WO2023035099A1 - Precipitated silicon dioxide for green tire and preparation method for precipitated silicon dioxide - Google Patents

Precipitated silicon dioxide for green tire and preparation method for precipitated silicon dioxide Download PDF

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Publication number
WO2023035099A1
WO2023035099A1 PCT/CN2021/116857 CN2021116857W WO2023035099A1 WO 2023035099 A1 WO2023035099 A1 WO 2023035099A1 CN 2021116857 W CN2021116857 W CN 2021116857W WO 2023035099 A1 WO2023035099 A1 WO 2023035099A1
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Prior art keywords
treatment
value
preparation
slurry
ammonia water
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PCT/CN2021/116857
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French (fr)
Chinese (zh)
Inventor
陈南飞
卢爱平
王明贺
陈辰
陈家树
史彤
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无锡恒诚硅业有限公司
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Priority to PCT/CN2021/116857 priority Critical patent/WO2023035099A1/en
Priority to CN202180002650.8A priority patent/CN113905985B/en
Publication of WO2023035099A1 publication Critical patent/WO2023035099A1/en

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/113—Silicon oxides; Hydrates thereof
    • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
    • C01B33/18—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof
    • C01B33/186—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof from or via fluosilicic acid or salts thereof by a wet process
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/12—Surface area
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/80—Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
    • Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction 

Definitions

  • the application relates to the field of green tire reinforcement, in particular to precipitated silica for green tires and a preparation method thereof.
  • precipitated silica or white carbon black has been widely used as a new reinforcing material instead of carbon black due to its good performance.
  • CN109096799A discloses a secondary modified silica for tires, comprising the following steps: selecting a carbon source with a mesh number of 1100-1200 silica and a particle diameter of 6-15nm to carry out drying treatment respectively, and respectively drying the silica ,
  • the carbon source is dried in a vacuum dryer, the drying temperature is 20-40 °C, the drying time is based on the moisture content of the silica and the carbon source itself is less than 0.2%, and then the above-mentioned silica and carbon source are attached Charge treatment to obtain secondary modified white carbon black for tires.
  • the secondary modified silica for tires first modifies and modifies the surface of the silica and then grafts the polymer to construct a rough structure on the surface of the secondary modified silica, so that the surface of the silica is formed
  • the silica with uniform thickness and good dispersion effect makes the silica have hydrophobic properties, which enhances the contact area between the silica and the rubber used in the rubber, and can enhance the tear strength and tensile strength of the tire when used in the preparation of tires .
  • CN111171410A discloses a modified white carbon black reinforced rubber tire material and a preparation method thereof.
  • the modified white carbon black reinforced rubber tire material is composed of solution polystyrene butadiene rubber, rare earth butadiene rubber, butadiene rubber, modified white carbon Black, starch nanocrystals, cellulose acetate, calcium oxide, anti-slip agent, nano-zinc oxide, stearic acid, anti-aging agent, accelerator, vulcanizing agent, the preparation steps of the modified silica reinforced rubber tire material Including: the preparation of modified white carbon black, the mixing of processing aids, the mixing and milling of rubber, the mixing and heating of additives and rubber, and vulcanization molding.
  • the dispersion of silica in rubber is improved, and then the dispersion of silica is further enhanced by adding and mixing with processing aids in batches, reducing internal friction and fatigue heat generation Decrease, the ability to resist external mechanical force is enhanced, and the wear resistance and aging resistance are enhanced, thereby prolonging the service life of the rubber material.
  • the precipitated silica obtained by the current preparation method still needs to be modified before it can be directly used as a reinforcing material in tires. Although there are some schemes in the prior art that can directly prepare reinforcing precipitated silica for tires, the obtained precipitates The dispersibility of silica is still poor, and the tire cannot meet expectations after reinforcement.
  • This application provides a kind of precipitated silica for green tires and its preparation method.
  • the problem of poor dispersion and reinforcement of white carbon black directly prepared at present is solved.
  • the problem of insufficient performance is solved.
  • the application provides a method for preparing precipitated silica for green tires, the preparation method comprising the steps of:
  • step (2) mixing the first slurry obtained in step (1) with the ammonium salt solution for a second treatment to obtain a second slurry
  • step (3) The second slurry obtained in step (2) is mixed with ammonia water B to perform the third treatment.
  • the pH value of the filtrate is adjusted to a predetermined value after the solid-liquid separation is performed every time the pH value is reduced by 0.2-0.5.
  • the pH value is continuously processed until no precipitate is formed and the solid phase obtained by the solid-liquid separation is mixed to obtain the precipitated silica for green tires.
  • the method provided by this application realizes the preparation of high-performance precipitated silica by improving the composition of the raw material liquid and adopting multiple treatments during the treatment process.
  • the obtained precipitated silica has a particle size of 15-30nm and a BET specific surface area of 210- 230m 2 /g, tensile strength 44.2-52.6MPa, abrasion resistance 0.18-0.3cm 3 /1.6km, tear strength 150-180kN/m.
  • the ammonium salt may be one or a combination of at least two soluble ammonium salts such as ammonium sulfate, ammonium chloride, ammonium nitrate, and ammonium fluoride.
  • the mass concentration of the ammonium salt solution is 10-15%.
  • the molar ratio of fluosilicic acid and sodium silicate in step (1) is 1:(1.2.-1.8), for example, it can be 1:1.2, 1:1.22, 1:1.24, 1 :1.26, 1:1.28, 1:1.3, 1:1.32, 1:1.34, 1:1.36, 1:1.38, 1:1.4, 1:1.42, 1:1.44, 1:1.46, 1:1.48, 1:1.45 , 1:1.52, 1:1.54, 1:1.56, 1:1.58, 1:1.6, 1:1.62, 1:1.64, 1:1.66, 1:1.68, 1:1.7, 1:1.72, 1:1.74, 1 :1.76, 1:1.78 or 1:1.8, etc., but not limited to the listed values, other unlisted combinations within this range are also applicable.
  • the molar concentration of silicon in the mixed solution described in step (1) is 10-12mol/L, such as 10mol/L, 10.1mol/L, 10.2mol/L, 10.3mol/L, 10.4mol/L , 10.5mol/L, 10.6mol/L, 10.7mol/L, 10.8mol/L, 10.9mol/L, 11mol/L, 11.1mol/L, 11.2mol/L, 11.3mol/L, 11.4mol/L, 11.5mol/L, 11.6mol/L, 11.7mol/L, 11.8mol/L, 11.9mol/L or 12mol/L, etc., but not limited to the listed values, other unlisted combinations within this range are also applicable.
  • the mass concentration of ammonia water A in step (1) is 10-15%, for example, it can be 10%, 10.5%, 11%, 11.5%, 12%, 12.5%, 13%, 13.5% %, 14%, 14.5% or 15%, but not limited to the listed values, other unlisted combinations within this range are also applicable.
  • the pH value of the first treatment in step (1) is 3.6-4, such as 3.6, 3.7, 3.8, 3.9 or 4, etc., but not limited to the listed values, other unlisted combinations within this range The same applies.
  • the temperature of the first treatment in step (1) is 80-90°C, such as 80°C, 81°C, 82°C, 83°C, 84°C, 85°C, 86°C, 87°C, 88°C, 89°C or 90°C, etc., but not limited to the listed values, and other unlisted combinations within this range are also applicable.
  • the time for the first treatment in step (1) is 90-120min, such as 90min, 92min, 94min, 96min, 98min, 100min, 102min, 104min, 106min, 108min, 110min, 112min, 114min, 116min, 118min or 120min, etc., but not limited to the listed values, other unlisted combinations within this range are also applicable.
  • the formation of the precursor in the first treatment can be enhanced by adopting a specific ratio of raw material liquid composition, which is beneficial to the subsequent nucleation of precipitated silica.
  • the mass ratio of the slurry and the ammonium salt solution described in step (2) is 1:(0.2-0.5), such as 1:0.2, 1:0.22, 1:0.24, 1:0.26, 1:0.28, 1:0.3, 1:0.32, 1:0.34, 1:0.36, 1:0.38, 1:0.4, 1:0.42, 1:0.44, 1:0.46, 1:0.48 or 1:0.5, etc., but Not limited to the listed values, other unlisted combinations within this range are also applicable.
  • the temperature of the second treatment in step (2) is 120-130°C, for example, it can be 120°C, 121°C, 122°C, 123°C, 124°C, 125°C, 126°C, 127°C °C, 128 °C, 129 °C, or 130 °C, etc., but not limited to the listed values, and other unlisted combinations within this range are also applicable.
  • the time for the second treatment in step (2) is 20-35min, such as 20min, 21min, 22min, 23min, 24min, 25min, 26min, 27min, 28min, 29min, 30min, 31min, 32min, 33min, 34min or 35min, etc., but not limited to the listed values, other unlisted combinations within this range are also applicable.
  • the second treatment in step (2) is carried out under an ammonia atmosphere.
  • the volume fraction of ammonia in the ammonia atmosphere is 7-12%, such as 7%, 7.5%, 8%, 8.5%, 9%, 9.5%, 10%, 10.5%, 11%, 11.5% or 12%, etc., but not limited to the listed values, other unlisted combinations within this range are also applicable.
