Preparation method of supported high-dispersion white carbon black

Abstract

The invention belongs to the technical field of rubber fillers, and particularly discloses a preparation method of supported high-dispersion white carbon black, which comprises the following steps: mixing a nanotube carrier with a water glass solution, and adding a precipitant to pre-polymerize and co-precipitate to obtain a precursor; preparing bottom alkali water glass in a carbonation process, heating the bottom alkali water glass, adding a nucleating agent and the obtained precursor into the bottom alkali water glass, continuously stirring, and introducing carbon dioxide to start to prepare colloid after the temperature is stable; after the colloid is prepared, stopping introducing the carbon dioxide and keeping stirring to homogenize the particles; and preparing liquid-combining water glass in a carbon separation process, adding the liquid-combining water glass and carbon dioxide into the colloidal liquid, and heating and coprecipitating to obtain the supported high-dispersion white carbon black. According to the preparation method, treatment is directly started from the superior raw material water glass of the white carbon black, the finished product carbon nanotube emulsion or halloysite nanotubes are adopted for preparation, in-situ growth of the white carbon black on the surfaces of the nanotubes is ensured, the structure can be effectively controlled, and the dispersing performance of the product is greatly improved.

Description

Technical Field

[0001] The invention belongs to the technical field of rubber fillers and relates to the preparation of white carbon black, in particular to a method for preparing loaded highly dispersed white carbon black. Background Art

[0002] Tire anti-skid performance, low rolling resistance and high wear resistance are called the "magic triangle" of tires. Among them, high wear resistance can provide longer service life, safety, fuel saving, low noise, environmental protection, etc. Low rolling resistance can reduce heat generation, save fuel and increase tire life. When the tire is subjected to periodic deformation, the rubber material is subjected to dynamic alternating stress. Under the action of external force, the rubber molecular chain and the filling particles move relative to each other, causing relative sliding between the molecular chains in the rubber, between the molecular chains and the filling particles, and between the filling particles. The part of the material that contacts the ground will experience compression, shearing and stretching. Microscopically speaking, the wear of rubber is due to its continuous compression, shearing and stretching under the action of periodic stress. Each compression, shearing and stretching process causes changes in the internal structure of the rubber and generates energy loss. The heat generated by these energy losses and the dynamic stress together accelerate the aging and fracture of the rubber molecules. This change occurs repeatedly, eventually leading to fatigue damage of the rubber material. The wear resistance of rubber is quantitatively related to the friction force and the crack propagation characteristics of rubber. Adding rod-shaped rigid materials, such as carbon nanotubes and halloysite nanotubes, can effectively improve the structural strength of rubber and increase the wear of filled rubber. And rubber, like most polymers, is a poor conductor of heat, so it cannot quickly transfer the heat inside the rubber to the outside world. Macroscopically, it manifests as obvious internal heat generation and high energy consumption, which accelerates rubber aging and leads to a decrease in the safety and life of rubber products. Therefore, high-component, high-thermal conductivity carbon nanotubes also provide a new method for controlling the dynamic temperature rise of rubber. In this case, the ideal state of loaded filler is to partially load white carbon black on the surface of carbon nanotubes. On the one hand, it can make the thermal conductivity of carbon nanotubes effective, and on the other hand, it can avoid the agglomeration of carbon nanotubes. The agglomeration of white carbon black is solved by the silane system.

[0003] The common filling and rubber processing and mixing technology is to directly add the materials into the mixing process and process them together. For the silica rubber system, due to the extremely high specific surface area of ​​carbon nanotubes / halloysite nanotubes, strong adsorption and serious agglomeration, it will lead to uneven mixing and later agglomeration. However, the use of loading method to mix silica with carbon nanotubes / halloysite nanotubes in advance and then perform the mixing process can greatly reduce the agglomeration of the two fillers, increase dispersion, and improve performance, but at the same time may face the problem of rising costs. This type of loading material requires high-conductivity carbon nanotubes / halloysite nanotubes as the matrix, and partially loads silica on its surface, so as to simultaneously achieve the reinforcement of silica and the high conductivity / structural strength performance of carbon nanotubes or the structural strength performance of halloysite nanotubes.

