CN114644841B - Carbon black nano material based on gel casting and preparation method thereof - Google Patents
Carbon black nano material based on gel casting and preparation method thereof Download PDFInfo
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- CN114644841B CN114644841B CN202210306640.XA CN202210306640A CN114644841B CN 114644841 B CN114644841 B CN 114644841B CN 202210306640 A CN202210306640 A CN 202210306640A CN 114644841 B CN114644841 B CN 114644841B
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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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/56—Acrylamide; Methacrylamide
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/36—Amides or imides
- C08F222/38—Amides
- C08F222/385—Monomers containing two or more (meth)acrylamide groups, e.g. N,N'-methylenebisacrylamide
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Abstract
The invention relates to the technical field of nano materials, in particular to a carbon black nano material based on gel casting and a preparation method thereof. The composite material comprises the following raw materials in parts by weight: 20-30 parts of carbon black, 1-5 parts of modifier, 1-5 parts of reinforcing agent, 1-3 parts of gel monomer, 1-3 parts of cross-linking agent, 0.1-1 part of dispersing agent and the balance of deionized water; according to the carbon black nano material based on gel casting and the preparation method thereof, the strength of the carbon black is improved and the dispersibility of the carbon black is improved through the added modifier and reinforcing agent, and the carbon black nano material prepared by the method has the advantages of stronger dispersibility, lower particle size and better strength.
Description
Technical Field
The invention relates to the technical field of nano materials, in particular to a carbon black nano material based on gel casting and a preparation method thereof.
Background
The gel casting process is a new wet forming process developed in recent years, and the product of the traditional ceramic forming process and polymer chemistry uses organic solvent or water as the dispersion medium of powder, and adds a certain amount of organic monomer into the suspension formed by adding dispersing agent to form uniform and stable suspension, and the curing process of the powder is completed by utilizing the polymerization of the organic monomer.
Carbon black is a carbon material with very special microstructure particle morphology and surface performance, and is fine granular black powdery substance carbon black formed by cracking and incompletely burning hydrocarbon such as hydrocarbon substance oil or natural gas; because the specific surface area of the carbon black is large, the carbon black is easy to aggregate, and the carbon black is difficult to uniformly disperse in a polymer matrix or an organic solvent, so that the maximum exertion of the potential performance of the carbon black is limited.
Disclosure of Invention
The invention aims to provide a carbon black nano material based on gel casting and a preparation method thereof, so as to solve the problems in the background technology.
In order to achieve the above object, in one aspect, the present invention provides a carbon black nanomaterial based on gel casting, comprising the following raw materials in parts by weight: 20-30 parts of carbon black, 1-5 parts of modifier, 1-5 parts of reinforcing agent, 1-3 parts of gel monomer, 1-3 parts of cross-linking agent, 0.1-1 part of dispersing agent and the balance of deionized water.
As a further improvement of the technical scheme, the modifier is at least one selected from vinyl monomers and polycarbonate, and 99% of carbon black particle size modified by the polycarbonate and the vinyl monomers is concentrated below 30 nm.
As a further improvement of the technical scheme, the reinforcing agent, namely one of glycidyl methacrylate and methacrylic acid, has the reinforcing effect by modifying the carbon black by the glycidyl methacrylate and the methacrylic acid, and improves the dispersibility of the carbon black.
As a further improvement of the technical scheme, the gel monomer is acrylamide, and the addition of the gel monomer not only plays a role in changing the slurry into gel, but also can improve the rheological property of the slurry, thereby being beneficial to the next degassing and injection molding.
As a further improvement of the technical scheme, the cross-linking agent is N, N-methylene bisacrylamide.
As a further improvement of the technical scheme, the dispersing agent is at least one selected from ammonium citrate, polyethylene glycol and ammonium polyacrylate, has the advantages of high stability and good water solubility, and can effectively improve the dispersibility and the stability by adding the dispersing agent, so that the solid phase content of the slurry is improved.