  • the remaining volume in the ammonia atmosphere is replaced by gases that will not participate, such as nitrogen or inert gases.
  • the aggregation of precipitated silica particles in the third treatment process can be significantly reduced to ensure that the final precipitated silica has good dispersibility and ensure the obtained Precipitated silica can achieve good reinforcement.
  • the mass concentration of ammonia water B in step (3) is 20-30%, for example, it can be 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27% %, 28%, 29% or 30%, etc., but not limited to the listed values, other unlisted combinations within this range are also applicable.
  • the pH value of the third treatment in step (3) is 6.5-8, such as 6.5, 6.6, 6.7, 6.8, 6.9, 7, 7.1, 7.2, 7.3, 7.4, 7.5, 7.6, 7.7, 7.8 , 7.9 or 8, etc., but not limited to the listed values, other unlisted combinations within this range are also applicable.
  • the temperature of the third treatment in step (3) is 80-90°C, such as 80°C, 81°C, 82°C, 83°C, 84°C, 85°C, 86°C, 87°C, 88°C, 89°C or 90°C, etc., but not limited to the listed values, and other unlisted combinations within this range are also applicable.
  • the predetermined pH value in step (3) is equal to the pH value of the third treatment.
  • a specific treatment process is adopted in the third treatment, and solid-liquid separation is carried out every time the pH decreases by 0.2-0.5 during the treatment process, so as to further ensure that the problem of particle aggregation will not occur during the formation of precipitated silica . That is, solid-liquid separation is carried out every time the pH decreases by 0.2-0.5, and then the pH value is adjusted to the pH value of the third treatment for reaction, and the operation is repeated until no precipitation is formed.
  • the total time for the third treatment is 45-80 minutes, including solid-liquid separation and generation of precipitated silica. If only precipitated silica is involved, the generation time is 30-60min.
  • the preparation method includes the following steps:
  • step (2) mixing the first slurry and the ammonium salt solution obtained in step (1) for the second treatment to obtain the second slurry; the mass ratio of the slurry and the ammonium salt solution is 1:(0.2-0.5);
  • the temperature of the second treatment is 120-130°C; the time of the second treatment is 20-35min; the second treatment is carried out under an ammonia atmosphere; the volume fraction of ammonia in the ammonia atmosphere is 7- 12%; and
  • step (3) The second slurry obtained in step (2) is mixed with ammonia water B for the third treatment, and the pH value of the filtrate is adjusted to a predetermined pH after the solid-liquid separation is carried out every time the pH is reduced by 0.2-0.5 in the second treatment value continues to be processed until no precipitation is formed and the solid phase obtained by mixing the solid-liquid separation is obtained to obtain the precipitated silica for green tires; the mass concentration of the ammonia water B is 20-30%; the third treatment The pH value is 6.5-8; the temperature of the third treatment is 80-90° C.; the predetermined pH value is equal to the pH value of the third treatment.
  • the application provides the precipitated silica for green tires obtained by the preparation method described in the first aspect, wherein the precipitated silica for green tires has a particle size of 15-30nm and a BET ratio of The surface area is 210-230m 2 /g, the tensile strength is 44.2-52.6MPa, the wear resistance is 0.18-0.3cm 3 /1.6km, and the tear strength is 150-180kN/m.
  • the particle size of the obtained precipitated silica is 15-30nm
  • the BET specific surface area is 210-230m 2 /g
  • the tensile strength is 44.2-52.6MPa
  • the wear resistance is 0.18-0.3 cm 3 /1.6km
  • the tear strength is 150-180kN/m.
  • the present embodiment provides a kind of preparation method for the precipitated silica of green tire, and described preparation method comprises the following steps:
  • step (2) The first slurry obtained in step (1) is mixed with the ammonium salt solution (ammonium chloride) for the second treatment to obtain the second slurry; the mass ratio of the slurry and the ammonium salt solution is 1:0.35; The temperature of the second treatment is 125°C; the time of the second treatment is 27min; the second treatment is carried out under an ammonia atmosphere; the volume fraction of ammonia in the ammonia atmosphere is 9%;
  • step (3) The second slurry obtained in step (2) is mixed with ammonia water B for the third treatment.
  • the pH value of the filtrate is adjusted to a predetermined pH value after the solid-liquid separation is carried out every time the pH is reduced by 0.3. Treat until no precipitation is formed and mix the solid phase obtained by the solid-liquid separation to obtain the precipitated silica for green tires; the mass concentration of the ammonia water B is 25%; the pH value of the third treatment is 7; the temperature of the third treatment is 85° C.; the predetermined pH value is equal to the pH value of the third treatment.
  • the present embodiment provides a kind of preparation method for the precipitated silica of green tire, and described preparation method comprises the following steps:
  • step (2) The first slurry obtained in step (1) is mixed with the ammonium salt solution (ammonium sulfate) for the second treatment to obtain the second slurry; the mass ratio of the slurry and the ammonium salt solution is 1:0.5;
  • the temperature of the second treatment is 120°C; the time of the second treatment is 35min; the second treatment is carried out under an ammonia atmosphere; the volume fraction of ammonia in the ammonia atmosphere is 7%;
  • step (3) The second slurry obtained in step (2) is mixed with ammonia water B for the third treatment.
  • the pH value of the filtrate is adjusted to a predetermined pH value after the solid-liquid separation is carried out every time the pH is reduced by 0.5. Treat until no precipitation is formed and mix the solid phase obtained by the solid-liquid separation to obtain the precipitated silica for green tires; the mass concentration of the ammonia water B is 20%; the pH value of the third treatment is 6.5; the temperature of the third treatment is 90°C; the predetermined pH value is equal to the pH value of the third treatment.
  • the present embodiment provides a kind of preparation method for the precipitated silica of green tire, and described preparation method comprises the following steps:
  • step (2) The first slurry obtained in step (1) is mixed with the ammonium salt solution (ammonium fluoride) for the second treatment to obtain the second slurry; the mass ratio of the slurry and the ammonium salt solution is 1:0.2;
  • the temperature of the second treatment is 130°C; the time of the second treatment is 20min; the second treatment is carried out under an ammonia atmosphere; the volume fraction of ammonia in the ammonia atmosphere is 12%;
  • step (3) The second slurry obtained in step (2) is mixed with ammonia water B for the third treatment, and the pH value of the filtrate is adjusted to a predetermined pH value after the solid-liquid separation is performed every time the pH is reduced by 0.2 in the second treatment. Treat until no precipitation is formed and mix the solid phase obtained by the solid-liquid separation to obtain the precipitated silica for green tires; the mass concentration of the ammonia water B is 30%; the pH value of the third treatment is 8; the temperature of the third treatment is 80° C.; the predetermined pH value is equal to the pH value of the third treatment.
  • the present embodiment provides a kind of preparation method for the precipitated silica of green tire, and described preparation method comprises the following steps:
  • step (2) The first slurry obtained in step (1) is mixed with the ammonium salt solution (ammonium acetate) for the second treatment to obtain the second slurry; the mass ratio of the slurry and the ammonium salt solution is 1:0.33;
  • the temperature of the second treatment is 122°C; the time of the second treatment is 33min; the second treatment is carried out under an ammonia atmosphere; the volume fraction of ammonia in the ammonia atmosphere is 11%;
  • step (3) The second slurry obtained in step (2) is mixed with ammonia water B for the third treatment.
  • the pH value of the filtrate is adjusted to a predetermined pH value after the solid-liquid separation is carried out every time the pH is reduced by 0.4. Treat until no precipitation is formed and mix the solid phase obtained by the solid-liquid separation to obtain the precipitated silica for green tires; the mass concentration of the ammonia water B is 22%; the pH value of the third treatment is 7.7; the temperature of the third treatment is 82°C; the predetermined pH value is equal to the pH value of the third treatment.
  • Example 1 The difference from Example 1 is only that the sodium silicate in the mixed solution is replaced by an equivalent amount of sodium fluorosilicate.
  • the performance index and application performance of the obtained precipitated silica for green tires are shown in Table 1.
  • Example 1 The difference from Example 1 is only that the second treatment of step (2) is not carried out, and the slurry and ammonia water are directly mixed for the third treatment.
  • the performance index and application performance of the obtained precipitated silica for green tires are shown in Table 1.
  • Example 1 The difference from Example 1 is that the pH value of the third treatment is directly controlled to be 7 to the end of the treatment, and solid-liquid separation is not carried out in the middle, and the treatment time is the same as that of Example 1.
  • the performance index and application performance of the obtained precipitated silica for green tires are shown in Table 1.
  • Example 1 The difference with Example 1 is only that the ammonium salt solution in the step (2) is replaced with the ammoniacal liquor of equal concentration.
  • the performance index and application performance of the obtained precipitated silica for green tires are shown in Table 1.
  • Example 1 The difference from Example 1 is that the solid-liquid separation is performed every time the pH value decreases by 1.
  • the performance index and application performance of the obtained precipitated silica for green tires are shown in Table 1.
  • the test of the BET specific surface area in the present embodiment and comparative examples is measured according to GB/T19587-2017; the particle size analysis is by ultrasonically dispersing the white carbon black dispersed in the ethanol solution, and then dripping and dispersing it on a specific copper grid.
