A tire apex composition, a tire apex, and a method of making the same

Abstract

The application provides a tire apex composition, a tire apex and a preparation method thereof, and relates to the technical field of tire manufacturing. The tire apex composition comprises the following components in parts by weight: raw rubber 100 parts, modified carbon nanotube / carbon black aggregate 10-40 parts, active agent 1-12 parts, accelerator 0.8-6 parts, vulcanizing agent 0.8-6 parts, antioxidant 3-7 parts, tackifying resin 0.5-4 parts, white carbon black 0-25 parts, silane coupling agent 0-2.5 parts, protective wax 0-2.5 parts, and anti-scorching agent 0-0.3 parts. The modified carbon nanotube / carbon black aggregate is obtained by high-temperature jetting of a modifier and carbon nanotube / carbon black aggregate. The modified carbon nanotube / carbon black aggregate is added to the tire apex composition, which reduces filler aggregation, provides mechanical properties and wear resistance of the tire apex, and further reduces the heat generation of the tire apex.

Description

Technical Field

[0001] This invention relates to the field of tire manufacturing technology, and in particular to a tire tread rubber composition, a tire tread rubber compound, and a method for preparing the same. Background Technology

[0002] The tire bead is a crucial component, located above the steel wire bead and situated between the rigid bead and the flexible tire carcass. It not only serves as a filler, ensuring a smooth bead contour, but also primarily acts as a stress buffer and modulus transition, bearing load and transmitting drive force. It withstands complex compressive and shear stresses. Especially under harsh road conditions, the bead experiences even greater shear and impact forces. As stress concentration and heat accumulation increase, the temperature rises, making the bead prone to vulcanization reaction, which breaks the cross-links and degrades performance. Therefore, the bead compound must possess high hardness and high modulus, along with excellent low heat generation, heat resistance, and thermal conductivity.

[0003] Currently, in order to ensure that the triangular rubber has a high modulus and hardness, the existing technical method is to add the following to the rubber: (1) high amount of fine carbon black, (2) hard carbon black and soft carbon black in combination, (3) high sulfur content, (4) reinforcing resin, such as phenolic resin, high styrene resin, cobalt salt and other hardeners. (5) micron short fibers, such as nylon, polyester, polyester fiber, aramid short fibers, etc. The existing carbon black has a small particle size, a large aggregate specific area, and a high surface free energy, which makes it 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, resulting in serious heat generation and rapid and violent temperature rise, 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 will easily cause stress softening and increased deformation in the tire bead area. Although the reinforcing resin can increase mechanical strength, it has problems such as softening at high temperature. Short fibers are relatively long, making it difficult to disperse evenly in the rubber matrix. They have poor processing performance, and the modulus of the composite material will decrease after dynamic heating.

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

[0005] The purpose of this invention is to provide a tire tread rubber compound composition, a tire tread rubber compound, and a method for preparing the same. The tire tread rubber compound composition of this invention, by adding modified carbon nanotube / carbon black aggregates, significantly enhances the mechanical properties of the tire tread rubber compound, reduces heat generation, and improves wear resistance.

[0006] To solve the above-mentioned technical problems, the present invention adopts the following technical solution: In a first aspect, the present invention provides a tire triangular rubber compound composition, the tire triangular rubber compound composition comprising, by weight, the following components: 100 parts raw rubber 10-40 parts of modified carbon nanotube / carbon black aggregate 1-12 parts of surfactant Accelerator 0.8~6 parts 0.8 to 6 parts of vulcanizing agent Anti-aging agent 3-7 parts 0.5 to 4 parts of tackifying resin 0-25 parts of silica 0-2.5 parts of silane coupling agent Protective wax 0-2.5 parts Anti-scorching agent 0~0.3 parts; The modified carbon nanotube / carbon black aggregate is obtained by high-temperature jetting of a modifier and a carbon nanotube / carbon black aggregate; the modifier is selected from any one or a combination of at least two of the compounds shown in Formulas I to V: ; Where 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; R1 and R2 are 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 aggregate is obtained by powder spraying of carbon nanotubes and primary carbon black particles.

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

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

[0011] Preferably, the modified carbon nanotube / carbon black aggregate is prepared by the following steps: (a) By powder spraying, a suspension of carbon nanotubes is sprayed into a carbon black reactor, where carbon nanotubes and primary carbon black particles combine to form a pre-aggregate; through the aggregation of carbon black, a carbon nanotube / carbon black aggregate is formed. (b) The modifier is combined with the carbon nanotube / carbon black aggregate by high-temperature jetting to obtain the modified carbon nanotube / carbon black aggregate.

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

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

[0014] Preferably, in step (a), the temperatures at which the prepolymer and carbon black aggregates are formed are each independently 800~1000°C.

[0015] Preferably, in step (b), the injection flow 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℃.