[0004] At present, in the carbon nanotube loading process: Patent No. CN115433391A discloses a loading method, in which the carbon nanotube aqueous dispersion is modified with plant polyphenols, the finished silica aqueous dispersion is modified with olefin compounds, and the two are mixed and combined into a loading material through hydrogen bonds; Patent No. CN115584060A discloses a loading method, in which sodium carboxymethyl cellulose is added to the carbon nanotube and the finished silica aqueous dispersion, and then acid is added to generate carboxymethyl cellulose in situ, which acts as a binder to bond the two to generate a loading material; Patent No. CN112635734B discloses a loading method, in which the finished silica is subjected to an amination treatment with toluene as a solvent to obtain a colloid, the carbon nanotube is subjected to a carboxylation treatment with an acid, and then the two are blended and vacuum dried to obtain a loading material, but this method uses a large amount of solvent, which brings There is a post-processing risk, and its high-temperature reduction step also has a high energy consumption risk; Patent CN107603280A discloses a loading method, which is to mix the finished white carbon black and the carbon source aqueous solution and then carbonize and reduce them to obtain a loaded material; Patent CN110342528A discloses a gas phase in-situ process, in which the carbon source gas is added to react together to prepare the loaded material; Patent CN110372911A discloses a loading method, first preparing white carbon black loaded with a metal catalyst from a white carbon black filter cake, and then using a CVD reaction to react the carbon source gas in situ into carbon nanotubes after high-temperature reduction to obtain a loaded material; Patent CN105836749A discloses a loading method, which is to mix the finished white carbon black and a nickel-based catalyst, reduce them at high temperature, and then cause a CVD reaction in the air to obtain a loaded material. In the process of halloysite loading: CN117164961A discloses a loading method, firstly using silane to modify halloysite, precipitating water glass with sulfuric acid in the presence of ethanol solvent, generating silica in situ, and then drying to obtain a loading material; CN105924677B discloses a loading method, wherein one of the white carbon black product / halloysite nanotubes is subjected to silane modification, and then both are dispersed in a solvent, and a loading material is prepared by electrostatic self-assembly; CN109020472A and a series of similar patents, CN117358164A, CN118652 633A, CN114053881B, etc. disclose a loading method, which first uses silane and other modifiers to modify halloysite nanotubes, and then mixes and polymerizes with tetraethyl orthosilicate to prepare a loaded material; CN106279772B discloses a loading method, which first uses ammonia water and a catalyst to modify halloysite, and then mixes and co-precipitates with methyl / ethyl orthosilicate or sodium silicate silicon source to generate silica in situ, thereby preparing a loaded material; CN118459900B discloses a loading method, which uses silane to modify halloysite nanotubes, and then mixes and polymerizes with silane to prepare a loaded material.

[0005] Most of the above-mentioned carbon nanotube-loaded silica patents use finished silica. In addition to the high-temperature granulation process during the granulation itself, high-temperature granulation is performed again after modification. The process mostly uses the process of in-situ generation of carbon nanotubes, which belongs to the growth of carbon nanotubes on the surface of silica, and there is a risk of agglomeration of carbon nanotubes. Most of the patents for halloysite nanotube-loaded silica use ammonia water and organic silane to assist in the dispersion and modification of halloysite nanotubes. The process is complicated and there are reagent risks; the silicon source mostly uses a system of methyl / ethyl orthosilicate plus solvent, which has solvent risks. Some use finished silica, and there is also a problem of secondary granulation energy consumption; the precipitant part uses sulfuric acid to precipitate silica, and some halloysite nanotubes will be replaced by aluminum hydrogen into silica, resulting in the loss of halloysite nanotubes. Summary of the invention

[0006] In view of the shortcomings of the prior art, the purpose of the present invention is to provide a method for preparing loaded highly dispersed white carbon black. The present invention directly starts with water glass, the upper raw material of white carbon black, and adopts finished carbon nanotube emulsion or halloysite nanotube for preparation, thereby ensuring the in-situ growth of white carbon black on the surface of carbon nanotube or halloysite nanotube, which can not only effectively control the structure but also greatly improve the dispersion performance of the product.

[0007] The present invention is achieved through the following technical solutions:

[0008] A method for preparing supported highly dispersed white carbon black comprises the following steps:

[0009] (1) Prepolymerization: After the carrier and the water glass solution are mixed in proportion, a precipitant is added to prepolymerize and precipitate to obtain a precursor;

[0010] (2) Preparation of colloid: prepare the bottom alkali water glass solution in the carbon separation process and heat it to 40-95°C, then add the nucleating agent and the precursor obtained in step (1) thereto, continue stirring, and after the temperature stabilizes, introduce carbon dioxide to start preparing the colloid;

[0011] (3) Homogenization: After the colloid is prepared, stop introducing carbon dioxide and keep stirring to make the particles homogenous;

[0012] (4) Precipitation: Prepare the water glass solution used in the carbon separation process, add it to the colloidal liquid together with carbon dioxide, maintain the temperature at 40-95°C, and precipitate together to obtain highly dispersed carbon nanotube-loaded white carbon black;

[0013] The carrier is carbon nanotube emulsion or halloysite nanotube.

[0014] A further improvement of the present invention is:

[0015] The concentration of the carbon nanotube emulsion is 0.1-5 wt %.

[0016] Furthermore, the modulus of the water glass raw material is 1.0-3.5, and the concentration of the water glass solution is 1.96-20 SiO2wt%.

[0017] Preferably, the water glass solution concentration is 3.84-8.23 SiO2wt%.

[0018] The concentration of the bottom alkali water glass solution is 2.00-9.00 SiO2wt%;

[0019] The concentration of the mixed water glass solution is 4.70-15.0 SiO2wt%;

[0020] Furthermore, based on the mass of SiO2 and carbon nanotubes, the ratio of the carbon nanotube emulsion to the water glass solution is 1:0.1-1, and the ratio of the halloysite nanotubes to the water glass solution is 1:0.1-12.

[0021] Preferably, based on the mass of SiO2 and carbon nanotubes, the ratio of the carbon nanotube emulsion to the water glass solution is 1:0.4-0.6, and the ratio of the halloysite nanotubes to the water glass solution is 1:2-10.

[0022] Furthermore, the precipitant in step (1) is one or a mixture of two or more of sulfuric acid, hydrochloric acid, nitric acid or carbonic acid.

