Modified carbon nanotube / carbon black aggregate as well as preparation method and application thereof

Abstract

The invention provides a modified carbon nanotube / carbon black aggregate as well as a preparation method and application thereof, and relates to the technical field of tire manufacturing. The modified carbon nanotube / carbon black aggregate is obtained by high-temperature jet flow of a modifier and a carbon nanotube / carbon black aggregate. The preparation method comprises the following steps: spraying turbid liquid of a carbon nano tube into a carbon black reaction furnace through powder spraying, and combining the carbon nano tube with primary particles of the carbon black to form a pre-agglomerate; forming a carbon nanotube / carbon black aggregate through carbon black aggregation; and combining the modifier with the carbon nanotube / carbon black aggregate through high-temperature jet flow to obtain the modified carbon nanotube / carbon black aggregate. After the modifier is combined with the carbon nanotube / carbon black aggregate, the aggregate is endowed with a relatively large length-diameter ratio of the carbon nanotube, excellent performance of the carbon nanotube is exerted, and meanwhile, the dispersity and the reinforcing property of the carbon nanotube and the carbon black in a rubber matrix and the reaction activity of the carbon nanotube and the carbon black with rubber groups are improved.

Description

Technical Field

[0001] The invention relates to the technical field of tire manufacturing, and in particular to a modified carbon nanotube / carbon black aggregate and a preparation method and application thereof. Background Art

[0002] Automobile tires are one of the important parts of automobiles. They are in direct contact with the road surface. Together with the automobile suspension, they can mitigate the impact of the automobile when driving, ensure good friction adhesion between the automobile wheels and the road surface, and improve the traction, braking and passing performance of the automobile. As a material with high elasticity and resilience to deformation under stress, rubber materials usually need to be added with fillers when they are made into tire-related products. Carbon black is the most important reinforcing filler in the rubber industry. After filling with carbon black, the strength, blackness or conductivity of the matrix material is improved. However, the original particles of carbon black are small, have a certain aggregation, have a large tendency to self-aggregate between particles, have a low content of surface functional groups, and have weak interaction with polymers, which makes it difficult to disperse evenly in the polymer matrix, affecting the full play of its characteristics and limiting its scope of application. In addition, in order to further improve the various properties of tires, carbon materials such as graphene, multilayer graphite, and carbon nanotubes are often added.

[0003] Among them, carbon nanotubes are considered to be a very promising new type of rubber reinforcing nanomaterial due to their high specific surface area, high aspect ratio, and excellent mechanical, electrical and thermal properties. However, carbon nanotubes have large van der Waals forces, huge specific surface area, and large aspect ratio, so they usually exist in the form of entangled aggregates. In addition, in addition to the strong agglomeration effect of nanoparticles, carbon nanotubes in the state of entangled aggregates also have a unique entanglement phenomenon; the two effects combined together make carbon nanotube aggregates more solid and more difficult to disperse evenly. Therefore, it is easy to aggregate into useless lumps during the mixing process of rubber materials, resulting in uneven dispersion problems, which not only affects the filling and modification effect, but also damages the performance of rubber materials.

[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 modified carbon nanotube / carbon black aggregate and a preparation method and application thereof. The modified carbon nanotube / carbon black aggregate of the present invention is obtained by high-temperature jetting of a modifier and carbon nanotube / carbon black aggregate, which further improves the dispersibility of the carbon nanotube / carbon black aggregate and reduces the agglomeration of the modified carbon nanotube / carbon black aggregate in the rubber composition, thereby further enhancing the mechanical properties of the rubber composition, reducing heat generation and improving wear.

[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 modified carbon nanotube / carbon black aggregate, 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 formula I to formula 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 selected from 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: .

[0008] Preferably, the content of the modifier is 0.05-5% of the total mass of the modified carbon nanotube / carbon black aggregate.

[0009] Preferably, the carbon nanotube / carbon black aggregates are obtained by powder spraying carbon nanotubes and carbon black primary particles.

[0010] Preferably, the content of the carbon nanotubes is 1-10% of the total mass of the carbon nanotube / carbon black aggregate.

[0011] Preferably, the carbon black native particles are selected from any one of N134 carbon black native particles, N234 carbon black native particles, N115 carbon black native particles, N330 carbon black native particles, N326 carbon black native particles, N375 carbon black native particles or N660 carbon black native particles, or a combination of at least two thereof.