In another aspect, the present invention provides a method for preparing the gel casting-based carbon black nanomaterial described in any one of the above, comprising the steps of:
s1, adding carbon black, a modifier and a reinforcing agent into a mixing roll for mixing to prepare nano carbon black;
s2, mixing gel monomers, a cross-linking agent and deionized water to prepare a premix;
s3, adding nano carbon black into the premix, adjusting the pH value, adding a dispersing agent, and ball milling for 24-28 hours to obtain slurry;
s4, adding the slurry into an initiator and a catalyst, uniformly stirring, pumping air, injecting into a mold, and curing to obtain a carbon black blank;
s5, drying the blank body to obtain the carbon black nano material.
Preferably, in the step S1, the rotation speed of the mixing mill is 50-70r/min, and the mixing time is 28-32min.
Preferably, in the step S4, the air suction time is 60-80min.
Preferably, in the step S5, the drying temperature is 50-60 ℃.
Compared with the prior art, the invention has the beneficial effects that:
according to the carbon black nano material based on gel casting and the preparation method thereof, the strength of the carbon black is improved and the dispersibility of the carbon black is improved through the added modifier and reinforcing agent, and the carbon black nano material prepared by the method has the advantages of stronger dispersibility, lower particle size and better strength.
Drawings
Fig. 1 is an overall flow diagram of the present invention.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1 carbon black nanomaterial based on gel casting and method for preparing the same, comprising:
1. slurry preparation
1. Adding 20 parts of carbon black, 1 part of modifier and 1 part of reinforcing agent into a mixing roll for mixing to obtain nano carbon black, wherein the rotating speed of the mixing roll is 50r/min, and the mixing time is 28min;
2. mixing 1 part of gel monomer, 1 part of cross-linking agent and deionized water to prepare a premix;
3. adding nano carbon black into the premix, regulating the pH value, adding 0.1 part of dispersing agent, and ball milling for 24 hours to prepare slurry;
2. preparation of carbon black nano material
1. Adding the slurry into an initiator and a catalyst, uniformly stirring, pumping air for 60min, injecting into a mold, and curing to obtain a carbon black blank;
2. and drying the blank to obtain the carbon black nano material, wherein the drying temperature is 50 ℃.
Example 2 carbon black nanomaterial based on gel casting and method for preparing the same, comprising:
1. slurry preparation
1. Adding 23 parts of carbon black, 2 parts of modifier and 2 parts of reinforcing agent into a mixing roll for mixing to obtain nano carbon black, wherein the rotating speed of the mixing roll is 55r/min, and the mixing time is 29min;
2. mixing 1 part of gel monomer, 1 part of cross-linking agent and deionized water to prepare a premix;
3. adding nano carbon black into the premix, regulating the pH value, adding 0.3 part of dispersing agent, and ball milling for 25 hours to prepare slurry;
2. preparation of carbon black nano material
1. Adding the slurry into an initiator and a catalyst, uniformly stirring, pumping air for 60min, injecting into a mold, and curing to obtain a carbon black blank;
2. and drying the blank to obtain the carbon black nano material, wherein the drying temperature is 50 ℃.
Example 3 carbon black nanomaterial based on gel casting and method for preparing the same, comprising:
1. slurry preparation
1. Adding 25 parts of carbon black, 3 parts of modifier and 3 parts of reinforcing agent into a mixing roll for mixing to obtain nano carbon black, wherein the rotating speed of the mixing roll is 60r/min, and the mixing time is 30min;
2. mixing 2 parts of gel monomer, 2 parts of cross-linking agent and deionized water to prepare a premix;
3. adding nano carbon black into the premix, regulating the pH value, adding 0.5 part of dispersing agent, and ball milling for 26 hours to prepare slurry;
2. preparation of carbon black nano material
1. Adding the slurry into an initiator and a catalyst, uniformly stirring, pumping air for 70min, injecting into a mold, and curing to obtain a carbon black blank;
2. and drying the blank to obtain the carbon black nano material, wherein the drying temperature is 55 ℃.
Example 4 carbon black nanomaterial based on gel casting and method for preparing the same, comprising:
1. slurry preparation
1. Adding 27 parts of carbon black, 4 parts of modifier and 4 parts of reinforcing agent into a mixing roll for mixing to obtain nano carbon black, wherein the rotating speed of the mixing roll is 65r/min, and the mixing time is 31min;
2. mixing 3 parts of gel monomer, 3 parts of cross-linking agent and deionized water to prepare a premix;
3. adding nano carbon black into the premix, regulating the pH value, adding 0.7 part of dispersing agent, and ball milling for 27 hours to prepare slurry;
2. preparation of carbon black nano material
1. Adding the slurry into an initiator and a catalyst, uniformly stirring, pumping air for 80min, injecting into a mold, and curing to obtain a carbon black blank;
2. and drying the blank to obtain the carbon black nano material, wherein the drying temperature is 60 ℃.
