Highly bio-based elastomer tire bead protection rubber composition

Abstract

The present invention provides a high bio-based elastomer bead filler rubber composition, specifically relating to the technical field of tire manufacturing. The porous three-phase alloy is mainly obtained by subjecting carbon black and natural ore powder to high-temperature jetting; 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 mouth protective rubber composition. Background Art

[0002] The bead guard, also known as the toe guard, is the part where the tire rubber contacts the tire rim. It mainly protects the tire carcass cord and the steel wire bead wrap. It is located at the bead position of the tire and directly contacts the rim. It is the concentrated area where the tire bears load stress. Therefore, it needs to have strong rigidity, excellent thermal conductivity, low heat generation, heat resistance and low deformation.

[0003] In the preparation process of existing rubber for the tyre, the raw materials used have poor thermal conductivity, which leads to the easy accumulation of heat during the use of the tire, thereby accelerating the aging of the rubber for the tyre. This heat accumulation not only affects the heat resistance of the rubber for the tyre, but also causes a decrease in its comprehensive performance, such as hardness and tear resistance, thereby affecting the overall performance and service life of the tire. In addition, in a high temperature environment, if the heat dissipation effect of the rubber for the tyre is not good, it may also cause fatigue damage of the material, further affecting the stability and safety of the tire. Therefore, improving the thermal conductivity and heat resistance of the rubber for the tyre is the key to improving tire performance and safety.

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

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

[0006] One of the purposes of the present invention is to provide a high bio-based elastomer tire bead protection rubber composition.

[0007] The second object of the present invention is to provide a high bio-based elastomer tire mouth protection 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-biobased elastomer tire mouth protection rubber composition, which comprises, by weight:

[0010] 70-90 parts of natural rubber, 10-30 parts of butadiene rubber, 5-10 parts of trans-polyisoprene, 15-50 parts of porous three-phase alloy, 30-50 parts of rice husk gray carbon black, 2-5 parts of silane coupling agent, 3-6 parts of activator, 4-6 parts of antioxidant, 1-3 parts of tackifying resin, 1.8-4 parts of vulcanizing agent and 0.05-0.5 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 polyethylene glycol, choline chloride and thiourea in a molar ratio of 1-3:1-3:3-6.

[0024] The average molecular weight of the polyethylene glycol is 200-1000.

[0025] Furthermore, the specific surface area of ​​the rice husk gray carbon black is 165~240m 2 / g, particle size is 0.8~7.8μm.

[0026] The brands of the silane coupling agent include at least one of TESPT, Si75, OTES and Si747.

[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 C5 and / or C9.

[0031] The second aspect of the present invention provides a high-biobased elastomer tire bead protection rubber, mainly the high-biobased elastomer tire bead protection rubber composition is obtained by mixing.

[0032] Furthermore, the mixing method comprises the following steps:

[0033] The first masterbatch is obtained by mixing natural rubber, butadiene rubber, trans-polyisoprene, porous three-phase alloy, rice husk gray carbon black, silane coupling agent, activator, antioxidant and tackifying resin and then kneading them in one stage.

[0034] Then, the first masterbatch is subjected to two-stage mixing to obtain the second masterbatch.

[0035] Finally, the vulcanizing agent and the super vulcanizing aid are added into the second masterbatch and mixed, and then three-stage mixing is performed to obtain a high bio-based elastomer tire mouth protection 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 135-155° C. for debonding.

[0038] The three-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 95-112° C. for debonding.

[0039] Compared with the prior art, the present invention has at least the following beneficial effects:

[0040] 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.

[0041] The application of the porous three-phase alloy provided by the present invention, in view of the advantages of the above-mentioned porous three-phase alloy, enables the prepared high-biobased elastomer tire mouth protection rubber composition to have better thermal conductivity and mechanical strength and a lower thermal expansion coefficient.

