CN116515169A - Preparation method of wet modified white carbon black, masterbatch and vulcanized rubber - Google Patents

Preparation method of wet modified white carbon black, masterbatch and vulcanized rubber Download PDF

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CN116515169A
CN116515169A CN202210064271.8A CN202210064271A CN116515169A CN 116515169 A CN116515169 A CN 116515169A CN 202210064271 A CN202210064271 A CN 202210064271A CN 116515169 A CN116515169 A CN 116515169A
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carbon black
white carbon
rubber
masterbatch
solution
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姚红
张建
张立群
田鑫
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Beijing University of Chemical Technology
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Beijing University of Chemical Technology
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/22—Expanded, porous or hollow particles
    • C08K7/24—Expanded, porous or hollow particles inorganic
    • C08K7/26—Silicon- containing compounds
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/80—Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
    • Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction 

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  • Health & Medical Sciences (AREA)
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Abstract

The invention discloses a preparation method of wet modified white carbon black, the wet modified white carbon black, a masterbatch and a vulcanized rubber. The preparation method of the wet modified white carbon black comprises the following steps: uniformly dispersing the white carbon black in an organic solvent to prepare slurry, adding a silane coupling agent to react, and then adding tea polyphenol to react to obtain the wet modified white carbon black. According to the invention, the tea polyphenol and the silane coupling agent are used together, the white carbon black is modified in the organic solvent, so that the uniformity of the dispersion of the white carbon black in the organic solvent and the stability of the white carbon black in existence can be improved, the hydrophilicity of the white carbon black is reduced, the agglomeration is reduced, the modified white carbon black has better dispersion in a rubber matrix, the wear resistance and compression heat generating performance of vulcanized rubber are improved higher along with the addition of the tea polyphenol, and the vulcanized rubber has higher 100% and 300% stretching stress and has better application.

Description

Preparation method of wet modified white carbon black, masterbatch and vulcanized rubber
Technical Field
The invention relates to the technical field of rubber nanocomposite materials, in particular to a preparation method of wet modified white carbon black, the wet modified white carbon black, masterbatch and vulcanized rubber.
Background
Carbon black and white carbon black are the most commonly used reinforcing fillers for elastomer composites, and especially white carbon black is a promising candidate for replacing traditional carbon black, which is important to the green tire industry because white carbon black has been used as a filler in tires to reduce fuel consumption in private and specialty vehicles. However, the white carbon black surface has very high polarity, and a large number of hydroxyl groups exist on the surface; this makes it highly prone to agglomeration and interaction with the rubber. Fortunately, these can be overcome by surface modification of the white carbon black with organic compounds, reducing the number of surface active hydroxyl groups.
The modification process of the white carbon black can be mainly divided into three types, namely in-situ modification, dry modification and wet modification. In-situ modification is the simplest, white carbon black and a coupling agent are mixed with a matrix, and the white carbon black and the coupling agent react to complete modification through a certain condition method such as a catalyst, vacuum and the like, but the modification effect of the method is not ideal at the same time, and the three raw materials are difficult to ensure even mixing reaction, so that the modification process is difficult to control, and various factors are limited. The wet modification in Chinese patent CN103203810A and Chinese patent CN105602047A is to mix the coupling agent with white carbon black in a liquid solvent and modify under certain conditions. Compared with dry modification, the white carbon black and the coupling agent are uniformly mixed, the reaction controllability is high, but the activity of the coupling agent reaction limits the further modification of the white carbon black and the dispersion of the white carbon black in a rubber matrix and the interface effect of the white carbon black and the rubber, so that a new white carbon black modification method is necessary to be developed and explored to further improve the dispersion of the white carbon black in the rubber matrix so as to prepare the composite material with higher performance.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a preparation method of wet modified white carbon black, the wet modified white carbon black, a masterbatch and a vulcanized rubber. The preparation method of the wet modified white carbon black comprises the following steps: uniformly dispersing the white carbon black in an organic solvent to prepare slurry, adding a silane coupling agent to react, and then adding tea polyphenol to react to obtain the wet modified white carbon black. According to the invention, the tea polyphenol and the silane coupling agent are used together, the white carbon black is modified in the organic solvent, so that the uniformity of the dispersion of the white carbon black in the organic solvent and the stability of the white carbon black in existence can be improved, the hydrophilicity of the white carbon black is reduced, the agglomeration is reduced, the modified white carbon black has better dispersion in a rubber matrix, and the abrasion resistance and compression heat generating performance of vulcanized rubber are improved higher along with the addition of the tea polyphenol, and the vulcanized rubber has higher 100% and 300% stretching stress and has better application.
The invention aims at providing a preparation method of wet modified white carbon black.
The method comprises the following steps:
uniformly dispersing the white carbon black in an organic solvent to prepare slurry, adding a silane coupling agent to react, and then adding tea polyphenol to react to obtain the wet modified white carbon black.
In a preferred embodiment of the present invention,
the silane coupling agent may be added in one-time or dropwise.
In a preferred embodiment of the present invention,
the white carbon black can adopt a precipitation method or a gas phase method which are conventional in the prior art, and the specific surface area is 50-300 m 2 Preferably 100 to 200m 2 Per gram, the oil absorption value is 0.3-3 ml/g, preferably 0.5-1.5 ml/g; and/or the number of the groups of groups,
the organic solvent is a good solvent for rubber and can dissolve the silane coupling agent without participating in the reaction, and is preferably cyclohexane or n-hexane.
