Tire apex composition, tire apex and preparation method of tire apex

Abstract

The invention provides a tire apex composition, a tire apex and a preparation method of the tire apex, and relates to the technical field of tire manufacturing. The tire bead filler composition is prepared from the following components in parts by weight: 100 parts of raw rubber, 10 to 40 parts of modified carbon nanotube / carbon black aggregate, 1 to 12 parts of active agent, 0.8 to 6 parts of accelerant, 0.8 to 6 parts of vulcanizing agent, 3 to 7 parts of anti-aging agent, 0.5 to 4 parts of tackifying resin, 0 to 25 parts of white carbon black, 0 to 2.5 parts of silane coupling agent, 0 to 2.5 parts of protective wax and 0 to 0.3 part of scorch retarder, wherein the modified carbon nanotube / carbon black aggregate is obtained by carrying out high-temperature jet flow on a modifier and a carbon nanotube / carbon black aggregate. According to the invention, the modified carbon nanotube / carbon black aggregate is added into the tire apex composition, so that filler agglomeration is reduced, mechanical properties and wear resistance of the tire apex are improved, and heat generation of the tire apex can be further reduced.

Description

Technical Field

[0001] The invention relates to the technical field of tire manufacturing, and in particular to a tire apex rubber composition, a tire apex rubber and a preparation method thereof. Background Art

[0002] The tire apex is an important part of the tire bead. It is located on the upper part of the tire wire ring, between the rigid tire bead and the flexible tire body. It not only fills the tire to make the tire bead profile transition uniform, but also plays a major role in stress buffering and modulus transition, carrying loads and transmitting drive. It is subject to complex compression and shear stress. Especially when driving on relatively harsh road conditions, the apex is subjected to greater shear and impact forces. When the apex is subjected to more and more stress concentration, more and more heat is accumulated, and the temperature is getting higher and higher, it is easy to cause the apex to produce vulcanization reverse phenomenon, thereby causing the cross-linking bonds of the apex to break and the performance to decline. Therefore, the apex material is required to have high hardness and high modulus, and it is also required to have excellent low heat generation, heat resistance and thermal conductivity.

[0003] At present, in order to ensure that the apex rubber has a high modulus and hardness, the existing technical method is to add to the rubber: (1) a high amount of fine particle carbon black, (2) a combination of hard carbon black and soft carbon black, (3) a high amount of sulfur, (4) reinforcing resin, such as phenolic resin, high styrene resin, cobalt salt and other hardeners. (5) micron short fibers, such as nylon, polyester, polyester, aramid short fibers, etc. The existing carbon black has a small particle size, a relatively large aggregate specific area, and a high surface free energy. It is very easy to flocculate into agglomerates during processing. Therefore, when the amount of carbon black is large, it is difficult for the carbon black to be evenly dispersed in the rubber matrix, heat generation is serious, and the temperature rise is rapid and violent, thereby affecting the various properties of the rubber material. Increasing the amount of sulfur will lead to a decrease in heat resistance, resulting in a continuous decrease in the tensile stress of the rubber compound, which is likely to cause stress softening and increased deformation in the tire bead area. Although reinforcing resin can increase mechanical strength, it has problems such as high temperature softening. The short fibers are long and difficult to disperse evenly in the rubber matrix, resulting in poor processing performance and a decrease in the modulus of the composite material after dynamic heating.

[0004] In view of this, the present invention is proposed. Summary of the invention

[0005] The purpose of the present invention is to provide a tire apex rubber composition, a tire apex rubber and a preparation method thereof. The tire apex rubber composition of the present invention significantly enhances the mechanical properties of the tire apex rubber, reduces heat generation and improves wear by adding modified carbon nanotubes / carbon black aggregates.

[0006] In order to solve the above technical problems, the present invention particularly adopts the following technical solutions: In a first aspect, the present invention provides a tire apex rubber composition, wherein the tire apex rubber composition comprises the following components in parts by weight: 100 pieces of raw rubber Modified carbon nanotube / carbon black aggregate 10~40 parts 1~12 parts of active agent Accelerator 0.8~6 parts Vulcanizing agent 0.8~6 parts 3~7 parts of antioxidant 0.5~4 parts of tackifying resin White carbon black 0~25 parts Silane coupling agent 0~2.5 parts Protective wax 0~2.5 parts Anti-scorch agent 0~0.3 parts; Wherein, the modified carbon nanotube / carbon black aggregate is obtained by high-temperature jetting of a modifier and carbon nanotube / carbon black aggregate; the modifier is selected from any one or a combination of at least two of the compounds represented by the following formulas I to V: ; Wherein, n and m are each independently selected from positive integers between 1 and 10; M is selected from alkali metals and / or alkaline earth metals; R 1 and R 2 Each independently selected from or , p is a positive integer between 1 and 5.

[0007] Preferably, the modifier is selected from any one or a combination of at least two of the following compounds: ; Preferably, the content of the modifier is 0.05-5% of the total mass of the modified carbon nanotube / carbon black aggregate.

[0008] Preferably, the carbon nanotube / carbon black aggregates are obtained by powder spraying carbon nanotubes and carbon black primary particles.

[0009] Preferably, the content of the carbon nanotubes is 1-10% of the total mass of the carbon nanotube / carbon black aggregate.

[0010] Preferably, the carbon black native particles are N326 carbon black native particles.

[0011] Preferably, the modified carbon nanotube / carbon black aggregate is prepared by the following steps: (a) Spraying a suspension of carbon nanotubes into a carbon black reaction furnace through powder injection, the carbon nanotubes and carbon black primary particles are combined to form a pre-agglomerate; and carbon black is aggregated to form a carbon nanotube / carbon black aggregate; (b) combining the modifier with the carbon nanotube / carbon black aggregate by high temperature jet to obtain the modified carbon nanotube / carbon black aggregate.

[0012] Preferably, in step (a), the carbon nanotube suspension comprises, by mass percentage, 15-25% carbon nanotubes and the remainder water.

[0013] Preferably, in step (a), the injection rate of the carbon nanotube suspension is 50-200 kg / h.

[0014] Preferably, in step (a), the temperatures for combining to form the pre-agglomerate and the aggregation of the carbon black are independently 800-1000°C.

[0015] Preferably, in step (b), the injection rate of the modifier is 20-100 kg / h.

[0016] Preferably, in step (b), the temperature at which the modifier combines with the carbon nanotube / carbon black aggregate is 100-480°C.

[0017] Preferably, in step (b), after the modifier is combined with the carbon nanotube / carbon black aggregate, the following post-treatment step is also included: After cooling, filtering and collecting and separating, a powdery product is obtained; the powdery product, a binder and water are mixed, granulated and then dried to obtain the modifier and carbon nanotube / carbon black aggregates.

[0018] Preferably, the mass ratio of the powdered product, the binder and water is (80~100):(0.1~2):(0.01~10).

[0019] Preferably, the binder is selected from lignin and / or molasses.

[0020] Preferably, the particle size of the modifier and the carbon nanotube / carbon black aggregate is 0.1-3 μm.

[0021] Preferably, the raw rubber comprises natural rubber.

[0022] Preferably, the active agent comprises stearic acid and / or zinc oxide.

[0023] Preferably, the accelerator comprises accelerator NS.