[0017] Preferably, in step (b), after the modifier is combined with the carbon nanotube / carbon black aggregate, the following post-processing step is further included: After cooling, filtration, and collection and separation, a powdered product is obtained; the powdered product, binder, and water are mixed, granulated, and dried to obtain the modifier and carbon nanotube / carbon black aggregate.

[0018] Preferably, the mass ratio of the powdered product, 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 includes natural rubber.

[0022] Preferably, the activator includes stearic acid and / or zinc oxide.

[0023] Preferably, the accelerator includes accelerator NS.

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

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

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

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

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

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

[0030] In a second aspect, the present invention provides a tire triangle compound, which is obtained by mixing the tire triangle compound composition as described in the first aspect.

[0031] Thirdly, the present invention provides a method for preparing the tire triangular rubber compound as described in the second aspect, the method comprising: (1) The raw rubber, modified carbon nanotube / carbon black aggregate, silica, silane coupling agent, activator, antioxidant, tackifying resin and protective wax are mixed and kneaded for one stage to obtain carbon nanotube / carbon black masterbatch. (2) The carbon nanotube / carbon black masterbatch, vulcanizing agent, accelerator and anti-scorching agent are mixed and mixed in two stages to obtain the tire triangle rubber compound.

[0032] Preferably, in step (1), the mixed raw materials further include processing aids.

[0033] Preferably, in step (1), the mixing process includes the following steps in sequence: mixing for 20-40 seconds, lifting the top plug, holding for 10-15 seconds, and pressing the top plug back on; mixing until the temperature reaches 135-145°C, lifting the top plug, holding for 10-15 seconds, and pressing the top plug back on; and mixing until the temperature reaches 145-155°C and then discharging the adhesive.

[0034] Preferably, in step (2), the two-stage mixing includes the following steps performed sequentially: mixing for 10-60 seconds, then lifting the top plug, holding for 0-15 seconds, and pressing the top plug back on; mixing until the temperature reaches 70-85℃, then lifting the top plug, holding for 0-15 seconds, and pressing the top plug back on; and mixing until the temperature reaches 100-120℃, then discharging the adhesive.

[0035] Compared with the prior art, the present invention has the following beneficial effects: (1) In the preparation process of the modified carbon nanotube / carbon black aggregate described in this invention, in the presence of the modifier, the carbon nanotubes can be more uniformly dispersed in the carbon black primary particles by jet technology, which significantly improves the dispersion performance of carbon nanotubes.

[0036] (2) The present invention adds modified carbon nanotube / carbon black aggregates to the tire triangular rubber compound composition. The surface modification enhances the interaction between rubber and filler, reduces filler agglomeration, and provides mechanical properties and wear resistance of tire triangular rubber compound. At the same time, it can further reduce the heat generation of tire triangular rubber compound.

[0037] (3) In this invention, the carbon nanotube / carbon black aggregate is modified by a modifier before being added to the triangular rubber compound composition to form a dual "physical-chemical" enhancement mechanism. Compared with the two being added to the rubber composition only in the form of physical blending later, the triangular rubber compound has better dispersibility, stronger mechanical properties, and higher stability. Moreover, modifying the carbon nanotube / carbon black aggregate first has higher functionalization efficiency from a process perspective, which helps to improve processing performance. Attached Figure Description

[0038] To more clearly illustrate the specific embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the specific embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are some embodiments of the present invention. For those skilled in the art, other drawings can be obtained from these drawings without creative effort.

[0039] Figure 1 Scanning electron microscope image of the modified carbon nanotube / carbon black aggregates prepared in Example 1.

[0040] Figure 2 Scanning electron microscope image of the modified carbon nanotube / carbon black aggregates prepared in Example 2.

[0041] Figure 3 Scanning electron microscope image of the modified carbon nanotube / carbon black aggregates prepared in Example 3.

[0042] Figure 4 Scanning electron microscope image of the modified carbon nanotube / carbon black aggregates prepared in Example 4.

[0043] Figure 5 Scanning electron microscope image of the modified carbon nanotube / carbon black aggregates prepared in Example 5.

[0044] Figure 6 Scanning electron microscope image of the modified carbon nanotube / carbon black aggregates prepared in Example 6.

[0045] Figure 7 The scanning electron microscope image of the unmodified carbon nanotube / carbon black aggregates provided in Preparation Example 1 is shown for comparison. Detailed Implementation

[0046] To make the objectives, technical solutions, and advantages of this invention clearer, the technical solutions in the embodiments of this invention will be clearly and completely described below in conjunction with the embodiments of this invention. Obviously, the described embodiments are only some embodiments of this invention, and not all embodiments. The components of the embodiments of this invention can be arranged and designed in various different configurations.

