Highly bio-based elastomer tire sidewall rubber composition

Abstract

The present invention provides a high bio-based elastomer tire sidewall rubber composition, specifically relating to the technical field of tire manufacturing. The porous three-phase alloy is mainly obtained by high-temperature jetting of carbon black and natural ore powder; the content of silicon dioxide in the natural ore powder is 40-60%, and the content of aluminum oxide is 30-40%; the specific surface area of the natural ore powder is 30-70 m<supgt;2< / supgt> / g, the pore volume is 0.20-0.40 cm<supgt;3< / supgt> / g, the number of pores is 100 million - 300 million per gram, and the D50 particle size is 0.25-5 μm. The porous three-phase alloy provided by the present invention is a novel aluminum-silicon-carbon aggregate, which not only has high hardness and wear resistance, but also has a low coefficient of thermal expansion, which is beneficial to maintaining the dimensional stability of the rubber composition in a high-temperature environment. The aluminum-silicon-carbon aggregate shows good interfacial bonding, reducing the interfacial thermal resistance, thereby improving the thermal conduction efficiency of the aggregate.

Description

Technical Field

[0001] The invention relates to the technical field of tire manufacturing, in particular to a high-biobased elastomer tire sidewall rubber composition. Background Art

[0002] The sidewall rubber plays a vital role in the tire structure. It is not only located on the outside of the tire-rim contact area, but also protects the internal structure of the tire, such as the cord layer and the wire ring, from external damage and wear. This protective function is crucial because it ensures the overall stability and durability of the tire. In addition, the elasticity and flexibility of the sidewall rubber enable it to adapt to various road conditions, effectively reducing the impact and vibration during driving, and improving driving comfort and safety. More importantly, the sidewall rubber also has good air tightness, which not only helps maintain the air pressure inside the tire and prevent air leakage, but also further enhances the service life and performance of the tire. Therefore, the sidewall rubber is not only a protective layer of the tire, but also a key factor in ensuring the overall performance of the tire.

[0003] However, in the preparation process of existing sidewall rubber, the raw materials used have poor thermal conductivity and insufficient heat resistance, which leads to reduced rigidity and creep problems when the produced tires are used at high temperatures.

[0004] In addition, the raw materials used to make sidewall rubber mostly come from petroleum and petrochemical products, which are difficult to meet green and environmentally friendly requirements and may have a negative impact on the environment after the tire's service life ends. At the same time, attempts to use bio-based carbon as an alternative raw material will cause problems such as slow sulfur rate and low thermal conductivity. Even if the amount of vulcanizer is increased to increase the sulfur rate, the rubber will become brittle, and the heat resistance and physical properties will deteriorate, further affecting the overall performance of the sidewall rubber.

[0005] In view of this, the present invention is proposed. Summary of the invention

[0006] One of the objects of the present invention is to provide a bio-based elastomer tire sidewall rubber composition.

[0007] A second object of the present invention is to provide a high bio-based elastomer tire sidewall rubber.

[0008] In order to solve the above-mentioned technical problems, the present invention particularly adopts the following technical solutions:

[0009] The first aspect of the present invention provides a high bio-based elastomer tire sidewall rubber composition, which comprises, by weight:

[0010] 50-70 parts of natural rubber, 30-50 parts of lithium-based butadiene rubber, 5-15 parts of porous three-phase alloy, 20-40 parts of rice husk gray white carbon black, 1-4 parts of silane coupling agent, 1-2 parts of silane synergist, 3-6 parts of activator, 4-6 parts of antioxidant, 2-4 parts of tackifying resin, 1-3 parts of tearing resin, 1.5-5 parts of microcrystalline wax, 2-4 parts of vulcanizing agent and 0.2-0.5 parts of super vulcanizing aid.

[0011] The porous three-phase alloy is mainly obtained by high-temperature jetting of carbon black and natural ore powder.

[0012] The content of silicon dioxide in the natural ore powder is 40-60%, and the content of aluminum oxide is 30-40%.

[0013] The natural ore powder has a rich microporous structure and a specific surface area of ​​30-70m 2 / g, pore volume 0.20~0.40cm 3 / g, the number of pores is 100-300 million / g, and the D50 particle size is 0.25-5μm.

[0014] Furthermore, the mass ratio of the carbon black to the natural ore powder is 5-9:1-5.

[0015] The grades of the carbon black include at least one of N134, N220, N234, N330, N375 and N550.

[0016] Furthermore, the high temperature jet process includes:

[0017] The natural ore powder suspension mixed by the jet system is sprayed into the carbon black reaction furnace, and the carbon black reacts with the natural ore powder to generate an aluminum-silicon-carbon structure, which is aggregated to form an aluminum-silicon-carbon aggregate to obtain the porous three-phase alloy.

[0018] The concentration of the natural ore powder suspension is 15-25wt.%.

[0019] The injection flow rate of the natural ore powder suspension is 4000-6000 kg / h.

[0020] The reaction temperature is 1000-1500°C.

[0021] Furthermore, the brand of the vulcanizing agent includes HDOT20.

[0022] The super vulcanization aid is a low eutectic solvent.