  • Use JEM-2100 Jopan Electronics Co., Ltd.
  • transmission electron microscope to observe and analyze microscopic particles; the mechanical properties of rubber directly determine the application performance and application fields of tire rubber.
  • this application prepares precipitated silica into mixed rubber, and according to GB/T528-2009, the vulcanized rubber after 24 hours is cut into "dumbbell-shaped" tensile splines under the mold, using AI-7000S (Gaotie Testing Instrument Co., Ltd.) tensile machine, testing the tensile strength of vulcanized rubber at a tensile speed of 500mm/min.
  • AI-7000S Gaotie Testing Instrument Co., Ltd.
  • Abrasion resistance is one of the three important indicators to characterize the performance of tire rubber. According to the regulations of GB/T9867-2008, this study adopts the GT-7012-D (Gaotie Testing Instrument Co., Ltd.) wear resistance testing machine to measure the mass loss value of the vulcanized rubber, and calculate the relative volumetric wear of the rubber through the formula , thus reflecting the wear resistance of rubber.
  • GT-7012-D Gaotie Testing Instrument Co., Ltd.

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Abstract

The present application relates to precipitated silicon dioxide for a green tire and a preparation method for the precipitated silicon dioxide. The preparation method comprises the following steps: adding ammonia water into a mixed solution of fluosilicic acid and sodium silicate for treatment to obtain first slurry; mixing the obtained first slurry with an ammonium salt solution for treatment to obtain second slurry; mixing the obtained second slurry with ammonia water for treatment, performing solid-liquid separation once every time the pH value is decreased by 0.2-0.5 in the treatment, then adjusting the pH value of a filtrate to a preset pH value, and continuously treating till no precipitate is formed then to mix a solid phase obtained by the solid-liquid separation to obtain the precipitated silicon dioxide for the green tire. By improving the composition of raw material liquid and using a mode of multiple times of treatment in the treatment process, the preparation of the high-performance precipitated silicon dioxide is achieved, the wear resistance of the obtained precipitated silicon dioxide is 0.18-0.3 cm3/1.6 km, and the tear strength is 150-180 kN/m.

Description

一种用于绿色轮胎的沉淀二氧化硅及其制备方法A kind of precipitated silica for green tire and preparation method thereof 技术领域technical field
本申请涉及绿胎补强领域，具体涉及一种用于绿色轮胎的沉淀二氧化硅及其制备方法。The application relates to the field of green tire reinforcement, in particular to precipitated silica for green tires and a preparation method thereof.
背景技术Background technique
目前，沉淀二氧化硅即白炭黑由于具有良好的性能，已取代炭黑作为新的补强材料广泛使用。At present, precipitated silica or white carbon black has been widely used as a new reinforcing material instead of carbon black due to its good performance.
如CN109096799A公开了一种轮胎用二次改性白炭黑，包括以下步骤：选用目数为1100～1200白炭黑、粒径为6～15nm的碳源分别进行干燥处理，分别将白炭黑、碳源置于真空干燥器中进行干燥，干燥温度为20～40℃，干燥时间以白炭黑、碳源自身含水量低于0.2％为准，然后将上述白炭黑、碳源进行附电荷处理，得到轮胎用二次改性白炭黑。所述轮胎用二次改性白炭黑首先是对白炭黑表面进行修饰改性后再接枝聚合物，构造了二次改性白炭黑表面的粗糙结构，从而使得白炭黑的表面形成厚度均匀，分散效果好的白炭黑，使得白炭黑具有疏水性能，增强了白炭黑用于橡胶中的与橡胶的接触面积，用于制备轮胎能够增强轮胎的撕裂强度与拉伸强度。For example, CN109096799A discloses a secondary modified silica for tires, comprising the following steps: selecting a carbon source with a mesh number of 1100-1200 silica and a particle diameter of 6-15nm to carry out drying treatment respectively, and respectively drying the silica , The carbon source is dried in a vacuum dryer, the drying temperature is 20-40 °C, the drying time is based on the moisture content of the silica and the carbon source itself is less than 0.2%, and then the above-mentioned silica and carbon source are attached Charge treatment to obtain secondary modified white carbon black for tires. The secondary modified silica for tires first modifies and modifies the surface of the silica and then grafts the polymer to construct a rough structure on the surface of the secondary modified silica, so that the surface of the silica is formed The silica with uniform thickness and good dispersion effect makes the silica have hydrophobic properties, which enhances the contact area between the silica and the rubber used in the rubber, and can enhance the tear strength and tensile strength of the tire when used in the preparation of tires .
CN111171410A公开了一种改性白炭黑增强橡胶轮胎材料及其制备方法，所述改性白炭黑增强橡胶轮胎材料由溶聚丁苯胶、稀土丁二橡胶、顺丁橡胶、改性白炭黑、淀粉纳米晶、醋酸纤维素、氧化钙、防滑剂、纳米氧化锌、硬脂酸、防老剂、促进剂、硫化剂制备而成，所述改性白炭黑增强橡胶轮胎材料的制备步骤包括：改性白炭黑的制备、加工助剂的混合、橡胶的混合开炼、助剂与橡胶的混合加热成型、硫化成型。通过加入改性的白炭黑，提高了白炭黑在橡胶中的分散性，之后通过与加工助剂分批添加混合的方式进一步增强了白炭黑的分散性，内摩擦减少，疲劳生热下降，抵抗外界机械力的能力增强，耐磨性、抗老化性增强，从而延长了橡胶材料的使用寿命。CN111171410A discloses a modified white carbon black reinforced rubber tire material and a preparation method thereof. The modified white carbon black reinforced rubber tire material is composed of solution polystyrene butadiene rubber, rare earth butadiene rubber, butadiene rubber, modified white carbon Black, starch nanocrystals, cellulose acetate, calcium oxide, anti-slip agent, nano-zinc oxide, stearic acid, anti-aging agent, accelerator, vulcanizing agent, the preparation steps of the modified silica reinforced rubber tire material Including: the preparation of modified white carbon black, the mixing of processing aids, the mixing and milling of rubber, the mixing and heating of additives and rubber, and vulcanization molding. By adding modified silica, the dispersion of silica in rubber is improved, and then the dispersion of silica is further enhanced by adding and mixing with processing aids in batches, reducing internal friction and fatigue heat generation Decrease, the ability to resist external mechanical force is enhanced, and the wear resistance and aging resistance are enhanced, thereby prolonging the service life of the rubber material.
当前制备方法得到的沉淀二氧化硅仍需要改性后方可直接用于轮胎中做补强材料，虽然现有技术中已有部分方案可直接制备轮胎用的补强沉淀二氧化硅，但是所得沉淀二氧化硅的分散性仍较差，轮胎补强后仍不能达到预期。The precipitated silica obtained by the current preparation method still needs to be modified before it can be directly used as a reinforcing material in tires. Although there are some schemes in the prior art that can directly prepare reinforcing precipitated silica for tires, the obtained precipitates The dispersibility of silica is still poor, and the tire cannot meet expectations after reinforcement.
发明内容Contents of the invention
本申请提供了一种用于绿色轮胎的沉淀二氧化硅及其制备方法，通过对现有制备方法的改进，选择合适的原料和工艺解决了目前直接制备得到的白炭黑分散性差，补强性能不足的问题。This application provides a kind of precipitated silica for green tires and its preparation method. By improving the existing preparation method and selecting suitable raw materials and processes, the problem of poor dispersion and reinforcement of white carbon black directly prepared at present is solved. The problem of insufficient performance.
第一方面，本申请提供了一种用于绿色轮胎的沉淀二氧化硅的制备方法，所述制备方法包括如下步骤：In a first aspect, the application provides a method for preparing precipitated silica for green tires, the preparation method comprising the steps of:
(1)向氟硅酸和硅酸钠的混合溶液中加入氨水A进行第一处理，得到第一浆液；(1) adding ammonia water A to the mixed solution of fluorosilicic acid and sodium silicate for the first treatment to obtain the first slurry;
(2)将步骤(1)得到的所述第一浆液和铵盐溶液混合进行第二处理，得到第二浆液；以及(2) mixing the first slurry obtained in step (1) with the ammonium salt solution for a second treatment to obtain a second slurry; and
(3)将步骤(2)得到的所述第二浆液和氨水B混合进行第三处理，所述第二处理中pH值每降低0.2-0.5进行一次固液分离之后调整滤液的pH值至预定pH值继续进行处理，至无沉淀形成混合所述固液分离得到的固相得到所述用于绿色轮胎的沉淀二氧化硅。(3) The second slurry obtained in step (2) is mixed with ammonia water B to perform the third treatment. In the second treatment, the pH value of the filtrate is adjusted to a predetermined value after the solid-liquid separation is performed every time the pH value is reduced by 0.2-0.5. The pH value is continuously processed until no precipitate is formed and the solid phase obtained by the solid-liquid separation is mixed to obtain the precipitated silica for green tires.