[0047] It should be noted that, in this document, relational terms such as "first" and "second" are used only to distinguish one entity or operation from another, and do not necessarily require or imply any such actual relationship or order between these entities or operations. Furthermore, the terms "comprising," "including," or any other variations thereof are intended to cover non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements includes not only those elements but also other elements not expressly listed, or elements inherent to such process, method, article, or apparatus.

[0048] In a first aspect, the present invention provides a tire triangular rubber compound composition, the tire triangular rubber compound composition comprising, by weight, the following components: 100 parts raw rubber 10-40 parts of modified carbon nanotube / carbon black aggregate 1-12 parts of surfactant Accelerator 0.8~6 parts 0.8 to 6 parts of vulcanizing agent Anti-aging agent 3-7 parts 0.5 to 4 parts of tackifying resin 0-25 parts of silica 0-2.5 parts of silane coupling agent Protective wax 0-2.5 parts Anti-scorching agent 0~0.3 parts; The modified carbon nanotube / carbon black aggregate is obtained by high-temperature jetting of a modifier and a carbon nanotube / carbon black aggregate; the modifier is selected from any one or a combination of at least two of the compounds shown in Formulas I to V: ; Where 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; R1 and R2 are 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, 10.

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

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

[0053] In this invention, during the preparation of the modified carbon nanotube / carbon black aggregate, in the presence of the modifiers shown in Formulas I to V, carbon nanotubes can be more uniformly dispersed among the primary carbon black particles using jet technology, significantly improving the dispersion performance of carbon nanotubes. Furthermore, by adding this modified carbon nanotube / carbon black aggregate to the tire tread compound composition, this invention enhances the interaction between the rubber and the filler, reduces the agglomeration of the filler carbon nanotubes / carbon black itself, and improves the mechanical and abrasion resistance of the tire tread compound while further reducing the heat generation of the tire tread compound.

[0054] It is important to note that this invention uses a modifier to first modify the carbon nanotube (CNT) / carbon black (CB) aggregates before adding them to the rubber matrix. Compared to adding the two components to the rubber composition only through physical blending later, the reason for the significant improvement in rubber performance is as follows: 1. Superior dispersibility: This invention fixes the modifier with chemical bonds, and the grafting modification binds the coupling agent more firmly to the surface of the aggregate through covalent bonds, forming a stable surface modification layer. As mentioned above, this chemical bonding can effectively reduce the van der Waals forces between aggregates, reduce the tendency to agglomerate, and reduce the risk of CNT breakage, thereby maintaining its original aspect ratio. In contrast, carbon black that is only attached to the surface through physical adsorption or weak interactions (such as hydrogen bonds) is easily detached under the high shear force of rubber processing (such as mixing and extrusion), causing the carbon black to re-agglomerate.

[0055] 2. Enhanced mechanical properties: The modifier in this application not only acts as a "bridge" to form a CNT-CB hybrid structure, but also connects to the CNT / CB aggregate at one end and reacts chemically with the rubber molecular chain at the other end, forming a strong chemical bond interface between the CNT / CB aggregate and the rubber. This improves the interfacial bonding ability and gives the rubber stronger mechanical properties. In contrast, when only physical mixing is used, the interface between the modifier and the rubber relies only on physical adsorption or a small amount of reaction, resulting in low interfacial bonding strength, poor stress transfer efficiency, and easy debonding.

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

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

[0058] 5. Improved 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 (the aspect ratio is better); while unmodified CNTs are prone to rubber degradation or CNT structural damage if higher shear force is required for dispersion during mixing.

[0059] As an optional embodiment, the content of modified carbon nanotube / carbon black aggregate in the tire triangular rubber compound composition 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, the content of activator in the tire triangular rubber composition 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, the content of the accelerator in the tire triangle rubber composition is 0.8 to 6 parts, for example, it can be 0.8 parts, 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, 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, more preferably 0.8 to 1.2 parts.

[0062] As an optional embodiment, the content of vulcanizing agent in the tire triangular rubber compound composition is 0.8 to 6 parts, for example, it can be 0.8 parts, 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, 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, more preferably 3.1 to 3.2 parts.

[0063] As an optional embodiment, the antioxidant content in the tire triangular rubber compound composition 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, the content of tackifying resin in the tire triangular rubber compound composition 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, the content of silica in the tire triangular rubber compound composition 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 part, 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, the content of silane coupling agent in the tire triangular rubber compound composition 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 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, the content of protective wax in the tire triangular rubber composition 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 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 0.1 to 1 part, and more preferably 0.4 to 0.6 parts.

[0068] As an optional embodiment, the content of the anti-scorching agent in the tire triangular rubber compound composition 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 implementation, the modifier is selected from any one or a combination of at least two of the following compounds: .

[0070] As an optional implementation, 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 aggregate is obtained by powder spraying of carbon nanotubes and primary carbon black particles.

[0072] As an optional implementation, the content of carbon nanotubes is 1 to 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 implementation, the primary carbon black particles are N326 primary carbon black particles.