[0023] Preferably, the precipitant is a combination of carbonic acid and sulfuric acid, and the specific process is: first, carbon dioxide is bubbled into the prepolymer liquid until the pH value becomes constant, and then sulfuric acid is used to adjust the pH value of the prepolymer liquid to 6.0-7.0, wherein the gas flow rate of carbon dioxide is 200-600L / h.

[0024] Preferably, the gas flow rate of carbon dioxide is 400-600 L / h.

[0025] Furthermore, the nucleating agent described in step (2) is a monovalent metal salt, such as sodium or potassium carbonate, bicarbonate, hydroxide, sulfate, chloride, nitrate, acetate, etc.; an amino compound, such as ammonia water, urea, or tetrapropylammonium hydroxide, etc.; a surfactant, such as one or more of the three categories of sodium dodecyl sulfate, sodium dodecylbenzene sulfonate, hexadecyltrimethylammonium bromide, polyethylene glycol, etc.

[0026] Preferably, the nucleating agent is one or more of sodium carbonate, sodium bicarbonate, sodium hydroxide, potassium carbonate, potassium bicarbonate, potassium hydroxide and the like.

[0027] Furthermore, the stirring rate in step (2) is 5-100 Hz; and the carbon dioxide flow rate is 200-600 L / h.

[0028] Preferably, in step (2), the temperature is heated to 80-90° C.; the carbon dioxide flow rate is 300-500 L / h; and the stirring rate is 35-45 Hz.

[0029] Furthermore, in step (4), the temperature is 80-90°C; the carbon dioxide flow rate is 200-600 L / h; and the stirring rate is 5-100 Hz.

[0030] Preferably, the carbon dioxide flow rate is 300-500 L / h; and the stirring rate is 35-45 Hz.

[0031] In the present invention, the bottom alkali water glass solution is a low-concentration water glass solution used for the early preparation of silicate sol; the parallel liquid water glass solution is a high-concentration water glass solution used for adding into the sol in the second stage for further polymerization precipitation, and adopts a parallel flow mode, so it is called parallel liquid.

[0032] A further improvement of the present invention is:

[0033] The application of the prepared loaded highly dispersed silica in the preparation of rubber.

[0034] Compared with the prior art, the present invention has the following beneficial effects:

[0035] The present invention adopts a one-step co-precipitation method, which reduces one high-temperature granulation process compared to the finished white carbon black, greatly reduces energy consumption, and has a greater energy consumption advantage than the gas phase method; no additional modifier or organic solvent is used, reducing the process difficulty and cost; no additional metal elements are introduced, ensuring the purity of the product.

[0036] The present invention directly starts with water glass, the upper raw material of white carbon black, and adopts finished carbon nanotube emulsion or halloysite nanotube for preparation, so as to ensure the in-situ growth of white carbon black on the surface of carbon nanotube or halloysite nanotube, which can not only effectively control the structure, but also greatly improve the dispersion performance of the product. The process of the present invention has no demulsification phenomenon, the obtained loaded product has good loading effect, and the agglomeration phenomenon of carbon nanotube or halloysite nanotube is relatively light.

[0037] The present invention is highly related to the carbon separation process of white carbon black, and its properties, such as specific surface area, particle size, surface hydroxyl content, etc., can be freely adjusted without being restricted by white carbon black products on the market.

[0038] In the carbon nanotube or halloysite nanotube-loaded white carbon black of the present invention, the carbon nanotube component can be controlled to be 0.01-50wt%, and the halloysite nanotube component can be controlled to be 0.01-200wt%. BRIEF DESCRIPTION OF THE DRAWINGS

[0039] Figure 1 TEM spectra of carbon nanotube-loaded white carbon black prepared in some comparative examples and embodiments of the present invention;

[0040] Figure 2 The following are SEM images of carbon nanotube-loaded white carbon black prepared in some comparative examples and embodiments of the present invention. DETAILED DESCRIPTION

[0041] The present invention is described in detail below in conjunction with specific embodiments.

[0042] Materials and instruments used in the embodiments of the present invention:

[0043] The concentration of the carbon nanotube emulsion used is 0-5wt%, and the dispersant in the emulsion: carbon nanotube = 10%; the purity of the halloysite nanotube used is more than 99%; the water glass modulus is 1.0-3.3; the SiO2 concentration in the water glass solution is 4.75-8.23%; the ammonia concentration is 26%; the sulfuric acid concentration is 50%; carbon dioxide and each nucleating agent are chemically pure, and the prepolymerization effect is tested by TEM, SEM and BET.

[0044] TEM testing instrument information: American FEI Tecnai F20.

[0045] SEM testing instrument information: Japan Hitachi Regulus 8100.

[0046] BET test instrument information: Beijing Jingwei Gaobo JW-BK222-01.

[0047] Comparative Example 1

[0048] The carbon nanotubes and white carbon black were blended in a ratio of 2:100 and stirred at a high speed to prepare a sample.