本申请提供的方法，通过改进原料液的组成及处理过程中采用多次处理的方式实现了高性能沉淀二氧化硅的制备，所得沉淀二氧化硅粒度为15-30nm，BET比表面积为210-230m 2/g，拉伸强度为44.2-52.6MPa，耐磨性能为0.18-0.3cm 3/1.6km，撕裂强度为150-180kN/m。 The method provided by this application realizes the preparation of high-performance precipitated silica by improving the composition of the raw material liquid and adopting multiple treatments during the treatment process. The obtained precipitated silica has a particle size of 15-30nm and a BET specific surface area of 210- 230m 2 /g, tensile strength 44.2-52.6MPa, abrasion resistance 0.18-0.3cm 3 /1.6km, tear strength 150-180kN/m.
本申请中，所述铵盐可以是硫酸铵，氯化铵，硝酸铵，氟化铵等可溶性铵盐中的1种或至少2种的组合。铵盐溶液的质量浓度为10-15％。In the present application, the ammonium salt may be one or a combination of at least two soluble ammonium salts such as ammonium sulfate, ammonium chloride, ammonium nitrate, and ammonium fluoride. The mass concentration of the ammonium salt solution is 10-15%.
作为本申请优选的技术方案，步骤(1)所述氟硅酸和硅酸钠的摩尔比为1:(1.2.-1.8)，例如可以是1:1.2、1:1.22、1:1.24、1:1.26、1:1.28、1:1.3、1:1.32、1:1.34、1:1.36、1:1.38、1:1.4、1:1.42、1:1.44、1:1.46、1:1.48、1:1.45、1:1.52、1:1.54、1:1.56、1:1.58、1:1.6、1:1.62、1:1.64、1:1.66、1:1.68、1:1.7、1:1.72、1:1.74、1:1.76、1:1.78或1:1.8等，但不限于所列举的数值，该范围内其他未列举的组合同样适用。As a preferred technical solution of the present application, the molar ratio of fluosilicic acid and sodium silicate in step (1) is 1:(1.2.-1.8), for example, it can be 1:1.2, 1:1.22, 1:1.24, 1 :1.26, 1:1.28, 1:1.3, 1:1.32, 1:1.34, 1:1.36, 1:1.38, 1:1.4, 1:1.42, 1:1.44, 1:1.46, 1:1.48, 1:1.45 , 1:1.52, 1:1.54, 1:1.56, 1:1.58, 1:1.6, 1:1.62, 1:1.64, 1:1.66, 1:1.68, 1:1.7, 1:1.72, 1:1.74, 1 :1.76, 1:1.78 or 1:1.8, etc., but not limited to the listed values, other unlisted combinations within this range are also applicable.
优选地，步骤(1)所述混合溶液中硅元素的摩尔浓度为10-12mol/L，例如可以是10mol/L、10.1mol/L、10.2mol/L、10.3mol/L、10.4mol/L、10.5mol/L、10.6mol/L、10.7mol/L、10.8mol/L、10.9mol/L、11mol/L、11.1mol/L、11.2mol/L、11.3mol/L、11.4mol/L、11.5mol/L、11.6mol/L、11.7mol/L、11.8mol/L、11.9mol/L 或12mol/L等，但不限于所列举的数值，该范围内其他未列举的组合同样适用。Preferably, the molar concentration of silicon in the mixed solution described in step (1) is 10-12mol/L, such as 10mol/L, 10.1mol/L, 10.2mol/L, 10.3mol/L, 10.4mol/L , 10.5mol/L, 10.6mol/L, 10.7mol/L, 10.8mol/L, 10.9mol/L, 11mol/L, 11.1mol/L, 11.2mol/L, 11.3mol/L, 11.4mol/L, 11.5mol/L, 11.6mol/L, 11.7mol/L, 11.8mol/L, 11.9mol/L or 12mol/L, etc., but not limited to the listed values, other unlisted combinations within this range are also applicable.
作为本申请优选的技术方案，步骤(1)所述氨水A的质量浓度为10-15％，例如可以是10％、10.5％、11％、11.5％、12％、12.5％、13％、13.5％、14％、14.5％或15％等，但不限于所列举的数值，该范围内其他未列举的组合同样适用。As a preferred technical solution of the present application, the mass concentration of ammonia water A in step (1) is 10-15%, for example, it can be 10%, 10.5%, 11%, 11.5%, 12%, 12.5%, 13%, 13.5% %, 14%, 14.5% or 15%, but not limited to the listed values, other unlisted combinations within this range are also applicable.
优选地，步骤(1)所述第一处理的pH值为3.6-4，例如可以是3.6、3.7、3.8、3.9或4等，但不限于所列举的数值，该范围内其他未列举的组合同样适用。Preferably, the pH value of the first treatment in step (1) is 3.6-4, such as 3.6, 3.7, 3.8, 3.9 or 4, etc., but not limited to the listed values, other unlisted combinations within this range The same applies.
优选地，步骤(1)所述第一处理的温度为80-90℃，例如可以是80℃、81℃、82℃、83℃、84℃、85℃、86℃、87℃、88℃、89℃或90℃等，但不限于所列举的数值，该范围内其他未列举的组合同样适用。Preferably, the temperature of the first treatment in step (1) is 80-90°C, such as 80°C, 81°C, 82°C, 83°C, 84°C, 85°C, 86°C, 87°C, 88°C, 89°C or 90°C, etc., but not limited to the listed values, and other unlisted combinations within this range are also applicable.
优选地，步骤(1)所述第一处理的时间为90-120min，例如可以是90min、92min、94min、96min、98min、100min、102min、104min、106min、108min、110min、112min、114min、116min、118min或120min等，但不限于所列举的数值，该范围内其他未列举的组合同样适用。Preferably, the time for the first treatment in step (1) is 90-120min, such as 90min, 92min, 94min, 96min, 98min, 100min, 102min, 104min, 106min, 108min, 110min, 112min, 114min, 116min, 118min or 120min, etc., but not limited to the listed values, other unlisted combinations within this range are also applicable.
本申请中，通过采用特定的配比的原料液组成可以强化第一处理中前体的形成，有利于后续的沉淀二氧化硅的成核。In the present application, the formation of the precursor in the first treatment can be enhanced by adopting a specific ratio of raw material liquid composition, which is beneficial to the subsequent nucleation of precipitated silica.
作为本申请优选的技术方案，步骤(2)所述浆液和铵盐溶液的质量比为1:(0.2-0.5)，例如可以是1:0.2、1:0.22、1:0.24、1:0.26、1:0.28、1:0.3、1:0.32、1:0.34、1:0.36、1:0.38、1:0.4、1:0.42、1:0.44、1:0.46、1:0.48或1:0.5等，但不限于所列举的数值，该范围内其他未列举的组合同样适用。As the preferred technical scheme of the present application, the mass ratio of the slurry and the ammonium salt solution described in step (2) is 1:(0.2-0.5), such as 1:0.2, 1:0.22, 1:0.24, 1:0.26, 1:0.28, 1:0.3, 1:0.32, 1:0.34, 1:0.36, 1:0.38, 1:0.4, 1:0.42, 1:0.44, 1:0.46, 1:0.48 or 1:0.5, etc., but Not limited to the listed values, other unlisted combinations within this range are also applicable.
作为本申请优选的技术方案，步骤(2)所述第二处理的温度为120-130℃，例如可以是120℃、121℃、122℃、123℃、124℃、125℃、126℃、127℃、128℃、129℃或130℃等，但不限于所列举的数值，该范围内其他未列举的组合同样适用。As a preferred technical solution of this application, the temperature of the second treatment in step (2) is 120-130°C, for example, it can be 120°C, 121°C, 122°C, 123°C, 124°C, 125°C, 126°C, 127°C °C, 128 °C, 129 °C, or 130 °C, etc., but not limited to the listed values, and other unlisted combinations within this range are also applicable.
优选地，步骤(2)所述第二处理的时间为20-35min，例如可以是20min、21min、22min、23min、24min、25min、26min、27min、28min、29min、30min、31min、32min、33min、34min或35min等，但不限于所列举的数值，该范围内其他未列举的组合同样适用。Preferably, the time for the second treatment in step (2) is 20-35min, such as 20min, 21min, 22min, 23min, 24min, 25min, 26min, 27min, 28min, 29min, 30min, 31min, 32min, 33min, 34min or 35min, etc., but not limited to the listed values, other unlisted combinations within this range are also applicable.
作为本申请优选的技术方案，步骤(2)所述第二处理在氨气氛围下进行。As a preferred technical solution of the present application, the second treatment in step (2) is carried out under an ammonia atmosphere.
优选地，所述氨气氛围中氨气的体积分数为7-12％，例如可以是7％、7.5％、8％、8.5％、9％、9.5％、10％、10.5％、11％、11.5％或12％等，但不限于所列举 的数值，该范围内其他未列举的组合同样适用。Preferably, the volume fraction of ammonia in the ammonia atmosphere is 7-12%, such as 7%, 7.5%, 8%, 8.5%, 9%, 9.5%, 10%, 10.5%, 11%, 11.5% or 12%, etc., but not limited to the listed values, other unlisted combinations within this range are also applicable.
本申请中，氨气气氛中剩余的体积采用氮气或惰性气体等不会参与的气体代替。In this application, the remaining volume in the ammonia atmosphere is replaced by gases that will not participate, such as nitrogen or inert gases.
