CN112175418B

CN112175418B - Modified white carbon black, preparation method thereof and masterbatch

Info

Publication number: CN112175418B
Application number: CN201910602994.7A
Authority: CN
Inventors: 吴晓辉; 尹田雨; 李晓林; 王益庆; 丁爱武; 丁小芳; 张立群
Original assignee: Hainan Zhongoak Technology Co ltd; Beijing University of Chemical Technology
Current assignee: Hainan Zhongoak Technology Co ltd; Beijing University of Chemical Technology
Priority date: 2019-07-05
Filing date: 2019-07-05
Publication date: 2022-05-17
Anticipated expiration: 2039-07-05
Also published as: CN112175418A; WO2021003814A1

Abstract

The invention discloses a preparation method of modified white carbon black, a masterbatch containing the modified white carbon black and a preparation method of the masterbatch. The preparation method comprises the following steps: (1) mixing aliphatic polyoxyethylene ether and a silane coupling agent under stirring to obtain a composite coupling agent; (2) and grinding the white carbon black water slurry with the solid content of 1-25 wt% for 5-40 minutes, adding the obtained composite coupling agent, and continuously grinding for 5-40 minutes to obtain the modified white carbon black. The high-filling white carbon black/rubber master batch is prepared by compounding the modified white carbon black and rubber through emulsion and spray drying, and compared with an in-situ modification-dry blending method, the method disclosed by the invention can effectively shorten the mixing time and obviously improve the strength and dynamic performance of the composite material.

Description

Modified white carbon black, preparation method thereof and masterbatch

Technical Field

The invention relates to the technical field of composite material preparation, in particular to a preparation method of modified white carbon black, a masterbatch containing the modified white carbon black and a preparation method of the masterbatch.

Background

The white carbon black has a plurality of internal gaps and a large specific surface area, and is an excellent rubber reinforcing filler, the rubber composite material prepared by blending the white carbon black and rubber is beneficial to reducing the rolling resistance of the tire and reducing the oil consumption of automobiles, and the tire using the white carbon black as a main filler is called a green tire. The white carbon black is white powder on a macroscopic scale, the surface of the white carbon black contains a large number of hydrophilic hydroxyl groups on a microscopic scale, and the mutual attraction of the hydroxyl groups also causes the white carbon black to be easy to self-aggregate. Therefore, the preparation of the high-filling white carbon black/natural rubber nano composite material needs to perform surface modification on white carbon black, reduce self-aggregation between white carbon black and improve the compatibility of the white carbon black and rubber.

Generally, the modifier applied to the white carbon black can chemically react with a large amount of silicon hydroxyl on the surface of the white carbon black. Most of the silica modifiers commonly used in the rubber industry are sulfur-containing siloxane structural coupling agents, such as Si69, Si75, Si747 and the like. The coupling agent with the siloxane structure mainly plays two roles of modifying the surface of the white carbon black and constructing a chemical connection structure between the white carbon black and the rubber.

The dry mixing method is the most important method for preparing the high-filling white carbon black rubber nano composite material at present, namely, the filling and the dispersion of the white carbon black are completed completely depending on the strong shearing force and the high temperature. However, it is often difficult to complete the mixing and dispersion of the white carbon black in the rubber matrix within a limited mixing time. Michelin company develops an in-situ modification and dispersion technology, and solves the problem of poor dispersion of white carbon black in rubber by using high temperature and high shear. The in-situ modification-dry blending method is an important breakthrough in the technology for preparing the white carbon black/rubber nano composite material, and the surface modification of the white carbon black is completed in the mixing process of the white carbon black and the rubber by selecting a modifier and controlling the temperature. Through in-situ modification and dry blending, the white carbon black can be filled into the rubber matrix and can be chemically combined with a siloxane structure coupling agent, so that the hydrophilicity of the white carbon black is reduced, the self-aggregation of the white carbon black is reduced, and the white carbon black is promoted to be uniformly dispersed into the rubber matrix. However, the technology has harsh requirements on equipment, complex processing and preparation flow and high energy consumption in the mixing process. Therefore, most tire factories do not adopt the technology for producing the white carbon black/rubber composite material on a large scale.