The following reasons for selecting the organic solvent as the modifying solvent in the present invention are: considering that most of rubber is an organic solvent in the actual solution polymerization process, the solvent used in the rubber production process is selected, so that the solvent can be prevented from being removed by rubber manufacturers, the solvent can be prevented from being removed by white carbon black after modification, and the energy consumption and the cost of rubber finished products can be reduced in the process.
The silane coupling agent may be at least one of bis- [ gamma- (triethoxysilane) propyl ] tetrasulfide (Si 69), bis- [ gamma- (triethoxysilane) propyl ] disulfide (Si 75), 3-thiocyanopropyltriethoxysilane, gamma-mercaptopropyl triethoxysilane (KH 580), gamma-aminopropyl triethoxysilane (KH 550), gamma-methacryloxypropyl trimethoxysilane (KH 570) which are conventional in the art.
In a preferred embodiment of the present invention,
the solid content of the white carbon black in the organic solvent is 5-20%, preferably 14-16%;
the dosage of the silane coupling agent is 3-15% of the mass of the white carbon black, preferably 8-12%;
the tea polyphenol is used in an amount of 1 to 5% by mass, preferably 1 to 4% by mass, more preferably 1.4 to 2.1% by mass of the white carbon black.
In a preferred embodiment of the present invention,
the reaction temperature after the addition of the silane coupling agent is 10-80 ℃, and the reaction time is 0.1-5 h, preferably 0.5-3 h, more preferably 0.5-1.5 h;
the reaction temperature after the tea polyphenol is added is 5-50 ℃, and the reaction time is 0.1-3 h, preferably 0.1-1.5 h, more preferably 0.5-1 h.
The silane coupling agent is soluble in an organic solvent, and the silane coupling agent modified white carbon black has two mechanisms at present, namely, the ethoxy on the silane coupling agent directly reacts with the silicon hydroxyl on the white carbon black (the high reaction difficulty of the activation energy), and the ethoxy firstly hydrolyzes to generate the silicon hydroxyl and then reacts with the silicon hydroxyl on the white carbon black (the reaction is simple). If tea polyphenol and a silane coupling agent are added simultaneously, competition effect is caused on the surface of white carbon black: firstly, the hydroxyl groups of the tea polyphenol and the hydroxyl groups on the white carbon black form hydrogen bonds, secondly, the silane coupling agent reacts with the hydroxyl groups on the white carbon black, the hydroxyl groups on the white carbon black and the tea polyphenol do not react with the coupling agent after forming the hydrogen bonds, so that the efficiency of the coupling agent is reduced, and further, the prepared rubber performance is greatly reduced. In the application, the coupling agent is added into the organic solvent for reaction, and then the tea polyphenol is added for further modification, so that the modification efficiency of the coupling agent is not affected. The surface of tea polyphenol contains adjacent phenolic hydroxyl groups, can form five-membered rings with the surface of white carbon black, and does not have macromolecular long chains to be dissociated in rubber to perform plasticization.
The purpose of the wet modified white carbon black is to further improve the modification effect of the white carbon black on the basis of the modified white carbon black by the coupling agent, and the addition of tea polyphenol can improve the lipophilicity of the white carbon black, further improve the compatibility of the white carbon black with rubber and improve the dispersion of the white carbon black. The tea polyphenol is used for modifying the white carbon black independently, so that the dispersibility of the white carbon black in rubber can only be improved, the interaction between the rubber and the white carbon black cannot be established (the tea polyphenol cannot be connected to the rubber), and the prepared vulcanized rubber cannot meet the use requirement. The wet modified white carbon black of the invention has the main function of further improving the service performance of vulcanized rubber on the basis of the current main production process. The performance of the white carbon black modified by the coupling agent can be further improved by adding tea polyphenol.
It is a second object of the present invention to provide a wet-modified white carbon black prepared by the method of one of the objects of the present invention.
The third object of the invention is to provide a masterbatch comprising the wet modified white carbon black of the second object of the invention.
The masterbatch is prepared from a rubber solution and the wet modified white carbon black.
In a preferred embodiment of the present invention,
the rubber solution is a solution prepared by dissolving a polymer rubber solution or rubber in an organic solvent;
the solution polymerization rubber can be conventional solution polymerization rubber in the prior art, preferably at least one of solution polymerization styrene-butadiene rubber, polyisoprene rubber and butadiene rubber; and/or the number of the groups of groups,
the rubber can be at least one of natural rubber and butyl rubber which are conventional in the prior art, and the molecular weight range is 5 ten thousand to 500 ten thousand, preferably 10 ten thousand to 200 ten thousand; and/or the number of the groups of groups,
the organic solvent is the same as or different from the organic solvent used in the preparation process of the wet-process modified white carbon black, and is preferably cyclohexane or n-hexane independently;
in a preferred embodiment of the present invention,
the solid content of the rubber solution is 10% -50%, preferably 10% -15%; the mass of the white carbon black is 1-100% of the mass of rubber or soluble polymer rubber, preferably 50-100%, and more preferably 65-75%.