本申请中，通过引入特定的第二处理过程，经过处理后，可以显著降低在第三处理过程中沉淀二氧化硅颗粒的聚集，保证最终得到的沉淀二氧化硅具有良好的分散性，确保得到的沉淀二氧化硅可以实现良好的补强作用。In this application, by introducing a specific second treatment process, after treatment, the aggregation of precipitated silica particles in the third treatment process can be significantly reduced to ensure that the final precipitated silica has good dispersibility and ensure the obtained Precipitated silica can achieve good reinforcement.
作为本申请优选的技术方案，步骤(3)所述氨水B的质量浓度为20-30％，例如可以是20％、21％、22％、23％、24％、25％、26％、27％、28％、29％或30％等，但不限于所列举的数值，该范围内其他未列举的组合同样适用。As a preferred technical solution of the present application, the mass concentration of ammonia water B in step (3) is 20-30%, for example, it can be 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27% %, 28%, 29% or 30%, etc., but not limited to the listed values, other unlisted combinations within this range are also applicable.
优选地，步骤(3)所述第三处理的pH值为6.5-8，例如可以是6.5、6.6、6.7、6.8、6.9、7、7.1、7.2、7.3、7.4、7.5、7.6、7.7、7.8、7.9或8等，但不限于所列举的数值，该范围内其他未列举的组合同样适用。Preferably, the pH value of the third treatment in step (3) is 6.5-8, such as 6.5, 6.6, 6.7, 6.8, 6.9, 7, 7.1, 7.2, 7.3, 7.4, 7.5, 7.6, 7.7, 7.8 , 7.9 or 8, etc., but not limited to the listed values, other unlisted combinations within this range are also applicable.
优选地，步骤(3)所述第三处理的温度为80-90℃，例如可以是80℃、81℃、82℃、83℃、84℃、85℃、86℃、87℃、88℃、89℃或90℃等，但不限于所列举的数值，该范围内其他未列举的组合同样适用。Preferably, the temperature of the third treatment in step (3) is 80-90°C, such as 80°C, 81°C, 82°C, 83°C, 84°C, 85°C, 86°C, 87°C, 88°C, 89°C or 90°C, etc., but not limited to the listed values, and other unlisted combinations within this range are also applicable.
作为本申请优选的技术方案，步骤(3)所述预定pH值和所述第三处理的pH值相等。As a preferred technical solution of the present application, the predetermined pH value in step (3) is equal to the pH value of the third treatment.
本申请中，在第三处理中通过采用特定的处理过程，并在处理过程pH每降低0.2-0.5则进行一次固液分离，以进一步确保沉淀二氧化硅生成过程中不会出现颗粒聚集的问题。即pH每降低0.2-0.5即进行一次固液分离，之后将pH值调整至第三处理的pH值进行反应，如此循环操作，直至无沉淀形成。In this application, a specific treatment process is adopted in the third treatment, and solid-liquid separation is carried out every time the pH decreases by 0.2-0.5 during the treatment process, so as to further ensure that the problem of particle aggregation will not occur during the formation of precipitated silica . That is, solid-liquid separation is carried out every time the pH decreases by 0.2-0.5, and then the pH value is adjusted to the pH value of the third treatment for reaction, and the operation is repeated until no precipitation is formed.
本申请中，第三处理的总时间为45-80min，包括固液分离和沉淀二氧化硅的生成。若仅涉及沉淀二氧化硅的生成时间为30-60min。In this application, the total time for the third treatment is 45-80 minutes, including solid-liquid separation and generation of precipitated silica. If only precipitated silica is involved, the generation time is 30-60min.
作为本申请优选的技术方案，所述制备方法包括如下步骤：As a preferred technical solution of the present application, the preparation method includes the following steps:
(1)向氟硅酸和硅酸钠的混合溶液中加入氨水进行第一处理，得到第一浆液；所述氟硅酸和硅酸钠的摩尔比为1:(1.2.-1.8)；所述混合溶液中硅元素的摩尔浓度为10-12mol/L；所述氨水A的质量浓度为10-15％；所述第一处理的pH值为3.6-4；所述第一处理的温度为80-90℃；所述第一处理的时间为90-120min；(1) Add ammonia water to the mixed solution of fluorosilicic acid and sodium silicate for the first treatment to obtain the first slurry; the molar ratio of the fluorosilicic acid and sodium silicate is 1:(1.2.-1.8); The molar concentration of silicon in the mixed solution is 10-12mol/L; the mass concentration of the ammonia water A is 10-15%; the pH value of the first treatment is 3.6-4; the temperature of the first treatment is 80-90°C; the time for the first treatment is 90-120min;
(2)将步骤(1)得到的所述第一浆液和铵盐溶液混合进行第二处理，得到第二浆液；所述浆液和铵盐溶液的质量比为1:(0.2-0.5)；所述第二处理的温度 为120-130℃；所述第二处理的时间为20-35min；所述第二处理在氨气氛围下进行；所述氨气氛围中氨气的体积分数为7-12％；以及(2) mixing the first slurry and the ammonium salt solution obtained in step (1) for the second treatment to obtain the second slurry; the mass ratio of the slurry and the ammonium salt solution is 1:(0.2-0.5); The temperature of the second treatment is 120-130°C; the time of the second treatment is 20-35min; the second treatment is carried out under an ammonia atmosphere; the volume fraction of ammonia in the ammonia atmosphere is 7- 12%; and
(3)将步骤(2)得到的所述第二浆液和氨水B混合进行第三处理，所述第二处理中pH每降低0.2-0.5进行一次固液分离之后调整滤液的pH值至预定pH值继续进行处理，至无沉淀形成混合所述固液分离得到的固相得到所述用于绿色轮胎的沉淀二氧化硅；所述氨水B的质量浓度为20-30％；所述第三处理的pH值为6.5-8；所述第三处理的温度为80-90℃；所述预定pH值和所述第三处理的pH值相等。(3) The second slurry obtained in step (2) is mixed with ammonia water B for the third treatment, and the pH value of the filtrate is adjusted to a predetermined pH after the solid-liquid separation is carried out every time the pH is reduced by 0.2-0.5 in the second treatment value continues to be processed until no precipitation is formed and the solid phase obtained by mixing the solid-liquid separation is obtained to obtain the precipitated silica for green tires; the mass concentration of the ammonia water B is 20-30%; the third treatment The pH value is 6.5-8; the temperature of the third treatment is 80-90° C.; the predetermined pH value is equal to the pH value of the third treatment.
第二方面，本申请提供了如第一方面所述制备方法得到的用于绿色轮胎的沉淀二氧化硅，其中，所述用于绿色轮胎的沉淀二氧化硅的粒度为15-30nm，BET比表面积为210-230m 2/g，拉伸强度为44.2-52.6MPa，耐磨性能为0.18-0.3cm 3/1.6km，撕裂强度为150-180kN/m。 In a second aspect, the application provides the precipitated silica for green tires obtained by the preparation method described in the first aspect, wherein the precipitated silica for green tires has a particle size of 15-30nm and a BET ratio of The surface area is 210-230m 2 /g, the tensile strength is 44.2-52.6MPa, the wear resistance is 0.18-0.3cm 3 /1.6km, and the tear strength is 150-180kN/m.
与现有技术方案相比，本申请至少具有以下有益效果：Compared with the prior art solutions, the present application has at least the following beneficial effects:
(1)本申请中通过采用特定的处理过程，实现了高分散沉淀二氧化硅的高效制备，通过引入特定的第二处理过程，避免了后续处理过程中沉淀二氧化硅的聚集，保证了沉淀二氧化硅的高分散性。(1) In this application, by adopting a specific treatment process, the efficient preparation of highly dispersed precipitated silica is realized. By introducing a specific second treatment process, the aggregation of precipitated silica in the subsequent treatment process is avoided, and the precipitation is ensured. High dispersion of silica.
(2)采用本申请的制备方法，得到的沉淀二氧化硅的粒度为15-30nm，BET比表面积为210-230m 2/g，拉伸强度为44.2-52.6MPa，耐磨性能为0.18-0.3cm 3/1.6km，撕裂强度为150-180kN/m。 (2) Using the preparation method of the present application, the particle size of the obtained precipitated silica is 15-30nm, the BET specific surface area is 210-230m 2 /g, the tensile strength is 44.2-52.6MPa, and the wear resistance is 0.18-0.3 cm 3 /1.6km, the tear strength is 150-180kN/m.