[0049] Comparative Example 2

[0050] The carbon nanotube emulsion was diluted to a concentration of 1.1wt%, 2727g of the diluted emulsion and 320g of a water glass solution with a modulus of 2 and a SiO2 content of 4.75wt% were put into a reaction bottle and mixed evenly, carbon dioxide was introduced at room temperature at a flow rate of 500L / h until the pH no longer changed, and then the pH was adjusted to 6.0-7.0 with 50wt% sulfuric acid to obtain a prepolymer. The prepolymer was added to 21.68kg of a bottom alkali water glass solution with a SiO2 content of 4.75wt%, a certain amount of sodium carbonate was added, and a colloid was prepared by passing 500L / h of carbon dioxide, and then 12.00kg of a liquid water glass solution with a SiO2 content of 8.23wt% was added after homogenization, and carbon dioxide was introduced for coprecipitation to prepare a load material.

[0051] Comparative Example 3

[0052] The carbon nanotube emulsion was diluted to a concentration of 1.1wt%, 2727g of the diluted emulsion and 427g of a water glass solution with a modulus of 3.25 and a SiO2 content of 4.75wt% were put into a reaction bottle and mixed evenly, carbon dioxide was introduced at room temperature at a flow rate of 500L / h until the pH no longer changed, and then the pH was adjusted to 6.0-7.0 with 50wt% sulfuric acid to obtain a prepolymer. The prepolymer was added to 21.57kg of a bottom alkali water glass solution with a SiO2 content of 4.75wt%, a certain amount of sodium carbonate was added, and a colloid was prepared by passing 500L / h of carbon dioxide, and then 12.00kg of a liquid water glass solution with a SiO2 content of 8.23wt% was added after homogenization, and carbon dioxide was introduced for coprecipitation to prepare a load material.

[0053] Comparative Example 4

[0054] The carbon nanotube emulsion was diluted to a concentration of 1.1wt%, 2727g of the diluted emulsion and 533g of a water glass solution with a modulus of 3.25 and a SiO2 content of 4.75wt% were put into a reaction bottle and mixed evenly, carbon dioxide was introduced at room temperature at a flow rate of 500L / h until the pH no longer changed, and then the pH was adjusted to 6.0-7.0 with 50wt% sulfuric acid to obtain a prepolymer. The prepolymer was added to 21.47kg of a bottom alkali water glass solution with a SiO2 content of 4.75wt%, a certain amount of sodium carbonate was added, and a colloid was prepared by passing 500L / h of carbon dioxide, and then 12.00kg of a liquid water glass solution with a SiO2 content of 8.23wt% was added after homogenization, and carbon dioxide was introduced for coprecipitation to prepare a load material.

[0055] Comparative Example 5

[0056] The carbon nanotube emulsion was diluted to a concentration of 1.1wt%, 2727g of the diluted emulsion and 640g of a water glass solution with a modulus of 3.25 and a SiO2 content of 4.75wt% were put into a reaction bottle and mixed evenly, carbon dioxide was introduced at room temperature at a flow rate of 500L / h until the pH no longer changed, and then the pH was adjusted to 6.0-7.0 with 50wt% sulfuric acid to obtain a prepolymer. The prepolymer was added to 21.36kg of a bottom alkali water glass solution with a SiO2 content of 4.75wt%, a certain amount of sodium carbonate was added, and a colloid was prepared by passing 500L / h of carbon dioxide, and then 12.00kg of a liquid water glass solution with a SiO2 content of 8.23wt% was added after homogenization, and carbon dioxide was introduced for coprecipitation to prepare a load material.

[0057] Comparative Example 6

[0058] The carbon nanotube emulsion was diluted to a concentration of 6wt%, 500g of the diluted emulsion and 320g of a water glass solution with a modulus of 3.25 and a SiO2 content of 4.75wt% were put into a reaction bottle and mixed evenly, carbon dioxide was introduced at room temperature at a flow rate of 500L / h until the pH no longer changed, and then the pH was adjusted to 6.0-7.0 with 50wt% sulfuric acid to obtain a prepolymer. The prepolymer was added to 21.68kg of a bottom alkali water glass solution with a SiO2 content of 4.75wt%, a certain amount of sodium carbonate was added, and a colloid was prepared by passing 500L / h of carbon dioxide, and then 12.00kg of a liquid water glass solution with a SiO2 content of 8.23wt% was added after homogenization, and carbon dioxide was introduced for coprecipitation to prepare a load material.

[0059] Comparative Example 7

[0060] The carbon nanotube emulsion was diluted to a concentration of 1.1wt%, 2727g of the diluted emulsion and 320g of a water glass solution with a modulus of 3.25 and a SiO2 content of 4.75wt% were put into a reaction bottle and mixed evenly, carbon dioxide was introduced at room temperature at a flow rate of 300L / h until the pH no longer changed, and then 50wt% sulfuric acid was used to adjust the pH to 6.0-7.0 to obtain a prepolymer. The prepolymer was added to 21.68kg of a bottom alkali water glass solution with a SiO2 content of 4.75wt%, a certain amount of sodium carbonate was added, and a colloid was prepared by passing 500L / h of carbon dioxide, and then 12.00kg of a liquid water glass solution with a SiO2 content of 8.23wt% was added after homogenization, and carbon dioxide was introduced for coprecipitation to prepare a load material.