The fourth object of the invention is to provide a method for preparing the masterbatch of the third object of the invention.
The method comprises the following steps:
and uniformly mixing the wet modified white carbon black and the rubber solution according to the mass ratio, and removing the solvent to obtain the masterbatch.
In a preferred embodiment of the present invention,
the solvent removal may be performed by any method known in the art.
It is a fifth object of the present invention to provide a vulcanized rubber comprising the masterbatch of the third object of the present invention or the masterbatch prepared by the method of the fourth object of the present invention.
The vulcanized rubber is obtained by mixing and vulcanizing the components including the masterbatch, an activating agent, an anti-aging agent, an accelerator and a vulcanizing agent.
In a preferred embodiment of the present invention,
the activating agent, the anti-aging agent, the accelerator and the vulcanizing agent can be conventional activating agents, anti-aging agents, accelerators and vulcanizing agents in the prior art, the dosage of the activating agents, the anti-aging agents, the accelerators and the vulcanizing agents is also conventional, and the technical personnel can adjust the activating agents, the anti-aging agents, the accelerators and the vulcanizing agents according to actual conditions.
The invention can preferably adopt the following specific technical scheme:
firstly dispersing white carbon black in an organic solvent, firstly carrying out liquid phase modification on the white carbon black by using a silane coupling agent under the condition of mechanical grinding or mechanical stirring, then adding tea polyphenol into the white carbon black for further modification after the modification is finished, and finally obtaining the uniformly dispersed wet-process modified white carbon black.
The beneficial effects of the invention are as follows:
because the activity of the coupling agent is limited, the hydroxyl groups on the surface of the white carbon black are not completely reacted, residual hydroxyl groups can form hydrogen bonds under certain conditions to cause agglomeration of the white carbon black, macroscopic properties (such as compression heat generation and the like) are reduced, and in order to maintain stable dispersion of small particles of the white carbon black after grinding, the hydroxyl groups on the surface of the white carbon black need to be further covered to prevent the agglomeration of the white carbon black.
According to the invention, the tea polyphenol and the silane coupling agent are used together, the white carbon black is modified in an organic solvent, and the hydrogen bond formed by the tea polyphenol and the silicon hydroxyl on the surface of the white carbon black is further reduced on the basis of modifying the white carbon black by using the traditional coupling agent, so that the uniformity of the white carbon black in the organic solvent can be improved, the existing stability can be maintained, the agglomeration is reduced, the white carbon black after wet modification has better dispersion in a rubber matrix, and meanwhile, the entanglement of the long-chain physical effect of the tea polyphenol macromolecules can also promote the interface effect and the dispersion of the white carbon black. Tea polyphenol (macromolecule) and a silane coupling agent are used together, complement each other and have better modification effect. The combination of the two further improves the dispersion effect of the white carbon black in the rubber matrix compared with the single use of the silane coupling agent.
The invention adopts wet modified white carbon black and adopts a one-step liquid phase mixing method, namely silane coupling agent, tea polyphenol and white carbon black are directly modified in sequence in an organic solvent liquid phase environment to obtain uniform and stable wet modified white carbon black, and then the uniform and stable wet modified white carbon black is directly mixed and stirred with rubber solution, so that the step of separating modified white carbon black from liquid phase is reduced, the energy consumption is reduced, the preparation period of master batch is shortened, and the self-polymerization process of the coupling agent can be reduced by modifying in the organic phase environment. According to the invention, the fact that most of the rubber is an organic solvent in the actual solution polymerization process is considered, so that the organic solvent used in the rubber production process is selected, the solvent can be prevented from being removed by rubber manufacturers, white carbon black can be prevented from being removed after modification, the whole process is simple and efficient, the energy consumption can be reduced, and the cost of rubber finished products is reduced.
The modified silica gel has good modification effect on silica gel, can effectively improve the dispersibility of the silica gel in a rubber matrix, further improve the dynamic performance of the composite material, effectively improve the wear resistance of vulcanized rubber along with the addition of tea polyphenol, reduce compression heat generation, and has higher 100% and 300% stretching stress and better application.
In addition, the tea polyphenol can enhance the heat resistance and aging resistance of the tread rubber, and the more the dosage is, the better the improvement effect is. And the tea polyphenol has low cost and simple extraction, and can be directly used as a modifier to reduce the cost if the tea polyphenol has higher performance improvement on tread rubber.
Detailed Description
The present invention is described in detail below with reference to specific embodiments, and it should be noted that the following embodiments are only for further description of the present invention and should not be construed as limiting the scope of the present invention, and some insubstantial modifications and adjustments of the present invention by those skilled in the art from the present disclosure are still within the scope of the present invention.
The starting materials used in the examples were all conventional commercially available.
