Tire sidewall rubber composition, tire sidewall rubber and preparation method thereof

Abstract

The invention provides a tire sidewall rubber composition, a tire sidewall rubber and a preparation method of the tire sidewall rubber, and relates to the technical field of tire manufacturing. The tire sidewall rubber composition is prepared from the following components in parts by weight: 100 parts of raw rubber, 10 to 45 parts of modified carbon nanotube / carbon black aggregate, 1 to 12 parts of active agent, 0.8 to 6 parts of accelerant, 0.8 to 6 parts of vulcanizing agent, 3 to 7 parts of anti-aging agent, 1 to 5 parts of environment-friendly oil, 1 to 4 parts of tackifying resin, 0.8 to 4 parts of tearing resin, 1.5 to 4 parts of protective wax, 0 to 25 parts of white carbon black, 0 to 2.5 parts of silane coupling agent and 0 to 0.3 part of scorch retarder. Wherein the modified carbon nanotube / carbon black aggregate is obtained by carrying out high-temperature jet flow on a modifier and a carbon nanotube / carbon black aggregate. According to the tire sidewall rubber composition disclosed by the invention, the modified carbon nanotube / carbon black aggregate is added, so that the mechanical property of the tire sidewall rubber is remarkably enhanced, heat generation is reduced, and abrasion is improved.

Description

Technical Field

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

[0002] The sidewall of a tire is located on the outer surface of the tire and is between the tread and the bead. The tire sidewall mainly functions to protect the carcass and buffer external impacts, and bears relatively large stresses. If fatigue cracks appear on the sidewall during use, the carcass steel wires inside the tire are easily damaged by air and moisture erosion, and ultimately lead to the damage of the tire. Therefore, the tire sidewall rubber usually needs to have good flexing cut growth resistance performance, and at the same time, good tear resistance, low heat generation, cut resistance, and aging resistance are also required.

[0003] Since carbon nanotubes have a surface structure and chemical composition similar to those of carbon black, the combination of the two is an ideal reinforcing filler that can be used in rubber composites, endowing rubber products with high strength, high wear resistance, high conductivity, high thermal conductivity, etc. However, both carbon nanotubes and carbon black have defects such as small particle size, large specific surface area, high surface energy, and extremely easy agglomeration. In addition, carbon nanotubes in the entangled agglomerate state have not only the strong agglomeration effect of nanoparticles but also a unique entanglement phenomenon; the combination of the two effects makes the carbon nanotube agglomerates more firm and uniform dispersion more difficult. As a result, it is very difficult to directly mix carbon nanotubes and carbon black evenly in the rubber matrix material, that is, it is very easy to aggregate into useless lumps during the mixing process with the rubber material, resulting in the problem of uneven dispersion. This will not only affect the filling and modification effect, but also cannot achieve the synergistic effect of carbon nanotubes and carbon black at all, and will also damage the performance of the rubber material.

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

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

[0006] To solve the above technical problems, the present invention specifically adopts the following technical solutions: In the first aspect, the present invention provides a tire sidewall rubber composition, and the tire sidewall rubber composition includes the following components by weight: 100 parts of raw rubber 10 - 45 parts of modified carbon nanotube / carbon black aggregates 1 - 12 parts of activator 0.8 - 6 parts of accelerator Vulcanizing agent: 0.8 - 6 parts Antioxidant: 3 - 7 parts Environmentally friendly oil: 1 - 5 parts Tackifying resin: 1 - 4 parts Tear resin: 0.8 - 4 parts Protecting wax: 1.5 - 4 parts White carbon black: 0 - 25 parts Silane coupling agent: 0 - 2.5 parts Antiscorching agent: 0 - 0.3 parts; Among them, the modified carbon nanotube / carbon black aggregate is obtained by high-temperature jetting of a modifier and a carbon nanotube / carbon black aggregate; the modifier is selected from any one or a combination of at least two of the compounds shown in the following Formulas I - V: ; Among them, n and m 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 , and p is selected from positive integers 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 0.5 - 5% of the total mass of the modified carbon nanotube / carbon black aggregate.

[0009] Preferably, the carbon nanotube / carbon black aggregate is obtained by powder jetting of 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 primary particles are N375 carbon black primary particles.

[0012] Preferably, the modified carbon nanotube / carbon black aggregate is prepared by the following steps: (a) Through powder jetting, a suspension of carbon nanotubes is sprayed into a carbon black reaction furnace, and a pre-aggregate is formed by the combination of carbon nanotubes and carbon black primary particles; through the aggregation of carbon black, a carbon nanotube / carbon black aggregate is formed; (b) Through high-temperature jetting, the modifier is combined with the carbon nanotube / carbon black aggregate to obtain the modified carbon nanotube / carbon black aggregate.

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

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

[0015] Preferably, in step (a), the temperatures for the combination to form pre-aggregates and aggregates of carbon black are each independently 600-1000 °C.

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

[0017] Preferably, in step (b), the temperature for the combination of the modifier and the carbon nanotube / carbon black aggregates is 100-480 °C.

[0018] Preferably, in step (b), after the combination of the modifier and the carbon nanotube / carbon black aggregates, the following post-treatment steps are further 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 the carbon nanotube / carbon black aggregates.

[0019] Preferably, the mass ratio of the powdery 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 aggregates is 0.1-2.5 μm.

[0022] Preferably, the raw rubber comprises natural rubber and cis-butadiene rubber, and the content of the cis-butadiene rubber accounts for more than 40% of the total weight of the raw 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 comprises insoluble sulfur OT-20.

[0026] Preferably, the anti-aging agent comprises anti-aging agent 4020 and / or anti-aging agent RD.

[0027] Preferably, the environmental protection oil comprises environmental protection aromatic oil and / or naphthenic oil.

[0028] Preferably, the tackifying resin includes any one or a combination of at least two of tert-butylphenol formaldehyde tackifying resin, tert-butylphenol novolak tackifying resin, octylphenol formaldehyde tackifying resin, or Keresin resin.

[0029] Preferably, the tearing resin includes DCPD.

[0030] Preferably, the protective wax includes microcrystalline wax.

[0031] Preferably, the silane coupling agent includes silane coupling agent Si-69.

[0032] Preferably, the scorch retarder includes scorch retarder CTP.