[0061] Comparative Example 8

[0062] The carbon nanotube emulsion was diluted to a concentration of 1.1wt%, 2727g of the diluted emulsion and 320g of a water glass solution with a modulus of 3.25 and a SiO2 content of 4.75wt% were put into a reaction bottle and mixed evenly, and the pH was adjusted to 6.0-7.0 with 50wt% sulfuric acid at room temperature to obtain a prepolymer. The prepolymer was added to 21.68kg of a bottom alkali water glass solution with a SiO2 content of 4.75wt%, a certain amount of sodium carbonate was added, and 500L / h of carbon dioxide was passed to prepare a colloid, and then 12.00kg of a liquid water glass solution with a SiO2 content of 8.23wt% was added after homogenization, and carbon dioxide was passed to prepare a load material by coprecipitation.

[0063] Comparative Example 9

[0064] Halloysite nanotubes and silica were blended at a mass ratio of 14.3:100 and stirred at high speed to obtain a sample.

[0065] Comparative Example 10

[0066] 300g of halloysite nanotubes were added to 22kg of bottom alkali water glass solution with a SiO2 content of 4.75wt%, and after adding a certain amount of sodium carbonate, 500L / h of carbon dioxide was passed to prepare a colloid. After homogenization, 12kg of a mixed liquid water glass solution with a SiO2 content of 8.23wt% was added, and carbon dioxide was passed to co-precipitate to prepare a loaded material.

[0067] Comparative Example 11

[0068] Disperse 300g of halloysite nanotubes in 2000g of water, add 200ml of 26% ammonia water and 1g of tetrabutylammonium bromide, and stir ultrasonically for 30min. Add the dispersion into 22kg of bottom alkali water glass solution with SiO2 content of 4.75wt%, add a certain amount of sodium carbonate, pass carbon dioxide at a flow rate of 500L / h to prepare a colloid, and then add 12kg of liquid water glass solution with SiO2 content of 8.23wt% after homogenization, and pass carbon dioxide for co-precipitation to prepare a loaded material.

[0069] Comparative Example 12

[0070] 30g of Halloysite nanotubes and 300g of water glass solution with a modulus of 3.25 and a SiO2 content of 4.75wt% were put into a reaction bottle and mixed evenly, and carbon dioxide was introduced at room temperature at a flow rate of 500L / h until the pH no longer changed and the viscosity increased apparent to obtain a prepolymer. The prepolymer was added to 21.7Kg of a base alkali water glass solution with a SiO2 content of 4.75wt%, and a certain amount of sodium carbonate was added. After the colloid was prepared by passing carbon dioxide at a flow rate of 500L / h, 12.00kg of a liquid water glass solution with a SiO2 content of 8.23wt% was added after homogenization, and carbon dioxide was introduced for coprecipitation to prepare a load material.

[0071] Comparative Example 13

[0072] 90g of Halloysite nanotubes and 300g of water glass solution with a modulus of 3.25 and a SiO2 content of 4.75wt% were put into a reaction bottle and mixed evenly, and carbon dioxide was introduced at room temperature at a flow rate of 500L / h until the pH no longer changed and the viscosity increased apparent to obtain a prepolymer. The prepolymer was added to 21.7kg of a bottom alkali water glass solution with a SiO2 content of 4.75wt%, and a certain amount of sodium carbonate was added. After the colloid was prepared by passing carbon dioxide at a flow rate of 500L / h, 12.00kg of a liquid water glass solution with a SiO2 content of 8.23wt% was added after homogenization, and carbon dioxide was introduced for coprecipitation to prepare a load material.

[0073] Comparative Example 14

[0074] 200g of Halloysite nanotubes and 300g of water glass solution with a modulus of 3.25 and a SiO2 content of 4.75wt% were put into a reaction bottle and mixed evenly, and carbon dioxide was introduced at room temperature at a flow rate of 500L / h until the pH no longer changed and the viscosity increased apparent to obtain a prepolymer. The prepolymer was added to 21.7Kg of a base water glass solution with a SiO2 content of 5.75wt%, and a certain amount of sodium carbonate was added. After the colloid was prepared by passing carbon dioxide at a flow rate of 500L / h, 12.00kg of a liquid water glass solution with a SiO2 content of 8.23wt% was added after homogenization, and carbon dioxide was introduced for coprecipitation to prepare a load material.

[0075] Example 1

[0076] The carbon nanotube emulsion was diluted to a concentration of 1.1wt%, 2727g of the diluted emulsion and 107g of a water glass solution with a modulus of 3.25 and a SiO2 content of 4.75wt% were put into a reaction bottle and mixed evenly, carbon dioxide was introduced at room temperature at a flow rate of 500L / h until the pH no longer changed, and then 50wt% sulfuric acid was used to adjust the pH to 6.0-7.0 to obtain a prepolymer. The prepolymer was added to 21.89kg of a bottom alkali water glass solution with a SiO2 content of 4.75wt%, a certain amount of sodium carbonate was added, and a colloid was prepared by passing 500L / h of carbon dioxide, and then 12.00kg of a liquid water glass solution with a SiO2 content of 8.23wt% was added after homogenization, and carbon dioxide was introduced for coprecipitation to prepare a load material.

[0077] Example 2

[0078] The carbon nanotube emulsion was diluted to a concentration of 1.1wt%, 2727g of the diluted emulsion and 213g of a water glass solution with a modulus of 3.25 and a SiO2 content of 4.75wt% were put into a reaction bottle and mixed evenly, carbon dioxide was introduced at room temperature at a flow rate of 500L / h until the pH no longer changed, and then the pH was adjusted to 6.0-7.0 with 50wt% sulfuric acid to obtain a prepolymer. The prepolymer was added to 21.79kg of a bottom alkali water glass solution with a SiO2 content of 4.75wt%, a certain amount of sodium carbonate was added, and a colloid was prepared by passing 500L / h of carbon dioxide, and then 12.00kg of a liquid water glass solution with a SiO2 content of 8.23wt% was added after homogenization, and carbon dioxide was introduced for coprecipitation to prepare a load material.