具体实施方式Detailed ways
为更好地说明本申请，便于理解本申请的技术方案，本申请的典型但非限制性的实施例如下：In order to better describe the present application and facilitate the understanding of the technical scheme of the present application, the typical but non-limiting examples of the present application are as follows:
实施例1Example 1
本实施例提供一种用于绿色轮胎的沉淀二氧化硅的制备方法，所述制备方法包括如下步骤：The present embodiment provides a kind of preparation method for the precipitated silica of green tire, and described preparation method comprises the following steps:
(1)向氟硅酸和硅酸钠的混合溶液中加入氨水进行第一处理，得到第一浆液；所述氟硅酸和硅酸钠的摩尔比为1:1.5；所述混合溶液中硅元素的摩尔浓度为11mol/L；所述氨水A的质量浓度为12％；所述第一处理的pH值为3.8；所述第一处理的温度为85℃；所述第一处理的时间为105min；(1) Add ammonia water to the mixed solution of fluorosilicic acid and sodium silicate for the first treatment to obtain the first slurry; the molar ratio of the fluorosilicic acid and sodium silicate is 1:1.5; silicon in the mixed solution The molar concentration of the element is 11mol/L; the mass concentration of the ammonia water A is 12%; the pH value of the first treatment is 3.8; the temperature of the first treatment is 85°C; the time of the first treatment is 105min;
(2)将步骤(1)得到的所述第一浆液和铵盐溶液(氯化铵)混合进行第二处理，得到第二浆液；所述浆液和铵盐溶液的质量比为1:0.35；所述第二处理的温度为125℃；所述第二处理的时间为27min；所述第二处理在氨气氛围下进行；所述氨气氛围中氨气的体积分数为9％；(2) The first slurry obtained in step (1) is mixed with the ammonium salt solution (ammonium chloride) for the second treatment to obtain the second slurry; the mass ratio of the slurry and the ammonium salt solution is 1:0.35; The temperature of the second treatment is 125°C; the time of the second treatment is 27min; the second treatment is carried out under an ammonia atmosphere; the volume fraction of ammonia in the ammonia atmosphere is 9%;
(3)将步骤(2)得到的所述第二浆液和氨水B混合进行第三处理，所述第二处理中pH每降低0.3进行一次固液分离之后调整滤液的pH值至预定pH值继续进行处理，至无沉淀形成混合所述固液分离得到的固相得到所述用于绿色轮胎的沉淀二氧化硅；所述氨水B的质量浓度为25％；所述第三处理的pH值为7；所述第三处理的温度为85℃；所述预定pH值和所述第三处理的pH值相等。(3) The second slurry obtained in step (2) is mixed with ammonia water B for the third treatment. In the second treatment, the pH value of the filtrate is adjusted to a predetermined pH value after the solid-liquid separation is carried out every time the pH is reduced by 0.3. Treat until no precipitation is formed and mix the solid phase obtained by the solid-liquid separation to obtain the precipitated silica for green tires; the mass concentration of the ammonia water B is 25%; the pH value of the third treatment is 7; the temperature of the third treatment is 85° C.; the predetermined pH value is equal to the pH value of the third treatment.
所得用于绿色轮胎的沉淀二氧化硅的性能指标和应用性能详见表1。The performance index and application performance of the obtained precipitated silica for green tires are shown in Table 1.
实施例2Example 2
本实施例提供一种用于绿色轮胎的沉淀二氧化硅的制备方法，所述制备方法包括如下步骤：The present embodiment provides a kind of preparation method for the precipitated silica of green tire, and described preparation method comprises the following steps:
(1)向氟硅酸和硅酸钠的混合溶液中加入氨水进行第一处理，得到第一浆液；所述氟硅酸和硅酸钠的摩尔比为1:1.2；所述混合溶液中硅元素的摩尔浓度为10mol/L；所述氨水A的质量浓度为15％；所述第一处理的pH值为4；所述第一处理的温度为90℃；所述第一处理的时间为90min；(1) Add ammonia water to the mixed solution of fluorosilicic acid and sodium silicate for the first treatment to obtain the first slurry; the molar ratio of the fluorosilicic acid and sodium silicate is 1:1.2; silicon in the mixed solution The molar concentration of the element is 10mol/L; the mass concentration of the ammonia water A is 15%; the pH value of the first treatment is 4; the temperature of the first treatment is 90°C; the time of the first treatment is 90min;
(2)将步骤(1)得到的所述第一浆液和铵盐溶液(硫酸铵)混合进行第二处理，得到第二浆液；所述浆液和铵盐溶液的质量比为1:0.5；所述第二处理的温度为120℃；所述第二处理的时间为35min；所述第二处理在氨气氛围下进行；所述氨气氛围中氨气的体积分数为7％；(2) The first slurry obtained in step (1) is mixed with the ammonium salt solution (ammonium sulfate) for the second treatment to obtain the second slurry; the mass ratio of the slurry and the ammonium salt solution is 1:0.5; The temperature of the second treatment is 120°C; the time of the second treatment is 35min; the second treatment is carried out under an ammonia atmosphere; the volume fraction of ammonia in the ammonia atmosphere is 7%;
(3)将步骤(2)得到的所述第二浆液和氨水B混合进行第三处理，所述第二处理中pH每降低0.5进行一次固液分离之后调整滤液的pH值至预定pH值继续进行处理，至无沉淀形成混合所述固液分离得到的固相得到所述用于绿色轮胎的沉淀二氧化硅；所述氨水B的质量浓度为20％；所述第三处理的pH值为6.5；所述第三处理的温度为90℃；所述预定pH值和所述第三处理的pH值相等。(3) The second slurry obtained in step (2) is mixed with ammonia water B for the third treatment. In the second treatment, the pH value of the filtrate is adjusted to a predetermined pH value after the solid-liquid separation is carried out every time the pH is reduced by 0.5. Treat until no precipitation is formed and mix the solid phase obtained by the solid-liquid separation to obtain the precipitated silica for green tires; the mass concentration of the ammonia water B is 20%; the pH value of the third treatment is 6.5; the temperature of the third treatment is 90°C; the predetermined pH value is equal to the pH value of the third treatment.
所得用于绿色轮胎的沉淀二氧化硅的性能指标和应用性能详见表1。The performance index and application performance of the obtained precipitated silica for green tires are shown in Table 1.
实施例3Example 3
本实施例提供一种用于绿色轮胎的沉淀二氧化硅的制备方法，所述制备方法包括如下步骤：The present embodiment provides a kind of preparation method for the precipitated silica of green tire, and described preparation method comprises the following steps:
(1)向氟硅酸和硅酸钠的混合溶液中加入氨水进行第一处理，得到第一浆液；所述氟硅酸和硅酸钠的摩尔比为1:1.8；所述混合溶液中硅元素的摩尔浓度为12mol/L；所述氨水A的质量浓度为10％；所述第一处理的pH值为3.6；所述第一处理的温度为80℃；所述第一处理的时间为120min；(1) Add ammonia water to the mixed solution of fluorosilicic acid and sodium silicate for the first treatment to obtain the first slurry; the molar ratio of the fluorosilicic acid and sodium silicate is 1:1.8; silicon in the mixed solution The molar concentration of the element is 12mol/L; the mass concentration of the ammonia water A is 10%; the pH value of the first treatment is 3.6; the temperature of the first treatment is 80°C; the time of the first treatment is 120min;
(2)将步骤(1)得到的所述第一浆液和铵盐溶液(氟化铵)混合进行第二处理，得到第二浆液；所述浆液和铵盐溶液的质量比为1:0.2；所述第二处理的温度为130℃；所述第二处理的时间为20min；所述第二处理在氨气氛围下进行；所述氨气氛围中氨气的体积分数为12％；(2) The first slurry obtained in step (1) is mixed with the ammonium salt solution (ammonium fluoride) for the second treatment to obtain the second slurry; the mass ratio of the slurry and the ammonium salt solution is 1:0.2; The temperature of the second treatment is 130°C; the time of the second treatment is 20min; the second treatment is carried out under an ammonia atmosphere; the volume fraction of ammonia in the ammonia atmosphere is 12%;
(3)将步骤(2)得到的所述第二浆液和氨水B混合进行第三处理，所述第二处理中pH每降低0.2进行一次固液分离之后调整滤液的pH值至预定pH值继续进行处理，至无沉淀形成混合所述固液分离得到的固相得到所述用于绿色轮胎的沉淀二氧化硅；所述氨水B的质量浓度为30％；所述第三处理的pH值为8；所述第三处理的温度为80℃；所述预定pH值和所述第三处理的pH值相等。(3) The second slurry obtained in step (2) is mixed with ammonia water B for the third treatment, and the pH value of the filtrate is adjusted to a predetermined pH value after the solid-liquid separation is performed every time the pH is reduced by 0.2 in the second treatment. Treat until no precipitation is formed and mix the solid phase obtained by the solid-liquid separation to obtain the precipitated silica for green tires; the mass concentration of the ammonia water B is 30%; the pH value of the third treatment is 8; the temperature of the third treatment is 80° C.; the predetermined pH value is equal to the pH value of the third treatment.
所得用于绿色轮胎的沉淀二氧化硅的性能指标和应用性能详见表1。The performance index and application performance of the obtained precipitated silica for green tires are shown in Table 1.