[0024] Preferably, the vulcanizing agent includes insoluble sulfur OT-20.

[0025] Preferably, the antioxidant includes antioxidant 4020 and / or antioxidant RD.

[0026] Preferably, the tackifying resin includes any one of tert-butylphenol formaldehyde tackifying resin, tert-butylphenol phenol formaldehyde tackifying resin, octylphenol formaldehyde tackifying resin or Keresin resin, or a combination of at least two thereof.

[0027] Preferably, the silane coupling agent includes silane coupling agent Si-69.

[0028] Preferably, the protective wax comprises microcrystalline wax.

[0029] Preferably, the anti-scorch agent includes anti-scorch agent CTP.

[0030] In a second aspect, the present invention provides a tire apex rubber material, wherein the tire apex rubber material is obtained by mixing the tire apex rubber material composition as described in the first aspect.

[0031] In a third aspect, the present invention provides a method for preparing the tire apex rubber material as described in the second aspect, the preparation method comprising: (1) mixing the raw rubber, modified carbon nanotube / carbon black aggregate, white carbon, silane coupling agent, activator, antioxidant, tackifying resin and protective wax, and kneading them in one step to obtain a carbon nanotube / carbon black masterbatch; (2) The carbon nanotube / carbon black masterbatch, the vulcanizing agent, the accelerator and the anti-scorching agent are mixed and kneaded in two stages to obtain the tire apex rubber material.

[0032] Preferably, in step (1), the mixed raw materials also include a processing aid.

[0033] Preferably, in step (1), the mixing stage comprises the following steps: mixing for 20 to 40 seconds, lifting the top pin, pausing for 10 to 15 seconds, and pressing the top pin; mixing to a temperature of 135 to 145°C, lifting the top pin, pausing for 10 to 15 seconds, and pressing the top pin; mixing to a temperature of 145 to 155°C, and then debonding.

[0034] Preferably, in step (2), the two-stage mixing includes the following steps: after mixing for 10 to 60 seconds, lifting the top bolt, pausing for 0 to 15 seconds, and pressing the top bolt; mixing until the temperature reaches 70 to 85°C, lifting the top bolt, pausing for 0 to 15 seconds, and pressing the top bolt; mixing until the temperature reaches 100 to 120°C for debonding.

[0035] Compared with the prior art, the present invention has the following beneficial effects: (1) During the preparation process of the modified carbon nanotube / carbon black aggregates of the present invention, in the presence of a modifier, the carbon nanotubes can be more evenly dispersed in the carbon black primary particles by jet technology, thereby significantly improving the dispersion performance of the carbon nanotubes.

[0036] (2) The present invention adds modified carbon nanotubes / carbon black aggregates to the tire apex rubber composition. The surface modification enhances the interaction between rubber and filler, reduces filler agglomeration, improves the mechanical properties and wear resistance of the tire apex rubber, and further reduces the heat generation of the tire apex rubber.

[0037] (3) The present invention uses a modifier to first modify the carbon nanotube / carbon black aggregates and then add them to the apex rubber composition, forming a "physical-chemical" dual reinforcement mechanism. Compared with the two being added to the rubber composition in the form of physical blending at a later stage, the apex rubber has better dispersibility, stronger mechanical properties, and higher stability. In addition, from a process perspective, modifying the carbon nanotube / carbon black aggregates first also has higher functionalization efficiency, which helps to improve processing performance. BRIEF DESCRIPTION OF THE DRAWINGS

[0038] 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.

[0039] Figure 1 This is a scanning electron microscope image of the modified carbon nanotube / carbon black aggregate prepared in Preparation Example 1.

[0040] Figure 2 This is a scanning electron microscope image of the modified carbon nanotube / carbon black aggregate prepared in Preparation Example 2.

[0041] Figure 3 This is a scanning electron microscope image of the modified carbon nanotube / carbon black aggregate prepared in Preparation Example 3.

[0042] Figure 4 This is a scanning electron microscope image of the modified carbon nanotube / carbon black aggregate prepared in Preparation Example 4.

[0043] Figure 5 This is a scanning electron microscope image of the modified carbon nanotube / carbon black aggregate prepared in Preparation Example 5.

[0044] Figure 6 This is a scanning electron microscope image of the modified carbon nanotube / carbon black aggregate prepared in Preparation Example 6.

[0045] Figure 7 This is a scanning electron microscope image of the unmodified carbon nanotube / carbon black aggregate provided in Comparative Preparation Example 1. DETAILED DESCRIPTION

[0046] 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.

[0047] 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.

[0048] In a first aspect, the present invention provides a tire apex rubber composition, wherein the tire apex rubber composition comprises the following components in parts by weight: 100 pieces of raw rubber Modified carbon nanotube / carbon black aggregate 10~40 parts 1~12 parts of active agent Accelerator 0.8~6 parts Vulcanizing agent 0.8~6 parts 3~7 parts of antioxidant 0.5~4 parts of tackifying resin White carbon black 0~25 parts Silane coupling agent 0~2.5 parts Protective wax 0~2.5 parts Anti-scorch agent 0~0.3 parts; Wherein, the modified carbon nanotube / carbon black aggregate is obtained by high-temperature jetting of a modifier and carbon nanotube / carbon black aggregate; the modifier is selected from any one or a combination of at least two of the compounds represented by the following formulas I to V: ; Wherein, n and m are each independently selected from positive integers between 1 and 10; M is selected from alkali metals and / or alkaline earth metals; R 1 and R 2 Each independently selected from or , p is a positive integer between 1 and 5.

[0049] As an optional implementation, n is selected from a positive integer between 1 and 10, for example, it can be 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10.

[0050] As an optional implementation, m is selected from a positive integer between 1 and 10, for example, it can be 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10.

[0051] As an optional implementation, p is selected from a positive integer between 1 and 5, for example, it can be 1, 2, 3, 4, or 5.

[0052] As an optional embodiment, M is selected from alkali metals and / or alkaline earth metals, for example, Li, Na, K, Mg, Ca, etc., preferably Na.

[0053] In the present invention, during the preparation process of the modified carbon nanotube / carbon black aggregate of the present invention, in the presence of the modifier shown in Formula I to Formula V, the carbon nanotube can be more evenly dispersed in the carbon black primary particles by jet technology, significantly improving the dispersion performance of the carbon nanotube. Furthermore, the present invention adds the modified carbon nanotube / carbon black aggregate to the tire apex rubber composition, thereby enhancing the interaction between the rubber and the filler, reducing the agglomeration of the filler carbon nanotube / carbon black itself, and providing the mechanical properties and wear resistance of the tire apex rubber, while further reducing the heat generation of the tire apex rubber.

[0054] It should be noted that the present invention uses a modifier to first modify the carbon nanotube (CNT) / carbon black (CB) aggregates and then add them to the rubber matrix. Compared with adding the two to the rubber composition in the form of physical blending at a later stage, the reason why the rubber performance is significantly improved is that: 1. Better dispersibility: The present invention fixes the modifier through chemical bonds, and the graft modification uses covalent bonds to more firmly bind the coupling agent and wrap it on the surface of the aggregate to form a stable surface modification layer. As mentioned above, this chemical bonding can effectively reduce the van der Waals force between aggregates, reduce the tendency to agglomerate, and reduce the risk of CNT breakage, thereby maintaining its original aspect ratio; while it only attaches to the surface of carbon black through physical adsorption or weak interactions (such as hydrogen bonds), and is easy to fall off under the high shear force of rubber processing (such as mixing and extrusion), resulting in the re-agglomeration of carbon black.