[0079] Example 3

[0080] The carbon nanotube emulsion was diluted to a concentration of 1.1wt%, 2727g of the diluted emulsion and 320g of a water glass solution with a modulus of 3.25 and a SiO2 content of 4.75wt% were put into a reaction bottle and mixed evenly, carbon dioxide was introduced at room temperature at a flow rate of 500L / h until the pH no longer changed, and then the pH was adjusted to 6.0-7.0 with 50wt% sulfuric acid to obtain a prepolymer. The prepolymer was added to 21.68kg of a bottom alkali water glass solution with a SiO2 content of 4.75wt%, a certain amount of sodium carbonate was added, and a colloid was prepared by passing 500L / h of carbon dioxide, and then 12.00kg of a liquid water glass solution with a SiO2 content of 8.23wt% was added after homogenization, and carbon dioxide was introduced for coprecipitation to prepare a load material.

[0081] Example 4

[0082] The carbon nanotube emulsion is diluted to a concentration of 2wt%, 1500g of the diluted emulsion and 320g of a water glass solution with a modulus of 3.25 and a SiO2 content of 4.75wt% are put into a reaction bottle and mixed evenly, carbon dioxide is introduced at room temperature at a flow rate of 500L / h until the pH no longer changes, and then the pH is adjusted to 6.0-7.0 with 50wt% sulfuric acid to obtain a prepolymer. The prepolymer is added to 21.68kg of a bottom alkali water glass solution with a SiO2 content of 4.75wt%, a certain amount of sodium carbonate is added, and a colloid is prepared by passing 500L / h of carbon dioxide, and then 12.00kg of a liquid water glass solution with a SiO2 content of 8.23wt% is added after homogenization, and carbon dioxide is introduced for coprecipitation to prepare a load material.

[0083] Embodiment 5:

[0084] The carbon nanotube emulsion was diluted to a concentration of 5wt%, 600g of the diluted emulsion and 320g of a water glass solution with a modulus of 3.25 and a SiO2 content of 4.75wt% were put into a reaction bottle and mixed evenly, carbon dioxide was introduced at room temperature at a flow rate of 500L / h until the pH no longer changed, and then the pH was adjusted to 6.0-7.0 with 50wt% sulfuric acid to obtain a prepolymer. The prepolymer was added to 21.68kg of a bottom alkali water glass solution with a SiO2 content of 4.75wt%, a certain amount of sodium carbonate was added, and a colloid was prepared by passing 500L / h of carbon dioxide, and then 12.00kg of a liquid water glass solution with a SiO2 content of 8.23wt% was added after homogenization, and carbon dioxide was introduced for coprecipitation to prepare a load material.

[0085] Example 6

[0086] The carbon nanotube emulsion was diluted to a concentration of 1.1wt%, 2727g of the diluted emulsion and 320g of a water glass solution with a modulus of 3.25 and a SiO2 content of 4.75wt% were put into a reaction bottle and mixed evenly, carbon dioxide was introduced at room temperature at a flow rate of 400L / h until the pH no longer changed, and then the pH was adjusted to 6.0-7.0 with 50wt% sulfuric acid to obtain a prepolymer. The prepolymer was added to 21.68kg of a bottom alkali water glass solution with a SiO2 content of 4.75wt%, a certain amount of sodium carbonate was added, and a colloid was prepared by passing 400L / h of carbon dioxide, and then 12.00kg of a liquid water glass solution with a SiO2 content of 8.23wt% was added after homogenization, and carbon dioxide was introduced for coprecipitation to prepare a load material.

[0087] Example 7

[0088] The carbon nanotube emulsion was diluted to a concentration of 1.1wt%, 2727g of the diluted emulsion and 320g of a water glass solution with a modulus of 2 and a SiO2 content of 4.75wt% were put into a reaction bottle and mixed evenly, carbon dioxide was introduced at room temperature at a flow rate of 500L / h until the pH no longer changed, and then the pH was adjusted to 6.0-7.0 with 50wt% sulfuric acid to obtain a prepolymer. The prepolymer was added to 21.68kg of a bottom alkali water glass solution with a SiO2 content of 4.75wt%, a certain amount of ammonia water was added, and a colloid was prepared by passing 500L / h of carbon dioxide, and then 12.00kg of a liquid water glass solution with a SiO2 content of 8.23wt% was added after homogenization, and carbon dioxide was introduced for coprecipitation to prepare a load material.

[0089] Example 8

[0090] The carbon nanotube emulsion was diluted to a concentration of 1.1wt%, 2727g of the diluted emulsion and 320g of a water glass solution with a modulus of 2 and a SiO2 content of 4.75wt% were put into a reaction bottle and mixed evenly, carbon dioxide was introduced at room temperature at a flow rate of 500L / h until the pH no longer changed, and then 50wt% sulfuric acid was used to adjust the pH to 6.0-7.0 to obtain a prepolymer. The prepolymer was added to 21.68kg of a bottom alkali water glass solution with a SiO2 content of 4.75wt%, a certain amount of sodium dodecyl sulfate was added, and a colloid was prepared by passing 500L / h of carbon dioxide, and then 12.00kg of a liquid water glass solution with a SiO2 content of 8.23wt% was added after homogenization, and carbon dioxide was introduced for coprecipitation to prepare a load material.

