WO2023097549A1

WO2023097549A1 - Hydrophobic white carbon black rubber reinforcing agent, preparation method therefor, and application thereof

Info

Publication number: WO2023097549A1
Application number: PCT/CN2021/134748
Authority: WO
Inventors: 陈南飞; 卢爱平; 王明贺; 陈辰; 陈家树; 史彤
Original assignee: 无锡恒诚硅业有限公司
Priority date: 2021-12-01
Filing date: 2021-12-01
Publication date: 2023-06-08
Also published as: CN114286800B; CN114286800A

Abstract

Provided are a hydrophobic white carbon black rubber reinforcing agent, a preparation method therefor, and an application thereof. The preparation method comprises the following steps: (1) mixing a sodium silicate aqueous solution and a modified organic solution, and adjusting the pH value to 8 to 9 in the mixing process to obtain a mixed solution; and (2) dropwise adding an acid solution to the mixed solution obtained in step (1) until the pH value is adjusted to 3.5 to 4.5, carrying out a precipitation reaction, and then carrying out solid-liquid separation to obtain the hydrophobic white carbon black rubber reinforcing agent. The modified organic solvent in step (1) comprises a silane coupling agent, a surfactant and an organic solvent, and the surfactant comprises lauryl diethanolamide and/or cetyltrimethylammonium bromide. The sodium silicate aqueous solution and the silane coupling agent organic solution are directly mixed so that sodium silicate is obtained by means of reaction in a solvent containing the silane coupling agent, thereby enhancing the dispersion effect of the silane coupling agent upon the white carbon black and improving the hydrophobic performance of the white carbon black final product.

Description

A kind of hydrophobic white carbon black rubber reinforcing agent and its preparation method and application

technical field

The application belongs to the technical field of green tires and relates to a rubber reinforcing agent, in particular to a hydrophobic white carbon black rubber reinforcing agent and its preparation method and application.

Background technique

The main component of precipitated silica is hydrated silica. There are many groups on the surface of silica, including hydroxyl, siloxane, etc., so it has strong hydrophilicity and is easy to form agglomerates or secondary aggregation. At present, the main use of silica is in the rubber industry, which can be used to produce high-quality rubber products, such as increasing wear resistance and wet skid resistance, effectively reducing rolling resistance and rubber heat generation. Therefore, silica is used in green tires field plays an important role. However, due to the presence of a large number of hydroxyl groups on the surface of silica, which is highly hydrophilic, it is not easy to combine with the rubber matrix, thus affecting the performance of rubber products.

At present, the methods of industrial production of white carbon black include liquid phase precipitation method and gas phase method. The precipitation method uses water glass and inorganic acid as raw materials, and the white carbon black product is obtained through precipitation reaction, aging, washing, drying and granulation. The production process Simple, cheap and easy-to-obtain raw materials, less equipment investment, and low energy consumption. However, the silica prepared by the conventional precipitation method has insufficient dispersibility, and it is difficult to meet the use requirements of tire rubber or high-grade silicone rubber, and there are problems such as serious structure, poor reinforcing effect, and easy yellowing. The gas phase method uses silicon tetrachloride as a raw material and reacts at high temperature to form silicon dioxide. The resulting product has small particle size, high yield and superior performance. However, this method has high energy consumption, low production efficiency, and relatively expensive products.

CN110746794A discloses a kind of preparation method of superhydrophobic white carbon black, comprises the following steps: (1) silane coupling agent, organic solvent and water are mixed by volume ratio 1:(1-8):(1-2) , to obtain a silane coupling agent modification solution; (2) add a silane coupling agent modification solution to the silica suspension, and stir at 50-90°C for 0.5-24h; then add a nonionic surfactant and Fluoropolymer, stirred at 40-95°C for 0.5-20h to obtain a composite modified silica suspension; (3) filter, dry and pulverize the composite modified silica suspension to obtain superhydrophobic silica black. However, it needs to prepare silica first, and then modify the silica, which is difficult to ensure the uniformity of silica modification. Therefore, the performance of modified silica needs to be further improved.

