CN111994911A - Preparation method of precipitated white carbon black for high-modulus tire rubber - Google Patents
Preparation method of precipitated white carbon black for high-modulus tire rubber Download PDFInfo
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Abstract
The invention discloses a preparation method of precipitated silica white for high modulus tire rubber, (1) pre-adding water and 2.47 +/-0.2N sodium silicate solution in a reaction kettle container, wherein the addition of the sodium silicate solution accounts for 0.35-0.55 of the total addition; forming 0.25-0.45N aqueous alkali with higher sodium silicate concentration, and heating to 81-84 ℃; (2) carrying out a first-step reaction under the condition of stirring, wherein only concentrated sulfuric acid is added in the first-step reaction, the acid adding reaction time in the first step is 40-60 min, the reaction is finished when the neutralization rate reaches 50-85%, and the stirring is continued for 0-15 min; (3) carrying out a second step of reaction, namely adding concentrated sulfuric acid and sodium silicate solution at the same time to obtain a parallel flow acid and alkali addition reaction, wherein the reaction time is 50-80min, and the neutralization rate is 50-80%; (4) acidifying with peracid until the pH value of the reaction system is less than 5, and controlling the peracid time within 40min according to the flow rate of concentrated sulfuric acid; (5) stirring for 10min after the peracid reaction is finished; (6) and carrying out filter pressing, washing and drying on the reaction slurry to obtain the precipitated white carbon black for the high-modulus tire rubber. The invention has high production efficiency and low product cost.
Description
Technical Field
The invention relates to a preparation method of an inorganic powder material for reinforcing tire rubber, in particular to a preparation method of precipitated white carbon black for high-modulus tire rubber.
Background
The rubber reinforced by precipitated white carbon black is mainly used for shoes, tires and other light-colored rubber products. In China, the consumption proportion of the precipitated white carbon black for rubber products is as high as 81 percent, wherein the consumption proportion of the precipitated white carbon black for the tire industry accounts for about 38 percent.
White carbon black is one of the main reinforcing materials of rubber, and the change of the microstructure such as specific surface area, particle size, pore structure, surface hydroxyl content and the like greatly affects the physical and mechanical properties of tires. In order to adapt to different environments and application scenes, the automobile industry puts various requirements on the performance of tires, such as low rolling resistance, high wet skid resistance, high wear resistance, low noise, low exhaust emission, weather resistance and the like.
Modulus, a physical quantity describing the ability of a material to resist deformation, includes elastic deformation and plastic deformation. High modulus in tire rubber refers primarily to high modulus of elasticity. The elastic modulus can be regarded as an index for measuring the difficulty of the material in elastic deformation, and the larger the value of the elastic modulus, the larger the stress for causing the material to generate certain elastic deformation, that is, the higher the rigidity of the material, that is, the smaller the elastic deformation generated under the action of certain stress. The rubber modulus is mainly related to the composition of the rubber formula and the properties of the reinforcing material, and the reinforcing material has the greatest influence on the rubber modulus for fixing the rubber formula.
At present, when most non-racing tires on the market are large in steering angle, the grip capacity is slightly insufficient, the white carbon black product for high-modulus tire rubber can effectively improve the steering grip capacity of the tires, the product usually has high specific surface and high dispersion characteristics, and the white carbon black product can be applied to tire rubber to prepare the high-modulus rubber tires and improve the turning performance of automobile tires. However, in the actual production and preparation process, on one hand, the preparation of the precipitated silica white with high specific surface area requires the formation of a large number of crystal nuclei with small particles under the reaction condition of high supersaturation degree, but because the interior of the silica white is formed by the alternate connection of Si-O bonds, a spatially compact network structure is easily formed under high supersaturation degree, and a gel which is not easy to disperse is formed; on the other hand, the surface hydroxyl group density of the precipitated silica is generally increased along with the increase of the specific surface area, so that the precipitated silica with high specific surface area is easy to agglomerate in a dispersion system of rubber, paint and the like. Therefore, in actual production and application, the balance between high specific surface area and high dispersibility is difficult to realize, and the method becomes a technical difficulty in developing the precipitated silica with high dispersion and high specific surface area.