Example 5 carbon black nanomaterial based on gel casting and method for preparing the same, comprising:
1. slurry preparation
1. Adding 30 parts of carbon black, 5 parts of modifier and 5 parts of reinforcing agent into a mixing roll for mixing to obtain nano carbon black, wherein the rotating speed of the mixing roll is 70r/min, and the mixing time is 32min;
2. mixing 3 parts of gel monomer, 3 parts of cross-linking agent and deionized water to prepare a premix;
3. adding nano carbon black into the premix, regulating the pH value, adding 1 part of dispersing agent, and ball milling for 28 hours to prepare slurry;
2. preparation of carbon black nano material
1. Adding the slurry into an initiator and a catalyst, uniformly stirring, pumping air for 80min, injecting into a mold, and curing to obtain a carbon black blank;
2. and drying the blank to obtain the carbon black nano material, wherein the drying temperature is 60 ℃.
In the above examples 1 to 5, the modifier was at least one selected from the group consisting of a vinyl monomer and a polycarbonate, and 99% of the carbon black particle diameter modified by the polycarbonate and the vinyl monomer was concentrated at 30nm or less;
at least one of the reinforcing agents glycidyl methacrylate and methacrylic acid, through the modification of the carbon black by the glycidyl methacrylate and the methacrylic acid, the reinforcing effect is achieved, and the dispersibility of the carbon black is improved;
the gel monomer is acrylamide, and the addition of the gel monomer not only plays a role in changing the slurry into gel, but also can improve the rheological property of the slurry, thereby being beneficial to the next degassing and injection molding;
the cross-linking agent is N, N-methylene bisacrylamide;
the dispersing agent is at least one of ammonium citrate, polyethylene glycol and ammonium polyacrylate, and has the advantages of high stability and good water solubility, and the dispersing agent can be added to effectively improve the dispersibility and stability of the dispersing agent, so that the solid phase content of the slurry is improved.
Specific indexes of the carbon black nano material based on gel casting and molding prepared by the invention are shown in table 1:
TABLE 1
According to Table 1, the carbon black nanomaterial in examples 1-5 all have a particle size of 30 or less and a hardness of 75 or more, which is sufficient to demonstrate the better performance of the carbon black nanomaterial prepared by the present invention.
Comparative example 1 carbon black nanomaterial based on gel casting and a method for preparing the same, comprising:
1. slurry preparation
1. Adding 25 parts of carbon black and 3 parts of reinforcing agent into a mixing roll for mixing to obtain nano carbon black, wherein the rotating speed of the mixing roll is 60r/min, and the mixing time is 30min;
2. mixing 2 parts of gel monomer, 2 parts of cross-linking agent and deionized water to prepare a premix;
3. adding nano carbon black into the premix, regulating the pH value, adding 0.5 part of dispersing agent, and ball milling for 26 hours to prepare slurry;
2. preparation of carbon black nano material
1. Adding the slurry into an initiator and a catalyst, uniformly stirring, pumping air for 70min, injecting into a mold, and curing to obtain a carbon black blank;
2. and drying the blank to obtain the carbon black nano material, wherein the drying temperature is 55 ℃.
Comparative example 2 carbon black nanomaterial based on gel casting and a method for preparing the same, comprising:
1. slurry preparation
1. Adding 25 parts of carbon black and 3 parts of modifier into a mixing roll for mixing to obtain nano carbon black, wherein the rotating speed of the mixing roll is 60r/min, and the mixing time is 30min;
2. mixing 2 parts of gel monomer, 2 parts of cross-linking agent and deionized water to prepare a premix;
3. adding nano carbon black into the premix, regulating the pH value, adding 0.5 part of dispersing agent, and ball milling for 26 hours to prepare slurry;
2. preparation of carbon black nano material
1. Adding the slurry into an initiator and a catalyst, uniformly stirring, pumping air for 70min, injecting into a mold, and curing to obtain a carbon black blank;
2. and drying the blank to obtain the carbon black nano material, wherein the drying temperature is 55 ℃.