[0033] In a second aspect, the present invention provides a tire sidewall rubber compound, which is obtained by mixing the tire sidewall rubber compound composition as described in the first aspect.

[0034] In a third aspect, the present invention provides a method for preparing a tire sidewall rubber compound as described in the second aspect, and the preparation method includes: (1) Mix the raw rubber, modified carbon nanotube / carbon black aggregate, activator, antioxidant, environmentally friendly aromatic oil, tackifying resin, tearing resin, protective wax, silica, and silane coupling agent, and perform a first-stage mixing to obtain a carbon nanotube / carbon black masterbatch; (2) Mix the carbon nanotube / carbon black masterbatch, vulcanizing agent, accelerator, and scorch retarder, and perform a second-stage mixing to obtain the tire sidewall rubber compound.

[0035] Preferably, in step (1), the first-stage mixing includes successively: lifting the upper ram after mixing for 20 to 40 s, staying for 10 to 15 s, and pressing down the upper ram; lifting the upper ram when the temperature reaches 135 to 145 °C, staying for 10 to 15 s and pressing down the upper ram; discharging the rubber when the temperature reaches 145 to 155 °C.

[0036] Preferably, in step (2), the second-stage mixing includes successively: lifting the upper ram after mixing for 10 to 60 s, staying for 0 to 15 s, and pressing down the upper ram; lifting the upper ram when the temperature reaches 70 to 85 °C, staying for 0 to 15 s and pressing down the upper ram; discharging the rubber when the temperature reaches 100 to 120 °C.

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

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

[0039] (3) In the present invention, the modifier is first used to modify the carbon nanotube / carbon black aggregates and then added to the tire sidewall rubber composition to form a "physical-chemical" double reinforcement mechanism. Compared with the case where the two are only physically blended into the rubber composition later, the tire sidewall rubber has better dispersibility, stronger mechanical properties, and higher stability. Moreover, modifying the carbon nanotube / carbon black aggregates first also has a higher functionalization efficiency from a process perspective, which helps to improve the processing performance. BRIEF DESCRIPTION OF THE DRAWINGS

[0040] In order to more clearly illustrate the specific embodiments of the present invention or the technical solutions in the prior art, the following will briefly introduce the drawings required for the description of the specific embodiments or the prior art. Obviously, the drawings in the following description are some embodiments of the present invention. For those of ordinary skill in the art, other drawings can be obtained based on these drawings without creative efforts.

[0041] Figure 1 SEM image of the modified carbon nanotube / carbon black aggregates obtained in Preparation Example 1.

[0042] Figure 2 SEM image of the modified carbon nanotube / carbon black aggregates obtained in Preparation Example 2.

[0043] Figure 3 SEM image of the modified carbon nanotube / carbon black aggregates obtained in Preparation Example 3.

[0044] Figure 4 SEM image of the modified carbon nanotube / carbon black aggregates obtained in Preparation Example 4.

[0045] Figure 5 SEM image of the modified carbon nanotube / carbon black aggregates obtained in Preparation Example 5.

[0046] Figure 6 SEM image of the unmodified carbon nanotube / carbon black aggregates provided in Comparative Preparation Example 1. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0047] To make the objectives, technical solutions, and advantages of the present invention clearer, the following will clearly and completely describe the technical solutions in the embodiments of the present invention in conjunction with the embodiments of the present invention. Obviously, the described embodiments are part of the embodiments of the present invention, rather than all of the embodiments. The components of the embodiments of the present invention can be arranged and designed in various different configurations.

[0048] It should be noted that, in this article, relational terms such as first and second are only used to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply any actual relationship or order between these entities or operations. Moreover, the term "comprising", "including" or any other variation thereof is intended to cover non-exclusive inclusion, so that a process, method, article or device including a series of elements not only includes those elements, but also includes other elements not explicitly listed, or also includes elements inherent to such process, method, article or device.

[0049] In a first aspect, the present invention provides a tire sidewall rubber composition, and the tire sidewall rubber composition comprises the following components by weight parts: Raw rubber 100 parts Modified carbon nanotube / carbon black aggregate 10 - 45 parts Activator 1 - 12 parts Accelerator 0.8 - 6 parts Vulcanizing agent 0.8 - 6 parts Antioxidant 3 - 7 parts Environmentally friendly aromatic oil 1 - 5 parts Tackifying resin 1 - 4 parts Tear resin 0.8 - 4 parts Protecting wax 1.5 - 4 parts Silica 0 - 25 parts Silane coupling agent 0 - 2.5 parts Antiscorching agent 0 - 0.3 parts; Wherein, the modified carbon nanotube / carbon black aggregate is obtained by high-temperature jet of a modifier and a carbon nanotube / carbon black aggregate; the modifier is selected from any one or a combination of at least two of the compounds shown in the following Formula I - 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 are each independently selected from or , and p is selected from positive integers between 1 and 5.

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

[0051] As an alternative embodiment, m is selected from positive integers between 1 and 10, and can be, for example, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10.

[0052] As an alternative embodiment, p is selected from positive integers between 1 and 5, and can be, for example, 1, 2, 3, 4, 5.

[0053] As an alternative embodiment, M is selected from alkali metals and / or alkaline earth metals, and can be, for example, Li, Na, K, Mg, Ca, etc., and preferably Na.

[0054] In the present invention, during the preparation 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 nanotubes can be more uniformly dispersed in the carbon black primary particles by jet technology, significantly improving the dispersion performance of the carbon nanotubes. Further, the present invention adds the modified carbon nanotube / carbon black aggregate to the tire sidewall rubber composition, enhancing the interaction between the rubber and the filler, reducing the agglomeration of the filler carbon nanotube / carbon black itself, providing the mechanical properties and wear resistance of the tire sidewall rubber, and further reducing the heat generation of the tire sidewall rubber.

[0055] It should be noted that in the present invention, the modifier is first used to modify the carbon nanotube (CNT) / carbon black (CB) aggregate and then added to the rubber matrix. Compared with the case where the two are only physically blended and added to the rubber composition later, the reason for the significant improvement in rubber properties is as follows: 1. Better dispersibility: In the present invention, the modifier is fixed by chemical bonds. The graft modification firmly binds and wraps the coupling agent on the surface of the aggregate through covalent bonds to form a stable surface modification layer. As described above, this chemical bonding can effectively reduce the van der Waals force between the aggregates, reduce the agglomeration tendency, and reduce the risk of CNT breakage, thereby maintaining its original aspect ratio; while only physically adsorbed or weakly interacted (such as hydrogen bonds) on the surface of carbon black, it is easily detached under the high shear force during rubber processing (such as internal mixing, extrusion), resulting in re-agglomeration of carbon black.