实施例4Example 4
本实施例提供一种用于绿色轮胎的沉淀二氧化硅的制备方法，所述制备方法包括如下步骤：The present embodiment provides a kind of preparation method for the precipitated silica of green tire, and described preparation method comprises the following steps:
(1)向氟硅酸和硅酸钠的混合溶液中加入氨水进行第一处理，得到第一浆液；所述氟硅酸和硅酸钠的摩尔比为1:1.6；所述混合溶液中硅元素的摩尔浓度为10.4mol/L；所述氨水A的质量浓度为11％；所述第一处理的pH值为3.8；所述第一处理的温度为88℃；所述第一处理的时间为111min；(1) Add ammonia water to the mixed solution of fluorosilicic acid and sodium silicate for the first treatment to obtain the first slurry; the molar ratio of the fluorosilicic acid and sodium silicate is 1:1.6; silicon in the mixed solution The molar concentration of the element is 10.4mol/L; the mass concentration of the ammonia water A is 11%; the pH value of the first treatment is 3.8; the temperature of the first treatment is 88°C; the time of the first treatment 111min;
(2)将步骤(1)得到的所述第一浆液和铵盐溶液(醋酸铵)混合进行第二处理，得到第二浆液；所述浆液和铵盐溶液的质量比为1:0.33；所述第二处理的温度为122℃；所述第二处理的时间为33min；所述第二处理在氨气氛围下进行；所述氨气氛围中氨气的体积分数为11％；(2) The first slurry obtained in step (1) is mixed with the ammonium salt solution (ammonium acetate) for the second treatment to obtain the second slurry; the mass ratio of the slurry and the ammonium salt solution is 1:0.33; The temperature of the second treatment is 122°C; the time of the second treatment is 33min; the second treatment is carried out under an ammonia atmosphere; the volume fraction of ammonia in the ammonia atmosphere is 11%;
(3)将步骤(2)得到的所述第二浆液和氨水B混合进行第三处理，所述第二处理中pH每降低0.4进行一次固液分离之后调整滤液的pH值至预定pH 值继续进行处理，至无沉淀形成混合所述固液分离得到的固相得到所述用于绿色轮胎的沉淀二氧化硅；所述氨水B的质量浓度为22％；所述第三处理的pH值为7.7；所述第三处理的温度为82℃；所述预定pH值和所述第三处理的pH值相等。(3) The second slurry obtained in step (2) is mixed with ammonia water B for the third treatment. In the second treatment, the pH value of the filtrate is adjusted to a predetermined pH value after the solid-liquid separation is carried out every time the pH is reduced by 0.4. Treat until no precipitation is formed and mix the solid phase obtained by the solid-liquid separation to obtain the precipitated silica for green tires; the mass concentration of the ammonia water B is 22%; the pH value of the third treatment is 7.7; the temperature of the third treatment is 82°C; the predetermined pH value is equal to the pH value of the third treatment.
所得用于绿色轮胎的沉淀二氧化硅的性能指标和应用性能详见表1。The performance index and application performance of the obtained precipitated silica for green tires are shown in Table 1.
对比例1Comparative example 1
与实施例1的区别仅在于将混合溶液中的硅酸钠替换为等量的氟硅酸钠。所得用于绿色轮胎的沉淀二氧化硅的性能指标和应用性能详见表1。The difference from Example 1 is only that the sodium silicate in the mixed solution is replaced by an equivalent amount of sodium fluorosilicate. The performance index and application performance of the obtained precipitated silica for green tires are shown in Table 1.
对比例2Comparative example 2
与实施例1的区别仅在于不进行步骤(2)的第二处理，直接将浆液和氨水混合进行第三处理。所得用于绿色轮胎的沉淀二氧化硅的性能指标和应用性能详见表1。The difference from Example 1 is only that the second treatment of step (2) is not carried out, and the slurry and ammonia water are directly mixed for the third treatment. The performance index and application performance of the obtained precipitated silica for green tires are shown in Table 1.
对比例3Comparative example 3
与实施例1的区别仅在于直接控制第三处理的pH值为7至处理结束，中间不进行固液分离，处理和实施例1相同的时间。所得用于绿色轮胎的沉淀二氧化硅的性能指标和应用性能详见表1。The difference from Example 1 is that the pH value of the third treatment is directly controlled to be 7 to the end of the treatment, and solid-liquid separation is not carried out in the middle, and the treatment time is the same as that of Example 1. The performance index and application performance of the obtained precipitated silica for green tires are shown in Table 1.
对比例4Comparative example 4
与实施例1的区别仅在于将步骤(2)中的铵盐溶液替换为等量等浓度的氨水。所得用于绿色轮胎的沉淀二氧化硅的性能指标和应用性能详见表1。The difference with Example 1 is only that the ammonium salt solution in the step (2) is replaced with the ammoniacal liquor of equal concentration. The performance index and application performance of the obtained precipitated silica for green tires are shown in Table 1.
对比例5Comparative example 5
与实施例1的区别仅在于pH值每降低1进行固液分离。所得用于绿色轮胎的沉淀二氧化硅的性能指标和应用性能详见表1。The difference from Example 1 is that the solid-liquid separation is performed every time the pH value decreases by 1. The performance index and application performance of the obtained precipitated silica for green tires are shown in Table 1.
本实施例和对比例的中BET比表面积的测试依据GB/T19587-2017进行测定；粒径分析通过将分散在乙醇溶液中的白炭黑超声分散后，滴加分散在特定的铜网上，釆用JEM-2100型(日本电子株式会社)透射电镜进行微观粒子的观测分析；橡胶的力学性能直接决定了轮胎橡胶的应用性能及其应用领域。本申请按照HG/T2404-2008将沉淀二氧化硅制备成混炼胶，按GB/T528-2009规定将放置24h后的硫化胶，在模具下裁剪成“哑铃型”的拉伸样条，采用AI-7000S型(高铁检测仪器有限公司)拉力机，以500mm/min的拉伸速度测试硫化胶的拉伸强度。The test of the BET specific surface area in the present embodiment and comparative examples is measured according to GB/T19587-2017; the particle size analysis is by ultrasonically dispersing the white carbon black dispersed in the ethanol solution, and then dripping and dispersing it on a specific copper grid. Use JEM-2100 (Japan Electronics Co., Ltd.) transmission electron microscope to observe and analyze microscopic particles; the mechanical properties of rubber directly determine the application performance and application fields of tire rubber. According to HG/T2404-2008, this application prepares precipitated silica into mixed rubber, and according to GB/T528-2009, the vulcanized rubber after 24 hours is cut into "dumbbell-shaped" tensile splines under the mold, using AI-7000S (Gaotie Testing Instrument Co., Ltd.) tensile machine, testing the tensile strength of vulcanized rubber at a tensile speed of 500mm/min.
耐磨性是表征轮胎橡胶性能好坏的三大重要指标之一。本研究按GB/T9867-2008规定，采用GT-7012-D型(高铁检测仪器有限公司)耐磨耗试验机，测定硫化胶的质量损失值，并通过公式计算出胶料的相对体积磨耗量，从而反应橡胶的耐磨性能。Abrasion resistance is one of the three important indicators to characterize the performance of tire rubber. According to the regulations of GB/T9867-2008, this study adopts the GT-7012-D (Gaotie Testing Instrument Co., Ltd.) wear resistance testing machine to measure the mass loss value of the vulcanized rubber, and calculate the relative volumetric wear of the rubber through the formula , thus reflecting the wear resistance of rubber.
表1Table 1
 the 粒度/nmParticle size/nm BET比表面积/m 2/g BET specific surface area/m 2 /g 拉伸强度/MPaTensile strength/MPa 耐磨性能/mm 3 Wear resistance/mm 3
实施例1Example 1 20-3020-30 215215 25.225.2 120120
实施例2Example 2 19-2819-28 210210 23.323.3 110110
实施例3Example 3 16-2416-24 220220 22.222.2 125125
实施例4Example 4 15-2215-22 230230 24.524.5 112112
对比例1Comparative example 1 40-4740-47 190190 11.511.5 160160
对比例2Comparative example 2 37-4537-45 197197 13.613.6 182182
对比例3Comparative example 3 38-4238-42 188188 16.816.8 176176
对比例4Comparative example 4 40-4940-49 200200 17.717.7 167167
对比例5Comparative example 5 35-4635-46 182182 14.414.4 169169
通过上述实施例和对比例的结果可知，本申请中通过采用特定的处理过程，实现了高分散沉淀二氧化硅的高效制备，通过引入特定的第二处理过程，避免了后续处理过程中沉淀二氧化硅的聚集，保证了沉淀二氧化硅的高分散性。From the results of the above examples and comparative examples, it can be seen that in the present application, by adopting a specific treatment process, the efficient preparation of highly dispersed precipitated silica has been realized, and by introducing a specific second treatment process, precipitation secondary in the subsequent treatment process is avoided. The aggregation of silica ensures high dispersion of precipitated silica.
申请人声明，本申请通过上述实施例来说明本申请的详细结构特征，但本申请并不局限于上述详细结构特征，即不意味着本申请必须依赖上述详细结构特征才能实施。所属技术领域的技术人员应该明了，对本申请的任何改进，对本申请所选用部件的等效替换以及辅助部件的增加、具体方式的选择等，均落在本申请的保护范围和公开范围之内。The applicant declares that the present application illustrates the detailed structural features of the present application through the above embodiments, but the present application is not limited to the above detailed structural features, that is, it does not mean that the application must rely on the above detailed structural features to be implemented. Those skilled in the art should understand that any improvement to the application, equivalent replacement of the components selected in the application, addition of auxiliary components, selection of specific methods, etc., all fall within the scope of protection and disclosure of the application.
以上详细描述了本申请的优选实施方式，但是，本申请并不限于上述实施方式中的具体细节，在本申请的技术构思范围内，可以对本申请的技术方案进行多种简单变型，这些简单变型均属于本申请的保护范围。The preferred embodiments of the present application have been described in detail above, but the present application is not limited to the specific details in the above-mentioned embodiments. Within the scope of the technical concept of the present application, various simple modifications can be made to the technical solutions of the present application. These simple modifications All belong to the scope of protection of this application.