[0074] As an optional implementation, the modified carbon nanotube / carbon black aggregate is prepared by the following steps: (a) By powder spraying, a suspension of carbon nanotubes is sprayed into a carbon black reactor, where carbon nanotubes and primary carbon black particles combine to form a pre-aggregate; through the aggregation of carbon black, a carbon nanotube / carbon black aggregate is formed. (b) The modifier is combined with the carbon nanotube / carbon black aggregate by high-temperature jetting to obtain the modified carbon nanotube / carbon black aggregate.

[0075] In this invention, the powder spraying in step (a) specifically involves: carbon nanotubes being transported to a precisely quantitative embedded double helix via a mechanical arch-breaking device, an airflow arch-breaking device in the storage bin, and a plow-like stirring device at the bottom of the bin. After being weighed by a weighing system and precisely metered by the helix, the carbon nanotubes enter the mass transfer chamber of the high-speed spray mixer and are instantly mixed with the spray carrier, i.e., the process water. During the movement, the carbon nanotubes are forcibly dispersed into the spray carrier and rapidly diffused into a uniform suspension in the diffuser at the tail of the sprayer through pressure changes, and then transported to the pressure atomization system.

[0076] In this invention, the combination in step (b) specifically involves: adding a modifier to the flue gas containing suspended carbon nanotubes / carbon black aggregates using high-temperature jet technology; further, after cooling, filtration, and collection and separation by a main bag filter, the separated exhaust gas is used for heating in a tail gas furnace and power generation in a boiler; finally, the powdered carbon nanotubes / carbon black aggregates are stirred with an appropriate amount of water and binder in a granulator to granulate them, and then the aggregate particles are sent to a rotary dryer for drying to remove moisture, ultimately obtaining the modified carbon nanotubes / carbon black aggregates.

[0077] In this invention, the modifier, when combined with the carbon nanotube / carbon black aggregate, endows the aggregate with the ability to maintain the large aspect ratio of the carbon nanotube itself and exert the excellent performance of the carbon nanotube, while also improving the dispersibility, reinforcement and reactivity of the carbon nanotube and carbon black in the rubber matrix with the rubber groups.

[0078] As an optional implementation, in step (a), the suspension of carbon nanotubes includes, by mass percentage, 15-25% carbon nanotubes, for example, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, etc., with the remainder being water.

[0079] As an optional implementation, 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, 150 kg / h, 160 kg / h, 180 kg / h, 200 kg / h, etc.

[0080] As an optional implementation, in step (a), the temperature at which the prepolymer and carbon black are aggregated is independently 800~1000℃, for example, 800℃, 820℃, 840℃, 850℃, 860℃, 880℃, 900℃, 920℃, 940℃, 950℃, 960℃, 980℃, 1000℃, etc.

[0081] As an optional implementation, 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 implementation, in step (b), the temperature at which the modifier combines with the carbon nanotube / carbon black aggregate is 100~480℃, for example, it can be 100℃, 120℃, 140℃, 150℃, 160℃, 180℃, 200℃, 220℃, 240℃, 250℃, 260℃, 280℃, 300℃, 320℃, 340℃, 350℃, 360℃, 380℃, 400℃, 420℃, 440℃, 450℃, 460℃, 480℃, etc.

[0083] As an optional implementation, step (b) further includes the following post-processing step after the modifier is combined with the carbon nanotube / carbon black aggregate: After cooling, filtration, and collection and separation, a powdered product is obtained; the powdered product, binder, and water are mixed, granulated, and dried to obtain the modifier and carbon nanotube / carbon black aggregate.

[0084] As an optional implementation, the mass ratio of the powdered product, 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.; Among them, "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 implementation, the binder is selected from lignin and / or molasses.

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

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

[0088] As an optional implementation, the activator includes stearic acid and / or zinc oxide.

[0089] In a preferred embodiment, the activator is composed of stearic acid and zinc oxide.

[0090] In a preferred embodiment, when the activator 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 implementation, the accelerator includes accelerator NS.

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

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

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

[0095] As an optional implementation, when the antioxidant is composed 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 or a combination of at least two of tert-butylphenol-formaldehyde tackifying resin, tert-butylphenol-formaldehyde tackifying resin, octylphenol-formaldehyde tackifying resin, or Keresin resin.

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

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

[0099] As an optional implementation, the silica includes GR175.

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

[0101] In a second aspect, the present invention provides a tire triangle compound, which is obtained by mixing the tire triangle compound composition as described in the first aspect.

[0102] Thirdly, the present invention provides a method for preparing the tire triangular rubber compound as described in the second aspect, the method comprising: (1) The raw rubber, modified carbon nanotube / carbon black aggregate, silica, silane coupling agent, activator, antioxidant, tackifying resin and protective wax are mixed and kneaded for one stage to obtain carbon nanotube / carbon black masterbatch. (2) The carbon nanotube / carbon black masterbatch, vulcanizing agent, accelerator and anti-scorching agent are mixed and mixed in two stages to obtain the tire triangle rubber compound.

