CN111849217A - Nano SiO2-Preparation method of carbon black dual-phase filler - Google Patents

Nano SiO2-Preparation method of carbon black dual-phase filler Download PDF

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CN111849217A
CN111849217A CN202010767537.6A CN202010767537A CN111849217A CN 111849217 A CN111849217 A CN 111849217A CN 202010767537 A CN202010767537 A CN 202010767537A CN 111849217 A CN111849217 A CN 111849217A
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carbon black
dual
phase filler
preparation
sio
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陈建
闵丹
谭苏芸
雷智强
李新跃
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Sichuan University of Science and Engineering
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Sichuan University of Science and Engineering
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/44—Carbon
    • C09C1/48—Carbon black
    • C09C1/56—Treatment of carbon black ; Purification
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • 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
    • 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
    • C08K9/08—Ingredients agglomerated by treatment with a binding agent
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/006—Combinations of treatments provided for in groups C09C3/04 - C09C3/12
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/06—Treatment with inorganic compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/08—Treatment with low-molecular-weight non-polymer organic 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives

Abstract

The invention discloses a nano SiO2The preparation method of the carbon black dual-phase filler comprises the steps of adsorbing a surfactant by carbon black to generate physical and hydrogen bond interaction, and generating SiO by an in-situ sol-gel method2The carbon black influences the SiO by means of surfactants2While generating chemical bond interaction, so that SiO2And production of carbon blackGenerating stronger binding force. SiO in the biphase filler prepared by the invention2The chemical bond formed between the carbon black and the carbon black is not easy to be damaged by the shearing force during mixing, and the carbon black and the SiO are effectively exerted2The rubber has excellent reinforcing property to rubber, reduces rolling resistance, improves traction force, does not reduce wear resistance, and has excellent mechanical property.

Description

Nano SiO2-Preparation method of carbon black dual-phase filler
Technical Field
The invention belongs to the technical field of rubber packing, and particularly relates to nano SiO2-a process for the preparation of carbon black dual-phase filler.
Background
With the social development and the progress of science and technology, people put higher demands on various performances of rubber products. Wherein the filler plays an important role in the rubber industry, which is called reinforcement, and the reinforcing effect of the filler promotes the rapid development of the rubber industry. When the filler particles are used for reinforcing the rubber material, the surface energy of the filler and the surface energy of the rubber are greatly different, and the inorganic filler is easy to aggregate to reduce the surface energy, so that the inorganic filler and the rubber lack thermodynamic driving force when being mixed; meanwhile, because the surfaces of the inorganic particles contain a large number of polar functional groups, and the rubber matrix is generally nonpolar, the inorganic filler is difficult to achieve a relatively ideal dispersion effect in the rubber matrix, most of the filler particles generally exist in the rubber matrix in the form of aggregates, and the dispersion degree of the filler in the rubber matrix is improved to a critical degree.
Currently, the main reinforcing fillers used in rubber products are carbon black and white carbon black (SiO)2). Carbon black imparts good tensile strength and abrasion resistance to the vulcanizate, but hysteresis heat is relatively high. SiO 22The filling vulcanized rubber has high tearing strength and low rolling resistance of the tire, keeps better wet skid resistance, but has poor processing performance due to the fact that silanol groups on the surface of the filling vulcanized rubber are hydrophilic and are seriously agglomerated. This results from the fact that a two-phase filler comprising two phases, SiO2The phase is dispersed in the carbon phase to realize the carbon black and SiO2The advantages are complementary, and the abrasion resistance is not reduced while the rolling resistance is reduced and the traction force is improved. It is reported in the literature that the degree of dispersion can be greatly improved by forming a dual phase filler.
At present, the following method is mainly adopted to prepare the dual-phase filler: (1) spraying organic silicon-containing compound in the production process of carbon black, and making SiO by oxygen-deficient combustion2The nano powder is deposited on the surface of carbon black particles, but the preparation method has higher implementation cost and is not suitable for the deep research in a laboratory. (2) Most of the laboratory research methods areThe carbon black is prepared into an aqueous solution and is deposited with a sodium silicate solution or silica sol to finally achieve the effect of nano doping, but the carbon black and the white carbon black are physically combined and are easy to be damaged by shearing force during mixing so as not to achieve the expected reinforcing effect. (3) In the production process of the carbon black, a proper amount of white carbon black is mixed to chemically modify the carbon black, active areas on the surfaces of carbon black particles are increased, and the compatibility of the carbon black particles and the active areas is improved by adding the silane coupling agent, so that a good effect is obtained. Thus, the range of applications of the existing dual-phase filler is limited.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a nano SiO2The preparation method of the carbon black dual-phase filler solves the problems of easy agglomeration, weak binding force between the fillers and the like of the existing reinforcing filler.
In order to achieve the purpose, the invention adopts the following technical scheme: nano SiO2-a process for the preparation of a carbon black dual-phase filler comprising the steps of:
1) crushing and drying carbon black to obtain a carbon black powder sample, adding a surfactant, fully stirring and dissolving, and centrifuging, filtering and drying to obtain modified carbon black;
2) adding the modified carbon black obtained in the step 1) into absolute ethyl alcohol, performing ultrasonic dispersion, sequentially adding deionized water and ammonia water under the stirring condition, fully mixing, adding tetraethoxysilane, fully reacting, centrifugally collecting solids after the reaction is finished, drying the solids, calcining in a nitrogen atmosphere, and naturally cooling to room temperature to obtain the dual-phase filler.
Preferably, the surfactant is PVP, CTAB or alkylphenol ethoxylates.
Preferably, the surfactant is used in an amount of 1 to 5 wt% of the carbon black.
Preferably, the reaction time in the step 2) is 12-24 h.
Preferably, the concentration of the ammonia water is 1.3-2.1 mol/L.
Preferably, the ammonia water: deionized water: modified carbon black: the volume mass ratio of the ethyl orthosilicate is 10-16 ml: 2 ml: 2 g: 1-7 g.
Preferably, the calcination is carried out at the temperature of 600-800 ℃ for 1-3 h.
Preferably, the reaction temperature in the step 2) is 40-80 ℃.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention provides nano SiO2The preparation method of the carbon black dual-phase filler comprises the steps of adsorbing a surfactant by carbon black to generate physical and hydrogen bond interaction, and generating SiO by an in-situ sol-gel method2The carbon black influences the SiO by means of surfactants2While generating chemical bond interaction, so that SiO2And the carbon black generates stronger binding force and is used for reinforcing rubber, so that the comprehensive performance of the rubber vulcanized rubber is improved. Thereby solving the problems of carbon black and SiO2The binding force of (2) is poor, and the dispersion of the filler in the rubber matrix is not uniform.
2. The invention adds the surface active agent into the absolute ethyl alcohol solution of the carbon black for adsorption treatment, different from the carbon black treated by acid, and after a period of adsorption, the SiO can be directly carried out2The method has the advantages of simple operation steps, low requirement on temperature environment, no need of discharging a large amount of waste liquid and environmental friendliness. Prepared SiO2Small and uniform size and good dispersibility, and ensures that the prepared dual-phase filler has good reinforcement.
3. The nanometer SiO prepared by the invention2Carbon black dual-phase filler, pre-treating carbon black by surfactant and growing SiO in situ2The chemical bond formed between the carbon black and the SiO is not easy to be damaged by the shearing force during mixing, and the carbon black and the SiO are effectively exerted2The rubber has excellent reinforcing property on rubber, and the abrasion resistance is not reduced while the rolling resistance is reduced and the traction force is improved. Compared with carbon black, the tensile strength of the prepared bidirectional filler is improved by 21.41 percent, and the elongation at break is improved by 30.82 percent; compared with white carbon black, the tensile strength is improved by 50.06%, and the elongation at break is improved by 9%.41 percent and has excellent comprehensive performance.
Drawings
FIG. 1 shows the nano SiO prepared by the invention2-infrared spectrum of carbon black dual-phase filler.
FIG. 2 shows the nano SiO prepared by the invention2-XRD pattern of carbon black dual phase filler.
FIG. 3 shows the nano SiO prepared by the invention2SEM picture of carbon black dual phase filler; a is carbon black original shape, B is nano SiO2-carbon black dual-phase filler.
FIG. 4 shows the nano SiO prepared by the invention2TEM images of carbon black dual-phase fillers; a is carbon black original shape, B is nano SiO2-carbon black dual-phase filler.
FIG. 5 shows the nano SiO prepared by the present invention2Stress-strain diagram of carbon black dual-phase filler.
Detailed Description
The present invention will be described in further detail with reference to the following specific embodiments and the accompanying drawings. The experimental procedures are not specifically described in the following examples, and are carried out in a conventional manner using reagents which are generally commercially available.
Firstly, the nano SiO prepared by the invention2Process for the preparation of a carbon black dual-phase filler
Example 1
1) Placing carbon black in a sealed sample preparation grinder for grinding for 2 min to obtain a carbon black powder sample, after the grinding is finished, placing the carbon black powder sample in a 125 ℃ oven for drying for 1h, during heating, ensuring that the thickness of a carbon black layer is not more than 10mm as far as possible by using an open container for containing the carbon black powder sample, and placing the dried carbon black in a sealed moisture-proof container for cooling to room temperature for later use.
2) Measuring a certain amount of deionized water in a beaker, adding 0.06g of PVP (K30) as a coupling agent into the beaker, stirring and dissolving, adding 2g of carbon black powder obtained in the step 1) after drying, mechanically stirring for 24 hours at room temperature to allow the carbon black to fully adsorb the PVP, and carrying out centrifugal filtration and drying to obtain the modified carbon black.
3) Adding 2g of the modified carbon black obtained in the step 2) into 100mL of absolute ethyl alcohol, accelerating the dispersion of the carbon black in a solvent by ultrasonic treatment, and thenSequentially adding 2mL of deionized water and 16mL of alkaline catalyst ammonia water (the concentration is 2.1 mol/L) under the stirring condition, fully mixing, adding 7g of tetraethoxysilane, reacting for 12 hours at 60 ℃, pouring the reaction solution into a centrifugal bottle after the reaction is finished, carrying out solid-liquid separation by using a 13000r/min high-speed centrifugation mode, washing the obtained solid by using solvent absolute ethyl alcohol, centrifuging for 3-4 times, drying, calcining for 2 hours at 600 ℃ in a nitrogen atmosphere, removing impurities left in the sol-gel method, and naturally cooling to room temperature to obtain the nano SiO2Carbon black dual-phase filler.
Example 2
1) Placing carbon black in a sealed sample preparation grinder for grinding for 2 min to obtain a carbon black powder sample, after the grinding is finished, placing the carbon black powder sample in a 125 ℃ oven for drying for 1h, during heating, ensuring that the thickness of a carbon black layer is not more than 10mm as far as possible by using an open container for containing the carbon black powder sample, and placing the dried carbon black in a sealed moisture-proof container for cooling to room temperature for later use.
2) Measuring a certain amount of deionized water in a beaker, adding 0.02g of coupling agent PVP (K30) into the beaker, stirring and dissolving, adding 2g of carbon black powder obtained in the step 1) after drying, mechanically stirring for 24 hours at room temperature to allow the carbon black to fully adsorb the PVP, and centrifugally filtering and drying to obtain the modified carbon black.
3) Adding 2g of the modified carbon black obtained in the step 2) into 100mL of absolute ethyl alcohol, accelerating dispersion of the carbon black in a solvent by ultrasonic treatment, then sequentially adding 2mL of deionized water and 14mL of alkaline catalyst ammonia water (the concentration is 1.8 mol/L) under the stirring condition, fully mixing, adding 5g of ethyl orthosilicate, reacting for 16h at 40 ℃, pouring a reaction solution into a centrifugal bottle after the reaction is finished, carrying out solid-liquid separation by using a 13000r/min high-speed centrifugation mode, washing the obtained solid with the solvent absolute ethyl alcohol, then centrifuging for 3-4 times, drying, calcining for 2h at 700 ℃ in a nitrogen atmosphere, removing impurities remained in the sol-gel method, naturally cooling to room temperature, and obtaining the nano SiO2Carbon black dual-phase filler.
Example 3
1) Placing carbon black in a sealed sample preparation grinder for grinding for 2 min to obtain a carbon black powder sample, after the grinding is finished, placing the carbon black powder sample in a 125 ℃ oven for drying for 1h, during heating, ensuring that the thickness of a carbon black layer is not more than 10mm as far as possible by using an open container for containing the carbon black powder sample, and placing the dried carbon black in a sealed moisture-proof container for cooling to room temperature for later use.
2) Measuring a certain amount of deionized water in a beaker, adding 0.08g of CTAB coupling agent into the beaker, stirring and dissolving, adding 2g of carbon black powder obtained in the step 1) to obtain dried carbon black powder, mechanically stirring the mixture for 24 hours at room temperature to ensure that the carbon black fully adsorbs CTAB, and carrying out centrifugal filtration and drying to obtain the modified carbon black.
3) Adding 2g of the modified carbon black obtained in the step 2) into 100mL of absolute ethyl alcohol, accelerating dispersion of the carbon black in a solvent by ultrasonic treatment, then sequentially adding 2mL of deionized water and 12mL of alkaline catalyst ammonia water (the concentration is 1.6 mol/L) under the stirring condition, fully mixing, adding 5g of ethyl orthosilicate, reacting for 20 hours at 60 ℃, pouring a reaction solution into a centrifugal bottle after the reaction is finished, carrying out solid-liquid separation by using a 13000r/min high-speed centrifugation mode, washing the obtained solid with the solvent absolute ethyl alcohol, then centrifuging for 3-4 times, drying, calcining for 1 hour at 800 ℃ in a nitrogen atmosphere, removing impurities remained in the sol-gel method, and naturally cooling to room temperature to obtain the nano SiO2Carbon black dual-phase filler.
Example 4
1) Placing carbon black in a sealed sample preparation grinder for grinding for 2 min to obtain a carbon black powder sample, after the grinding is finished, placing the carbon black powder sample in a 125 ℃ oven for drying for 1h, during heating, ensuring that the thickness of a carbon black layer is not more than 10mm as far as possible by using an open container for containing the carbon black powder sample, and placing the dried carbon black in a sealed moisture-proof container for cooling to room temperature for later use.
2) Measuring a certain amount of deionized water in a beaker, adding 0.1g of coupling agent alkylphenol polyoxyethylene ether (op-10) into the beaker, stirring and dissolving, adding 2g of carbon black powder obtained in the step 1), mechanically stirring for 24 hours at room temperature to allow the carbon black to fully adsorb the alkylphenol polyoxyethylene ether, and centrifugally filtering and drying to obtain the modified carbon black.
3) Adding 2g of the modified carbon black obtained in the step 2) into 100mL of absolute ethyl alcohol, accelerating the dispersion of the carbon black in a solvent by ultrasonic treatment, and then stirringSequentially adding 2mL of deionized water and 10mL of alkaline catalyst ammonia water (the concentration is 1.3 mol/L) under the condition, fully mixing, adding 1g of tetraethoxysilane, reacting for 24 hours at 80 ℃, pouring the reaction solution into a centrifugal bottle after the reaction is finished, carrying out solid-liquid separation by using a 13000r/min high-speed centrifugation mode, washing the obtained solid by using solvent absolute ethyl alcohol, centrifuging for 3-4 times, drying, calcining for 3 hours at 600 ℃ in a nitrogen atmosphere, removing the residual impurities prepared by a sol-gel method, and naturally cooling to room temperature to obtain the nano SiO2Carbon black dual-phase filler.
Second, performance verification
1. Untreated carbon black, white carbon black, carbon black-PVP and the nano SiO prepared in the example2The results of Fourier Infrared Spectroscopy tests on carbon black dual-phase fillers are shown in FIG. 1.
As can be seen from FIG. 1, the carbon black-PVP was 1289cm in comparison with the carbon black as it is-1Has a C-N stretching vibration peak of 1646cm-1The peak of C ═ O stretching vibration appears at 2859cm-1The asymmetric stretching vibration peak of C-H, 2924 cm-1C-H symmetric stretching vibration peaks appear nearby, and the C-H symmetric stretching vibration peaks are all characteristic absorption peaks of PVP, which indicates that the carbon black successfully adsorbs the PVP. The biphase filler is 1109cm-1、799 cm-1And 478 cm-1The characteristic peak of Si-O-Si is consistent with the characteristic peak of white carbon black prepared by a sol-gel method, thereby proving the existence of the white carbon black, but the peak is 1109cm-1And 478 cm-1The peaks at the left and right parts can not completely correspond to each other, so that the two kinds of white carbon black are different in chemical environment, and the two-phase filler is 880cm-1The oscillation peak of Si-C bond appears, which indicates that the white carbon black phase and the carbon black phase in the dual-phase filler are combined by chemical bond.
2. Untreated carbon black, nano SiO prepared in example 12-carbon black dual-phase filler and SiO prepared by sol-gel method2XRD testing was performed and the results are shown in FIG. 2.
As can be seen from fig. 2, XRD diffraction peaks of carbon black are shown at 2 θ =24.2 ° and 43.3 °, which are characteristic diffraction peaks of microcrystalline graphite on the surface of carbon black of (002) and (100) planes, respectively. The XRD diffraction peak of the prepared white carbon black only has a peak with 2 theta =21.2 degrees, which is a typical non-crystalline structure diffraction peak in the white carbon black prepared by a sol-gel method. In the XRD pattern of the dual-phase filler prepared by the invention, diffraction peaks respectively appear at 2 theta =23.2 degrees and 2 theta =42.2 degrees, wherein the diffraction peak at 23.2 degrees is between the peaks of carbon black and white carbon black, and a diffraction peak appears at 2 theta =43.2 degrees, which proves that the load of the white carbon black influences the orderliness of the surface of the carbon black, namely the structure of the carbon black phase in the dual-phase filler is changed.
3. Untreated carbon black and the nano SiO obtained in example 12SEM test of the carbon black dual-phase filler, the results are shown in figure 3.
As can be seen from the figure, the primary particles of the carbon black N330 are about 30 nm-40 nm, and are agglomerated together due to small particles and large specific surface area, or are fused together at high temperature in the generation process, and exist in the form of carbon black primary aggregates and secondary aggregates. Compared with N330, the particle size of the dual-phase filler prepared by the invention is not changed greatly, but the outline between partial particles is not clear of carbon black, presumably because the content of the white carbon black in the dual-phase filler is higher, partial carbon black is coated by a layer of white carbon black, the acting force between partial filler and the filler is increased due to the strong hydrogen bond action between hydroxyl on the surface of the white carbon black and the hydroxyl, and the macro expression shows that the particles are contacted more tightly and the outline is fuzzy.
4. Untreated carbon black and the nano SiO obtained in example 12TEM tests of the dual-phase carbon black filler, the results are shown in FIG. 4.
As can be seen from the figure, the graphite layers in the as-received carbon black particles form a continuous concentrically oriented network around one or several centers, similar to a fingerprint. The part of the concentric orientation network structure in the bidirectional filler is a carbon black phase, and the part of the other amorphous structure state is a white carbon black phase, so that the white carbon black particles are tightly attached to carbon black aggregates, and single or white carbon black aggregates are not scattered around, so that the carbon black grows in situ on the surface of the carbon black under the action of physical and chemical bonds, the binding force between the carbon black and the white carbon black is strong, and the structure of the carbon black is increased. Meanwhile, the dispersion of the white carbon black in the rubber can be improved, so that the white carbon black and the carbon black can play a better synergistic effect, and the reinforcing effect on the rubber is enhanced.
5. The stress-strain performance test is carried out on 3 fillers of carbon black, bidirectional filler and white carbon black used for reinforcing the natural rubber, and the stress-strain diagram of the three fillers for reinforcing the natural rubber is measured, and the result is shown in fig. 5.
As can be seen from the figure, the tensile strength of the dual-phase filler prepared by the present invention is improved by 21.41% and the elongation at break is improved by 30.82% compared to carbon black. Compared with white carbon black, the tensile strength of the dual-phase filler prepared by the invention is improved by 50.06%, the elongation at break is improved by 9.41%, and the dual-phase filler has excellent comprehensive performance. The dual-phase filler contains two phases of carbon black and white carbon black, the carbon black phase adsorbs a rubber macromolecular chain to generate physical acting force, the white carbon black phase generates chemical acting force with the rubber macromolecular chain through a silane coupling agent, and the two phases generate synergistic action by the two acting forces, so that the reinforcing effect on the rubber is enhanced.
In summary, after the carbon black is treated by the surfactant, the hydrophobic group of the surfactant interacts with the carbon black, and the hydrophilic group interacts with SiO2Strong hydrogen bonding and chemical bonding are generated. Namely carbon black and SiO2Joined together by chemical bonds, SiO2Can be tightly combined with carbon black to make SiO2Generates stronger binding force with the carbon black, chemical bonds formed between the carbon black and the carbon black are not easy to be damaged by shearing force during mixing, and the carbon black and the SiO are effectively exerted2The rubber has excellent reinforcing property to rubber, reduces rolling resistance, improves traction force, and simultaneously does not reduce wear resistance, thereby improving comprehensive performance of rubber vulcanized rubber.
Finally, the above embodiments are only for illustrating the technical solutions of the present invention and not for limiting, although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, and all of them should be covered in the claims of the present invention.

Claims (8)

1. Nano SiO2-a process for the preparation of a carbon black dual-phase filler, characterized in that it comprises the following steps:
1) crushing and drying carbon black to obtain a carbon black powder sample, adding a surfactant, fully stirring and dissolving, and centrifuging, filtering and drying to obtain modified carbon black;
2) adding the modified carbon black obtained in the step 1) into absolute ethyl alcohol, performing ultrasonic dispersion, sequentially adding deionized water and ammonia water under the stirring condition, fully mixing, adding tetraethoxysilane, fully reacting, centrifugally collecting solids after the reaction is finished, drying the solids, calcining in a nitrogen atmosphere, and naturally cooling to room temperature to obtain the dual-phase filler.
2. The nano SiO of claim 12-a process for the preparation of carbon black dual-phase filler, characterized in that the surfactant is PVP, CTAB or alkylphenol ethoxylates.
3. The nano SiO of claim 12The preparation method of the carbon black dual-phase filler is characterized in that the dosage of the surfactant is 1-5 wt% of the carbon black.
4. The nano SiO of claim 12The preparation method of the carbon black dual-phase filler is characterized in that the reaction time in the step 2) is 12-24 hours.
5. The nano SiO of claim 12The preparation method of the carbon black dual-phase filler is characterized in that the concentration of the ammonia water is 1.3-2.1 mol/L.
6. The nano SiO of claim 12-process for the preparation of a carbon black dual-phase filler, characterized in that said aqueous ammonia: deionized water: modified carbon black: the volume mass ratio of the ethyl orthosilicate is 10-16 ml: 2 ml: 2 g: 1-7 g.
7. The nano SiO of claim 12The preparation method of the carbon black dual-phase filler is characterized in that the calcination is carried out for 1-3 hours at the temperature of 600-800 ℃.
8. The nano SiO of claim 12The preparation method of the carbon black dual-phase filler is characterized in that the reaction temperature in the step 2) is 40-80 ℃.
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CN114574002A (en) * 2022-01-29 2022-06-03 新疆德欣精细化工有限公司 Carbon black nano material with high filtering precision and preparation method thereof
CN114656807A (en) * 2022-04-22 2022-06-24 青岛黑猫新材料研究院有限公司 Process method for improving wear resistance of carbon black
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CN114656807A (en) * 2022-04-22 2022-06-24 青岛黑猫新材料研究院有限公司 Process method for improving wear resistance of carbon black
CN115322592A (en) * 2022-08-10 2022-11-11 青岛黑猫新材料研究院有限公司 Preparation method and application of surface modified carbon black material
CN115322592B (en) * 2022-08-10 2023-10-13 青岛黑猫新材料研究院有限公司 Preparation method and application of surface modified carbon black material
CN115873425A (en) * 2022-12-27 2023-03-31 江苏臻远生物科技有限公司 Preparation method of nanoparticles for enhancing laser marking effect of black master batch

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