Carbon black-silicate hybrid particles and their preparation method and application

Abstract

The present invention discloses a carbon black-silicate hybrid particle and its preparation method and application, belonging to the technical field of carbon black production and preparation. The present invention introduces silicon-based particles at the front end of carbon black production and manufacturing to form hybrid particles in which silicon-based inorganic particles penetrate into the gaps of carbon black aggregates or adsorb on the surface of carbon black. This can achieve hybrid compounding of micron- or even nanometer-scale carbon-silicon particles, thereby obtaining highly dispersed carbon black-silicate hybrid particles, thereby achieving dispersion of hybrid particles in polymers such as rubber on a smaller scale; at the same time, it can remain unchanged in the existing carbon black production process and does not increase the environmental pressure of exhaust gas treatment. The preparation method provided by the present invention can obtain highly dispersed carbon black-silicate hybrid particles, which are used to prepare rubber materials and can improve the mechanical properties of rubber materials.

Description

Technical Field

[0001] The present invention belongs to the technical field of carbon black production and preparation, and in particular relates to carbon black-silicate hybrid particles and a preparation method and application thereof. Background Art

[0002] Carbon black is an inorganic filler for rubber, primarily serving as a reinforcement and a key factor in determining the ultimate performance of rubber composites. However, pure carbon black is relatively expensive. Therefore, to reduce costs, existing technologies typically mechanically blend carbon black with finished silicon-based fillers (such as silica, kaolin, halloysite, etc.) to prepare composite materials. However, this method results in uneven dispersion of the resulting composite material within the rubber, which can negatively impact the rubber's performance.

[0003] To address the above issues, the existing technology has proposed a method of introducing silicon-based particles into the carbon black production end. For example, patent CN202010945404.3 discloses a dual-phase carbon black production process. This solution mainly involves the reactor section of carbon black preparation, where silicon lattice powder is introduced through process water to generate C-Si dual-phase particles at high temperature. The structure of the C-Si particles can be controlled by adjusting factors such as the flow rate of raw oil, process water flow rate, reactor cracking temperature, and flue gas residence time. However, the subsequent exhaust contains silicon, which has a certain impact on exhaust gas treatment and emissions, and even the exhaust gas combustion heat transfer efficiency. This poses certain environmental emission risks to the existing traditional carbon black production process. Summary of the Invention

[0004] In order to solve the above technical problems, the present invention proposes a carbon black-silicate hybrid particle and a preparation method and application thereof.

[0005] To achieve the above objectives, the present invention provides the following technical solutions:

[0006] The present invention provides a method for preparing carbon black-silicate hybrid particles, comprising the following steps:

[0007] (1) feeding a carbon black structure inhibitor solution and crude oil into a reactor for combustion and cracking reaction, followed by cooling, filtering and crushing to obtain primary carbon black particles;

[0008] (2) mixing silicate and granulation water to obtain a silicate suspension; adding the obtained silicate suspension, the primary carbon black particles obtained in step (1) and the adhesive solution into a granulator for granulation to obtain the carbon black-silicate hybrid particles.

[0009] Technical principle:

[0010] The present invention introduces silicon particles at the front end of carbon black production to form hybrid particles in which silicon inorganic particles penetrate into the voids of carbon black aggregates or adsorb on the surface of carbon black. This can achieve hybrid compounding of micron or even nanometer-scale carbon-silicate particles, thereby obtaining highly dispersed carbon black-silicate hybrid particles, thereby achieving dispersion of hybrid particles in polymers such as rubber on a smaller scale. At the same time, it can do so without changing the existing carbon black production process and without adding additional environmental pressure to exhaust gas treatment.

[0011] Preferably, in step (1), the mass concentration of the carbon black structure inhibitor solution is 0.06-0.10%; the mass content of the carbon black structure inhibitor in the carbon black structure inhibitor solution is 0.04-0.08% of the mass of the crude oil; the flow rate of the carbon black structure inhibitor solution is 10-19 kg / h; the carbon black structure inhibitor in the carbon black structure inhibitor solution is selected from at least one of potassium carbonate and potassium formate.

