A rubber composite, a method for the preparation thereof and the resulting tyre

Abstract

The application provides a rubber composite material, a preparation method thereof and a resultant tire, and belongs to the technical field of tire rubber materials.The rubber composite material provided by the application uses carbon fraction white carbon black as a reinforcing agent, so that the vulcanization characteristics Tc90 of the obtained rubber composite material reaches 14.82 min, the MH reaches 31.28 dNm, the tear strength of the vulcanized rubber reaches 68.15 kN / m, and the tear strength after aging reaches 31.86 kN / m, which are significantly better than the vulcanization, mechanical and aging properties of a traditional acid precipitation method white carbon black reinforced rubber composite material, and effectively improve the production efficiency, driving safety and service life of the tire.In addition, the carbon fraction white carbon black used in the rubber composite material is a carbon dioxide recycling chemical, and the reasonable use of the carbon fraction white carbon black in the rubber composite material has a positive effect on promoting the sustainable development of modern industry and achieving carbon peak and carbon neutralization, and at the same time avoids environmental pollution problems such as sulfuric acid leakage caused by the traditional acid precipitation method.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of tire rubber materials, and particularly relates to a rubber composite material, a preparation method thereof and a tire obtained. BACKGROUND

[0002] White carbon black is widely used as a reinforcing filler in the tire rubber industry, has the advantages of good chemical stability, high temperature resistance, porosity, and large specific surface area, and can significantly improve the mechanical properties, heat generation, and wet skid resistance of tire rubber. At present, the white carbon black used in tire rubber composites is mostly acid precipitation white carbon black, which has more silanol groups on the surface and is mostly acidic in pH, which can reduce the vulcanization speed of the rubber compound, increase the production cost of the tire, and the ordinary acid precipitation white carbon black also has the disadvantages of relatively large particle size, small specific surface area and structure, which can weaken the reinforcing effect of the white carbon black.

[0003] CO2 is an industrial by-product, with a global emission of 36.8 billion tons in 2023, showing a continued upward trend compared to 2022. Carbon emission reduction and the rational recycling of carbon dioxide have become a key link in the current ecological environment protection and sustainable development. If the carbon dioxide recycling products can be used in the production of radial tire formulations, it will have a positive effect on promoting the sustainable development of modern industry and achieving carbon peak and carbon neutralization. SUMMARY

[0004] The present application provides a rubber composite material, a preparation method thereof and a tire obtained, which uses carbon fraction white carbon black as a reinforcing agent, overcoming the problems of traditional acid precipitation white carbon black, such as delayed vulcanization, relatively small specific surface area and structure, and poor reinforcing performance of the rubber compound, and has a positive effect on promoting the sustainable development of modern industry and accelerating carbon peak and carbon neutralization.

[0005] In order to achieve the above-mentioned purpose, the present application provides a rubber composite material, which uses carbon fraction white carbon black as a reinforcing agent, and the obtained rubber composite material has a vulcanization characteristic Tc90 of 14.82 min, a MH of 31.28 dNm, a tear strength of the vulcanized rubber of 68.15 kN / m, and a tear strength after aging of 31.86 kN / m after 40 min of vulcanization test at 151℃.

[0006] As preferred, the rubber composite further comprises natural rubber, carbon black, vulcanizing agent and vulcanizing accelerator, and the mass ratio of carbon black to natural rubber, carbon black, vulcanizing agent and vulcanizing accelerator is 2-2.2:20-22:8.8-9:1-1.1:0.18-0.2. It can be understood that the scheme limits the addition ratio of each component, and too much or too little of any component in the above ratio will cause the processing performance of the rubber composite to be poor, the vulcanization speed, the Mooney viscosity, the hardness to be too high or too low, and thus affect the mechanical properties and other related properties of the rubber composite.

[0007] As preferred, the carbon black is carbon black N375, the BET is 103 m 2 / g; the vulcanizing agent is insoluble sulfur HD-OT20-A grade; and the vulcanizing accelerator is vulcanizing accelerator NS.

[0008] As preferred, the rubber composite further comprises active agent, adhesive and antioxidant, and the mass ratio of carbon black to active agent, adhesive and antioxidant is 2-2.2:1.5-1.7:1.4-1.6:0.4-0.41. It can be understood that the scheme limits the addition ratio of each component, and too much or too little of any component in the above ratio will cause the processing performance of the rubber composite to be poor, the vulcanization speed, the Mooney viscosity, the hardness to be too high or too low, and thus affect the mechanical properties and other related properties of the rubber composite.