[0042] The high-biobased elastomer tire mouth protection rubber composition provided by the present invention significantly increases the proportion of bio-based components by using natural rubber and trans-polyisoprene; the addition of butadiene rubber helps to improve the elasticity and toughness of the rubber; 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 achieves the sustainable development of the rubber industry. Bio-based carbon black causes problems such as poor physical properties, slow sulfur rate, and low efficiency. The use of super vulcanization aids can perfectly solve this problem and 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.

[0043] The high-biobased elastomer tire bead protection rubber provided by the present invention, in view of the advantages of the above-mentioned rubber composition, enables the tire bead protection rubber prepared therefrom to have better performance and be more environmentally friendly, meets the performance requirements of different fields, and promotes the development of the tire industry. BRIEF DESCRIPTION OF THE DRAWINGS

[0044] 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.

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

[0046] Figure 2 This is a scanning electron microscope image at another magnification obtained in Characterization Example 1;

[0047] Figure 3 This is a scanning electron microscope image at the third magnification obtained in Characterization Example 1. DETAILED DESCRIPTION

[0048] 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.

[0049] 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.

[0050] 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.

[0051] The content of silicon dioxide in the natural ore powder is 40-60%, and the content of aluminum oxide is 30-40%.

[0052] 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.

[0053] 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.

[0054] 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.

[0055] 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%.

[0056] 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.

[0057] Furthermore, the mass ratio of the carbon black to the natural ore powder is 5-9:1-5.

[0058] 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.

[0059] 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.

[0060] The grades of the carbon black include at least one of N134, N220, N234, N330, N375 and N550.

[0061] Furthermore, the high temperature jet process includes:

[0062] 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.

[0063] The concentration of the natural ore powder suspension is 15-25wt.%.

[0064] The injection flow rate of the natural ore powder suspension is 4000-6000 kg / h.

[0065] The reaction temperature is 1000-1500°C.

[0066] 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-. Typically but not limiting, the concentration of the natural mineral powder suspension can be 15wt.%, 16wt.%, 17wt.%, 18wt.%, 19wt.%, 20wt.%, 21wt.%, 22wt.%, 23wt.%, 24wt.% or 25wt.%, or 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 described in the first aspect in the preparation of a high-biobased elastomer tire mouth protection rubber composition.

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

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

[0072] 70-90 parts of natural rubber, 10-30 parts of butadiene rubber, 5-10 parts of trans-polyisoprene, 15-50 parts of the porous three-phase alloy described in the first aspect, 30-50 parts of rice husk gray white carbon black, 2-5 parts of silane coupling agent, 3-6 parts of activator, 4-6 parts of antioxidant, 1-3 parts of tackifying resin, 1.8-4 parts of vulcanizing agent and 0.05-0.5 parts of super vulcanizing aid.

[0073] The high-biobased elastomer tire mouth protection rubber composition provided by the present invention significantly increases the proportion of bio-based components by using natural rubber and trans-polyisoprene; the addition of butadiene rubber helps to improve the elasticity and toughness of the rubber; 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 achieves the sustainable development of the rubber industry. Bio-based carbon black causes problems such as poor physical properties, slow sulfur rate, and low efficiency. The use of super vulcanization aids can perfectly solve this problem and 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] Typically but not restrictively, in the high bio-based elastomer tire mouth protection rubber composition, the weight proportion of natural rubber can be, for example, 70 parts, 75 parts, 80 parts, 85 parts or 90 parts, or any value within the range of 70-90 parts; the weight proportion of butadiene rubber can be, for example, 10 parts, 15 parts, 20 parts, 25 parts or 30 parts, or any value within the range of 10-30 parts; the weight proportion of trans-polyisoprene can be, for example, 5 parts, 7 parts, 9 parts or 10 parts, or any value within the range of 5-10 parts; the weight proportion of porous three-phase alloy can be, for example, 15 parts, 20 parts, 30 parts, 40 parts or 50 parts, or any value within the range of 15-50 parts; the weight proportion of rice husk gray white carbon black can be, for example, 30 parts, 35 parts, 40 parts, 45 parts or 50 parts, or any value within the range of 30-50 parts. the weight portion of the silane coupling agent can be, for example, 2 parts, 3 parts, 4 parts or 5 parts, or any value within the range of 2 to 5 parts; the weight portion of the activator can be, for example, 3 parts, 4 parts, 5 parts or 6 parts, or any value within the range of 3 to 6 parts; the weight portion of the antioxidant can be, for example, 4 parts, 5 parts or 6 parts, or any value within the range of 4 to 6 parts; the weight portion of the tackifying resin can be, for example, 1 part, 2 parts or 3 parts, or any value within the range of 1 to 3 parts; the weight portion of the vulcanizing agent can be, for example, 1.8 parts, 2.5 parts, 3.2 parts or 4 parts, or any value within the range of 1.8 to 4 parts; the weight portion of the super vulcanizing aid can be, for example, 0.05 parts, 0.15 parts, 0.25 parts, 0.35 parts or 0.5 parts, or any value within the range of 0.05 to 0.5 parts.