[0012] Preferably, in step (1), the temperature of the combustion cracking reaction is 1800-2000°C.

[0013] Preferably, in step (2), the silicate is selected from at least one of white carbon black, kaolin, and halloysite.

[0014] Preferably, in step (2), a pretreatment step is further included before the silicate and granulation water are mixed; the pretreatment method includes surface treatment or particle size refinement; and / or,

[0015] The surfactant used for the surface treatment is selected from at least one of bis-[γ-(triethoxysilyl)propyl]tetrasulfide, γ-aminopropyltriethoxysilane, and γ-methacryloxypropyltrimethoxysilane; the amount of the surfactant used is 0.5-1.0% of the mass of the silicate; and / or,

[0016] The particle size refinement method is pot milling for 2 to 5 hours.

[0017] Preferably, in step (2), the mass concentration of silicate in the silicate suspension is 10-30%; the flow rate of the silicate suspension during addition to the granulator is 800-1500 kg / h, and the temperature is 75-85°C.

[0018] Preferably, in step (2), the mass concentration of the adhesive solution is 5-20%; the mass content of the binder in the adhesive solution is 1-3% of the theoretical total mass of carbon black; the flow ratio of the adhesive solution to the silicate suspension is (2-6):1; the adhesive in the adhesive solution is selected from at least one of lignin, molasses, and maltose.

[0019] The present invention provides carbon black-silicate hybrid particles prepared by the preparation method described in the above technical solution.

[0020] The present invention also provides a rubber composite material comprising the carbon black-silicate hybrid particles described in the above technical solution.

[0021] Preferably, based on 100 phr of the raw rubber, the amount of the carbon black-silicate hybrid particles is 10 to 50 phr.

[0022] Compared with the prior art, the present invention has the following advantages and technical effects:

[0023] Existing methods of introducing silicon-based particles into carbon black production produce exhaust gases containing silicon, which can impact exhaust gas treatment and emissions, and even exhaust combustion and heat transfer efficiency, posing environmental risks to conventional carbon black production processes. The preparation method provided by the present invention maintains the existing carbon black production process and does not impose additional environmental pressures on exhaust gas treatment.

[0024] The preparation method provided by the present invention can obtain highly dispersed carbon black-silicate hybrid particles, which are used to prepare rubber materials and can improve the mechanical properties of the rubber materials.

[0025] The present invention introduces low-cost silicate particles, thereby increasing the output of hybrid carbon black and significantly reducing the cost of carbon black particles, thereby obtaining a high-quality and low-cost product. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] The accompanying drawings, which constitute part of the present invention, are provided to provide a further understanding of the present invention. The exemplary embodiments of the present invention and their descriptions are provided to explain the present invention and do not constitute an undue limitation of the present invention. In the accompanying drawings:

[0027] Figure 1 The equipment flow chart of the existing carbon black production process;

[0028] Among them, 1-reaction furnace; 2-main air supply fan; 3-air preheater; 4-raw oil preheater; 5-quenching water pump; 6-raw oil pump; 7-main bag filter; 8-exhaust fan; 9-micron crusher; 10-air supply fan; 11-collecting cyclone separator; 12-return fan; 13-powdered carbon black storage tank; 14-wet granulator; 15-rotary dryer; 16-exhaust bag filter; 17-bucket elevator; 18-rejected product storage tank; 19-screening machine; 20-magnetic separator; 21-screw conveyor; 22-product storage tank; 23-tank truck;

[0029] Figure 2 TEM image of carbon black-silica hybrid particles prepared in Example 1;

[0030] Figure 3 This is a dark field transmission electron microscope image of the carbon black-silica hybrid particles prepared in Example 1;

[0031] Figure 4 Elemental composition analysis of the carbon black-silica hybrid particles prepared in Example 1;

[0032] Figure 5 TEM image of carbon black-silica hybrid particles prepared in Example 2;

[0033] Figure 6 This is a dark field transmission electron microscope image of the carbon black-silica hybrid particles prepared in Example 2;

[0034] Figure 7 Elemental composition analysis of the carbon black-silica hybrid particles prepared in Example 2. DETAILED DESCRIPTION

[0035] The following will clearly and completely describe the technical solutions in the embodiments of the present invention in conjunction with the accompanying drawings. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of the present invention.