CN109942003A discloses a method for dry grinding modified precipitated white carbon black, the specific steps are as follows: different types and different amounts of surfactants are added to a certain amount of absolute ethanol solution to obtain ethanol solutions of active agents with different concentrations . Add different concentrations of ethanol solutions of active agents into the white carbon black at a certain rate, and grind with a grinder. It utilizes the chemical mechanical force generated in the grinding process to make the surface modifier chemically react with the hydroxyl groups on the surface of the white carbon black, thereby improving the dispersibility and hydrophobicity of the white carbon black. However, the grinding machine is easy to destroy the structure and morphology of silica, and the grinding and mixing time is long, otherwise it is difficult to obtain a good modification effect.

CN113150389A discloses a preparation method of hydrophobic white carbon black, comprising the following steps: weighing each component according to parts by weight: 2-8 parts of emulsifier, 10-25 parts of modifier, 2 parts of nonionic surfactant -5 parts, 3-6 parts of fluorine-containing high molecular polymer, 6-100 parts of white carbon black; pour the emulsifier and modifier into the mixing tank, and mix evenly at high speed; In the barrel, stir and mix for 0.5-1h under the environment of 50-90°C. It uses a modifier composed of silane coupling agent, dichloromethane and dilute sulfuric acid to modify the white carbon black. The silane coupling agent performs surface grafting treatment on the white carbon black, and dilute sulfuric acid is used to improve the modification effect. But it also has the problem of directly modifying white carbon black, and the modification effect is poor.

Therefore, it is necessary to provide a silica rubber reinforcing agent with better hydrophobic properties and its preparation method and application.

Contents of the invention

The application provides a hydrophobic silica rubber reinforcing agent and its preparation method and application. The preparation method is simple to operate, and the dispersion effect of silica is improved through process regulation, and the hydrophobicity of the final silica is improved. .

First aspect, the application provides a kind of preparation method of hydrophobic silica rubber reinforcing agent, described preparation method comprises the steps:

(1) mixing the sodium silicate aqueous solution and the modified organic solution, and adjusting the pH value to 8-9 during the mixing process to obtain a mixed solution;

(2) Add acid solution dropwise to the mixed solution obtained in step (1), adjust the pH value to 3.5-4.5, carry out precipitation reaction, and then carry out solid-liquid separation to obtain the hydrophobic silica rubber reinforcing agent;

Wherein, the modified organic solvent described in step (1) includes a silane coupling agent, a surfactant and an organic solvent;

The surfactant includes lauroyl diethanolamine and/or cetyltrimethylammonium bromide.

In this application, by directly mixing sodium silicate aqueous solution and modified organic solution, sodium silicate is obtained by reacting sodium silicate in modified organic solution, which improves the modification effect of silane coupling agent and surfactant on white carbon black, and reduces the amount of white carbon black. The surface energy of black improves the hydrophobicity of silica, so that it can show good compatibility and dispersion in the application of tires.

Preferably, the concentration of the silane coupling agent in the modified organic solution described in step (1) is 3-5wt%, such as 3wt%, 3.5wt%, 4wt%, 4.5wt% or 5wt%, but not limited to Listed values, other unlisted values within the range of values also apply.

Preferably, the concentration of the surfactant in the modified organic solution described in step (1) is 0.3-0.8wt%, such as 0.3wt%, 0.4wt%, 0.5wt%, 0.6wt%, 0.7wt% or 0.8wt%. wt%, but not limited to the listed values, other unlisted values within the range of values are also applicable.

Preferably, the organic solvent in the modified organic solution in step (1) includes absolute ethanol.

Preferably, the silane coupling agent in the organic solution of the silane coupling agent includes γ-(methacryloyloxy)propyltrimethoxysilane (KH-570) and/or γ-aminopropyltriethoxy Silane (KH-550).

Preferably, the concentration of the sodium silicate aqueous solution in step (1) is 0.5-2mol/L, such as 0.5mol/L, 0.8mol/L, 1mol/L, 1.2mol/L, 1.5mol/L, 1.8 mol/L or 2mol/L, but not limited to the listed values, other unlisted values within the range of values are also applicable.

Preferably, in the mixed solution described in step (1), the concentration of the silane coupling agent is 0.5-1wt%, such as 0.5wt%, 0.6wt%, 0.7wt%, 0.8wt%, 0.9wt% or 1wt% , but not limited to the listed values, other unlisted values within the range of values are also applicable.

Preferably, the pH value adjusted in step (1) is adjusted by bubbling CO ₂ .

Preferably, the temperature of the precipitation reaction in step (2) is 85-90° C., and the time is 30-60 min.