The high-dispersion high-specific surface area white carbon black products are new products which are developed and launched in recent years and are suitable for high-performance tires, and are represented by Zeosil 1200MP and Premium200MP of Solvay, Belgium, and Premium SW launched on the international tire design and technical exposition in 2017 held by Hannover, Germany, and 9000GR of the Germany winning industry group (original Desigus) and series products thereof, wherein the BET specific surface area of the products is more than 200m2The content is much higher than that of the traditional white carbon black for tire rubber. The development of the domestic precipitated silica with high specific surface area begins at the end of the last 20 th century. The research shows that the coating has high specific surfaceThe preparation of the white carbon black by the precipitation method is mainly realized by adding a dispersant into a reaction system and by a low-temperature seed crystal method. Synthesis of ultrafine SiO with high specific surface area by precipitation, as published in inorganic materials journal, 1997, Wangzizi et al2", it uses water glass and hydrochloric acid as raw material, adds non-ionic or cationic surfactant in the course of synthesis, and adds stabilizing agent before pulping and drying so as to obtain the specific surface area up to 1000m2Fine silica powder (g); chenjunhua of the Anhui scientific and technological institute in 2012 "preparation and characterization of high specific surface area sulfuric acid precipitation method nanometer white carbon black", it adds organic dispersant in reaction system, the specific surface area of the obtained white carbon black product is 400m2(ii)/g; 2013, Cheng Bei Hei of Xiamen university (Nature science edition), published by Tang Bei Hei et al in Xiamen university2The process research of (1) comprises adding NaCl salting-out agent and surfactant PEG into the reaction system, further soaking the precipitate with n-butanol, washing and drying to obtain silica sample with specific surface area up to 841m2Is obviously higher than that of the general precipitated SiO2Specific surface area (300- & lt 400 & gt m)2In terms of/g). The patent of Cheng Si chemical Co., Ltd in 2018 discloses a method for improving the specific surface area and pore volume of white carbon black, which comprises adding sodium benzoate and sodium sulfate into the synthesis reaction at concentrations of 20-30g/L and 30-50g/L, respectively, wherein the specific surface area of the white carbon black prepared in the example is 200-2(ii)/g; 2015, the finished silicon chemical company Limited discloses 'white carbon black with high specific surface area and a production method thereof', and the method adopts a two-step synthesis method: adding a proper amount of water and a dilute water glass solution into a reaction kettle in advance, adding a salt composition of an imidacloprid polymer as an electrolyte, carrying out acid addition reaction at a low temperature in the first step, and carrying out parallel flow reaction at a temperature of between 70 and 100 ℃ in the second step for 50 to 100min, wherein the specific surface area of the white carbon black prepared by the method is 200-450m2The rubber product has good performances such as wear resistance, breaking strength and the like; 2017, Fujian province Sanming Jufeng chemical Co., Ltd discloses a preparation method of high oil absorption and high reinforcement silicon dioxide for rubber products, and the method adopts a two-step synthesis methodThe first step of acid addition reaction is carried out at 60 ℃, then stirring is stopped and aging is carried out for 30min until jelly is generated, then the temperature of the reaction system is raised to 85 ℃ under the stirring condition, the second step of parallel flow reaction is started, and the obtained product has the specific surface area of 230-260m2A white carbon black product with DBP oil absorption value of 3.2-3.8 mL/g; 2018 Zhejiang Xinna Material science and technology Limited company discloses a method for preparing white carbon black with high specific surface area and high oil absorption, which adopts a two-step synthesis method, quaternary ammonium salt (preferably cetyl trimethyl ammonium bromide) is added into a reaction system, the reaction temperature of the first step is 45-55 ℃, the reaction temperature of the second step is 80-90 ℃, and the specific surface area of the prepared white carbon black reaches 200-2The oil absorption value reaches 3.0-3.5mL/g, and the polyurethane resin has good extinction performance when being used for paint coatings.
The above is the current situation of the preparation technology of white carbon black by high specific surface precipitation method at home and abroad. Most products and methods disclosed in China still stay in the laboratory stage, the industrialization is little, a few white carbon black enterprises in China currently adopt a two-step synthesis method to prepare the high specific surface area precipitation method white carbon black products, the industries such as coatings are oriented, the added value of the products is improved, but the method is limited in the prior production process technology that the first step of acidification reaction needs to be carried out at a low temperature, and the second step of cocurrent reaction needs to be carried out at a relatively high temperature, so that the production efficiency is low, the production cost is high, and the high specific surface area precipitation method white carbon black products are not suitable for producing rubber products by using a high filling rubber formula.
Disclosure of Invention
The invention aims to provide a preparation method of precipitated white carbon black for high-modulus tire rubber, which has the advantages of high production efficiency and low product cost, and the prepared product has high specific surface and high dispersion characteristics.