[0023] The super vulcanization aid is mainly prepared from zinc chloride, choline chloride and thiourea in a molar ratio of 1-3:1-3:3-6.

[0024] Furthermore, the specific surface area of ​​the rice husk gray carbon black is 165~240m 2 / g, particle size is 0.8~7.8μm.

[0025] The brands of the silane coupling agent include at least one of TESPT, Si75, OTES and Si747.

[0026] The brands of the silane synergist include DST-100H.

[0027] The activator includes stearic acid and / or zinc oxide.

[0028] The brands of the antioxidant include at least one of antioxidant 4020, antioxidant RD and antioxidant 4010NA.

[0029] The tackifying resin includes at least one of tert-butylphenol-formaldehyde resin, alkylphenol-formaldehyde resin and petroleum resin.

[0030] The grades of the petroleum resin include at least one of C5, C9 and C54.

[0031] The brand of the tearing resin includes at least one of R-110, DCPD and CSR200.

[0032] The second aspect of the present invention provides a high bio-based elastomer tire sidewall rubber, which is mainly obtained by mixing the high bio-based elastomer tire sidewall rubber composition described in the first aspect.

[0033] Furthermore, the mixing method comprises the following steps:

[0034] The first masterbatch is obtained by mixing natural rubber, lithium-based butadiene rubber, porous three-phase alloy, rice husk gray carbon black, silane coupling agent, silane synergist, activator, antioxidant, tackifying resin, tearing resin and microcrystalline wax and performing a mixing step.

[0035] Finally, the vulcanizing agent and the super vulcanizing aid are added into the first masterbatch and mixed, and then two-stage mixing is performed to obtain a high bio-based elastomer tire sidewall rubber.

[0036] Furthermore, the first stage of mixing includes mixing for 30-50 seconds, mixing with the plug lifted and pressed for 20-30 seconds, and then mixing with the plug lifted and pressed to 140-155° C. for debonding in this order.

[0037] The two-stage mixing includes mixing for 30-50 seconds, mixing with the plug lifted and the plug pressed for 20-30 seconds, and then mixing with the plug lifted and the plug pressed until the temperature reaches 95-105° C. for debonding.

[0038] Compared with the prior art, the present invention has at least the following beneficial effects:

[0039] The porous three-phase alloy provided by the present invention forms a new type of aluminum-silicon-carbon aggregate by imparting the advantageous properties of carbon black to natural ore powder. This aggregate not only has high hardness and wear resistance, but also has a low thermal expansion coefficient, which is conducive to maintaining the dimensional stability of the rubber composition under high temperature conditions. At the same time, the aggregate exhibits excellent high temperature resistance and can maintain its mechanical properties under extreme temperature conditions. The high thermal conductivity of aluminum makes the formed aluminum-silicon-carbon aggregate perform well in interface bonding, reduces the interface thermal resistance, and thus improves the thermal conduction efficiency of the aggregate. In addition, the thermal expansion coefficients of aluminum, silicon and carbon are relatively matched, which reduces the thermal stress caused by uneven thermal expansion and further promotes the stable transfer of thermal energy. The role of silicon and carbon particles in the aggregate is to reduce thermal resistance, improve the efficiency of the heat conduction path, and make the overall aggregate perform well in heat conduction.

[0040] The application of the porous three-phase alloy provided by the present invention, in view of the advantages of the porous three-phase alloy, enables the prepared high-biobased elastomer tire sidewall rubber composition to have better thermal conductivity and mechanical strength and lower thermal expansion coefficient.

[0041] The high bio-based elastomer tire sidewall rubber composition provided by the present invention uses natural rubber and lithium-based butadiene rubber as the basis, can obtain better mechanical properties and elasticity, and is helpful to improve the load-bearing capacity and impact resistance of the tire. At the same time, the addition of bio-based carbon black reduces the use cost of carbon black, reduces environmental pollution, saves fossil resources, and realizes the sustainable development of the rubber industry. Bio-based carbon black causes the problems of poor physical properties, slow sulfur rate, and low efficiency. The use of super vulcanization additives can perfectly solve this problem, improve vulcanization efficiency and vulcanization quality. At the same time, the addition of porous three-phase alloy makes the rubber composition have low heat generation, high thermal conductivity and excellent heat resistance, which improves the performance of rubber products. The raw materials in the composition cooperate with each other, so that the rubber composition has significant technical effects in improving rubber performance and enhancing environmental friendliness.

[0042] The high-biobased elastomer tire sidewall rubber provided by the present invention, in view of the advantages of the above-mentioned rubber composition, enables the prepared sidewall rubber to have better performance and be more environmentally friendly, meet the performance requirements of different fields, and promote the development of the tire industry. BRIEF DESCRIPTION OF THE DRAWINGS

[0043] In order to more clearly illustrate the specific implementation methods of the present invention or the technical solutions in the prior art, the drawings required for use in the specific implementation methods or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are some implementation methods of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0044] Figure 1 This is a scanning electron microscope image at a magnification obtained in Characterization Example 1;

[0045] Figure 2 This is a scanning electron microscope image at another magnification obtained in Characterization Example 1;

[0046] Figure 3 This is a scanning electron microscope image at the third magnification obtained in Characterization Example 1. DETAILED DESCRIPTION

[0047] To make the purpose, technical solution and advantages of the present invention clearer, the technical solution in the embodiment of the present invention will be clearly and completely described below in combination with the embodiment of the present invention. Obviously, the described embodiment is a part of the embodiment of the present invention, but not all of the embodiments. The components of the embodiment of the present invention can be arranged and designed in various different configurations.

