtain a silica composite edible fungus cultivation body;

[0031] The silicon dioxide composite edible fungus cultivation body is mixed with edible fungi to culture the edible fungi; after the culture is completed, the edible fungi are removed and the discarded cultivation body is retained;

[0032] (2) Carbonizing the discarded culture medium in step (1) to obtain a SiO2 / C composite material.

[0033] In the present invention, the edible fungus culture medium in step (1) preferably includes a biomass carbon source, which includes but is not limited to one or more of cottonseed hulls, corn cobs, leaf and wood chips, bean straw powder, wheat straw powder, peanut shells, bran and rice bran.

[0034] In the present invention, the source of the edible fungus culture medium in step (1) is not limited, and commercially available or non-commercially available products known to those skilled in the art may be used.

[0035] In the present invention, the porous silica in step (1) preferably includes one or more of silica powder, carbon monoxide, diatomaceous earth, diatom shale, opal, zeolite and montmorillonite, and further preferably includes silica powder, diatomaceous earth, diatom shale, opal, zeolite or montmorillonite, and more preferably silica powder.

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

[0037] In the present invention, the particle size of the porous silica in step (1) is preferably 500 nm to 100 μm, more 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, more preferably 60 to 300 m 2 / g, more preferably 60 to 200 m 2 / g; the pore size is preferably 2 to 100 nm; the porosity is preferably 0.1 to 5 cm 3 / g, more preferably 0.1 to 3 cm 3 / g, more preferably 0.1 to 2 cm 3 / g.

[0038] In the present invention, the mass ratio of the porous silica to the edible fungus culture medium in step (1) is preferably 1:1-10, more preferably 1:2-4, and even more preferably 1:2.

[0039] In the present invention, the step (1) preferably further comprises: sterilizing the silica composite edible fungus cultivation body before mixing the silica composite edible fungus cultivation body with the edible fungus.

[0040] In the present invention, the conditions for the sterilization treatment are not limited, and a method familiar to those skilled in the art can be used. Specifically, in the embodiment of the present invention, the sterilization treatment is carried out at 120° C. for 1.5 h or more.

[0041] In the present invention, the edible fungi in step (1) preferably include but are not limited to shiitake mushrooms, oyster mushrooms or black fungus. Preferably, the embodiment of the present invention takes black fungus as an example for cultivation.

[0042] In the present invention, the time to complete the culture in step (1) is preferably ≥3 months, more preferably ≥3.5 months, and more preferably 4 months.

[0043] In the present invention, step (2) preferably further comprises: naturally drying the waste culture medium of step (1) before the carbonization. The natural drying time is preferably 5 to 24 hours, more preferably 12 to 24 hours, and more preferably 24 hours.

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

[0045] In the present invention, 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, more preferably nitrogen or argon, and more preferably nitrogen.

[0046] In the present invention, in step (2), the carbonization temperature is preferably 600-950°C, more preferably 700-900°C, and more preferably 800°C; the time is preferably 10-60 min, more preferably 30-60 min, and 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 more preferably 5°C / min.

[0047] In the present invention, the carbonization in step (2) preferably further comprises: crushing and screening in sequence.

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

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

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

[0051] In the present invention, the particle size D of the screening in step (2) is 50 It is preferably 500 nm to 45 μm, more preferably 500 nm to 20 μm, and still more preferably 500 nm to 10 μm.

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

[0053] In the present invention, the activator preferably includes one or more of stearic acid, zinc oxide, zinc stearate and lignin zinc salt; the preparation method of the lignin zinc salt refers to patent CN115678038B.

[0054] In the present invention, the vulcanizing agent preferably includes one or more of insoluble sulfur, accelerator NS and accelerator CZ.

[0055] In the present invention, the antioxidant preferably includes one or more of antioxidant 4020, antioxidant RD and antioxidant DTPD.

[0056] In the present invention, the preparation method of the tire cushion rubber preferably comprises the following steps:

[0057] The natural rubber, filler, SiO2 / C composite material, activator and antioxidant are mixed and kneaded for the first time to obtain a masterbatch; the masterbatch and vulcanizing agent are mixed and kneaded for the second time to obtain the tire cushion rubber.