The emulsion blending method is mainly developed for rubber varieties with emulsion forms, and in the application of the method, the surface modification of the white carbon black is still required to be realized through modification. The difference from the traditional method is that the white carbon black is subjected to surface modification in a liquid phase by using the emulsion blending method, the modified white carbon black water slurry and the latex are uniformly mixed, and finally, the rubber/white carbon black master batch is obtained by flocculation and other modes. The rubber/white carbon black composite material prepared by the emulsion blending method can reduce the number of mixing stages in the preparation process, is beneficial to realizing a continuous mixing process, can also shorten the mixing time, and can reduce the mixing energy consumption and reduce the dust pollution. However, the conventional silica modifier-silane coupling agent is difficult to hydrolyze, and cannot modify the silica in the water phase well. AEO (aliphatic polyoxyethylene ether) as a nonionic surfactant can be well dissolved in water, and can effectively solve the problems that a silane coupling agent is difficult to hydrolyze and easy to self-polymerize after hydrolysis.

Disclosure of Invention

In order to solve the problems in the prior art, the invention provides a preparation method of modified white carbon black and a master batch containing the modified white carbon black.

According to the invention, under the conditions of specific frequency and rotation speed, a very small amount of AEO and a silane coupling agent are used together, the surface modification of the white carbon black is completed under the condition of a water phase, and the white carbon black master batch with high filling part is prepared by adopting a spray drying technology.

One of the purposes of the invention is to provide a preparation method of modified white carbon black, which comprises the following steps:

(1) mixing aliphatic polyoxyethylene ether and a silane coupling agent under a stirring condition to obtain a composite coupling agent, wherein the mass ratio of the aliphatic polyoxyethylene ether to the silane coupling agent is 9: 1-1: 29;

(2) grinding the white carbon black water slurry with the solid content of 1-25 wt% for 5-25 minutes, adding the composite coupling agent obtained in the step (1), and continuously grinding for 5-40 minutes to obtain the modified white carbon black, wherein the using amount of the composite coupling agent is 1-20 wt% of the white carbon black, and the grinding conditions comprise that the frequency is 10-100 Hz, the rotating speed is 6000-30000 rpm, the linear speed is 47-94 m/s, and the temperature of the system is controlled to be below 10 ℃.

The silane coupling agent is selected from silane coupling agents commonly used in the field, and preferably at least one selected from bis- [ gamma- (triethoxysilyl) propyl ] tetrasulfide (Si69), bis- [ gamma- (triethoxysilyl) propyl ] -disulfide (Si75) and gamma-mercaptopropyl-ethoxybis (propyl hexapropoxy) silane (Si 747).

The aliphatic polyoxyethylene ether is selected from aliphatic polyoxyethylene ethers commonly used in the field, and preferably at least one of aliphatic polyoxyethylene ether 3(AEO3), aliphatic polyoxyethylene ether 5(AEO5), aliphatic polyoxyethylene ether 7(AEO7) and aliphatic polyoxyethylene ether 9(AEO 9).

In a preferred embodiment of the present invention,

in the step (1), the mass ratio of the aliphatic polyoxyethylene ether to the silane coupling agent is 3: 1-1: 19.

In the step (1), the stirring condition is that the temperature is 30-60 ℃, the rotating speed is 300-600 rpm, and the stirring time is 5-15 minutes.

In the step (2), the solid content of the white carbon black water slurry is 1-15 wt%, and the dosage of the composite coupling agent is 1-10 wt% of the white carbon black.

In the step (2), the grinding conditions include a frequency of 60-70 Hz, a rotation speed of 12000-14000 rpm, a linear speed of 64-72 m/s, and a grinding time of 10-30 minutes.

In a more preferable technical scheme of the invention, the mass ratio of the aliphatic polyoxyethylene ether to the silane coupling agent is 1: 3-1: 19, and the using amount of the composite coupling agent is 5-10 wt% of the white carbon black.