[0075] It should be noted that the natural rubber, butadiene rubber and trans-polyisoprene are used as base rubbers, and the total amount of the three is 100 parts.

[0076] Furthermore, the brand of the vulcanizing agent includes HDOT20.

[0077] The super vulcanization aid is a low eutectic solvent.

[0078] The super vulcanization aid is mainly prepared from polyethylene glycol, choline chloride and thiourea in a molar ratio of 1-3:1-3:3-6.

[0079] The low eutectic solvent is prepared by mixing polyethylene glycol, choline chloride and thiourea in a certain proportion, and forming 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.

[0080] Typically but not limiting, the molar ratio of polyethylene glycol, 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.

[0081] The average molecular weight of the polyethylene glycol is 200-1000.

[0082] Typically, but not limiting, the grade of polyethylene glycol may be, for example, PEG200, PEG400, PEG600, PEG800 or PEG1000.

[0083] Furthermore, the specific surface area of ​​the rice husk gray carbon black is 165~240m 2 / g, particle size is 0.8~7.8μm.

[0084] 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.

[0085] The brands of the silane coupling agent include at least one of TESPT, Si75, OTES and Si747.

[0086] The activator includes stearic acid and / or zinc oxide.

[0087] The brands of the antioxidant include at least one of antioxidant 4020, antioxidant RD and antioxidant 4010NA.

[0088] The tackifying resin includes at least one of tert-butylphenol-formaldehyde resin, alkylphenol-formaldehyde resin and petroleum resin.

[0089] The grades of the petroleum resin include C5 and / or C9.

[0090] The fourth aspect of the present invention provides a high-biobased elastomer tire bead protection rubber, mainly the high-biobased elastomer tire bead protection rubber composition is obtained by mixing.

[0091] The high-biobased elastomer tire bead protection rubber provided by the present invention, in view of the advantages of the above-mentioned rubber composition, enables the tire bead protection rubber prepared therefrom to have better performance and be more environmentally friendly, meets the performance requirements of different fields, and promotes the development of the tire industry.

[0092] Furthermore, the mixing method comprises the following steps:

[0093] The first masterbatch is obtained by mixing natural rubber, butadiene rubber, trans-polyisoprene, porous three-phase alloy, rice husk gray carbon black, silane coupling agent, activator, antioxidant and tackifying resin and then kneading them in one stage.

[0094] Then, the first masterbatch is subjected to two-stage mixing to obtain the second masterbatch.

[0095] Finally, the vulcanizing agent and the super vulcanizing aid are added into the second masterbatch and mixed, and then three-stage mixing is performed to obtain a high bio-based elastomer tire mouth protection rubber.

[0096] 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.

[0097] 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 135-155° C. for debonding.

[0098] The three-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 95-112° C. for debonding.

[0099] 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.

[0100] 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 135°C, 138°C, 141°C, 145°C, 150°C or 155°C for rubber discharge.

[0101] Typically but not limiting, the temperature and time of the three-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, 105°C, 110°C or 112°C for rubber discharge.

[0102] 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.

[0103] The raw materials used in the examples and comparative examples are shown in Table 1 below.

[0104] Table 1

[0105]

[0106] Example 1

[0107] This embodiment provides a porous three-phase alloy, and the preparation method is as follows:

[0108] 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.