[0009] As preferred, the active agent is indirect zinc oxide;

[0010] The adhesive is a mixture of resorcinol formaldehyde resin, cobalt decanoate and adhesive RA;

[0011] The antioxidant is a mixture of antioxidant 4020 and antioxidant RD.

[0012] As preferred, the mass ratio of resorcinol formaldehyde resin, cobalt decanoate and adhesive RA in the adhesive is 1:0.7-0.8:3.2-3.4;

[0013] The mass ratio of antioxidant 4020 and antioxidant RD in the antioxidant is 1:0.3-0.4.

[0014] As preferred, the carbon black prepared by the carbon separation method has a pH of 7.2, a BET of 224.4 m 2 / g, and a DBP absorption value of 2.64 cm 3 / g; when used in a rubber composite, compared with acid precipitation method carbon black, it can improve the vulcanization speed of the rubber composite compound, and the Tc90 reaches 14.82 min.

[0015] It can be understood that, compared with traditional acid precipitation method white carbon black, carbon separation method white carbon black has larger specific surface area and structure degree at the same time, which can make rubber composite material have better tear strength and aging performance, and can effectively improve the vulcanization speed, mechanical properties and aging performance of rubber composite material. Carbon separation method white carbon black is a carbon dioxide recycling chemical, and its reasonable use in rubber composite material has a positive effect on promoting the sustainable development of modern industry and realizing carbon peak and carbon neutral. Compared with traditional acid precipitation method white carbon black, carbon separation method white carbon black can provide the required alkaline catalytic conditions for the vulcanization reaction of sulfur atoms and rubber molecular chains, and improve the vulcanization speed of the rubber. The acidic environment provided by the acid precipitation method white carbon black with acidic surface will have the opposite effect, that is, it will delay vulcanization. Compared with traditional acid precipitation method white carbon black, carbon separation method white carbon black has larger specific surface area and structure degree, and can be better dispersed in the composite material when reinforcing rubber composite material, thereby improving the mechanical properties such as tear strength of the rubber composite material. The high chemical stability, high temperature chemical resistance and more stable chemical bonds formed by the physical hydrogen bonds between white carbon black and rubber enable carbon separation method white carbon black to have good dispersion in the rubber matrix, thereby endowing the rubber composite material with better thermal oxidative aging performance.

[0016] The application further provides a preparation method of the rubber composite material according to any one of the above technical solutions, comprising the following steps:

[0017] The carbon separation method white carbon black, natural rubber, carbon black, active agent, adhesive and anti-aging agent are placed in a banbury mixer, and mixed at 140-160 DEG C for 2-4 min; after uniform mixing, the rubber is discharged and pressed into a sheet to obtain a first-stage masterbatch;

[0018] The obtained first-stage masterbatch, vulcanizing agent, vulcanization accelerator and adhesive are placed in a banbury mixer, and mixed uniformly; after discharging the rubber, the rubber is pressed into a sheet to obtain a final rubber compound;

[0019] The obtained final rubber compound is placed in a vulcanizing machine and vulcanized at 151 DEG C for 30 min to obtain a rubber composite material.

[0020] Preferably, the vulcanization characteristics Tc90 of the obtained rubber composite material reaches 14.82 min, the MH reaches 31.28 dNm, the tear strength of the vulcanized rubber reaches 68.15 kN / m, and the tear strength after aging reaches 31.86 kN / m.

[0021] The application further provides a tire prepared from the rubber composite material according to any one of the above technical solutions.

[0022] Compared with the prior art, the application has the advantages and positive effects that:

[0023] 1. The rubber composite provided by the present application uses carbon separation method white carbon black as a reinforcing agent, so that the vulcanization characteristics Tc90 of the obtained rubber composite can reach 14.82 min, the MH can reach 31.28 dNm, the tear strength of the vulcanized rubber can reach 68.15 kN / m, and the tear strength after aging can reach 31.86 kN / m, which is significantly better than the vulcanization, mechanical properties and aging properties of traditional acid precipitation method white carbon black reinforced rubber composite, effectively improving the production efficiency, driving safety and service life of the tire.

[0024] 2. The carbon separation method white carbon black used in the rubber composite provided by the present application is a carbon dioxide recycling chemical, and its reasonable use in the rubber composite has a positive effect on promoting the sustainable development of modern industry and achieving carbon peak and carbon neutralization, and at the same time avoids the environmental pollution problems such as sulfuric acid leakage caused by traditional acid precipitation method. DETAILED DESCRIPTION

[0025] The technical solutions in the embodiments of the present application will be described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present application, not all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor belong to the scope of protection of the present application.