[0055] 2. Stronger mechanical properties: The modifier of the present application not only acts as a "bridge" to form a CNT-CB hybrid structure, but also can connect CNT / CB aggregates at one end and react chemically with rubber molecular chains at the other end to form a strong chemical bonding interface of CNT / CB aggregates-rubber, thereby improving the interfacial bonding ability and making the rubber have stronger mechanical properties; while when only physically mixed, the interface between the modifier and the rubber only relies on physical adsorption or a small amount of reaction, the interfacial bonding strength is low, the stress transfer efficiency is poor, and it is easy to cause interfacial debonding.

[0056] 3. Higher stability: After grafting modification, the modifier is covalently locked on the surface of the CNT / CB aggregate, and will not migrate or precipitate during rubber processing and use, with high long-term stability; while physically mixed coupling agents may migrate due to poor compatibility with rubber or changes in processing temperature, resulting in local uneven concentration or performance attenuation.

[0057] 4. Higher functionalization efficiency: Chemical grafting can precisely control the coverage density and distribution of the modifier on the surface of CNT / CB aggregates, making full use of the functional groups of the modifier (such as amino groups) to react with rubber; while physical mixed modifiers may be randomly adsorbed on the CNT / CB aggregates or rubber surfaces, and some modifiers will not participate in the subsequent interfacial bonding, resulting in low utilization rate.

[0058] 5. Improve processing performance: Chemically grafted CNT / CB aggregates are easier to disperse in rubber, reducing mixing time and energy consumption, and avoiding CNT breakage due to high shear force (better retention of aspect ratio). If unmodified CNTs require higher shear force to disperse during mixing, it is easy to cause rubber degradation or CNT structure damage.

[0059] As an optional embodiment, in the tire apex rubber composition, the content of modified carbon nanotubes / carbon black aggregates is 10 to 40 parts, for example, it can be 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts, 16 parts, 17 parts, 18 parts, 19 parts, 20 parts, 21 parts, 22 parts, 23 parts, 24 parts, 25 parts, 26 parts, 27 parts, 28 parts, 29 parts, 30 parts, 31 parts, 32 parts, 33 parts, 34 parts, 35 parts, 36 parts, 37 parts, 38 parts, 39 parts, 40 parts, etc., preferably 20 to 30 parts, and more preferably 25 to 30 parts.

[0060] As an optional embodiment, in the tire apex rubber composition, the content of the active agent is 1 to 12 parts, for example, it can be 1 part, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, 11 parts, 12 parts, etc., preferably 6 to 9 parts, and more preferably 7.5 to 8.5 parts.

[0061] As an optional embodiment, in the tire apex rubber composition, the content of the accelerator is 0.8 to 6 parts, for example, it can be 0.8 parts, 1 parts, 1.2 parts, 1.4 parts, 1.5 parts, 1.6 parts, 1.8 parts, 2 parts, 2.2 parts, 2.4 parts, 2.5 parts, 2.6 parts, 2.8 parts, 3 parts, 3.2 parts, 3.4 parts, 3.5 parts, 3.6 parts, 3.8 parts, 4 parts, 4.2 parts, 4.4 parts, 4.5 parts, 4.6 parts, 4.8 parts, 5 parts, 5.2 parts, 5.4 parts, 5.6 parts, 5.8 parts, 6 parts, etc., preferably 0.8 to 2 parts, and more preferably 0.8 to 1.2 parts.

[0062] As an optional embodiment, in the tire apex rubber composition, the content of the vulcanizing agent is 0.8 to 6 parts, for example, it can be 0.8 parts, 1 parts, 1.2 parts, 1.4 parts, 1.5 parts, 1.6 parts, 1.8 parts, 2 parts, 2.2 parts, 2.4 parts, 2.5 parts, 2.6 parts, 2.8 parts, 3 parts, 3.2 parts, 3.4 parts, 3.5 parts, 3.6 parts, 3.8 parts, 4 parts, 4.2 parts, 4.4 parts, 4.5 parts, 4.6 parts, 4.8 parts, 5 parts, 5.2 parts, 5.4 parts, 5.6 parts, 5.8 parts, 6 parts, etc., preferably 3 to 3.5 parts, and more preferably 3.1 to 3.2 parts.

[0063] As an optional embodiment, in the tire apex rubber composition, the content of the antioxidant is 3 to 7 parts, for example, it can be 3 parts, 3.2 parts, 3.4 parts, 3.5 parts, 3.6 parts, 3.8 parts, 4 parts, 4.2 parts, 4.4 parts, 4.5 parts, 4.6 parts, 4.8 parts, 5 parts, 5.2 parts, 5.4 parts, 5.5 parts, 5.6 parts, 5.8 parts, 6 parts, 6.2 parts, 6.4 parts, 6.5 parts, 6.6 parts, 6.8 parts, 7 parts, etc., preferably 3 to 4 parts.

[0064] As an optional embodiment, in the tire apex rubber composition, the content of tackifying resin is 0.5 to 4 parts, for example, it can be 1 part, 1.2 parts, 1.4 parts, 1.5 parts, 1.6 parts, 1.8 parts, 2 parts, 2.2 parts, 2.4 parts, 2.5 parts, 2.6 parts, 2.8 parts, 3 parts, 3.2 parts, 3.4 parts, 3.5 parts, 3.6 parts, 3.8 parts, 4 parts, etc., preferably 0.8 to 1.2 parts.

[0065] As an optional embodiment, in the tire apex rubber composition, the content of white carbon black is 0 to 25 parts, for example, it can be 0, 0.01 parts, 0.05 parts, 0.1 parts, 0.2 parts, 0.4 parts, 0.5 parts, 0.6 parts, 0.8 parts, 1 parts, 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts, 16 parts, 17 parts, 18 parts, 19 parts, 20 parts, 21 parts, 22 parts, 23 parts, 24 parts, 25 parts, etc., preferably 15 to 25 parts, and more preferably 18 to 22 parts.

[0066] As an optional embodiment, in the tire apex rubber composition, the content of silane coupling agent is 0 to 2.5 parts, for example, it can be 0 part, 0.1 part, 0.2 part, 0.4 part, 0.5 part, 0.6 part, 0.7 part, 0.8 part, 0.9 part, 1 part, 1.2 parts, 1.4 parts, 1.5 parts, 1.6 parts, 1.8 parts, 2 parts, 2.2 parts, 2.4 parts, 2.5 parts, etc., preferably 1.5 to 2.5 parts, and more preferably 1.8 to 2.2 parts.

[0067] As an optional embodiment, in the tire apex rubber composition, the content of protective wax is 0 to 2.5 parts, for example, it can be 0 parts, 0.1 parts, 0.2 parts, 0.4 parts, 0.5 parts, 0.6 parts, 0.7 parts, 0.8 parts, 0.9 parts, 1 parts, 1.2 parts, 1.4 parts, 1.5 parts, 1.6 parts, 1.8 parts, 2 parts, 2.2 parts, 2.4 parts, 2.5 parts, etc., preferably 0.1 to 1 parts, and more preferably 0.4 to 0.6 parts.