In order to realize the purpose, the preparation method of the precipitated silica white for high modulus tire rubber adopts a two-step precipitation method to prepare the high specific surface and high dispersion precipitated silica white, and the specific process steps are as follows:
(1) adding water and a sodium silicate solution into a reaction kettle container in advance, wherein the concentration of the sodium silicate solution is 2.47 +/-0.2 equivalent concentration, the volume ratio of the sodium silicate solution added at the stage to the total added sodium silicate is 0.35-0.55, forming an alkali solution with the sodium silicate concentration of 0.25-0.45 equivalent concentration, and heating to 81-84 ℃;
(2) carrying out a first-step reaction under the condition of stirring, wherein only concentrated sulfuric acid is added in the first-step reaction, the acid adding reaction time in the first step is 40-60 min, the first-step reaction is finished after the neutralization rate reaches 50-85%, and the stirring is continued for 0-15 min;
(3) carrying out a second step of reaction, namely adding concentrated sulfuric acid and sodium silicate solution at the same time to obtain a parallel flow acid and alkali addition reaction, wherein the reaction time is 50-80min, and the neutralization rate is 50-80%;
(4) acidifying with peracid until the pH value of the reaction system is less than 5, and controlling the peracid time within 40min according to the flow rate of concentrated sulfuric acid;
(5) stirring for 10min after the peracid reaction is finished;
(6) and carrying out filter pressing, washing and drying on the reaction slurry to obtain the precipitated white carbon black for the high-modulus tire rubber.
The peracid time of the step (4) is 25 min.
The preparation method of the precipitated white carbon black for the high-modulus tire rubber adopts an originally-created improved two-step synthesis method process, has the advantages of obvious high efficiency and low cost compared with the traditional two-step synthesis method process, almost no gel exists in the product, and the method is very suitable for reinforcing the tire rubber and has the following technical characteristics:
in one aspect, the reaction process for precipitating the white carbon black comprises silica nucleation, nucleus growth and particle-to-particle collision aggregation, wherein thermodynamic and kinetic parameters of the silica nucleation, the nucleus growth and the particle-to-particle collision aggregation are closely related to various reaction process parameters. The preparation of the white carbon black product with high specific surface area needs silica nucleation reaction under the condition of high degree of over saturation so as to be beneficial to forming a large number of fine crystal nuclei, but the defect is that the silica crystal nuclei are easy to agglomerate to form gel which is difficult to disperse under the condition. According to the invention, the stirring strength of the reaction vessel is enhanced, and the acid adding mode of the first-step reaction is improved, so that the reaction of the reaction system is more uniform; and raising the reaction temperature of the first step to increase the reaction rate. The two improvements can effectively inhibit the agglomeration between the initial crystal nuclei of the reaction system and avoid the formation of gel.
On the other hand, the silicon dioxide particles in the reaction system are aggregated to form a certain spatial structure, and products with the apparent same nitrogen adsorption BET specific surface area have different spatial structures, mainly the pore size distribution formed by aggregation is different, so that the products have different CTAB specific surface areas. According to the invention, the thermodynamic and kinetic parameters of particle collision aggregation are controlled by adjusting the acid-base neutralization rate, the pre-alkali addition amount and the co-current alkali amount ratio after the first-step reaction is finished, so that a white carbon black product with CTAB/BET <0.5 is prepared; the white carbon black product with CTAB/BET of less than 0.5 is prepared by controlling the neutralization rate of acid and alkali, the pre-alkali addition amount and the co-current alkali amount ratio after the first-step reaction is finished, and key process parameters for controlling the CTAB specific surface area index of the white carbon black product with high dispersion and high specific surface area are determined through empirical summary obtained through a large amount of creative work.
The preparation method of the precipitated white carbon black for the high-modulus tire rubber has the following beneficial effects:
(1) different from the traditional two-step synthesis process, the temperature of the first step of acid addition reaction is consistent with that of the second step of concurrent acid addition and alkali addition reaction, and the temperature rise reaction does not need to be carried out at low temperature in advance, so that the production efficiency is improved, and the production cost is reduced;
(2) the high-specific-ratio surface-white carbon black product prepared by the preparation method has the characteristic that CTAB/BET is less than 0.5, and can endow rubber with high elastic modulus.
Detailed Description
In order to illustrate the technical content, technical characteristics, achieved objects and effects of the preparation method of precipitated silica for high modulus tire rubber of the present invention in detail, the following detailed description is given with reference to the implementation examples. The total charged volume in the following examples is taken as 100 parts.