[0026] Embodiment 1

[0027] Preparation of carbon separation method white carbon black rubber composite:

[0028] 2.2 parts of carbon separation method white carbon black, 21 parts of natural rubber, 8.8 parts of carbon black N375, 1.6 parts of indirect method zinc oxide, 0.3 parts of resorcinol formaldehyde adhesive resin, 0.24 parts of cobalt decanoate, 0.3 parts of antioxidant 4020 and 0.1 parts of antioxidant RD were placed in a mixer, mixed at 150℃ for 3min, and then the rubber was pressed into a sheet after uniform mixing, to obtain a first-stage masterbatch;

[0029] The obtained first-stage masterbatch, 1 part of insoluble sulfur OT20, 0.19 parts of vulcanization accelerator NS and 1 part of adhesive RA were placed in a mixer, mixed uniformly, and then the rubber was pressed into a sheet after rubber discharge, to obtain a final rubber;

[0030] The obtained final rubber was placed in a vulcanizing machine and vulcanized at 151℃ for 30min to obtain a carbon separation method white carbon black rubber composite.

[0031] The carbon separation method white carbon black rubber composite prepared in this embodiment was subjected to performance detection, and the detection standards of the mixing rubber vulcanization characteristics Tc90, MH and the vulcanized rubber tear strength, hot air aging corresponded to GB / T 16584-1996, GB / T529-2008 and GB / T 3512-2001 respectively.

[0032] The results show that the mixing rubber of the carbon separation method white carbon black rubber composite material prepared in this embodiment has vulcanization characteristics Tc90 of 14.52 min, MH of 31.05 dNm, vulcanized rubber tear strength of 66.87 kN / m, and aging tear strength of 30.74 kN / m after 40 min of vulcanization test at 151°C, which is significantly better than the performance of the rubber composite material prepared by the traditional ordinary acid precipitation method white carbon black, effectively improving the production efficiency, driving safety and service life of the tire.

[0033] Example 2

[0034] Preparation of carbon separation method white carbon black rubber composite material:

[0035] Put 2 parts of carbon separation method white carbon black, 22 parts of natural rubber, 9 parts of carbon black N375, 1.7 parts of indirect method zinc oxide, 0.32 parts of resorcinol formaldehyde adhesive resin, 0.25 parts of cobalt decanoate, 0.3 parts of antioxidant 4020 and 0.11 parts of antioxidant RD in an internal mixer, mix at 150°C for 3 min, and after uniform mixing, discharge and press into a sheet to obtain a first-stage masterbatch;

[0036] Put the obtained first-stage masterbatch, 1.1 parts of insoluble sulfur OT20, 0.2 parts of vulcanization accelerator NS and 1.03 parts of adhesive RA in an internal mixer, mix uniformly, discharge and press into a sheet to obtain a final rubber;

[0037] Put the obtained final rubber in a vulcanizing machine and vulcanize at 151°C for 30 min to obtain a carbon separation method white carbon black rubber composite material.

[0038] The carbon separation method white carbon black rubber composite material prepared in this embodiment was subjected to performance detection, and the mixing rubber vulcanization characteristics Tc90, MH and vulcanized rubber tear strength, hot air aging detection standards corresponded to GB / T 16584-1996, GB / T529-2008, GB / T 3512-2001 respectively.

[0039] The results show that the mixing rubber of the carbon separation method white carbon black rubber composite material prepared in this embodiment has vulcanization characteristics Tc90 of 14.52 min, MH of 31.05 dNm, vulcanized rubber tear strength of 66.87 kN / m, and aging tear strength of 30.74 kN / m after 40 min of vulcanization test at 151°C, which is significantly better than the performance of the rubber composite material prepared by the traditional ordinary acid precipitation method white carbon black, effectively improving the production efficiency, driving safety and service life of the tire.