[0056] 2. Stronger mechanical properties: The modifier in this application not only forms a CNT-CB hybrid structure as a "bridge", but also can chemically react with the rubber molecular chain at one end while connecting to the CNT / CB aggregate at the other end, forming a strong chemical bonding interface between the CNT / CB aggregate and the rubber, improving the interface bonding ability and endowing the rubber with stronger mechanical properties. When only physically mixed, the interface between the modifier and the rubber only depends on physical adsorption or a small amount of reaction, with low interface bonding strength and poor stress transfer efficiency, which is prone to interface debonding.

[0057] 3. Higher stability: After graft 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. However, the physically mixed coupling agent may migrate due to poor compatibility with the rubber or changes in processing temperature, resulting in uneven local concentration or performance attenuation.

[0058] 4. Higher functionalization efficiency: Chemical grafting can precisely control the coverage density and distribution of the modifier on the surface of the CNT / CB aggregate, making full use of the functional groups (such as amino groups) of the modifier to react with the rubber. In contrast, physically mixed modifiers may randomly adsorb on the surface of the CNT / CB aggregate or the rubber, and some modifiers do not participate in interface bonding subsequently, with low utilization rate.

[0059] 5. Improved processing performance: Chemically grafted CNT / CB aggregates are more easily dispersed in rubber, reducing mixing time and energy consumption, and avoiding CNT breakage caused by high shear force (better retention of aspect ratio). When unmodified CNTs need to be dispersed with higher shear force during mixing, it is easy to cause rubber degradation or CNT structure damage.

[0060] As an optional implementation mode, in the tire sidewall rubber composition, the content of the modified carbon nanotube / carbon black aggregate is 10-45 parts, such as 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts, 16 parts, 17 parts, 18 parts, 19 parts, 20 parts, 21 parts, 22 parts, 23 parts, 24 parts, 25 parts, 26 parts, 27 parts, 28 parts, 29 parts, 30 parts, 31 parts, 32 parts, 33 parts, 34 parts, 35 parts, 36 parts, 37 parts, 38 parts, 39 parts, 40 parts, 41 parts, 42 parts, 43 parts, 44 parts, 45 parts, etc., preferably 20-45 parts, and more preferably 40-45 parts.

[0061] As an optional implementation mode, in the tire sidewall rubber composition, the content of the activator is 1-12 parts, such as 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 3-8 parts, and more preferably 4.5-5.5 parts.

[0062] As an alternative embodiment, in the tire sidewall rubber composition, the content of the accelerator is 0.8 to 6 parts, for example, it can be 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, 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 3 parts, and more preferably 1 to 2 parts.

[0063] As an alternative embodiment, in the tire sidewall rubber composition, the content of the vulcanizing agent is 0.8 to 6 parts, for example, it can be 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, 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 4 parts, and more preferably 1 to 3 parts.

[0064] As an alternative embodiment, in the tire sidewall rubber composition, the content of the anti-aging agent is 3 to 7 parts, for example, it can be 3 parts, 3.2 parts, 3.4 parts, 3.5 parts, 3.6 parts, 3.8 parts, 4 parts, 4.2 parts, 4.4 parts, 4.5 parts, 4.6 parts, 4.8 parts, 5 parts, 5.2 parts, 5.4 parts, 5.5 parts, 5.6 parts, 5.8 parts, 6 parts, 6.2 parts, 6.4 parts, 6.5 parts, 6.6 parts, 6.8 parts, 7 parts, etc., preferably 4 to 6 parts.

[0065] As an alternative embodiment, in the tire sidewall rubber composition, the content of the environmentally friendly oil 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 1 to 3 parts.

[0066] As an alternative embodiment, in the tire sidewall rubber composition, the content of the tackifying resin is 1 to 4 parts, for example, it can be 1 part, 1.2 parts, 1.4 parts, 1.5 parts, 1.6 parts, 1.8 parts, 2 parts, 2.2 parts, 2.4 parts, 2.5 parts, 2.6 parts, 2.8 parts, 3 parts, 3.2 parts, 3.4 parts, 3.5 parts, 3.6 parts, 3.8 parts, 4 parts, etc., preferably 1 to 3 parts.

[0067] As an alternative embodiment, in the tire sidewall rubber composition, the content of the tearing resin is 0.8 to 4 parts, for example, it can be 0.8 part, 0.9 part, 1 part, 1.2 parts, 1.4 parts, 1.5 parts, 1.6 parts, 1.8 parts, 2 parts, 2.2 parts, 2.4 parts, 2.5 parts, 2.6 parts, 2.8 parts, 3 parts, 3.2 parts, 3.4 parts, 3.5 parts, 3.6 parts, 3.8 parts, 4 parts, etc., and preferably 0.8 to 2 parts.

[0068] As an alternative embodiment, in the tire sidewall rubber composition, the content of the protective wax is 1.5 to 4 parts, for example, it can be 1.5 parts, 1.6 parts, 1.8 parts, 2 parts, 2.2 parts, 2.4 parts, 2.5 parts, 2.6 parts, 2.8 parts, 3 parts, 3.2 parts, 3.4 parts, 3.5 parts, 3.6 parts, 3.8 parts, 4 parts, etc., and preferably 2 to 3 parts.

[0069] As an alternative embodiment, in the tire sidewall rubber composition, the content of the silica is 0 to 25 parts, for example, it can be 0, 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, 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts, 16 parts, 17 parts, 18 parts, 19 parts, 20 parts, 21 parts, 22 parts, 23 parts, 24 parts, 25 parts, etc.

[0070] As an alternative embodiment, in the tire sidewall rubber composition, the content of the silane coupling agent is 0 to 2.5 parts, for example, it can be 0 part, 0.1 part, 0.2 part, 0.4 part, 0.5 part, 0.6 part, 0.7 part, 0.8 part, 0.9 part, 1 part, 1.2 parts, 1.4 parts, 1.5 parts, 1.6 parts, 1.8 parts, 2 parts, 2.2 parts, 2.4 parts, 2.5 parts, etc., and preferably 1 to 3 parts.

