A modified white carbon black-based white carbon black wet glue, a preparation method and application thereof

Abstract

The application discloses modified white carbon black wet rubber glue based on white carbon black as well as a preparation method and application thereof, and belongs to the technical field of rubber.The solution blending method is used in the embodiment of the application, and the prepared modified white carbon black can be easily uniformly dispersed in a rubber matrix.Compared with the prior art, the application can further improve the dispersion of high filling amount white carbon black in the rubber material, and can adjust the types and contents of two silane coupling components to control the mechanical properties and fatigue resistance of the wet rubber glue.The white carbon black wet rubber glue can be applied in tire preparation and has excellent comprehensive performance.

Description

Technical Field

[0001] This invention relates to the field of rubber technology, and in particular to a wet-process precipitated silica rubber based on modified silica, its preparation method, and its application. Background Technology

[0002] Carbon black and silica are the most commonly used reinforcing fillers in rubber, and are usually blended for use in rubber material processing. Compared with carbon black, silica is not only a renewable resource, but it can also increase the wet skid resistance and reduce the rolling resistance of tire treads, making it an ideal filler for producing "green tires." However, silica contains a large number of silanol groups on its surface, exhibiting strong polarity, which contrasts sharply with the non-polarity of natural rubber, styrene-butadiene rubber, and butadiene rubber. Due to this significant difference in polarity, the microscopic interaction between silica particles and rubber macromolecular chains is weak, and the shearing action of traditional dry mixing processes is insufficient to break down the aggregates formed by hydrogen bonding between silica particles. The use of specific silane coupling agents and improvements in mixing processes and equipment can improve the dispersion of silica to some extent, but for systems with high silica filler content, current technologies still struggle to effectively solve the silica dispersion problem.

[0003] Compared to dry mixing, wet mixing can reduce the viscosity of the system by using a liquid medium, further improving the dispersion of silica in rubber. Currently, emulsion blending is the most commonly used wet mixing method, which was mainly developed for rubber varieties with emulsion forms. For high-regularity rubber materials prepared by solution polymerization, such as solution-polymerized styrene-butadiene rubber, solution blending is the optimal wet mixing method. Compared to emulsion blending, solution blending is the method that can truly achieve "molecular-level" blending of silica and rubber. Therefore, uniform dispersion of silica in synthetic rubber can be achieved through solution blending.

[0004] The key to preparing highly dispersed silica wet-process rubber lies in achieving uniform dispersion of silica in organic solvents. This requires modifying polar silica into non-polar silica using a large amount of silane coupling agent. Currently, sulfur-containing silane coupling agents are commonly used. To modify polar silica into non-polar silica, a large amount of sulfur-containing silane coupling agent needs to be grafted onto the silica surface. However, excessively high sulfur content on the silica surface leads to excessively high tensile stress and excessively low elongation at break in the wet-process rubber, resulting in poor fatigue resistance and a short service life for tires made from it. Therefore, there is an urgent need to develop a silica grafted with an appropriate amount of sulfur-containing silane coupling agent and with excellent oleophilic properties to prepare highly dispersed and performance-tunable silica / rubber wet-process rubber. Summary of the Invention

[0005] Based on this, the present invention provides a silica wet-process adhesive based on modified silica, its preparation method and application. The present invention can develop a silica wet-process adhesive with uniform filler dispersion and controllable performance. The prepared wet-process adhesive has excellent mechanical properties and is beneficial for application in tire rubber compounds.

[0006] This invention provides a method for preparing modified silica, comprising the following steps:

[0007] In a solvent, a silane coupling agent is used to perform a surface modification reaction on silica to obtain modified silica, which is then used in silica wet-process adhesives.

[0008] The silane coupling agent includes a first silane coupling component and a second silane coupling component, wherein the first silane coupling component is a sulfur-containing silane coupling agent and the second silane coupling component is an alkylsilane coupling agent with 3-16 carbon atoms.

[0009] The mass ratio of the silica, the first silane coupling component, and the second silane coupling component is 100:1~15:2~30.