[0058] In the present invention, the first mixing preferably comprises the following steps: starting an internal mixer, setting the speed of the internal mixer to 45-55r / min, adding natural rubber, filler, SiO2 / C composite material, activator and antioxidant, mixing for 30-50s, lifting the bolt and pressing the bolt after mixing for 20-30s, lifting the bolt and pressing the bolt to mix to 145-165°C for rubber discharge to obtain a masterbatch; the speed of the internal mixer is preferably 45-55r / min, more preferably 47-53r / min, and more preferably 50r / min; the mixing time is preferably 30-50s, more preferably 35-45s, and more preferably 40s; the mixing time of lifting the bolt and pressing the bolt is preferably 20-30s, more preferably 22-28s, and more preferably 25s; the temperature of rubber discharge is preferably 145-165°C, more preferably 150-160°C, and more preferably 152-155°C.

[0059] In the present invention, the second mixing preferably comprises the following steps: starting the internal mixer, setting the speed of the internal mixer to 25-35r / min, adding the masterbatch and the vulcanizing agent, mixing for 30-50s, lifting the bolt and pressing the bolt after the mixing is completed, mixing for 20-30s, lifting the bolt and pressing the bolt to mix to 95-110°C for rubber discharge, and obtaining the tire cushion rubber; the speed of the internal mixer is preferably 25-35r / min, more preferably 27-33r / min, and more preferably 30r / min; the mixing time is preferably 30-50s, more preferably 35-45s, and more preferably 40s; the mixing time of lifting the bolt and pressing the bolt is preferably 20-30s, more preferably 22-28s, and more preferably 25s; the temperature of rubber discharge is preferably 95-110°C, more preferably 100-105°C, and more preferably 102-103°C.

[0060] The technical solutions provided by the present invention are described in detail below in conjunction with the embodiments, but they should not be construed as limiting the protection scope of the present invention.

[0061] Example 1

[0062] The components and their weight fractions in this embodiment 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 Auricularia auricula culture (from the Science and Technology Demonstration Park of Dongjingcheng Forestry Bureau, Heilongjiang) and 200 g of silica powder (D 50 -8μm, model TSI-1, manufacturer is Harbin Silicon New Materials Co., Ltd., particle size is 500nm~10μm, specific surface area is 60~200m 2 / g, pore size is 2~100nm, porosity is 0.1~2cm 3 / g) and evenly mixed to obtain a silicon dioxide composite edible fungus culture body;

[0066] After sterilizing the silica composite edible fungus culture body at 120° C. for 1.5 h, inoculating the auricularia auricula into the silica composite edible fungus culture body for cultivation, and after the auricularia auricula has been cultivated for 3 months, removing the mature auricularia auricula and retaining the discarded culture body;

[0067] The waste culture body was naturally dried for 24 hours, and then placed in a carbonization furnace, heated to 800°C at a heating rate of 5°C / min under nitrogen protection for carbonization for 60 minutes, and the carbonized silicon-carbon composite was ball-milled in a planetary ball mill at a speed of 500r / min for 30 minutes, and then the ball-milled sample was sieved by a centrifugal classifier to obtain a particle size D 50 Samples with a diameter of ≤3 μm were used to obtain SiO2 / C composite materials;

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

[0069] Start the internal mixer, set the speed of the internal mixer to 25r / min, add the masterbatch and vulcanizer, mix for 30s, lift the bolt and press the bolt after mixing for 20s, lift the bolt and press the bolt to mix until the glue is discharged at 105℃ to obtain the tire cushion rubber.

[0070] Example 2

[0071] The other conditions in Example 1 remain unchanged, the mass fraction of filler (carbon black N330) is modified to 10 parts, the mass fraction of SiO2 / C composite material is modified to 30 parts, and the mass fraction of silane coupling agent (Si-69) is modified to 3 parts, to obtain tire cushion rubber.

[0072] Comparative Example 1

[0073] The other conditions in Example 1 remain unchanged, the mass fraction of the filler (carbon black N330) is modified to 32 parts, and the mass fraction of the SiO2 / C composite material is modified to 0 parts, to obtain a tire cushion rubber.