另外需要说明的是，在上述具体实施方式中所描述的各个具体技术特征，在不矛盾的情况下，可以通过任何合适的方式进行组合，为了避免不必要的重复，本申请对各种可能的组合方式不再另行说明。In addition, it should be noted that the various specific technical features described in the above specific embodiments can be combined in any suitable way if there is no contradiction. The combination method will not be described separately.
此外，本申请的各种不同的实施方式之间也可以进行任意组合，只要其不 违背本申请的思想，其同样应当视为本申请所公开的内容。In addition, any combination of various implementations of the present application is also possible, as long as it does not violate the idea of the present application, it should also be regarded as the content disclosed in the present application.

Claims (12)

  1. 一种用于绿色轮胎的沉淀二氧化硅的制备方法，其包括如下步骤：A preparation method for precipitated silica for green tires, comprising the steps of:
    (1)向氟硅酸和硅酸钠的混合溶液中加入氨水A进行第一处理，得到第一浆液；(1) adding ammonia water A to the mixed solution of fluorosilicic acid and sodium silicate for the first treatment to obtain the first slurry;
    (2)将步骤(1)得到的所述第一浆液和铵盐溶液混合进行第二处理，得到第二浆液；以及(2) mixing the first slurry obtained in step (1) with the ammonium salt solution for a second treatment to obtain a second slurry; and
    (3)将步骤(2)得到的所述第二浆液和氨水B混合进行第三处理，所述第二处理中pH值每降低0.2-0.5进行一次固液分离之后调整滤液的pH值至预定pH值继续进行处理，至无沉淀形成混合所述固液分离得到的固相得到所述用于绿色轮胎的沉淀二氧化硅。(3) The second slurry obtained in step (2) is mixed with ammonia water B for the third treatment, and the pH value of the filtrate is adjusted to a predetermined value after the solid-liquid separation is performed every time the pH value is reduced by 0.2-0.5 in the second treatment. The pH value is continuously processed until no precipitate is formed and the solid phase obtained by the solid-liquid separation is mixed to obtain the precipitated silica for green tires.
  2. 如权利要求1所述的制备方法，其中，步骤(1)所述氟硅酸和硅酸钠的摩尔比为1:(1.2.-1.8)。The preparation method according to claim 1, wherein the mol ratio of fluosilicic acid and sodium silicate in step (1) is 1:(1.2.-1.8).
  3. 如权利要求1或2所述的制备方法，其中，步骤(1)所述混合溶液中硅元素的摩尔浓度为10-12mol/L。The preparation method according to claim 1 or 2, wherein the molar concentration of silicon in the mixed solution in step (1) is 10-12mol/L.
  4. 如权利要求1-3所述的制备方法，其中，步骤(1)所述氨水A的质量浓度为10-15％。The preparation method according to claims 1-3, wherein the mass concentration of ammonia water A in step (1) is 10-15%.
  5. 如权利要求1-4任一项所述的制备方法，其中，步骤(1)所述第一处理的pH值为3.6-4；The preparation method according to any one of claims 1-4, wherein the pH value of the first treatment in step (1) is 3.6-4;
    任选地，步骤(1)所述第一处理的温度为80-90℃；Optionally, the temperature of the first treatment in step (1) is 80-90°C;
    任选地，步骤(1)所述第一处理的时间为90-120min。Optionally, the time for the first treatment in step (1) is 90-120 minutes.
  6. 如权利要求1-5任一项所述的制备方法，其中，步骤(2)所述浆液和铵盐溶液的质量比为1:(0.2-0.5)。The preparation method according to any one of claims 1-5, wherein the mass ratio of the slurry and the ammonium salt solution in step (2) is 1:(0.2-0.5).
  7. 如权利要求1-6任一项所述的制备方法，其中，步骤(2)所述第二处理的温度为120-130℃；The preparation method according to any one of claims 1-6, wherein the temperature of the second treatment in step (2) is 120-130°C;
    任选地，步骤(2)所述第二处理的时间为20-35min。Optionally, the time for the second treatment in step (2) is 20-35min.
  8. 如权利要求1-7任一项所述的制备方法，其中，步骤(2)所述第二处理在氨气氛围下进行；The preparation method according to any one of claims 1-7, wherein the second treatment in step (2) is carried out under an ammonia atmosphere;
    任选地，所述氨气氛围中氨气的体积分数为7-12％。Optionally, the volume fraction of ammonia in the ammonia atmosphere is 7-12%.
  9. 如权利要求1-8任一项所述的制备方法，其中，步骤(3)所述氨水B的质量浓度为20-30％；The preparation method according to any one of claims 1-8, wherein the mass concentration of ammonia water B in step (3) is 20-30%;
    任选地，步骤(3)所述第三处理的pH值为6.5-8；Optionally, the pH value of the third treatment in step (3) is 6.5-8;
    任选地，步骤(3)所述第三处理的温度为80-90℃。Optionally, the temperature of the third treatment in step (3) is 80-90°C.
  10. 如权利要求1-9任一项所述的制备方法，其中，步骤(3)所述预定pH值和所述第三处理的pH值相等。The preparation method according to any one of claims 1-9, wherein the predetermined pH value in step (3) is equal to the pH value of the third treatment.
  11. 如权利要求1-10任一项所述的制备方法，其中，所述制备方法包括如下步骤：The preparation method according to any one of claims 1-10, wherein the preparation method comprises the steps of:
    (1)向氟硅酸和硅酸钠的混合溶液中加入氨水进行第一处理，得到第一浆液；其中，所述氟硅酸和硅酸钠的摩尔比为1:(1.2.-1.8)；所述混合溶液中硅元素的摩尔浓度为10-12mol/L；所述氨水A的质量浓度为10-15％；所述第一处理的pH值为3.6-4；所述第一处理的温度为80-90℃；所述第一处理的时间为90-120min；(1) adding ammonia water to the mixed solution of fluosilicic acid and sodium silicate for the first treatment to obtain the first slurry; wherein, the molar ratio of fluosilicic acid and sodium silicate is 1:(1.2.-1.8) The molar concentration of silicon in the mixed solution is 10-12mol/L; the mass concentration of the ammonia water A is 10-15%; the pH value of the first treatment is 3.6-4; The temperature is 80-90°C; the time for the first treatment is 90-120min;
    (2)将步骤(1)得到的所述第一浆液和铵盐溶液混合进行第二处理，得到第二浆液；其中，所述浆液和铵盐溶液的质量比为1:(0.2-0.5)；所述第二处理的温度为120-130℃；所述第二处理的时间为20-35min；所述第二处理在氨气氛围下进行；所述氨气氛围中氨气的体积分数为7-12％；以及(2) mixing the first slurry obtained in step (1) with the ammonium salt solution for the second treatment to obtain the second slurry; wherein the mass ratio of the slurry and the ammonium salt solution is 1:(0.2-0.5) The temperature of the second treatment is 120-130°C; the time of the second treatment is 20-35min; the second treatment is carried out under an ammonia atmosphere; the volume fraction of ammonia in the ammonia atmosphere is 7-12%; and
    (3)将步骤(2)得到的所述第二浆液和氨水B混合进行第三处理，所述第二处理中pH值每降低0.2-0.5进行一次固液分离之后调整滤液的pH值至预定pH值继续进行处理，至无沉淀形成混合所述固液分离得到的固相得到所述用于绿色轮胎的沉淀二氧化硅；其中，所述氨水B的质量浓度为20-30％；所述第三处理的pH值为6.5-8；所述第三处理的温度为80-90℃；所述预定pH值和所述第三处理的pH值相等。(3) The second slurry obtained in step (2) is mixed with ammonia water B to perform the third treatment. In the second treatment, the pH value of the filtrate is adjusted to a predetermined value after the solid-liquid separation is performed every time the pH value is reduced by 0.2-0.5. The pH value continues to be processed until no precipitate is formed and the solid phase obtained by mixing the solid-liquid separation is obtained to obtain the precipitated silica for green tires; wherein, the mass concentration of the ammonia water B is 20-30%; the The pH value of the third treatment is 6.5-8; the temperature of the third treatment is 80-90° C.; the predetermined pH value is equal to the pH value of the third treatment.
  12. 如权利要求1-11任一项所述制备方法得到的用于绿色轮胎的沉淀二氧化硅，其粒度为15-30nm，BET比表面积为210-230m 2/g，拉伸强度为44.2-52.6MPa，耐磨性能为0.18-0.3cm 3/1.6km，撕裂强度为150-180kN/m。 The precipitated silica used for green tires obtained by the preparation method according to any one of claims 1-11 has a particle size of 15-30nm, a BET specific surface area of 210-230m2 /g, and a tensile strength of 44.2-52.6 MPa, wear resistance of 0.18-0.3cm 3 /1.6km, tear strength of 150-180kN/m.
PCT/CN2021/116857 2021-09-07 2021-09-07 Precipitated silicon dioxide for green tire and preparation method for precipitated silicon dioxide WO2023035099A1 (en)

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