[0071] As an alternative embodiment, in the tire sidewall rubber composition, the content of the scorch retarder is 0 to 0.3 part, for example, it can be 0 part, 0.01 part, 0.05 part, 0.1 part, 0.15 part, 0.2 part, 0.25 part, 0.3 part, etc., and preferably 0.1 to 0.3 part.

[0072] As an alternative embodiment, the modifier is selected from any one or a combination of at least two of the following compounds: .

[0073] As an alternative embodiment, the content of the modifier is 0.05% to 5% of the total mass of the modified carbon nanotube / carbon black aggregate, and 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.

[0074] As an alternative embodiment, the carbon nanotube / carbon black aggregate is obtained by powder spraying of carbon nanotubes and carbon black primary particles.

[0075] As an alternative embodiment, the content of the carbon nanotubes is 1% to 10% of the total mass of the carbon nanotube / carbon black aggregate, and 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.

[0076] As an alternative embodiment, the carbon black primary particles are N375 carbon black primary particles.

[0077] As an alternative embodiment, the modified carbon nanotube / carbon black aggregate is prepared by the following steps: (a) Through powder spraying, a suspension of carbon nanotubes is sprayed into a carbon black reaction furnace, and a pre-aggregate is formed by the combination between the carbon nanotubes and the carbon black primary particles; through the aggregation of carbon black, a carbon nanotube / carbon black aggregate is formed; (b) Through high-temperature jetting, the modifier is combined with the carbon nanotube / carbon black aggregate to obtain the modified carbon nanotube / carbon black aggregate.

[0078] In the present invention, the powder spraying in step (a) is specifically as follows: the carbon nanotubes are conveyed to an interlocking double helix that can be precisely quantified through mechanical arch breaking, air flow arch breaking devices in a storage bin and a plow blade stirring device at the lower part of the bin. The carbon nanotubes that have passed through the weighing system and the precisely quantified spiral metering enter the mass transfer cavity of a high-speed jet mixer, and are instantaneously mixed with a jet carrier, namely process water. During the movement process, the carbon nanotubes are forced to be dispersed into the jet carrier, and are rapidly diffused into a uniform suspension through pressure change in a diffuser at the tail of the injector, and then conveyed to a pressure atomization system.

[0079] In the present invention, the combination in step (b) specifically refers to: adding a modifier to the suspended carbon nanotube / carbon black aggregate flue gas through high-temperature jet technology; further, after cooling, filtering, and collecting and separating by a main bag filter, the separated tail gas is used for heating a tail gas furnace and power generation in a boiler. Finally, the powdered carbon nanotube / carbon black aggregate is stirred with an appropriate amount of water and a binder in a granulator to granulate it, and then the aggregate particles are sent into a rotary dryer for drying. After removing the moisture, the modified carbon nanotube / carbon black aggregate is finally obtained.

[0080] In the present invention, after the modifier is combined with the carbon nanotube / carbon black aggregate, the aggregate can maintain a large aspect ratio of the carbon nanotubes themselves, exhibit excellent properties of the carbon nanotubes, and at the same time improve the dispersibility, reinforcement, and reaction activity with rubber groups of the carbon nanotubes and carbon black in the rubber matrix.

[0081] As an optional implementation manner, in step (a), the suspension of carbon nanotubes by mass percentage includes: 15% - 25% of carbon nanotubes, such as 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, etc., and the balance is water.

[0082] As an optional implementation manner, in step (a), the injection flow rate of the suspension of carbon nanotubes is 50 - 200 kg / h, such as 50 kg / h, 60 kg / h, 80 kg / h, 100 kg / h, 120 kg / h, 140 kg / h, 150 kg / h, 160 kg / h, 180 kg / h, 200 kg / h, etc.

[0083] As an optional implementation manner, in step (a), the temperatures for forming the pre-aggregate and the aggregation of carbon black are each independently 600 - 1000 °C, such as 600 °C, 620 °C, 640 °C, 650 °C, 660 °C, 680 °C, 700 °C, 720 °C, 740 °C, 760 °C, 780 °C, 800 °C, 820 °C, 840 °C, 860 °C, 880 °C, 900 °C, 920 °C, 940 °C, 960 °C, 980 °C, 1000 °C, etc.

[0084] As an optional implementation manner, in step (b), the injection flow rate of the modifier is 20 - 100 kg / h, such as 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.

[0085] As an alternative embodiment, in step (b), the temperature at which the modifier binds to the carbon nanotube / carbon black aggregate is 100-480 °C, for example, it can be 100 °C, 120 °C, 140 °C, 160 °C, 180 °C, 200 °C, 220 °C, 240 °C, 260 °C, 280 °C, 300 °C, 320 °C, 340 °C, 360 °C, 380 °C, 400 °C, 420 °C, 440 °C, 460 °C, 480 °C, etc.

[0086] As an alternative embodiment, in step (b), after the modifier binds to the carbon nanotube / carbon black aggregate, the following post-treatment steps are further included: After cooling, filtering and collecting and separating, a powdery product is obtained; the powdery product, binder and water are mixed, granulated and then dried to obtain the modifier and the carbon nanotube / carbon black aggregate.

[0087] As an alternative embodiment, the mass ratio of the powdery product, binder and water is (80-100):(0.1-2):(0.01-10); Among them, "80-100" can be, for example, 80, 82, 84, 85, 86, 88, 90, 92, 94, 95, 96, 98, 100; Among them, "0.1-2" can be, for example, 0.1, 0.2, 0.4, 0.6, 0.8, 1, 1.2, 1.4, 1.5, 1.6, 1.8, 2, etc.; Among them, "0.01-10" can be, for example, 0.01, 0.02, 0.05, 0.08, 0.1, 0.2, 0.3, 0.4, 0.6, 0.8, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, etc.

[0088] As an alternative embodiment, the binder is selected from lignin and / or molasses.

[0089] As an alternative embodiment, the particle size of the modified carbon nanotube / carbon black aggregate is 0.1-2.5 μm, for example, it can be 0.1 μm, 0.2 μm, 0.4 μm, 0.5 μm, 0.6 μm, 0.8 μm, 1 μm, 1.2 μm, 1.4 μm, 1.5 μm, 1.6μm, 1.8 μm, 2 μm, 2.2 μm, 2.4 μm, 2.5 μm, etc.