The main raw materials have the following specifications:
the relevant performance test methods and apparatus of the examples are shown in table 1:
table 1 related Performance test methods and apparatus
Table 2 rubber formulations for examples and comparative examples
Example 1
Adding 70g of white carbon black into cyclohexane, stirring to prepare white carbon black cyclohexane dispersion liquid with the solid content of 15%, dripping 7gSi69 into the dispersion liquid, stirring and reacting for 1h at 15 ℃, then heating to 30 ℃, adding 1.4g of tea polyphenol, and stirring for 30min to obtain slurry, namely the wet modified white carbon black. Then adding the slurry into 833g of solution polymerized styrene-butadiene rubber cyclohexane solution (the mass of the solution polymerized styrene-butadiene rubber is 100 g), and stirring and mixing uniformly to obtain modified mixed glue solution. Pouring the mixed glue solution into hot water with the temperature of more than 95 ℃ to precipitate and agglomerate to obtain the SSBR/white carbon black master batch. And then, uniformly mixing the dried master batch, 3g of zinc oxide, 2g of stearic acid and 2g of anti-aging agent 4020 in an internal mixer, discharging, and performing heat treatment at 150 ℃ for 5min to obtain the rubber compound. Adding 1.7g of accelerator CZ, 1.8g of accelerator DPG and 1.7g of sulfur into the cooled mixed rubber on an open mill, uniformly mixing, discharging slices, standing for 12 hours, and vulcanizing on a flat vulcanizing machine at 150 ℃ until the vulcanized rubber is obtained.
Example 2
Adding 70g of white carbon black into cyclohexane, stirring to prepare white carbon black cyclohexane dispersion liquid with the solid content of 15%, dripping 7gSi69 into the dispersion liquid, stirring at 55 ℃ for reaction for 1h, cooling to 30 ℃, adding 1.4g of tea polyphenol, and stirring for 30min to obtain slurry, namely the wet modified white carbon black. Then adding the slurry into 833g of solution polymerized styrene-butadiene rubber cyclohexane solution (the mass of the solution polymerized styrene-butadiene rubber is 100 g), and stirring and mixing uniformly to obtain modified mixed glue solution. Pouring the mixed glue solution into hot water with the temperature of more than 95 ℃ to precipitate and agglomerate to obtain the SSBR/white carbon black master batch. And then, uniformly mixing the dried master batch, 3g of zinc oxide, 2g of stearic acid and 2g of anti-aging agent 4020 in an internal mixer, discharging, and performing heat treatment at 150 ℃ for 5min to obtain the rubber compound. Adding 1.7g of accelerator CZ, 1.8g of accelerator DPG and 1.7g of sulfur into the cooled mixed rubber on an open mill, uniformly mixing, discharging slices, standing for 12 hours, and vulcanizing on a flat vulcanizing machine at 150 ℃ until the vulcanized rubber is obtained.
Example 3
Adding 70g of white carbon black into cyclohexane, stirring to prepare white carbon black cyclohexane dispersion liquid with the solid content of 15%, dripping 7gSi69 into the dispersion liquid, stirring and reacting for 1h at 75 ℃, then cooling to 30 ℃, adding 1.4g of tea polyphenol, and stirring for 30min to obtain slurry, namely the wet modified white carbon black. Then adding the slurry into 833g of solution polymerized styrene-butadiene rubber cyclohexane solution (the mass of the solution polymerized styrene-butadiene rubber is 100 g), and stirring and mixing uniformly to obtain modified mixed glue solution. Pouring the mixed glue solution into hot water with the temperature of more than 95 ℃ to precipitate and agglomerate to obtain the SSBR/white carbon black master batch. And then, uniformly mixing the dried master batch, 3g of zinc oxide, 2g of stearic acid and 2g of anti-aging agent 4020 in an internal mixer, discharging, and performing heat treatment at 150 ℃ for 5min to obtain the rubber compound. Adding 1.7g of accelerator CZ, 1.8g of accelerator DPG and 1.7g of sulfur into the cooled mixed rubber on an open mill, uniformly mixing, discharging slices, standing for 12 hours, and vulcanizing on a flat vulcanizing machine at 150 ℃ until the vulcanized rubber is obtained.
Comparative example 1
Adding 70g of white carbon black into cyclohexane, stirring to prepare white carbon black cyclohexane dispersion liquid with the solid content of 15%, dripping 7g of Si69 into the dispersion liquid, stirring at 55 ℃ for reaction for 1h, adding the slurry into 833g of solution polymerized styrene-butadiene rubber cyclohexane solution (the mass of the solution polymerized styrene-butadiene rubber is 100 g), and stirring and mixing uniformly to obtain modified mixed glue solution. Pouring the mixed glue solution into hot water with the temperature of more than 95 ℃ to precipitate and agglomerate to obtain the SSBR/white carbon black master batch. And then, uniformly mixing the dried master batch and 1.4g of tea polyphenol in an internal mixer, then adding 3g of zinc oxide, 2g of stearic acid and 2g of anti-aging agent 4020, uniformly mixing, discharging, and performing heat treatment at 150 ℃ for 5min to obtain the rubber compound. Adding 1.7g of accelerator CZ, 1.8g of accelerator DPG and 1.7g of sulfur into the cooled mixed rubber on an open mill, uniformly mixing, discharging slices, standing for 12 hours, and vulcanizing on a flat vulcanizing machine at 150 ℃ until the vulcanized rubber is obtained.