The temperature of the precipitation reaction described in this application is 85-90°C, for example, it can be 85°C, 86°C, 87°C, 88°C, 89°C or 90°C, but it is not limited to the listed values, other unlisted values within the range Numerical values also apply.

The precipitation reaction time described in this application is 30-60min, for example, it can be 30min, 35min, 40min, 45min, 50min, 55min or 60min, but it is not limited to the listed values, and other unlisted values within the numerical range are also applicable.

Preferably, the process of the precipitation reaction in step (2) is accompanied by stirring, and the stirring speed is 300-600r/min, such as 300r/min, 350r/min, 400r/min, 450r/min, 500r/min , 550r/min or 600r/min, but not limited to the listed values, other unlisted values within the range of values are also applicable.

Preferably, the solid-liquid separation method in step (2) includes spray drying.

Preferably, the acid solution described in step (2) comprises citric acid and/or sulfuric acid, preferably a mixed acid of citric acid and sulfuric acid.

Preferably, the mass ratio of citric acid to sulfuric acid is 1:(3-5), such as 1:3, 1:3.5, 1:4, 1:4.5 or 1:5, but not limited to the listed Numerical values, other unrecited numerical values within the numerical range also apply.

Preferably, the temperature of the dropwise addition of the acid solution in step (2) is 85-90°C, and the time is 50-60min.

In step (2) of the present application, the temperature for adding the acid solution is 85-90°C, for example, it can be 85°C, 86°C, 87°C, 88°C, 89°C or 90°C, but it is not limited to the listed values, the range of values Other unlisted values also apply.

The time for adding the acid solution in step (2) of the present application is 50-60min, such as 50min, 51min, 52min, 53min, 54min, 55min, 56min, 57min, 58min, 59min or 60min, but not limited to the listed values , other unlisted values within the value range are also applicable.

Preferably, the process of adding the acid solution in step (2) is accompanied by stirring, and the stirring speed is 300-600r/min, such as 300r/min, 350r/min, 400r/min, 450r/min, 500r /min, 550r/min or 600r/min, but not limited to the listed values, other unlisted values within the range of values are also applicable.

Preferably, the mixed solution in step (1) further includes a modifier.

The modifier includes any one or a combination of at least two of alkylphenol polyoxyethylene ethers, fatty alcohol polyoxyethylene ethers, or polyol fatty acid esters. Typical but non-limiting combinations include alkylphenol polyoxyethylene ethers. The combination of oxyethylene ether and fatty alcohol polyoxyethylene ether, the combination of fatty alcohol polyoxyethylene ether and polyol fatty acid ester, the combination of alkylphenol polyoxyethylene ether and polyol fatty acid ester, or the combination of alkylphenol polyoxyethylene ether Combination of vinyl ether, fatty alcohol polyoxyethylene ether and polyol fatty acid ester.

Preferably, the concentration of the modifier in the mixed solution in step (1) is 0.1-0.5wt%, such as 0.1wt%, 0.2wt%, 0.3wt%, 0.4wt% or 0.5wt%, but not limited to For the numerical values listed, other unlisted numerical values within the numerical range are also applicable.

As a preferred technical solution of the preparation method described in the first aspect of the present application, the preparation method includes the following steps:

(1) mixing the sodium silicate aqueous solution and the modified organic solution, and blowing _CO into during the mixing process to adjust the pH value to 8-9 to obtain a mixed solution; the concentration of the silane coupling agent in the mixed solution is 0.5-1wt%;

(2) Under the condition of 85-90°C, add acid solution dropwise to the mixed solution obtained in step (1) for 50-60min, adjust the pH value to 3.5-4.5, the process of adding acid solution is accompanied by stirring, and the stirring speed 300-600r/min; 85-90°C precipitation reaction for 30-60min, the process of precipitation reaction is accompanied by stirring, the stirring speed is 300-600r/min; then spray drying to obtain the hydrophobic silica rubber strong agent;

Optionally, the mixed solution in step (1) also includes a modifying agent with a concentration of 0.1-0.5 wt %;

The modified organic solvent in step (1) includes a silane coupling agent, a surfactant and absolute ethanol; the surfactant includes lauroyl diethanolamine and/or cetyltrimethylammonium bromide.

In a second aspect, the present application provides a hydrophobic silica rubber reinforcing agent, which is obtained by the preparation method described in the first aspect.

