CN111808441B - Precipitation method white carbon black surface modification method - Google Patents
Precipitation method white carbon black surface modification method Download PDFInfo
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- CN111808441B CN111808441B CN202010747415.0A CN202010747415A CN111808441B CN 111808441 B CN111808441 B CN 111808441B CN 202010747415 A CN202010747415 A CN 202010747415A CN 111808441 B CN111808441 B CN 111808441B
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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
- C09C1/28—Compounds of silicon
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- 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
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- 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
- C09C3/04—Physical treatment, e.g. grinding, treatment with ultrasonic vibrations
- C09C3/041—Grinding
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- 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
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- 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
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Abstract
The invention discloses a method for modifying the surface of white carbon black by a precipitation method, wherein in the modification method, vitamin C powder is selected as a carbon source to carry out coating reaction on the white carbon black prepared by the precipitation method, firstly, the vitamin C powder and the white carbon black powder carry out condensation reaction of surface hydroxyl under the condition of mechanical grinding, the white carbon black and the vitamin C are connected together in a carbon-oxygen-silicon covalent bond mode through dehydration to form a single product, and then, carbonization reaction is carried out at the temperature of 200-230 ℃ to obtain the modified white carbon black with the surface covered with a carbon layer. The modified white carbon black has the advantages of high dispersibility, hydrophobicity and the like, and the stability and the service life of a modified product are greatly improved due to the existence of a covalent bond. The method has the advantages of cheap and easily-obtained raw materials, short process flow, simple and convenient operation, environmental protection, uniform reaction product, high product yield and high purity.
Description
Technical Field
The invention relates to the technical field of white carbon black, in particular to a method for modifying the surface of white carbon black by a precipitation method.
Background
White carbon black has a wide and irreplaceable role in the field of national life. Because the compound has stable property at normal temperature and is insoluble in acid (except hydrofluoric acid) and strong base, the compound has important application in the fields of feed, pesticide, papermaking and the like; the filler has excellent stability, reinforcing property, thickening property and thixotropy, and is one of important fillers of products such as rubber, plastics, paint and the like; white carbon black is usually added in the production process of rubber, the white carbon black mainly plays roles of crosslinking and reinforcing in rubber materials, the using amount of the white carbon black accounts for about 70-80% of the total output of the white carbon black, the addition of the white carbon black can greatly improve the physical properties of the rubber materials, reduce hysteresis and reduce rolling resistance, and the energy consumed by the rolling resistance of tires accounts for 20-30% of the total energy consumption of automobiles.
The preparation method of the white carbon black comprises a precipitation method and a gas phase method, the precipitation method is low in white carbon black manufacturing cost and simple to operate, but the product is more hydroxyl on the surface and strong in hydrophilicity, and is not easy to combine with a rubber matrix, so that the performance of a rubber product is influenced; although the white carbon black prepared by the gas phase method has few surface hydroxyl groups, the operation process is complex, the cost is high, the white carbon black cannot be widely popularized due to the high requirements of equipment and the complexity of the process, more researches in China are focused on carrying out technical modification on the white carbon black prepared by the precipitation method in order to obtain excellent products which are comparable to the white carbon black, the purpose of the modification is to reduce or eliminate the number of the hydroxyl groups on the surface of the white carbon black through reaction, organic groups are grafted on the white carbon black, the surface property of the white carbon black is changed from hydrophilicity to lipophilicity, the white carbon black can be better dispersed in an organic medium, and the interaction between the white carbon black filler and a polymer is enhanced. The modification method mainly has two directions: firstly, a surfactant is added to modify the surface hydroxyl of the white carbon black, such as the surfactant and a high molecular material reported in a patent with the publication number of CN110746794 to modify the surface hydroxyl of the silicon dioxide; another method is a modification method for carbonizing the surface of the white carbon black to obtain special properties, such as a modification method for coating carbon nanotubes on the surface of silica as described in patent publication No. CN105836749 and a modification method for coating a carbon layer on the surface of the white carbon black by dehydrating starch, lignin, glycerol, oligosaccharide and the like at a high temperature as a carbon source as described in patent publication No. CN 107603280.