[0091] Example 9

[0092] The carbon nanotube emulsion was diluted to a concentration of 1.1wt%, 2727g of the diluted emulsion and 320g of a water glass solution with a modulus of 3.25 and a SiO2 content of 4.75wt% were put into a reaction bottle and mixed evenly, carbon dioxide was introduced at room temperature at a flow rate of 600L / h until the pH no longer changed, and then 50wt% sulfuric acid was used to adjust the pH to 6.0-7.0 to obtain a prepolymer. The prepolymer was added to 21.68kg of a bottom alkali water glass solution with a SiO2 content of 4.75wt%, a certain amount of sodium carbonate was added, and a 600L / h flow rate of carbon dioxide was introduced to prepare a colloid, and then 12.00kg of a liquid water glass solution with a SiO2 content of 8.23wt% was added after homogenization, and carbon dioxide was introduced for coprecipitation to prepare a load material.

[0093] Example 10

[0094] The carbon nanotube emulsion was diluted to a concentration of 1.1wt%, 6818g of the diluted emulsion and 800g of a water glass solution with a modulus of 3.25 and a SiO2 content of 4.75wt% were put into a reaction bottle and mixed evenly, carbon dioxide was introduced at room temperature at a flow rate of 500L / h until the pH no longer changed, and then the pH was adjusted to 6.0-7.0 with 50wt% sulfuric acid to obtain a prepolymer. The prepolymer was added to 21.20kg of a bottom alkali water glass solution with a SiO2 content of 4.75wt%, a certain amount of sodium carbonate was added, and a colloid was prepared by passing 500L / h of carbon dioxide, and then 12.00kg of a liquid water glass solution with a SiO2 content of 8.23wt% was added after homogenization, and carbon dioxide was introduced for coprecipitation to prepare a load material.

[0095] Embodiment 11

[0096] The carbon nanotube emulsion was diluted to a concentration of 1.1wt%, 13636g of the diluted emulsion and 1600g of a water glass solution with a modulus of 3.25 and a SiO2 content of 4.75wt% were put into a reaction bottle and mixed evenly, carbon dioxide was introduced at room temperature at a flow rate of 500L / h until the pH no longer changed, and then the pH was adjusted to 6.0-7.0 with 50% sulfuric acid to obtain a prepolymer. The prepolymer was added to 20.40kg of a bottom alkali water glass solution with a SiO2 content of 4.75wt%, a certain amount of sodium carbonate was added, and a colloid was prepared by passing 500L / h of carbon dioxide, and then 12.00kg of a liquid water glass solution with a SiO2 content of 8.23wt% was added after homogenization, and carbon dioxide was introduced for coprecipitation to prepare a load material.

[0097] Example 12

[0098] The carbon nanotube emulsion was diluted to a concentration of 1.1wt%, 27273g of the diluted emulsion and 3200g of a water glass solution with a modulus of 3.25 and a SiO2 content of 4.75wt% were put into a reaction bottle and mixed evenly, carbon dioxide was introduced at room temperature at a flow rate of 500L / h until the pH no longer changed, and then the pH was adjusted to 6.0-7.0 with 50wt% sulfuric acid to obtain a prepolymer. The prepolymer was added to 18.80kg of a bottom alkali water glass solution with a SiO2 content of 4.75wt%, a certain amount of sodium carbonate was added, and a colloid was prepared by passing 500L / h of carbon dioxide, and then 12.00kg of a liquid water glass solution with a SiO2 content of 8.23wt% was added after homogenization, and carbon dioxide was introduced for coprecipitation to prepare a load material.

[0099] Embodiment 13

[0100] The carbon nanotube emulsion was diluted to a concentration of 1.1wt%, 2727g of the diluted emulsion and 320g of a water glass solution with a modulus of 3.25 and a SiO2 content of 4.75wt% were put into a reaction bottle and mixed evenly, carbon dioxide was introduced at room temperature at a flow rate of 500L / h until the pH no longer changed, and then the pH was adjusted to 6.0-7.0 with 50wt% sulfuric acid to obtain a prepolymer. The prepolymer was added to 14.68kg of a bottom alkali water glass solution with a SiO2 content of 6.53wt%, a certain amount of sodium carbonate was added, and a colloid was prepared by passing 500L / h of carbon dioxide, and then 12.00kg of a liquid water glass solution with a SiO2 content of 8.23wt% was added after homogenization, and carbon dioxide was introduced for coprecipitation to prepare a load material.

[0101] Embodiment 14

[0102] 300g of Halloysite nanotubes and 1500g of water glass solution with a modulus of 3.25 and a SiO2 content of 4.75wt% were put into a reaction bottle and mixed evenly, and carbon dioxide was introduced at a flow rate of 500L / h at room temperature until the pH no longer changed and the viscosity increased apparent to obtain a prepolymer. The prepolymer was added to 20.5kg of a base water glass solution with a SiO2 content of 4.75wt%, and a certain amount of sodium carbonate was added. After the colloid was prepared by passing carbon dioxide at a flow rate of 500L / h, 12.00kg of a liquid water glass solution with a SiO2 content of 8.23wt% was added after homogenization, and carbon dioxide was introduced for coprecipitation to prepare a load material.