The equipment used in the method of the present invention is the equipment which is available in the prior art and can provide proper rotating speed and frequency, such as a colloid mill, etc.

The second purpose of the invention is to provide the modified white carbon black obtained by the preparation method.

The invention also aims to provide a master batch which is prepared from the raw materials of rubber and the modified white carbon black obtained by the preparation method through emulsion compounding-spray drying.

In the master batch, the amount of the white carbon black in the modified white carbon black is 30-100 wt% of the rubber, and preferably 60-100 wt%.

The rubber is at least one selected from natural rubber, styrene butadiene rubber and butadiene-pyridine rubber.

The fourth object of the invention is to provide a preparation method of the master batch, which comprises the following steps:

and mixing rubber latex and the water slurry of the modified white carbon black, stirring for 5-30 min at the rotating speed of 40-70 r/min to obtain a suspension, and then performing closed-loop circulating spray drying to obtain the master batch.

The solid content of the rubber latex is preferably 5-30%.

The spray drying used is closed-cycle spray drying, using closed-cycle spray drying methods customary in the art. The following steps may preferably be employed: and introducing nitrogen into the drying tower, controlling the oxygen content in the tower to be lower than 8%, controlling the rotation speed of an atomizer to be 6000-20000 rpm, controlling the air inlet temperature to be 200-400 ℃ and controlling the air outlet temperature to be 70-150 ℃.

The invention uses closed cycle spray drying, solves the problem that the common spray drying is easy to catch fire, and the dried water can be condensed and recovered, and has the characteristics of safety and environmental protection.

The master batch can be used by matching with an auxiliary agent commonly used in the rubber field, and is processed on an internal mixer and an open mill to obtain a mixed rubber, and then the mixed rubber is subjected to flat vulcanization to obtain the required rubber product.

According to the invention, a very small amount of AEO and the silane coupling agent are used together, the amount of the AEO can be reduced to 0.33% of the mass of the white carbon black, the water phase compatibility of the silane coupling agent is improved under the action of a colloid mill, the white carbon black is modified in the water phase by a wet method, and the highly-filled white carbon black/rubber master batch is prepared by spray drying.

The invention can be realized by the following technical scheme:

(1) preparing a novel coupling agent: and stirring the mixed solution of the AEO and the silane coupling agent by using a stirrer, wherein the stirring condition is that the temperature is 30-60 ℃, the stirring time is 5-15 minutes, and the rotating speed is 300-600 rpm (based on the formation of a stable vortex). The components are prepared according to different mass ratios of AEO to silane coupling agent.

(2) Treating modified white carbon black: the preparation method comprises the steps of accurately weighing white carbon black powder and water level to prepare white carbon black water slurry with the solid content of 1-25%, weighing the white carbon black water slurry with the solid content of 1-25%, feeding the white carbon black water slurry into a colloid mill, adjusting the frequency to be 10-100 Hz, the rotating speed to be 6000-30000 rpm, the linear speed to be 47-94 m/s, controlling the system temperature to be within 10 ℃, grinding for 5-25 minutes under high shear, adding the novel coupling agent obtained in the step (1) to obtain 1-20% of the mass of the white carbon black, continuously grinding for 5-40 minutes to obtain uniform and stable white carbon black modified water slurry, and discharging.

(3) Preparing a master batch: and (3) adding water to dilute the natural latex until the solid content is 5-30%, mixing the natural latex with the modified white carbon black water slurry obtained in the step (2) according to the required white carbon black filling part, stirring the mixed suspension at the speed of 40-70 r/min for 5-30 min to uniformly mix the suspension to obtain a suspension, then performing closed cycle spray drying, and collecting the obtained masterbatch.

(4) And (4) processing the master batch obtained in the step (3) on an internal mixer and an open mill according to a rubber formula to obtain a mixed rubber, and performing flat vulcanization to obtain the required rubber product.