[0048] It should be noted that, in this article, relational terms such as first and second, etc. are only used to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply any such actual relationship or order between these entities or operations. Moreover, the terms "include", "comprise" or any other variants thereof are intended to cover non-exclusive inclusion, so that a process, method, article or device including a series of elements includes not only those elements, but also other elements not explicitly listed, or also includes elements inherent to such process, method, article or device.

[0049] A first aspect of the present invention provides a porous three-phase alloy, wherein the porous three-phase alloy is mainly obtained by high-temperature jetting of carbon black and natural ore powder.

[0050] The content of silicon dioxide in the natural ore powder is 40-60%, and the content of aluminum oxide is 30-40%.

[0051] The natural ore powder has a rich microporous structure and a specific surface area of ​​30-70m 2 / g, pore volume 0.20~0.40cm 3 / g, the number of pores is 100-300 million / g, and the D50 particle size is 0.25-5μm.

[0052] The porous three-phase alloy provided by the present invention forms a new type of aluminum-silicon-carbon aggregate by imparting the advantageous properties of carbon black to natural ore powder. This aggregate not only has high hardness and wear resistance, but also has a low thermal expansion coefficient, which is conducive to maintaining the dimensional stability of the rubber composition under high temperature conditions. At the same time, the aggregate exhibits excellent high temperature resistance and can maintain its mechanical properties under extreme temperature conditions. The high thermal conductivity of aluminum makes the formed aluminum-silicon-carbon aggregate perform well in interface bonding, reduces the interface thermal resistance, and thus improves the thermal conduction efficiency of the aggregate. In addition, the thermal expansion coefficients of aluminum, silicon and carbon are relatively matched, which reduces the thermal stress caused by uneven thermal expansion and further promotes the stable transfer of thermal energy. The role of silicon and carbon particles in the aggregate is to reduce thermal resistance, improve the efficiency of the heat conduction path, and make the overall aggregate perform well in heat conduction.

[0053] The present invention limits the content of silicon dioxide and aluminum oxide in the natural ore powder in order to ensure a reasonable ratio of each raw material in the aluminum-silicon-carbon aggregate, thereby optimizing the performance of the porous three-phase alloy.

[0054] Typically but not limiting, the content of silicon dioxide in the natural ore powder can be 40%, 45%, 50%, 55%, 60%, or any value in the range of 40% to 60%; the content of aluminum oxide can be 30%, 35%, 40%, or any value in the range of 30% to 40%.

[0055] The present invention limits the specific surface area, pore volume, number of pores and D50 particle size of the natural mineral powder in order to ensure the rich pore structure of the natural mineral powder, so as to increase the growth of carbon black primary particles on the pore surface, secondly, to facilitate the combination of the rubber molecular chain ends with the pores, and thirdly, the particle size of the mineral powder and the carbon black particle size form a gradient particle size distribution.

[0056] Furthermore, the mass ratio of the carbon black to the natural ore powder is 5-9:1-5.

[0057] Controlling the mass ratio of carbon black to natural mineral powder within the range of 5~9:1~5 will ensure that the primary carbon black particles are coated on the surface of the porous structure of the natural mineral powder, rather than the natural mineral powder coating the carbon black, ensuring that the prepared filler has a good reinforcement effect.

[0058] Typically but not limiting, the mass ratio of carbon black to natural ore powder can be 5:5, 6:4, 7:3, 8:2, 9:1, or any value within the range of 5-9:1-5.

[0059] The grades of the carbon black include at least one of N134, N220, N234, N330, N375 and N550.

[0060] Furthermore, the high temperature jet process includes:

[0061] The natural ore powder suspension mixed by the jet system is sprayed into the carbon black reaction furnace, and the carbon black reacts with the natural ore powder to generate an aluminum-silicon-carbon structure, which is aggregated to form an aluminum-silicon-carbon aggregate to obtain the porous three-phase alloy.

[0062] The concentration of the natural ore powder suspension is 15-25wt.%.

[0063] The injection flow rate of the natural ore powder suspension is 4000-6000 kg / h.

[0064] The reaction temperature is 1000-1500°C.

[0065] During the high-temperature jet process, the powdered natural mineral powder and the carbon black primary particles are chemically combined at high temperature to form short-chain structures of -Si-C- and -Si-OC-.

[0066] Typically but not limiting, the concentration of the natural ore powder suspension can be 15wt.%, 16wt.%, 17wt.%, 18wt.%, 19wt.%, 20wt.%, 21wt.%, 22wt.%, 23wt.%, 24wt.% or 25wt.%, or it can be any value within the range of 15wt.% to 25wt.%.

[0067] Typically but not limiting, the injection rate of the natural ore powder suspension can be 4000 kg / h, 4500 kg / h, 5000 kg / h, 5500 kg / h, 6000 kg / h, or any value within the range of 4000 kg / h to 6000 kg / h.

