CN110964349B - Oxidation modified carbon black and preparation method thereof - Google Patents
Oxidation modified carbon black and preparation method thereof Download PDFInfo
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- CN110964349B CN110964349B CN201811156954.6A CN201811156954A CN110964349B CN 110964349 B CN110964349 B CN 110964349B CN 201811156954 A CN201811156954 A CN 201811156954A CN 110964349 B CN110964349 B CN 110964349B
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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
- C09C1/565—Treatment of carbon black ; Purification comprising an oxidative treatment with oxygen, ozone or oxygenated compounds, e.g. when such treatment occurs in a region of the furnace next to the carbon black generating reaction zone
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- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/22—Rheological behaviour as dispersion, e.g. viscosity, sedimentation stability
Abstract
The invention provides modified carbon black, which is prepared by passing carbon black through heteropoly acid-H2O2The compound oxidation system is oxidized to obtain the product. The invention introduces heteropoly acid into a hydrogen peroxide oxidation system to obtain heteropoly acid-H2O2The composite oxidation system can effectively improve the oxidation capacity and efficiency of the oxidant, can well combine heteropoly acid and organic matters to generate certain specific reactions, increases hydrophilic functional groups on the surface of carbon black, and improves the dispersibility and stability of carbon black particles in a water-soluble system. The method has the advantages of environmental friendliness, low corrosion to equipment, mild reaction conditions, high reaction speed and the like, greatly improves the oxygen content of the modified carbon black, increases hydrophilic functional groups on the surface of the carbon black, has excellent water dispersion performance and dispersion stability, is more suitable for large-scale industrial production, and has profound significance in the application in the field of carbon black oxidation modification.
Description
Technical Field
The invention belongs to the technical field of carbon black materials, relates to modified carbon black and a preparation method thereof, and particularly relates to oxidized modified carbon black and a preparation method thereof.
Background
Carbon black (carbon black), also known as carbon black, is an amorphous carbon, a particulate of elemental carbon, a light, loose and extremely fine black powder, having a large surface area ranging from 10 to 3000m2The specific gravity is 1.8-2.1, and generally, carbonaceous substances (coal, natural gas, heavy oil, fuel oil and the like) are subjected to incomplete combustion or thermal decomposition under the condition of insufficient air, hydrogen elements and oxygen elements in the carbonaceous substances are converted into water, and carbon elements are separated from molecules to form carbon black when the carbon elements are not sufficiently combusted. It is common in the industry to make "gas black" from natural gas, lamp black "from oils, and acetylene black" from acetylene. In addition, "channel black" and "furnace black" are also included. According to the properties of carbon black, there are "reinforcing carbon black", "conductive carbon black"abrasion resistant carbon black" and the like. Can be used as black dye for manufacturing Chinese ink, printing ink, paint and the like, and also can be used as reinforcing agent of rubber.
The carbon black particles have a microcrystalline structure, in the carbon black, the arrangement mode of carbon atoms is similar to that of graphite to form a hexagonal plane, generally 3-5 layers form a microcrystal, and the arrangement of the carbon atoms in each graphite layer of the carbon black microcrystal is orderly, and the arrangement of the carbon atoms between adjacent layers is disordered, so the carbon black particles are called quasi-graphite crystals. The structural properties of carbon black are expressed by the degree of chain-like or grape-like aggregation among carbon black particles. Carbon black consisting of agglomerates composed of the size, form and number of particles per agglomerate is called high structure carbon black. The higher the carbon black structure, the more easily a space network channel is formed and the less easily it is destroyed. The high-structure carbon black particles are fine, the reticular chains are tightly stacked, the specific surface area is large, the number of particles per unit mass is large, the chain type conductive structure can be formed in the polymer, and the carbon black particles with wide particle size distribution can better endow the polymer with conductivity than the carbon black particles with narrow particle size distribution.
Generally, carbon black particles are not isolated, but a plurality of particles are interpenetrated with each other through a carbon crystal layer to form a chain branch. According to the production process, the method can be divided into gas black, lamp black, channel black and furnace black, and different production processes can obtain carbon black particles with extremely wide particle size ranges, the products obtained by the lamp black production process are relatively coarse, the gas black production process can obtain fine products, and the furnace black production process can obtain carbon black with almost all particle size ranges. Due to the above structural composition, carbon black has excellent blackness, tinting strength and stability, and is widely used as a filler and a colorant in water-based paints, inks and the like.