[0068] As an optional embodiment, in the tire apex rubber composition, the content of the anti-scorch agent is 0 to 0.3 parts, for example, it can be 0 parts, 0.01 parts, 0.05 parts, 0.1 parts, 0.15 parts, 0.2 parts, 0.25 parts, 0.3 parts, etc., preferably 0.1 to 0.3 parts.

[0069] As an optional embodiment, the modifier is selected from any one or a combination of at least two of the following compounds: .

[0070] As an optional embodiment, the content of the modifier is 0.05-5% of the total mass of the modified carbon nanotube / carbon black aggregate, for example, it can be 0.05%, 0.06%, 0.08%, 0.1%, 0.2%, 0.4%, 0.5%, 0.6%, 0.8%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, etc.

[0071] As an optional implementation, the carbon nanotube / carbon black aggregates are obtained by powder spraying carbon nanotubes and carbon black primary particles.

[0072] As an optional embodiment, the content of the carbon nanotubes is 1-10% of the total mass of the carbon nanotube / carbon black aggregate, for example, it can be 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5%, 10%, etc.

[0073] As an optional embodiment, the carbon black native particles are N326 carbon black native particles.

[0074] As an optional embodiment, the modified carbon nanotube / carbon black aggregate is prepared by the following steps: (a) Spraying a suspension of carbon nanotubes into a carbon black reaction furnace through powder injection, the carbon nanotubes and carbon black primary particles are combined to form a pre-agglomerate; and carbon black is aggregated to form a carbon nanotube / carbon black aggregate; (b) combining the modifier with the carbon nanotube / carbon black aggregate by high temperature jet to obtain the modified carbon nanotube / carbon black aggregate.

[0075] In the present invention, the powder injection in step (a) is specifically as follows: the carbon nanotubes are transported to the interlocking double helices that can be precisely quantified through the mechanical arch breaking device, the airflow arch breaking device and the plow blade stirring device at the bottom of the silo in the storage bin, and the carbon nanotubes measured by the weighing system and the precise quantitative spiral enter the mass transfer cavity of the high-speed injection mixer and are instantly mixed with the injection carrier, i.e., process water. The carbon nanotubes are forced to disperse into the injection carrier during the movement, and are rapidly diffused into a uniform suspension through pressure changes in the diffuser at the tail of the injector, and are transported to the pressure atomization system.

[0076] In the present invention, the combination in step (b) is specifically as follows: adding a modifier and combining it with the flue gas of the suspended carbon nanotubes / carbon black aggregates through high-temperature jet technology; further, after cooling, filtering and collection and separation by the main bag filter, the separated tail gas is used for heating in the tail gas furnace and power generation in the boiler, and finally the powdered carbon nanotubes / carbon black aggregates are stirred with an appropriate amount of water and a binder in a granulator to be granulated, and then the aggregate particles are sent to a rotary dryer for drying, and the modified carbon nanotubes / carbon black aggregates are finally obtained after removing the moisture.

[0077] In the present invention, after the modifier is combined with the carbon nanotube / carbon black aggregate, the aggregate is given the ability to maintain the carbon nanotube's own larger aspect ratio and exert the excellent performance of the carbon nanotube, while also improving the dispersion, reinforcement and reaction activity of the carbon nanotube and carbon black in the rubber matrix with the rubber group.

[0078] As an optional embodiment, in step (a), the carbon nanotube suspension comprises, by mass percentage, 15-25% carbon nanotubes, for example, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, etc., and the balance is water.

[0079] As an optional embodiment, in step (a), the injection flow rate of the carbon nanotube suspension is 50~200 kg / h, for example, it can be 50 kg / h, 60 kg / h, 70 kg / h, 80 kg / h, 100 kg / h, 120 kg / h, 140 kg / h, 150kg / h, 160 kg / h, 180 kg / h, 200 kg / h, etc.

[0080] As an optional embodiment, in step (a), the temperature of combining to form the pre-agglomerate and the aggregation of carbon black is independently 800-1000°C, for example, it can be 800°C, 820°C, 840°C, 850°C, 860°C, 880°C, 900°C, 920°C, 940°C, 950°C, 960°C, 980°C, 1000°C, etc.

[0081] As an optional embodiment, in step (b), the injection flow rate of the modifier is 20-100 kg / h, for example, it can be 20 kg / h, 30 kg / h, 40 kg / h, 50 kg / h, 60 kg / h, 70 kg / h, 80 kg / h, 90 kg / h, 100 kg / h, etc.

[0082] As an optional embodiment, in step (b), the temperature at which the modifier is combined with the carbon nanotube / carbon black aggregate is 100-480°C, for example, it can be 100°C, 120°C, 140°C, 150°C, 160°C, 180°C, 200°C, 220°C, 240°C, 250°C, 260°C, 280°C, 300°C, 320°C, 340°C, 350°C, 360°C, 380°C, 400°C, 420°C, 440°C, 450°C, 460°C, 480°C, etc.

[0083] As an optional embodiment, in step (b), after the modifier is combined with the carbon nanotube / carbon black aggregate, the following post-treatment step is also included: After cooling, filtering and collecting and separating, a powdery product is obtained; the powdery product, a binder and water are mixed, granulated and then dried to obtain the modifier and carbon nanotube / carbon black aggregates.

[0084] As an optional embodiment, the mass ratio of the powdered product, the binder and water is (80-100):(0.1-2):(0.01-10); Among them, "80~100" can be, for example, 80, 85, 90, 95, 100, etc.; Here, “0.1~2” can be, for example, 0.1, 0.5, 1, 1.5, 2, etc.; Among them, “0.01~10” can be, for example, 0.01, 0.05, 0.1, 0.5, 1, 2, 4, 5, 6, 8, 10, etc.

[0085] As an optional embodiment, the binder is selected from lignin and / or molasses.

[0086] As an optional embodiment, the particle size of the modified carbon nanotube / carbon black aggregate is 0.1-3 μm, for example, 0.1 μm, 0.5 μm, 1 μm, 1.5 μm, 2 μm, 2.5 μm, 3 μm, etc.

[0087] As an optional embodiment, the raw rubber includes natural rubber.

[0088] As an optional embodiment, the active agent includes stearic acid and / or zinc oxide.

[0089] As a preferred embodiment, the active agent consists of stearic acid and zinc oxide.

[0090] As a preferred embodiment, when the active agent is composed of stearic acid and zinc oxide, the mass ratio of stearic acid to zinc oxide is 1:(3~5), for example, it can be 1:3, 1:3.2, 1:3.4, 1:3.5, 1:3.6, 1:3.8, 1:4, 1:4.2, 1:4.4, 1:4.5, 1:4.6, 1:4.8, 1:5, etc.

[0091] As an optional embodiment, the accelerator includes accelerator NS.

[0092] As an optional embodiment, the vulcanizing agent includes insoluble sulfur OT-20.

[0093] As an optional embodiment, the antioxidant includes antioxidant 4020 and / or antioxidant RD.

[0094] As an optional implementation, the antioxidant consists of antioxidant 4020 and antioxidant RD.