Example 1
The preparation method of the precipitated white carbon black for the high-modulus tire rubber is carried out according to the following process steps:
(1) preparing a reaction alkali: putting solid sodium silicate, also called water glass, and water into a static pressure kettle or a roller rotary spherical digester according to the mass ratio of about 1:1.5, introducing steam for heating and dissolving, diluting the water glass solution obtained by dissolving, preparing the sodium silicate solution with the target concentration of 2.47N, and finally conveying the sodium silicate solution to a high-level alkali tank.
(2) Pre-alkali adding stage: adding 65 parts by volume of water and 15.0 parts by volume of sodium silicate solution into a reaction kettle in advance, uniformly stirring, heating to 83 ℃, and controlling the temperature of a reaction system to be 83 ℃ in a subsequent reaction process.
(3) The first step is acid reaction: under the condition of stirring, concentrated sulfuric acid is added at the flow rate of 0.60 volume part/h, the acid adding reaction time in the first step is 60min, and the neutralization rate after the reaction is finished is about 59.6%.
(4) And (2) a second-step parallel flow reaction: after the first step of acid addition reaction is finished and stirring is continued for 5min, simultaneously adding sodium silicate solution and concentrated sulfuric acid solution of about 0.60 volume parts/h at the flow rate of 13.0 volume parts/h, and carrying out cocurrent acid-base neutralization at the rate of 68.8 percent, and after 80min of cocurrent reaction, finishing the cocurrent reaction.
(5) Peracid: adding concentrated sulfuric acid at the flow rate of 1.60 parts by volume/h until the pH value of the reaction system is 4, stopping adding, and continuing to age at the constant temperature for 10 min.
(6) Washing and drying: and transferring the aged reaction system to an intermediate tank, performing filter pressing and washing, pulping the washed filter cake up to the standard, and performing spray drying to obtain white particles and fine powder to obtain the high-specific-surface high-dispersion precipitation-method white carbon black product, wherein the main physical property parameters are shown in table 1.
Example 2
The preparation method of the precipitated white carbon black for the high-modulus tire rubber is carried out according to the following process steps:
(1) preparing a reaction alkali: putting solid sodium silicate, also called water glass, and water into a static pressure kettle or a roller rotary spherical digester according to the mass ratio of about 1:1.5, introducing steam for heating and dissolving, diluting the water glass solution obtained by dissolving, preparing the sodium silicate solution with the target concentration of 2.47N, and finally conveying the sodium silicate solution to a high-level alkali tank.
(2) Pre-alkali adding stage: adding 68 parts by volume of water and 12.0 parts by volume of sodium silicate solution into a reaction kettle in advance, uniformly stirring, heating to 81 ℃, and controlling the temperature of a reaction system to be 81 ℃ in a subsequent reaction process.
(3) The first step is acid reaction: under the condition of stirring, concentrated sulfuric acid is added at the flow rate of 0.90 volume portion/h, the acid adding reaction time in the first step is 40min, and the neutralization rate after the reaction is finished is about 74.5%.
(4) And (2) a second-step parallel flow reaction: after the first step of acid addition reaction is finished and stirring is continued for 5min, simultaneously adding sodium silicate solution and concentrated sulfuric acid solution of about 0.60 volume part/h at the flow rate of 15.2 volume parts/h, wherein the concurrent flow acid-base neutralization rate is 58.8 percent, the concurrent flow reaction time is 80min, and after the concurrent flow reaction is finished, stirring is continued for 10 min.
(5) Peracid: adding concentrated sulfuric acid at the flow rate of 1.00 volume part/h until the pH value of the reaction system is 4, stopping adding, and continuing constant-temperature aging for 10 min.
(6) Washing and drying: and transferring the aged reaction system to an intermediate tank, performing filter pressing and washing, pulping the washed filter cake up to the standard, and performing spray drying to obtain white particles and fine powder to obtain the high-specific-surface high-dispersion precipitation-method white carbon black product, wherein the main physical property parameters are shown in table 1.
Example 3
The preparation method of the precipitated white carbon black for the high-modulus tire rubber is carried out according to the following process steps:
(1) preparing a reaction alkali: putting solid sodium silicate, also called water glass, and water into a static pressure kettle or a roller rotary spherical digester according to the mass ratio of about 1:1.5, introducing steam for heating and dissolving, diluting the water glass solution obtained by dissolving, preparing the sodium silicate solution with the target concentration of 2.47N, and finally conveying the sodium silicate solution to a high-level alkali tank.
(2) Pre-alkali adding stage: 62 parts by volume of water and 18.0 parts by volume of sodium silicate solution are added into a reaction kettle in advance, the temperature is raised to 83.5 ℃ after uniform stirring, and the temperature of a reaction system is controlled to be 83.5 ℃ in the subsequent reaction process.