The invention aims to prepare a high-filling white carbon black/natural rubber nano composite material by a wet method and apply the high-filling white carbon black/natural rubber nano composite material to a tire tread. The surface modification of the white carbon black is completed by treating the silane coupling agent under the water phase condition by utilizing the strong shearing of a colloid mill and the emulsification of AEO so as to adapt to an emulsion compounding process; the spray drying technology is adopted to prepare the master batch, so that the white carbon black master batch with high filling part can be prepared. The invention effectively shortens the mixing time, reduces the dust flying, can simultaneously and obviously improve the strength and the dynamic performance of the composite material, reduces the heat generation and the Akron abrasion, and solves the problems of difficult material feeding, high heat generation and poor dispersion of the existing composite material preparation technology.

Drawings

FIGS. 1 and 2 show the dynamic mechanical properties RPA of the white carbon black/natural rubber composite materials of example 1 and comparative example 1.

FIGS. 3 and 5 show the dynamic mechanical properties RPA of the white carbon black/natural rubber composite materials of example 2 and comparative example 2.

Fig. 4 is a partially enlarged view of fig. 3.

FIGS. 6 and 7 show the dynamic mechanical properties RPA of the white carbon black/natural rubber composite materials of example 3 and comparative example 3.

FIGS. 8 and 9 are the dynamic mechanical properties RPA of the white carbon black/natural rubber composite material of example 4 and comparative example 4.

FIGS. 10-1 to 10-11 are processing and mixing curves of the white carbon black/natural rubber composite of example 4 and comparative example 4.

Detailed Description

For a better understanding of the present invention, the present invention is further illustrated below with reference to the following specific examples, in which natural rubber latex having a solid content of 60% is manufactured by Hainan Natural rubber Co., Ltd; the styrene-butadiene latex is obtained by petrochemical purchase of a Duzi mountain; all other raw materials are commercially available.

Example one

(1) Preparing AEO9 and Si69 according to different mass ratios, putting the mixture into a 60 ℃ water bath for heating, adjusting the rotating speed to be 500r/min, and continuously stirring for 10 min.

(2) 300g of white carbon black powder (VN3) is accurately weighed and uniformly mixed with 2700g of water to obtain white carbon black water slurry with the solid content of 10%. Pouring the white carbon black water slurry into a colloid mill, adjusting the frequency of the colloid mill to 70Hz, the rotating speed to 14000rpm and the linear speed to 72m/s, and continuously grinding for 10 min. And (3) adding 30g of the composite coupling agent obtained in the step (1) which is 10 percent of the mass of the white carbon black, continuously grinding for 10min to obtain uniform and stable modified white carbon black slurry, and discharging.

(3) And (3) adding water into the natural latex to dilute the natural latex until the solid content is 10%, mixing the natural latex with the modified white carbon black water slurry obtained in the step (2) according to the white carbon black filling part of 100phr (namely the mass ratio of the white carbon black to the natural latex is 100%), stirring the mixed suspension at the speed of 60r/min for 10min to uniformly mix the suspension, then performing closed-loop circulation spray drying, and collecting the obtained master batch.

(4) And (4) processing the master batch obtained in the step (3) on an internal mixer and an open mill according to a rubber formula to obtain a mixed rubber, and performing flat vulcanization to obtain the required rubber product. The basic formulation used is shown in table one below.

Comparative example 1

(1) And adding acid into the natural latex, stirring, flocculating and drying to obtain the natural rubber for later use.

(2) Accurately weighing 300g of white carbon black VN3 powder and 2700g of water, and uniformly mixing to obtain white carbon black water slurry with the solid content of 10%. Pouring the white carbon black water slurry into a colloid mill, adjusting the frequency of the colloid mill to 70Hz, the rotating speed to 14000rpm and the linear speed to 72m/s, and continuously grinding for 20 min. Then spray drying to obtain unmodified white carbon black powder.

(3) Processing the white carbon black powder obtained in the step (2) and the natural rubber obtained in the step (1) on an internal mixer and an open mill according to a rubber formula to obtain a rubber compound, and carrying out flat vulcanization to obtain the required rubber product. The basic formulation used is shown in table one below, wherein the coupling agent used is Si 69.