Comparative example 2
Adding 70g of white carbon black into cyclohexane, stirring to prepare white carbon black cyclohexane dispersion liquid with the solid content of 15%, adding 1.4g of tea polyphenol into the dispersion liquid at the temperature of 30 ℃, stirring for 30min, adding the slurry into 833g of solution polymerized styrene-butadiene rubber cyclohexane solution (the mass of the solution polymerized styrene-butadiene rubber is 100 g), and stirring and mixing uniformly to obtain modified mixed glue liquid. Pouring the mixed glue solution into hot water with the temperature of more than 95 ℃ to precipitate and agglomerate to obtain the SSBR/white carbon black master batch. And then, uniformly mixing the dried master batch, 3g of zinc oxide, 2g of stearic acid and 2g of anti-aging agent 4020 in an internal mixer, discharging, and performing heat treatment at 150 ℃ for 5min to obtain the rubber compound. Adding 1.7g of accelerator CZ, 1.8g of accelerator DPG and 1.7g of sulfur into the cooled mixed rubber on an open mill, uniformly mixing, discharging slices, standing for 12 hours, and vulcanizing on a flat vulcanizing machine at 150 ℃ until the vulcanized rubber is obtained.
TABLE 3 physical Properties of the vulcanizates of examples 1-3, comparative examples 1-2
Examples 1, 2, 3 differ in that: the temperature of the coupling agent modified white carbon black is 15 ℃,55 ℃ and 75 ℃ respectively. Comparative example 1 differs from the example only in that: the tea polyphenols of examples 1, 2 and 3 were added during the modification of white carbon black, while the tea polyphenols of comparative example 1 were added during the mixing process, and comparative example 2 was different from the examples in that: comparative example 2 did not add a coupling agent relative to examples 1, 2, 3 and comparative example 1.
As can be seen from Table 3, the mechanical properties, compression heat generation, aldrich abrasion properties and wet skid resistance of the vulcanizates prepared in examples 1, 2, and 3 were the best as the white carbon black was modified with the liquid phase coupling agent at a certain temperature, but an excessively high temperature resulted in a loss of the coupling agent, resulting in a decrease in the modification efficiency. In addition, the tensile strength, 100% elongation stress and 300% elongation stress of examples 1, 2 and 3 are significantly higher than those of comparative example 1, and the mechanical properties of example 2 are the best, and the elongation at break and tear strength are substantially consistent. The vulcanized rubber of examples 1, 2 and 3 has better mechanical properties from the standpoint of combining various properties. The vulcanizates obtained from examples 1, 2, 3 had lower compression heat generation and lower acle abrasion volume with a reduction of up to 5.9 ℃ compared to comparative example 1. The loss factor at 0 ℃ is obviously increased, and the wet skid resistance is better. It can be seen from the table that the vulcanized rubber obtained by using the tea polyphenol of comparative example 2 alone has lower mechanical properties, poorer compression heat generation and wear resistance and poorer service performance than those of the examples.
Example 4
Adding 70g of white carbon black into cyclohexane, stirring to prepare white carbon black cyclohexane dispersion liquid with the solid content of 15%, dripping 7gSi69 into the dispersion liquid, stirring and reacting for 30min at 55 ℃, then cooling to 30 ℃, adding 1.4g of tea polyphenol, and stirring for 30min to obtain slurry, namely the wet modified white carbon black. Then adding the slurry into 833g of solution polymerized styrene-butadiene rubber cyclohexane solution (the mass of the solution polymerized styrene-butadiene rubber is 100 g), and stirring and mixing uniformly to obtain modified mixed glue solution. Pouring the mixed glue solution into hot water with the temperature of more than 95 ℃ to precipitate and agglomerate to obtain the SSBR/white carbon black master batch. And then, uniformly mixing the dried master batch, 3g of zinc oxide, 2g of stearic acid and 2g of anti-aging agent 4020 in an internal mixer, discharging, and performing heat treatment at 150 ℃ for 5min to obtain the rubber compound. Adding 1.7g of accelerator CZ, 1.8g of accelerator DPG and 1.8g of sulfur into the cooled mixed rubber on an open mill, uniformly mixing, discharging slices, standing for 12 hours, and vulcanizing on a flat vulcanizing machine at 150 ℃ until the vulcanized rubber is obtained.
Example 5
Adding 70g of white carbon black into cyclohexane, stirring to prepare white carbon black cyclohexane dispersion liquid with the solid content of 15%, dripping 7gSi g of white carbon black cyclohexane dispersion liquid into the dispersion liquid, stirring at 55 ℃ for reaction for 2h, cooling to 30 ℃, adding 1.4g of tea polyphenol, and stirring for 30min to obtain slurry, namely the wet modified white carbon black. Then adding the slurry into 833g of solution polymerized styrene-butadiene rubber cyclohexane solution (the mass of the solution polymerized styrene-butadiene rubber is 100 g), and stirring and mixing uniformly to obtain modified mixed glue solution. Pouring the mixed glue solution into hot water with the temperature of more than 95 ℃ to precipitate and agglomerate to obtain the SSBR/white carbon black master batch. And then, uniformly mixing the dried master batch, 3g of zinc oxide, 2g of stearic acid and 2g of anti-aging agent 4020 in an internal mixer, discharging, and performing heat treatment at 150 ℃ for 5min to obtain the rubber compound. Adding 1.7g of accelerator CZ, 1.8g of accelerator DPG and 1.7g of sulfur into the cooled mixed rubber on an open mill, uniformly mixing, discharging slices, standing for 12 hours, and vulcanizing on a flat vulcanizing machine at 150 ℃ until the vulcanized rubber is obtained.