[0095] As an optional embodiment, when the antioxidant consists of antioxidant 4020 and antioxidant RD, the mass ratio of antioxidant 4020 to antioxidant RD is 1:(0.5~1), for example, it can be 1:0.5, 1:0.6, 1:0.7, 1:0.8, 1:0.9, 1:1, etc.

[0096] As an optional embodiment, the tackifying resin includes any one of tert-butylphenol formaldehyde tackifying resin, tert-butylphenol aldehyde phenol tackifying resin, octylphenol formaldehyde tackifying resin or Keresin resin, or a combination of at least two thereof.

[0097] As an optional embodiment, the silane coupling agent includes silane coupling agent Si-69.

[0098] As an optional embodiment, the protective wax includes microcrystalline wax.

[0099] As an optional embodiment, the white carbon black includes GR175.

[0100] As an optional implementation, the anti-scorch agent includes anti-scorch agent CTP.

[0101] In a second aspect, the present invention provides a tire apex rubber material, wherein the tire apex rubber material is obtained by mixing the tire apex rubber material composition as described in the first aspect.

[0102] In a third aspect, the present invention provides a method for preparing the tire apex rubber material as described in the second aspect, the method for preparing the tire apex rubber material comprising: (1) mixing the raw rubber, modified carbon nanotube / carbon black aggregate, white carbon, silane coupling agent, activator, antioxidant, tackifying resin and protective wax, and kneading them in one step to obtain a carbon nanotube / carbon black masterbatch; (2) The carbon nanotube / carbon black masterbatch, the vulcanizing agent, the accelerator and the anti-scorching agent are mixed and kneaded in two stages to obtain the tire apex rubber material.

[0103] As an optional embodiment, in step (1), the mixed raw materials also include a processing aid.

[0104] As an optional implementation, step (1) specifically comprises: mixing the raw rubber, modified carbon nanotube / carbon black aggregate, white carbon, silane coupling agent, activator, antioxidant, tackifying resin, protective wax and processing aid, and performing a mixing step to obtain a carbon nanotube / carbon black masterbatch.

[0105] As an optional embodiment, in step (1), the mixing is: starting an internal mixer, setting the rotor speed of the internal mixer to 40-55 rpm (for example, 40 rpm, 42 rpm, 44 rpm, 45 rpm, 46 rpm, 48 rpm, 50 rpm, 52 rpm, 54 rpm, 55 rpm, etc.), and the mixing pressure to 4.5-6.5 MPa (for example, 4.5 MPa, 4.6 MPa, 4.8 MPa, 5 MPa, 5.2 MPa, 5.4 MPa, 5.5 MPa, 5.6 MPa, 5.8 MPa, 6 MPa, 6.2 MPa, 6.4 MPa, 6.5 MPa, etc.), the cooling water temperature is 30-40°C (for example, it can be 30°C, 32°C, 34°C, 35°C, 36°C, 38°C, 40°C, etc.), the rotor temperature is 30-40°C (for example, it can be 30°C, 32°C, 34°C, 35°C, 36°C, 38°C, 40°C, etc.), the raw rubber, modified carbon nanotube / carbon black aggregates, white carbon black, silane coupling agent, activator, antioxidant, tackifying resin, protective wax and processing aid are added.

[0106] As an optional embodiment, in step (1), the mixing stage includes the following steps: mixing for 20 to 40 s (for example, 20 s, 22 s, 24 s, 25 s, 26 s, 28 s, 30 s, 32 s, 34 s, 35 s, 36 s, 38 s, 40 s, etc.), lifting the top pin, staying for 10 to 15 s (for example, 10 s, 11 s, 12 s, 13 s, 14 s, 15 s, etc.), and pressing the top pin; mixing to a temperature of 135 to 145°C (for example, 135°C, 136°C, 138°C, 140°C, 142°C, 144°C, 145°C, etc.), lifting the top pin, staying for 10 to 15 s (for example, 10 s, 11 s, 12 s, 13 s, 14 s, 15 s, etc.), and pressing the top pin; mixing to a temperature of 135 to 145°C (for example, 135°C, 136°C, 138°C, 140°C, 142°C, 144°C, 145°C, etc.), lifting the top pin, staying for 10 to 15 s (for example, 10 s, 11 s, 12 s, 13 s, 14 s, 15 s, etc.) to press the top bolt; mix until the temperature is 145-155°C (for example, it can be 145°C, 146°C, 148°C, 150°C, 152°C, 154°C, 155°C, etc.) to discharge the glue.

[0107] As an optional embodiment, in step (2), the mixing is: starting an internal mixer, setting the rotor speed of the internal mixer to 15-40 rmp (for example, 15 rmp, 16 rmp, 18 rmp, 20 rmp, 22 rmp, 24 rmp, 25 rmp, 26 rmp, 28 rmp, 30 rmp, 32 rmp, 34 rmp, 35 rmp, 36 rmp, 38 rmp, 40 rmp, etc.), and the mixing pressure to 4.0-6.0 MPa (for example, 4.0 MPa, 4.2 MPa, 4.4 MPa, 4.5 MPa, 4.6 MPa, 4.8 MPa, 5.0 MPa, 5.2 MPa, 5.4 MPa, 5.6 MPa, 5.8 MPa, 6.0 MPa, etc.), the cooling water temperature is 30-40°C (for example, it can be 30°C, 32°C, 34°C, 35°C, 36°C, 38°C, 40°C, etc.), the rotor temperature is 30-45°C (for example, it can be 30°C, 32°C, 34°C, 35°C, 36°C, 38°C, 40°C, 42°C, 44°C, 45°C, etc.), the carbon nanotube / carbon black masterbatch, vulcanizing agent, accelerator and scorch retarder are added.

[0108] As an optional embodiment, in step (2), the two-stage mixing includes sequentially performing the following steps: mixing for 10 to 60 s (for example, 10 s, 15 s, 20 s, 22 s, 24 s, 25 s, 26 s, 28 s, 30 s, 32 s, 34 s, 35 s, 36 s, 38 s, 40 s, 45 s, 50 s, 55 s, 60 s, etc.), then lifting the top bolt and staying for 0 to 15 s (for example, 0 s, 1 s, 2 s, 4 s, 5 s, 6 s, 8 s, 10 s, 12 s, 14 s, 15 s, etc.), press the top bolt; mix until the temperature is 70-85℃ (for example, it can be 70℃, 72℃, 74℃, 75℃, 76℃, 78℃, 80℃, 82℃, 84℃, 85℃, etc.), lift the top bolt, stay for 0-15 s (for example, it can be 0 s, 1 s, 2 s, 4 s, 5 s, 6 s, 8 s, 10 s, 12 s, 14 s, 15 s, etc.) and press the top bolt; mix until the temperature is 100-120℃ (for example, it can be 100℃, 102℃, 104℃, 105℃, 106℃, 108℃, 110℃, 115℃, 120℃, etc.) to discharge the glue.

[0109] 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.

[0110] The raw materials used in the following examples are shown in Table 1.

[0111] Table 1

[0112] Among them, SUMILINK @ The structural formula of 200 is .