[0074] Comparative Example 2

[0075] The other conditions in Example 1 are kept unchanged, the mass fraction of the silane coupling agent (Si-69) is changed to 3 parts, the types of fillers are changed to carbon black N330 and white carbon black GR175 (purchased from Quecheng Silicon Chemical Co., Ltd.), wherein the mass fraction of carbon black N330 is 10 parts, the mass fraction of white carbon black GR175 is 30 parts, and the mass fraction of the SiO2 / C composite material is changed to 0 parts, to obtain a tire cushion rubber.

[0076] The tire cushion rubbers obtained in Examples 1 to 2 and Comparative Examples 1 to 2 were subjected to performance tests, and the performance test results of the tire cushion rubbers obtained in Examples 1 to 2 and Comparative Examples 1 to 2 were obtained, as shown in Table 1.

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

[0078]

[0079] It can be seen from the above comparative examples 1 and 2 and examples 1 and 2 that the reinforcing effect of the SiO2 / C composite material is similar to that of white carbon black GR175 and 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 rubber prepared by the SiO2 / C composite material of the present invention has low heat generation performance and good high temperature resistance performance.

[0080] It can be seen from the above embodiments that the present invention provides an application of SiO2 / C composite material in tire cushion rubber, and the tire cushion rubber contains the following components by mass: 100 parts of natural rubber, 0-40 parts of filler, 10-50 parts of SiO2 / C composite material, 4-10 parts of activator, 3-6 parts of vulcanizer and 2-5 parts of antioxidant. The SiO2 / C composite material is used to prepare tire cushion rubber, which can effectively replace white carbon black or carbon black. The prepared tire cushion rubber has low heat generation performance and good high temperature resistance. Specifically, the present invention utilizes the carbonization of edible fungi and organically combines with silica to form SiO2 / C aggregates with high dispersibility, which can play a role in reducing the Payne effect of filler, thereby reducing heat generation; secondly, since porous silica material is selected when preparing SiO2 / C composite material, SiO2 and C can be tightly combined, and the porosity of SiO2 / C composite material promotes the tight combination of rubber and filler, and the tightly combined glue formed makes the prepared tire cushion rubber composition have excellent high temperature resistance. The rubber composition prepared by the present invention is used for tire cushion rubber, which has the characteristics of low heat generation, good flex resistance, good high temperature resistance, excellent tensile tearing resistance and elasticity.

[0081] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.

Claims

1. Application of SiO2 / C composite material in tire cushion rubber, characterized in that: The tire cushion rubber comprises the following components in parts by mass: 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 vulcanizer and 2-5 parts of antioxidant.

2. The use of the SiO2 / C composite material in tire cushion rubber according to claim 1, characterized in that: The filler includes one or more of N330, N375, N234, N660 and N326.

3. The use of the SiO2 / C composite material as claimed in claim 1 or 2 in tire cushion rubber, characterized in that: The preparation method of the SiO2 / C composite material comprises the following steps: (1) mixing the edible fungus cultivation body with porous silica to obtain a silica composite edible fungus cultivation body; The silicon dioxide composite edible fungus cultivation body is mixed with edible fungi to culture the edible fungi; after the culture is completed, the edible fungi are removed and the discarded cultivation body is retained; (2) Carbonizing the discarded culture medium in step (1) to obtain a SiO2 / C composite material.

4. The use of the SiO2 / C composite material in tire cushion rubber according to claim 3, characterized in that: The silane coupling agent includes one or more of Si-69, Si-75 and Si-747.

5. The use of the SiO2 / C composite material in tire cushion rubber according to claim 4, characterized in that: The activator comprises one or more of stearic acid, zinc oxide, zinc stearate and lignin zinc salt.

6. The use of the SiO2 / C composite material in tire cushion rubber according to claim 5, characterized in that: The vulcanizing agent includes one or more of insoluble sulfur, accelerator NS and accelerator CZ.

7. The use of the SiO2 / C composite material in tire cushion rubber according to claim 6, characterized in that: The antioxidant includes one or more of antioxidant 4020, antioxidant RD and antioxidant DTPD.

8. The use of the SiO2 / C composite material in tire cushion rubber according to claim 7, characterized in that: The preparation method of the tire cushion rubber comprises the following steps: The natural rubber, filler, SiO2 / C composite material, activator and antioxidant are mixed and kneaded for the first time to obtain a masterbatch; the masterbatch and vulcanizing agent are mixed and kneaded for the second time to obtain the tire cushion rubber.

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