Table 4 physical properties of the vulcanizates of examples 2, 4, and 5
Examples 2, 4, 5 differ in that: the time for modifying the white carbon black by the coupling agent is 1h, 0.5h and 2h respectively.
As can be seen from Table 4, the coupling agent modified white carbon black requires a certain time at 55 ℃, and the 1h modification effect is best in the tested sample, and the coupling agent modified white carbon black has better mechanical property, compression heat generating property, wear resistance and wet skid resistance. The method is characterized in that the white carbon black cannot be sufficiently modified by the coupling agent in a short time, the coupling agent is lost in self-polymerization due to the overlong time, the content of the monomer coupling agent is reduced in the heat treatment stage, and the modification effect of the white carbon black is reduced.
Comparative example 3
Adding 70g of white carbon black into cyclohexane, stirring to prepare white carbon black cyclohexane dispersion liquid with the solid content of 15%, dripping 7gSi g of white carbon black cyclohexane dispersion liquid into the dispersion liquid, stirring at 55 ℃ for reaction for 1h, adding the slurry into 833g of solution polymerized styrene-butadiene rubber cyclohexane solution (the mass of the solution polymerized styrene-butadiene rubber is 100 g), and stirring and mixing uniformly to obtain modified mixed glue solution. Pouring the mixed glue solution into hot water with the temperature of more than 95 ℃ to precipitate and agglomerate to obtain the SSBR/white carbon black master batch. And then, uniformly mixing the dried master batch, 3g of zinc oxide, 2g of stearic acid and 2g of anti-aging agent 4020 in an internal mixer, discharging, and performing heat treatment at 150 ℃ for 5min to obtain the rubber compound. Adding 1.7g of accelerator CZ, 1.8g of accelerator DPG and 1.7g of sulfur into the cooled mixed rubber on an open mill, uniformly mixing, discharging slices, standing for 12 hours, and vulcanizing on a flat vulcanizing machine at 150 ℃ until the vulcanized rubber is obtained.
Example 6
Adding 70g of white carbon black into cyclohexane, stirring to prepare white carbon black cyclohexane dispersion liquid with the solid content of 15%, dripping 7gSi69 into the dispersion liquid, stirring at 55 ℃ for reaction for 1h, cooling to 30 ℃, adding 2.1g of tea polyphenol, and stirring for 30min to obtain slurry, namely the wet modified white carbon black. Then adding the slurry into 833g of solution polymerized styrene-butadiene rubber cyclohexane solution (the mass of the solution polymerized styrene-butadiene rubber is 100 g), and stirring and mixing uniformly to obtain modified mixed glue solution. Pouring the mixed glue solution into hot water with the temperature of more than 95 ℃ to precipitate and agglomerate to obtain the SSBR/white carbon black master batch. And then, uniformly mixing the dried master batch, 3g of zinc oxide, 2g of stearic acid and 2g of anti-aging agent 4020 in an internal mixer, discharging, and performing heat treatment at 150 ℃ for 5min to obtain the rubber compound. Adding 1.7g of accelerator CZ, 1.8g of accelerator DPG and 1.7g of sulfur into the cooled mixed rubber on an open mill, uniformly mixing, discharging slices, standing for 12 hours, and vulcanizing on a flat vulcanizing machine at 150 ℃ until the vulcanized rubber is obtained.
Example 7
Adding 70g of white carbon black into cyclohexane, stirring to prepare white carbon black cyclohexane dispersion liquid with the solid content of 15%, dripping 7gSi g of white carbon black cyclohexane dispersion liquid into the dispersion liquid, stirring at 55 ℃ for reaction for 1h, cooling to 30 ℃, adding 2.8g of tea polyphenol, and stirring for 30min to obtain slurry, namely the wet modified white carbon black. Then adding the slurry into 833g of solution polymerized styrene-butadiene rubber cyclohexane solution (the mass of the solution polymerized styrene-butadiene rubber is 100 g), and stirring and mixing uniformly to obtain modified mixed glue solution. Pouring the mixed glue solution into hot water with the temperature of more than 95 ℃ to precipitate and agglomerate to obtain the SSBR/white carbon black master batch. And then, uniformly mixing the dried master batch, 3g of zinc oxide, 2g of stearic acid and 2g of anti-aging agent 4020 in an internal mixer, discharging, and performing heat treatment at 150 ℃ for 5min to obtain the rubber compound. Adding 1.7g of accelerator CZ, 1.8g of accelerator DPG and 1.7g of sulfur into the cooled mixed rubber on an open mill, uniformly mixing, discharging slices, standing for 12 hours, and vulcanizing on a flat vulcanizing machine at 150 ℃ until the vulcanized rubber is obtained.
TABLE 5 physical Properties of vulcanizates of example 2, example 6, example 7, and comparative example 3
Examples 2, 6, 7 differ only in: the dosage of the tea polyphenol is 1.4g, 2.1g and 2.8g respectively. The mechanical properties of the vulcanized rubber modified by different amounts of tea polyphenol are shown in Table 5, and as can be seen from the data of examples 2, 6 and 7, the 100% fixed extension and 300% fixed extension of the vulcanized rubber show a reduced trend by increasing the amount of tea polyphenol after the tea polyphenol is introduced into the composite system. When the amount of tea polyphenol added was small, the abrasion volume of the rubber material was decreased, that is, the abrasion resistance was improved, but as the amount was increased, the abrasion resistance was deteriorated but still higher than that of comparative example 3 in which no tea polyphenol was added. The compression heat generating properties of the white carbon black/solvent-poly butylbenzene composite material vulcanized rubber with different tea polyphenol dosages are shown in a table, the data are analyzed from the table, the bottom temperature rise is continuously reduced along with the increase of the tea polyphenol dosages, and the dynamic heat generating property of the rubber material is improved.