[0113] Preparation Example 1 This preparation example provides a modified carbon nanotube / carbon black aggregate, and the modified carbon nanotube / carbon black aggregate is prepared by the following steps: (a) In a jet system, carbon nanotubes and process water are uniformly mixed by powder injection technology, and the concentration of the carbon nanotube suspension is controlled to be 10wt%; then, the carbon nanotube suspension is sprayed into a carbon black reactor, and the injection flow rate of the carbon nanotube suspension is controlled to be 150 kg / h. The temperature in the carbon black reactor is set to 900°C, and the carbon nanotubes and carbon black primary particles N326 are combined to form a pre-agglomerate; then, carbon black is aggregated to form a carbon nanotube / carbon black aggregate; wherein the content of the carbon nanotube is 2% of the total mass of the carbon nanotube / carbon black aggregate; (b) adding 0.8 wt% of sebacic acid dihydrazide to the reactor of step (a) by high-temperature jet technology, controlling the injection flow rate of sebacic acid dihydrazide to 80 kg / h, and setting the temperature in the carbon black reactor to 380°C, so that it combines with the carbon nanotube / carbon black aggregate to obtain the modified carbon nanotube / carbon black aggregate; cooling, filtering and collecting and separating to obtain a powdery product; mixing the powdery product, lignin and water in a mass ratio of 100:0.1:0.1, granulating and drying to obtain the modifier and carbon nanotube / carbon black aggregate.

[0114] like Figure 1 As shown, the aggregate can maintain the larger aspect ratio of the carbon nanotubes themselves, and the carbon nanotubes are more evenly dispersed in the carbon black.

[0115] Preparation Example 2 This preparation example provides a modified carbon nanotube / carbon black aggregate, which differs from Preparation Example 1 only in that 0.8 wt % of sebacic acid dihydrazide is replaced by 0.8 wt % of isophthalic acid dihydrazide, and the other steps are exactly the same as Preparation Example 1.

[0116] like Figure 2 As shown, the aggregate can maintain the larger aspect ratio of the carbon nanotubes themselves, and the carbon nanotubes are more evenly dispersed in the carbon black.

[0117] Preparation Example 3 This preparation example provides a modified carbon nanotube / carbon black aggregate, which differs from Preparation Example 1 only in that 0.8 wt % of sebacic acid dihydrazide is replaced by 0.8 wt % of SUMILINK @ 200, and the other steps are exactly the same as those in Preparation Example 1.

[0118] like Figure 3 As shown, the aggregate can maintain the larger aspect ratio of the carbon nanotubes themselves, and the carbon nanotubes are more evenly dispersed in the carbon black.

[0119] Preparation Example 4 This preparation example provides a modified carbon nanotube / carbon black aggregate, which differs from Preparation Example 1 only in that 0.8 wt % of sebacic acid dihydrazide is replaced by 0.8 wt % of a mixture of sebacic acid dihydrazide and isophthalic acid hydrazide (in the mixture, the mass ratio of sebacic acid dihydrazide to isophthalic acid hydrazide is 1:1), and the other steps are exactly the same as Preparation Example 1.

[0120] like Figure 4 As shown, the aggregate can maintain the larger aspect ratio of the carbon nanotubes themselves, and the carbon nanotubes are more evenly dispersed in the carbon black.

[0121] Preparation Example 5 This preparation example provides a modified carbon nanotube / carbon black aggregate, which is different from the preparation example 1 in that 0.8 wt% of sebacic acid dihydrazide is replaced by 0.8 wt% of isophthalic acid hydrazide and SUMILINK @ 200 mixture (in which isophthalic acid hydrazide and SUMILINK @ The mass ratio of 200 is 1:1), and the other steps are exactly the same as those in Preparation Example 1.

[0122] like Figure 5 As shown, the aggregate can maintain the larger aspect ratio of the carbon nanotubes themselves, and the carbon nanotubes are more evenly dispersed in the carbon black.

[0123] Preparation Example 6 This preparation example provides a modified carbon nanotube / carbon black aggregate, which is different from the preparation example 1 in that 0.8 wt% of sebacic acid dihydrazide is replaced by 0.8 wt% of sebacic acid dihydrazide, isophthalic acid dihydrazide and SUMILINK @ 200 (in which sebacic acid dihydrazide, isophthalic acid dihydrazide and SUMILINK @ The mass ratio of 200 is 2:4:4), and the other steps are exactly the same as those in Preparation Example 1.

[0124] like Figure 6 As shown, the aggregate can maintain the larger aspect ratio of the carbon nanotubes themselves, and the carbon nanotubes are more evenly dispersed in the carbon black.

[0125] Preparation Example 7 This preparation example provides a modified carbon nanotube / carbon black aggregate, which is different from Preparation Example 1 only in that the content of sebacic acid dihydrazide is reduced to 0.4 wt %, and the other steps are exactly the same as Preparation Example 1.

[0126] Preparation Example 8 This preparation example provides a modified carbon nanotube / carbon black aggregate, which is different from Preparation Example 1 only in that the content of sebacic acid dihydrazide is increased to 1.2 wt %, and the other steps are exactly the same as Preparation Example 1.

[0127] Preparation Example 9 This preparation example provides a modified carbon nanotube / carbon black aggregate, which differs from Preparation Example 1 only in that 0.8 wt % of sebacic acid dihydrazide is replaced by 0.8 wt % of compound I-1, and the other steps are completely consistent with Preparation Example 1; wherein the structural formula of compound I-1 is: .

[0128] Preparation Example 10 This preparation example provides a modified carbon nanotube / carbon black aggregate, which is different from Preparation Example 1 only in that the content of the carbon nanotubes is 1% of the total mass of the carbon nanotube / carbon black aggregate, and the other steps are exactly the same as Preparation Example 1.

[0129] Preparation Example 11 This preparation example provides a modified carbon nanotube / carbon black aggregate, which is different from Preparation Example 1 only in that the content of the carbon nanotubes is 10% of the total mass of the carbon nanotube / carbon black aggregate, and the other steps are exactly the same as Preparation Example 1.

[0130] Preparation Example 12 This preparation example provides a modified carbon nanotube / carbon black aggregate, which differs from Preparation Example 1 only in that the carbon black native particles N326 are replaced with carbon black native particles N660 of equal mass, and the other steps are exactly the same as Preparation Example 1.

[0131] Comparative Preparation Example 1 This comparative example provides a carbon nanotube / carbon black aggregate, which is different from Example 1 only in that the modification of step (b) is not performed, and the other steps are completely consistent with Preparation Example 1.

[0132] like Figure 7 As shown, it is obvious that a large part of the unmodified carbon nanotubes are entangled together and not well dispersed.

[0133] Test Example 1 Test samples: modified carbon nanotube / carbon black aggregates provided in Preparation Examples 1 to 12, and carbon nanotube / carbon black aggregates provided in Comparative Preparation Example 1.

[0134] Test methods: total specific surface area BET-N2, pour density of carbon nanotubes in aggregates GB3778-2011, aspect ratio of carbon nanotubes in aggregates using SEM.

[0135] The test results are shown in Table 2 and Figure 1 to Figure 7 As shown: Table 2

[0136] As shown in Table 2 above, the specific surface area of ​​the modified carbon nanotube / carbon black aggregate of the present invention is (45~104)×10 3 m 2 / kg, the pouring density of carbon nanotubes in the aggregate is 413~478 kg / m 3 , the aspect ratio of carbon nanotubes in the aggregate can be maintained at 5420~5745.