In a third aspect, the present application provides an application of the hydrophobic silica rubber reinforcing agent described in the second aspect for green tires.

The numerical ranges described in this application not only include the above-mentioned point values, but also include any point values between the above-mentioned numerical ranges that are not listed. Due to space limitations and for the sake of brevity, this application no longer exhaustively lists the described ranges. The specific pip value to include.

Compared with the prior art, the beneficial effects of the present application are:

Detailed ways

The technical solutions of the present application will be further described below through specific implementation methods.

Example 1

The present embodiment provides a kind of preparation method of hydrophobic silica rubber reinforcing agent, and described preparation method comprises the following steps:

(1) Mix sodium silicate aqueous solution and modified organic solution, blow into _CO in the mixing process Adjust pH value to be 8.5, obtain mixed solution; The concentration of silane coupling agent is 0.8wt% in the mixed solution; The sodium silicate aqueous solution The concentration is 1.2mol/L;

(2) Under the condition of 88°C, add acid solution (mixed acid of citric acid and sulfuric acid with a mass ratio of 1:4) to the mixed solution obtained in step (1) for 55 minutes, adjust the pH value to 4, and add the acid solution dropwise Accompanied by stirring, the stirring speed is 500r/min; 88 ° C precipitation reaction for 45min, the process of precipitation reaction is accompanied by stirring, the stirring speed is 500r/min; then spray drying to obtain the hydrophobic silica rubber strong agent;

The modified organic solvent of step (1) includes silane coupling agent, surfactant and dehydrated alcohol; The silane coupling agent is γ-(methacryloyloxy)propyltrimethoxysilane (KH-570 ); the surfactant includes lauroyldiethanolamine and cetyltrimethylammonium bromide in a mass ratio of 1:1; the concentration of the silane coupling agent in the modified organic solution is 4wt%; in the modified organic solution The concentration of surfactant was 0.5 wt%.

Example 2

(1) mix sodium silicate aqueous solution and modified organic solution, blow into _CO in the mixing process Adjust pH value to be 8, obtain mixed liquor; The concentration of silane coupling agent is 0.5wt% in the mixed liquor; The sodium silicate aqueous solution The concentration is 0.5mol/L;

(2) Under the condition of 85°C, add acid solution (mixed acid of citric acid and sulfuric acid with a mass ratio of 1:3) to the mixed solution obtained in step (1) for 60 minutes, adjust the pH value to 3.5, and drop the acid solution Accompanied by stirring, the stirring speed is 600r/min; 85 ℃ precipitation reaction 60min, the process of precipitation reaction is accompanied by stirring, the stirring speed is 600r/min; then spray drying to obtain the hydrophobic silica rubber strong agent;

The modified organic solvent described in step (1) includes a silane coupling agent, a surfactant and dehydrated alcohol; the silane coupling agent is γ-aminopropyltriethoxysilane (KH-550); the surface The active agent includes lauroyl diethanolamine and cetyltrimethylammonium bromide in a mass ratio of 1:3; the concentration of the silane coupling agent in the modified organic solution is 3wt%; the concentration of the surfactant in the modified organic solution is 0.3wt%.

Example 3

(1) mix sodium silicate aqueous solution and modified organic solution, blow into _CO in the mixing process Adjust pH value to be 9, obtain mixed liquor; The concentration of silane coupling agent is 1wt% in the mixed liquor; The concentration of sodium silicate aqueous solution 2mol/L;

(2) Under the condition of 90°C, add acid solution (mixed acid of citric acid and sulfuric acid with a mass ratio of 1:5) to the mixed solution obtained in step (1) for 30 minutes, adjust the pH value to 4.5, and add the acid solution dropwise Accompanied by stirring, the stirring speed is 300r/min; 90 ° C precipitation reaction for 50min, the process of precipitation reaction is accompanied by stirring, the stirring speed is 300r/min; then spray drying to obtain the hydrophobic silica rubber strong agent;

The modified organic solvent described in step (1) includes a silane coupling agent, a surfactant and dehydrated alcohol; the silane coupling agent is γ-aminopropyltriethoxysilane (KH-550); the surface The active agent comprises lauroyl diethanolamine and cetyltrimethylammonium bromide in a mass ratio of 3:1; the concentration of the silane coupling agent in the modified organic solution is 5wt%; the concentration of the surfactant in the modified organic solution is 0.8wt%.