Example 8
Adding 70g of white carbon black into cyclohexane, stirring to prepare white carbon black cyclohexane dispersion liquid with the solid content of 15%, dropwise adding 8.4g of Si69 into the dispersion liquid, stirring at 55 ℃ for reaction for 1h, cooling to 30 ℃, adding 1.4g of tea polyphenol, and stirring for 30min to obtain slurry, namely the wet modified white carbon black. Then adding the slurry into 833g of solution polymerized styrene-butadiene rubber cyclohexane solution (the mass of the solution polymerized styrene-butadiene rubber is 100 g), and stirring and mixing uniformly to obtain modified mixed glue solution. Pouring the mixed glue solution into hot water with the temperature of more than 95 ℃ to precipitate and agglomerate to obtain the SSBR/white carbon black master batch. And then, uniformly mixing the dried master batch, 3g of zinc oxide, 2g of stearic acid and 2g of anti-aging agent 4020 in an internal mixer, discharging, and performing heat treatment at 150 ℃ for 5min to obtain the rubber compound. Adding 1.7g of accelerator CZ, 1.8g of accelerator DPG and 1.7g of sulfur into the cooled mixed rubber on an open mill, uniformly mixing, discharging slices, standing for 12 hours, and vulcanizing on a flat vulcanizing machine at 150 ℃ until the vulcanized rubber is obtained.
TABLE 6 physical Properties of the vulcanizates of example 2, example 8
Examples 2 and 8 differ in that: the dosage of the coupling agent in the process of modifying the white carbon black by the coupling agent is different and is respectively 10 percent and 12 percent of the mass of the white carbon black. Under the condition of a small amount of coupling agent, the consumption of the coupling agent is in direct proportion to the mechanical property and the abrasion property, and as the consumption of the coupling agent is increased to an excessive amount, the mechanical property and the abrasion property of the coupling agent tend to be increased and then reduced, the modification of the white carbon black cannot be completed due to the too small amount of the coupling agent, and the excessive coupling agent can be dispersed in a rubber matrix to play a role of a plasticizer, so that the mechanical property and the abrasion property are reduced. Compression heat generation decreases with increasing amount of coupling agent, because of the improved dispersibility of white carbon black in rubber.
Example 9
Adding 70g of white carbon black into cyclohexane, stirring to prepare white carbon black cyclohexane dispersion liquid with the solid content of 15%, dripping 7gSi g of white carbon black cyclohexane dispersion liquid into the dispersion liquid, stirring at 55 ℃ for reaction for 1h, cooling to 10 ℃, adding 1.4g of tea polyphenol, and stirring for 30min to obtain slurry, namely the wet modified white carbon black. Then adding the slurry into 833g of solution polymerized styrene-butadiene rubber cyclohexane solution (the mass of the solution polymerized styrene-butadiene rubber is 100 g), and stirring and mixing uniformly to obtain modified mixed glue solution. Pouring the mixed glue solution into hot water with the temperature of more than 95 ℃ to precipitate and agglomerate to obtain the SSBR/white carbon black master batch. And then, uniformly mixing the dried master batch, 3g of zinc oxide, 2g of stearic acid and 2g of anti-aging agent 4020 in an internal mixer, discharging, and performing heat treatment at 150 ℃ for 5min to obtain the rubber compound. Adding 1.7g of accelerator CZ, 1.8g of accelerator DPG and 1.7g of sulfur into the cooled mixed rubber on an open mill, uniformly mixing, discharging slices, standing for 12 hours, and vulcanizing on a flat vulcanizing machine at 150 ℃ until the vulcanized rubber is obtained.
Example 10
Adding 70g of white carbon black into cyclohexane, stirring to prepare white carbon black cyclohexane dispersion liquid with the solid content of 15%, dripping 7gSi g of white carbon black cyclohexane dispersion liquid into the dispersion liquid, stirring at 55 ℃ for reaction for 1h, cooling to 40 ℃, adding 1.4g of tea polyphenol, and stirring for 30min to obtain slurry, namely the wet modified white carbon black. Then adding the slurry into 833g of solution polymerized styrene-butadiene rubber cyclohexane solution (the mass of the solution polymerized styrene-butadiene rubber is 100 g), and stirring and mixing uniformly to obtain modified mixed glue solution. Pouring the mixed glue solution into hot water with the temperature of more than 95 ℃ to precipitate and agglomerate to obtain the SSBR/white carbon black master batch. And then, uniformly mixing the dried master batch, 3g of zinc oxide, 2g of stearic acid and 2g of anti-aging agent 4020 in an internal mixer, discharging, and performing heat treatment at 150 ℃ for 5min to obtain the rubber compound. Adding 1.7g of accelerator CZ, 1.8g of accelerator DPG and 1.7g of sulfur into the cooled mixed rubber on an open mill, uniformly mixing, discharging slices, standing for 12 hours, and vulcanizing on a flat vulcanizing machine at 150 ℃ until the vulcanized rubber is obtained.
TABLE 7 physical Properties of vulcanizates of example 2, example 9, and example 10
Examples 2, 9, 10 differ in that: as can be seen from Table 7, the temperature of the tea polyphenol modified white carbon black was 30℃at 10℃and 40℃at the same time, and the effect of changing the temperature on the tea polyphenol modified white carbon black was not great in the set temperature range.
Comparative example 4
Adding 70g of white carbon black into cyclohexane, stirring to prepare white carbon black cyclohexane dispersion liquid with the solid content of 15%, adding 7g of Si69 and 2.8g of tea polyphenol into the dispersion liquid, stirring at 55 ℃ for reaction for 1h, adding the slurry into 833g of solution polymerized styrene-butadiene rubber cyclohexane solution (the mass of the solution polymerized styrene-butadiene rubber is 100 g), and stirring and mixing uniformly to obtain modified mixed glue solution. Pouring the mixed glue solution into hot water with the temperature of more than 95 ℃, precipitating and condensing, precipitating white carbon black in the process, heating 4g of the obtained master batch to 700 ℃ under the protection of a muffle nitrogen atmosphere, and preserving the heat for 30min to obtain 1.3g of ash, wherein the master batch of the examples 1-10 and the comparative examples 1-3 has 1.7g of ash residue (only white carbon black can remain ash at 700 ℃) under the same test conditions. The mode of co-addition can cause a certain loss of the white carbon black during solvent removal (if the modification effect is good, the white carbon black can not be separated out during the solvent removal).
As can be seen from examples 1 to 10 and comparative examples 1 to 4: the modified silica gel has good modification effect on silica gel, can effectively improve the dispersibility of the silica gel in a rubber matrix, further improve the dynamic performance of the composite material, effectively improve the wear resistance of vulcanized rubber along with the addition of tea polyphenol, reduce compression heat generation, and has higher 100% and 300% stretching stress and better application.

Claims (10)

1. The preparation method of the wet modified white carbon black is characterized by comprising the following steps:
uniformly dispersing the white carbon black in an organic solvent to prepare slurry, adding a silane coupling agent to react, and then adding tea polyphenol to react to obtain the wet modified white carbon black.
2. The method of manufacturing according to claim 1, wherein:
the specific surface area of the white carbon black is 50-300 m 2 Preferably 100 to 200m 2 Per gram, the oil absorption value is 0.3-3 ml/g, preferably 0.5-1.5 ml/g; and/or the number of the groups of groups,
the organic solvent is a good solvent of rubber, preferably cyclohexane or n-hexane; and/or the number of the groups of groups,
the silane coupling agent is at least one of bis- [ gamma- (triethoxysilane) propyl ] tetrasulfide, bis- [ gamma- (triethoxysilane) propyl ] disulfide, 3-thiocyanopropyl triethoxysilane, gamma-mercaptopropyl triethoxysilane, gamma-aminopropyl triethoxysilane and gamma-methacryloxypropyl trimethoxysilane.
3. The method of manufacturing according to claim 1, wherein:
the solid content of the white carbon black in the organic solvent is 5% -20%;
the dosage of the silane coupling agent is 3-15% of the mass of the white carbon black;
the tea polyphenol accounts for 1-5% of the weight of the white carbon black, and is preferably 1-4%.
4. The method of manufacturing according to claim 1, wherein:
the reaction temperature after the addition of the silane coupling agent is 10-80 ℃ and the reaction time is 0.1-5 h;
the reaction temperature after the tea polyphenol is added is 5-50 ℃ and the reaction time is 0.1-3 h.
5. A wet-process modified white carbon black prepared by the method of any one of claims 1-4.
6. A masterbatch comprising the wet-modified white carbon of claim 5, characterized in that:
the masterbatch is prepared from a rubber solution and the wet modified white carbon black.
7. The masterbatch according to claim 6 wherein:
the rubber solution is a solution prepared by dissolving a polymer rubber solution or rubber in an organic solvent;
the solution polymerized rubber is at least one of solution polymerized styrene-butadiene rubber, polyisoprene rubber and butadiene rubber; and/or the number of the groups of groups,
the rubber is at least one of natural rubber and butyl rubber.
8. The masterbatch of claim 7 wherein:
the solid content of the rubber solution is 10% -50%; the mass of the white carbon black is 1-100% of that of rubber or soluble polymer rubber, and is preferably 50-100%.
9. A process for the preparation of a masterbatch according to any one of claims 6-8 characterized in that it comprises:
and uniformly mixing the wet modified white carbon black and the rubber solution according to the mass ratio, and removing the solvent to obtain the masterbatch.
10. A vulcanized rubber comprising the masterbatch of any one of claims 6-8 or prepared by the process of claim 9, characterized in that:
the vulcanized rubber is obtained by mixing and vulcanizing the components including the masterbatch, an activating agent, an anti-aging agent, an accelerator and a vulcanizing agent.
CN202210064271.8A 2022-01-20 2022-01-20 Preparation method of wet modified white carbon black, masterbatch and vulcanized rubber Pending CN116515169A (en)

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