[0036] In order to make the above-mentioned objects, features and advantages of the present invention more obvious and easy to understand, the present invention is further described in detail below with reference to the accompanying drawings and specific embodiments.

[0037] An embodiment of the present invention provides a method for preparing carbon black-silicate hybrid particles, comprising the following steps:

[0038] (1) feeding a carbon black structure inhibitor solution and crude oil into a reactor for combustion and cracking reaction, followed by cooling, filtering and crushing to obtain primary carbon black particles;

[0039] (2) mixing silicate and granulation water to obtain a silicate suspension; adding the obtained silicate suspension, the primary carbon black particles obtained in step (1) and the adhesive solution into a granulator for granulation to obtain the carbon black-silicate hybrid particles.

[0040] In a preferred embodiment, in step (1), the mass concentration of the carbon black structure inhibitor solution is 0.06-0.10%; the mass content of the carbon black structure inhibitor in the carbon black structure inhibitor solution is 0.04-0.08% of the mass of the crude oil; the flow rate of the carbon black structure inhibitor solution is 10-19 kg / h; and the carbon black structure inhibitor in the carbon black structure inhibitor solution is selected from at least one of potassium carbonate and potassium formate. The present invention produces highly structured primary carbon black particles by controlling the concentration, dosage, flow rate, and type of the carbon black structure inhibitor solution, thereby facilitating the production of highly dispersed carbon black-silicate hybrid particles. Changing the concentration, dosage, flow rate, or type of the carbon black structure inhibitor solution will affect the structure of the primary carbon black particles, and ultimately affect the dispersibility of the carbon black-silicate hybrid particles.

[0041] In a preferred embodiment, in step (1), the temperature of the combustion cracking reaction is 1800-2000°C.

[0042] In a preferred embodiment, in step (2), the granulation water is deionized water.

[0043] In a preferred embodiment, in step (2), the silicate is selected from at least one of white carbon black, kaolin, and halloysite. By introducing low-cost silicate particles, the present invention can significantly reduce the cost of carbon black particles while increasing the yield of hybrid carbon black, thereby obtaining a high-quality and low-cost product.

[0044] In a preferred embodiment, in step (2), a pretreatment step is further included before the silicate and granulation water are mixed; the pretreatment method includes surface treatment or particle size refinement. The present invention improves the compatibility of the silicate with carbon black by pretreating the silicate.

[0045] In a preferred embodiment, the surface treatment comprises a surfactant selected from at least one of bis-[γ-(triethoxysilyl)propyl]tetrasulfide, γ-aminopropyltriethoxysilane, and γ-methacryloxypropyltrimethoxysilane; the amount of the surfactant used is 0.5-1.0% of the mass of the silicate. Using a surfactant for surface treatment has the advantages of preventing particle agglomeration and improving material uniformity and stability.

[0046] In a preferred embodiment, the particle size reduction method is jar milling for 2-5 hours; the grinding balls used in the jar mill are zirconia beads; the mass ratio of the zirconia beads to the silicate is 5:1, and the mass ratio of the large, medium and small zirconia beads is 3:5:2; the jar milling speed is 500-700 rpm. Using jar milling to refine the silicate particle size has the advantage of simple operation.

[0047] In a preferred embodiment, in step (2), the mass concentration of silicate in the silicate suspension is 10-30%; the flow rate of the silicate suspension during addition to the granulator is 800-1500 kg / h, and the temperature is 75-85°C. The concentration and flow rate of the silicate suspension jointly determine the amount of silicate added during the granulation process, and further determine the mass proportion of silicate particles in the carbon black-silicate hybrid particles obtained. If the concentration of the silicate suspension or the flow rate of the silicate suspension is too high, the content of silicate particles in the obtained carbon black-silicate hybrid particles will be too high, which will cause the compatibility of the carbon black-silicate hybrid particles with the rubber matrix to decrease, and the reinforcing effect of the hybrid particles on the rubber matrix to be weakened. If the concentration of the silicate suspension or the flow rate of the silicate suspension is too low, the content of silicate particles in the obtained carbon black-silicate hybrid particles will be too low, which will result in the hybrid particles not being able to effectively reinforce the ductility of the rubber and reducing the fracture deformation of the material.