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

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

[0105] As an optional implementation, in step (1), the mixing is as follows: starting the internal mixer, setting the rotor speed of the internal mixer to 40~55 rpm (e.g., 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 (e.g., 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). MPa, etc.), cooling water temperature 30~40℃ (e.g., 30℃, 32℃, 34℃, 35℃, 36℃, 38℃, 40℃, etc.), rotor temperature 30~40℃ (e.g., 30℃, 32℃, 34℃, 35℃, 36℃, 38℃, 40℃, etc.), and the raw rubber, modified carbon nanotube / carbon black aggregate, white carbon black, silane coupling agent, activator, antioxidant, tackifying resin, protective wax and processing aids are added.

[0106] As an optional implementation, in step (1), the mixing process includes the following steps performed sequentially: mixing for 20-40 seconds (e.g., 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 bolt, holding for 10-15 seconds (e.g., 10 s, 11 s, 12 s, 13 s, 14 s, 15 s, etc.), pressing the top bolt back up; mixing until the temperature reaches 135-145℃ (e.g., 135℃, 136℃, 138℃, 140℃, 142℃, 144℃, 145℃, etc.), lifting the top bolt, holding for 10-15 seconds (e.g., 10 s, 11 s, 12 s, 13 s, 14 s, 15 s, etc.). Press the top bolt (s, etc.) onto the mixture; mix until the temperature is 145~155℃ (e.g., 145℃, 146℃, 148℃, 150℃, 152℃, 154℃, 155℃, etc.) and then discharge the glue.

[0107] As an optional implementation, in step (2), the mixing is as follows: starting the internal mixer, setting the rotor speed of the internal mixer to 15~40 rpm (for example, it can be 15 rpm, 16 rpm, 18 rpm, 20 rpm, 22 rpm, 24 rpm, 25 rpm, 26 rpm, 28 rpm, 30 rpm, 32 rpm, 34 rpm, 35 rpm, 36 rpm, 38 rpm, 40 rpm, etc.), and the mixing pressure to 4.0~6.0 MPa (for example, it can be 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). The cooling water temperature is 30~40℃ (e.g., 30℃, 32℃, 34℃, 35℃, 36℃, 38℃, 40℃, etc.), and the rotor temperature is 30~45℃ (e.g., 30℃, 32℃, 34℃, 35℃, 36℃, 38℃, 40℃, 42℃, 44℃, 45℃, etc.). The carbon nanotube / carbon black masterbatch, vulcanizing agent, accelerator and anti-scorching agent are added.

[0108] As an optional implementation, in step (2), the two-stage mixing includes the following sequential processes: mixing for 10-60 seconds (e.g., 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 pausing for 0-15 seconds (e.g., 0 s, 1 s, 2 s, 4 s, 5 s, 6 s, 8 s, 10 s, 12 s, 14 s, 15 s, etc.). (e.g., s), press the top bolt; mix until the temperature is 70~85℃ (e.g., 70℃, 72℃, 74℃, 75℃, 76℃, 78℃, 80℃, 82℃, 84℃, 85℃, etc.), lift the top bolt, hold for 0~15 s (e.g., 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 100~120℃ (e.g., 100℃, 102℃, 104℃, 105℃, 106℃, 108℃, 110℃, 115℃, 120℃, etc.), and discharge the glue.

[0109] The following detailed description of some embodiments of the present invention is provided in conjunction with examples. Unless otherwise specified, the following embodiments and features can be combined with each other. Raw materials used in the embodiments and comparative examples of the present invention, unless otherwise specified, were carried out under conventional conditions or conditions recommended by the manufacturer. Reagents or instruments used, unless otherwise specified, are all commercially available conventional products.

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

[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, which is prepared by the following steps: (a) In the jet system, carbon nanotubes are uniformly mixed with process water using powder spraying technology, and the concentration of the carbon nanotube suspension is controlled at 10 wt%. Subsequently, the carbon nanotube suspension is sprayed into a carbon black reactor, and the spraying flow rate is controlled at 150 kg / h. The temperature inside the carbon black reactor is set to 900°C, and the carbon nanotubes and primary carbon black particles N326 combine to form a pre-aggregate. Then, through the aggregation of carbon black, a carbon nanotube / carbon black aggregate is formed. The content of the carbon nanotubes is 2% of the total mass of the carbon nanotube / carbon black aggregate. (b) Using high-temperature jet technology, 0.8 wt% sebacic acid dihydrazide is added to the reactor of step (a), the injection flow rate of sebacic acid dihydrazide is controlled at 80 kg / h, and the temperature inside the carbon black reactor is set to 380°C, so that it combines with the carbon nanotube / carbon black aggregate to obtain the modified carbon nanotube / carbon black aggregate; after cooling, filtration and collection separation, a powder product is obtained; the powder product, lignin and water in a mass ratio of 100:0.1:0.1 are mixed, granulated and dried to obtain the modifier and carbon nanotube / carbon black aggregate.