[0010] In the embodiments of this application, the silica is precipitated silica and / or fumed silica; the particle size of the silica is 20nm-30μm; and the surface water content of the silica is 3~10wt%.

[0011] In the embodiments of this application, the solvent is one or more selected from n-hexane, cyclohexane, heptane, dichloromethane, chloroform, diethyl ether, toluene, xylene, tetrahydrofuran, and N,N-dimethylformamide;

[0012] The modification reaction is carried out at a temperature below 100°C and with stirring for no more than 24 hours to obtain a suspension containing modified silica; the concentration of the suspension containing modified silica is 0.01~0.2 g / mL.

[0013] In the embodiments of this application, the first silane coupling component is one or more selected from 3-octanoylthiopropyltriethoxysilane, 3-mercaptopropylmethyldiethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, bis-(3-triethoxysilylpropyl)tetrasulfide, bis-(3-triethoxysilylpropyl)disulfide, 3-thiocyanopropyltriethoxysilane, and 3-mercaptopropylethoxybis-(propane-hexaethoxysiloxane);

[0014] The second silane coupling component is one or more of the following: n-dodecyltrimethoxysilane, n-dodecyltriethoxysilane, cyclohexyltrimethoxysilane, isobutyltriethoxysilane, n-hexadecyltrimethoxysilane, n-hexyltriethoxysilane, n-propyltriethoxysilane, n-propyltrimethoxysilane, n-octyltrimethoxysilane, and n-octyltriethoxysilane.

[0015] Compared with existing technologies, this invention uses sulfur-containing silane coupling agents and C3-16 alkylsilane coupling agents to modify silica in a certain proportion, thereby constructing modified silica particles that possess both oleophilic and vulcanizing functions. Based on this modified silica, this invention can obtain highly dispersed and tunable silica wet-process adhesives, which are beneficial for applications.

[0016] This application provides a wet-process silica adhesive, comprising a rubber matrix and a reinforcing filler compounded with the rubber matrix, wherein the reinforcing filler is modified silica obtained by the preparation method described above.

[0017] This application provides a method for preparing the aforementioned wet-process silica adhesive, comprising the following steps:

[0018] The rubber was mixed with the modified silica obtained by the preparation method described above in an organic solvent medium to obtain a mixed solution;

[0019] The organic solvent medium is removed by steam azeotropic drying, spray drying, or flocculation drying, and then dried to obtain wet-mixed masterbatch.

[0020] In the embodiments of this application, the rubber is formulated into a rubber solution with an organic solvent medium, and then mixed with the modified silica;

[0021] The organic solvent medium is one or more selected from n-hexane, cyclohexane, heptane, dichloromethane, chloroform, diethyl ether, toluene, xylene, tetrahydrofuran, and N,N-dimethylformamide; the concentration of the rubber solution is 0.02-0.1 g / mL.

[0022] In the embodiments of this application, the rubber is one or more of natural rubber, solution-polymerized styrene-butadiene rubber, emulsion-polymerized styrene-butadiene rubber, cis-butadiene rubber, trans-polyisoprene, and isoprene rubber.

[0023] In the embodiments of this application, the mixing is carried out at a temperature below 80°C and for no more than 24 hours; the mixing method is one or more of mechanical mixing, ultrasonic mixing, and high-speed jet mixing; the drying temperature is 30-100°C.

[0024] This application provides the use of silica wet-process rubber as described above in tire manufacturing.

[0025] This invention employs a solution blending method, which easily and uniformly disperses the prepared modified silica in a rubber matrix. Compared with existing technologies, this invention not only further improves the dispersion of high-filler silica in rubber materials, but also allows for the control of the mechanical properties and fatigue resistance of the wet-process rubber by adjusting the types and contents of the two silane coupling components. More importantly, the prepared wet-process rubber exhibits excellent comprehensive properties, such as excellent anti-skid properties, abrasion resistance, mechanical properties, wear resistance, fatigue resistance, and low rolling resistance, which is beneficial for its application in tires. Detailed Implementation

[0026] The technical solutions in the embodiments of this application are described clearly and completely below. Obviously, the described embodiments are only some embodiments of this application, and not all embodiments. Based on the embodiments in this application, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of this application.