[0068] Likewise, the reaction temperature may be 1000°C, 1100°C, 1200°C, 1300°C, 1400°C, 1500°C, or any value within the range of 1000°C to 1500°C.

[0069] The second aspect of the present invention provides the use of the porous three-phase alloy in preparing a high bio-based elastomer tire sidewall rubber composition.

[0070] The application of the porous three-phase alloy provided by the present invention, in view of the advantages of the porous three-phase alloy, enables the prepared high-biobased elastomer tire sidewall rubber composition to have better thermal conductivity and mechanical strength and lower thermal expansion coefficient.

[0071] The third aspect of the present invention provides a high bio-based elastomer tire sidewall rubber composition, which comprises, by weight:

[0072] 50-70 parts of natural rubber, 30-50 parts of lithium-based butadiene rubber, 5-15 parts of the porous three-phase alloy described in the first aspect, 20-40 parts of rice husk gray white carbon black, 1-4 parts of silane coupling agent, 1-2 parts of silane synergist, 3-6 parts of activator, 4-6 parts of antioxidant, 2-4 parts of tackifying resin, 1-3 parts of tearing resin, 1.5-5 parts of microcrystalline wax, 2-4 parts of vulcanizing agent and 0.2-0.5 parts of super vulcanizing aid.

[0073] The high bio-based elastomer tire sidewall rubber composition provided by the present invention uses natural rubber and lithium-based butadiene rubber as the basis, can obtain better mechanical properties and elasticity, and is helpful to improve the load-bearing capacity and impact resistance of the tire. At the same time, the addition of bio-based carbon black reduces the use cost of carbon black, reduces environmental pollution, saves fossil resources, and realizes the sustainable development of the rubber industry. Bio-based carbon black causes the problems of poor physical properties, slow sulfur rate, and low efficiency. The use of super vulcanization additives can perfectly solve this problem, improve vulcanization efficiency and vulcanization quality. At the same time, the addition of porous three-phase alloy makes the rubber composition have low heat generation, high thermal conductivity and excellent heat resistance, which improves the performance of rubber products. The raw materials in the composition cooperate with each other, so that the rubber composition has significant technical effects in improving rubber performance and enhancing environmental friendliness.

[0074] Specifically, the combination of natural rubber and lithium-based butadiene rubber significantly enhances structural stability and gives it better mechanical properties and elasticity, which not only improves the tire's load-bearing capacity but also enhances its impact resistance. At the same time, the introduction of rice husk ash and white carbon black effectively improves the rubber's wear resistance and extends the tire's service life.

[0075] In addition, the use of silane coupling agent and silane synergist improves the adhesion between rubber and reinforcing materials, further improving the overall performance of the tire. The addition of activator optimizes the processing performance of rubber, making the mixing and molding process smoother. In terms of aging resistance, the addition of antioxidant significantly improves the heat resistance, ozone resistance and chemical aging resistance of the sidewall rubber, ensuring the stable performance of the tire under changing environmental conditions.

[0076] The synergistic effect of tackifying resin and tearing resin effectively improves the tear strength of the sidewall rubber and enhances the tire's resistance to damage. The addition of microcrystalline wax reduces the heat generated during tire driving while improving the rubber's flexibility and low-temperature performance. The combination of vulcanizer and super vulcanizing aid further optimizes the vulcanization performance, not only improving the vulcanization effect, but also improving the rubber's heat resistance and fatigue resistance.

[0077] It is worth mentioning that the addition of porous three-phase alloy, due to its unique structure, enhances the thermal conductivity of the tire, reduces heat accumulation on the sidewall, and thus improves safety during use.

[0078] Typically but not limiting, in the sidewall rubber composition, the amount of natural rubber can be 50 parts, 55 parts, 60 parts, 65 parts, 70 parts, or any amount within the range of 50 to 70 parts; the amount of lithium-based butadiene rubber is 50 parts, 45 parts, 40 parts, 35 parts, 30 parts. It should be noted that the natural rubber and lithium-based butadiene rubber are used as base rubbers, and the total amount of the two is 100 parts.

[0079] Typically but not limiting, in the sidewall rubber composition, the amount of the porous three-phase alloy may be 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, 11 parts, 12 parts, 13 parts, 14 parts or 15 parts, or any amount within the range of 5 to 15 parts. The amount of rice husk ash white carbon black may be 20 parts, 22 parts, 24 parts, 26 parts, 28 parts, 30 parts, 35 parts or 40 parts, or any amount within the range of 20 to 40 parts.

[0080] Typically but not limitatively, in the sidewall rubber composition, the amount of the silane coupling agent can be 1 part, 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, or any amount within the range of 1 to 4 parts; the amount of the silane synergist can be 1 part, 1.1 parts, 1.5 parts, 1.9 parts, 2 parts, or any amount within the range of 1 to 2 parts.

[0081] Typically but not limitatively, in the sidewall rubber composition, the amount of activator can be 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5 parts, 5.5 parts, 6 parts, or any amount within the range of 3 to 6 parts; the amount of antioxidant can be 4 parts, 4.5 parts, 5 parts, 5.5 parts, 6 parts, or any amount within the range of 4 to 6 parts.