The surfactant is used for modification, and mainly a chemical method is adopted to react with hydroxyl on the surface of the white carbon black, and various other chemical raw materials are introduced, so that the chemical reagent is easily polluted, and the post-treatment is troublesome; the product performance obtained by carbonizing and modifying the surface of the white carbon black is outstanding and the application range is wide, but the currently reported modification method mainly uses saccharides or organic micromolecules as carbon sources for modification, although the white carbon black product with the surface covered by the carbon layer can be obtained, the carbon coating is only simple physical coating, and because the polysaccharide carbon source molecules have large volume and cannot be used for accurately coating the surface of the white carbon black, a simple large-block coating without covalent bonds is often formed, the coated carbon layer is easy to fall off, and the service performance is greatly influenced.
Disclosure of Invention
In order to solve the technical problems that the modification of a surfactant is easy to cause the pollution of a chemical reagent, a carbon layer in the surface carbon-coating modification of silicon dioxide by a conventional precipitation method is easy to fall off and the like, the invention discloses a method for modifying the surface of white carbon black by the precipitation method, which comprises the following modification steps:
s1, fully mixing the white carbon black powder and the vitamin C powder according to the mass part ratio, and introducing into a ball mill; the white carbon black powder is prepared by a precipitation method, and the mesh number of the vitamin C powder is more than or equal to that of the white carbon black powder;
s2, introducing dry inert gas into the ball mill, and then grinding at the temperature of 20-60 ℃; the rotating speed of the ball mill is 200-300 r/min;
in the step, the white carbon black powder and the vitamin powder react as follows,
s3, heating and reacting the ground product obtained in the step S2 in flowing hot air;
the mass ratio of the white carbon black powder to the vitamin C powder is 1: 0.8-1;
the mesh number of the white carbon black powder is 100-200 meshes, and the mesh number of the vitamin C powder is 200-300 meshes.
Preferably, in step S1, the white carbon black powder and the vitamin C powder are mixed by a mixer for 30 min.
Preferably, the rotating speed of the ball mill in the step S2 is 250-260 r/min; the inert gas is nitrogen or argon, and the flow rate of the inert gas is 40-80 ml/min; and the grinding time of the white carbon black powder and the vitamin C powder is 2-4 h.
Preferably, the flow rate of the hot air in the step S3 is 180-240 ml/min, the temperature of the hot air is 200-230 ℃, and the heating time is 2-2.5 h.
The invention has the beneficial effects that:
according to the invention, the white carbon black powder and the vitamin C powder are subjected to chemical reaction in a solid grinding mode, so that the carbon, the oxygen and the silicon are combined in a covalent bond mode, and then carbonization treatment is carried out, so that a modified product of the white carbon black with the surface covered by the carbon layer is obtained, and the modified product has the advantages of the white carbon black and the carbon black. Because two different products are combined in a covalent bond mode, the stability, the wear resistance and the service life of the product are more excellent than those of the products on the market at present, the defect that the white carbon black is easy to agglomerate is overcome, and the dispersion performance of the white carbon black is improved. In addition, the modified white carbon black surface has a series of excellent properties due to the unique structural layer, the three-dimensional loose surface carbon layer structure has stronger buffering and adsorption effects on impact force, particularly the balance performance of a 'magic triangle' area required by the green tire tread is obviously improved, and meanwhile, the structure can quickly dissipate the friction generated heat, thereby being beneficial to the constancy of temperature. The series of unique properties have great reference function in the research field of special rubber and military tires.
Detailed Description
The following provides preferred embodiments of the present invention in order to facilitate the understanding of the concept of the present invention by the skilled person.
Example 1:
the white carbon black in the embodiment is modified as follows,
(1) mixing, namely adding the white carbon black powder prepared by the precipitation method into a mixer to mix with 300-mesh vitamin C powder according to the mass ratio of 1:1 after the white carbon black powder is 200 meshes, mixing for 30min, and transferring the mixture into a ball mill after the mixing is finished.
(2) Performing ball milling reaction at the temperature of 25 ℃, the rotating speed of a ball mill is 230r/min, and the ball milling time is 2 h. During the reaction, dry nitrogen gas was introduced at a rate of 40ml/min to take away the water generated during the ball milling.