[0027] Currently, some existing technologies use rubber latex as raw material and employ emulsion blending to prepare silica / rubber wet-process rubber, which requires silica to have strong hydrophilicity. To improve the compatibility between polar silica and non-polar rubber, efflorescent modification (also known as hydrophobic modification) of silica is necessary. In the preparation of silica / rubber wet-process rubber using emulsion blending, the hydrophilic and efflorescent properties of silica directly affect the degree of silica dispersion in rubber and the interfacial interaction between silica and rubber. Furthermore, there is a certain contradiction between uniform dispersion of silica and strong interfacial interaction between silica and rubber in this system. Specifically, when silica has strong efflorescent properties, the compatibility between silica and rubber is good, and the filler-rubber interfacial interaction is strong. However, silica disperses poorly in water and is prone to precipitation, resulting in poor dispersion in rubber. When silica has strong hydrophilic properties, it disperses well in water, resulting in uniform dispersion in rubber. However, silica with high polarity has poor compatibility with non-polar rubber, and the filler-rubber interface effect is weak.

[0028] This invention provides a method for preparing modified silica, comprising the following steps:

[0029] In a solvent, a silane coupling agent is used to perform a surface modification reaction on silica to obtain modified silica, which is then used in silica wet-process adhesives.

[0030] The silane coupling agent comprises a first silane coupling component and a second silane coupling component, wherein the first silane coupling component is a sulfur-containing silane coupling agent and the second silane coupling component is an alkylsilane coupling agent with 3-16 carbon atoms; the mass ratio of the silica, the first silane coupling component and the second silane coupling component is 100:1~15:2~30.

[0031] The modified silica prepared by this invention has certain oleophilicity and vulcanization function, and can be uniformly and stably dispersed in non-polar solvents, which is beneficial for its application in rubber reinforcement.

[0032] In this embodiment of the invention, silica and silane coupling agent are added to a reaction apparatus containing solvent and stirred at a temperature of room temperature to 100°C to carry out a modification reaction, thereby obtaining a slurry containing modified silica (or a modified silica suspension).

[0033] This invention does not impose any special limitations on the type of silica used; commercially available precipitated silica and fumed silica are both acceptable. In some embodiments, the particle size of the silica is 20 nm-30 μm, preferably 20 nm-800 nm, and more preferably 20 nm-300 nm. Preferably, the silica surface contains 3-10 wt% water, with 4-8 wt% being more desirable, to facilitate chemical modification.

[0034] The silane coupling agent described in this embodiment of the invention includes a first silane coupling component and a second silane coupling component (which can be correspondingly represented as silane coupling agent I and silane coupling agent II). The first silane coupling component is a sulfur-containing silane coupling agent, such as some mercapto-based silane coupling agents. It is preferably one or more of 3-octanoylthiopropyltriethoxysilane, 3-mercaptopropylmethyldiethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, bis-(3-triethoxysilylpropyl)tetrasulfide, bis-(3-triethoxysilylpropyl)disulfide, 3-thiocyanopropyltriethoxysilane, and 3-mercaptopropylethoxybis-(propane-hexaethoxysiloxane), and more preferably bis-(3-triethoxysilylpropyl)tetrasulfide or 3-mercaptopropyltriethoxysilane.

[0035] Furthermore, the second silane coupling component is an alkylsilane coupling agent with 3-16 carbon atoms, and its structure can be a straight-chain alkyl, branched alkyl, or aliphatic cycloalkyl, and more preferably a straight-chain alkyl, while the alkoxy group is mainly trimethoxy or triethoxy; such alkyl silane coupling agents are beneficial for obtaining suitable lipophilicity, etc. Preferably, the second silane coupling component is one or more of n-dodecyltrimethoxysilane, n-dodecyltriethoxysilane, cyclohexyltrimethoxysilane, isobutyltriethoxysilane, n-hexadecyltrimethoxysilane, n-hexyltriethoxysilane, n-propyltriethoxysilane, n-propyltrimethoxysilane, n-octyltrimethoxysilane, and n-octyltriethoxysilane.