[0109] Example 2

[0110] This embodiment provides a porous three-phase alloy, and the preparation method is as follows:

[0111] 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.

[0112] Example 3

[0113] This embodiment provides a porous three-phase alloy, and the preparation method is as follows:

[0114] 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℃. 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.

[0115] Example 4

[0116] 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.

[0117] Example 5

[0118] 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.

[0119] Example 6

[0120] 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.

[0121] Example 7

[0122] 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.

[0123] Example 8

[0124] 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.

[0125] Test Example 1

[0126] 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.

[0127] 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.

[0128] The results are shown in Table 2 below.

[0129] Table 2

[0130]

[0131] 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.

[0132] Characterization Example 1

[0133] 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.

[0134] Examples 9-13 and Comparative Examples 1-2

[0135] These embodiments provide a high bio-based elastomer tire bead rubber, which is made of a high bio-based elastomer tire bead rubber composition, and the formula of the high bio-based elastomer tire bead rubber composition is shown in Table 3. The porous three-phase alloy used is the porous three-phase alloy provided in Example 1.

[0136] Table 3

[0137]

[0138] Note: “ / ” indicates that the substance is not added.

[0139] In the above-mentioned Examples 9 to 13, the super vulcanization aid is polyethylene glycol PEG400, which is obtained by melting choline chloride and thiourea in a molar ratio of 1:1:4.

[0140] Embodiment 14

[0141] This embodiment provides a high bio-based elastomer tire bead protection rubber, wherein the formula of the high bio-based elastomer tire bead protection rubber composition is different from that of Example 9 in that the super vulcanizing aid is polyethylene glycol PEG400, and choline chloride and thiourea are obtained by co-melting in a molar ratio of 1:1:3. Other raw materials and methods are the same as those of Example 9 and will not be repeated here.

[0142] Embodiment 15

[0143] This embodiment provides a high bio-based elastomer tire bead protection rubber, wherein the formula of the high bio-based elastomer tire bead protection rubber composition is different from that of Example 9 in that the super vulcanizing aid is polyethylene glycol PEG400, and choline chloride and thiourea are obtained by co-melting at a molar ratio of 1:1:2. Other raw materials and methods are the same as those of Example 9 and will not be repeated here.

[0144] Example 16

[0145] The present embodiment provides a high bio-based elastomer tire bead protection rubber, wherein the formula of the high bio-based elastomer tire bead protection rubber composition is different from that of Example 9 in that the super vulcanizing aid is polyethylene glycol PEG400, and choline chloride and thiourea are obtained by co-melting at a molar ratio of 1:1:1. Other raw materials and methods are the same as those of Example 9 and will not be repeated here.

[0146] Comparative Example 3

[0147] This comparative example provides a high-biobased elastomer tire bead protection rubber, wherein the formula of the high-biobased elastomer tire bead protection rubber composition is different from that of Example 9 in that an equal amount of natural mineral 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.

[0148] Comparative Example 4

[0149] This comparative example provides a high bio-based elastomer tire bead protection rubber, wherein the formula of the high bio-based elastomer tire bead protection 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.

[0150] Examples 9 to 16 and Comparative Examples 1 to 4 were prepared according to the following preparation method:

[0151] First masterbatch: Start the tandem kneading internal mixer, set the speed to 45-55 rpm, add natural rubber, butadiene rubber, trans-polyisoprene, porous three-phase alloy, rice husk gray carbon black (or carbon black), silane coupling agent, activator, antioxidant and tackifying resin according to the formula, mix for 40 seconds, lift the plug and press the plug to mix for 25 seconds, lift the plug and press the plug to mix until 147°C to discharge the glue, and obtain the first masterbatch.

[0152] Second masterbatch: Start the internal mixer and set the speed to 25-35 rpm. First add the first masterbatch and mix for 40 seconds. Then, mix for 25 seconds with the plug raised and the plug pressed. Then, mix until the temperature reaches 140℃ and the rubber is discharged to obtain the second masterbatch.