However, the main production method of carbon black is furnace production, i.e. furnace black, which results in small oxygen-containing functional groups and polarity on the surface and generally in alkaline pH value range, which are not favorable for the dispersion of carbon black in aqueous system, and the surface oxidation treatment can be carried out for improving the dispersion stability of furnace carbon black in aqueous system. After the oxidation modification, the oxygen-containing polar functional groups on the surface of the carbon black are increased, so that the adsorption force among carbon black particles is reduced, and the dispersion of the carbon black particles in an aqueous system is improved.
The conventional oxidation modification methods mainly include: gas phase oxidation method, liquid phase oxidation method. Generally, the modification effect of the gas phase method is unstable and the efficiency is low; the liquid phase oxidation method can be fully contacted with the carbon black, and the oxidation effect is better than that of gas phase oxidation. The liquid phase oxidant comprises nitric acid, hydrogen peroxide and the like, although the content of introduced oxygen is high in the nitric acid oxidation method, a large amount of nitrogen oxides discharged in the wet granulation process by the nitric acid mild oxidation cause environmental pollution, and the deep oxidation method has harsh reaction conditions and complex reaction equipment and post-treatment. As for hydrogen peroxide, the hydrogen peroxide has high utilization rate, is clean and cheap, and generally receives attention of people. But H2O2The oxidation capability is weak during oxidation, so that the oxidation effect is poor, the oxidation degree of the carbon black cannot be improved by singly raising the temperature and prolonging the time, a method of multiple oxidation is needed, and the problems of complex operation, overlong reaction time, increased consumption of hydrogen peroxide and the like can be caused. Therefore, the problems of the two conventional oxidizing agents have limited the application of the oxidizing agents in the oxidation modification of carbon black.
Therefore, how to find a more suitable method for oxidizing carbon black overcomes the defects of the traditional liquid phase oxidation method, expands the application range of the oxidized carbon black, and becomes one of the focuses of extensive attention of researchers with foresight in the field.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide a modified carbon black and a preparation method thereof, particularly a preparation method of an oxidized modified carbon black. The modification method provided by the invention improves the oxidation capacity and the oxidation efficiency, increases the hydrophilic functional groups on the surface of the carbon black, improves the dispersibility and stability of carbon black particles in a water-soluble system, is simple and mild in preparation method, and is suitable for large-scale industrial production.
The invention provides modified carbon black, which is prepared by passing carbon black through heteropoly acid-H2O2The compound oxidation system is oxidized to obtain the product.
Preferably, the carbon black comprises furnace carbon black;
the oxygen content of the carbon black is 0.1-2%;
the pH value of the carbon black is 7-10.
Preferably, the heteropolyacid comprises one or more of phosphotungstic acid, silicotungstic acid, phosphomolybdic acid and silicomolybdic acid;
the oxygen content of the modified carbon black is 5-20%;
the pH value of the modified carbon black is 3-6.
Preferably, the oxidation is primary oxidation;
the oxygen content of the modified carbon black increases with increasing temperature and/or time of oxidation.
The invention also provides a preparation method of the modified carbon black, which comprises the following steps:
A) mixing carbon black, heteropoly acid and hydrogen peroxide, and reacting to obtain the modified carbon black.
Preferably, the carbon black is pretreated carbon black;
the pretreatment comprises grinding and/or drying;
the particle size of the carbon black is 10-100 mu m.
Preferably, the mass ratio of the carbon black to the heteropoly acid is (100-500): 1;
the mass ratio of the carbon black to the hydrogen peroxide is 1: (4-10).
Preferably, the concentration of the hydrogen peroxide is 3-30%;
the reaction temperature is 30-80 ℃;
the reaction time is 1.0-6.0 h.
Preferably, the mixing mode is ultrasonic mixing;
the mixing time is 0.5-2 h;
the reaction mode is that the reaction is carried out under the condition of water bath.
Preferably, the reaction also comprises a post-treatment step;
the post-treatment comprises one or more of filtration, water washing and drying.
The invention provides modified carbon black, which is prepared by passing carbon black through heteropoly acid-H2O2The compound oxidation system is oxidized to obtain the product. Compared with the prior art, the invention aims at the problems that the existing oxidation modified carbon black, particularly the carbon black by a liquid phase oxidation furnace method has poor oxidation effect, the oxidation degree of the carbon black cannot be improved by single temperature rise and time extension, multiple oxidation is needed, the operation is complicated, the reaction time is too long, the consumption of hydrogen peroxide is increased, and the like.
The invention provides a catalyst with excellent catalytic performance and an environment-friendly oxidant for composite oxidation of modified carbon black, and the heteropolyacid is creatively introduced into a hydrogen peroxide oxidation system to obtain heteropolyacid-H2O2When the heteropoly acid and the hydrogen peroxide oxidant are used in a composite mode, the heteropoly acid is used as a catalytic oxidant, and the hydrogen peroxide is used as an oxidant, so that the oxidizing capacity and efficiency of the oxidant can be effectively improved, the heteropoly acid and an organic matter can be well combined and certain specific reactions can be generated, hydrophilic functional groups on the surface of carbon black are increased, and the dispersibility and stability of carbon black particles in a water-soluble system are improved. Meanwhile, the heteropoly acid has the characteristics of high catalysis efficiency and environmental friendliness, and has the advantages of high regeneration speed, high selectivity, high catalytic activity and the like when being used as a catalyst of the composite oxidant.
Compared with a hydrogen peroxide oxidant, the method for surface oxidation modification of carbon black provided by the invention has heteropoly acid-H2O2The composite oxidation system has the advantages of environmental friendliness, low corrosion to equipment, mild reaction conditions, high reaction speed and the like, the oxygen content of the modified carbon black is greatly improved, hydrophilic functional groups on the surface of the carbon black are increased, the composite oxidation system has excellent water dispersion performance and dispersion stability, is more suitable for large-scale industrial production, and has profound significance in the application in the field of carbon black oxidation modification.
Experimental results show that the oxygen content of the carbon black is increased from about 1% to about 10% initially, the dispersibility of the carbon black in water is obviously improved, and the modified carbon black has no layering phenomenon for at least 50 days in the water, so that the carbon black has better dispersion stability.
Detailed Description
For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the invention, and not to limit the scope of the claims.
All of the starting materials of the present invention, without particular limitation as to their source, may be purchased commercially or prepared according to conventional methods well known to those skilled in the art.
All the raw materials of the present invention are not particularly limited in their purity, and the present invention preferably employs the purity of the conventional one used in the field of analytical purification or carbon black production.
All the raw materials, the marks and the acronyms thereof belong to the conventional marks and acronyms in the field, each mark and acronym is clear and definite in the field of related application, and the raw materials can be purchased from the market or prepared by a conventional method by the technical staff in the field according to the marks, the acronyms and the corresponding application.
The invention provides modified carbon black, which is prepared by passing carbon black through heteropoly acid-H2O2The compound oxidation system is oxidized to obtain the product.
The carbon blacks are not particularly restricted in principle by the present invention, and those known to the skilled worker are suitable, can be prepared by conventional methods and are also commercially available, and can be selected and adapted by the skilled worker according to the actual application, the product requirements and the quality requirements, and preferably include furnace blacks. The oxygen content of the carbon black can be 0.1-2%, also can be 0.3-1.8%, also can be 0.5-1.5%, also can be 0.8-1.2%. The pH value of the carbon black can be 7-10, can also be 7.5-9.5, and can also be 8-9.
The heteropoly acid is not particularly limited in principle by the present invention, and can be selected and adjusted by those skilled in the art according to the actual application, product requirements and quality requirements, and preferably comprises one or more of phosphotungstic acid, silicotungstic acid, phosphomolybdic acid and silicomolybdic acid, more preferably phosphotungstic acid, silicotungstic acid, phosphomolybdic acid or silicomolybdic acid, in order to ensure better oxidation modification effect.
Compared with the existing hydrogen peroxide oxidation process, the oxidation effect is poor, the oxidation degree of the carbon black cannot be improved through single temperature rise and time extension, a multi-oxidation method is needed, and the problems of complex operation, overlong reaction time, increased hydrogen peroxide consumption and the like are caused. The oxidation in the invention is preferably a one-time oxidation, i.e. only a single oxidation modification is required. The invention can change the oxygen content of the modified carbon black by adjusting the time and temperature of the oxidation process, and realize that the oxygen content of the modified carbon black is increased along with the increase of the oxidation temperature and/or the oxidation time. The modified carbon black of the present invention has an oxygen content of preferably 5% to 20%, more preferably 8% to 18%, and still more preferably 10% to 15%. The pH value of the modified carbon black is preferably 3-6, more preferably 3.5-5.5, and more preferably 4-5.
The invention also provides a preparation method of the modified carbon black, which comprises the following steps:
A) mixing carbon black, heteropoly acid and hydrogen peroxide, and reacting to obtain the modified carbon black.
The raw material selection, composition and corresponding optimization principle in the preparation method of the modified carbon black can correspond to the raw material selection, composition and corresponding optimization principle in the modified carbon black, and are not described in detail herein.
The carbon black of the present invention is not particularly limited in principle, and can be prepared by conventional methods or can be purchased commercially, and can be selected and adjusted by those skilled in the art according to actual production conditions, product requirements and quality requirements. The pre-treatment according to the present invention preferably comprises grinding and/or drying, more preferably grinding and drying. The particle size of the carbon black is preferably 10-100 μm, more preferably 30-80 μm, and more preferably 50-60 μm.