[0036] The mass ratio of silica, silane coupling agent I, and silane coupling agent II described in this invention is 100:1~15:2~30, a more preferred ratio is 100:4~12:4~20, and a further preferred ratio is 100:6~10:6~16. Silane coupling agent I can be 1wt%~15wt% of the mass of silica, preferably 4wt%~12wt%; silane coupling agent II can be 4wt%~30wt% of the mass of silica, preferably 4wt%~20wt%.

[0037] The silane compounding modification scheme described in this invention not only enables the uniform and stable dispersion of silica in a non-polar solvent, achieving uniform dispersion of silica in rubber through solution blending, but more importantly, by changing the type and ratio of the two silane coupling agents, the rolling resistance, tensile properties, and fatigue resistance of the silica / rubber composite material can be controlled, resulting in a silica / rubber composite material with excellent overall performance.

[0038] The chemical modification process in this embodiment of the invention does not have many requirements; conventional solution modification is sufficient. Preferably, in this embodiment, the components of the two silane coupling agents are added to a container in the aforementioned proportions; then, they are blended using a stirring device to obtain a silane coupling agent premix. The stirring device is a conventional device, and the specific blending temperature can be room temperature to 80°C, with a preferred blending temperature of 30 to 60°C; the mixing time can be 0.5 h to 5 h, with a preferred time of 1 to 3 h.

[0039] In some embodiments, silica and silane coupling agents can be added to a solvent and mixed, then stirred and reacted at room temperature to 100°C to obtain a suspension containing modified silica, which can be directly used for subsequent applications. Characterization of the modified silica includes FTIR characterization, TG characterization, and hydrophilic / oleophilic angle measurement. The oleophilic contact angle is measured by dropping water droplets onto a silica tablet using appropriate equipment, photographing the droplets, and determining the angle. Better hydrophilicity results in water droplets tending to spread evenly on the sample, while better oleophilicity results in nearly spherical water droplets dispersed on the sample.

[0040] This application employs a one-step preparation process, directly modifying silica by silanization in a solvent. The room temperature is generally between 10 and 30°C; the stirring temperature is preferably between room temperature and 80°C, and the stirring time is within 24 hours, preferably 0.5 to 24 hours, further 1-12 hours or 2-10 hours. The solvent can be a non-polar solvent, including but not limited to one or more combinations of n-hexane, cyclohexane, heptane, dichloromethane, chloroform, diethyl ether, toluene, xylene, tetrahydrofuran, and N,N-dimethylformamide, such as cyclohexane, to obtain a modified silica slurry. In this step of the embodiment, the concentration of the modified silica slurry can be 0.01 to 0.2 g / mL, preferably 0.02 to 0.15 g / mL, further 0.03 to 0.1 g / mL, such as 0.04 g / mL, 0.05 g / mL, 0.08 g / mL, or 0.1 g / mL.

[0041] This invention provides a wet-process silica adhesive, comprising a rubber matrix and a reinforcing filler composited with the rubber matrix, wherein the reinforcing filler is modified silica obtained by the preparation method described above. The wet-process silica adhesive provided by this invention exhibits uniform filler dispersion and excellent comprehensive properties (such as mechanical properties, fatigue resistance, and rolling resistance), which is beneficial for its application.

[0042] Furthermore, embodiments of the present invention provide a method for preparing the wet-process silica adhesive as described above, comprising the following steps:

[0043] The rubber and the modified silica obtained by the preparation method described above are mixed in an organic solvent medium to obtain a mixed solution;

[0044] The organic solvent medium is removed by steam azeotropic drying, spray drying, or flocculation drying, and then dried to obtain wet-process compounded masterbatch (which can be referred to as wet-process masterbatch).