[0103] Embodiment 15

[0104] 3000g of Halloysite nanotubes and 15kg of water glass solution with a modulus of 3.25 and a SiO2 content of 4.75wt% were put into a reaction bottle and mixed evenly, and carbon dioxide was introduced at room temperature at a flow rate of 500L / h until the pH no longer changed and the viscosity increased apparent to obtain a prepolymer. The prepolymer was added to 7kg of a bottom alkali water glass solution with a SiO2 content of 4.75wt%, and a certain amount of sodium carbonate was added. After the colloid was prepared by passing carbon dioxide at a flow rate of 500L / h, 12.00kg of a liquid water glass solution with a SiO2 content of 8.23wt% was added after homogenization, and carbon dioxide was introduced for coprecipitation to prepare a load material.

[0105] The analytical data of the products obtained in the comparative examples and embodiments are shown in the table below.

[0106]

[0107]

[0108] It can be seen from the above table that the present invention does not need to rely on finished silica, has controllable performance and more macropores, and is more conducive to rubber filler reinforcement.

[0109] The morphological characteristics of white carbon black obtained in some comparative examples and embodiments are shown in Figure 1 and Figure 2 .Depend on Figure 1 and Figure 2 It can be seen that the product provided by the method of the present invention has good dispersibility, good loading effect and less agglomeration.

[0110] The above embodiments are only for illustrating the technical concept and features of the present invention, and their purpose is to enable people familiar with the technology to understand the content of the present invention and implement it accordingly, and they cannot be used to limit the protection scope of the present invention. Any equivalent transformation or modification made according to the spirit of the present invention should be included in the protection scope of the present invention.

Claims

1. A method for preparing a supported highly dispersed white carbon black, characterized in that: The following steps are involved: (1) Prepolymerization: After the carrier and the water glass solution are mixed in proportion, a precipitant is added to prepolymerize and precipitate to obtain a precursor; (2) Preparation of colloid: prepare the bottom alkali water glass in the carbon separation process and heat it to 40-95°C, then add the nucleating agent and the precursor obtained in step (1) into it, continue stirring, and after the temperature stabilizes, introduce carbon dioxide to start preparing the colloid; (3) Homogenization: After the colloid is prepared, stop introducing carbon dioxide and keep stirring to make the particles homogenous; (4) Precipitation: Add the mixed water glass and carbon dioxide in the carbon separation process into the colloidal liquid, keep the temperature at 40-95°C, and precipitate together to obtain supported highly dispersed white carbon black; The carrier is carbon nanotube emulsion or halloysite nanotube.

2. The method for preparing a supported highly dispersed white carbon black according to claim 1, characterized in that: The concentration of the carbon nanotube emulsion is 0.1-5 wt %.

3. The method for preparing a supported highly dispersed silica according to claim 1, characterized in that: The modulus of the water glass raw material is 1.0-3.5, and the concentration of the water glass solution is 1.96-20wt%.

4. The method for preparing a supported highly dispersed silica according to claim 1, characterized in that: Calculated by the mass of SiO2 and carbon nanotubes, the ratio of the carbon nanotube emulsion to the water glass solution is 1:0.1-1, and calculated by the mass of SiO2 and halloysite nanotubes, the ratio of the halloysite nanotubes to the water glass solution is 1:0.1-12.

5. The method for preparing a supported highly dispersed silica according to claim 1, characterized in that: The nucleating agent is a monovalent metal salt, such as carbonate, bicarbonate, hydroxide, sulfate, chloride, nitrate, acetate of sodium or potassium; an amino compound, such as ammonia water, urea or tetrapropylammonium hydroxide; a surfactant, such as sodium dodecyl sulfate, sodium dodecylbenzene sulfonate, hexadecyltrimethylammonium bromide, polyethylene glycol, etc., or a mixture of two or more of the above three categories.

6. The method for preparing a supported highly dispersed silica according to claim 1, characterized in that: The precipitant is one or a mixture of two or more of sulfuric acid, hydrochloric acid, nitric acid or carbonic acid.

7. The method for preparing a supported highly dispersed white carbon black according to claim 6, characterized in that: The precipitant is a combination of carbonic acid and sulfuric acid, and the specific process is: first, carbon dioxide is bubbled into the prepolymer liquid until the pH value is constant, and then sulfuric acid is used to adjust the pH value of the prepolymer liquid to 6.0-7.0, wherein the gas flow rate of carbon dioxide is 200-600L / h.

8. The method for preparing a supported highly dispersed silica according to claim 1, characterized in that: The stirring rate in step (2) is 5-100 Hz; the carbon dioxide flow rate is 200-600 L / h.

9. The method for preparing a supported highly dispersed white carbon black according to claim 1, characterized in that: In step (4), the temperature is 80-90° C.; the carbon dioxide flow rate is 200-600 L / h; and the stirring rate is 5-100 Hz.

10. Use of the supported highly dispersed silica obtained by the method of claims 1 to 9 in the preparation of rubber.

Images