[0114] like Figure 1 As shown, the aggregate can maintain the large aspect ratio of the carbon nanotubes themselves, and the carbon nanotubes are more uniformly 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% sebacic acid dihydrazide is replaced with 0.8 wt% isophthalic acid dihydrazide, while the other steps are completely consistent with Preparation Example 1.

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

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

[0118] like Figure 3 As shown, the aggregate can maintain the large aspect ratio of the carbon nanotubes themselves, and the carbon nanotubes are more uniformly 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 with 0.8 wt% of a mixture of sebacic acid dihydrazide and isophthalic acid dihydrazide (in which the mass ratio of sebacic acid dihydrazide to isophthalic acid dihydrazide is 1:1), and the other steps are completely consistent with Preparation Example 1.

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

[0121] Preparation Example 5 This preparation example provides a modified carbon nanotube / carbon black aggregate, differing from Preparation Example 1 only in that 0.8 wt% of sebacic acid dihydrazide is replaced with 0.8 wt% of isophthalic acid dihydrazide and SUMILINK. @ A mixture of 200 (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 large aspect ratio of the carbon nanotubes themselves, and the carbon nanotubes are more uniformly dispersed in the carbon black.

[0123] Preparation Example 6 This preparation example provides a modified carbon nanotube / carbon black aggregate, differing from Preparation Example 1 only in that 0.8 wt% of sebacic acid dihydrazide is replaced with 0.8 wt% of sebacic acid dihydrazide, isophthalic acid dihydrazide, and SUMILINK. @ A mixture of 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 large aspect ratio of the carbon nanotubes themselves, and the carbon nanotubes are more uniformly dispersed in the carbon black.

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

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

[0127] Preparation Example 9 This preparation example provides a modified carbon nanotube / carbon black aggregate, differing from Preparation Example 1 only in that 0.8 wt% of sebacic acid dihydrazide is replaced with 0.8 wt% of compound I-1; all other steps are identical to Preparation Example 1. The structural formula of compound I-1 is: .

[0128] Preparation Example 10 This preparation example provides a modified carbon nanotube / carbon black aggregate, which differs 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, while the other steps are completely consistent with Preparation Example 1.

[0129] Preparation Example 11 This preparation example provides a modified carbon nanotube / carbon black aggregate, which differs 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, while the other steps are completely consistent with 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 primary particles N326 are replaced with carbon black primary particles N660 of equal mass, while the other steps are completely the same as those in Preparation Example 1.

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

[0132] like Figure 7 As shown, it is evident from the aggregate that a large portion of the unmodified carbon nanotubes are still tangled together and not well dispersed.

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

[0134] Test methods: Total specific surface area BET-N2, carbon nanotube infill density in aggregates GB3778-2011, and aspect ratio of carbon nanotubes in aggregates were determined by SEM.

[0135] The test results are shown in Table 2 below. Figures 1-7 As shown: Table 2

[0136] As shown in Table 2 above, the specific surface area of ​​the modified carbon nanotube / carbon black aggregate of this invention is (45~104)×10 3 m 2 / kg, the carbon nanotube infusion density in the aggregates is 413~478 kg / m³ 3 The aspect ratio of carbon nanotubes in the aggregates can be maintained at 5420~5745.

[0137] Example 1 This embodiment provides a tire triangle compound, which is obtained by mixing the following tire triangle compound composition; wherein, as shown in Table 3 below, the tire triangle compound composition includes the following components by weight: Table 3

[0138] The tire triangular rubber compound described in this embodiment is prepared by the following steps: (1) First stage of 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℃, the rotor temperature to 35℃, add the raw rubber, modified carbon nanotube / carbon black aggregate, white carbon black, activator, antioxidant, tackifying resin and protective wax, mix for 30 s, lift the top plug, hold for 12 s, press the top plug, mix until the temperature reaches 140℃, lift the top plug, hold for 12 s, press the top plug, wait until the temperature reaches 150℃ to discharge the rubber, and obtain carbon nanotube / carbon black masterbatch.

[0139] (2) Two-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℃, the rotor temperature to 40℃, add carbon nanotube / carbon black masterbatch, vulcanizing agent, accelerator and anti-scorching agent, mix for 35 s and then lift the top plug, hold for 8 s and press the plug, mix until the temperature is 78℃ and then lift the top plug, hold for 7 s and press the top plug, wait until the rubber temperature is 110℃ and then lift the plug to discharge the rubber, and then cool the sheet to room temperature to obtain the tire triangle rubber material.