TABLE-100 phr filled white carbon black/natural rubber composite rubber formulation

The vulcanizate prepared in example one and the vulcanizate prepared in comparative example one were subjected to a tensile test according to the standard GB/T528-1998; the tear strength was measured according to rubber tear test Standard GB/T529-1999 with specific dynamic mechanical Properties, Heat Generation, abrasion Properties as shown in Table 1-1 and dynamic mechanical Properties RPA as shown in FIGS. 1 and 2.

(the mixed rubber test conditions comprise a scanning temperature of 60 ℃, a scanning frequency of 1Hz and a strain range of 0-400%. the vulcanized rubber test conditions comprise a vulcanization temperature of 143 ℃, a scanning temperature of 60 ℃, a scanning frequency of 10Hz and a strain range of 0-42%)

TABLE 1-1100 phr white carbon black/Natural rubber composite Properties Table

Example two

(1) Mixing AEO9 and Si69 according to a mass ratio of 1:3, preparing, placing in a 60 ℃ water bath for heating, adjusting the rotating speed to 500r/min, and continuously stirring for 10 min.

(2) Accurately weighing 300g of white carbon black powder (VN3), and uniformly mixing with 2700g of water to obtain white carbon black water slurry with the solid content of 10%. Pouring the white carbon black water slurry into a colloid mill, adjusting the frequency of the colloid mill to 70Hz, the rotating speed to 14000rpm and the linear speed to 72m/s, and continuously grinding for 10 min. Adding 30g of the coupling agent obtained in the step (1) which is 10 percent of the mass of the white carbon black, continuously grinding for 10min to obtain uniform and stable modified white carbon black water slurry, and discharging.

(4) And (3) mixing the master batch obtained in the step (3) with crude rubber obtained by flocculating natural latex according to a rubber formula, processing on an internal mixer and an open mill to obtain mixed rubber, and performing flat vulcanization to obtain the required rubber product. The basic formulation used is shown in table two below.

Comparative example No. two

(2) Accurately weighing 300g of white carbon black VN3 powder and 2700g of water, and uniformly mixing to obtain white carbon black water slurry with the solid content of 10%. Pouring the white carbon black water slurry into a colloid mill, adjusting the frequency of the colloid mill to 70Hz, the rotating speed to 14000rpm and the linear speed to 72m/s, and continuously grinding for 20 min. Then spray drying to obtain the unmodified white carbon black powder.

(3) Processing the white carbon black powder obtained in the step (2) and the natural rubber obtained in the step (1) on an internal mixer and an open mill according to a rubber formula to obtain a rubber compound, and carrying out flat vulcanization to obtain the required rubber product. The basic formulation used is shown in table two below.

Table two dilution combined experimental rubber formula

The vulcanizate prepared in example two and the vulcanizate prepared in comparative example two were subjected to a tensile test according to the standard GB/T528-1998; the tear strength was measured according to rubber tear test Standard GB/T529-1999 with specific dynamic mechanical Properties, Heat Generation, abrasion Properties as shown in Table 2-1 and dynamic mechanical Properties RPA as shown in FIGS. 3-5.

TABLE 2-1 dilution and performance table for filled white carbon black/natural rubber composite material

EXAMPLE III

(2) 300g of white carbon black powder (VN3) is accurately weighed and uniformly mixed with 2700g of water to obtain white carbon black water slurry with the solid content of 10%. Pouring the white carbon black water slurry into a colloid mill, adjusting the frequency of the colloid mill to 70Hz, the rotating speed to 14000rpm and the linear speed to 72m/s, and continuously grinding for 10 min. Adding 30g of the coupling agent obtained in the step (1) which is 10 percent of the mass of the white carbon black, continuously grinding for 10min to obtain uniform and stable modified white carbon black water slurry, and discharging.

(3) And (3) adding water into the natural latex to dilute the natural latex until the solid content is 10%, mixing the natural latex with the modified white carbon black water slurry obtained in the step (2) according to the white carbon black filling part of 60phr (namely the mass ratio of the white carbon black to the natural latex is 60%), stirring the mixed suspension at the speed of 60r/min for 10min to uniformly mix the suspension, then performing closed-loop circulation spray drying, and collecting the obtained master batch.