[0153] Vulcanization: Start the internal mixer and set the speed to 25-35 rpm. First add the second masterbatch, vulcanizer and super vulcanizing agent and mix for 40 seconds. Then mix for 25 seconds with the bolt raised and the bolt pressed. Then mix until the temperature reaches 100°C for rubber discharge to obtain a high bio-based elastomer tire mouth protective rubber.

[0154] Test Example 2

[0155] During the preparation of the spigot protection 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, and 90% vulcanization time TC90.

[0156] The test conditions are 151℃*60min.

[0157] The obtained data are shown in Table 4 below.

[0158] Table 4

[0159]

[0160] As can be seen from Table 4, through Example 9 and Comparative Example 1, it can be seen that the use of super vulcanization aid DES can effectively solve the sulfur rate problem without affecting the MH value. The use of ore powder will cause the MH value to decrease.

[0161] Test Example 3

[0162] The physical properties and dynamic mechanical properties of the spout protective rubber obtained in Examples 9 to 16 and Comparative Examples 1 to 4 were tested.

[0163] Specifically, it includes 300% tensile stress M300, tear burst force TB, elongation at break EB%, tangent value of loss angle tanδ / 60℃ at 60℃ and flexural fatigue (grade 6 crack).

[0164] 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; flexural fatigue (level 6 crack) shall be carried out in accordance with the provisions of GB / T 13934-2006.

[0165] The test data are shown in Table 5 below.

[0166] Table 5

[0167]

[0168] It can be seen from Table 5 that the super vulcanization additive DES has little effect on the physical properties. When the mineral powder is directly added, the heat generation is high, the elongation is low, and the fatigue life will deteriorate.

[0169] Test Example 4

[0170] The thermal conductivity of the spout protective rubber obtained in Examples 9 to 16 and Comparative Examples 1 to 4 was tested.

[0171] Specific thermal conductivity λ and thermal diffusion coefficient α, wherein the thermal conductivity λ is carried out in accordance with the provisions of GB / T 11205-2009; the thermal diffusion coefficient α is carried out in accordance with the provisions of GB / T 11205-2009.

[0172] The test data are shown in Table 6 below.

[0173] Table 6

[0174]

[0175] It can be seen from Table 6 that, through Comparative Example 4 and Example 1, it can be seen that the porous three-term alloy can effectively improve the thermal conductivity.

[0176] 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 mouth protection rubber composition, characterized in that: In parts by weight, the composition comprises: 70-90 parts of natural rubber, 10-30 parts of butadiene rubber, 5-10 parts of trans-polyisoprene, 15-50 parts of porous three-phase alloy, 30-50 parts of rice husk gray carbon black, 2-5 parts of silane coupling agent, 3-6 parts of activator, 4-6 parts of antioxidant, 1-3 parts of tackifying resin, 1.8-4 parts of vulcanizing agent and 0.05-0.5 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 polyethylene glycol, choline chloride and thiourea in a molar ratio of 1-3:1-3:3-6.

2. The high bio-based elastomer tire mouth protection 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 mouth protection 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 mouth protection rubber composition according to claim 1, characterized in that: The grades of the vulcanizing agent include HDOT20; The average molecular weight of the polyethylene glycol is 200-1000.

5. The high bio-based elastomer tire mouth protection 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 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 C5 and / or C9.

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

7. The high bio-based elastomer tire mouth protection rubber according to claim 6, characterized in that: The mixing method comprises the following steps: The first masterbatch is obtained by mixing natural rubber, butadiene rubber, trans-polyisoprene, porous three-phase alloy, rice husk gray carbon black, silane coupling agent, activator, antioxidant and tackifying resin and performing mixing in one stage; Then, the first masterbatch is subjected to two-stage mixing to obtain a second masterbatch; Finally, the vulcanizing agent and the super vulcanizing aid are added into the second masterbatch and mixed, and then three-stage mixing is performed to obtain a high bio-based elastomer tire mouth protection rubber.

8. The high bio-based elastomer tire mouth protection 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 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 135-155° C. for debonding; The three-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 95-112° C. for debonding.

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