[0140] Example 2 This embodiment provides a tire triangular rubber compound, 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 proportion of the modified carbon nanotube / carbon black aggregate provided in Preparation Example 2.

[0141] Example 3 This embodiment provides a tire triangular rubber compound, 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 proportion of the modified carbon nanotube / carbon black aggregate provided in Preparation Example 3.

[0142] Example 4 This embodiment provides a tire triangular rubber compound, 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 proportion of the modified carbon nanotube / carbon black aggregate provided in Preparation Example 4.

[0143] Example 5 This embodiment provides a tire triangular rubber compound, 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 proportion of the modified carbon nanotube / carbon black aggregate provided in Preparation Example 5.

[0144] Example 6 This embodiment provides a tire triangular rubber compound, 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 proportion of the modified carbon nanotube / carbon black aggregate provided in Preparation Example 6.

[0145] Example 7 This embodiment provides a tire triangular rubber compound, 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 proportion of the modified carbon nanotube / carbon black aggregate provided in Preparation Example 7.

[0146] Example 8 This embodiment provides a tire triangular rubber compound, 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 proportion of the modified carbon nanotube / carbon black aggregate provided in Preparation Example 8.

[0147] Example 9 This embodiment provides a tire triangular rubber compound, 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 proportion of the modified carbon nanotube / carbon black aggregate provided in Preparation Example 9.

[0148] Example 10 This embodiment provides a tire triangular rubber compound, 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 proportion of the modified carbon nanotube / carbon black aggregate provided in Preparation Example 10.

[0149] Example 11 This embodiment provides a tire triangular rubber compound, 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 proportion of the modified carbon nanotube / carbon black aggregate provided in Preparation Example 11.

[0150] Example 12 This embodiment provides a tire triangular rubber compound, 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 proportion of the modified carbon nanotube / carbon black aggregate provided in Preparation Example 12.

[0151] Comparative Examples 1-5 These comparative examples provide tire triangle compounds with different components, made using corresponding tire triangle compound compositions, as shown in Table 4 below. The tire triangle compound compositions comprise the following components by weight: Table 4

[0152] The preparation methods of the tire triangular rubber materials provided in Comparative Examples 1 to 5 are the same as those in Example 1.

[0153] Comparative Examples 6-9 These comparative examples provide tire triangle compounds with different components, made using corresponding tire triangle compound compositions, as shown in Table 5 below. The tire triangle compound compositions comprise the following components by weight: Table 5

[0154] The preparation methods of the tire triangular rubber materials provided in Comparative Examples 6 to 9 are the same as those in Example 1.

[0155] Test Example 2 Test samples: tire triangle rubber compounds provided in Examples 1-12 and tire triangle rubber compounds provided in Comparative Examples 1-9.

[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 vulcanizate; TB is the tensile strength of the vulcanizate; EB% is the elongation at break of the vulcanizate; tanδ / 60℃ is the loss factor of the vulcanizate 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 triangular rubber compounds provided in Examples 1-12 is 11.6-12.3 MPa, TB is 28.9-29.8 MPa, EB% is 538-569%, and Tanδ is 0.044-0.050. This indicates that, during the preparation process of the modified carbon nanotube / carbon black aggregate described in this invention, in the presence of a modifier, the carbon nanotubes can be more uniformly dispersed in the primary carbon black particles through jet technology, significantly improving the dispersion performance of the carbon nanotubes. Furthermore, by adding this modified carbon nanotube / carbon black aggregate to the tire triangular rubber compound composition, this invention enhances the interaction between the rubber and the filler, reduces the agglomeration of the filler carbon nanotubes / carbon black itself, and improves the mechanical properties and wear resistance of the tire triangular rubber compound while further reducing the heat generation of the tire triangular rubber compound.

[0159] It is evident from Comparative Examples 1 and 7 that adding a modifier to the carbon black formulation can reduce heat generation by 24.4%. Comparative Examples 1, 8, and 1 show that adding the modifier to the carbon nanotube / N326 carbon black aggregate during the production of carbon nanotube / N326 carbon black aggregate using jet technology can further reduce heat generation, decreasing by 28.2% compared to the unmodified form and by 9.6% compared to Comparative Example 1. Moreover, Comparative Examples 1, 7, and 1 demonstrate that the addition of a modifier can reduce heat generation, especially when the modifier is added to the carbon nanotube / N326 carbon black aggregate during its production.

[0160] As can be seen from the comparative examples and the examples, different modifiers, used alone or in combination, contribute to heat generation. Compared with comparative examples 1-6, the heat generation tanδ is significantly reduced.