[0082] Typically but not limitatively, in the sidewall rubber composition, the amount of tackifying resin can be 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, or any amount within the range of 2 to 4 parts; the amount of tearing resin can be 1 part, 1.5 parts, 2 parts, 2.5 parts, 3 parts, or any amount within the range of 1 to 3 parts.

[0083] Typically but not limitatively, in the sidewall rubber composition, the amount of microcrystalline wax can be 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5 parts, or any amount within the range of 1.5 to 5 parts; the amount of vulcanizing agent can be 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, or any amount within the range of 2 to 4 parts.

[0084] Typically but not limiting, in the sidewall rubber composition, the amount of the super vulcanization aid may be 0.2 part, 0.3 part, 0.4 part, 0.5 part, or any amount within the range of 0.2-0.5 part.

[0085] Furthermore, the brand of the vulcanizing agent includes HDOT20.

[0086] The super vulcanization aid is mainly prepared from zinc chloride, choline chloride and thiourea in a molar ratio of 1-3:1-3:3-6.

[0087] The low eutectic solvent is prepared by mixing zinc chloride, choline chloride and thiourea in a certain proportion to form a liquid molten state at a temperature lower than the melting point of each individual substance. The melting point of the obtained low eutectic solvent is lower than the melting point of each component.

[0088] Typically but not limiting, the molar ratio of zinc chloride, choline chloride and thiourea can be 1:1:3, 1:2:4, 1:3:6 or 3:3:6, or any ratio combination within the range of 1-3:1-3:3-6.

[0089] Furthermore, the specific surface area of ​​the rice husk gray carbon black is 165~240m 2 / g, particle size is 0.8~7.8μm.

[0090] Typically, but not limiting, the specific surface area of ​​the rice husk ash white carbon black may be 165 m 2 / g, 170 m 2 / g, 180m 2 / g, 190 m 2 / g, 200 m 2 / g, 210 m 2 / g, 220 m 2 / g, 230 m 2 / g or 240 m 2 / g, or 165 m 2 / g ~240 m 2 / g; the particle size of rice husk gray white carbon black can be 0.8 μm, 1.0 μm, 1.5 μm, 2.0 μm, 3.0 μm, 4.0 μm, 5.0 μm, 6.0 μm or 7.8 μm, or it can be any value in the range of 0.8 μm ~7.8 μm.

[0091] The brands of the silane coupling agent include at least one of TESPT, Si75 and Si747.

[0092] The brands of the silane synergist include DST-100H.

[0093] The activator includes stearic acid and / or zinc oxide.

[0094] The brands of the antioxidant include at least one of antioxidant 4020, antioxidant RD and antioxidant 4010NA.

[0095] The tackifying resin includes at least one of tert-butylphenol-formaldehyde resin, alkylphenol-formaldehyde resin and petroleum resin.

[0096] The grades of the petroleum resin include at least one of C5, C9 and C54.

[0097] The brand of the tearing resin includes at least one of R-110, DCPD and CSR200.

[0098] The fourth aspect of the present invention provides a high bio-based elastomer tire sidewall rubber, which is mainly obtained by mixing the high bio-based elastomer tire sidewall rubber composition described in the third aspect.

[0099] The high-biobased elastomer tire sidewall rubber provided by the present invention, in view of the advantages of the above-mentioned rubber composition, enables the prepared sidewall rubber to have better performance and be more environmentally friendly, meet the performance requirements of different fields, and promote the development of the tire industry.

[0100] Furthermore, the mixing method comprises the following steps:

[0101] The first masterbatch is obtained by mixing natural rubber, lithium-based butadiene rubber, porous three-phase alloy, rice husk gray carbon black, silane coupling agent, silane synergist, activator, antioxidant, tackifying resin, tearing resin and microcrystalline wax and performing a mixing step.

[0102] Finally, the vulcanizing agent and the super vulcanizing aid are added into the first masterbatch and mixed, and then two-stage mixing is performed to obtain a high bio-based elastomer tire sidewall rubber.

[0103] Furthermore, the first stage of mixing includes mixing for 30-50 seconds, mixing with the plug lifted and pressed for 20-30 seconds, and then mixing with the plug lifted and pressed to 140-155° C. for debonding in this order.

[0104] The two-stage mixing includes mixing for 30-50 seconds, mixing with the plug lifted and the plug pressed for 20-30 seconds, and then mixing with the plug lifted and the plug pressed until the temperature reaches 95-105° C. for debonding.

[0105] Typically but not limiting, the temperature and time of the mixing process can be specifically as follows: the initial mixing stage can last for 30s, 35s, 40s or 50s, followed by the bolt lifting and bolt pressing mixing, which can last for 20s, 25s or 30s. After the bolt lifting and bolt pressing mixing is completed, the mixing is continued until the rubber temperature reaches 140°C, 143°C, 145°C or 155°C when the rubber is discharged.

[0106] Typically but not limiting, the temperature and time of the two-stage mixing process can be specifically as follows: the initial mixing stage can last for 30s, 35s, 40s or 50s, followed by the bolt lifting and bolt pressing mixing, which can last for 20s, 25s or 30s. After the bolt lifting and bolt pressing mixing is completed, the mixing is continued until the rubber temperature reaches 95°C, 98°C, 101°C or 105°C, and the rubber is discharged.

[0107] In conjunction with the examples, some embodiments of the present invention are described in detail below. In the absence of conflict, the following examples and features in the examples can be combined with each other. The raw materials used in the examples and comparative examples of the present invention, if no specific conditions are specified, are carried out under normal conditions or conditions recommended by the manufacturer. The reagents or instruments used, if the manufacturer is not specified, are all conventional products that can be purchased commercially.

[0108] The raw materials used in the examples and comparative examples are shown in Table 1 below.

[0109] Table 1

[0110]

[0111] Example 1

[0112] This embodiment provides a porous three-phase alloy, and the preparation method is as follows:

[0113] In the jet system, the natural ore powder and process water are mixed evenly by powder injection technology, and the concentration of the natural ore powder suspension is controlled to be 20wt.%. The natural ore powder suspension is then sprayed into the carbon black reactor by the jet system, with a spray flow rate of 5000kg / h, and the mass ratio of carbon black to natural ore powder is controlled to be 8:2. The temperature in the carbon black reactor is set to 1000°C. Carbon black reacts with natural ore powder to form an aluminum-silicon-carbon structure, which is aggregated to form an aluminum-silicon-carbon aggregate to obtain the porous three-phase alloy.

[0114] Example 2

[0115] This embodiment provides a porous three-phase alloy, and the preparation method is as follows:

[0116] In the jet system, the natural ore powder and process water are mixed evenly by powder injection technology, and the concentration of the natural ore powder suspension is controlled to be 15wt.%. The natural ore powder suspension is then sprayed into the carbon black reactor by the jet system, with a spray flow rate of 6000kg / h, and the mass ratio of carbon black to natural ore powder is controlled to be 8:2. The temperature in the carbon black reactor is set to 1200°C. Carbon black reacts with natural ore powder to form an aluminum-silicon-carbon structure, which is aggregated to form an aluminum-silicon-carbon aggregate to obtain the porous three-phase alloy.

[0117] Example 3

[0118] This embodiment provides a porous three-phase alloy, and the preparation method is as follows:

[0119] In the jet system, the natural ore powder and process water are mixed evenly by powder injection technology, and the concentration of the natural ore powder suspension is controlled to be 25wt.%. The natural ore powder suspension is then sprayed into the carbon black reactor by the jet system, with a spray flow rate of 4000kg / h, and the mass ratio of carbon black to natural ore powder is controlled to be 8:2. The temperature in the carbon black reactor is set to 1500°C. Carbon black reacts with natural ore powder to form an aluminum-silicon-carbon structure, which is aggregated to form an aluminum-silicon-carbon aggregate to obtain the porous three-phase alloy.

[0120] Example 4

[0121] This embodiment provides a porous three-phase alloy. Different from the embodiment, the mass ratio of carbon black to natural ore powder is 9:1, and the remaining raw materials and steps are the same as those in embodiment 1, which will not be repeated here.

[0122] Example 5

[0123] This embodiment provides a porous three-phase alloy. Different from the embodiment, the mass ratio of carbon black to natural ore powder is 7:3, and the remaining raw materials and steps are the same as those in embodiment 1, which will not be repeated here.

[0124] Example 6

[0125] This embodiment provides a porous three-phase alloy. Different from the embodiment, the mass ratio of carbon black to natural ore powder is 6:4, and the remaining raw materials and steps are the same as those in embodiment 1, which will not be repeated here.

[0126] Example 7

[0127] This embodiment provides a porous three-phase alloy. Different from the embodiment, the mass ratio of carbon black to natural ore powder is 5:5, and the remaining raw materials and steps are the same as those in embodiment 1, which will not be repeated here.

[0128] Example 8

[0129] This embodiment provides a porous three-phase alloy. Different from the embodiment, the mass ratio of carbon black to natural ore powder is 2:8, and the remaining raw materials and steps are the same as those in embodiment 1, which will not be repeated here.

[0130] Test Example 1

[0131] The porous three-phase alloys obtained in Examples 1 to 8 were subjected to performance tests, specifically including thermal conductivity and thermal expansion coefficient measurements.

[0132] The thermal conductivity shall be determined in accordance with the provisions of GB / T 8722-2019; the thermal expansion coefficient shall be determined in accordance with the provisions of GB / T9966.16-2021.

[0133] The results are shown in Table 2 below.

[0134] Table 2

[0135]

[0136] It can be seen from Table 2 that the thermal conductivity of the porous three-phase alloy is 0.223W / m·K~0.288W / m·K, and the thermal expansion coefficient is 0.11 / °C~0.18 / °C.

[0137] Characterization Example 1

[0138] The porous three-phase alloy obtained in Example 1 was subjected to a scanning electron microscope, and the obtained image is as follows Figure 1 , Figure 2 and Figure 3 As shown. Figure 1-Figure 3 It can be seen that the carbon black is organically complexed with the porous mineral powder.

[0139] Examples 9-13 and Comparative Examples 1-2

[0140] These embodiments provide a high bio-based elastomer tire sidewall rubber, which is made of a high bio-based elastomer tire sidewall rubber composition, and the formula of the high bio-based elastomer tire sidewall rubber composition is shown in Table 3. The porous three-phase alloy used is the porous three-phase alloy provided in Example 2.

[0141] Table 3

[0142]

[0143] Note: “ / ” indicates that the substance is not added.

[0144] In the above-mentioned Examples 9 to 13, the super vulcanization aid DES is obtained by melting zinc chloride, choline chloride and thiourea in a molar ratio of 1:1:4.

[0145] Embodiment 14

[0146] This embodiment provides a high bio-based elastomer tire sidewall rubber, wherein the formula of the high bio-based elastomer tire sidewall rubber composition is different from that of Example 9 in that the super vulcanizing agent DES is obtained by co-melting zinc chloride, choline chloride and thiourea in a molar ratio of 1:1:3, and other raw materials and methods are the same as those of Example 9, which will not be repeated here.

[0147] Embodiment 15

[0148] This embodiment provides a high bio-based elastomer tire sidewall rubber, wherein the formula of the high bio-based elastomer tire sidewall rubber composition is different from that of Example 9 in that the super vulcanizing aid DES is obtained by co-melting zinc chloride, choline chloride and thiourea in a molar ratio of 1:1:2, and other raw materials and methods are the same as those of Example 9, which will not be repeated here.

[0149] Example 16

[0150] This embodiment provides a high bio-based elastomer tire sidewall rubber, wherein the formula of the high bio-based elastomer tire sidewall rubber composition is different from that of Example 9 in that the super vulcanizing agent DES is obtained by co-melting zinc chloride, choline chloride and thiourea in a molar ratio of 1:1:1, and other raw materials and methods are the same as those of Example 9 and will not be repeated here.

[0151] Comparative Example 3

[0152] This comparative example provides a high bio-based elastomer tire sidewall rubber, wherein the formula of the high bio-based elastomer tire sidewall rubber composition is different from that of Example 9 in that an equal amount of natural ore powder is used to replace the porous three-phase alloy, and other raw materials and methods are the same as those of Example 9 and will not be repeated here.

[0153] Comparative Example 4

[0154] This comparative example provides a high bio-based elastomer tire sidewall rubber, wherein the formula of the high bio-based elastomer tire sidewall rubber composition is different from that of Example 9 in that no porous three-phase alloy is added, and other raw materials and methods are the same as those of Example 9, which will not be repeated here.

[0155] Examples 9 to 16 and Comparative Examples 1 to 4 were prepared according to the following preparation method:

[0156] First masterbatch: start the tandem kneading internal mixer, set the speed to 45-55 rpm, add natural rubber, lithium-based butadiene rubber (or nickel-based butadiene rubber), porous three-phase alloy, rice husk gray carbon black (or carbon black), silane coupling agent, silane synergist, activator, antioxidant, tackifying resin, tearing resin and microcrystalline wax according to the formula, mix for 40 seconds, lift the bolt and press the bolt to mix for 25 seconds, lift the bolt and press the bolt to mix until the glue is discharged at 147°C to obtain the first masterbatch.

[0157] Second masterbatch: Start the internal mixer and set the speed to 25-35 rpm. First add the first masterbatch, vulcanizer and super vulcanizing agent DES and mix for 40 seconds. Mix for 25 seconds with the bolt raised and the bolt pressed. Mix until the temperature reaches 100°C to discharge the rubber and obtain a high bio-based elastomer sidewall rubber.

[0158] Test Example 2

[0159] During the preparation of the sidewall rubber in Examples 9 to 16 and Comparative Examples 1 to 4, the rubber was tested, including low Mooney value ML, high Mooney value MH, Ts2 time, 10% vulcanization time TC10, 30% vulcanization time TC30, 60% vulcanization time TC60, 90% vulcanization time TC90 and 100% vulcanization time TC100.

[0160] The test conditions are 151℃*60min.

[0161] The obtained data are shown in Table 4 below.

[0162] Table 4

[0163]

[0164] As can be seen from Table 4, it can be seen from Example 9 and Comparative Example 1 that the use of super vulcanization aid DES can effectively solve the sulfur speed problem without affecting the MH value. It can be seen from Examples 9-16 that different proportions of zinc chloride, choline chloride and thiourea all contribute to the sulfur speed. It can be seen from Comparative Example 2 and Example 9 that the sulfur speed of rice husk gray carbon black is slow, and the use of DES can effectively improve the sulfur speed, and has little effect on MH-ML.

[0165] Test Example 3

[0166] The physical properties and dynamic mechanical properties of the sidewall rubbers obtained in Examples 9 to 16 and Comparative Examples 1 to 4 were tested.

[0167] Specifically, it includes 300% tensile stress M300, tear burst force TB, elongation at break EB% and tangent value of loss angle tanδ / 60℃ at 60℃.

[0168] 300% elongation stress M300 shall be carried out in accordance with the provisions of GB / T528-2009; tear burst strength TB shall be carried out in accordance with the provisions of GB / T528-2009; elongation at break EB% shall be carried out in accordance with the provisions of GB / T528-2009; the tangent value of the loss angle at 60°C, tanδ / 60°C, shall be carried out in accordance with the provisions of GB / T528-2009.