[0045] In a specific embodiment of this invention, rubber is added to a reaction apparatus containing an organic solvent medium to prepare a rubber solution. The rubber can be natural rubber, synthetic isoprene rubber (including trans-polyisoprene), cis-butadiene rubber, styrene-butadiene rubber (including solution-polymerized styrene-butadiene rubber and emulsion-polymerized styrene-butadiene rubber), or a combination of the above. The rubber solution in this embodiment can be obtained by dissolving block rubber or by directly using solution polymerization. Specifically, commercially available solution-polymerized styrene-butadiene rubber can be used. The grade and molecular chain structure of the rubber have little effect on the dispersion of the filler, and this method is applicable to both.

[0046] Furthermore, the liquid medium is primarily a non-polar organic solvent, preferably one or more of n-hexane, cyclohexane, heptane, dichloromethane, chloroform, diethyl ether, toluene, xylene, tetrahydrofuran, and N,N-dimethylformamide, and more preferably n-hexane or cyclohexane. Preferably, in this embodiment of the invention, the rubber solution is obtained by stirring at room temperature to 100°C for 0.5-12 hours, wherein the temperature is further 40-80°C or 50-70°C, and the stirring time can be 1-10 hours, 2-8 hours, or 3-6 hours; the concentration of the rubber solution can be 0.02-0.1 g / mL, preferably 0.05-0.08 g / mL.

[0047] In a preferred embodiment of the present invention, the rubber solution is mixed with the modified silica slurry and stirred at room temperature to 80°C to obtain a mixed solution. The mixing method of the modified silica slurry and the rubber solution can be one or more of mechanical mixing, ultrasonic mixing, ultrasonic / mechanical mixing, and high-speed jet mixing; conventional mixing processes are acceptable. The stirring time is generally within 24 hours, and can be between 0.5 and 24 hours. In this embodiment of the invention, the solution blending method using a non-aqueous solvent requires that the oleophilic properties of the silica are much greater than its hydrophilic properties to ensure that the silica can be stably and uniformly dispersed in the organic solvent, thereby achieving uniform dispersion of silica in the rubber.

[0048] After obtaining the mixed solution, the solvent is removed by conventional methods such as steam azeotropic drying, spray drying, or flocculation drying in this embodiment of the invention. The solution is then dried at 30-100℃ to obtain wet-process silica masterbatch (i.e., wet-process silica rubber). The three methods for solvent removal are mature processes. For example, ethanol flocculation drying involves gradually adding the rubber / silica mixture to ethanol within a temperature range of 30-60℃ to remove the solvent.

[0049] Furthermore, embodiments of the present invention also provide the application of the aforementioned wet-process silica rubber compound in tire manufacturing. That is, the aforementioned wet-process silica rubber compound can be used as a tire compound for tire production.

[0050] Furthermore, the application formula of the silica wet-process rubber compound includes: the silica wet-process rubber, activator, accelerator, and sulfur. Each component can be a conventional material. For example, the activator is zinc oxide and stearic acid; the accelerator can be TBBS, whose Chinese name is N-tert-butyl-2-benzothiazole sulfenamide. For example, the physical properties of the wet-process masterbatch were evaluated using a standard formulation. The raw materials in this evaluation formulation include raw rubber, silica, zinc oxide, stearic acid, accelerator TBBS, and sulfur. The raw rubber and silica are presented together in the form of wet-process rubber. The proportions of zinc oxide, stearic acid, accelerator TBBS, and sulfur, based on 100 phr of raw rubber (80 phr of silica) in the wet-process rubber, are 5 phr, 2 phr, 0.7 phr, and 2.25 phr, respectively.

[0051] According to the standard formulation, the prepared wet-process adhesive has excellent comprehensive properties, such as excellent mechanical properties, wear resistance and low rolling resistance.

[0052] To better understand the technical content of this invention, specific embodiments are provided below to further illustrate the invention. The substances used in these embodiments are commercially available.