(3) The first step is acid reaction: under the condition of stirring, concentrated sulfuric acid is added at the flow rate of 0.6 volume portion/h, the first-step acid adding reaction time is 60min, and the neutralization rate after the reaction is finished is about 50.0%.
(4) And (2) a second-step parallel flow reaction: after the first step of acid addition reaction is finished and stirring is continued for 5min, simultaneously adding sodium silicate solution and concentrated sulfuric acid solution of about 0.80 volume part/h at the flow rate of 14.2 volume parts/h, wherein the concurrent flow acid-base neutralization rate is about 84.0 percent, the concurrent flow reaction time is 60min, and after the concurrent flow reaction is finished, stirring is continued for 5 min.
(5) Peracid: adding concentrated sulfuric acid at the flow rate of 1.50 parts by volume/h until the pH value of the reaction system is 4, and continuing to age for 10min at constant temperature.
(6) Washing and drying: and transferring the aged reaction system to an intermediate tank, performing filter pressing and washing, pulping the washed filter cake up to the standard, and performing spray drying to obtain white particles and fine powder to obtain the high-specific-surface high-dispersion precipitation-method white carbon black product, wherein the main physical property parameters are shown in table 1.
TABLE 1 examples key physical properties of white carbon
| Test items (Unit) | Example 1 | Example 2 | Example 3 |
| BET specific surface area (m)2/g) | 223 | 234 | 229 |
| CTAB specific surface area (m)2/g) | 106 | 114 | 97 |
| CTAB/BET | 0.475 | 0.487 | 0.423 |
As can be seen from Table 1, the precipitated silica products obtained in the above three examples all satisfy the BET specific surface area higher than 200m2(iv) g and CTAB/BET<0.5, can be used as high-specific-ratio surface-precipitation white carbon black for high-modulus tire rubber.
The above description is only an embodiment of the present invention, and not intended to limit the scope of the present invention, and all modifications of equivalent structures and equivalent processes, or direct and indirect applications in other related fields, which are made by the contents of the present specification, are included in the scope of the present invention.
Claims (2)
1. A preparation method of precipitated silica for high modulus tire rubber adopts a two-step precipitation method to prepare high specific surface and high dispersion precipitated silica, and is characterized in that: the specific process steps are as follows:
(1) adding water and a sodium silicate solution into a reaction kettle container in advance, wherein the concentration of the sodium silicate solution is 2.47 +/-0.2 equivalent concentration, the volume ratio of the sodium silicate solution added at the stage to the total added sodium silicate is 0.35-0.55, forming an alkali solution with the sodium silicate concentration of 0.25-0.45 equivalent concentration, and heating to 81-84 ℃;
(2) carrying out a first-step reaction under the condition of stirring, wherein only concentrated sulfuric acid is added in the first-step reaction, the acid adding reaction time in the first step is 40-60 min, the first-step reaction is finished after the neutralization rate reaches 50-85%, and the stirring is continued for 0-15 min;
(3) carrying out a second step of reaction, namely adding concentrated sulfuric acid and sodium silicate solution at the same time to obtain a parallel flow acid and alkali addition reaction, wherein the reaction time is 50-80min, and the neutralization rate is 50-80%;
(4) acidifying with peracid until the pH value of the reaction system is less than 5, and controlling the peracid time within 40min according to the flow rate of concentrated sulfuric acid;
(5) stirring for 10min after the peracid reaction is finished;
(6) and carrying out filter pressing, washing and drying on the reaction slurry to obtain the precipitated white carbon black for the high-modulus tire rubber.
2. The preparation method of the precipitated silica white for high modulus tire rubber as claimed in claim 1, which is characterized by comprising the following steps: the peracid time of the step (4) is 25 min.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113830773A (en) * | 2021-10-11 | 2021-12-24 | 福建正盛无机材料股份有限公司 | Preparation method of white carbon black by large pore volume precipitation method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100473603C (en) * | 2001-09-20 | 2009-04-01 | 德古萨公司 | Precipitated silica with a high BET/CTAB ratio |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN100473603C (en) * | 2001-09-20 | 2009-04-01 | 德古萨公司 | Precipitated silica with a high BET/CTAB ratio |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113830773A (en) * | 2021-10-11 | 2021-12-24 | 福建正盛无机材料股份有限公司 | Preparation method of white carbon black by large pore volume precipitation method |
| CN113830773B (en) * | 2021-10-11 | 2023-10-24 | 福建正盛无机材料股份有限公司 | Preparation method of white carbon black by large pore volume precipitation method |
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Application publication date: 20201127 |