The amount of the heteropoly acid used in the invention is not particularly limited in principle, and can be selected and adjusted by the ordinary amount well known to the skilled in the art according to the actual production situation, the product requirement and the quality requirement, and in order to ensure the excellent effect of the oxidation modified carbon black, the mass ratio of the carbon black and the heteropoly acid is preferably (100-500): 1, more preferably (150 to 450): 1, more preferably (200 to 400): 1, more preferably (250 to 350): 1.
the dosage of the hydrogen peroxide is not particularly limited in principle, and the conventional dosage well known to those skilled in the art can be used, and those skilled in the art can select and adjust the dosage according to the actual production situation, the product requirement and the quality requirement, and in order to ensure the excellent effect of the oxidation modified carbon black, the mass ratio of the carbon black to the hydrogen peroxide is preferably 1: (4-10), more preferably 1: (5-9), more preferably 1: (6-8). The concentration of the hydrogen peroxide is preferably 3-30%, more preferably 8-25%, and more preferably 13-20%.
The mixing means and conditions are in principle not particularly restricted by the present invention, and can be selected and adjusted by the person skilled in the art according to the actual production situation, the product requirements and the quality requirements in a conventional manner known to the person skilled in the art, and the mixing means of the present invention is preferably ultrasonic mixing. The mixing time of the invention is preferably 0.5-2 h, more preferably 0.8-1.8 h, and more preferably 1.0-1.5 h.
The reaction mode and conditions are not particularly limited in principle, and conventional reaction modes and conditions known to those skilled in the art can be adopted, and the selection and adjustment can be performed by the skilled in the art according to the actual production condition, the product requirements and the quality requirements, and the reaction temperature is preferably 30-80 ℃, more preferably 40-70 ℃, and more preferably 50-60 ℃ in order to ensure the excellent oxidation effect of the oxidation modified carbon black by adjusting the reaction time and temperature and changing the oxygen content of the oxidation modified carbon black. The reaction time is preferably 1.0-6.0 h, more preferably 2.0-5.0 h, and more preferably 3.0-4.0 h. The reaction mode of the invention is preferably to carry out the reaction under the condition of water bath.
In order to further improve the quality of the oxidation modified carbon black and ensure the performance of a final product, the method preferably further comprises a post-treatment step after the reaction. The post-treatment step of the present invention preferably comprises one or more of filtration, washing with water and drying, more preferably filtration, washing with water and drying.
In order to further refine and complete the preparation process and ensure the performance of the final product, the preparation method of the oxidation modified carbon black specifically comprises the following steps:
(1) finely grinding industrial carbon black, and then putting the industrial carbon black into a constant-temperature drying oven for drying treatment;
(2) preparing H with a certain concentration2O2A solution;
(3) mixing a certain amount of dried carbon black with a certain amount of catalyst and H2O2Mixing the solutions, carrying out ultrasonic dispersion for a certain time, and then stirring and reacting for several hours in a water bath at a certain temperature;
(4) and (3) carrying out suction filtration on the carbon black, washing the carbon black to be neutral, and carrying out vacuum drying to obtain the modified carbon black.
The invention provides an oxidation modified carbon black and a preparation method thereof, wherein a catalyst with excellent catalytic performance and an environment-friendly oxidant are adopted to compound to form a composite oxidation system oxidation modified carbon black, and heteropolyacid is creatively introduced into a hydrogen peroxide oxidation system to obtain heteropolyacid-H2O2When the heteropoly acid and the hydrogen peroxide oxidant are used in a composite mode, the heteropoly acid is used as a catalytic oxidant, and the hydrogen peroxide is used as an oxidant, so that the oxidizing capacity and efficiency of the oxidant can be effectively improved, the heteropoly acid and an organic matter can be well combined and certain specific reactions can be generated, hydrophilic functional groups on the surface of carbon black are increased, and the dispersibility and stability of carbon black particles in a water-soluble system are improved. Simultaneously, the heteropoly acid has the characteristics of high catalytic efficiency and environmental friendliness, is used as a catalyst of a composite oxidant, and also has the characteristics of high catalytic efficiency and environmental friendlinessHigh regeneration speed, high selectivity, high catalytic activity and the like.
The method for modifying the surface of the carbon black provided by the invention has the advantages that the carbon black is used as a raw material, hydrogen peroxide is used as an oxidant, heteropoly acid is used as a catalytic oxidant, and oxidation is carried out under a certain condition by a specific proportion, so that hydrophilic functional groups on the surface of the carbon black are increased, the adsorption force among carbon black particles is reduced, and the dispersion of the carbon black particles in an aqueous system is improved. Particularly, the oxidation degree of the carbon black can be improved only through a single oxidation process by virtue of the conditional reaction temperature and time, the problem that the traditional hydrogen peroxide oxidation is not beneficial is effectively solved, the complexity of the operation is reduced, the reaction time and the consumption of the hydrogen peroxide are shortened, the method is more suitable for large-scale industrial production, the application in the field of carbon black oxidation modification has profound significance, and the method can be applied to the fields of water-soluble coatings, printing ink and the like. .
Experimental results show that the oxygen content of the carbon black is increased from about 1% to about 10% initially, the dispersibility of the carbon black in water is obviously improved, and the modified carbon black has no layering phenomenon for at least 50 days in the water, so that the carbon black has better dispersion stability.
For further illustration of the present invention, the following will describe in detail a modified carbon black and its preparation method with reference to the following examples, but it should be understood that these examples are carried out on the premise of the technical scheme of the present invention, and the detailed embodiments and specific procedures are given, only for further illustration of the features and advantages of the present invention, not for limitation of the claims of the present invention, and the scope of protection of the present invention is not limited to the following examples.
Example 1
A500 ml three-neck flask with a thermometer and a condenser is added with a stirring magneton, 0.5g of phosphotungstic acid catalyst, 50g of carbon black and 300ml of hydrogen peroxide. And (3) putting the three-neck flask into a magnetic stirring water bath kettle, stirring and heating, starting timing reaction for 6 hours when the temperature is heated to 50 ℃, carrying out suction filtration on a carbon black solution after the reaction is finished, washing the carbon black solution to be neutral, and carrying out vacuum drying to obtain a solid, namely the oxidation modified carbon black.
The oxygen content of the oxidatively modified carbon black prepared in example 1 of the present invention was measured.
The results show that the oxygen content of the oxidatively modified carbon black of example 1 of the present invention is increased from 1% to 8.3% of the original carbon black, which indicates that the surface functional groups of the carbon black are greatly increased and have better hydrophilicity.
The oxidized modified carbon black prepared in example 1 of the present invention was examined.
Weighing 0.1g of the oxidized modified carbon black prepared in the embodiment, adding the oxidized modified carbon black into 50mL of distilled water, carrying out ultrasonic oscillation for half an hour, respectively pouring the mixture into beakers, standing the mixture for 48 hours, measuring 2mL of supernatant and 2mL of distilled water, adding the supernatant and the 2mL of distilled water into a centrifuge tube, centrifuging the mixture at a rotating speed of 5000r/min for 20min, sucking the centrifuged supernatant into a cuvette by a needle tube, and measuring the transmittance at a wavelength of 510nm to be 24%.
The dispersion remaining in the beaker was also observed and recorded to have a dispersion stability of 50 days without delamination.
The result is consistent with the oxygen content test result of the carbon black, and the oxidation modified carbon black prepared by the invention is further proved to have better dispersion stability under a water system.
Referring to Table 1, Table 1 compares the performance index of the oxidized modified carbon blacks prepared in the examples of the present invention with that of the unmodified carbon blacks.
Example 2
A500 ml three-neck flask with a thermometer and a condenser is added with stirring magnetons, 1g of phosphotungstic acid catalyst, 50g of carbon black and 300ml of hydrogen peroxide. And (3) putting the three-neck flask into a magnetic stirring water bath kettle, stirring and heating, starting timing reaction for 4 hours when the temperature is heated to 60 ℃, carrying out suction filtration on a carbon black solution after the reaction is finished, washing the carbon black solution to be neutral, and carrying out vacuum drying to obtain a solid, namely the oxidation modified carbon black.
The oxygen content of the oxidatively modified carbon black prepared in example 2 of the present invention was measured.
The results show that the oxygen content of the oxidatively modified carbon black of example 2 of the present invention increased from 1% to 9.4% of the original carbon black, which indicates that the surface functional groups of the carbon black were greatly increased and had better hydrophilicity.
The oxidized modified carbon black prepared in example 2 of the present invention was examined.
Weighing 0.1g of the oxidized modified carbon black prepared in the embodiment, adding the oxidized modified carbon black into 50mL of distilled water, carrying out ultrasonic oscillation for half an hour, respectively pouring the mixture into beakers, standing the mixture for 48 hours, measuring 2mL of supernatant and 2mL of distilled water, adding the supernatant and the 2mL of distilled water into a centrifuge tube, centrifuging the mixture at the rotating speed of 5000r/min for 20min, sucking the centrifuged supernatant into a cuvette by a needle tube, and measuring the transmittance at the wavelength of 510nm to be 20%.
The dispersion remaining in the beaker was also observed and recorded to have a dispersion stability of 55 days without delamination.
The result is consistent with the oxygen content test result of the carbon black, and the oxidation modified carbon black prepared by the invention is further proved to have better dispersion stability under a water system.
Referring to Table 1, Table 1 compares the performance index of the oxidized modified carbon blacks prepared in the examples of the present invention with that of the unmodified carbon blacks.
Referring to Table 1, Table 1 compares the performance index of the oxidized modified carbon blacks prepared in the examples of the present invention with that of the unmodified carbon blacks.
Example 3
A500 ml three-neck flask with a thermometer and a condenser is added with a stirring magneton, 0.5g of silicotungstic acid catalyst, 50g of carbon black and 500ml of hydrogen peroxide. And (3) putting the three-neck flask into a magnetic stirring water bath kettle, stirring and heating, starting timing reaction for 2 hours when the temperature is heated to 80 ℃, carrying out suction filtration on a carbon black solution after the reaction is finished, washing the carbon black solution to be neutral, and carrying out vacuum drying to obtain a solid, namely the oxidation modified carbon black.
The oxygen content of the oxidatively modified carbon black prepared in example 3 of the present invention was measured.
The results show that the oxygen content of the oxidatively modified carbon black of example 3 of the present invention increased from 1% to 12.4% of the original carbon black, which indicates that the surface functional groups of the carbon black were greatly increased and had better hydrophilicity.
The oxidized modified carbon black prepared in example 3 of the present invention was tested.
Weighing 0.1g of the oxidized modified carbon black prepared in the embodiment, adding the oxidized modified carbon black into 50mL of distilled water, carrying out ultrasonic oscillation for half an hour, respectively pouring the mixture into beakers, standing the mixture for 48 hours, measuring 2mL of supernatant and 2mL of distilled water, adding the supernatant and the 2mL of distilled water into a centrifuge tube, centrifuging the mixture at a rotating speed of 5000r/min for 20min, sucking the centrifuged supernatant into a cuvette by a needle tube, and measuring the transmittance at a wavelength of 510nm to be 10%.
The dispersion remaining in the beaker was also observed and recorded to have a dispersion stability of 70 days without delamination.
The result is consistent with the oxygen content test result of the carbon black, and the oxidation modified carbon black prepared by the invention is further proved to have better dispersion stability under a water system.
Referring to Table 1, Table 1 compares the performance index of the oxidized modified carbon blacks prepared in the examples of the present invention with that of the unmodified carbon blacks.
Example 4
A500 ml three-neck flask with a thermometer and a condenser is added with stirring magnetons, 1g of phosphomolybdic acid catalyst, 50g of carbon black and 400ml of hydrogen peroxide. And (3) putting the three-neck flask into a magnetic stirring water bath kettle, stirring and heating, starting timing reaction for 1 hour when the temperature is heated to 70 ℃, after the reaction is finished, carrying out suction filtration on a carbon black solution, washing the carbon black solution to be neutral, and carrying out vacuum drying to obtain a solid, namely the oxidation modified carbon black.
The oxygen content of the oxidatively modified carbon black prepared in example 4 of the present invention was measured.
The results show that the oxygen content of the oxidatively modified carbon black of example 4 of the present invention increased from 1% to 11.2% of the original carbon black, which indicates that the surface functional groups of the carbon black were greatly increased and had better hydrophilicity.
The oxidized modified carbon black prepared in example 4 of the present invention was tested.
Weighing 0.1g of the oxidized modified carbon black prepared in the embodiment, adding the oxidized modified carbon black into 50mL of distilled water, carrying out ultrasonic oscillation for half an hour, respectively pouring the mixture into beakers, standing the mixture for 48 hours, measuring 2mL of supernatant and 2mL of distilled water, adding the supernatant and the 2mL of distilled water into a centrifuge tube, centrifuging the mixture at the rotating speed of 5000r/min for 20min, sucking the centrifuged supernatant into a cuvette by a needle tube, and measuring the transmittance at the wavelength of 510nm to be 15%.
The dispersion remaining in the beaker was also observed and recorded to have a dispersion stability of 60 days without delamination.
The result is consistent with the oxygen content test result of the carbon black, and the oxidation modified carbon black prepared by the invention is further proved to have better dispersion stability under a water system.
Referring to Table 1, Table 1 compares the performance index of the oxidized modified carbon blacks prepared in the examples of the present invention with that of the unmodified carbon blacks.
Example 5
A500 ml three-neck flask with a thermometer and a condenser is added with a stirring magneton, 0.5g of silicomolybdic acid catalyst, 50g of carbon black and 200ml of hydrogen peroxide. And (3) putting the three-neck flask into a magnetic stirring water bath kettle, stirring and heating, starting timing reaction for 2 hours when the temperature is heated to 70 ℃, carrying out suction filtration on a carbon black solution after the reaction is finished, washing the carbon black solution to be neutral, and carrying out vacuum drying to obtain a solid, namely the oxidation modified carbon black.
The oxygen content of the oxidatively modified carbon black prepared in example 5 of the present invention was measured.
The results show that the oxygen content of the oxidatively modified carbon black of example 5 of the present invention increased from 1% to 8.9% of the original carbon black, which indicates that the surface functional groups of the carbon black were greatly increased and had better hydrophilicity.
The oxidized modified carbon black prepared in example 5 of the present invention was tested.
Weighing 0.1g of the oxidized modified carbon black prepared in the embodiment, adding the oxidized modified carbon black into 50mL of distilled water, carrying out ultrasonic oscillation for half an hour, respectively pouring the mixture into beakers, standing the mixture for 48 hours, measuring 2mL of supernatant and 2mL of distilled water, adding the supernatant and the 2mL of distilled water into a centrifuge tube, centrifuging the mixture at the rotating speed of 5000r/min for 20min, sucking the centrifuged supernatant into a cuvette by a needle tube, and measuring the transmittance at the wavelength of 510nm to be 19%.
The dispersion remaining in the beaker was also observed and recorded to have a dispersion stability of 55 days without delamination.
The result is consistent with the oxygen content test result of the carbon black, and the oxidation modified carbon black prepared by the invention is further proved to have better dispersion stability under a water system.
Referring to Table 1, Table 1 compares the performance index of the oxidized modified carbon blacks prepared in the examples of the present invention with that of the unmodified carbon blacks.
TABLE 1
The above results show that, compared with the water dispersibility of furnace carbon black, the dispersibility and dispersion stability of the carbon black modified by oxidation in water are obviously improved, and usually, the carbon black modified by oxidation does not settle and delaminate within 50 days, while the unmodified carbon black settles and delaminates in less than 1 day after being ultrasonically dispersed in water, which is consistent with the conclusion obtained from the transmittance of the supernatant. In the comparative example, by adopting a larger amount of hydrogen peroxide and higher temperature and time, the oxygen content of the carbon black is not changed greatly and is lower than that of the invention, and after two times of oxidation, the result is still lower than that of the invention. Thus, via heteropoly acid-H2O2The carbon black oxidized and modified by the composite oxidation system has obvious improvement on water solubility, and can be applied to the fields of water-soluble paint, ink and the like.
Comparative example 1
A500 ml three-neck flask with a thermometer and a condenser is added with stirring magnetons, 50g of carbon black and 600ml of hydrogen peroxide. And (3) putting the three-neck flask into a magnetic stirring water bath kettle, stirring and heating, starting timing reaction for 5 hours when the temperature is heated to 80 ℃, carrying out suction filtration on a carbon black solution after the reaction is finished, washing the carbon black solution to be neutral, and carrying out vacuum drying to obtain a solid, namely the oxidation modified carbon black.
The oxygen content of the oxidized modified carbon black prepared in comparative example 1 of the present invention was measured.
The results show that the oxygen content of the oxidatively modified carbon black of comparative example 1 of the present invention is increased from 1% to 4.8% of the original carbon black, which indicates that the surface functional group of the carbon black is increased to have hydrophilicity.
The oxidized modified carbon black prepared in comparative example 1 of the present invention was examined.
0.1g of each of the oxidized modified carbon blacks prepared in the comparative example 1 is weighed, added into 50mL of distilled water for half an hour of ultrasonic oscillation, then respectively poured into beakers, stood for 48 hours, 2mL of supernatant and 2mL of distilled water are measured and added into a centrifuge tube together, the centrifuge tube is centrifuged at the rotating speed of 5000r/min for 20min, the centrifuged supernatant is sucked into a cuvette by a needle tube, and the transmittance is 58% at the wavelength of 510 nm.
The dispersion remaining in the beaker was also observed and recorded to have a dispersion stability of only 20 days without delamination.
This indicates that the results obtained are consistent with the results of the carbon black oxygen content test.
Referring to Table 1, Table 1 compares the performance index of the oxidatively modified carbon blacks prepared in the examples of the present invention with that of conventional oxidatively modified, unmodified carbon blacks.
Comparative example 2
A500 ml three-neck flask with a thermometer and a condenser is added with stirring magnetons, 50g of carbon black and 600ml of hydrogen peroxide. And (2) putting the three-neck flask into a magnetic stirring water bath kettle, stirring and heating, starting timing reaction for 6 hours when the three-neck flask is heated to 90 ℃, taking a part of samples for detection after the reaction is finished, repeatedly performing oxidation modification according to the steps after the suction filtration of the rest carbon black solution, performing suction filtration and water washing on the carbon black solution to be neutral after the secondary reaction is finished, and performing vacuum drying to obtain a solid, namely the oxidation modified carbon black.
The oxygen content of the oxidized modified carbon black prepared in comparative example 2 of the present invention was examined.
The results show that the oxygen content of the oxidatively modified carbon black of comparative example 2 of the present invention increases from 1% of the initial carbon black to 4.9% after the first oxidation and to 7.9% after the second oxidation, which indicates that although the reaction time and temperature are increased, the oxidation degree of the oxidatively modified carbon black is substantially unchanged, and the surface functional group is increased again only after the second oxidation, thereby increasing the hydrophilicity.
The secondary oxidation modified carbon black prepared in comparative example 2 of the present invention was examined.
Weighing 0.1g of each secondary oxidation modified carbon black prepared in the comparative example 2, adding 50mL of distilled water into the mixture, carrying out ultrasonic oscillation for half an hour, respectively pouring the mixture into beakers, standing the mixture for 48 hours, weighing 2mL of supernatant and 2mL of distilled water, adding the supernatant and the 2mL of distilled water into a centrifuge tube, centrifuging the mixture at the rotating speed of 5000r/min for 20min, sucking the centrifuged supernatant into a cuvette by a needle tube, and measuring the transmittance at the wavelength of 510nm to be 32%.
The dispersion remaining in the beaker was also observed and recorded to have a dispersion stability of 35 days without delamination.
This indicates that the results obtained are consistent with the results of the carbon black oxygen content test.
Referring to Table 1, Table 1 compares the performance index of the oxidatively modified carbon blacks prepared in the examples of the present invention with that of conventional oxidatively modified, unmodified carbon blacks.
While the present invention has been described in detail with respect to a method for making an oxidatively modified carbon black and a method for making the same, and while the principles and embodiments of the present invention have been described herein in terms of specific examples, the foregoing examples are intended only to facilitate an understanding of the principles of the method and its core concepts, including the best mode, and also to enable any person skilled in the art to practice the invention, including making and using any devices or systems and performing any incorporated methods. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention. The scope of the invention is defined by the claims and may include other embodiments that occur to those skilled in the art. Such other embodiments are intended to be within the scope of the claims if they have structural elements that do not differ from the literal language of the claims, or if they include equivalent structural elements with insubstantial differences from the literal languages of the claims.
Claims (4)
1. The preparation method of the modified carbon black is characterized in that the carbon black is processed by heteropoly acid-H2O2Complex oxidation systemAfter oxidation, modified carbon black is obtained;
the oxygen content of the modified carbon black is 5-20%;
the pH value of the modified carbon black is 3-6;
the preparation method specifically comprises the following steps:
A) mixing carbon black, heteropoly acid and hydrogen peroxide, and reacting to obtain modified carbon black;
the carbon black includes furnace carbon black;
the oxygen content of the carbon black is 0.1-2%;
the pH value of the carbon black is 7-10;
the heteropoly acid comprises one or more of phosphotungstic acid, silicotungstic acid, phosphomolybdic acid and silicomolybdic acid;
the mass ratio of the carbon black to the heteropoly acid is (100-500): 1;
the mass ratio of the carbon black to the hydrogen peroxide is 1: (4-10);
the concentration of the hydrogen peroxide is 3-30%;
the reaction temperature is 30-80 ℃;
the reaction time is 1.0-6.0 h;
the mixing mode is ultrasonic mixing;
the mixing time is 0.5-2 h;
the reaction mode is that the reaction is carried out under the condition of water bath.
2. The production method according to claim 1, wherein the oxidation is primary oxidation;
the oxygen content of the modified carbon black increases with increasing temperature and/or time of oxidation.
3. The production method according to claim 1, wherein the carbon black is a carbon black after pretreatment;
the pretreatment comprises grinding and/or drying;
the particle size of the carbon black is 10-100 mu m.
4. The method of claim 1, further comprising a post-treatment step after the reaction;
the post-treatment comprises one or more of filtration, water washing and drying.
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| CN113105762A (en) * | 2021-04-13 | 2021-07-13 | 云南云维飞虎化工有限公司 | Method for improving dispersibility of carbon black |
| CN116041987A (en) * | 2022-12-12 | 2023-05-02 | 上海色如丹数码科技股份有限公司 | Preparation method of self-dispersing water-based carbon black |
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