[0090] As an alternative embodiment, the raw rubber includes natural rubber and cis-butadiene rubber, and the content of the cis-butadiene rubber accounts for more than 40% of the total weight of the raw rubber, for example, it can be 40%, 42%, 44%, 46%, 48%, 50%, 52%, 54%, 56%, 58%, 60%, 65%, 70%, etc.

[0091] As a preferred embodiment, the raw rubber comprises, by mass percentage: 40-60% of natural rubber and 40-60% of cis-butadiene rubber.

[0092] As a preferred embodiment, based on the total mass of the raw rubber being 100%, the content of natural rubber is 40-60%, for example, it can be 40%, 42%, 44%, 45%, 46%, 48%, 50%, 52%, 54%, 55%, 56%, 58%, 60%, etc.

[0093] As a preferred embodiment, based on the total mass of the raw rubber being 100%, the content of cis-butadiene rubber is 40-60%, for example, it can be 40%, 42%, 44%, 45%, 46%, 48%, 50%, 52%, 54%, 55%, 56%, 58%, 60%, etc.

[0094] As an alternative embodiment, the activator comprises stearic acid and / or zinc oxide.

[0095] As a preferred embodiment, the activator consists of stearic acid and zinc oxide.

[0096] As a preferred embodiment, when the activator consists of stearic acid and zinc oxide, the mass ratio of stearic acid to zinc oxide is 1:(3-5), for example, it can be 1:3, 1:3.2, 1:3.4, 1:3.5, 1:3.6, 1:3.8, 1:4, 1:4.2, 1:4.4, 1:4.5, 1:4.6, 1:4.8, 1:5, etc.

[0097] As an alternative embodiment, the accelerator comprises accelerator NS.

[0098] As an alternative embodiment, the vulcanizing agent comprises insoluble sulfur OT-20.

[0099] As an alternative embodiment, the anti-aging agent comprises anti-aging agent 4020 and / or anti-aging agent RD.

[0100] As an alternative embodiment, the anti-aging agent consists of anti-aging agent 4020 and anti-aging agent RD.

[0101] As an alternative embodiment, when the anti-aging agent consists of anti-aging agent 4020 and anti-aging agent RD, the mass ratio of anti-aging agent 4020 to anti-aging agent RD is (3-5):1, for example, it can be 3:1, 3.2:1, 3.4:1, 3.5:1, 3.6:1, 3.8:1, 4:1, 4.2:1, 4.4:1, 4.6:1, 4.8:1, 5:1, etc.

[0102] As an alternative embodiment, the environment-friendly oil includes environment-friendly aromatic oil and / or naphthenic oil.

[0103] As a preferred embodiment, the environment-friendly oil is environment-friendly aromatic oil.

[0104] As an alternative embodiment, the environment-friendly aromatic oil includes V700.

[0105] As an alternative embodiment, the tackifying resin includes any one or a combination of at least two of tert-butylphenol formaldehyde tackifying resin, tert-butylphenol phenolic tackifying resin, octylphenol formaldehyde tackifying resin or Keresin resin.

[0106] As an alternative embodiment, the tearing resin includes DCPD.

[0107] As an alternative embodiment, the protective wax includes microcrystalline wax.

[0108] As an alternative embodiment, the silane coupling agent includes silane coupling agent Si-69.

[0109] As an alternative embodiment, the scorch retarder includes scorch retarder CTP.

[0110] In a second aspect, the present invention provides a tire sidewall rubber compound, which is obtained by mixing the tire sidewall rubber compound composition as described in the first aspect.

[0111] In a third aspect, the present invention provides a preparation method of a tire sidewall rubber compound as described in the second aspect, and the preparation method of the tire sidewall rubber compound includes: (1) Mixing the raw rubber, modified carbon nanotube / carbon black aggregate, activator, antioxidant, environment-friendly aromatic oil, tackifying resin, tearing resin, protective wax, white carbon black and silane coupling agent, and performing a first-stage mixing to obtain a carbon nanotube / carbon black masterbatch; (2) Mixing the carbon nanotube / carbon black masterbatch, vulcanizing agent, accelerator and scorch retarder, and performing a second-stage mixing to obtain the tire sidewall rubber compound.

[0112] As an alternative embodiment, in step (1), the mixing is as follows: Start the internal mixer, set the rotor speed of the internal mixer to 40 - 55 rpm (e.g., it can be 40 rpm, 42 rpm, 44 rpm, 45 rpm, 46 rpm, 48 rpm, 50 rpm, 52 rpm, 54 rpm, 55 rpm, etc.), the mixing pressure to 4.5 - 6.5 MPa (e.g., it can be 4.5 MPa, 4.6 MPa, 4.8 MPa, 5 MPa, 5.2 MPa, 5.4 MPa, 5.5 MPa, 5.6 MPa, 5.8 MPa, 6 MPa, 6.2 MPa, 6.4 MPa, 6.5 MPa, etc.), the cooling water temperature to 30 - 40 °C (e.g., it can be 30 °C, 32 °C, 34 °C, 35 °C, 36 °C, 38 °C, 40 °C, etc.), the rotor temperature to 30 - 40 °C (e.g., it can be 30 °C, 32 °C, 34 °C, 35 °C, 36 °C, 38 °C, 40 °C, etc.), and add the raw rubber, modified carbon nanotube / carbon black aggregates, activator, antioxidant, environmentally friendly aromatic oil, tackifying resin, tearing resin, protective wax, white carbon black, and silane coupling agent.

[0113] As an alternative embodiment, in step (1), the first - stage mixing includes the following steps carried out in sequence: Lift the top plug after mixing for 20 - 40 s (e.g., it can be 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.), stay for 10 - 15 s (e.g., it can be 10 s, 11 s, 12 s, 13 s, 14 s, 15 s, etc.), and then press down the top plug; Lift the top plug when the temperature reaches 135 - 145 °C (e.g., it can be 135 °C, 136 °C, 138 °C, 140 °C, 142 °C, 144 °C, 145 °C, etc.), stay for 10 - 15 s (e.g., it can be 10 s, 11 s, 12 s, 13 s, 14 s, 15 s, etc.), and then press down the top plug; Discharge the rubber when the temperature reaches 145 - 155 °C (e.g., it can be 145 °C, 146 °C, 148 °C, 150 °C, 152 °C, 154 °C, 155 °C, etc.).

[0114] As an alternative embodiment, in step (2), the mixing is as follows: Start the internal mixer, set the rotor speed of the internal mixer to 15 - 40 rpm (such as 15 rpm, 16 rpm, 18 rpm, 20 rpm, 22 rpm, 24 rpm, 25 rpm, 26 rpm, 28 rpm, 30 rpm, 32 rpm, 34 rpm, 35 rpm, 36 rpm, 38 rpm, 40 rpm, etc.), the mixing pressure to 4.0 - 6.0 MPa (such as 4.0 MPa, 4.2 MPa, 4.4 MPa, 4.5 MPa, 4.6 MPa, 4.8 MPa, 5.0 MPa, 5.2 MPa, 5.4 MPa, 5.6 MPa, 5.8 MPa, 6.0 MPa, etc.), the cooling water temperature to 30 - 40°C (such as 30°C, 32°C, 34°C, 35°C, 36°C, 38°C, 40°C, etc.), and the rotor temperature to 30 - 45°C (such as 30°C, 32°C, 34°C, 35°C, 36°C, 38°C, 40°C, 42°C, 44°C, 45°C, etc.), and then add the carbon nanotube / carbon black masterbatch, vulcanizing agent, accelerator, and scorch retarder.

[0115] As an alternative embodiment, in step (2), the secondary mixing includes the following steps carried out in sequence: After mixing for 10 - 60 s (such as 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.), lift the top plug, stay for 0 - 15 s (such as 0 s, 1 s, 2 s, 4 s, 5 s, 6 s, 8 s, 10 s, 12 s, 14 s, 15 s, etc.), and then lower the top plug; when the temperature reaches 70 - 85°C (such as 70°C, 72°C, 74°C, 75°C, 76°C, 78°C, 80°C, 82°C, 84°C, 85°C, etc.), lift the top plug, stay for 0 - 15 s (such as 0 s, 1 s, 2 s, 4 s, 5 s, 6 s, 8 s, 10 s, 12 s, 14 s, 15 s, etc.), and then lower the top plug; when the temperature reaches 100 - 120°C (such as 100°C, 102°C, 104°C, 105°C, 106°C, 108°C, 110°C, 115°C, 120°C, etc.), discharge the rubber.

[0116] The following will, in conjunction with embodiments, elaborate in detail some embodiments of the present invention. Without conflict, the following embodiments and the features in the embodiments can be combined with each other. For the raw materials used in the embodiments and comparative examples of the present invention, where no specific conditions are indicated, they are carried out according to conventional conditions or the conditions recommended by the manufacturer. For the reagents or instruments whose manufacturers are not indicated, they are all conventional products that can be obtained by purchasing in the market.

[0117] The raw materials used in the following examples are shown in Table 1 below.

[0118] Table 1

[0119] Among them, the structural formula of SUMILINK @ 200 is .

[0120] 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, through powder injection technology, carbon nanotubes are mixed evenly with process water, and the concentration of the carbon nanotube suspension is controlled to be 20 wt%; subsequently, the carbon nanotube suspension is sprayed into a carbon black reaction furnace, the spraying flow rate of the carbon nanotube suspension is controlled to be 150 kg / h, the temperature in the carbon black reaction furnace is set to 900 °C, and a pre-aggregate is formed by the combination between the carbon nanotubes and the carbon black primary particles N375; then, through the aggregation of carbon black, a carbon nanotube / carbon black aggregate is formed; wherein, the content of the carbon nanotubes is 4% of the total mass of the carbon nanotube / carbon black aggregate; (b) Through high-temperature jet technology, 0.8 wt% of sebacic dihydrazide is added to the reaction furnace in step (a), the spraying flow rate of sebacic dihydrazide is controlled to be 80 kg / h, the temperature in the carbon black reaction furnace is set to 380 °C, and it is combined with the carbon nanotube / carbon black aggregate to obtain the modified carbon nanotube / carbon black aggregate; after cooling, filtering and collecting and separating, a powdery product is obtained; the powdery product, lignin and water with a mass ratio of 100:0.1:0.1 are mixed, granulated and then dried to obtain the modifier and the carbon nanotube / carbon black aggregate.

[0121] As Figure 1 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 2 This preparation example provides a modified carbon nanotube / carbon black aggregate, which is only different from Preparation Example 1 in that 0.8 wt% of sebacic dihydrazide is replaced by 0.8 wt% of isophthaloyl dihydrazide, and other steps are exactly the same as those in Preparation Example 1.

[0123] As Figure 2 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 3 This preparation example provides a modified carbon nanotube / carbon black aggregate, which is only different from Preparation Example 1 in that 0.8 wt% of sebacic dihydrazide is replaced by 0.8 wt% of SUMILINK @ 200, and other steps are exactly the same as those in Preparation Example 1.

[0125] 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.

[0126] Preparation Example 4 This preparation example provides a modified carbon nanotube / carbon black aggregate, which is only different from Preparation Example 1 in that 0.8 wt% of sebacic dihydrazide is replaced by a mixture of 0.8 wt% of sebacic dihydrazide and isophthaloyl dihydrazide (in this mixture, the mass ratio of sebacic dihydrazide to isophthaloyl dihydrazide is 1:1), and other steps are exactly the same as those in Preparation Example 1.

[0127] 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.

[0128] Preparation Example 5 This preparation example provides a modified carbon nanotube / carbon black aggregate, which is only different from Preparation Example 1 in that 0.8 wt% of sebacic 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 other steps are exactly the same as those in Preparation Example 1.

[0129] 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.

[0130] Preparation Example 6 This preparation example provides a modified carbon nanotube / carbon black aggregate, which is different from Preparation Example 1 only in that the content of sebacic acid dihydrazide is reduced to 0.4 wt %, and the other steps are exactly the same as Preparation Example 1.

[0131] 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 increased to 1.2 wt %, and the other steps are exactly the same as Preparation Example 1.

[0132] Preparation Example 8 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: .

[0133] Preparation Example 9 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.

[0134] 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 10% of the total mass of the carbon nanotube / carbon black aggregate, and the other steps are exactly the same as Preparation Example 1.