The carbon black nano material based on gel injection molding, which is prepared by the invention, has smaller particle size and hardness, has larger relation with the added modifier and reinforcing agent, and in order to verify the related technical scheme, the applicant performs the following test:
comparative examples 1-2: the method of example 3 was used to detect the relevant index of the carbon black prepared, with the modifier and the reinforcing agent removed, respectively, and see in particular table 2:
TABLE 2
| Comparative example 1 | Comparative example 2 | Example 3 | |
| Particle size (nm) | 201 | 32 | 25 |
| Hardness (HA) | 75 | 55 | 83 |
According to Table 2, comparative example 1 and comparative example 3 show that the particle size of the prepared carbon black is larger in the case where the modifier is removed alone, and comparative example 2 and comparative example 3 show that the hardness of the prepared carbon black is lower in the case where the reinforcing agent is removed alone, so that it can be demonstrated that the effect of the carbon black nanomaterial prepared in the present invention is better.
The foregoing has shown and described the basic principles, principal features and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the above-described embodiments, and that the above-described embodiments and descriptions are only preferred embodiments of the present invention, and are not intended to limit the invention, and that various changes and modifications may be made therein without departing from the spirit and scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (5)
1. The carbon black nano material based on gel casting is characterized by comprising the following raw materials in parts by weight: 20-30 parts of carbon black, 1-5 parts of modifier, 1-5 parts of reinforcing agent, 1-3 parts of gel monomer, 1-3 parts of cross-linking agent, 0.1-1 part of dispersing agent and the balance of deionized water;
the modifier is at least one selected from vinyl monomers and polycarbonate;
one of glycidyl methacrylate and methacrylic acid as the reinforcing agent;
the gel monomer is acrylamide;
the cross-linking agent is N, N-methylene bisacrylamide;
the dispersing agent is at least one selected from ammonium citrate, polyethylene glycol and ammonium polyacrylate.
2. A method for preparing the gel-casting-based carbon black nanomaterial as claimed in claim 1, comprising the steps of:
s1, adding carbon black, a modifier and a reinforcing agent into a mixing roll for mixing to prepare nano carbon black;
s2, mixing gel monomers, a cross-linking agent and deionized water to prepare a premix;
s3, adding nano carbon black into the premix, adjusting the pH value, adding a dispersing agent, and ball milling for 24-28 hours to obtain slurry;
s4, adding the slurry into an initiator and a catalyst, uniformly stirring, pumping air, injecting into a mold, and curing to obtain a carbon black blank;
s5, drying the blank body to obtain the carbon black nano material.
3. The method for preparing the carbon black nanomaterial based on gel casting according to claim 2, wherein the method comprises the following steps: in the step S1, the rotating speed of the mixing mill is 50-70r/min, and the mixing time is 28-32min.
4. The method for preparing the carbon black nanomaterial based on gel casting according to claim 2, wherein the method comprises the following steps: in the step S4, the air extraction time is 60-80min.
5. The method for preparing the carbon black nanomaterial based on gel casting according to claim 2, wherein the method comprises the following steps: in the step S5, the drying temperature is 50-60 ℃.
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| CN1635008A (en) * | 2004-12-07 | 2005-07-06 | 天津大学 | Macromolecular grafted carbon black containing sulfonic groups and method for preparation |
| CN102807338A (en) * | 2012-08-17 | 2012-12-05 | 天津大学 | The method for preparing macroscopic body of porous carbon nano tube by gelcasting |
| CN104529460A (en) * | 2014-12-08 | 2015-04-22 | 中国建筑材料科学研究总院 | Water-base C/Si slurry and gel casting method for C/SiC green body |
| CN106634059B (en) * | 2016-12-16 | 2018-05-25 | 江南大学 | A kind of preparation method of aqueous self-dispersing nano carbon black |
| US20210147658A1 (en) * | 2017-09-11 | 2021-05-20 | Dow Global Technologies Llc | Polyethylene composition |
| CN113307645A (en) * | 2021-06-17 | 2021-08-27 | 山田研磨材料有限公司 | Method for preparing special-shaped silicon carbide ceramic by combining gel casting with reactive sintering process |
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