[0040] Example 3

[0041] Preparation of carbon separation method white carbon black rubber composite material:

[0042] Put 2 parts of carbon separation method white carbon black, 20 parts of natural rubber, 8.8 parts of carbon black N375, 1.5 parts of indirect method zinc oxide, 0.3 parts of resorcinol formaldehyde adhesive resin, 0.22 parts of cobalt decanoate, 0.3 parts of antioxidant 4020 and 0.1 antioxidant RD into an internal mixer, mix at 150°C for 3min, after uniform mixing, extrude and press into a sheet to obtain a first-stage masterbatch;

[0043] Put the obtained first-stage masterbatch, 1 part of insoluble sulfur OT20, 0.19 parts of vulcanization accelerator NS and 0.95 parts of adhesive RA into an internal mixer, mix uniformly, extrude and press into a sheet to obtain a final rubber compound;

[0044] Put the obtained final rubber compound into a vulcanizing machine and vulcanize at 151°C for 30min to obtain a carbon separation method white carbon black rubber composite material.

[0045] The carbon separation method white carbon black rubber composite material prepared in this example was subjected to performance detection, and the detection standards of the mixing rubber vulcanization characteristics Tc90, MH and the vulcanized rubber tear strength, hot air aging were respectively corresponding to GB / T 16584-1996, GB / T 529-2008 and GB / T 3512-2001.

[0046] The results show that the mixing rubber of the carbon separation method white carbon black rubber composite material prepared in this example has a vulcanization characteristic Tc90 of 14.98min, a MH of 31.86dNm, a vulcanized rubber tear strength of 69.84kN / m and an aged tear strength of 33.59kN / m after vulcanization test at 151°C for 40min, which is significantly better than the performance of the rubber composite material prepared by the traditional ordinary acid precipitation method white carbon black, effectively improving the production efficiency, driving safety and service life of the tire.

[0047] Comparative Example 1

[0048] The same as Example 1, except that in the rubber composite material preparation step, no carbon separation method white carbon black is added, but 2.2 parts of traditional acid precipitation method white carbon black is used instead.

[0049] The detection standard is same with example 1. The results show that the rubber compound prepared by comparative example 1 is vulcanized at 151℃ for 40min, the vulcanization property Tc90 reaches 15.74min, the MH reaches 29.05dNm, the tear strength of vulcanized rubber reaches 63.76kN / m, and the tear strength after aging reaches 28.21kN / m. Compared with the rubber composite added with carbon separation method white carbon black, the vulcanization speed, MH, tear strength of vulcanized rubber and aging performance of the rubber composite added with traditional ordinary acid precipitation method white carbon black are all obviously decreased, because compared with the traditional acid precipitation method white carbon black, the carbon separation method white carbon black surface can provide the required alkaline catalytic conditions for the vulcanization reaction of sulfur atoms and rubber molecular chains, which improves the vulcanization speed of the rubber compound, and the acidic environment provided by the traditional ordinary acid precipitation method white carbon black will have the opposite effect, that is, it will delay the vulcanization. The carbon separation method white carbon black has larger specific surface area and structure than the traditional acid precipitation method white carbon black, and can be better dispersed in the composite material when properly processed, which improves the crosslinking density and tear strength of the rubber composite. The high chemical stability, high temperature chemical resistance and stable chemical bond formed by the physical hydrogen bond between the white carbon black and the rubber enable the carbon separation method white carbon black to have good dispersion in the rubber matrix, which gives the rubber composite better thermal oxidative aging performance.

[0050] Comparative example 2

[0051] The same as example 1, the difference is that in the preparation step of the rubber composite, the amount of carbon separation method white carbon black is changed from 2.2 parts to 1.8 parts.

[0052] The detection standard is same with example 1. The results show that the rubber compound prepared by comparative example 1 is vulcanized at 151℃ for 40min, the vulcanization property Tc90 reaches 15.74min, the MH reaches 29.05dNm, the tear strength of vulcanized rubber reaches 63.76kN / m, and the tear strength after aging reaches 28.21kN / m. Compared with the rubber composite added with carbon separation method white carbon black, the vulcanization speed, MH, tear strength of vulcanized rubber and aging performance of the rubber composite added with traditional ordinary acid precipitation method white carbon black are all obviously decreased, because compared with the traditional acid precipitation method white carbon black, the carbon separation method white carbon black surface can provide the required alkaline catalytic conditions for the vulcanization reaction of sulfur atoms and rubber molecular chains, which improves the vulcanization speed of the rubber compound, and the acidic environment provided by the traditional ordinary acid precipitation method white carbon black will have the opposite effect, that is, it will delay the vulcanization. The carbon separation method white carbon black has larger specific surface area and structure than the traditional acid precipitation method white carbon black, and can be better dispersed in the composite material when properly processed, which improves the crosslinking density and tear strength of the rubber composite. The high chemical stability, high temperature chemical resistance and stable chemical bond formed by the physical hydrogen bond between the white carbon black and the rubber enable the carbon separation method white carbon black to have good dispersion in the rubber matrix, which gives the rubber composite better thermal oxidative aging performance.