[0012] In a second aspect, the present invention provides a method for preparing the modified carbon nanotube / carbon black aggregate as described in the first aspect, the preparation method comprising: (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.

[0013] Preferably, in step (a), the carbon nanotube suspension comprises, by mass percentage, 15-25% carbon nanotubes and the remainder water.

[0014] Preferably, in step (a), the injection rate of the carbon nanotube suspension is 50-200 kg / h.

[0015] 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.

[0016] Preferably, in step (b), the injection rate of the modifier is 20-100 kg / h.

[0017] Preferably, in step (b), the temperature at which the modifier combines with the carbon nanotube / carbon black aggregate is 100-480°C.

[0018] 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.

[0019] Preferably, the mass ratio of the powdered product, the binder and water is (80~100):(0.1~2):(0.01~10).

[0020] Preferably, the binder is selected from lignin and / or molasses.

[0021] Preferably, the particle size of the modifier and the carbon nanotube / carbon black aggregate is 0.1-3 μm.

[0022] In a third aspect, the present invention provides a use of the modified carbon nanotube / carbon black aggregate as described in the first aspect in preparing a tire cushion rubber composition.

[0023] In a fourth aspect, the present invention provides a tire cushion rubber composition, wherein the tire cushion rubber composition comprises the following components in parts by weight: 100 pieces of raw rubber Modified carbon nanotube / carbon black aggregate 25~50 parts 1~12 parts of active agent Accelerator 0.8~6 parts Vulcanizing agent 0.8~6 parts Anti-aging agent 1~5 parts Tackifying resin 0~3 parts White carbon black 0~20 parts Anti-scorch agent 0~0.3 parts; Wherein, the modified carbon nanotube / carbon black aggregate includes the modified carbon nanotube / carbon black aggregate as described in the first aspect.

[0024] Preferably, the raw rubber comprises natural rubber and / or butadiene rubber.

[0025] Preferably, the active agent comprises stearic acid and / or zinc oxide.

[0026] Preferably, the accelerator comprises accelerator NS.

[0027] Preferably, the vulcanizing agent includes insoluble sulfur OT-20.

[0028] Preferably, the antioxidant includes antioxidant 4020 and / or antioxidant RD.

[0029] 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.

[0030] Preferably, the anti-scorch agent includes anti-scorch agent CTP.

[0031] In a fifth aspect, the present invention provides a tire cushion rubber, which is obtained by mixing the tire cushion rubber composition as described in the fourth aspect.

[0032] In a sixth aspect, the present invention provides a method for preparing the tire cushion rubber according to the fifth aspect, the preparation method comprising: (1) mixing the raw rubber, modified carbon nanotube / carbon black aggregate, active agent, antioxidant, tackifying resin and white carbon black, and performing a mixing 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 cushion rubber.

[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 165°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) The present invention obtains a modified filler by subjecting a modifier and carbon nanotube / carbon black aggregates to high-temperature jet treatment. The modifier imparts to the aggregates a property that can maintain a large aspect ratio of the carbon nanotubes themselves and exert the excellent performance of the carbon nanotubes; at the same time, the addition of the modifier and the high-temperature jet treatment can make the carbon nanotubes more evenly dispersed in the carbon black, thereby further improving the dispersibility of the modified carbon nanotube / carbon black aggregates.

[0036] (2) The present invention enhances the interaction between rubber and filler, reduces filler agglomeration, and further enhances the mechanical properties of the rubber composition, reduces heat generation, and improves wear by surface modification of carbon nanotube / carbon black aggregates.

[0037] (3) The inventors use a modifier to first modify the carbon nanotube / carbon black aggregates and then add them to the rubber matrix, 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 rubber has better dispersibility, stronger mechanical properties, and higher stability. In addition, modifying the carbon nanotube / carbon black aggregates first also has higher functionalization efficiency from a process perspective, 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 Example 1.

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

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

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

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

[0044] Figure 6This is a scanning electron microscope image of the unmodified carbon nanotube / carbon black aggregate provided in Comparative Example 1. DETAILED DESCRIPTION

[0045] 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.

[0046] 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.

[0047] In a first aspect, the present invention provides a modified carbon nanotube / carbon black aggregate, 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 formula I to formula 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 selected from a positive integer between 1 and 5.

[0048] 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.

[0049] 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.

[0050] 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.

[0051] As an optional embodiment, M is selected from alkali metals and / or alkaline earth metals, for example, it can be Li, Na, K, Mg, Ca, etc., preferably Na.

[0052] In the present invention, during the carbon black manufacturing process, carbon nanotubes can be uniformly dispersed in the carbon black through the jet technology, which can improve the dispersion of the carbon nanotubes, thereby improving the mechanical properties, reducing heat generation and improving wear resistance; further, through carbon black and carbon nanotube modifiers, the dispersibility of carbon nanotube / carbon black aggregates is further improved, and at the same time, surface modification enhances the interaction between rubber and filler, reduces filler agglomeration, and further enhances the mechanical properties of the rubber composition, reduces heat generation and improves wear.

[0053] As an optional embodiment, the modifier is selected from any one or a combination of at least two of the following compounds: .

[0054] 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.

[0055] As an optional implementation, the carbon nanotube / carbon black aggregates are obtained by powder spraying carbon nanotubes and carbon black primary particles.

[0056] 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.

[0057] As an optional embodiment, the carbon black native particles are selected from any one of N134 carbon black native particles, N234 carbon black native particles, N115 carbon black native particles, N330 carbon black native particles, N326 carbon black native particles, N375 carbon black native particles or N660 carbon black native particles, or a combination of at least two thereof, preferably N660 carbon black native particles.

[0058] In a second aspect, the present invention provides a method for preparing the modified carbon nanotube / carbon black aggregate as described in the first aspect, the preparation method comprising: (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.

[0059] In the present invention, in the step (a) of preparing the carbon nanotube / carbon black aggregate, first, a suspension of carbon nanotubes (a suspension formed by uniformly mixing carbon nanotubes and process water) is sprayed into a carbon black reactor, and the carbon nanotubes will be tightly combined with the carbon black primary particles at high temperature to form a pre-agglomerate; wherein, the powder injection is: the carbon nanotubes are transported to the precisely quantitative interlocking double helix 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., the process water, and 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. Furthermore, through the aggregation of carbon black, carbon nanotube / carbon black aggregates are formed.

[0060] In the present invention, during the preparation of the modified carbon nanotube / carbon black aggregates in step (b), a modifier is added by high-temperature jet technology to combine it with the flue gas of the suspended carbon nanotube / carbon black aggregates to form powdered modified carbon nanotube / carbon black aggregates; subsequently, the modified carbon nanotube / carbon black aggregates can be cooled, filtered and collected and separated by a main bag filter, and the separated tail gas is used for heating in the tail gas furnace and power generation in the boiler, while the separated powdered modified carbon nanotube / 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 dried, and the water is removed to finally obtain the modified carbon nanotube / carbon black aggregates.

[0061] 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.

[0062] 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.

[0063] 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.

[0064] 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.

[0065] 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.

[0066] 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.

[0067] 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.

[0068] As an optional embodiment, the binder is selected from lignin and / or molasses.

[0069] As an optional embodiment, the particle size of the modifier and the 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.

[0070] In a third aspect, the present invention provides a use of the modified carbon nanotube / carbon black aggregate as described in the first aspect in preparing a tire cushion rubber composition.

[0071] In a fourth aspect, the present invention provides a tire cushion rubber composition, wherein the tire cushion rubber composition comprises the following components in parts by weight: 100 pieces of raw rubber Modified carbon nanotube / carbon black aggregate 25~50 parts 1~12 parts of active agent Accelerator 0.8~6 parts Vulcanizing agent 0.8~6 parts 1~5 parts of antioxidant Tackifying resin 0~3 parts White carbon black 0~20 parts Anti-scorch agent 0~0.3 parts; Wherein, the modified carbon nanotube / carbon black aggregate includes the modified carbon nanotube / carbon black aggregate as described in the first aspect.

[0072] As an optional embodiment, in the tire cushion rubber composition, the content of modified carbon nanotubes / carbon black aggregates is 25 to 50 parts, for example, it can be 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, 41 parts, 42 parts, 43 parts, 44 parts, 45 parts, 46 parts, 48 ​​parts, 49 parts, 50 parts, etc., preferably 25 to 40 parts, and more preferably 30 to 35 parts.

[0073] As an optional embodiment, in the tire cushion 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 5 to 10 parts, and more preferably 8 to 9 parts.

[0074] As an optional embodiment, in the tire cushion 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 1 to 1.5 parts.

[0075] As an optional embodiment, in the tire cushion 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 2 to 4 parts, and more preferably 3 to 4 parts.

[0076] As an optional embodiment, in the tire cushion rubber composition, the content of the antioxidant is 1 to 5 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, 4.2 parts, 4.4 parts, 4.5 parts, 4.6 parts, 4.8 parts, 5 parts, etc., preferably 2 to 4 parts.

[0077] As an optional embodiment, in the tire cushion rubber composition, the content of tackifying resin is 0~3 parts, for example, it can be 0 part, 0.01 part, 0.05 part, 0.1 part, 0.2 part, 0.4 part, 0.5 part, 0.6 part, 0.8 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, 2.6 parts, 2.8 parts, 3 parts, etc., preferably 1.5~2.5 parts.

[0078] As an optional embodiment, in the tire cushion rubber composition, the content of white carbon black is 0-20 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, 1.2 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, 6.5 parts, 7 parts, 7.5 parts, 8 parts, 8.5 parts, 9 parts, 9.5 parts, 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts, etc., preferably 10 to 20 parts, and more preferably 12 to 18 parts.

[0079] As an optional embodiment, in the tire cushion rubber composition, the content of the anti-scorch agent is 0~0.3 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 0.1~0.3 parts.

[0080] As an optional embodiment, the raw rubber includes natural rubber and / or butadiene rubber.

[0081] As an optional embodiment, the raw rubber is natural rubber.

[0082] As an optional embodiment, the active agent includes stearic acid and / or zinc oxide.

[0083] As a preferred embodiment, the active agent consists of stearic acid and zinc oxide.

[0084] 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:(7-8), for example, it can be 1:7, 1:7.2, 1:7.4, 1:7.5, 1:7.6, 1:7.8, 1:8, etc. As an optional embodiment, the accelerator includes accelerator NS.

[0085] As an optional embodiment, the antioxidant includes antioxidant 4020 and / or antioxidant RD.

[0086] As an optional embodiment, the antioxidant consists of antioxidant 4020 and antioxidant RD.

[0087] As an optional embodiment, when the antioxidant is composed of antioxidant 4020 and antioxidant RD, the mass ratio of antioxidant 4020 and antioxidant RD is (0.8~1.2):(0.8~1.2), for example, it can be 0.8:1, 0.9:1, 1:1, 1.1:1, 1.2:1, 1:0.8, 1:0.9, 1:1.1, 1:1.2, etc.

[0088] As an optional embodiment, 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.

[0089] As an optional embodiment, the white carbon black includes GR175. As an optional embodiment, the anti-scorch agent includes anti-scorch agent CTP.

[0090] In a fifth aspect, the present invention provides a tire cushion rubber, which is obtained by mixing the tire cushion rubber composition as described in the fourth aspect.

[0091] In a sixth aspect, the present invention provides a method for preparing the tire cushion rubber according to the fifth aspect, the preparation method comprising: (1) mixing the raw rubber, modified carbon nanotube / carbon black aggregate, active agent, antioxidant, tackifying resin and white carbon black, and performing a mixing 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 cushion rubber.

[0092] After the modifier is combined with the carbon nanotube / carbon black aggregate, the aggregate is given the ability to maintain a large aspect ratio of the carbon nanotube itself and exert the excellent performance of the carbon nanotube, and at the same time, the dispersion, reinforcement and reaction activity of the carbon nanotube and carbon black in the rubber matrix with the rubber group can be improved. The present invention obtains a modified filler by subjecting the modifier and the carbon nanotube / carbon black aggregate to high-temperature jet. The modifier gives the aggregate the ability to maintain a large aspect ratio of the carbon nanotube itself and exert the excellent performance of the carbon nanotube; at the same time, the addition of the modifier and the high-temperature jet treatment can make the carbon nanotube more uniformly dispersed in the carbon black, thereby further improving the dispersibility of the modified carbon nanotube / carbon black aggregate. In addition, the present invention enhances the interaction between rubber and filler, reduces filler agglomeration, and further enhances the mechanical properties of the rubber composition, reduces heat generation and improves wear by surface modification of the carbon nanotube / carbon black aggregate.

[0093] It should be noted that the inventors first modified the carbon nanotube (CNT) / carbon black (CB) aggregates with a modifier and then added 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.

[0094] 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; 2. When only physically mixed, the interface between the modifier and the rubber relies only 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.

[0095] 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.

[0096] 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.

[0097] 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.

[0098] 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 145-165°C (for example, it can be 145°C, 146°C, 148°C, 150°C, 152°C, 154°C, 156°C, 158°C, 160°C, etc.) to discharge the glue.

[0099] 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.

[0100] 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.

[0101] The raw materials used in the following examples are shown in Table 1.

[0102] Table 1

[0103] Among them, SUMILINK @ The structural formula of 200 is .

[0104] Example 1 This embodiment 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 10 wt%; 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 N660 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.

[0105] 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.

[0106] Example 2 This embodiment provides a modified carbon nanotube / carbon black aggregate, which is different from Embodiment 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 completely consistent with Embodiment 1.

[0107] 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.

[0108] Example 3 This embodiment provides a modified carbon nanotube / carbon black aggregate, which is different from the embodiment 1 only in that 0.8 wt % of sebacic acid dihydrazide is replaced by 0.8 wt % of SUMILINK @ 200, the other steps are completely consistent with those in Example 1.

[0109] 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.

[0110] Example 4 This embodiment provides a modified carbon nanotube / carbon black aggregate, which is different from 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 Example 1.

[0111] 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.

[0112] Example 5 This embodiment provides a modified carbon nanotube / carbon black aggregate, which is different from Example 1 only in that 0.8 wt % of sebacic acid dihydrazide is replaced by 0.8 wt % of a mixture of isophthalic acid hydrazide and SUMILINK@200 (in the mixture, the mass ratio of isophthalic acid hydrazide to SUMILINK@200 is 1:1), and the other steps are exactly the same as Example 1.

[0113] 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.

[0114] Example 6 This embodiment provides a modified carbon nanotube / carbon black aggregate, which is different from Embodiment 1 only in that the content of sebacic acid dihydrazide is reduced to 0.4 wt %, and the other steps are completely consistent with Embodiment 1.

[0115] Example 7 This embodiment provides a modified carbon nanotube / carbon black aggregate, which is different from the embodiment 1 only in that the content of sebacic acid dihydrazide is increased to 1.2 wt %, and the other steps are completely consistent with the embodiment 1.

[0116] Example 8 This embodiment provides a modified carbon nanotube / carbon black aggregate, which is different from the embodiment 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 the embodiment 1; wherein the structural formula of compound I-1 is: .

[0117] Example 9 This embodiment provides a modified carbon nanotube / carbon black aggregate, which is different from Embodiment 1 only in that the content of the carbon nanotube is 1% of the total mass of the carbon nanotube / carbon black aggregate, and the other steps are completely consistent with Embodiment 1.

[0118] Example 10 This embodiment provides a modified carbon nanotube / carbon black aggregate, which is different from Embodiment 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 completely consistent with Embodiment 1.

[0119] Embodiment 11 This embodiment provides a modified carbon nanotube / carbon black aggregate, which is different from Embodiment 1 only in that the carbon black native particles N660 are replaced with carbon black native particles N330 of equal mass, and the other steps are exactly the same as Embodiment 1.

[0120] Example 12 This embodiment provides a modified carbon nanotube / carbon black aggregate, which is different from Embodiment 1 only in that the carbon black native particles N660 are replaced with carbon black native particles N134 of equal mass, and the other steps are exactly the same as Embodiment 1.

[0121] Comparative 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 Example 1.

[0122] like Figure 6 As shown, it is obvious that a large part of the unmodified carbon nanotubes are entangled together and not well dispersed.

[0123] Test Example 1 Test samples: modified carbon nanotube / carbon black aggregates provided in Examples 1 to 12, and carbon nanotube / carbon black aggregates provided in Comparative Example 1.

[0124] 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.

[0125] The test results are shown in Table 2 and Figure 1 to Figure 6 As shown: Table 2

[0126] As shown in Table 2 above, the specific surface area of ​​the modified carbon nanotube / carbon black aggregate of the present invention is (45-127)×10 3 m 2 / kg, the pouring density of carbon nanotubes in aggregates is 352~451 kg / m 3 , the aspect ratio of carbon nanotubes in the aggregate can be maintained at 5321~5847.

[0127] Application Example 1 This application example provides a tire cushion rubber, which is obtained by mixing the following tire cushion rubber composition; wherein, as shown in Table 3 below, the tire cushion rubber composition includes the following components in parts by weight: Table 3

[0128] The tire cushion rubber described in this application example 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, activator, antioxidant, tackifying resin and white carbon black, 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, and wait until the temperature reaches 155°C to discharge the rubber to obtain the carbon nanotube / carbon black masterbatch.

[0129] (2) Second stage mixing: start the internal mixer, set the rotor speed of the internal mixer to 25 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 top 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 cushion rubber.

[0130] Application Example 2 This application example provides a tire cushion rubber, which differs from application example 1 only in that the modified carbon nanotube / carbon black aggregate provided in example 1 is replaced with an equal weight portion of the modified carbon nanotube / carbon black aggregate provided in example 2.

[0131] Application Example 3 This application example provides a tire cushion rubber, which differs from application example 1 only in that the modified carbon nanotube / carbon black aggregate provided in example 1 is replaced with an equal weight portion of the modified carbon nanotube / carbon black aggregate provided in example 3.

[0132] Application Example 4 This application example provides a tire cushion rubber, which differs from application example 1 only in that the modified carbon nanotube / carbon black aggregate provided in example 1 is replaced with an equal weight portion of the modified carbon nanotube / carbon black aggregate provided in example 4.

[0133] Application Example 5 This application example provides a tire cushion rubber, which differs from application example 1 only in that the modified carbon nanotube / carbon black aggregate provided in example 1 is replaced with an equal weight portion of the modified carbon nanotube / carbon black aggregate provided in example 5.

[0134] Application Example 6 This application example provides a tire cushion rubber, which differs from application example 1 only in that the modified carbon nanotube / carbon black aggregate provided in example 1 is replaced with an equal weight portion of the modified carbon nanotube / carbon black aggregate provided in example 6.

[0135] Application Example 7 This application example provides a tire cushion rubber, which differs from application example 1 only in that the modified carbon nanotube / carbon black aggregate provided in example 1 is replaced with an equal weight portion of the modified carbon nanotube / carbon black aggregate provided in example 7.

[0136] Application Example 8 This application example provides a tire cushion rubber, which differs from application example 1 only in that the modified carbon nanotube / carbon black aggregate provided in example 1 is replaced with an equal weight portion of the modified carbon nanotube / carbon black aggregate provided in example 8.

[0137] Application Example 9 This application example provides a tire cushion rubber, which differs from application example 1 only in that the modified carbon nanotube / carbon black aggregate provided in example 1 is replaced with an equal weight portion of the modified carbon nanotube / carbon black aggregate provided in example 9.

[0138] Application Example 10 This application example provides a tire cushion rubber, which differs from application example 1 only in that the modified carbon nanotube / carbon black aggregate provided in example 1 is replaced with an equal weight portion of the modified carbon nanotube / carbon black aggregate provided in example 10.

[0139] Application Example 11 This application example provides a tire cushion rubber, which differs from application example 1 only in that the modified carbon nanotube / carbon black aggregate provided in example 1 is replaced with an equal weight portion of the modified carbon nanotube / carbon black aggregate provided in example 11.

[0140] Application Example 12 This application example provides a tire cushion rubber, which differs from application example 1 only in that the modified carbon nanotube / carbon black aggregate provided in example 1 is replaced with an equal weight portion of the modified carbon nanotube / carbon black aggregate provided in example 12.

[0141] Comparative Application Examples 1~5 These comparative application examples provide tire cushion rubbers of different components, which are made using corresponding tire cushion rubber compositions, as shown in Table 4 below. The tire cushion rubber compositions include the following components in parts by weight: Table 4

[0142] The preparation methods of the tire cushion rubber provided in the above comparative application examples 1 to 5 are consistent with that in application example 1.

[0143] Comparative Application Examples 6~9 These comparative application examples provide tire cushion rubbers of different components, which are made using corresponding tire cushion rubber compositions, as shown in Table 5 below. The tire cushion rubber compositions include the following components in parts by weight: Table 5

[0144] The preparation methods of the tire cushion rubber provided in the above comparative application examples 6 to 9 are consistent with that in application example 1.

[0145] Test Example 2 Test samples: tire cushion rubber provided in application examples 1 to 12, and tire cushion rubber provided in comparative application examples 1 to 9.

[0146] 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℃.

[0147] The test results are shown in Table 6 below: Table 6

[0148] As shown in Table 6 above, the M300 of the tire cushion rubber provided by Application Examples 1 to 12 is 11.9 to 12.8 MPa, the TB is 22.1 to 23.4 MPa, the EB% is 532 to 539%, and the Tanδ is 0.054 to 0.056. This shows that the modified carbon nanotube / carbon black aggregate of the present invention is obtained by high-temperature jetting of the modifier and the carbon nanotube / carbon black aggregate, which further improves the dispersibility of the carbon nanotube / carbon black aggregate and reduces the agglomeration of the modified carbon nanotube / carbon black aggregate in the rubber composition, thereby further enhancing the mechanical properties of the rubber composition, reducing heat generation and improving wear.

[0149] It can be clearly seen from the above-mentioned comparative application example 1 and comparative application example 7 that adding a modifier to the carbon black formula can reduce heat generation by 11.1%. From the comparison of the above-mentioned comparative application example 1, comparative application example 8 and application example 1, it can be seen that by jet technology, adding a modifier to the carbon nanotube / N660 carbon black aggregate in the production of carbon nanotube / N660 carbon black aggregate can further generate heat, which is 25.3% lower than that without adding a modifier and 22% lower than that of comparative example 1; and it can also be seen from the comparison of comparative application example 1, comparative application example 7 and application example 1 that the addition of a modifier can reduce heat generation, especially when the modifier and carbon nanotube / N660 carbon black aggregate are added in the production of carbon nanotube / N660 carbon black aggregate.

[0150] It can be seen from the comparative examples and embodiments that different modifiers contribute to heat generation when used alone or in combination. The heat generation tanδ is significantly reduced by comparing application examples 1 to 5 with comparative application example 7. It can be seen from application example 1 and comparative application example 8 that the mechanical properties of the obtained rubber product (300% tensile strength of the vulcanized rubber and the tear strength of the vulcanized rubber) are significantly improved compared to adding them to the rubber composition in the form of physical blending, and the heat generation (loss factor of the vulcanized rubber at 60°C) is significantly reduced. Further compared with application example 1, the addition of carbon nanotubes / N660 carbon black aggregates produced by the modifier and carbon nanotubes / N660 carbon black aggregates can further reduce heat generation by 5%.

[0151] In addition, by comparing Application Example 6 with Application Example 1, it can be seen that the mechanical properties of the modified carbon nanotube / N660 carbon black aggregate are equivalent to those of N330, and the heat generation is lower than that of N330.

[0152] 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, 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 formula I to formula 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 a positive integer between 1 and 5.

2. The modified carbon nanotube / carbon black aggregate according to claim 1, 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 selected from any one of N134 carbon black native particles, N234 carbon black native particles, N115 carbon black native particles, N330 carbon black native particles, N326 carbon black native particles, N375 carbon black native particles or N660 carbon black native particles, or a combination of at least two thereof.

3. A method for preparing the modified carbon nanotube / carbon black aggregate according to claim 1 or 2, characterized in that: The preparation method comprises: (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.

4. The method for preparing modified carbon nanotube / carbon black aggregates according to claim 3, characterized in that: In step (a), the carbon nanotube suspension comprises, by mass percentage, 15-25% 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; And / or, 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; 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.

5. Use of the modified carbon nanotube / carbon black aggregate according to claim 1 or 2 in preparing a tire cushion rubber composition.

6. A tire cushion rubber composition, characterized in that: The tire cushion rubber composition comprises the following components by weight: 100 pieces of raw rubber Modified carbon nanotube / carbon black aggregate 25~50 parts 1~12 parts of active agent Accelerator 0.8~6 parts Vulcanizing agent 0.8~6 parts Anti-aging agent 1~5 parts Tackifying resin 0~3 parts White carbon black 0~20 parts Anti-scorch agent 0~0.3 parts; Wherein, the modified carbon nanotube / carbon black aggregate comprises the modified carbon nanotube / carbon black aggregate according to claim 1 or 2.

7. The tire cushion rubber composition according to claim 6, characterized in that: The raw rubber includes natural rubber and / or butadiene 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 anti-scorch agent includes anti-scorch agent CTP.

8. A tire cushion rubber, characterized in that: The tire cushion rubber is obtained by mixing the tire cushion rubber composition according to claim 6 or 7.

9. A method for preparing tire cushion rubber according to claim 8, characterized in that: The preparation method comprises: (1) mixing the raw rubber, modified carbon nanotube / carbon black aggregate, active agent, antioxidant, tackifying resin and white carbon black, and performing a mixing 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 cushion rubber.

10. The method for preparing tire cushion rubber according to claim 9, characterized in that: 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 165°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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