(4) And (4) processing the master batch obtained in the step (3) on an internal mixer and an open mill according to a rubber formula to obtain a mixed rubber, and performing flat vulcanization to obtain the required rubber product. The basic formulations used are shown in table three below.

Comparative example No. three

(1) Adding acid into natural latex, stirring, flocculating and drying to obtain natural rubber for later use.

(3) Processing the white carbon black powder obtained in the step (2) and the natural rubber obtained in the step (1) on an internal mixer and an open mill according to a rubber formula to obtain a rubber compound, and carrying out flat vulcanization to obtain the required rubber product. The basic formulation used is shown in table three below, where the coupling agent used is Si 69.

Experimental formula of filler white carbon black/natural rubber composite material with weight of 60phr

The vulcanizate prepared in example three and the vulcanizate prepared in comparative example three were subjected to a tensile test according to the standard GB/T528-1998; the tear strength was measured according to rubber tear test Standard GB/T529-1999 with specific dynamic mechanical Properties, Heat Generation, abrasion Properties as shown in Table 3-1 and dynamic mechanical Properties RPA as shown in FIGS. 6 and 7.

TABLE 3-160 phr white carbon black/natural rubber composite Property Table

Example four

(2) Accurately weighing 300g of white carbon black powder (1165), and uniformly mixing with 2700g of water to obtain white carbon black water slurry with the solid content of 10%. Pouring the white carbon black water slurry into a colloid mill, adjusting the frequency of the colloid mill to be 70Hz, the rotating speed to be 14000rpm and the linear speed to be 72m/s, and continuously grinding for 10 min. Adding 30g of the coupling agent obtained in the step (1) which is 10 percent of the mass of the white carbon black, continuously grinding for 10min to obtain uniform and stable modified white carbon black water slurry, and discharging.

(4) And (4) processing the master batch obtained in the step (3) on an internal mixer and an open mill according to a rubber formula to obtain a mixed rubber, and performing flat vulcanization to obtain the required rubber product. The basic formulation used is shown in table four below.

Comparative example No. four

(2) Accurately weighing 300g of white carbon black 1165 powder and 2700g of water, and uniformly mixing to obtain white carbon black water slurry with the solid content of 10%. Pouring the white carbon black water slurry into a colloid mill, adjusting the frequency of the colloid mill to be 70Hz, the rotating speed to be 14000rpm and the linear speed to be 72m/s, and continuously grinding for 20 min. Then spray drying to obtain the unmodified white carbon black powder.

(3) Processing the white carbon black powder obtained in the step (2) and the natural rubber obtained in the step (1) on an internal mixer and an open mill according to a rubber formula to obtain a rubber compound, and carrying out flat vulcanization to obtain the required rubber product. The basic formulation used is shown in Table four below, where the coupling agent used is Si 69.

TABLE IV 60phr filling white carbon black/natural rubber composite material experimental formula

The vulcanizate prepared in example four and the vulcanizate prepared in comparative example four were subjected to a tensile test according to the standard GB/T528-1998; the tearing strength is carried out according to the rubber tearing test standard GB/T529-1999, and the specific dynamic mechanical property, heat generation and abrasion performance are shown in the table 4-1;

TABLE 4-160 phr white carbon black/natural rubber composite Property Table

(the test conditions of the rubber compound are that the scanning temperature is 60 ℃, the scanning frequency is 1Hz, and the strain range is 0-400%. the test conditions of the vulcanized rubber are that the vulcanization temperature is 143 ℃, the scanning temperature is 60 ℃, the scanning frequency is 10Hz, and the strain range is 0-42%.) the dynamic mechanical property RPA is shown in figure 8 and figure 9, and the mixing curve is that the composite material is mixed by an internal mixer RM-200C torque rheometer, and the curve is shown in figure 10-1 to figure 10-11.

