Tire base rubber composition, tire base rubber and preparation method of tire base rubber

Abstract

The invention provides a tire base rubber composition, a tire base rubber and a preparation method of the tire base rubber, and relates to the technical field of tire manufacturing. The tire base rubber composition is prepared from the following components in parts by weight: 100 parts of raw rubber, 20 to 40 parts of modified carbon nanotube / carbon black aggregate, 1 to 12 parts of active agent, 0.8 to 6 parts of accelerant, 0.8 to 6 parts of vulcanizing agent, 1 to 5 parts of anti-aging agent, 0.5 to 3 parts of tackifying resin, 0.5 to 3 parts of protective wax, 0 to 15 parts of white carbon black and 0 to 0.3 part of scorch retarder. The modified carbon nano tube / carbon black aggregate is obtained by high-temperature jet flow of a modifier and a carbon nano tube / carbon black aggregate, the dispersity of the carbon nano tube / carbon black aggregate is further improved, meanwhile, the interaction between rubber and filler is enhanced through surface modification, filler agglomeration is reduced, and the service life of the filler is prolonged. The mechanical property of the tire base rubber composition is further enhanced, heat generation is reduced, and abrasion is improved.

Description

Technical Field

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

[0002] The tire tread is mainly composed of tread rubber, base rubber, shoulder rubber and conductive rubber. Among them, the main functions of the base rubber are: to transmit vehicle traction and braking force, improve the high-speed performance of the tire, absorb the vibration generated by the tire during driving, improve the comfort of the tire, prevent damage to the tire body, and cushion the impact of the tire during driving. As the tire drives, the base rubber deforms faster, so in addition to good heat resistance, the base rubber must also have low dynamic heat generation, high mechanical properties, and good wear resistance, so as to increase the service life of the tire.

[0003] At present, the wear resistance of tire base rubber is mainly achieved by reinforcing the filler of the filling system and adding reinforcing resin. The general base rubber mostly uses commercially available high-wear-resistant carbon black. This is because carbon black and rubber have high physical adsorption capacity, which brings high wear resistance. However, as the amount of carbon black increases, the wear resistance of the rubber is improved, while the heat generation and hysteresis loss of the filling system increase, which in turn leads to increased energy consumption of the tire and affects the service life. In addition, the existing carbon black has a small particle size, a relatively large aggregate specific area, and a high surface free energy. It is very easy to flocculate during the processing process. Therefore, when the amount of carbon black is large, it is difficult for the carbon black to be evenly dispersed in the rubber matrix, heat generation is serious, and the temperature rise is rapid and violent, thereby affecting the various properties of the rubber material.

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

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

[0006] In order to solve the above technical problems, the present invention particularly adopts the following technical solutions: In a first aspect, the present invention provides a tire base rubber composition, wherein the tire base rubber composition comprises the following components in parts by weight: 100 pieces of raw rubber Modified carbon nanotube / carbon black aggregate 20~40 parts 1~12 parts of active agent Accelerator 0.8~6 parts Vulcanizing agent 0.8~6 parts Anti-aging agent 1~5 parts 0.5~3 parts of tackifying resin 0.5~3 parts of protective wax White carbon black 0~15 parts Anti-scorch agent 0~0.3 parts; Wherein, 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 N330 carbon black native particles.

[0012] Preferably, the modified carbon nanotube / carbon black aggregate is prepared by the following steps: (a) Spraying a suspension of carbon nanotubes into a carbon black reaction furnace through powder injection, the carbon nanotubes and carbon black primary particles are combined to form a pre-agglomerate; and carbon black is aggregated to form a carbon nanotube / carbon black aggregate; (b) combining the modifier with the carbon nanotube / carbon black aggregate by high temperature jet to obtain the modified carbon nanotube / carbon black aggregate.

[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 modified carbon nanotube / carbon black aggregate is 0.1-3 μm.

[0022] Preferably, the raw rubber comprises natural rubber and / or butadiene rubber.

[0023] Preferably, the active agent comprises stearic acid and / or zinc oxide.

[0024] Preferably, the accelerator comprises accelerator NS.

[0025] Preferably, the vulcanizing agent includes insoluble sulfur OT-20.

[0026] Preferably, the antioxidant includes antioxidant 4020 and / or antioxidant RD.

[0027] 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.

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

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

[0030] Preferably, the tire base rubber composition further comprises 0 to 3 parts of a silane coupling agent.

[0031] Preferably, the silane coupling agent includes any one of Si-69, Si-75 or Si-747, or a combination of at least two of them.

[0032] In a second aspect, the present invention provides a tire base rubber material, wherein the tire base rubber material is obtained by mixing the tire base rubber material composition as described in the first aspect.

[0033] In a third aspect, the present invention provides a method for preparing a tire base rubber material as described in the second aspect, the method for preparing the tire base rubber material comprising: (1) mixing the raw rubber, modified carbon nanotube / carbon black aggregate, white carbon black, active agent, antioxidant, tackifying resin and protective wax, 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 base rubber material.

[0034] Preferably, in step (1), the mixed raw materials further include a silane coupling agent.

[0035] Preferably, in step (1), the mixing stage comprises the following steps: mixing for 20 to 40 seconds, lifting the top pin, pausing for 10 to 15 seconds, and pressing the top pin; mixing to a temperature of 135 to 145°C, lifting the top pin, pausing for 10 to 15 seconds, and pressing the top pin; mixing to a temperature of 145 to 155°C, and then debonding.

[0036] 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.

[0037] Compared with the prior art, the present invention has the following beneficial effects: (1) During the preparation process of the modified carbon nanotube / carbon black aggregates of the present invention, in the presence of a modifier, the carbon nanotubes can be more evenly dispersed in the carbon black primary particles by jet technology, thereby significantly improving the dispersion performance of the carbon nanotubes.

[0038] (2) The present invention adds modified carbon nanotubes / carbon black aggregates to the tire base rubber composition. The surface modification enhances the interaction between rubber and filler, reduces filler agglomeration, improves the mechanical properties and wear resistance of the tire base rubber, and further reduces the heat generation of the tire base rubber.

[0039] (3) The present invention uses a modifier to first modify the carbon nanotube / carbon black aggregates and then add them to the tire base rubber composition, forming a "physical-chemical" dual reinforcement mechanism. Compared with the two being added to the rubber composition in the form of physical blending at a later stage, the tire base 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

[0040] 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.

[0041] Figure 1 This is a scanning electron microscope image of the modified carbon nanotube / carbon black aggregate prepared in Preparation Example 1.

[0042] Figure 2 This is a scanning electron microscope image of the modified carbon nanotube / carbon black aggregate prepared in Preparation Example 2.

[0043] Figure 3 This is a scanning electron microscope image of the modified carbon nanotube / carbon black aggregate prepared in Preparation Example 3.

[0044] Figure 4 This is a scanning electron microscope image of the modified carbon nanotube / carbon black aggregate prepared in Preparation Example 4.

[0045] Figure 5 This is a scanning electron microscope image of the modified carbon nanotube / carbon black aggregate prepared in Preparation Example 5.

[0046] Figure 6 This is a scanning electron microscope image of the modified carbon nanotube / carbon black aggregate prepared in Preparation Example 6.

[0047] Figure 7 This is a scanning electron microscope image of the unmodified carbon nanotube / carbon black aggregate provided in Comparative Preparation Example 1. DETAILED DESCRIPTION

[0048] To make the purpose, technical solution and advantages of the present invention clearer, the technical solution in the embodiment of the present invention will be clearly and completely described below in combination with the embodiment of the present invention. Obviously, the described embodiment is a part of the embodiment of the present invention, but not all of the embodiments. The components of the embodiment of the present invention can be arranged and designed in various different configurations.

[0049] It should be noted that, in this article, relational terms such as first and second, etc. are only used to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply any such actual relationship or order between these entities or operations. Moreover, the terms "include", "comprise" or any other variants thereof are intended to cover non-exclusive inclusion, so that a process, method, article or device including a series of elements includes not only those elements, but also other elements not explicitly listed, or also includes elements inherent to such process, method, article or device.

[0050] In a first aspect, the present invention provides a tire base rubber composition, wherein the tire base rubber composition comprises the following components in parts by weight: 100 pieces of raw rubber Modified carbon nanotube / carbon black aggregate 20~40 parts 1~12 parts of active agent Accelerator 0.8~6 parts Vulcanizing agent 0.8~6 parts Anti-aging agent 1~5 parts 0.5~3 parts of tackifying resin 0.5~3 parts of protective wax White carbon black 0~15 parts Anti-scorch agent 0~0.3 parts; Wherein, the modified carbon nanotube / carbon black aggregate is obtained by high-temperature jetting of a modifier and carbon nanotube / carbon black aggregate; the modifier is selected from any one or a combination of at least two of the compounds represented by the following formulas I to V: ; Wherein, n and m are each independently selected from positive integers between 1 and 10; M is selected from alkali metals and / or alkaline earth metals; R 1 and R 2 Each independently selected from or , p is a positive integer between 1 and 5.

[0051] 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.

[0052] 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.

[0053] 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.

[0054] As an optional embodiment, M is selected from alkali metals and / or alkaline earth metals, for example, Li, Na, K, Mg, Ca, etc., preferably Na.

[0055] In the present invention, during the preparation process of the modified carbon nanotube / carbon black aggregate of the present invention, in the presence of the modifier shown in Formula I to Formula V, the carbon nanotube can be more evenly dispersed in the carbon black primary particles by the jet technology, significantly improving the dispersion performance of the carbon nanotube. Furthermore, the present invention adds the modified carbon nanotube / carbon black aggregate to the tire base rubber composition, thereby enhancing the interaction between the rubber and the filler, reducing the agglomeration of the filler carbon nanotube / carbon black itself, and providing the mechanical properties and wear resistance of the tire base rubber, while further reducing the heat generation of the tire base rubber.

[0056] It should be noted that the present invention uses a modifier to first modify the carbon nanotube (CNT) / carbon black (CB) aggregates and then add them to the rubber matrix. Compared with adding the two to the rubber composition in the form of physical blending at a later stage, the reason why the rubber performance is significantly improved is that: 1. Better dispersibility: The present invention fixes the modifier through chemical bonds, and the graft modification uses covalent bonds to more firmly bind the coupling agent and wrap it on the surface of the aggregate to form a stable surface modification layer. As mentioned above, this chemical bonding can effectively reduce the van der Waals force between aggregates, reduce the tendency to agglomerate, and reduce the risk of CNT breakage, thereby maintaining its original aspect ratio; while it only attaches to the surface of carbon black through physical adsorption or weak interactions (such as hydrogen bonds), and is easy to fall off under the high shear force of rubber processing (such as mixing and extrusion), resulting in the re-agglomeration of carbon black.

[0057] 2. Stronger mechanical properties: The modifier of the present application not only acts as a "bridge" to form a CNT-CB hybrid structure, but also can connect CNT / CB aggregates at one end and react chemically with rubber molecular chains at the other end to form a strong chemical bonding interface of CNT / CB aggregates-rubber, thereby improving the interfacial bonding ability and making the rubber have stronger mechanical properties; while when only physically mixed, the interface between the modifier and the rubber only relies on physical adsorption or a small amount of reaction, the interfacial bonding strength is low, the stress transfer efficiency is poor, and it is easy to cause interfacial debonding.

[0058] 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.

[0059] 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.

[0060] 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.

[0061] As an optional embodiment, in the tire base rubber composition, the content of modified carbon nanotubes / carbon black aggregates is 20 to 40 parts, for example, it can be 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 30 to 40 parts, and more preferably 36 to 39 parts.

[0062] As an optional embodiment, in the tire base 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 3 to 8 parts, and more preferably 5 to 6 parts.

[0063] As an optional embodiment, in the tire base 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 1 to 1.5 parts.

[0064] As an optional embodiment, in the tire base 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 1 to 2 parts.

[0065] As an optional embodiment, in the tire base 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 3 to 4 parts.

[0066] As an optional embodiment, in the tire base rubber composition, the content of the tackifier resin is 0.5 to 3 parts, for example, it can be 0.5 parts, 0.6 parts, 0.7 parts, 0.8 parts, 0.9 parts, 1 parts, 1.2 parts, 1.4 parts, 1.5 parts, 1.6 parts, 1.8 parts, 2 parts, 2.2 parts, 2.4 parts, 2.5 parts, 2.6 parts, 2.8 parts, 3 parts, etc., preferably 0.5 to 1.5 parts.

[0067] As an optional embodiment, in the tire base rubber composition, the content of protective wax is 0.5 to 3 parts, for example, it can be 0.5 parts, 0.6 parts, 0.7 parts, 0.8 parts, 0.9 parts, 1 parts, 1.2 parts, 1.4 parts, 1.5 parts, 1.6 parts, 1.8 parts, 2 parts, 2.2 parts, 2.4 parts, 2.5 parts, 2.6 parts, 2.8 parts, 3 parts, etc., preferably 0.4 to 0.6 parts.

[0068] As an optional embodiment, in the tire base rubber composition, the content of white carbon black is 0 to 15 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 , 3.2, 3.4, 3.5, 3.6, 3.8, 4, 4.2, 4.4, 4.5, 4.6, 4.8, 5, 5.2, 5.4, 5.6, 5.8, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, 10, 11, 12, 13, 14, 15 parts, etc., preferably 5 to 10 parts.

[0069] As an optional embodiment, in the tire base rubber composition, the content of the scorch retarder 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.

[0070] As an optional embodiment, the modifier is selected from any one or a combination of at least two of the following compounds: .

[0071] 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.

[0072] As an optional implementation, the carbon nanotube / carbon black aggregates are obtained by powder spraying carbon nanotubes and carbon black primary particles.

[0073] 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.

[0074] As an optional embodiment, the carbon black native particles are N330 carbon black native particles.

[0075] As an optional embodiment, the modified carbon nanotube / carbon black aggregate is prepared by the following steps: (a) Spraying a suspension of carbon nanotubes into a carbon black reaction furnace through powder injection, the carbon nanotubes and carbon black primary particles are combined to form a pre-agglomerate; and carbon black is aggregated to form a carbon nanotube / carbon black aggregate; (b) combining the modifier with the carbon nanotube / carbon black aggregate by high temperature jet to obtain the modified carbon nanotube / carbon black aggregate.

[0076] In the present invention, the powder injection in step (a) is specifically as follows: the carbon nanotubes are transported to the interlocking double helices that can be precisely quantified through the mechanical arch breaking device, the airflow arch breaking device and the plow blade stirring device at the bottom of the silo in the storage bin, and the carbon nanotubes measured by the weighing system and the precise quantitative spiral enter the mass transfer cavity of the high-speed injection mixer and are instantly mixed with the injection carrier, i.e., process water. The carbon nanotubes are forced to disperse into the injection carrier during the movement, and are rapidly diffused into a uniform suspension through pressure changes in the diffuser at the tail of the injector, and are transported to the pressure atomization system.

[0077] In the present invention, the combination in step (b) is specifically as follows: adding a modifier and combining it with the flue gas of the suspended carbon nanotubes / carbon black aggregates through high-temperature jet technology; further, after cooling, filtering and collection and separation by the main bag filter, the separated exhaust gas is used for heating in the exhaust furnace and power generation in the boiler, and finally the powdered carbon nanotubes / carbon black aggregates are stirred with an appropriate amount of water and a binder in a granulator to be granulated, and then the aggregate particles are sent to a rotary dryer for drying, and the modified carbon nanotubes / carbon black aggregates are finally obtained after removing the moisture.

[0078] In the present invention, after the modifier is combined with the carbon nanotube / carbon black aggregate, the aggregate is given the ability to maintain the carbon nanotube's own larger aspect ratio and exert the excellent performance of the carbon nanotube, while also improving the dispersion, reinforcement and reaction activity of the carbon nanotube and carbon black in the rubber matrix with the rubber group.

[0079] 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.

[0080] 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.

[0081] 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.

[0082] 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.

[0083] 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.

[0084] 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.

[0085] 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.

[0086] As an optional embodiment, the binder is selected from lignin and / or molasses.

[0087] As an optional embodiment, the particle size of the modified carbon nanotube / carbon black aggregate is 0.1-3 μm, for example, 0.1 μm, 0.5 μm, 1 μm, 1.5 μm, 2 μm, 2.5 μm, 3 μm, etc.

[0088] As an optional embodiment, the raw rubber includes natural rubber and / or butadiene rubber.

[0089] As a preferred embodiment, the raw rubber is natural rubber.

[0090] As an optional embodiment, the active agent includes stearic acid and / or zinc oxide.

[0091] As a preferred embodiment, the active agent consists of stearic acid and zinc oxide.

[0092] As a preferred embodiment, when the active agent consists of stearic acid and zinc oxide, the mass ratio of stearic acid to zinc oxide is 1:(1.5~2), for example, it can be 1:1.5, 1:1.6, 1:1.7, 1:1.8, 1:1.9, 1:2, etc.

[0093] As an optional embodiment, the accelerator includes accelerator NS.

[0094] As an optional embodiment, the vulcanizing agent includes insoluble sulfur OT-20.

[0095] As an optional embodiment, the antioxidant includes antioxidant 4020 and / or antioxidant RD.

[0096] As a preferred embodiment, the antioxidant consists of antioxidant 4020 and antioxidant RD.

[0097] As a preferred embodiment, when the antioxidant consists of antioxidant 4020 and antioxidant RD, the mass ratio of antioxidant 4020 to antioxidant RD is 1:(0.5~1), for example, it can be 1:0.5, 1:0.6, 1:0.7, 1:0.8, 1:0.9, 1:1, etc.

[0098] 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.

[0099] As an optional embodiment, the protective wax includes microcrystalline wax.

[0100] As an optional embodiment, the white carbon black includes GR175.

[0101] As an optional implementation, the anti-scorch agent includes anti-scorch agent CTP.

[0102] As an optional embodiment, the tire base rubber composition also includes 0 to 3 parts of a silane coupling agent, for example, 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.

[0103] As an optional embodiment, the silane coupling agent includes any one of Si-69, Si-75 or Si-747, or a combination of at least two of them.

[0104] In a second aspect, the present invention provides a tire base rubber material, wherein the tire base rubber material is obtained by mixing the tire base rubber material composition as described in the first aspect.

[0105] In a third aspect, the present invention provides a method for preparing a tire base rubber material as described in the second aspect, the method for preparing the tire base rubber material comprising: (1) mixing the raw rubber, modified carbon nanotube / carbon black aggregate, white carbon black, active agent, antioxidant, tackifying resin and protective wax, 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 base rubber material.

[0106] As an optional embodiment, in step (1), the mixed raw materials further include a silane coupling agent.

[0107] As an optional implementation, step (1) specifically comprises: mixing the raw rubber, modified carbon nanotube / carbon black aggregate, white carbon, silane coupling agent, activator, antioxidant, tackifying resin and protective wax, and performing a mixing step to obtain a carbon nanotube / carbon black masterbatch.

[0108] As an optional embodiment, in step (1), the mixing stage includes the following steps: mixing for 20 to 40 s (for example, 20 s, 22 s, 24 s, 25 s, 26 s, 28 s, 30 s, 32 s, 34 s, 35 s, 36 s, 38 s, 40 s, etc.), lifting the top pin, staying for 10 to 15 s (for example, 10 s, 11 s, 12 s, 13 s, 14 s, 15 s, etc.), and pressing the top pin; mixing to a temperature of 135 to 145°C (for example, 135°C, 136°C, 138°C, 140°C, 142°C, 144°C, 145°C, etc.), lifting the top pin, staying for 10 to 15 s (for example, 10 s, 11 s, 12 s, 13 s, 14 s, 15 s, etc.), and pressing the top pin; mixing to a temperature of 135 to 145°C (for example, 135°C, 136°C, 138°C, 140°C, 142°C, 144°C, 145°C, etc.), lifting the top pin, staying for 10 to 15 s (for example, 10 s, 11 s, 12 s, 13 s, 14 s, 15 s, etc.) to press the top bolt; mix until the temperature is 145-155°C (for example, it can be 145°C, 146°C, 148°C, 150°C, 152°C, 154°C, 155°C, etc.) to discharge the glue.

[0109] 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.

[0110] 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.

[0111] The raw materials used in the following examples are shown in Table 1.

[0112] Table 1

[0113] Among them, SUMILINK @ The structural formula of 200 is .

[0114] Preparation Example 1 This preparation example provides a modified carbon nanotube / carbon black aggregate, and the modified carbon nanotube / carbon black aggregate is prepared by the following steps: (a) In a jet system, carbon nanotubes and process water are uniformly mixed by powder injection technology, and the concentration of the carbon nanotube suspension is controlled to be 10wt%; then, the carbon nanotube suspension is sprayed into a carbon black reactor, and the injection flow rate of the carbon nanotube suspension is controlled to be 150 kg / h. The temperature in the carbon black reactor is set to 900°C, and the carbon nanotubes and carbon black primary particles N330 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.

[0115] 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.

[0116] Preparation Example 2 This preparation example provides a modified carbon nanotube / carbon black aggregate, which differs from Preparation Example 1 only in that 0.8 wt % of sebacic acid dihydrazide is replaced by 0.8 wt % of isophthalic acid dihydrazide, and the other steps are exactly the same as Preparation Example 1.

[0117] 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.

[0118] Preparation Example 3 This preparation example provides a modified carbon nanotube / carbon black aggregate, which is different from Preparation Example 1 only in that 0.8 wt% of sebacoyl dihydrazide is replaced by 0.8 wt% of SUMILINK @ 200, and the other steps are exactly the same as those in Preparation Example 1.

[0119] As Figure 3 shown, this aggregate can not only maintain the large aspect ratio of the carbon nanotubes themselves, but also the carbon nanotubes are more evenly dispersed in the carbon black.

[0120] Preparation Example 4 This preparation example provides a modified carbon nanotube / carbon black aggregate, which is different from Preparation Example 1 only in that 0.8 wt% of sebacoyl dihydrazide is replaced by a mixture of 0.8 wt% of sebacoyl dihydrazide and isophthaloyl dihydrazide (in this mixture, the mass ratio of sebacoyl dihydrazide to isophthaloyl dihydrazide is 1:1), and the other steps are exactly the same as those in Preparation Example 1.

[0121] As Figure 4 shown, this aggregate can not only maintain the large aspect ratio of the carbon nanotubes themselves, but also the carbon nanotubes are more evenly dispersed in the carbon black.

[0122] Preparation Example 5 This preparation example provides a modified carbon nanotube / carbon black aggregate, which is different from Preparation Example 1 only in that 0.8 wt% of sebacoyl dihydrazide is replaced by a mixture of 0.8 wt% of isophthaloyl dihydrazide and SUMILINK @ 200 (in this mixture, the mass ratio of isophthaloyl dihydrazide to SUMILINK @ 200 is 1:1), and the other steps are exactly the same as those in Preparation Example 1.

[0123] As Figure 5 shown, this aggregate can not only maintain the large aspect ratio of the carbon nanotubes themselves, but also the carbon nanotubes are more evenly dispersed in the carbon black.

[0124] Preparation Example 6 This preparation example provides a modified carbon nanotube / carbon black aggregate, which is different from Preparation Example 1 only in that 0.8 wt% of sebacoyl dihydrazide is replaced by a mixture of 0.8 wt% of sebacoyl dihydrazide, isophthaloyl dihydrazide and SUMILINK @ 200 (in this mixture, the mass ratio of sebacoyl dihydrazide, isophthaloyl dihydrazide to SUMILINK @ 200 is 2:4:4), and the other steps are exactly the same as those in the preparation example.

[0125] As Figure 6 shown, this aggregate can not only maintain the large aspect ratio of the carbon nanotubes themselves, but also the carbon nanotubes are more evenly dispersed in the carbon black.

[0126] Preparation Example 7 This preparation example provides a modified carbon nanotube / carbon black aggregate, which is different from Preparation Example 1 only in that the content of sebacic acid dihydrazide is reduced to 0.4 wt %, and the other steps are completely consistent with Example 1.

[0127] Preparation Example 8 This preparation example provides a modified carbon nanotube / carbon black aggregate, which is different from Preparation Example 1 only in that the content of sebacic acid dihydrazide is increased to 1.2 wt %, and the other steps are exactly the same as Preparation Example 1.

[0128] Preparation Example 9 This preparation example provides a modified carbon nanotube / carbon black aggregate, which differs from Preparation Example 1 only in that 0.8 wt % of sebacic acid dihydrazide is replaced by 0.8 wt % of compound I-1, and the other steps are completely consistent with Preparation Example 1; wherein the structural formula of compound I-1 is: .

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

[0130] Preparation Example 11 This preparation example provides a modified carbon nanotube / carbon black aggregate, which is different from Preparation Example 1 only in that the content of the carbon nanotubes is 10% of the total mass of the carbon nanotube / carbon black aggregate, and the other steps are exactly the same as Preparation Example 1.

[0131] Preparation Example 12 This preparation example provides a modified carbon nanotube / carbon black aggregate, which differs from Preparation Example 1 only in that the carbon black native particles N330 are replaced with carbon black native particles N660 of equal mass, and the other steps are exactly the same as Preparation Example 1.

[0132] Comparative Preparation Example 1 This comparative example provides a carbon nanotube / carbon black aggregate, which is different from Preparation Example 1 only in that the modification of step (b) is not performed, and the other steps are completely consistent with Preparation Example 1.

[0133] like Figure 7 As shown, it is obvious that a large part of the unmodified carbon nanotubes are entangled together and not well dispersed.

[0134] Test Example 1 Test samples: modified carbon nanotube / carbon black aggregates provided in Preparation Examples 1 to 12, and carbon nanotube / carbon black aggregates provided in Comparative Preparation Example 1.

[0135] 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.

[0136] The test results are shown in Table 2 and Figure 1 to Figure 7 As shown: Table 2

[0137] As shown in Table 2 above, the specific surface area of ​​the modified carbon nanotube / carbon black aggregate of the present invention is (45-112)×10 3 m 2 / kg, the pouring density of carbon nanotubes in the aggregate is 385~413 kg / m 3 , the aspect ratio of carbon nanotubes in the aggregate can be maintained at 5526~5845.

[0138] Example 1 This embodiment provides a tire base rubber material, which is obtained by mixing the following tire base rubber material composition; wherein, as shown in Table 3 below, the tire base rubber material composition includes the following components in parts by weight: Table 3

[0139] The tire base rubber material of this embodiment is prepared by the following steps: (1) One-stage mixing: start the internal mixer, set the rotor speed of the internal mixer to 50 rpm, the mixing pressure to 5.5 MPa, the cooling water temperature to 35°C, the rotor temperature to 35°C, add the raw rubber, modified carbon nanotube / carbon black aggregate, white carbon, activator, antioxidant, tackifying resin and protective wax, mix for 30 seconds, lift the top plug, stay for 12 seconds, press the top plug, mix to a temperature of 140°C, lift the top plug, stay for 12 seconds, press the top plug, wait until the temperature reaches 150°C, discharge the rubber, and obtain the carbon nanotube / carbon black masterbatch.

[0140] (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 base rubber.

[0141] Example 2 This embodiment provides a tire base rubber material, which is different from Example 1 only in that the modified carbon nanotube / carbon black aggregate provided in Preparation Example 1 is replaced with an equal weight portion of the modified carbon nanotube / carbon black aggregate provided in Preparation Example 2.

[0142] Example 3 This embodiment provides a tire base rubber material, which is different from Example 1 only in that the modified carbon nanotube / carbon black aggregate provided in Preparation Example 1 is replaced with an equal weight portion of the modified carbon nanotube / carbon black aggregate provided in Preparation Example 3.

[0143] Example 4 This embodiment provides a tire base rubber material, which is different from Example 1 only in that the modified carbon nanotube / carbon black aggregate provided in Preparation Example 1 is replaced with an equal weight portion of the modified carbon nanotube / carbon black aggregate provided in Preparation Example 4.

[0144] Example 5 This embodiment provides a tire base rubber material, which is different from Example 1 only in that the modified carbon nanotube / carbon black aggregate provided in Preparation Example 1 is replaced with an equal weight portion of the modified carbon nanotube / carbon black aggregate provided in Preparation Example 5.

[0145] Example 6 This embodiment provides a tire base rubber material, which is different from Example 1 only in that the modified carbon nanotube / carbon black aggregate provided in Preparation Example 1 is replaced with an equal weight portion of the modified carbon nanotube / carbon black aggregate provided in Preparation Example 6.

[0146] Example 7 This embodiment provides a tire base rubber material, which is different from Example 1 only in that the raw rubber is a mixture of 90 parts of natural rubber and 10 parts of butadiene rubber; at the same time, the modified carbon nanotube / carbon black aggregate provided in Preparation Example 1 is replaced by an equal weight portion of the modified carbon nanotube / carbon black aggregate provided in Preparation Example 6.

[0147] Example 8 This embodiment provides a tire base rubber material, which is different from Example 1 only in that the modified carbon nanotube / carbon black aggregate provided in Preparation Example 1 is replaced with an equal weight portion of the modified carbon nanotube / carbon black aggregate provided in Preparation Example 7.

[0148] Example 9 This embodiment provides a tire base rubber material, which is different from Example 1 only in that the modified carbon nanotube / carbon black aggregate provided in Preparation Example 1 is replaced with an equal weight portion of the modified carbon nanotube / carbon black aggregate provided in Preparation Example 8.

[0149] Example 10 This embodiment provides a tire base rubber material, which is different from Example 1 only in that the modified carbon nanotube / carbon black aggregate provided in Preparation Example 1 is replaced with an equal weight portion of the modified carbon nanotube / carbon black aggregate provided in Preparation Example 9.

[0150] Embodiment 11 This embodiment provides a tire base rubber material, which is different from Example 1 only in that the modified carbon nanotube / carbon black aggregate provided in Preparation Example 1 is replaced with an equal weight portion of the modified carbon nanotube / carbon black aggregate provided in Preparation Example 10.

[0151] Example 12 This embodiment provides a tire base rubber material, which is different from Example 1 only in that the modified carbon nanotube / carbon black aggregate provided in Preparation Example 1 is replaced with an equal weight portion of the modified carbon nanotube / carbon black aggregate provided in Preparation Example 11.

[0152] Embodiment 13 This embodiment provides a tire base rubber material, which is different from Example 1 only in that the modified carbon nanotube / carbon black aggregate provided in Preparation Example 1 is replaced with an equal weight portion of the modified carbon nanotube / carbon black aggregate provided in Preparation Example 12.

[0153] Embodiment 14 This embodiment provides a tire base rubber material, which is different from the embodiment 1 only in that 0.5 parts of silane coupling agent Si-69 is added.

[0154] Embodiment 15 This embodiment provides a tire base rubber material, which is different from the embodiment 1 only in that 1 part of silane coupling agent Si-747 is added.

[0155] Comparative Examples 1 to 5 These comparative examples provide tire base rubber materials of different components, which are prepared using corresponding tire base rubber compositions, as shown in Table 4 below. The tire base rubber compositions include the following components in parts by weight: Table 4

[0156] The preparation methods of the tire base rubber materials provided in the above Comparative Examples 1 to 5 are consistent with that in Example 1.

[0157] Comparative Examples 6-10 These comparative examples provide tire base rubber materials of different components, which are prepared using corresponding tire base rubber compositions, as shown in Table 5 below. The tire base rubber compositions include the following components in parts by weight: Table 5

[0158] The preparation methods of the tire base compounds provided in Comparative Examples 6 to 10 are the same as those in Example 1.

[0159] Test Example 2 Test samples: the tire base compounds provided in Examples 1 to 15 and the tire base compounds provided in Comparative Examples 1 to 10.

[0160] Test method: The DMA test conditions are 10 Hz, 7% ± 2; the tensile test standard adopts GB / T 528-2009. Among them, M300 is the 300% modulus at 100% elongation of the vulcanizate; TB is the tensile strength of the vulcanizate; E.B% is the elongation at break of the vulcanizate; tanδ / 60 °C is the loss factor of the vulcanizate at 60 °C.