[0048] In a preferred embodiment, in step (2), the mass concentration of the adhesive solution is 5-20%; the mass content of the binder in the adhesive solution is 1-3% of the theoretical total mass of the carbon black; the flow ratio of the adhesive solution to the silicate suspension is (2-6):1; and the binder in the adhesive solution is selected from at least one of lignin, molasses, and maltose. In the present invention, the concentration, amount, flow rate, and type of the adhesive solution all affect the structural parameters and porosity of the carbon black-silicate hybrid particles. Changing the concentration, amount, flow rate, and type of the adhesive solution will change the particle size distribution, structure, and porosity of the carbon black-silicate hybrid particles, thereby affecting the dispersibility of the hybrid particles.

[0049] The present invention provides carbon black-silicate hybrid particles prepared by the preparation method described in the above technical solution.

[0050] In a preferred embodiment, the carbon black-silicate hybrid particles are composed of carbon black and silicate; the mass ratio of the carbon black to the silicate is (2-4):1.

[0051] The present invention also provides a rubber composite material comprising the carbon black-silicate hybrid particles described in the above technical solution.

[0052] In a preferred embodiment, based on 100 phr of the raw rubber, the amount of the carbon black-silicate hybrid particles is 10 to 50 phr.

[0053] Unless otherwise specified, the raw materials in the examples of the present invention were purchased from commercial sources.

[0054] Example 1

[0055] A method for preparing carbon black-silicate hybrid particles, the specific steps are as follows, using the existing carbon black production process, the equipment flow chart is shown in Figure 1 :

[0056] (1) preparing a potassium carbonate solution with a mass concentration of 0.07% by weight by adding 0.06% potassium carbonate (based on the total mass of the crude oil) and then feeding the solution into a reactor at a flow rate of 15 kg / h together with the crude oil, performing a combustion cracking reaction at 1850° C. to generate carbon black flue gas, and cooling, filtering and pulverizing the generated carbon black flue gas to obtain primary carbon black particles;

[0057] (2) After being pot-milled for 2 hours, silica was dispersed in granulation water to obtain a silica suspension with a mass concentration of 20%, wherein the pot mill speed was 500 rpm, the grinding balls used in the pot mill were zirconia balls, the mass ratio of zirconia balls to silica was 5:1, and the mass ratio of large, medium and small zirconia balls was 3:5:2; a lignin solution with a mass concentration of 15% was prepared, and the amount of lignin in the lignin solution accounted for 1.5% of the theoretical total mass of carbon black; the prepared lignin solution and silica suspension were added to a granulator at a flow ratio of 4:1, wherein the flow rate of the silica suspension was 900 kg / h and the temperature of the silica suspension was 75°C; after the granulation was completed, carbon black-silica (CB-SiO2) hybrid particles were obtained, which were dried and packaged to obtain the finished product.

[0058] Figure 2 TEM image of carbon black-silica hybrid particles prepared in Example 1, Figure 3 This is a dark field transmission electron microscope image of the carbon black-white carbon black hybrid particles prepared in Example 1. Figures 2-3 It can be seen that Example 1 achieves successful hybridization of CB and silica.

[0059] Figure 4 Elemental composition analysis of the carbon black-silica hybrid particles prepared in Example 1.

[0060] The element ratio analysis of the carbon black-silica hybrid particles prepared in Example 1 is shown in Table 1.

[0061] Table 1 Element ratio analysis of CB-SiO2 hybrid particles prepared in Example 1

[0062] Element Name Mass fraction% C 70.22 Si 12.00 O 17.78

[0063] Depend on Figure 4 As can be seen from Table 1, the carbon black-white carbon black hybrid particles CB-SiO2 prepared in Example 1 have a C:SiO2 ratio of ≈2.35:1.