EXAMPLE five

(3) Diluting styrene-butadiene latex with water until the solid content is 10%, mixing the diluted styrene-butadiene latex with the modified white carbon black water slurry obtained in the step (2) according to the white carbon black filling part of 70phr (namely the mass ratio of the white carbon black to the styrene-butadiene latex is 70%), stirring the mixed suspension at the speed of 60r/min for 10min to uniformly mix the suspension, then performing closed-loop circulation spray drying, and collecting the obtained master batch.

(4) And (4) processing the master batch obtained in the step (3) on an internal mixer and an open mill according to a rubber formula to obtain a mixed rubber, and performing flat vulcanization to obtain the required rubber product. The basic formulation used is shown in table five below.

Comparative example five

(1) And adding acid into the styrene-butadiene latex, stirring, flocculating and drying to obtain styrene-butadiene rubber for later use.

(3) Processing the white carbon black powder obtained in the step (2) and the styrene butadiene rubber obtained in the step (1) on an internal mixer and an open mill according to a rubber formula to obtain a rubber compound, and performing flat vulcanization to obtain the required rubber product. The basic formulation used is shown in Table five below, where the coupling agent used is Si 69.

Table five 70phr filling white carbon black/butadiene styrene rubber composite material experiment formula

The vulcanizate prepared in example five and the vulcanizate prepared in comparative example five were subjected to a tensile test according to the standard GB/T528-1998; the tear strength was measured according to rubber tear test Standard GB/T529-1999, and the specific dynamic mechanical Properties, Heat Generation, and abrasion Properties are shown in Table 5-1.

TABLE 5-170 phr white carbon black/styrene butadiene rubber composite Performance Table

Claims

1. The preparation method of the modified white carbon black is characterized by comprising the following steps:

(1) mixing aliphatic polyoxyethylene ether and a silane coupling agent under a stirring condition to obtain a composite coupling agent, wherein the mass ratio of the aliphatic polyoxyethylene ether to the silane coupling agent is 1: 14-1: 19;

(2) grinding the white carbon black water slurry with the solid content of 1-25 wt% for 5-25 minutes, adding the composite coupling agent obtained in the step (1), and continuously grinding for 5-40 minutes to obtain the modified white carbon black, wherein the using amount of the composite coupling agent is 1-10 wt% of the white carbon black, the grinding conditions comprise that the frequency is 10-100 Hz, the rotating speed is 6000-30000 rpm, the linear speed is 47-94 m/s, and the temperature of the system is controlled to be below 10 ℃.

2. The preparation method of the modified white carbon black according to claim 1, which is characterized by comprising the following steps:

the silane coupling agent is selected from at least one of bis- [ gamma- (triethoxysilyl) propyl ] tetrasulfide, bis- [ gamma- (triethoxysilyl) propyl ] -disulfide and gamma-mercaptopropyl-ethoxybis (propyl hexapropoxy) silane;

the aliphatic polyoxyethylene ether is at least one selected from aliphatic polyoxyethylene ether 3, aliphatic polyoxyethylene ether 5, aliphatic polyoxyethylene ether 7 and aliphatic polyoxyethylene ether 9.

3. The preparation method of the modified white carbon black according to claim 1, which is characterized by comprising the following steps:

in the step (2), the solid content of the white carbon black water slurry is 1-15 wt%; the dosage of the composite coupling agent is 5-10 wt% of the white carbon black.

4. The preparation method of the modified white carbon black according to claim 1, which is characterized by comprising the following steps:

5. Modified white carbon black obtained by the preparation method according to any one of claims 1 to 4.

6. A masterbatch, characterized in that the masterbatch is prepared by emulsion compounding and spray drying from a raw material comprising rubber and the modified silica obtained by the method of any one of claims 1 to 4.

7. A masterbatch according to claim 6, characterized in that:

in the master batch, the amount of white carbon black in the modified white carbon black is 30-100 wt% of the rubber.

8. A masterbatch according to claim 7, characterized in that:

the amount of white carbon black in the modified white carbon black is 60-100 wt% of the rubber.

9. A masterbatch according to claim 6, characterized in that:

10. A method for preparing a masterbatch according to any one of claims 6 to 9, characterized by comprising the steps of: