CN113416348A - White carbon black modification method - Google Patents
White carbon black modification method Download PDFInfo
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- CN113416348A CN113416348A CN202110712919.3A CN202110712919A CN113416348A CN 113416348 A CN113416348 A CN 113416348A CN 202110712919 A CN202110712919 A CN 202110712919A CN 113416348 A CN113416348 A CN 113416348A
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- carbon black
- white carbon
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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
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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
- 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
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- 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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Abstract
The invention discloses a white carbon black modification method, which comprises the following steps: and carrying out heat treatment on the white carbon black and the atomized surface modifier. The white carbon black modification method provided by the invention is simple to operate, pollution-free, low in energy consumption and good in modification effect, can obviously improve the hydrophobicity of the surface of the white carbon black, and simultaneously realizes excellent modification uniformity.
Description
Technical Field
The invention relates to a white carbon black modification method.
Background
In the rubber industry, nano white carbon black is one of the most important reinforcing fillers, and is widely researched and applied as a substitute for carbon black because it can provide good mechanical properties, high wet skid resistance and low rolling resistance, and thus can be applied to green tire preparation.
However, the polar white carbon black has a large number of hydroxyl groups on the surface and is easy to agglomerate. While most general purpose rubbers, such as SBR, Natural Rubber (NR) and Butadiene Rubber (BR) are non-polar. Therefore, the white carbon black has poor dispersibility in rubber and weak interaction between rubber and white carbon black, which hinders the application of white carbon black.
A common solution is to surface modify the carbon blacks with silane coupling agents. The silane coupling agent is a common modifier of white carbon black. For example, Si69 can increase the hydrophobicity of the surface of white carbon black, increase the reversion resistance in the vulcanization process and enable the rubber product to have good heat aging performance. For another example, Si-747 is mercaptosilane (-SH) modified by long-chain alkyl, and one end of mercaptosilane has a long-chain substituent structure, so that the shielding effect is good, the surface of the white carbon black has hydrophobicity, the agglomeration problem of the white carbon black can be well solved, and good dispersibility is achieved.
The existing modification mode is wet modification, for example:
chinese patent document CN201610984215.0 discloses a method for modifying white carbon black by a boric acid ester surfactant wet method, and the white carbon black is modified by a precipitation method by a wet process and a route of an aqueous emulsion system.
Chinese patent document CN201510577913.4 discloses a precipitated white carbon black wet modification process, which takes a precipitated white carbon black filter cake as a raw material, adds citric acid polyethylene ester as a dispersing agent, and takes a rare earth coupling agent as a modifier to physically wrap white carbon black particles in an aqueous medium, so as to prevent the precipitated white carbon black particles from agglomerating and achieve the purpose of controlling the particle size of precipitated white carbon black powder particles.
In literature (study on properties of natural rubber reinforced by Si747 in-situ modified monodisperse white carbon black [ J ], organosilicon material, 2019, 33 (02): 77-83), Si-747 is adopted to modify the surface of monodisperse white carbon black in a liquid phase system, and a natural rubber composite material is prepared.
However, the wet modification has a long operation flow, the use of a solvent may cause pollution, and the energy consumption is high due to the post-treatment, so that improvement is needed.
Disclosure of Invention
The invention aims to overcome the defects of long operation flow, pollution and high energy consumption of the existing wet modification method, and provides the white carbon black modification method which is simple to operate, has no pollution, low energy consumption and good modification effect and can obviously improve the hydrophobicity and uniformity of the product.
The invention solves the technical problems through the following technical scheme:
the invention provides a white carbon black modification method, which comprises the following steps: and carrying out heat treatment on the white carbon black and the atomized surface modifier.
In the present invention, the white carbon black is preferably subjected to heat treatment under a condition of dispersion. Specifically, the white carbon black is stirred to be dispersed.
In the invention, the surface modifier can be white carbon black surface modifier conventional in the art, such as Si69, Si747, Si264, KH550, KH560 or KH 570. Wherein, Si69 not only can increase the surface hydrophobicity of the white carbon black, but also can increase the reversion resistance in the vulcanization process, and enables the rubber product to have good thermal aging performance; si-747 is mercaptosilane (-SH) modified by long-chain alkyl, and one end of mercaptosilane has a long-chain substituent structure, so that the shielding effect is good, the surface of the white carbon black has hydrophobicity, the agglomeration problem of the white carbon black can be well solved, and good dispersion is achieved. The dosage of the surface modifier can be conventional in the field, and is preferably 1-15% of the mass of the white carbon black, and more preferably 2.5-15%.
In the present invention, the atomized surface modifier can be prepared by the following method: atomizing the solution containing the surface modifier to obtain the surface modifier.
The solvent in the solution containing the surface modifier can be a solvent which is conventional in the art and can dissolve the surface modifier without influencing the modification reaction, such as methanol, ethanol, toluene or acetone, preferably ethanol. The amount of the atomized solvent is such that the surface modifier is atomized, preferably such that the concentration of the surface modifier is less than or equal to 0.5 g/mL.
Wherein the atomized surface modifier is obtainable by means of a conventional atomizer. The rate of addition of the surface modifier-containing solution to the atomizer is preferably from 0.5 to 3 mL/min. The solution containing the surface modifier can be added to the atomizer by means of a syringe pump. When the atomized surface modifier is added to contact with the white carbon black, the nozzle of the atomizer is preferably 3-10cm away from the white carbon black.
In the present invention, the heat treatment may be performed after the addition of the atomized surface modifier is completed, or the heat treatment may be performed while the atomized surface modifier is added.
In the invention, the temperature and the time of the heat treatment can be selected according to the temperature and the time of the conventional white carbon black modification in the field. The temperature of the heat treatment is preferably 120-200 ℃, more preferably 180 ℃. The time of the heat treatment is preferably 30 to 150min, more preferably 60 min.
In a preferred embodiment of the invention, after the addition of the atomized surface modifier (e.g., Si747) is completed, heating is carried out at 180 ℃ for 60min to obtain significantly improved hydrophobicity.
The white carbon black modification method can adopt a stirring, heating and atomizing integrated reactor.
On the basis of the common knowledge in the field, the above preferred conditions can be combined randomly to obtain the preferred embodiments of the invention.
The reagents and starting materials used in the present invention are commercially available.
The positive progress effects of the invention are as follows: the white carbon black modification method provided by the invention is simple to operate, pollution-free, low in energy consumption and good in modification effect, can obviously improve the hydrophobicity of the surface of the white carbon black, and simultaneously realizes excellent modification uniformity.
Drawings
FIG. 1 is a sectional view of a stirring, heating and atomizing integrated reactor used in examples 1 to 5;
1. a reaction chamber; 2. heating a tube; 3. an outer wall of the reactor; 4. a stirring paddle motor; 5. a base; 6. a stirring paddle; 7. an atomizer; 8. a telescopic rod.
FIG. 2 is a schematic view of the contact angle of the modified silica sample of example 1;
FIG. 3 is a schematic view of the contact angle of the modified silica sample of example 2;
FIG. 4 is a schematic view of the contact angle of the modified silica sample of example 3;
FIG. 5 is a schematic view of the contact angle of the modified silica sample of example 4;
FIG. 6 is a schematic view of the contact angle of the modified silica sample of example 5;
FIG. 7 is an infrared spectrum of samples of examples 1-5 and unmodified white carbon black.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention. The experimental methods without specifying specific conditions in the following examples were selected according to the conventional methods and conditions, or according to the commercial instructions.
The reactors used in examples 1 to 5 are shown in FIG. 1, the white carbon black used is commercially available 165GR, 165MP, etc., and the other reagents are commercially available products.
Example 1
5g of Si747 (5 percent of the white carbon black in mass) is added into 10mL of absolute ethyl alcohol to obtain 0.5g/mL of Si747 ethanol solution, the solution is added into a reactor filled with 100g of white carbon black (type: 165GR sold on the market) through an injection pump at the speed of 0.5mL/min, an atomizer is 3cm away from a nozzle, and the solution is stirred and heated for 2 hours at 120 ℃ to obtain the surface modified white carbon black powder.
Example 2
Adding 15g of Si69 (7.5 percent of the mass of the white carbon black) into 20mL of absolute ethyl alcohol to obtain 0.5g/mL of Si69 ethanol solution, adding the ethanol solution into a reactor filled with 200g of white carbon black (model: commercially available 165GR) at the speed of 1.0mL/min through an injection pump, enabling an atomizer to be 3cm away from a nozzle of the white carbon black, and stirring and heating for 60min at 180 ℃ after finishing the atomization and addition of the modifier to obtain the surface modified white carbon black powder.
Example 3
Adding 15g of Si747 (7.5 percent of the mass of the white carbon black) into 30mL of absolute ethyl alcohol to obtain 0.5g/mL of Si747 ethanol solution, adding the solution into a reactor filled with 200g of white carbon black (type: 165GR sold on the market) at the speed of 1.0mL/min through an injection pump, enabling an atomizer to be 3cm away from a nozzle, stirring and heating at 180 ℃ for 60min after finishing the atomization and feeding of a modifier, and thus obtaining the surface modified white carbon black powder.
Example 4
10g of Si69 (5% of white carbon black by mass) is added into 20mL of absolute ethyl alcohol to obtain 0.5g/mL of an ethanol solution of Si69, the ethanol solution is added into a reactor filled with 200g of white carbon black (type: 165MP sold on the market) through an injection pump at the speed of 1.0mL/min, an atomizer is 7cm away from a nozzle, and the mixture is stirred and heated for 90min at 180 ℃ to obtain the surface modified white carbon black powder.
Example 5
10g of Si69 (5% of white carbon black by mass) is added into 20mL of absolute ethyl alcohol to obtain 0.5g/mL of an ethanol solution of Si69, the ethanol solution is added into a reactor filled with 200g of white carbon black (type: 165MP sold on the market) at the speed of 1.0mL/min through an injection pump, an atomizer is spaced 9cm away from a nozzle, and the mixture is stirred and heated for 120min at the temperature of 200 ℃ to obtain the surface modified white carbon black powder.
Example 6
2g of Si264 (1 percent of the mass of the white carbon black) is added into 20mL of anhydrous methanol to obtain 0.2g/mL of a methanol solution of the Si264, the methanol solution is added into a reactor filled with 200g of white carbon black (type: 165GR commercially available) through a syringe pump at the speed of 0.5mL/min, an atomizer is 5cm away from a nozzle of the white carbon black, and the mixture is stirred and heated for 120min at the temperature of 120 ℃ to obtain the surface modified white carbon black powder.
Example 7
6g KH550 (3% of white carbon black by mass) was added to 20mL of toluene to obtain 0.3g/mL of toluene solution of KH550, which was then added to a reactor containing 200g of white carbon black (type: commercially available 165GR) at a rate of 1.0mL/min by means of a syringe pump, and the atomizer was spaced 7cm from the nozzle, followed by stirring and heating at 150 ℃ for 30min to obtain surface-modified white carbon black powder.
Example 8
Adding 30g KH560 (15% of white carbon black by mass) into 20mL acetone to obtain 0.4g/mL acetone solution of KH560, adding into a reactor containing 200g white carbon black (type: commercially available 165MP) at a speed of 1.5mL/min by using a syringe pump, separating the atomizer from the nozzle by 9cm, and stirring and heating at 180 deg.C for 90min to obtain surface-modified white carbon black powder.
Example 9
Adding 5g KH570 (2.5% of white carbon black) into 20mL of anhydrous ethanol to obtain 0.5g/mL KH570 ethanol solution, adding into a reactor containing 200g white carbon black (type: commercially available 165MP) at a speed of 3.0mL/min by using a syringe pump, separating an atomizer from a nozzle by 10cm, and stirring and heating at 200 deg.C for 150min to obtain surface-modified white carbon black powder.
Effect example 1
The contact angles of the modified white carbon blacks obtained in examples 1 to 5 were measured by a contact angle measuring instrument.
As shown in fig. 2 to 6, the modified white carbon black has improved hydrophobicity as compared to the unmodified white carbon black. The test results are shown in the following table.
| Sample (I) | Unmodified | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 |
| Contact withAngle/° degree | 0 | 35.6 | 38.9 | 107.0 | 36.4 | 35.7 |
The table shows that the contact angle of the modified white carbon black in the embodiment of the invention is larger than that of the unmodified white carbon black, and the hydrophobicity of the white carbon black is improved.
Effect example 2
The surface groups of the modified white carbon black obtained in examples 1 to 5 were tested by a fourier transform infrared spectrometer.
As shown in FIG. 7, the surface of the modified silica was 2960cm higher than that of the unmodified silica-1And 2860cm-1There is an absorption peak corresponding to-CH2and-CH3Shows that the surface modifier is chemically adsorbed on the surface of the white carbon black and is in 3430cm-1The relative strength of the hydroxyl peak is weakened, which shows that the hydrophobicity of the modified white carbon black is improved.
Claims (10)
1. The white carbon black modification method is characterized by comprising the following steps: and carrying out heat treatment on the white carbon black and the atomized surface modifier.
2. The method for modifying white carbon black according to claim 1, wherein the white carbon black is subjected to heat treatment under a condition of being stirred and dispersed.
3. The white carbon black modification method according to claim 1, wherein the surface modifier is Si69, Si747, Si264, KH550, KH560 or KH 570.
4. The silica modification method according to claim 1 or 3, wherein the amount of the surface modifier is 1 to 15% by mass, preferably 2.5 to 15% by mass, of the silica.
5. The white carbon black modification method according to claim 1, wherein the atomized surface modifier is prepared by the following method: atomizing the solution containing the surface modifier to obtain the surface modifier.
6. The white carbon black modification method according to claim 5, wherein the solvent in the solution containing the surface modifier is methanol, ethanol, toluene or acetone;
and/or the dosage of the solvent ensures that the concentration of the surface modifier is less than or equal to 0.5 g/mL.
7. The white carbon black modification method according to claim 5, wherein the atomized surface modifier is obtained by an atomizer;
the rate of adding the solution containing the surface modifier into the atomizer is 0.5-3 mL/min;
when the atomized surface modifier is added to be in contact with the white carbon black, the distance between the nozzle of the atomizer and the white carbon black is 3-10 cm.
8. The white carbon black modification method according to claim 1, wherein the heat treatment is performed after the addition of the atomized surface modifier is completed; alternatively, the heat treatment is carried out while adding the atomized surface modifier.
9. The method for modifying white carbon black according to claim 1, wherein the temperature of the heat treatment is 120-200 ℃, preferably 180 ℃;
and/or the time of the heat treatment is 30-150min, and preferably 60 min.
10. The white carbon black modification method according to claim 1, wherein after the addition of the atomized surface modifier is completed, the mixture is heated at 180 ℃ for 60 min; the surface modifier is preferably Si 747.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114014326A (en) * | 2021-10-12 | 2022-02-08 | 华东理工大学 | White carbon black modification method and modified white carbon black |
| CN114405446A (en) * | 2022-01-29 | 2022-04-29 | 华东理工大学 | Continuous modification device and method for continuously modifying white carbon black |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101798473A (en) * | 2010-02-10 | 2010-08-11 | 广州吉必盛科技实业有限公司 | Silane-modified white carbon black-carbon black composite filling and preparation method thereof |
| CN101817999A (en) * | 2009-05-25 | 2010-09-01 | 甘肃银光聚银化工有限公司 | Preparation method of twice-modified white carbon black |
| CN107686564A (en) * | 2017-10-30 | 2018-02-13 | 无锡恒诚硅业有限公司 | A kind of preparation method of hydrophabic silica |
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- 2021-06-25 CN CN202110712919.3A patent/CN113416348B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101817999A (en) * | 2009-05-25 | 2010-09-01 | 甘肃银光聚银化工有限公司 | Preparation method of twice-modified white carbon black |
| CN101798473A (en) * | 2010-02-10 | 2010-08-11 | 广州吉必盛科技实业有限公司 | Silane-modified white carbon black-carbon black composite filling and preparation method thereof |
| CN107686564A (en) * | 2017-10-30 | 2018-02-13 | 无锡恒诚硅业有限公司 | A kind of preparation method of hydrophabic silica |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114014326A (en) * | 2021-10-12 | 2022-02-08 | 华东理工大学 | White carbon black modification method and modified white carbon black |
| CN114014326B (en) * | 2021-10-12 | 2023-09-01 | 华东理工大学 | White carbon black modification method and modified white carbon black |
| CN114405446A (en) * | 2022-01-29 | 2022-04-29 | 华东理工大学 | Continuous modification device and method for continuously modifying white carbon black |
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