[0064] Example 2

[0065] A method for preparing carbon black-silicate hybrid particles, the specific steps are as follows, using the existing carbon black production process, the equipment flow chart is shown in Figure 1 :

[0066] (1) preparing a potassium carbonate solution with a mass concentration of 0.08% by weight by adding 0.05% potassium carbonate (based on the total mass of the crude oil) and then feeding the solution into a reactor at a flow rate of 15 kg / h together with the crude oil, performing a combustion and cracking reaction at 1900° C. to generate carbon black flue gas, and cooling, filtering and crushing the generated carbon black flue gas to obtain primary carbon black particles;

[0067] (2) Dispersing silica surface-treated with bis-[γ-(triethoxysilyl)propyl]tetrasulfide (the amount of bis-[γ-(triethoxysilyl)propyl]tetrasulfide is 0.6% of the mass of silica) in granulation water to obtain a silica suspension with a mass concentration of 18%; preparing a lignin solution with a mass concentration of 10%, wherein the amount of lignin in the lignin solution accounts for 1.5% of the theoretical total mass of carbon black; respectively adding the prepared lignin solution and silica suspension into a granulator at a flow ratio of 3.5:1, wherein the flow rate of the silica suspension is 800 kg / h and the temperature of the silica suspension is 75°C; after the granulation is completed, carbon black-silica (CB-SiO2) hybrid particles are obtained, which are dried and packaged to obtain finished products.

[0068] Figure 5 TEM image of carbon black-silica hybrid particles prepared in Example 2, Figure 6 This is a dark field transmission electron microscope image of the carbon black-white carbon black hybrid particles prepared in Example 2. Figures 5-6 It can be seen that Example 2 achieves successful hybridization of CB and silica.

[0069] Figure 7 Elemental composition analysis of the carbon black-silica hybrid particles prepared in Example 2.

[0070] The element ratio analysis of the carbon black-silica hybrid particles prepared in Example 2 is shown in Table 2.

[0071] Table 2 Element ratio analysis of CB-SiO2 hybrid particles prepared in Example 2

[0072] Element Name Mass fraction% C 72.85 Si 10.52 O 16.63

[0073] Depend on Figure 7 As can be seen from Table 2, in the carbon black-white carbon black hybrid particles CB-SiO2 prepared in Example 2, the C:SiO2 ratio is ≈2.70:1.

[0074] Example 3

[0075] A method for preparing carbon black-silicate hybrid particles, the specific steps are as follows, using the existing carbon black production process, the equipment flow chart is shown in Figure 1 :

[0076] (1) preparing a potassium formate solution with a mass concentration of 0.10% by weight by adding 0.08% potassium formate (based on the total mass of the crude oil) and then feeding the solution into a reactor at a flow rate of 10 kg / h together with the crude oil to carry out a combustion cracking reaction at 1950° C. to generate carbon black flue gas, which is then cooled, filtered, and crushed to obtain primary carbon black particles;

[0077] (2) Dispersing kaolin surface-treated with γ-aminopropyltriethoxysilane (the amount of γ-aminopropyltriethoxysilane is 0.8% of the mass of kaolin) in granulation water to obtain a kaolin suspension with a mass concentration of 25%; preparing a maltose solution with a mass concentration of 20%, wherein the amount of maltose in the maltose solution accounts for 2% of the theoretical total mass of carbon black; respectively adding the prepared maltose solution and kaolin suspension into a granulator at a flow ratio of 2:1, wherein the flow rate of the kaolin suspension is 850 kg / h and the temperature of the kaolin suspension is 85°C; after the granulation is completed, carbon black-kaolin (CB-Kaolin) hybrid particles are obtained, which are dried and packaged to obtain a finished product.

[0078] Comparative Example 1

[0079] The difference from Example 1 is that the potassium carbonate in step (1) is replaced by sodium carbonate, and the rest is the same as Example 1.

[0080] Comparative Example 2

[0081] The difference from Example 1 is that in step (1), 0.02% (based on the total mass of the raw oil) of potassium carbonate is used to prepare a potassium carbonate solution with a mass concentration of 0.07%, and the rest is the same as Example 1.