[0135] Preparation Example 11 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 N375 are replaced with carbon black native particles N330 of equal mass, and the other steps are exactly the same as Preparation Example 1.

[0136] Comparative Preparation Example 1 This comparative example provides a carbon nanotube / carbon black aggregate, which is different from Example 1 only in that the modification of step (b) is not performed, and the other steps are completely consistent with Preparation Example 1.

[0137] like Figure 6 As shown, it is obvious that a large part of the unmodified carbon nanotubes are entangled together and not well dispersed.

[0138] Test Example 1 Test samples: modified carbon nanotube / carbon black aggregates provided in Preparation Examples 1 to 11, and carbon nanotube / carbon black aggregates provided in Comparative Preparation Example 1.

[0139] Testing method: Total specific surface area BET-N2, apparent density of carbon nanotube / carbon black aggregates GB3778-2011, aspect ratio of carbon nanotubes in aggregates is measured by SEM.

[0140] The test results are shown in Table 2 below and Figures 1 to 6 as follows: Table 2

[0141] As shown in Table 2 above, the specific surface area of the modified carbon nanotube / carbon black aggregates of the present invention is (95~135)×10 3 m 2 / kg, the apparent density distribution of carbon nanotube / carbon black aggregates is 315~368 kg / m 3 , and the aspect ratio of carbon nanotubes in the aggregates can be maintained at 5598~5689.

[0142] Example 1 This example provides a tire sidewall rubber compound, which is obtained by mixing the following tire sidewall rubber compound composition; wherein, as shown in Table 3 below, the tire sidewall rubber compound composition includes the following components by weight: Table 3

[0143] The tire sidewall rubber compound of this example is prepared by the following steps: (1) First-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 aggregates, activator, antioxidant, environmental aromatic oil, tackifying resin, tearing resin, protective wax and silane coupling agent, lift the upper ram after mixing for 30 s, stay for 12 s, lower the upper ram, mix until the temperature reaches 140°C and lift the upper ram, stay for 12 s and lower the upper ram, and discharge the rubber when the temperature reaches 150°C to obtain the carbon nanotube / carbon black masterbatch.

[0144] (2) Second-stage mixing: Start the internal mixer, set the rotor speed of the internal mixer to 30 rpm, the mixing pressure to 5.0 MPa, the cooling water temperature to 35°C, the rotor temperature to 40°C, add the carbon nanotube / carbon black masterbatch, vulcanizing agent, accelerator and scorch retarder, lift the upper ram after mixing for 35 s, stay for 8 s and lower the ram, mix until the temperature reaches 78°C and lift the upper ram, stay for 7 s and lower the upper ram, and discharge the rubber when the rubber temperature reaches 110°C, take off the sheet and cool it to room temperature to obtain the tire sidewall rubber compound.

[0145] Example 2 This embodiment provides a tire sidewall rubber compound, which is only different from that of Embodiment 1 in that the modified carbon nanotube / carbon black aggregate provided in Preparation Example 1 is replaced with the modified carbon nanotube / carbon black aggregate provided in Preparation Example 2 in equal weight parts.

[0146] Embodiment 3 This embodiment provides a tire sidewall rubber compound, which is only different from that of Embodiment 1 in that the modified carbon nanotube / carbon black aggregate provided in Preparation Example 1 is replaced with the modified carbon nanotube / carbon black aggregate provided in Preparation Example 3 in equal weight parts.

[0147] Embodiment 4 This embodiment provides a tire sidewall rubber compound, which is only different from that of Embodiment 1 in that the modified carbon nanotube / carbon black aggregate provided in Preparation Example 1 is replaced with the modified carbon nanotube / carbon black aggregate provided in Preparation Example 4 in equal weight parts.

[0148] Embodiment 5 This embodiment provides a tire sidewall rubber compound, which is only different from that of Embodiment 1 in that the modified carbon nanotube / carbon black aggregate provided in Preparation Example 1 is replaced with the modified carbon nanotube / carbon black aggregate provided in Preparation Example 5 in equal weight parts.

[0149] Embodiment 6 This embodiment provides a tire sidewall rubber compound, which is only different from that of Embodiment 1 in that the modified carbon nanotube / carbon black aggregate provided in Preparation Example 1 is replaced with the modified carbon nanotube / carbon black aggregate provided in Preparation Example 5, and its content is reduced to 20 parts; at the same time, 20 parts of silica are added additionally.

[0150] Embodiment 7 This embodiment provides a tire sidewall rubber compound, which is only different from that of Embodiment 1 in that the modified carbon nanotube / carbon black aggregate provided in Preparation Example 1 is replaced with the modified carbon nanotube / carbon black aggregate provided in Preparation Example 6 in equal weight parts.

[0151] Embodiment 8 This embodiment provides a tire sidewall rubber compound, which is only different from that of Embodiment 1 in that the modified carbon nanotube / carbon black aggregate provided in Preparation Example 1 is replaced with the modified carbon nanotube / carbon black aggregate provided in Preparation Example 7 in equal weight parts.

[0152] Embodiment 9 This embodiment provides a tire sidewall rubber compound, which is only different from that of Embodiment 1 in that the modified carbon nanotube / carbon black aggregate provided in Preparation Example 1 is replaced with the modified carbon nanotube / carbon black aggregate provided in Preparation Example 8 in equal weight parts.

[0153] Embodiment 10 This embodiment provides a tire sidewall rubber compound, which is only different from that of Embodiment 1 in that the modified carbon nanotube / carbon black aggregate provided in Preparation Example 1 is replaced with the modified carbon nanotube / carbon black aggregate provided in Preparation Example 9 in equal weight parts.

[0154] Embodiment 11 This embodiment provides a tire sidewall rubber compound, which is only different from that of Embodiment 1 in that the modified carbon nanotube / carbon black aggregate provided in Preparation Example 1 is replaced with the modified carbon nanotube / carbon black aggregate provided in Preparation Example 10 in equal weight parts.

[0155] Embodiment 12 This embodiment provides a tire sidewall rubber compound, which is only different from that of Embodiment 1 in that the modified carbon nanotube / carbon black aggregate provided in Preparation Example 1 is replaced with the modified carbon nanotube / carbon black aggregate provided in Preparation Example 11 in equal weight parts.