[0161] The test results are shown in Table 6 below: Table 6

[0162] As shown in Table 6 above, for the tire base compounds provided in Examples 1 to 12, M300 is 12.5 to 13.3 MPa, TB is 29.5 to 30.4 MPa, E.B% is 521 to 539%, and Tanδ is 0.055 to 0.063. This shows that in the preparation process of the modified carbon nanotube / carbon black aggregates of the present invention, in the presence of the modifier, the carbon nanotubes can be more uniformly dispersed among the primary carbon black particles through the jet technology, significantly improving the dispersion performance of the carbon nanotubes. Further, by adding the modified carbon nanotube / carbon black aggregates to the tire base compound composition of the present invention, the interaction between the rubber and the filler is enhanced, the agglomeration of the filler carbon nanotube / carbon black itself is reduced, while providing the mechanical properties and wear resistance of the tire base compound, the heat generation of the tire base compound can be further reduced.

[0163] It can be clearly seen from Comparative Example 1 and Comparative Example 8 above that adding a modifier to the carbon black formulation can reduce the heat generation by 16.7%. From Comparative Example 1, Comparative Example 8 and Example 1, it can be seen that by using the jet technology, adding the modifier to the carbon nanotube / N330 carbon black aggregates during the production of carbon nanotube / N330 carbon black aggregates can further reduce the heat generation, which is 23% lower than that without adding the modifier and 2.8% lower than that of Comparative Example 1. And from Comparative Example 1, Comparative Example 8 and Example 1 above, it can be seen that the addition of the modifier can reduce the heat generation, especially when the modifier is added to the carbon nanotube / N330 carbon black aggregates during the production of carbon nanotube / N330 carbon black aggregates.

[0164] It can be seen from the comparative examples and examples that the single use and combined use of different modifiers all contribute to the heat generation. Comparing Comparative Examples 1 to 7 with Comparative Example 8, the heat generation tanδ decreases significantly.

[0165] It can be seen from Example 1 and Comparative Example 9 that, compared with adding the modifier to the rubber composition in the form of physical blending, the mechanical properties (tensile strength and elongation at break of the vulcanized rubber) of the obtained rubber product are significantly improved, and the heat generation (loss factor of the vulcanized rubber at 60°C) is significantly reduced. That is, compared with Example 1, the addition of the modifier to produce carbon nanotubes / N330 carbon black aggregates can further reduce the heat generation.

[0166] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or replace some or all of the technical features therein by equivalents. However, these modifications or replacements do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

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

2. A tire base rubber composition, characterized in that: The tire base rubber composition comprises the following components by weight: 100 pieces of raw rubber Modified carbon nanotube / carbon black aggregate 20~40 parts 1~12 parts of active agent Accelerator 0.8~6 parts Vulcanizing agent 0.8~6 parts Anti-aging agent 1~5 parts 0.5~3 parts of tackifying resin 0.5~3 parts of protective wax White carbon black 0~15 parts Anti-scorch agent 0~0.3 parts; Wherein, the modified carbon nanotube / carbon black aggregate is obtained by high-temperature jetting of a modifier and carbon nanotube / carbon black aggregate; the modifier is selected from any one or a combination of at least two of the compounds represented by the following formulas I to V: ； Wherein, n and m are each independently selected from a positive integer between 1 and 10; M is selected from an alkali metal and / or an alkaline earth metal; R1 and R2 are each independently selected from or , p is a positive integer between 1 and 5.

3. The tire base rubber composition according to claim 2, characterized in that: The modifier is selected from any one or a combination of at least two of the following compounds: ； and / or, the content of the modifier is 0.05-5% of the total mass of the modified carbon nanotube / carbon black aggregate; And / or, the carbon nanotube / carbon black aggregates are obtained by powder injection of carbon nanotubes and carbon black primary particles; and / or, the content of the carbon nanotubes is 1-10% of the total mass of the carbon nanotube / carbon black aggregate; And / or, the carbon black native particles are N330 carbon black native particles.

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

5. The tire base rubber composition according to claim 4, 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 temperatures for combining to form the pre-agglomerate and the aggregation of the carbon black are independently 800-1000°C.

6. The tire base rubber composition according to claim 4, characterized in that: 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 modified carbon nanotube / carbon black aggregate is 0.1-3 μm.

7. The tire base rubber composition according to claim 2, 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 protective wax comprises microcrystalline wax; And / or, the anti-scorch agent includes anti-scorch agent CTP; And / or, the tire base rubber composition further comprises 0 to 3 parts of a silane coupling agent; And / or, the silane coupling agent includes any one of Si-69, Si-75 or Si-747 or a combination of at least two thereof.

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

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

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

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