[0082] Comparative Example 3

[0083] The difference from Example 1 is that in step (1), 0.15% (based on the total mass of the raw material oil) of potassium carbonate is used to prepare a potassium carbonate solution with a mass concentration of 0.07%, and the rest is the same as Example 1.

[0084] Comparative Example 4

[0085] The difference from Example 1 is that in step (1), 0.06% (based on the total mass of the raw material oil) of potassium carbonate is used to prepare a potassium carbonate solution with a mass concentration of 0.20%, and the rest is the same as Example 1.

[0086] Comparative Example 5

[0087] The difference from Example 1 is that in step (1), the raw material oil is fed into the reactor at a flow rate of 25 kg / h. The rest is the same as Example 1.

[0088] Comparative Example 6

[0089] The difference from Example 1 is that in step (2), the white carbon black is directly dispersed in the granulation water, that is, no pot grinding is performed. The rest is the same as Example 1.

[0090] Comparative Example 7

[0091] The difference from Example 1 is that in step (2), the amount of lignin in the lignin solution accounts for 0.5% of the theoretical total mass of carbon black, and the rest is the same as Example 1.

[0092] Comparative Example 8

[0093] The difference from Example 1 is that in step (2), the white carbon black is pot-milled for 2 hours and then dispersed in granulation water to obtain a white carbon black suspension with a mass concentration of 35%. The rest is the same as Example 1.

[0094] Application Example 1

[0095] The carbon black-silica hybrid particles obtained in Example 1 were used to prepare a styrene-butadiene rubber (SBR) / carbon black composite material, and the specific steps were as follows:

[0096] (1) Plasticize the styrene-butadiene rubber on a two-roll mill for 2 minutes, then add zinc oxide and stearic acid in sequence, and mix for 2 minutes to evenly disperse the additives. During this period, thinly pass the mixture once and triangle wrap once;

[0097] (2) Add the carbon black-silica hybrid particles obtained in Example 1 (using the same amount of pure carbon black as a reference) to the mixing rubber roller obtained in step (1), and mix for 6 minutes. During this period, use a 3 / 4 knife to cut each side 3 times, a thin pass 2 times, and a triangular wrap 2 times to ensure that the particles are evenly dispersed in the rubber matrix;

[0098] (3) Add accelerator CZ and accelerator DM to the mixing rubber roll obtained in step (2) and mix for 2 minutes. During this period, use 3 / 4 knife to cut each side twice, make a thin pass once, and make a triangle wrap once.

[0099] (4) The mixed rubber obtained in step (3) is rolled, sulfur is added as a vulcanizing agent, and the mixing is continued for 2 minutes, during which 3 / 4 knife is used twice on each side, thinly passed once, and triangularly wrapped once;

[0100] (5) Roll the mixed rubber obtained in step (4) on an open mill with a roller spacing of 1.5 mm for 3 minutes, thinly pass through 5 times, and triangle wrap 5 times;

[0101] (6) The rubber compound obtained in step (5) was left overnight and heated on a flat vulcanizing press at 160°C xt c90 Hot pressing and vulcanization molding are performed to obtain SBR / CB-SiO2 composite materials;

[0102] Among them, based on the amount of SBR being 100 phr, the amount of zinc oxide is 5 phr, the amount of stearic acid is 2 phr, the amount of accelerator CZ is 1.5 phr, the amount of accelerator DM is 0.5 phr, the amount of sulfur is 1.5 phr, and the amount of pure carbon black or carbon black-white carbon black hybrid particles is 10 phr.

[0103] The mechanical properties of the composite material prepared in Application Example 1 were tested according to the test standard GB / T 528-2009 “Rubber, vulcanized or thermoplastic — Determination of tensile stress-strain properties”, where the tensile rate was 500 mm / min. The results are shown in Table 3.

[0104] Table 3 Mechanical properties of SBR / CB-SiO2 composite materials prepared in Application Example 1

[0105]

[0106] As can be seen from Table 1, compared with the use of pure carbon black as the filling material, the styrene-butadiene rubber filled with CB-SiO2 hybrid particles exhibits higher modulus, tensile strength and elongation at break, which has a significant effect of reinforcement and improvement of deformation rate, proving the advantages of the carbon black-silicate hybrid particles prepared by the present invention in carbon black-silicate composite filled styrene-butadiene rubber materials.

[0107] Application Example 2

[0108] The carbon black-silica hybrid particles obtained in Example 2 were used to prepare a natural rubber (NR) / carbon black composite material, and the specific steps were as follows:

[0109] (1) The natural rubber was masticated on a two-roll mill for 1.5 min, and then zinc oxide and stearic acid were added in sequence and mixed for 1.5 min to evenly disperse the additives. During this period, the rubber was thinly passed once and triangularly wrapped once;

[0110] (2) Add the carbon black-silica hybrid particles obtained in Example 2 (using the same amount of pure carbon black as a reference) to the mixing rubber roll obtained in step (1), and mix for 5 minutes. During this period, use a 3 / 4 knife to cut each side 3 times, a thin pass 2 times, and a triangular wrap 2 times to ensure that the particles are evenly dispersed in the rubber matrix;

[0111] (3) The mixing rubber obtained in step (2) was rolled and the accelerator TBBS was added to the roller, and the mixing was continued for 2 minutes. During the mixing, the 3 / 4 knife was used twice on each side, a thin pass was used once, and a triangle wrap was used once;

[0112] (4) The mixed rubber obtained in step (3) was rolled, sulfur was added as a vulcanizing agent, and the mixing was continued for 1.5 minutes, during which 3 / 4 knife was used twice on each side, thin-cut once, and triangular-wrapped once;

[0113] (5) Roll the mixed rubber obtained in step (4) on an open mill with a roller spacing of 1.5 mm for 3 minutes, thinly pass through 5 times, and triangle wrap 5 times;

[0114] (6) the rubber mix obtained in step (5) was left overnight, and hot-pressed and vulcanized on a flat vulcanizer at 143°C xtc90 to obtain a NR / CB-SiO2 composite material;

[0115] Wherein, based on the amount of NR being 100 phr, the amount of zinc oxide being 5 phr, the amount of stearic acid being 2 phr, the amount of accelerator TBBS being 1.5 phr, the amount of sulfur being 2.0 phr, and the amount of pure carbon black or carbon black-white carbon black hybrid particles being 50 phr.

[0116] The mechanical properties of the composite material prepared in Application Example 2 were tested according to the test standard GB / T 528-2009 “Rubber, vulcanized or thermoplastic — Determination of tensile stress-strain properties”, where the tensile rate was 500 mm / min. The results are shown in Table 4.

[0117] Table 4 Mechanical properties of NR / CB-SiO2 composite materials prepared in Application Example 2

[0118]

[0119] As shown in Table 4, compared with pure carbon black as the filler, the tensile stress of natural rubber filled with CB-SiO2 hybrid particles decreases slightly, but the elongation at break and tensile strength increase significantly. This higher deformation facilitates the tensile strain crystallization of the natural rubber itself, contributing to the improvement of the material's tensile strength. This demonstrates the advantages of the carbon black-silicate prepared in this invention for filling natural rubber materials.

[0120] Application Example 3

[0121] The difference from Application Example 2 is that the carbon black-white carbon black hybrid particles obtained in Example 1 in step (2) are replaced by the carbon black-kaolin (CB-Kaolin) hybrid particles obtained in Example 3, and the rest are the same as Application Example 2.

[0122] Comparative Application Examples 1-8

[0123] The difference from Application Example 1 is that the carbon black-white carbon black hybrid particles obtained in Example 1 in step (2) are replaced by the carbon black-silicate hybrid particles obtained in Comparative Examples 1-8, respectively. The rest is the same as Application Example 1.

[0124] The mechanical properties of the composite materials prepared in Application Example 3 and Comparative Application Examples 1-8 were tested according to the test standard GB / T 528-2009 “Rubber, vulcanized or thermoplastic — Determination of tensile stress-strain properties”, where the tensile rate was 500 mm / min. The results are shown in Table 5.