[0169] The test data are shown in Table 5 below.

[0170] Table 5

[0171]

[0172] It can be seen from Table 5 that the heat generation of the three alloy materials is equivalent to that of rice husk gray white carbon black; it can be seen from Comparative Example 1 and Example 1 that the use of rice husk gray white carbon black and the three alloy materials can significantly reduce tanδ / 60℃, and the elongation at break, tensile strength and elongation are equivalent to those of carbon black, and the tanδ at 60℃ decreases by 63.6%, indicating that the sidewall of the present invention has low heat generation performance.

[0173] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or replace some or all of the technical features therein by equivalents. However, these modifications or replacements do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A high bio-based elastomer tire sidewall rubber composition, characterized in that: In parts by weight, the composition comprises: 50-70 parts of natural rubber, 30-50 parts of lithium-based butadiene rubber, 5-15 parts of porous three-phase alloy, 20-40 parts of rice husk gray carbon black, 1-4 parts of silane coupling agent, 1-2 parts of silane synergist, 3-6 parts of activator, 4-6 parts of antioxidant, 2-4 parts of tackifying resin, 1-3 parts of tearing resin, 1.5-5 parts of microcrystalline wax, 2-4 parts of vulcanizing agent and 0.2-0.5 parts of super vulcanizing aid; The porous three-phase alloy is mainly obtained by high-temperature jetting of carbon black and natural ore powder; The content of silicon dioxide in the natural ore powder is 40-60%, and the content of aluminum oxide is 30-40%; The natural ore powder has a rich microporous structure and a specific surface area of ​​30-70m 2 / g, pore volume 0.20~0.40cm 3 / g, the number of pores is 100-300 million / g, and the D50 particle size is 0.25-5μm; The super vulcanization aid is a deep eutectic solvent; The super vulcanization aid is mainly prepared from zinc chloride, choline chloride and thiourea in a molar ratio of 1-3:1-3:3-6.

2. The high bio-based elastomer tire sidewall rubber composition according to claim 1, characterized in that: The mass ratio of carbon black to natural ore powder is 5-9:1-5; The grades of the carbon black include at least one of N134, N220, N234, N330, N375 and N550.

3. The high bio-based elastomer tire sidewall rubber composition according to claim 1, characterized in that: The high temperature jet process comprises: The natural ore powder suspension mixed by the jet system is sprayed into the carbon black reaction furnace, and the carbon black reacts with the natural ore powder to form an aluminum-silicon-carbon structure, and then forms an aluminum-silicon-carbon aggregate through aggregation to obtain the porous three-phase alloy; The concentration of the natural ore powder suspension is 15-25wt.%; The injection flow rate of the natural ore powder suspension is 4000-6000 kg / h; The reaction temperature is 1000-1500°C.

4. The high bio-based elastomer tire sidewall rubber composition according to claim 1, characterized in that: The grades of the vulcanizing agent include HDOT20.

5. The high bio-based elastomer tire sidewall rubber composition according to claim 1, characterized in that: The specific surface area of ​​the rice husk gray carbon black is 165~240m 2 / g, particle size is 0.8~7.8μm; The brand of the silane coupling agent includes at least one of TESPT, Si75 and Si747; The brands of the silane synergist include DST-100H; The activator comprises stearic acid and / or zinc oxide; The brand of the antioxidant includes at least one of antioxidant 4020, antioxidant RD and antioxidant 4010NA; The tackifying resin comprises at least one of tert-butylphenol-formaldehyde resin, alkylphenol-formaldehyde resin and petroleum resin; The grades of the petroleum resin include at least one of C5, C9 and C54; The brand of the tearing resin includes at least one of R-110, DCPD and CSR200.

6. A high bio-based elastomer tire sidewall rubber, characterized in that: The sidewall rubber is mainly obtained by mixing the high bio-based elastomer sidewall rubber composition according to any one of claims 1 to 5.

7. The high bio-based elastomer tire sidewall rubber according to claim 6, characterized in that: The mixing method comprises the following steps: The first masterbatch is obtained by mixing natural rubber, lithium-based butadiene rubber, porous three-phase alloy, rice husk gray carbon black, silane coupling agent, silane synergist, activator, antioxidant, tackifying resin, tearing resin and microcrystalline wax, and then kneading them in one step; Finally, the vulcanizing agent and the super vulcanizing aid are added into the first masterbatch and mixed, and then two-stage mixing is performed to obtain a high bio-based elastomer tire sidewall rubber.

8. The high bio-based elastomer tire sidewall rubber according to claim 7, characterized in that: The first stage of mixing includes mixing for 30-50 seconds, mixing with the bolt raised and the bolt pressed for 20-30 seconds, and then mixing with the bolt raised and the bolt pressed until the temperature reaches 140-155° C. for debonding; The two-stage mixing includes mixing for 30-50 seconds, mixing with the plug lifted and the plug pressed for 20-30 seconds, and then mixing with the plug lifted and the plug pressed until the temperature reaches 95-105° C. for debonding.

Images