(3) And (3) heating and carbonizing, transferring the ball-milled product into a reactor after the ball-milling reaction is finished, introducing hot air for carbonization reaction, wherein the temperature of the hot air is 200 ℃, the flow rate is 190ml/min, the heating time is 2.5h, and cooling to room temperature after the reaction is finished to obtain the modified white carbon black product with the surface covered with the carbon layer.
Example 2:
the white carbon black in the embodiment is modified as follows,
(1) mixing, namely adding the white carbon black powder prepared by the precipitation method into a mixer to mix with vitamin C powder of 200 meshes according to the mass ratio of 1:0.8, wherein the mixing time is 30min, and transferring the mixture into a ball mill after the mixing is finished.
(2) Performing ball milling reaction at the reaction temperature of 60 ℃, the rotating speed of a ball mill of 270r/min and the ball milling time of 2 h. During the reaction, dry nitrogen gas was introduced at a rate of 60ml/min to take away moisture generated during the ball milling.
(3) And heating and carbonizing, transferring the ball-milled product into a reactor after the ball-milling reaction is finished, introducing hot air for carbonization reaction, wherein the temperature of the hot air is 230 ℃, the flow rate is 190ml/min, the heating time is 2h, and cooling to room temperature after the reaction is finished to obtain the modified white carbon black product with the surface covered with the carbon layer.
Example 3:
the white carbon black in the embodiment is modified as follows,
(1) mixing, namely adding the white carbon black powder prepared by the precipitation method into a mixer to mix with vitamin C powder of 200 meshes according to the mass ratio of 1:0.9, wherein the mixing time is 30min, and transferring the mixture into a ball mill after the mixing is finished.
(2) Performing ball milling reaction at 40 ℃, wherein the rotating speed of the ball mill is 250r/min, and the ball milling time is 3 h. During the reaction, dry nitrogen gas was introduced at a rate of 50ml/min to take away moisture generated during the ball milling.
(3) And heating and carbonizing, transferring the ball-milled product into a reactor after the ball-milling reaction is finished, introducing hot air for carbonization reaction, wherein the temperature of the hot air is 230 ℃, the flow rate is 240ml/min, the heating time is 2h, and cooling to room temperature after the reaction is finished to obtain the modified white carbon black product with the surface covered with the carbon layer.
Example 4:
the white carbon black in the embodiment is modified as follows,
(1) mixing, namely adding the white carbon black powder prepared by the precipitation method into a mixer to mix with vitamin C powder of 260 meshes according to the mass ratio of 1:1 after the white carbon black powder is 200 meshes, mixing for 30min, and transferring the mixture into a ball mill after the mixture is mixed.
(2) Performing ball milling reaction at the reaction temperature of 50 ℃, the rotating speed of a ball mill of 250r/min and the ball milling time of 2 h. During the reaction, dry argon gas was introduced at a rate of 80ml/min to take away the water generated during the ball milling.
(3) And (3) heating and carbonizing, transferring the ball-milled product into a reactor after the ball-milling reaction is finished, introducing hot air for carbonization reaction, wherein the temperature of the hot air is 230 ℃, the flow rate is 200ml/min, the heating time is 2.5h, and cooling to room temperature after the reaction is finished to obtain the modified white carbon black product with the surface covered with the carbon layer.
The principle of the vitamin C powder in the above 4 examples for modifying the white carbon black powder is as follows: the existence of polyhydroxy in the vitamin C powder enables the vitamin C powder to have excellent oxidation resistance, and meanwhile, the existence of polyhydroxy functional groups enables the vitamin C powder and the white carbon black powder to have great modification potential, so that the vitamin C powder and the white carbon black powder can be subjected to chemical reaction under the action of mechanical force, and the hydroxyl between the vitamin C powder and the white carbon black powder is dehydrated to form ether bonds. Then the vitamin C can generate a dehydration carbonization effect under the condition of 200 ℃, and simultaneously the characteristics of polyhydroxy and micromolecule ensure that the vitamin C powder can be fully contacted with the white carbon black powder, so that the chemical reaction is more uniform. The volume of the vitamin C is increased sharply during carbonization, and the unreacted raw materials can be prevented from being wrapped by one group.