[0125] Table 5 Mechanical properties of NR / CB-Kaolin composites prepared in Application Example 3 and SBR / CB-SiO2 composites prepared in Comparative Application Examples 1-8

[0126]

[0127] As shown in Table 5, the tensile stress, tensile strength, and elongation at break of Example 3 are all higher than those of the pure CB-filled natural rubber system, demonstrating that CB-Kaolin achieves excellent reinforcement and a relatively high cost-effectiveness. Furthermore, analysis of the data from the application examples of Comparative Examples 1-8 shows that the reinforcing effect of the carbon black-silica hybrid particles as fillers is improved to a certain extent compared to the pure carbon black system. Varying the type, dosage, concentration, and flow rate of the structural inhibitor, the silicate pretreatment method, the concentration of the silicate suspension, and the amount of adhesive used results in varying degrees of reduction in the tensile stress, tensile strength, and elongation at break of the hybrid particle-filled SBR composite. This demonstrates that the use of highly structured carbon black particles and a silicate suspension within an appropriate concentration or mass range results in a more pronounced reinforcing effect of the hybrid particles.

[0128] The above are merely preferred embodiments of the present invention, but the scope of protection of the present invention is not limited thereto. Any changes or substitutions that can be easily conceived by a person skilled in the art within the technical scope disclosed in the present invention should be included in the scope of protection of the present invention. Therefore, the scope of protection of the present invention should be based on the scope of protection of the claims.

Claims

1. A method for preparing carbon black-silicate hybrid particles, characterized in that: The following steps are involved: (1) A carbon black structure inhibitor solution and crude oil are fed into a reactor for combustion cracking reaction, and then cooled, filtered and crushed to obtain primary carbon black particles; the mass concentration of the carbon black structure inhibitor solution is 0.06-0.10%; the mass content of the carbon black structure inhibitor in the carbon black structure inhibitor solution is 0.04-0.08% of the mass of the crude oil; the flow rate of the carbon black structure inhibitor solution is 10-19 kg / h; the carbon black structure inhibitor in the carbon black structure inhibitor solution is selected from at least one of potassium carbonate and potassium formate; (2) mixing silicate and granulation water to obtain a silicate suspension; adding the obtained silicate suspension, the primary carbon black particles obtained in step (1) and the binder solution into a granulator for granulation to obtain the carbon black-silicate hybrid particles; the silicate is selected from at least one of white carbon black and kaolin; and a pretreatment step is further included before the silicate and granulation water are mixed; The pretreatment method includes surface treatment or particle size refinement; the mass concentration of silicate in the silicate suspension is 10-30%; the mass content of the adhesive in the adhesive solution is 1-3% of the total mass of theoretical carbon black.

2. The method for preparing carbon black-silicate hybrid particles according to claim 1, characterized in that: In step (1), the temperature of the combustion cracking reaction is 1800-2000°C.

3. The method for preparing carbon black-silicate hybrid particles according to claim 1, characterized in that: In step (2), the surfactant used for the surface treatment is selected from at least one of bis-[γ-(triethoxysilyl)propyl]tetrasulfide, γ-aminopropyltriethoxysilane, and γ-methacryloxypropyltrimethoxysilane; the amount of the surfactant used is 0.5-1.0% of the mass of the silicate; and / or, The particle size refinement method is pot milling for 2 to 5 hours.

4. The method for preparing carbon black-silicate hybrid particles according to claim 1, characterized in that: In step (2), the flow rate of the silicate suspension during the addition of the granulator is 800-1500 kg / h and the temperature is 75-85°C.

5. The method for preparing carbon black-silicate hybrid particles according to claim 1, wherein: In step (2), the mass concentration of the adhesive solution is 5-20%; the flow ratio of the adhesive solution to the silicate suspension is (2-6):1; and the adhesive in the adhesive solution is selected from at least one of lignin, molasses, and maltose.

6. Carbon black-silicate hybrid particles prepared by the preparation method according to any one of claims 1 to 5.

7. A rubber composite material comprising the carbon black-silicate hybrid particles according to claim 6.

8. The rubber composite material according to claim 7, characterized in that Based on 100 phr of the raw rubber, the amount of the carbon black-silicate hybrid particles is 10 to 50 phr.

Images