[0161] As can be seen from Example 1 and Comparative Example 8, when the modifier is first compounded with carbon nanotube / carbon black aggregates, compared to adding it to the rubber composition only in the form of physical blending, the mechanical properties (tensile strength of the vulcanizate) of the resulting rubber product are significantly improved, while the heat generation (loss factor of the vulcanizate at 60°C) is significantly reduced. Specifically, compared to Example 1, the addition of carbon nanotube / N326 carbon black aggregates through the production of the modifier further reduces 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, and not to limit them. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some or all of the technical features therein. Such modifications or substitutions 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 tire triangular rubber compound composition, characterized in that, The tire triangular rubber compound composition comprises the following components by weight: 100 parts raw rubber 10-40 parts of modified carbon nanotube / carbon black aggregate 1-12 parts of surfactant Accelerator 0.8~6 parts 0.8 to 6 parts of vulcanizing agent Anti-aging agent 3-7 parts 0.5 to 4 parts of tackifying resin 0-25 parts of silica 0-2.5 parts of silane coupling agent Protective wax 0-2.5 parts Anti-scorching agent 0~0.3 parts; The modified carbon nanotube / carbon black aggregate is prepared by the following steps: (a) By powder spraying, a suspension of carbon nanotubes is sprayed into a carbon black reactor, where carbon nanotubes and primary carbon black particles combine to form a pre-aggregate; through the aggregation of carbon black, a carbon nanotube / carbon black aggregate is formed. (b) The modifier is combined with the carbon nanotube / carbon black aggregate by high-temperature jet to obtain the modified carbon nanotube / carbon black aggregate; the injection flow rate of the modifier is 20~100 kg / h; the temperature at which the modifier combines with the carbon nanotube / carbon black aggregate is 100~480℃. The modifier is selected from any one or a combination of at least two of the following compounds: ； The content of the modifier is 0.05-5% of the total mass of the modified carbon nanotube / carbon black aggregate; The content of the carbon nanotubes is 1-10% of the total mass of the carbon nanotube / carbon black aggregate; The primary carbon black particles are N326 primary carbon black particles.

2. The tire triangular rubber compound composition according to claim 1, characterized in that, In step (a), the suspension of carbon nanotubes comprises, by mass percentage: 15-40% carbon nanotubes, with the remainder being water; And / or, in step (a), the injection flow rate of the suspension of carbon nanotubes is 50~200 kg / h; And / or, in step (a), the temperatures at which the prepolymer and carbon black aggregates are formed are each independently 800-1000°C.

3. The tire triangular rubber compound composition according to claim 1, characterized in that, In step (b), after the modifier is combined with the carbon nanotube / carbon black aggregate, the following post-processing step is also included: After cooling, filtration, and collection and separation, a powdered product is obtained; the powdered product, binder, and water are mixed, granulated, and dried to obtain the modifier and carbon nanotube / carbon black aggregate; And / or, the mass ratio of the powdered product, 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 modifier and the carbon nanotube / carbon black aggregate have a particle size of 0.1~3 μm.

4. The tire triangular rubber compound composition according to claim 1, characterized in that, The raw rubber includes natural rubber; And / or, the active agent includes stearic acid and / or zinc oxide; And / or, the accelerator includes 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 includes any one or a combination of at least two of tert-butylphenol-formaldehyde tackifying resin, tert-butylphenol-formaldehyde tackifying resin, octylphenol-formaldehyde tackifying resin or Keresin resin. And / or, the silane coupling agent includes silane coupling agent Si-69; And / or, the protective wax includes microcrystalline wax; And / or, the anti-scorching agent includes the anti-scorching agent CTP.

5. A tire triangular rubber compound, characterized in that, The tire triangle compound is obtained by mixing the tire triangle compound composition according to any one of claims 1 to 4.

6. A method for preparing the tire triangular rubber compound according to claim 5, characterized in that, The preparation method includes: (1) The raw rubber, modified carbon nanotube / carbon black aggregate, silica, silane coupling agent, activator, antioxidant, tackifying resin and protective wax are mixed and kneaded for one stage to obtain carbon nanotube / carbon black masterbatch. (2) The carbon nanotube / carbon black masterbatch, vulcanizing agent, accelerator and anti-scorching agent are mixed and mixed in two stages to obtain the tire triangle rubber compound.

7. The method for preparing the tire triangular rubber compound according to claim 6, characterized in that, In step (1), the mixed raw materials also include processing aids; In step (1), the first mixing stage includes the following steps in sequence: mixing for 20-40 seconds, lifting the top bolt, holding for 10-15 seconds, and pressing the top bolt; mixing until the temperature reaches 135-145℃, lifting the top bolt, holding for 10-15 seconds, and pressing the top bolt; mixing until the temperature reaches 145-155℃ and discharging the glue. In step (2), the two-stage mixing includes the following steps: mixing for 10-60 seconds, then lifting the top bolt, holding for 0-15 seconds, and pressing the top bolt back up; mixing until the temperature is 70-85℃, then lifting the top bolt, holding for 0-15 seconds, and pressing the top bolt back up; mixing until the temperature is 100-120℃, then discharging the adhesive.

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