[0137] Example 1 The present embodiment provides a tire apex rubber material, wherein the tire apex rubber material is obtained by mixing the following tire apex rubber material composition; wherein, as shown in Table 3 below, the tire apex rubber material composition comprises the following components in parts by weight: Table 3

[0138] The tire apex rubber material described in this embodiment is prepared by the following steps: (1) One-stage mixing: start the internal mixer, set the rotor speed of the internal mixer to 50 rpm, the mixing pressure to 5.5 MPa, the cooling water temperature to 35°C, the rotor temperature to 35°C, add the raw rubber, modified carbon nanotube / carbon black aggregate, white carbon, activator, antioxidant, tackifying resin and protective wax, mix for 30 seconds, lift the top plug, stay for 12 seconds, press the top plug, mix to a temperature of 140°C, lift the top plug, stay for 12 seconds, press the top plug, wait until the temperature reaches 150°C, discharge the rubber, and obtain the carbon nanotube / carbon black masterbatch.

[0139] (2) Second stage mixing: start the internal mixer, set the rotor speed of the internal mixer to 30 rpm, the mixing pressure to 5.0 MPa, the cooling water temperature to 35°C, the rotor temperature to 40°C, add carbon nanotube / carbon black masterbatch, vulcanizer, accelerator and anti-scorch agent, mix for 35 seconds, lift the top plug, stay for 8 seconds and press the plug, mix until the temperature reaches 78°C, lift the top plug, stay for 7 seconds and press the top plug, when the rubber temperature reaches 110°C, lift the plug and discharge the rubber, and cool the lower sheet to room temperature to obtain the tire apex rubber material.

[0140] Example 2 This embodiment provides a tire apex rubber material, which differs from Example 1 only in that the modified carbon nanotube / carbon black aggregate provided in Preparation Example 1 is replaced with an equal weight portion of the modified carbon nanotube / carbon black aggregate provided in Preparation Example 2.

[0141] Example 3 This embodiment provides a tire apex rubber material, which differs from Example 1 only in that the modified carbon nanotube / carbon black aggregate provided in Preparation Example 1 is replaced with an equal weight portion of the modified carbon nanotube / carbon black aggregate provided in Preparation Example 3.

[0142] Example 4 This embodiment provides a tire apex rubber material, which differs from Example 1 only in that the modified carbon nanotube / carbon black aggregate provided in Preparation Example 1 is replaced with an equal weight portion of the modified carbon nanotube / carbon black aggregate provided in Preparation Example 4.

[0143] Example 5 This embodiment provides a tire apex rubber material, which differs from Example 1 only in that the modified carbon nanotube / carbon black aggregate provided in Preparation Example 1 is replaced with an equal weight portion of the modified carbon nanotube / carbon black aggregate provided in Preparation Example 5.

[0144] Example 6 This embodiment provides a tire apex rubber material, which differs from Example 1 only in that the modified carbon nanotube / carbon black aggregate provided in Preparation Example 1 is replaced with an equal weight portion of the modified carbon nanotube / carbon black aggregate provided in Preparation Example 6.

[0145] Example 7 This embodiment provides a tire apex rubber material, which differs from Example 1 only in that the modified carbon nanotube / carbon black aggregate provided in Preparation Example 1 is replaced with an equal weight portion of the modified carbon nanotube / carbon black aggregate provided in Preparation Example 7.

[0146] Example 8 This embodiment provides a tire apex rubber material, which differs from Example 1 only in that the modified carbon nanotube / carbon black aggregate provided in Preparation Example 1 is replaced with an equal weight portion of the modified carbon nanotube / carbon black aggregate provided in Preparation Example 8.

[0147] Example 9 This embodiment provides a tire apex rubber material, which differs from Example 1 only in that the modified carbon nanotube / carbon black aggregate provided in Preparation Example 1 is replaced with an equal weight portion of the modified carbon nanotube / carbon black aggregate provided in Preparation Example 9.

[0148] Example 10 This embodiment provides a tire apex rubber material, which differs from Example 1 only in that the modified carbon nanotube / carbon black aggregate provided in Preparation Example 1 is replaced with an equal weight portion of the modified carbon nanotube / carbon black aggregate provided in Preparation Example 10.

[0149] Embodiment 11 This embodiment provides a tire apex rubber material, which differs from Example 1 only in that the modified carbon nanotube / carbon black aggregate provided in Preparation Example 1 is replaced with an equal weight portion of the modified carbon nanotube / carbon black aggregate provided in Preparation Example 11.

[0150] Example 12 This embodiment provides a tire apex rubber material, which differs from Example 1 only in that the modified carbon nanotube / carbon black aggregate provided in Preparation Example 1 is replaced with an equal weight portion of the modified carbon nanotube / carbon black aggregate provided in Preparation Example 12.

[0151] Comparative Examples 1 to 5 These comparative examples provide tire apex rubbers of different components, which are prepared using corresponding tire apex rubber compositions, as shown in Table 4 below. The tire apex rubber compositions include the following components in parts by weight: Table 4

[0152] The preparation methods of the tire apex rubber materials provided in the above Comparative Examples 1 to 5 are consistent with that in Example 1.

[0153] Comparative Examples 6 to 9 These comparative examples provide tire apex rubbers of different components, which are prepared using corresponding tire apex rubber compositions, as shown in Table 5 below. The tire apex rubber compositions include the following components in parts by weight: Table 5

[0154] The preparation methods of the tire apex rubber materials provided in the above Comparative Examples 6 to 9 are consistent with that in Example 1.

[0155] Test Example 2 Test samples: tire apex rubber materials provided in Examples 1 to 12, and tire apex rubber materials provided in Comparative Examples 1 to 9.

[0156] Test method: DMA test conditions are 10Hz, 7%±2; tensile test standard adopts GB / T528-2009. Among them, M300 is the 300% tensile strength of the vulcanized rubber; TB is the tensile strength of the vulcanized rubber; EB% is the tensile elongation of the vulcanized rubber; tanδ / 60℃ is the loss factor of the vulcanized rubber at 60℃.

[0157] The test results are shown in Table 6 below: Table 6

[0158] As shown in Table 3 above, the M300 of the tire apex rubber provided in Examples 1 to 12 is 11.6 to 12.3 MPa, the TB is 28.9 to 29.8 MPa, the EB% is 538 to 569%, and the Tanδ is 0.044 to 0.050. This shows that during the preparation process of the modified carbon nanotube / carbon black aggregate of the present invention, in the presence of a modifier, the carbon nanotubes can be more evenly dispersed in the carbon black primary particles by the jet technology, significantly improving the dispersion performance of the carbon nanotubes. Furthermore, the present invention adds the modified carbon nanotube / carbon black aggregate to the tire apex rubber composition, thereby enhancing the interaction between the rubber and the filler, reducing the agglomeration of the filler carbon nanotube / carbon black itself, providing the mechanical properties and wear resistance of the tire apex rubber, and further reducing the heat generation of the tire apex rubber.

[0159] It can be clearly seen from the above Comparative Examples 1 and 7 that adding a modifier to the carbon black formula can reduce heat generation by 24.4%, and it can be seen from Comparative Examples 1, 8 and Example 1 that by using the jet technology, adding the modifier and carbon nanotube / N326 carbon black aggregates in the production of carbon nanotube / N326 carbon black aggregates can further generate heat, which is 28.2% lower than the ratio without adding the modifier and 9.6% lower than Comparative Example 1; and it can be seen from Comparative Examples 1, 7 and Example 1 that the addition of the modifier can reduce heat generation, especially when the modifier and carbon nanotube / N326 carbon black aggregates are added in the production of carbon nanotube / N326 carbon black aggregates.