[0053] Comparative example 3

[0054] The same as example 1, the difference is that in the preparation step of the rubber composite, the amount of carbon separation method white carbon black is changed from 2.2 parts to 2.5 parts.

[0055] The detection standard is the same as that of Example 1. The results show that the rubber compound prepared in Comparative Example 1 has a vulcanization property Tc90 of 15.22 min, a MH of 30.28 dNm, a tear strength of the vulcanized rubber of 64.28 kN / m, and an aged tear strength of 29.14 kN / m after 40 min of vulcanization test at 151 ℃. Compared with the rubber compound added with 2.2 parts of carbon method white carbon black, the vulcanization speed, MH, tear strength of the vulcanized rubber and aging performance of the rubber compound added with 2.5 parts of carbon method white carbon black all decrease to a certain extent, because the excessive carbon method white carbon black is not conducive to processing and dispersion, and its dispersion becomes poor, which leads to the decrease of crosslinking, tear strength and aging performance. The increase of the filling amount also affects the vulcanization time to a certain extent.

Claims

1. Rubber composite, characterized in that The carbon division method white carbon black is used as a reinforcing agent in the rubber composite material, and the vulcanization characteristics Tc90 of the rubber composite material reaches 14.82 min, the MH reaches 31.28 dNm, the tear strength of the vulcanized rubber reaches 68.15 kN / m, and the tear strength after aging reaches 31.86 kN / m after 40 min of vulcanization test at 151 ℃; The rubber composite material further comprises natural rubber, carbon black, a vulcanizing agent and a vulcanizing accelerator, and the mass ratio of the carbon division method white carbon black to the natural rubber, carbon black, vulcanizing agent and vulcanizing accelerator is 2-2.2:20-22:8.8-9:1-1.1:0.18-0.2; The rubber composite material further comprises an active agent, an adhesive and an antioxidant, and the mass ratio of the carbon division method white carbon black to the active agent, adhesive and antioxidant is 2-2.2:1.5-1.7:1.4-1.6:0.4-0.41; The active agent is indirect zinc oxide; The adhesive is a mixture of resorcinol formaldehyde resin, cobalt decanoate and adhesive RA; The antioxidant is a mixture of antioxidant 4020 and antioxidant RD; The mass ratio of resorcinol formaldehyde resin, cobalt decanoate and adhesive RA in the adhesive is 1:0.7-0.8:3.2-3.4; The mass ratio of antioxidant 4020 and antioxidant RD in the antioxidant is 1:0.3-0.

4.

2. The rubber composite of claim 1, wherein The carbon black is carbon black N375 with a BET of 103 m 2 / g; the vulcanizing agent is insoluble sulphur HD-OT 20-A grade; the vulcanization accelerator is vulcanization accelerator NS.

3. Rubber composite according to claim 1 or 2, characterized in that Carbon division method white carbon black pH is 7.2, BET is 224.4 m 2 / g, DBP absorption value is 2.64 cm 3 / g; When used in a rubber composite material, the carbon division method white carbon black can improve the vulcanization speed of the rubber composite material, and the Tc90 reaches 14.82 min.

4. Process for the preparation of a rubber composite according to any one of claims 1 to 3, characterized in that, The method comprises the following steps: The carbon division method white carbon black, natural rubber, carbon black, an active agent, resorcinol formaldehyde resin, cobalt decanoate and an antioxidant are placed in a banbury mixer, and mixed at 140-160 ℃ for 2-4 min, and then the rubber is discharged and pressed into a sheet to obtain a first-stage masterbatch; The first-stage masterbatch, a vulcanizing agent, a vulcanizing accelerator and an adhesive RA are placed in a banbury mixer, and mixed uniformly, and then the rubber is discharged and pressed into a sheet to obtain a final rubber compound; The final rubber compound is placed in a vulcanizing machine and vulcanized at 151 ℃ for 30 min to obtain a rubber composite material.

5. The preparation method according to claim 4, characterized in that, The vulcanization characteristics Tc90 of the rubber composite material reaches 14.82 min, the MH reaches 31.28 dNm, the tear strength of the vulcanized rubber reaches 68.15 kN / m, and the tear strength after aging reaches 31.86 kN / m.

6. Tire, characterized in that The tire is prepared from the rubber composite material according to any one of claims 1-3.