The carbon layer coating thickness and the water contact angle of the modified white carbon black prepared in the above 4 examples were measured, wherein the carbon layer coating thickness was measured by an electron microscope image obtained by a high-resolution projection electron microscope, the water contact angle was measured by a contact angle measuring instrument, and the data results are shown in table 1:
TABLE 1 carbon layer coating thickness and Water contact Angle measurement data for the products of the examples
The innovation of the invention focuses on the following aspects:
(1) the production process is simple, the operation steps are simple, and the production equipment is simple.
(2) Adopts vitamin C with low price as a carbon source. VC as a pure substance has more balanced action with white carbon black, and the generated product is more single and pure.
(3) The solid grinding method is used for reaction, so that the use of chemical reagents is directly avoided. And the reaction can be carried out by solid grinding at normal temperature and normal pressure, the investment of large-scale equipment is avoided, the occupied area is small, the power consumption is low, no pollution is caused, and the green development concept is completely met.
(4) The carbonization temperature is low, and the reaction can be carried out at the lowest temperature of 200 ℃. Compared with the carbonization temperature of other carbon sources, the method can greatly reduce the production energy consumption and the production cost.
(5) The production period is short, the shortest production period in the whole modification process can be less than 6 hours, and the method is simple to operate, safe and environment-friendly.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein. In addition, the technical solutions between the various embodiments can be combined with each other, but must be based on the realization of those skilled in the art; where combinations of features are mutually inconsistent or impractical, such combinations should not be considered as being absent and not within the scope of the claimed invention.
Claims (3)
1. The method for modifying the surface of white carbon black by a precipitation method is characterized by comprising the following modification steps:
s1, fully mixing the white carbon black powder and the vitamin C powder according to the mass part ratio, and introducing into a ball mill; the white carbon black powder is prepared by a precipitation method, and the mesh number of the vitamin C powder is more than or equal to that of the white carbon black powder;
s2, introducing dry inert gas into the ball mill, and then grinding at the temperature of 20-60 ℃; the rotating speed of the ball mill is 200-300 r/min;
s3, heating and reacting the ground product obtained in the step S2 in flowing hot air;
the mass ratio of the white carbon black powder to the vitamin C powder is 1: 0.8-1;
the mesh number of the white carbon black powder is 100-200 meshes, and the mesh number of the vitamin C powder is 200-300 meshes;
in step S3, the flow rate of the hot air is 180-240 ml/min, the temperature of the hot air is 200-230 ℃, and the heating time is 2-2.5 h.
2. The method for modifying the surface of precipitated silica according to claim 1, wherein the mixing of the silica powder and the vitamin C powder in step S1 is performed by a mixer for 30 min.
3. The precipitated silica white surface modification method according to claim 1, wherein the rotation speed of the ball mill in step S2 is 250-260 r/min; the inert gas is nitrogen or argon, and the flow rate of the inert gas is 40-80 ml/min; and the grinding time of the white carbon black powder and the vitamin C powder is 2-4 h.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103554997A (en) * | 2013-10-16 | 2014-02-05 | 张家港环纳环保科技有限公司 | Carbon-coated vanadium dioxide nanoparticles and preparation method thereof |
| CN103937293A (en) * | 2014-04-28 | 2014-07-23 | 北京化工大学 | Carbon-coated white carbon black |
| CN109233352A (en) * | 2018-08-03 | 2019-01-18 | 蚌埠市万科硅材料科技有限公司 | A kind of white carbon black surface treatment method |
| CN110171812A (en) * | 2019-05-27 | 2019-08-27 | 北京科技大学 | Multi-layer porous hollow bowl-type carbon material of one kind and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103554997A (en) * | 2013-10-16 | 2014-02-05 | 张家港环纳环保科技有限公司 | Carbon-coated vanadium dioxide nanoparticles and preparation method thereof |
| CN103937293A (en) * | 2014-04-28 | 2014-07-23 | 北京化工大学 | Carbon-coated white carbon black |
| CN109233352A (en) * | 2018-08-03 | 2019-01-18 | 蚌埠市万科硅材料科技有限公司 | A kind of white carbon black surface treatment method |
| CN110171812A (en) * | 2019-05-27 | 2019-08-27 | 北京科技大学 | Multi-layer porous hollow bowl-type carbon material of one kind and preparation method thereof |
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