Example 4

(1) Mix sodium silicate aqueous solution, modified organic solution and modifying agent, blow into CO in the mixing process Adjust pH value to be 8.5, obtain mixed liquor; The concentration of silane coupling agent is 0.8wt% in the mixed liquor, _change The concentration of neutralizing agent (AEO-9) is 0.3wt%; The concentration of sodium silicate aqueous solution is 1.2mol/L;

Example 5

(1) Mix sodium silicate aqueous solution, modified organic solution and modifying agent, blow into CO in the mixing process Adjust pH value to be 8.5, obtain mixed liquor; The concentration of silane coupling agent is 0.8wt% in the mixed _liquor , change The concentration of neutralizing agent (ZB-60) is 0.1wt%; The concentration of sodium silicate aqueous solution is 1.2mol/L;

Example 6

(1) Mix sodium silicate aqueous solution, modified organic solution and modifying agent, blow into CO in the mixing process Adjust pH value to be 8.5, obtain mixed liquor; The concentration of silane coupling agent is 0.8wt% in the mixed liquor, _change The concentration of neutralizing agent (OP-10) is 0.5wt%; The concentration of sodium silicate aqueous solution is 1.2mol/L;

Example 7

This example provides a method for preparing a hydrophobic silica rubber reinforcing agent, except that the surfactant is only lauroyl diethanolamine, the rest are the same as in Example 1.

Example 8

This example provides a method for preparing a hydrophobic silica rubber reinforcing agent, except that the surfactant is only cetyltrimethylammonium bromide, the rest are the same as in Example 1.

Example 9

This example provides a method for preparing a hydrophobic silica rubber reinforcing agent, which is the same as Example 1 except that the concentration of the surfactant in the modified organic solution is 1.2 wt%.

Example 10

This embodiment provides a kind of preparation method of hydrophobic silica rubber reinforcing agent, except that the acid solution in step (2) is the citric acid whose pH value is identical with mixed acid, all the other are the same as embodiment 1.

Example 11

This example provides a method for preparing a hydrophobic silica rubber reinforcing agent, except that the acid solution in step (2) is sulfuric acid with the same pH value as the mixed acid, and the others are the same as in Example 1.

Comparative example 1

This comparative example provides a preparation method of a white carbon black rubber reinforcing agent, except that the pH value is adjusted to 7.5 in step (1), the rest are the same as in Example 1.

Comparative example 2

This comparative example provides a preparation method of a white carbon black rubber reinforcing agent, except that the pH value is adjusted to 9.5 in step (1), the rest are the same as in Example 1.

Comparative example 3

This comparative example provides a preparation method of a white carbon black rubber reinforcing agent, except that the pH value is adjusted to 3 in step (2), the rest are the same as in Example 1.

Comparative example 4

This comparative example provides a preparation method of a white carbon black rubber reinforcing agent, except that the pH value is adjusted to 5 in step (2), the rest are the same as in Example 1.

Performance tests were performed on the hydrophobic silica rubber reinforcing agent provided in Examples 1-11 and the silica rubber reinforcing agent provided in Comparative Examples 1-4. Determine the specific surface area according to GB/T10722-2014 "Determination of Total Surface Area and External Area of Carbon Black by Nitrogen Adsorption Method"; determine the oil absorption value according to HGT 3072-2019 "Determination of Oil Absorption Value of Precipitated Hydrated Silica as Rubber Compounding Agent"; determine the oil absorption value according to GB/T10722-2014 T 32698-2016 "Determination of Particle Size Distribution of Precipitated Hydrated Silica in Rubber Compounding Agent by Laser Diffraction Method" to determine the apparent particle size; according to GB/T 6030-2006 "Evaluation of Carbon Black and Carbon Black Silica Dispersion in Rubber Quickly Comparative method" to measure the degree of dispersion.

The obtained results are shown in Table 1.

Table 1

In summary, this application directly mixes sodium silicate aqueous solution and modified organic solution, and reacts sodium silicate in modified organic solution, which improves the modification effect of silane coupling agent and surfactant on white carbon black , reduces the surface energy of silica, improves the hydrophobicity of silica, so that it can show good compatibility and dispersion in the application of tires.