[0053] Example 1

[0054] The preparation process of this embodiment is as follows: (1) Add silica and silane coupling agent to a reaction device containing solvent and stir at room temperature to 100°C to obtain modified silica slurry; the types and proportions of surface-modifying components are shown in Table 1. (2) Add rubber to a reaction device containing liquid medium and stir at room temperature to 100°C for 0.5-12 hours to obtain rubber solution. (3) Mix the rubber solution with the modified silica slurry and stir at room temperature to 80°C to obtain mixed solution. (4) Remove organic solvent by ethanol flocculation at room temperature to 50°C, and then dry the ethanol and residual solvent at 50°C to obtain wet-mixed masterbatch.

[0055] Example 2-3

[0056] The process is basically the same as in Example 1, except for the type of silane coupling agent.

[0057] Compare with Examples 1-4

[0058] The process is basically the same as in Example 1, except for the type of silane coupling agent.

[0059] The specific steps are as follows: Two silane coupling components are added to a container in a certain proportion; then, they are mixed using a stirring device to obtain a silane coupling premix. The mixing temperature is 60℃, and the mixing time is 2 hours.

[0060] For Comparative Examples 1-4 and Examples 1-3, conventional preparation methods were used, and the specific preparation technical parameters are as follows: the rubber selected was solution-polymerized styrene-butadiene rubber, grade M3626, with a styrene content of 23%; the silica selected was precipitated silica, type NEWSIL®155, with a nitrogen adsorption specific surface area of ​​135-165 m². 2 / g, primary particles 20-30nm. The concentration of the silica suspension was 0.05g / ml, and the concentration of the solution-polymerized styrene-butadiene rubber solution was 0.08g / ml. Cyclohexane was selected as the solvent for both silica modification and solution-polymerized styrene-butadiene rubber. The silica modification conditions were 60℃×10h, the solution-polymerized styrene-butadiene rubber dissolution conditions were 60℃×6h, and the mixing conditions for the modified silica suspension and solution-polymerized styrene-butadiene rubber solution were 60℃×24h. All solutions were mixed by mechanical stirring.

[0061] Table 1 shows the technical solutions used in Comparative Examples 1-4 and Examples 1-3.

[0062]

[0063] The physical properties of wet-process masterbatch were evaluated using a standard formulation. This formulation included raw rubber, silica, zinc oxide, stearic acid, TBBS accelerator, and sulfur. The raw rubber and silica were presented together in the form of wet-process masterbatch. The proportions of zinc oxide, stearic acid, TBBS accelerator, and sulfur, based on 100 phr of raw rubber (80 phr of silica) in the wet-process masterbatch, were 5 phr, 2 phr, 0.7 phr, and 2.25 phr, respectively.

[0064] The evaluation test results are as follows: the tensile properties of the rubber were tested using GB / T 528-2009; the dispersion of silica in the rubber was tested using GB / T 18251-2019; the Shore A hardness of the rubber was tested using GB / T 531.1-2008; the dynamic properties of the rubber were tested using GB / T 9870.1-2006; and the fatigue resistance of the rubber was tested using GB / T 13934-2006.

[0065] Table 2 Performance test results of wet-process adhesives

[0066]

[0067] The fillers in Comparative Examples 1-4 exhibited poor dispersion and overall performance, particularly in mechanical properties, rolling resistance, and fatigue resistance. In contrast, in this invention, the modified silica is uniformly and stably dispersed in a non-polar solvent; furthermore, uniform dispersion of silica in rubber is achieved through solution blending. Moreover, by altering the types and proportions of the two silane coupling components, the rolling resistance, tensile properties, and fatigue resistance of the silica / rubber composite material are controlled, resulting in a silica / rubber composite material with excellent overall performance, thereby extending tire service life.

[0068] This article uses specific examples to illustrate the principles and implementation methods of the present invention. The above examples are only for the purpose of helping to understand the method and core ideas of the present invention. The above descriptions are only preferred embodiments of the present invention. It should be noted that due to the limitations of textual expression, while there are objectively infinite specific structures, those skilled in the art can make several improvements, modifications, or changes without departing from the principles of the present invention, and can also combine the above technical features in an appropriate manner. These improvements, modifications, changes, or combinations, or the direct application of the inventive concept and technical solution to other situations without modification, should all be considered within the scope of protection of the present invention.

Claims

1. A method for preparing a modified white carbon black, characterized by, The method comprises the following steps: The surface modification reaction of the white carbon black is carried out in a solvent by using a silane coupling agent to obtain modified white carbon black, which is used for white carbon black wet rubber; the solvent is one or more of n-hexane, cyclohexane, heptane, dichloromethane, chloroform, diethyl ether, toluene, xylene, tetrahydrofuran and N,N dimethylformamide; The silane coupling agent comprises a first silane coupling component and a second silane coupling component, the first silane coupling component is one or more of 3-octanoylthiopropyl triethoxysilane, 3-mercaptopropyl methyldiethoxysilane, 3-mercaptopropyl methyldimethoxysilane, 3-mercaptopropyl triethoxysilane, 3-mercaptopropyl trimethoxysilane, bis-(3-triethoxysilylpropyl) tetrasulfide, bis-(3-triethoxysilylpropyl) disulfide, 3-thiocyanatopropyl triethoxysilane and 3-mercaptopropyl ethoxyl bis-(propane-hexaethoxysiloxane); The second silane coupling component is one or more of n-dodecyltrimethoxysilane, n-dodecyltriethoxysilane, cyclohexyltrimethoxysilane, isobutyltriethoxysilane, n-hexadecyltrimethoxysilane, n-hexyltriethoxysilane, n-propyltriethoxysilane, n-propyltrimethoxysilane, n-octyltrimethoxysilane and n-octyltriethoxysilane; The mass ratio of the white carbon black, the first silane coupling component and the second silane coupling component is 100:6-10:6-8; the water content on the surface of the white carbon black is 3-10 wt%.

2. The method for preparing modified silica according to claim 1, characterized in that, The white carbon black is precipitated white carbon black and / or fumed white carbon black; the particle size of the white carbon black is 20 nm-30 μm.

3. The method for preparing modified silica according to claim 1, characterized in that, The modification reaction is carried out below 100 ℃ and within 24 h of stirring to obtain a suspension containing modified white carbon black; the concentration of the suspension containing modified white carbon black is 0.01-0.2 g / mL.

4. A white carbon black wet gum, characterized by, The rubber base and the reinforcing filler compounded with the rubber base, the reinforcing filler being the modified white carbon black obtained by the preparation method of any one of claims 1-3.

5. The method for preparing wet-process silica adhesive as described in claim 4, characterized in that, The method comprises the following steps: The rubber is mixed with the modified white carbon black obtained by the preparation method of any one of claims 1-3 in an organic solvent medium to obtain a mixed solution; The organic solvent medium is removed by water vapor azeotropy or spray drying or flocculation drying, and then the mixed solution is dried to obtain a wet mixing master batch.

6. The method of claim 5, wherein the white carbon black wet gum is prepared by the steps of: The rubber is prepared into a rubber solution with the organic solvent medium, and then mixed with the modified white carbon black; The organic solvent medium is one or more of n-hexane, cyclohexane, heptane, dichloromethane, chloroform, diethyl ether, toluene, xylene, tetrahydrofuran and N,N dimethylformamide; the concentration of the rubber solution is 0.02-0.1 g / mL.

7. The method for preparing wet-process silica adhesive according to claim 5, characterized in that, The rubber is one or more of natural rubber, solution-polymerized styrene-butadiene rubber, emulsion-polymerized styrene-butadiene rubber, cis-butadiene rubber, trans-polyisoprene and isoprene rubber.

8. The process for the preparation of a white carbon wet gum according to any one of claims 5 to 7, characterized in that, The mixing is carried out below 80 ℃ and within 24 h of stirring; the mixing mode is one or more of mechanical mixing, ultrasonic mixing and jet mixing; the drying temperature is 30-100 ℃.

9. Application of the white carbon black wet rubber of claim 4 in tire production.

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