[0156] Comparative Examples 1-5 These comparative examples provide tire sidewall rubber compounds with different components, which are made using the corresponding tire sidewall rubber compound compositions. As shown in Table 4 below, the tire sidewall rubber compound compositions include the following components by weight parts: Table 4

[0157] The preparation methods of the tire sidewall rubber compounds provided in the above Comparative Examples 1-5 are the same as those of Embodiment 1.

[0158] Comparative Examples 6-9 These comparative examples provide tire sidewall rubber compounds with different components, which are made using the corresponding tire sidewall rubber compound compositions. As shown in Table 5 below, the tire sidewall rubber compound compositions include the following components by weight parts: Table 5

[0159] The preparation methods of the tire sidewall rubber compounds provided in the above Comparative Examples 6-9 are the same as those of Embodiment 1.

[0160] Test Example 2 Test samples: The tire sidewall rubber compounds provided in Embodiments 1-12, and the tire sidewall rubber compounds provided in Comparative Examples 1-9.

[0161] Test method: The DMA test conditions are 10 Hz, 7% ± 2; the tensile test standard adopts GB / T528-2009. 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.

[0162] The test results are shown in Table 6 below: Table 6

[0163] As shown in Table 6 above, the M300 of the tire sidewall rubber compounds provided in Examples 1 to 6 is 4.5 to 5.7 MPa, the TB is 21.3 to 23.5 MPa, the E.B% is 675 to 722%, and the Tanδ is 0.067 to 0.146. This shows that in 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 uniformly dispersed in the carbon black primary particles through jet technology, significantly improving the dispersion performance of the carbon nanotubes. Further, by adding the modified carbon nanotube / carbon black aggregates to the tire sidewall rubber 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 sidewall rubber compound, and the heat generation of the tire sidewall rubber compound can be further reduced.

[0164] It can be clearly seen from the above Comparative Example 1 and Comparative Example 7 that adding a modifier to the carbon black formulation can reduce heat generation by 16.7%. From Comparative Example 1, Comparative Example 8 and Example 1, it can be seen that by jet technology, adding the modifier to the carbon nanotube / N375 carbon black aggregates during the production of carbon nanotube / N375 carbon black aggregates can further reduce heat generation, which is 12.5% lower than that without adding a modifier and 10.9% lower than that of Comparative Example 1; moreover, from Comparative Example 1, Comparative Example 7 and Example 1, it can be seen that adding a modifier can reduce heat generation, especially when the modifier is added to the carbon nanotube / N375 carbon black aggregates during the production of carbon nanotube / N375 carbon black aggregates.

[0165] It can also be seen from the comparative examples and examples that the single use and combined use of different modifiers both contribute to heat generation. Comparing Comparative Examples 1 to 6 with Comparative Example 7, the heat generation tanδ decreases significantly.

[0166] It can be seen from Example 1 and Comparative Example 8 that first compounding the modifier with the carbon nanotube / carbon black aggregates, compared with simply adding them to the rubber composition in a physical blending form, the mechanical properties of the obtained rubber product (tensile strength at break and elongation at break of the vulcanizate) are significantly improved, and at the same time the heat generation (loss factor of the vulcanizate at 60 °C) is significantly reduced. That is, compared with Example 1, adding the carbon nanotube / N375 carbon black aggregates produced by the modifier and the carbon nanotube / N375 carbon black aggregates can further reduce heat generation by 10.7%.

[0167] 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 foregoing embodiments, those of ordinary skill in the art should understand that they can still modify the technical solutions described in the foregoing embodiments, or perform equivalent replacements on some or all of the technical features; and these modifications or replacements do not make the essence of the corresponding technical solutions 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 sidewall rubber composition, characterized in that: The modified carbon nanotube / carbon black aggregate is obtained by high-temperature jetting of a modifier and carbon nanotube / carbon black aggregate; the modifier is selected from any one or a combination of at least two of the compounds represented by the following formulas I to V: ； Wherein, n and m are each independently selected from a positive integer between 1 and 10; M is selected from an alkali metal and / or an alkaline earth metal; R1 and R2 are each independently selected from or , p is selected from a positive integer between 1 and 5.

2. A tire sidewall rubber composition, characterized in that: The tire sidewall rubber composition comprises the following components by weight: 100 pieces of raw rubber Modified carbon nanotube / carbon black aggregate 10~45 parts 1~12 parts of active agent Accelerator 0.8~6 parts Vulcanizing agent 0.8~6 parts 3~7 parts of antioxidant 1~5 parts of environmentally friendly oil 1~4 parts of tackifying resin Tear resin 0.8~4 parts 1.5~4 parts of protective wax White carbon black 0~25 parts Silane coupling agent 0~2.5 parts Anti-scorch agent 0~0.3 parts; Wherein, the modified carbon nanotube / carbon black aggregate is obtained by high-temperature jetting of a modifier and carbon nanotube / carbon black aggregate; the modifier is selected from any one or a combination of at least two of the compounds represented by the following formulas I to V: ； Wherein, n and m are each independently selected from a positive integer between 1 and 10; M is selected from an alkali metal and / or an alkaline earth metal; R1 and R2 are each independently selected from or , p is selected from a positive integer between 1 and 5.

3. The tire sidewall 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 0.5-5% 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 N375 carbon black native particles.

4. The tire sidewall 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 sidewall 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 each independently 600-1000°C.

6. The tire sidewall 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 0.1-2.5 μm.

7. The tire sidewall rubber composition according to claim 2, characterized in that: The raw rubber comprises natural rubber and butadiene rubber, and the content of the butadiene rubber accounts for more than 40% of the total weight of the raw 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 environmentally friendly oil includes environmentally friendly aromatic oil and / or naphthenic oil; And / or, the environmentally friendly aromatic oil includes V700; 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 tearing resin comprises DCPD; and / or, the protective wax comprises microcrystalline wax; And / or, the silane coupling agent includes silane coupling agent Si-69; And / or, the anti-scorch agent includes anti-scorch agent CTP.

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

9. A method for preparing a tire sidewall rubber material 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, environmentally friendly aromatic oil, tackifying resin, tearing resin, protective wax, white carbon black and silane coupling agent, 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 scorch retarder are mixed and kneaded in two stages to obtain the tire sidewall rubber material.

10. The method for preparing a tire sidewall rubber material 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 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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