[0160] It can be seen from the comparative examples and embodiments that different modifiers used alone or in combination contribute to heat generation. Compared with comparative examples 1 to 6 and comparative example 7, the heat generation tan δ is significantly reduced.

[0161] It can be seen from Example 1 and Comparative Example 8 that the mechanical properties (tear strength of vulcanized rubber) of the obtained rubber product are significantly improved, and the heat generation (loss factor of vulcanized rubber at 60°C) is significantly reduced when the modifier is first compounded with the carbon nanotube / carbon black aggregate, compared with adding it to the rubber composition in the form of physical blending. That is, compared with Example 1, the addition of the carbon nanotube / N326 carbon black aggregate produced by the modifier and the carbon nanotube / N326 carbon black aggregate can further reduce the heat generation by 10.7%.

[0162] 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 modified carbon nanotube / carbon black aggregate as a filler in the preparation of a tire apex rubber composition, characterized in that: The modified carbon nanotube / carbon black aggregate is obtained by high-temperature jetting of a modifier and carbon nanotube / carbon black aggregate; the modifier is selected from any one or a combination of at least two of the compounds represented by the following formulas I to V: ； Wherein, n and m are each independently selected from a positive integer between 1 and 10; M is selected from an alkali metal and / or an alkaline earth metal; R1 and R2 are each independently selected from or , p is selected from a positive integer between 1 and 5.

2. A tire apex rubber composition, characterized in that: The tire apex rubber composition comprises the following components by weight: 100 pieces of raw rubber Modified carbon nanotube / carbon black aggregate 10~40 parts 1~12 parts of active agent Accelerator 0.8~6 parts Vulcanizing agent 0.8~6 parts 3~7 parts of antioxidant 0.5~4 parts of tackifying resin White carbon black 0~25 parts Silane coupling agent 0~2.5 parts Protective wax 0~2.5 parts Anti-scorch agent 0~0.3 parts; Wherein, the modified carbon nanotube / carbon black aggregate is obtained by high-temperature jetting of a modifier and carbon nanotube / carbon black aggregate; the modifier is selected from any one or a combination of at least two of the compounds represented by the following formulas I to V: ； Wherein, n and m are each independently selected from a positive integer between 1 and 10; M is selected from an alkali metal and / or an alkaline earth metal; R1 and R2 are each independently selected from or , p is selected from a positive integer between 1 and 5.

3. The tire apex rubber composition according to claim 2, characterized in that: The modifier is selected from any one or a combination of at least two of the following compounds: ； and / or, the content of the modifier is 0.05-5% of the total mass of the modified carbon nanotube / carbon black aggregate; And / or, the carbon nanotube / carbon black aggregates are obtained by powder injection of carbon nanotubes and carbon black primary particles; and / or, the content of the carbon nanotubes is 1-10% of the total mass of the carbon nanotube / carbon black aggregate; And / or, the carbon black native particles are N326 carbon black native particles.

4. The tire apex rubber composition according to claim 2, characterized in that: The modified carbon nanotube / carbon black aggregate is prepared by the following steps: (a) Spraying a suspension of carbon nanotubes into a carbon black reaction furnace through powder injection, the carbon nanotubes and carbon black primary particles are combined to form a pre-agglomerate; and carbon black is aggregated to form a carbon nanotube / carbon black aggregate; (b) combining the modifier with the carbon nanotube / carbon black aggregate by high temperature jet to obtain the modified carbon nanotube / carbon black aggregate.

5. The tire apex rubber composition according to claim 4, characterized in that: In step (a), the carbon nanotube suspension comprises, by mass percentage, 15-40% carbon nanotubes and the remainder water; And / or, in step (a), the injection rate of the carbon nanotube suspension is 50-200 kg / h; And / or, in step (a), the temperature of the combination to form the pre-agglomerate and the aggregation of carbon black is independently 800-1000°C; And / or, in step (b), the injection rate of the modifier is 20-100 kg / h; And / or, in step (b), the temperature at which the modifier combines with the carbon nanotube / carbon black aggregate is 100-480°C.

6. The tire apex rubber composition according to claim 4, characterized in that: In step (b), after the modifier is combined with the carbon nanotube / carbon black aggregate, the following post-treatment steps are also included: After cooling, filtering and collecting and separating, a powdery product is obtained; the powdery product, a binder and water are mixed, granulated and then dried to obtain the modifier and carbon nanotube / carbon black aggregates; And / or, the mass ratio of the powdered product, the binder and water is (80-100):(0.1-2):(0.01-10); and / or, the binder is selected from lignin and / or molasses; And / or, the particle size of the modifier and the carbon nanotube / carbon black aggregate is 0.1-3 μm.

7. The tire apex rubber composition according to claim 2, characterized in that: The raw rubber includes natural rubber; and / or, the active agent comprises stearic acid and / or zinc oxide; and / or, the accelerator comprises accelerator NS; And / or, the vulcanizing agent includes insoluble sulfur OT-20; And / or, the antioxidant includes antioxidant 4020 and / or antioxidant RD; And / or, the tackifying resin comprises any one of tert-butylphenol formaldehyde tackifying resin, tert-butylphenol phenol formaldehyde tackifying resin, octylphenol formaldehyde tackifying resin or Keresin resin or a combination of at least two thereof; And / or, the silane coupling agent includes silane coupling agent Si-69; and / or, the protective wax comprises microcrystalline wax; And / or, the anti-scorch agent includes anti-scorch agent CTP.

8. A tire apex rubber material, characterized in that: The tire apex rubber material is obtained by mixing the tire apex rubber material composition according to any one of claims 2 to 7.

9. A method for preparing a tire apex rubber material according to claim 8, characterized in that: The preparation method comprises: (1) mixing the raw rubber, modified carbon nanotube / carbon black aggregate, white carbon, silane coupling agent, activator, antioxidant, tackifying resin and protective wax, and kneading them in one step to obtain a carbon nanotube / carbon black masterbatch; (2) The carbon nanotube / carbon black masterbatch, the vulcanizing agent, the accelerator and the anti-scorching agent are mixed and kneaded in two stages to obtain the tire apex rubber material.

10. The method for preparing a tire apex rubber material according to claim 9, characterized in that: In step (1), the mixed raw materials also include a processing aid; In step (1), the mixing stage includes the following steps: mixing for 20 to 40 seconds, lifting the top pin, staying for 10 to 15 seconds, and pressing the top pin; mixing until the temperature reaches 135 to 145°C, lifting the top pin, staying for 10 to 15 seconds, and pressing the top pin; mixing until the temperature reaches 145 to 155°C, and then removing the glue; In step (2), the two-stage mixing includes the following steps: after mixing for 10 to 60 seconds, lift the top plug, hold for 0 to 15 seconds, and press the top plug; after mixing until the temperature reaches 70 to 85°C, lift the top plug, hold for 0 to 15 seconds, and press the top plug; after mixing until the temperature reaches 100 to 120°C, remove the glue.

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