The specific embodiments described above have further described the technical solutions and beneficial effects of the application in detail. It should be understood that the above descriptions are only specific embodiments of the application and are not intended to limit the application. Within the spirit and principles of the application, any modifications, equivalent replacements, improvements, etc., shall be included in the protection scope of the application.

Claims

A kind of preparation method of hydrophobic white carbon black rubber reinforcing agent, it comprises the steps:

(1) mixing the sodium silicate aqueous solution and the modified organic solution, and adjusting the pH value to 8-9 during the mixing process to obtain a mixed solution;

(2) Add acid solution dropwise to the mixed solution obtained in step (1), adjust the pH value to 3.5-4.5, carry out precipitation reaction, and then carry out solid-liquid separation to obtain the hydrophobic silica rubber reinforcing agent;

Wherein, the modified organic solvent described in step (1) includes a silane coupling agent, a surfactant and an organic solvent;

The surfactant includes lauroyl diethanolamine and/or cetyltrimethylammonium bromide.
The preparation method according to claim 1, wherein the concentration of the silane coupling agent in the modified organic solution in step (1) is 3-5 wt%.
The preparation method according to claim 1, wherein the concentration of the surfactant in the modified organic solution in step (1) is 0.3-0.8wt%.
The preparation method according to claim 1, wherein the organic solvent in the modified organic solution of step (1) comprises dehydrated alcohol.
The preparation method according to any one of claims 1-4, wherein the silane coupling agent comprises γ-(methacryloyloxy)propyltrimethoxysilane and/or γ-aminopropyltriethoxy base silane.
The preparation method according to any one of claims 1-5, wherein the concentration of the sodium silicate aqueous solution in step (1) is 0.5-2mol/L;

Preferably, in the mixed solution described in step (1), the concentration of the silane coupling agent is 0.5-1wt%;

Preferably, the pH value adjusted in step (1) is adjusted by bubbling CO 2 .
The preparation method according to any one of claims 1-6, wherein the temperature of the precipitation reaction in step (2) is 85-90°C, and the time is 30-60min;

Preferably, the process of the precipitation reaction in step (2) is accompanied by stirring, and the stirring speed is 300-600r/min;

Preferably, the solid-liquid separation method in step (2) includes spray drying.
The preparation method according to any one of claims 1-7, wherein the acid solution in step (2) comprises citric acid and/or sulfuric acid, preferably a mixed acid of citric acid and sulfuric acid;

Preferably, the mass ratio of said citric acid to sulfuric acid is 1:(3-5);

Preferably, the temperature of the dropwise acid solution in step (2) is 85-90°C, and the time is 50-60min;

Preferably, the process of adding acid solution dropwise in step (2) is accompanied by stirring, and the stirring speed is 300-600 r/min.
The preparation method according to any one of claims 1-8, wherein the mixed solution in step (1) also includes a modifying agent;

The modifier includes any one or a combination of at least two of alkylphenol polyoxyethylene ethers, fatty alcohol polyoxyethylene ethers or polyol fatty acid esters;

Preferably, the concentration of the modifying agent in the mixed solution in step (1) is 0.1-0.5 wt%.
The preparation method according to any one of claims 1-9, wherein the preparation method comprises the steps of:

(1) mixing the sodium silicate aqueous solution and the modified organic solution, and blowing CO into during the mixing process to adjust the pH value to 8-9 to obtain a mixed solution; the concentration of the silane coupling agent in the mixed solution is 0.5-1wt%;

(2) Under the condition of 85-90°C, add acid solution dropwise to the mixed solution obtained in step (1) for 50-60min, adjust the pH value to 3.5-4.5, the process of adding acid solution is accompanied by stirring, and the stirring speed 300-600r/min; 85-90°C precipitation reaction for 30-60min, the process of precipitation reaction is accompanied by stirring, the stirring speed is 300-600r/min; then spray drying to obtain the hydrophobic silica rubber strong agent;

Optionally, the mixed solution in step (1) also includes a modifying agent with a concentration of 0.1-0.5 wt %;

The modified organic solvent in step (1) includes a silane coupling agent, a surfactant and absolute ethanol; the surfactant includes lauroyl diethanolamine and/or cetyltrimethylammonium bromide.
A hydrophobic silica rubber reinforcing agent obtained by the preparation method described in any one of claims 1-10.
A kind of hydrophobic white carbon black rubber reinforcing agent as claimed in claim 11 is used for the application of green tire.